Interpenetrated Three-Dimensional Networks of ... - ACS Publications

Interpenetrated Three-Dimensional Networks of Hydrogen-Bonded Organic Species: A Systematic Analysis of the Cambridge Structural Database Igor A. Baburin,† Vladislav A. Blatov,*,† Lucia Carlucci,‡ Gianfranco Ciani,‡ and Davide M. Proserpio*,‡

CRYSTAL GROWTH & DESIGN 2008 VOL. 8, NO. 2 519–539

Samara State UniVersity, Ac. PaVloV St. 1, 443011 Samara, Russia, and Dipartimento di Chimica Strutturale e Stereochimica Inorganica (DCSSI), UniVersità di Milano, Via G. Venezian 21, 20133 Milano, Italy ReceiVed June 21, 2007; ReVised Manuscript ReceiVed NoVember 8, 2007

ABSTRACT: Interpenetration in extended three-dimensional (3D) arrays has been investigated by a systematic analysis of the crystallographic structural databases, using an ad hoc version of the program package TOPOS. In this paper we describe the comprehensive results of our investigation of interpenetration in organic hydrogen-bonded 3D arrays from the Cambridge Structural Database. The great interest in the self-assembly of organic molecules into hydrogen-bonded supramolecular arrays has prompted us to investigate these systems at a rather unusual level; that is, beyond the formation of synthons, we have examined the topologies of the resulting networks and looked for their entanglements. Within 3D architectures we have extracted a complete list including 122 different motifs showing the phenomenon of interpenetration (76 unseen by the original authors). These organic networks include species assembled by a single or by different building blocks; they are discussed and classified according to the previously introduced classes of interpenetration and to other criteria peculiar of hydrogen-bonded organic species. Considerations of the possible relations of the building organic species and their network topology and on the factors determining interpenetration are here presented. The paper is also intended as a contribution to the study of the phenomena of polymorphism and supramolecular isomerism and of the crystal engineering of these complex architectures. Introduction 1

Interpenetrating networks are nowadays common, and threedimensional (3D) entangled arrays are often encountered in the field of crystal engineering of metal-organic and inorganic networks, as well as in the design of supramolecular arrays of weakly bonded organic molecules. To rationalize these complex systems we need to investigate both the topology of the individual networks and the “topology of interpenetration,”2 that is, the way in which the individual nets are multiply (n-fold) entangled. This difficult and troublesome analysis can only be carried out by computer. We have previously reported our studies on interpenetrating metal-organic2d and inorganic2e networks, using a tailored version of TOPOS (a package for multipurpose crystallochemical analysis). We describe now the comprehensive results of our analysis of interpenetration in organic hydrogen-bonded 3D arrays (strong hydrogen-bonds) from the Cambridge Structural Database (CSD, version 5.28 of November 2006). Organic structures were first chosen among other hydrogenbonded compounds because the existence of well-defined molecules connected by strong hydrogen bonds makes the conclusions about interpenetration phenomenon reliable and unambiguous. The other class of interpenetrating hydrogenbonded nets that include metal-organic frameworks will be considered in a further publication. The self-assembly of organic molecules into hydrogen-bonded supramolecular arrays has been the subject of a number of studies concerning the synthetic approaches, the classification and rationalization of the patterns, and the factors governing * To whom correspondence should be addressed. (D.M.P.) Phone: +390250314446. Fax: +39-0250314454. E-mail: [email protected]. (V.A.B.) Phone: +7-8463345445. Fax: +7-8463345417. E-mail: blatov@ ssu.samara.ru. † Samara State University. ‡ Università di Milano.

the crystal engineering of these molecular materials. In principle, molecular building blocks (tectons) can be combined using suitable strategies to construct networks of desired topology. Unfortunately, while specific links between the building blocks (supramolecular synthons)3 can sometimes be controlled, the process leading from molecules to their periodic supramolecular arrays in crystals is still “a major challenge in the crystal engineering of molecular solids”.3a In the attempt to get closer to this goal, as well as to possess a detailed knowledge of the synthons, more attention needs to be devoted to the topology of the final architecture (target network) through the analysis of related structures reported in the literature by searching for prototypical models that can fit the specific problem. The large number of networks recently reported offers a rich variety of new structural types that continuously increase our knowledge of these organic or metal-organic extended systems. Indeed, the “network approach” or topological approach to crystal chemistry4 is a useful tool for the analysis of network structures in that it simplifies complex species to schematized nets and allows easier comparisons among packing trends that may help in the rational design of such materials. However, many papers reporting crystal structures of hydrogen-bonded organic species, especially the less recent ones, do not discuss the supramolecular nets (connectivity, dimensionality) and their topology (or sometimes assign incorrect ones) and generally overlook entanglement and interpenetration phenomena (only a quarter of the structures described in this paper have been explicitly recognized as interpenetrated). The topological rationalization of hydrogen-bonded organic frames is more difficult than that of metal-organic frames (MOFs): in the latter case metallic nodes and organic spacers are usually well-recognizable entities, while in organic frames the selection of the nodes is more ambiguous and the alternative

10.1021/cg0705660 CCC: $40.75  2008 American Chemical Society Published on Web 01/23/2008

520 Crystal Growth & Design, Vol. 8, No. 2, 2008

choice of the single tecton or of an oligomeric group as node leads to different, although interrelated, topological classifications. The previously introduced classification of interpenetrated net arrays2d,e has also been applied here to hydrogen-bonded organic frames, together with some specific parameters, and the peculiar features of the interpenetration are discussed and compared with those observed in other classes of materials. Note that the world record of interpenetration (18-fold) has been observed in a hydrogen-bonded organic frame. Using the list of the resulting interpenetrated net arrays we have further searched the CSD, looking for other species with identical or very similar composition, to possibly obtain new information for the study of polymorphism and in crystal design. The TOPOS Approach. In this study we have considered all organic (i.e., not containing metal atoms) compounds whose crystal structures are completely determined (except, possibly, for all the positions of hydrogen atoms) and collected in the Cambridge Structural Database (CSD, version 5.28 of November 2006). To find the interpenetrating arrays in an automated mode we have used the program package TOPOS5 with some subroutines especially designed to process hydrogen-bonded structures. Only strong or moderately strong hydrogen bonds6 were considered. The following criteria were applied to recognize different types of intermolecular A-H · · · B hydrogen bonding (intramolecular hydrogen-bonds are irrelevant to our topological analysis): (1) Only A, B ) N, O, F were considered, although no interpenetrating arrays with F-H · · · B or A-H · · · F hydrogen bonds were found. (2) The distance restriction R(A · · · B) e 3.5 Å was used. If the pertinent hydrogen atom positions were available, additional restrictions R(H · · · B) e 2.5 Å and ∠A-H · · · B g 120° were applied. (3) In addition, the geometrical criteria derived from Voronoi-Dirichlet polyhedra (VDP) of A, B, and H atoms were considered. A VDP is a convex polyhedron whose faces are perpendicular to segments connecting a central atom to other (surrounding) atoms, with each face bisecting the corresponding segment. The atom size in the crystal structure can be evaluated as the volume of its VDP or as Rsd, the radius of a sphere of the same volume as the VDP. Inasmuch as all surrounding atoms influence the VDP characteristics, VDP enables one to take into account the whole environment of interacting atoms. In particular, any pair of neighbor atoms has to be separated by a common face for their VDPs, and the size of a face is larger for stronger bonds. We have assessed this size as the solid angle of the face (Ω) expressed in percentage of the sum of solid angles for all faces (4π steradian, see also Figure 1). All contacts H · · · B or A · · · B with Ω < 10% were discarded as weak hydrogen bonds. (4) As in previous papers,2d,e to find valence bonds we consider two spheres around each atom: an internal sphere of Slater’s radius and an external sphere with the radius equal to Rsd. A valence bonding is assumed to exist if there are at least two intersections between the spheres of interacting atoms.5 In addition, this criterion enabled us to automatically recognize symmetrical A-H-B and resonance A-H T H-B hydrogen bonds, by finding two valence contacts with participation of hydrogen atoms. The validity of these criteria was checked by comparison with 60 899 compounds where hydrogen bonds (A, B ) N, O) exist according to CSD information7 and with all hydrogen-bonded interpenetrating arrays listed by Batten (http://www.chem.mo-

Baburin et al.

Figure 1. Voronoi-Dirichlet polyhedron of a hydrogen atom in the crystal structure of β-quinol (HYQUIN05). Hydrogen bonds are shown by dash-and-dot lines. The solid angle of the pyramid at the oxygen atom, Ω(H · · · O) ) 20.1%, is equal to the solid angle of the corresponding VDP face.

nash.edu.au/staff/sbatten/interpen/examples.html), and no discrepancies were found. We have used the TOPOS algorithm as recently applied to study valence bonded metal-organic and inorganic 3D frameworks, including inorganic compounds with hydrogen-bonds.2d,e We consider here crystal structures that contain organic molecules only (except for few species containing also some inorganic counteranions) and, since often the location of water molecules is poorly determined, we discarded cases where water molecules take part in the hydrogen-bond network. 122 interpenetrating arrays were revealed (Table 1) consisting of isolated organic molecules linked into 3D frameworks by hydrogen bonds (no valence bonded polymeric substructures were found). The nodes of the networks are therefore single molecules (tectons), a choice that naturally comes out from the automatic search routine (we call this the “standard topology”). Alternative more complex nodes could also be envisaged by selecting groups of linked molecules (ring synthons, vide infra), thus producing different topologies. We use a number of previously proposed descriptors to classify the interpenetration patterns.2d,e Seventy-six interpenetrated net arrays formed by hydrogen bonds between the ligands of metal complexes have been also found, but they will be discussed in a separate publication. Let us emphasize that both search and classification of the interpenetrating hydrogen-bonded arrays are performed here for the first time using strict computer algorithms. Such approach allows one to find out all the cases irrespective of the crystal structure complexity and to avoid faults and misses of human handmade analysis. In particular, 71% of the structures listed in Table 1 were not recognized as interpenetrated by the authors of original works and were not presented in the most comprehensive Batten’s collection. Furthermore, in 25% of the structures the 3D nature of the hydrogen-bond interactions was not recognized. Analysis of the Results. The results of the present analysis are listed in Table 1, which includes 122 different interpenetrat-

JARBOU

HIVBET INUJUW

FAFXUF GESTAZ GIMSIE NTRTAC/01 TERRUD BAXKIV BERCUW BOLZIL CYANAM01 FEWSAC

JUTGOU OHUJOQ QUSMEW CINMER EJUZOY

XUVBEV

XEBTIH Si (VOJFAB) VOJFAB GEJVEW JADMAD XUVBAR

HNAFPY10 PAZHOO

UGUMUE SAYNAI01 QACPEP KAPFIR KANVUR SAYMUB01 ADENSL NUZKAU TIPKIM

QECNAN KUSTOH

IBUXIN AHEGOJ IQAFEL

REFCODE

3-connected nets 3,5-dinitrobenzamide hydrate 2-amino-4-(4-chlorophenylthio)-6-morpholinopyrimidine 2-bromo-6-ethoxy-7-hydroxy-6,7-dihydro-5H-imidazo[1,2-b][1,2,4] triazin-3-one 1-hydroxy-2-phenyl-1H-2,4,1-benzodiazaborin-3-one (2R,9S,12S,13R)-12-(cyclohexylmethyl)-9-[[(1,1-dimethylethoxy) carbonyl]amino]-13-hydroxy-2-(morpholinomethyl)-6,10,14-trioxo1,7-dioxa-11-azacyclotetradecane 5-(trifluoromethyl)uracil 3-(chloroacetamido)pyrazole 2-amino-5-n-butyl-3-ethyl-6-methyl-4(3H)pyrimidinone 2,6-diaminopyridinium 4-nitrophenolate 4-nitrophenol 4-hexyl-6-amino-3-phenyl-5-cyano-2H,4H-pyrano(2,3-c)pyrazole bis(benzene-1,3,5-tricarboxylic acid) tris(1,2-bis(4-pyridyl)ethane) adeninium sulfate methylammonium 4-nitrophenolate N′-((S)-N′-benzoyl-methyl-2-phenyltyrosyl)-(S)-phenylalanine cyclohexylamide 1-(4-acetyl-5-methyl-2-furyl)-1,3-dideoxy-3-nitro-β-D-xylopyranose 3-carboxypyridinium hydrogen chloranilate 4-connected nets tetrakis(4-(3-hydroxyphenyl)phenyl)methane bis(benzoquinone) (4-((6-oxopyrid-2-yl)ethynyl)phenyl)silane clathrate (4-((6-oxopyrid-2-yl)ethynyl)phenyl)methane clathrate adamantane-1,3,5,7-tetracarboxylic acid methanetetrapropionic acid (methanetetrayltetra-4,1-phenylene)tetrakis(boronic acid) - two different clathrates: XUVBIZ (silanetetrayltetra-4,1-phenylene)tetrakis(boronic acid) pentakis(ethyl acetate) hydrate clathrate 4-aminophenyl(4′-cyanophenyl)sulfone 16,20-dinitro-(3,4,8,9)-dibenzo-2,7-dioxa-5,10-diaza[4.4.4]propellane 2,6-dimethyl-1,3,5,7-cyclooctatetraene-1,3,5,7-tetracarboxylic acid pyridine 3,4-dicarboxylic acid cis,cis-1,3,5-cyclohexanetricarboxylate hemikis(1,4-bis(2-(4-pyridinio)ethenyl)benzene) (+)-pinoresinol methanetetracetic acid 2-oxo-6,6-dihydroxy-adamantane-1,3,5,7-tetracarboxylic acid nitrilotriacetic acid N-acetyl-L-glutamic acid ammonium bis(trans-1,2-bis(pyrid-4-yl)ethene N,N′-dioxide) junceine 2-hydroxy-N-methylcyanoacetamide cyanamide cis-anti-4a,8a-dimethyl-4b,5,8a,8b-tetrahydropyrido (2′,3′:3,4)cyclobuta(1,2-b)pyridine-2,6(1H,4aH)-dione genistein morpholine tetrakis(1,2-dihydro-2-oxo-5-pyridyl)silane - six different clathrates INUKAD,YINJOU/01,YINKAH,YINKEL,YINKIP 2,5-bis(4-aminophenyl)-1,3,4-oxadiazole

name

AA

AB (A) AA

AA AA AA AA AA AB (A) AA AA AA AA

AA AA AA AA AB (A)

AA

AB (A) AA AA AA AA AA

AA AB (AB)

AA AA AA ABC (AB) AA AB (A) AB (AB) AB (AB) AA

AA AA

AA AA AA

type (node)

dia

dia dia

dia dia dia dia dia dia dia dia dia dia

dia dia dia dia dia

dia

dia dia dia dia dia dia

ths ths

etb lig lig cds-3-Pnna pcu-h srs srs srs srs

dia-f eta

dia-f dia-f dia-f

net

Table 1. Interpenetrating Hydrogen-Bonded Networksa

2

2 2

3 3 3 3 3 2 2 2 2 2

4 4 4 3 3

5

11 8 7 5 5 5

3 2

2 3 2 3 2 18 2 2 2

2 2

6 2 2

Z

IIa

IIa Ia

Ia Ia Ia Ia Ia IIa Ia Ia IIa IIa

IIIa Ia IIIa Ia Ia

Ia

Ia Ia Ia Ia Ia Ia

Ia Ia

Ia Ia Ia Ia Ia IIIb IIa IIa Ia

Ia Ia

Ia Ia Ia

class

(8.12)/i (6.85) (11.09)/2-axis (5.28) (4.79)

i

i [0,0,1] (7.66–9.58)

[1,0,0] (8.25) [0,0,1] (8.96) [1,0,0] (7.33) [0,0,1] (6.49) [1,0,0] (4.90) 2-axis [1/2,1/2,0] (10.43) [0,1,0] (3.95) i i

[0,1,0] [1,0,0] [1,0,0] [0,0,1] [1,0,0]

[1,0,0] (10.84)

[0,0,1] (6.91) [1/2,1/2,1/2] (19.9) [0,1,0] (7.35) [1,0,0] (7.51) [1,0,0] (9.46) [1,0,0] (10.6–10.8)

[0,0,1] (17.98) [0,1,0] (5.43)

[0,0,1] (5.19) [0,0,1] (5.20) [0,0,1] (8.81) [1,0,0] (13.61) [1,1,1] (8.48) 4 PIVs/i i i [0,0,1] (10.68)

[0,0,1] (7.74) [0,0,1] (18.93)

[0,0,1] (6.00) [0,0,1] (7.01) [0,0,1] (4.22)

symmetry

1.00

1.00 2.00

1.00 2.00 2.00 1.00 1.50 1.00 1.00 1.00 1.00 1.00

1.00 1.00 1.00 1.00 1.00

2.00

1.00 2.00 2.00 2.00 2.00 2.00

1.33 1.00

1.33 1.33 1.33 1.25 1.33 1.00 1.67 1.00 1.33

1.33 2.00

1.33 1.33 1.33

HBRI

a

a

a,b a a a,b

a,b I I c VII, a

a a a a a

I

I I I I I

a a

a a IX, dia, a,b

I, nbo,a,b I, lvt,a I, lvt,a,b a VIII, nbo,a

I, lvt,a,b a,b

I, lvt, a,b,c I, lvt,a,b I, lvt,a,b

note

Interpenetrated 3D Networks of H-Bonded Organic Species Crystal Growth & Design, Vol. 8, No. 2, 2008 521

bis(1,3-dimethylureido)methane di(2-(2-hydroxyethoxy)phenyl) ditelluride bis(C-methylcalix[4]resorcinarene) tris(4,4′-bipyridyl) 4-amino-3-(1,2,4-triazol-1-ylmethyl)-1H-1,2,4-triazole-5(4H)-thione 1,1′-(1,2-ethanediyl)-bis(l-pyroglutamic acid) (E,E)-4-amino-3-cyano-4-methoxy-1-(4-methoxyphenyl)-2-aza-1,3butadiene 1-(carboxymethyl)uracil 2,6-dimethylideneadamantane-1,3,5,7-tetracarboxylic acid - three different clathrates VOBFEX, VOBFIB 2,6-dimethylideneadamantane-1,3,5,7-tetracarboxylic acid - two different clathrates VOBFUN 2,6-dimethylideneadamantane-1,3,5,7-tetracarboxylic acid clathrate 3-hydroxy-1-methyl-4-oxopyridine-6-carboxylic acid 6-methylisocytosine-5-acetic acid 6-methylisocytosine-5-propionic acid 5-hydroxyisophthalic acid - 4,4′-trimethylenedipyridine 3,4-dihydroxybenzaldehyde-4-nitrophenyl-hydrazone p-acetamidoperbenzoic acid p-propanamidoperbenzoic acid 1,3-diamino-2,4,6-trinitrobenzene 5-fluoro-1,3-diamino-2,4,6-trinitrobenzene 4-((2-(4-aminophenyl)ethyl)sulfanyl)phenol 4,5-dihydro-7-amino-5-oxo-[1,2,4]-triazolo[1,5-a] pyrimidine 4-aminoisothiazolo(4,3-d)isoxazole 4-carboxamido-1-cubanecarboxylic acid 2,2′-diamino-4,4′-bi-1,3-thiazolium fumarate 2-aminoethene-1,1,2-tricarbonitrile terephthalate bis dimethylammonium p-formamidobenzoic acid 2,7-dimethyltricyclo[4.3.1.13,8]undecane-syn-2,syn-7-diol - eight different clathrates: BUXRIV10, LORQOY, LORQUE, POLFIF, QULKOX, QULLAK, VUSYEN 2,7-dimethyl-9-thiatricyclo[4.3.1.13,8]undecane-anti-2,anti-7-diol anti-2,2′-bi(tricyclo[3.3.0.03,7]octylidene)-4,4′-diol acetamidine 3,3′,5,5′-tetramethyl-4,4′-bipyrazolyl 3,3′,5,5′-tetramethyl-4,4′-bipyrazolyl tris chloroform 3,3′,5,5′-tetramethyl-4,4′-bipyrazolyl methanol (3:1) 1,6-dihydroxydodecamethylhexasilane 3,3′-(ethylenedi-imino)-bis(3-methyl-2-butanone oxime) 3,3′-(trimethylenedi-imino)-bis(3-methyl-2-butanone oxime) 2,3-butanedione dihydrazone 6-amino-1,3-dimethyl-5-hydroxyiminomethyl-2,4(1H,3H)pyrimidinedione 11,23-di-t-butyl-3,7,15,19-tetra-azatricyclo (19.3.1.19,13) hexacosa-1(25),9(26),10,12,21,23-hexaene-2,8,14,20-tetraone 5,11,17,23-tetra-t-butyl-25,27-dihydroxy-26,28-bis(3hydroxybenzoyloxy)calix[4]arene trans-2,8-dihydroxy-2,4,4,6,6,8,10,10,12,12-decamethyl-5,11dicarbacyclohexasiloxane (-CH2-) trans-2,8-dihydroxy-2,4,4,6,6,8,10,10,12,12-decamethyl-5carbacyclohexasiloxane (-O-)

KERBAK LAYFUN LUYGAN PANGOB SEJSIJ SIVTUM

TAKFUH

TAKFER

MIZRIW

ICERAK

WOYLEB NUGNIM CALVAM UDAYUT02 HUXMIW HUXMUI LUVPUN BOLNOF CEYSOO FAXHOB01 HEKWUP

VOBGAU WEZPEW ZERMUE ZERNEP BEQVUO SIDVOQ ZUHHIT ZUHHOZ DATNBZ BEWYOR ENANIQ HOTSOY JIGCIL JUNQIS TADRUM TAPZOA WAKFOE WOVVUY BUXRIV

VOBFOH

TAQXAL VOBFAT

name

REFCODE

AA

AA

AA

AA

AA AA AA AA AA AB (A) AA AA AA AA AA

AA AA AA AA AB (A) AA AA AA AA AA AA AA AA AA AB (AB) AA AB (A) AA AA

AA

AA AA

AA AA AB (A) AA AA AA

type (node)

Table 1. Continued

lvt

lvt

lvt

lvt

gis gis gis lcv lcv lcv lvt lvt lvt lvt lvt

dia dia dia dia cds cds cds cds cds cds cds cds cds cds cds cds cds cds gis

dia

dia dia

dia dia dia dia dia dia

net

2 2 2 2 4 3 3 3 2 2 2 2 2 2 2 2 2 2 2

2

2 2

2 2 2 2 2 2

2

2

2

2

2 2 2 6 2+2 6 3 2 2 2 2

Z

Ia

Ia

IIa

Ia

IIa Ia Ia IIIa IIa+IIa IIIa Ia Ia IIa Ia IIa

Ia Ia Ia Ia IIIa Ia Ia Ia Ia Ia Ia Ia Ia Ia Ia Ia Ia Ia IIa

IIa

Ia IIa

IIa IIa Ia IIa Ia IIa

class

[0,0,1] (11.36)

[0,0,1] (9.85)

i

[0,0,1] (13.68)

i [0,0,1] (6.13) [0,0,1] (5.70) [0,0,1] (8.60)/c-glide i [0,1,0] (9.64)/i [0,0,1] (29.54) [0,0,1] (6.27) c-glide [0,0,1] (4.11) i

[0,0,1] (10.93) [0,1,0] (4.51) [1,0,0] (4.90) [1,0,0] (5.71) [0,1,0] (7.39)/i [1/2,1/2,0] (7.18) [1,0,0] (5.05) [1,0,0] (4.89) [0,1,0] (5.20) [0,1,0] (5.12) [0,1,0] (5.86) [1,0,0] (5.08) [0,1,0] (6.37) [0,1,0] (7.13) [1,0,0] (5.28) [0,1,0] (5.75) [1,0,0] (9.64) [0,1,0] (3.86) i

2-axis

[0,1,0] (4.63) i

i i [1/2,1/2,0] (15.28) i [1,0,0] (7.51) i

symmetry

1.00

1.00

1.00

1.00

1.00 1.00 1.00 1.33 1.00 1.00 1.00 1.00 1.00 1.00 1.00

2.00 1.00 1.50 2.50 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.50 1.00 1.50 1.50 1.00 1.00 1.00 1.00

2.00

2.00 2.00

1.00 1.00 2.00 1.00 1.00 1.00

HBRI

III, dia,a

III, dia,a

a

a,b

III, lvt III, lvt,a,b III, lvt,a II, srs II, srs II, srs III, dia,a a a,b a,b a,b

a III, lvt

a a a a a a I, new 6-c,a a,b c a c

I a,b IX,pcu,a,b IX, pcu,a,b

I

a I

a a a

a,b a

note

522 Crystal Growth & Design, Vol. 8, No. 2, 2008 Baburin et al.

acetylacetone dioxime (-)-phenylahistin 2,2′′,6,6′′-tetramethyl-4,4′′-terphenyldiol diethyl 2,5-diaminoterephthalate 1,4-bis(hydroxymethyl)cubane β-hydroquinone - eight different clathrates BICZIX, BUSPAG, HQUACN/01, HYQHCL/01, JAMKEN, QUOLSO/01, ZZZVLG01, ZZZVLI01 2,2′-dimethyl-4,4′-biimidazole [2-hydroxyphenyl)-(3,5-dihydroxyphenyl)methane] bis(4,4′-bipyridine) benfotiamine 1,3,5-tris(4-hydroxyphenyl)benzene 1,2-bis(3,4-dimethoxyphenyl)-1,2-ethanediol 4-hydroxybenzaldehyde (4-nitrophenyl)hydrazone 1,2,3-triamino-guanidinium nitrate 1,10-dihydroxybicyclo(8.8.8)hexacosane. 17R-phenyl-androst-5-ene-3β,17β-diol 5-connected nets protosappanin A 3,5-diamino-2,4,6-trinitrobenzoic acid C-methylcalix[4]resorcinarene bis(4-pyridylmethylidyne)hydrazine 1:2 6-connected nets 2,4-dihydrogen cis,trans,cis,trans-1,2,3,4-cyclobutanetetracarboxylate bis(imidazolium) 3′-deoxysangivamycin N-(carbamoylmethyl)iminodiacetic acid tetrakis(4-hydroxyphenyl)methane tetrakis(4-hydroxyphenyl)silane 3,3,9,9-tetrakis(4-(2,6-diaminotriazen-4-yl)benzyl)-2,4,8,10-tetraoxospiro [5.5]undecane, two different clathrates WUCYUC 8-connected nets 5,10,15,20-tetrakis(4-((N-n-butylcarbamoyl)methoxy)phenyl)porphyrin mixed connectivity nets malonic acid bis(isonicotinamide) 4-aminopyridin hemiperchlorate 4-aminopyridin hemiperchlorate hydroquinone bis(isonicotinamide) urea E-butenedioic acid (2:1) urea butanedioic acid (2:1) guanidinium hydrogen monofluorophosphate adenine hydrogen peroxide (1:1) 4,4′-biphenol bis(4,4′-biphenolate) meso-5,5,7,12,12,14-hexamethyl-1,4,8,11-tetra-azacyclotetradecane guanidinium 4-carboxybenzenesulfonate guanidinium 4-hydroxy-3-carboxybenzene sulfonate N,N,N′,N′-tetra-amino-piperazindiium bis azide (4,4′-bipyridine)3(2,3,5,6-tetrahydroxy-1,4-benzoquinone)2

VATPAI WEQSUG KAPVIH BASVUM01 HIKNOE HYQUIN05

a

AB (AB) AB (AB) AB (AB) AB (AB)

AB (AB) ABC (ABC) ABC (ABC) AB (AB) AB (AB) AB (AB) AB (AB) AB (AB) ABC (AB)

AA

AA AA AA AA AA

AB (A)

AA AA AB (A)

AA AB (A) AA AA AA AA AB (AB) AA AA

AA AA AA AA AA AA

gra hms rtl fsc

dmd bp5 bp4 bp2 bp2 bp2 dmc bp3 tfc

bcu

pcu pcu pcu pcu bp1

pcu

bnn nov sqp

nbo neb neb neb qtz sqc187 sra uoc uoc

lvt lvt nbo nbo nbo nbo

net

Table 1. Continued type (node) 2 2 4 2 2 2

2 2 2 3

3 2 2 3 2 2 2 3 3

2

2 2 2 2 2

2

2 2 3

2 8 2 2 2 2 2 1+1 3

Z

IIa IIa Ia Ia

Ia Ia IIa Ia Ia Ia Ia Ia Ia

IIa

Ia IIa IIa IIa IIa

IIa

IIa Ia Ia

Ia IIIa Ia IIa Ia IIa Ia heterointerpenetration Ia

Ia Ia Ia Ia Ia Ia

class

(8.39)

(9.66)

(5.00) (15.76)/i (14.43)

(5.98) (8.31) (10.01) (6.94) (5.73) (5.47)

[1,0,0] (6.41) [1,0,0] (8.89)

i

[0,0,1] (15.68) [1,0,0] (11.22) i [0,1,0] (5.41) [1,0,0] (5.54 Å) [1,0,0] (5.64 Å) [1,0,0] (6.78) [1/2,1/2,0] (6.97 Å) [1,0,0] (9.96)

i

[0,0,1] (5.08) i i i i

2-screw

2-screw [1,0,0] (7.25) [1,0,0] (13.81)

[0,0,1] (12.49)

[0,0,1] [0,0,1] [0,0,1] i [0,0,1] i [1,0,0]

[0,0,1] [0,0,1] [0,0,1] [0,0,1] [0,0,1] [0,0,1]

symmetry

For the column “note” see text. The references for the REFCODE are listed in alphabetical order from number 25 for AGLUAM10 to number 181 for ZZZVLI01.

HIBDED/01 ETIGAP TAPIPZ TIJKOM

ULAWEJ APYRDN APYRDN01 VAKVIN TIPWIY/01 VEJXAJ/01 XOMPOE JOZZED CUTYEV

BAWJUF

PICTIE QIFQIF UJOFEE UJOFII WUQYOW

MEQQUU

DOVSUC DACYEL MURQOF

LEBKUZ RASBOD JUKVOA MIGRID HAGPUA ITUXIE TAGUDN/01 DASDIL CAXROI

name

REFCODE

1.50 1.50 1.00 1.00

1.20 1.10 1.00 1.20 1.60 1.60 1.43 1.43 1.00

1.00

1.00 1.00 1.00 1.00 2.67

1.20

1.20 1.20 1.78

1.00 1.00 1.50 1.25 1.00 1.50 1.00 1.00 1.00

1.00 1.00 1.00 1.00 1.00 1.00

HBRI

I, a I, a a

I, pts, a N-H-N, sra,a N-H-N, lon,a I, cds, a I, a I, a I, rtf, a I, new (3,6)-c,a

a,b

c I, c

a,b a

I, a,b

a I, bcu,a

VI, pcu, a c I, lig, a a a,b a a III, dia, a, b III, dia,a,b

IV,dia,a,b a,b V, pcu a V, pcu,a,b V, pcu

note

Interpenetrated 3D Networks of H-Bonded Organic Species Crystal Growth & Design, Vol. 8, No. 2, 2008 523


ing 3D arrays. These species are reported in CSD with a greater number of entries since different Refcodes are attributed in CSD to multiple crystal structure determinations (e.g., NTRTAC, NTRTAC01) or to compounds that contain different guest solvents but give the same supramolecular architecture, that is, the same topology (e.g., XUVBAR, XUVBIZ). The columns of Table 1, besides the Refcode and the chemical formula, report the following information: (a) TYPE (NODE): AA (homomolecular), AB, or ABC are used for one, two, or three different building units that contribute to the networks (solvent molecules are not included); note, however, that these symbols do not give the actual ratio of the components. Homomolecular species with crystallographically different molecules are classified AA. The networks nodes, when necessary, are also specified; that is, for TYPE AB we can have as nodes only molecules A or both A and B: in the former situation the TYPE (NODE) indication is AB(A), while in the later one we give AB(AB). Moreover, note that a molecule, in principle, can work both as a node and as a spacer (2 connecting node) depending on the number and directionality of the hydrogen bonds. (b) TOPOLOGY: we give the three-letter symbol of the net proposed by O’Keeffe8 as can be retrieved from RCSR database (Reticular Chemistry Structure Resource, http://rcsr.anu.edu.au/). Seven nets found here are not listed in RCSR, but one (sqc187) was found in EPINET database (Euclidean Patterns in NonEuclidean Tilings, http://epinet.anu.edu.au/, names starting with sqc)9 and another (cds-3-Pnna) in the recent list produced by Blatov.10 Five nets are new, and we propose as names bp1, bp2, bp3, bp4, bp5. For the nomenclature and recognition of new nets we follow the lines in refs 1e and 5. The corresponding Schläfli Symbol before the three-letter symbol11 is also reported throughout the text and in the schemes showing the molecular building blocks (see later). In some cases for more detailed description of the net topology we use other topological indices such as Coordination Sequences and Vertex Symbols.1e,5 (c) Z/CLASS/SYMMETRY: the degree of interpenetration Z and the interpenetration Class2d,e are reported. The column SYMMETRY gives the interpenetration vectors (Å) and/or the symmetry operations that relate equivalent interpenetrating nets. (d) HBRI (H-Bond Ratio Index): this parameter gives the ratio (no. of total effective hydrogen bonds per asymmetric unit/ no. of theoretical single bonds required by connectivities of the nodes). The following equation can be used: HBRI ) [2(Ntot/Z') - HBS]/(Σ Con Nodes) with Ntot ) total number of intermolecular hydrogen bonds in the crystallographic unit cell; Z′ (corrected Z) ) number of effective repeated units (whole molecules) in the cell taking into account the possible special positions; HBS ) number of hydrogen bonds connecting the independent spacers (if any) to the nodes; Σ Con Nodes ) sum of the connectivities of all the independent nodes. A more direct evaluation can be performed by simple inspection of the molecular drawings reported in the schemes (see below). HBRI depends on the choice of the nodes and could be considered as an indication of the stability of the framework; that is, values >1 reveal the presence of multiple hydrogen-bond bridges joining the building blocks. Simple considerations for type AA nets, first introduced many years ago,12 based on the balance of the number of hydrogen-bond donor and acceptor groups in the building block show that only with even net connectivities we can have an exact match and HBRI ) 1, while with odd connectivities the value of HBRI must be >1. This seems also to indicate that in type AA nets

Baburin et al. Scheme 1

the odd connectivities, due to the possibility of facing the abovementioned mismatch in the balance, are less likely to occur (see below) because the molecular structure is not always such to form stable cyclic synthons or multiple hydrogen-bond bridges. (e) The NOTE column gives some extra information. The presence of a certain supramolecular “ring synthons” is reported giving the numbers from Scheme 1 (I–IX) and Figure 6 (X). When a certain “ring synthon” gives rise to a “ring synthon net” the different topology is also indicated. With “ring synthon net” we mean that the nodes of the alternative net are located at the center of the group of molecules (tectons) linked in the supramolecular synthon and the edges of the alternative net correspond to tectons (see below Figures 6 and 7). This demonstrates the unavoidable arbitrariness that, considering also the subjective choice of the Ω lower limit, is involved in the topology assignment of hydrogen-bonded organic nets. Note, however, that the topologies of the “standard” net and the corresponding “ring synthon net” are rigorously interrelated (vide infra).13a Further information is labeled as follows: (a) if the interpenetration was not recognized in the original paper (87 cases), (b) if 3D hydrogen-bonded nets were not detected (30 cases), (c) if connectivity and/or topology of the net were wrongly assigned, and/or some hydrogen-bonds were missed (seven cases). The topology distribution and the most frequently observed nets are shown in Figures 2 and 3. An evident difference from valence-bonded interpenetrating MOFs and from interpenetrating inorganic networks is that the main part of topologies are related to 4-c nets (ca. 68%), while 3-c (ca. 13%) and 6-c (5%) ones are rather rare. The rarity of 3-c nets can be considered in relation to the point quoted above (discussion on HBRI and on odd and even connectivities).12 The analysis of more than 2000 3D hydrogen-bonded homomolecular single nets in CSD13a,b is in very good agreement with the expected trend; that is, the even connectivities are largely dominant over the odd ones. At the same time, in the single nets high even connectivities (6-c or 8-c nets) are very frequent, a fact that can be related to the tendency to form a molecular close packing (see Figure 2 bottom and Figure 4 top). The different distribution of the topologies reported in Figure 2 with respect to other interpenetrating 3D systems is confirmed by the fact that diamondoid nets, the most numerous nets, are only 31.1% (vs. 42–44% in interpenetrated MOFs and inorganic networks).14 It may be surprising to some readers that the total number of interpenetrated nets is so small. Preliminary results reported in Figure 4 (bottom) show that the interpenetrated 3D nets are only a small fraction of all 3D nets; further, the incidence of interpenetration in hydrogen-bonded nets is 10 times smaller than that for valence bonded ones (MOFs). This striking result is in contrast to the fact that infinite hydrogen-bonded nets are

Interpenetrated 3D Networks of H-Bonded Organic Species

Crystal Growth & Design, Vol. 8, No. 2, 2008 525

Figure 3. The most frequently observed nets (see also Figure 2).

Figure 2. (top) Distribution of the net topologies within the 122 structures; (bottom) distribution of the connectivity of the nodes (n-c). The table shows the occurrence for nets assembled by a single (Type AA) or by different (Type AB) building blocks.

three times more frequent than MOFs: hydrogen-bond interactions more often form infinite motifs. It follows that it is easier to observe subnets that are cross-linked (hence destroying interpenetration) by such interactions giving a unique 3D net with high connectivity (>6, see Figure 4 top). Observing the other parameters we note that for the large majority of the nets the value of the degree of interpenetration is Z ) 2 (see Figure 5) and the classes of interpenetration are either Ia or IIa. There are few exceptions: in particular we must mention the case of the 103-srs net SAYMUB01, that has Z ) 18, by far the highest value ever found, and belongs to the rare Class IIIb.15 Other noteworthy species are XEBTIH, 66-dia with Z ) 11 and few net arrays belonging to the uncommon Class IIIa: RASBOD, 66-neb, Z ) 8, HUXMUI and UDAYUT02, 32.104-lcv, Z ) 6, BEQVUO, 65.8-cds, Z ) 4, JUTGOU and QUSMEW, 66-dia, Z ) 4. The values of HBRI are in many cases >1, as discussed above, showing that in hydrogen-bonded systems especially of type AA, the single molecules tend to use all the possible hydrogen bonds, according to the Donohue and Etter rules.16 In the following discussion, we will present the different topologies using various Schemes that show groups of structures in order of increasing connectivity. As already mentioned, for each Refcode we have also searched in the CSD for related structures differing only in some ‘minor’ structural details

considered not influent on the hydrogen-bond patterns (i.e., a different halogen atom, a different -R similar substituent group and so on). This was accomplished with the aim of possibly finding, by comparing the structures, elements useful for their rationalization and for the crystal engineering of these architectures. Hydrogen-Bonds and Network Topologies. We have found interpenetrating nets mainly possessing common topologies (Figure 3). Nevertheless we have also observed some cases with quite rare topologies and discovered a few examples of completely new ones. 3-c nets. Three-connected nets (only 16 cases) possess many different topologies (see Table 1 and Scheme 2). Four nets of type AA have the 4.142-dia-f topology using the molecular nodes, but all give 4-c nets of the 42.84-lvt topology with molecular dimer nodes (ring synthon I). The most interesting is IBUXIN, which is 6-fold interpenetrated while the other three (AHEGOJ, IQAFEL, QECNAN) are only 2-fold interpenetrated. The authors gave a different description of IBUXIN taking into account an intermolecular C-H · · · O interaction but neglecting an N-H · · · O one. By including these C-H · · · O contacts also, a unique single 5-c net with a new topology is produced. Drastic effects on the net topology are produced by the change of a substituent in the molecular tecton, though the same local hydrogen-bond pattern (i.e., the system of hydrogen-bonds formed by a molecule) is maintained. This is the case of QECNAN: by replacement of the phenyl group with a methyl one we have the species NUJQOY with the same hydrogen bonds but exhibiting a 2D 3-c net, with the 63-hcb honeycomb topology here as brick-wall. Moreover, in KANVUR, a 2-fold 6.102-pcu-h net (or a 64.82-nbo net considering dimer nodes), the substitution of the n-hexyl side chain by an i-propyl group results in KANWAY, which contains 1D polymers.


Figure 4. (top) Distribution by the node connectivity of single 3D homonuclear hydrogen-bonded nets from refs 13a and 13b. (bottom) Occurrence of infinite nets in MOFs and hydrogen-bonded frameworks divided by dimensionality.

Figure 5. Distribution of the degree of interpenetration Z (n-f). The table shows the occurrence for dia nets and for the remainder.

The two well-known 3-c 103 topologies (103-srs and 103ths) are present with four and two cases, respectively. Moreover, a novel 103 topology has been discovered in the 3-fold interpenetrated KAPFIR (103-cds-3-Pnna; Vertex Symbol [10.10.103]). This new net has been found in a recent search for net relations by Blatov;10 it is interesting to note that there are 27 known uniform nets with the Short Symbol 103 and 15 have the same Vertex Symbol [10.10.103]. The 103-srs nets include the world record of interpenetration: the exceptional 18-fold SAYMUB01. Since the nets of this topology are chiral it is of interest to establish the presence of

Baburin et al.

enantiomeric pairs. As we have previously suggested,2d in the presence of such pairs the interpenetration class cannot be simply translational (Class I). Indeed SAYMUB01 contains nine enantiomeric pairs, ADENSL and NUZKAU 1 pair, while TIPKIM contains two homochiral networks. In the latter case choosing dimers (ring synthon X, see Figure 6) gives rise to two translationally equivalent interpenetrating diamond nets. Indeed, the relationship between 66-dia and 103-srs nets is rather common for homomolecular hydrogen-bonded frameworks, as recently found by Baburin and Blatov.14 The vertices of the diamond net occupy one-third of the edge centers in the 103srs net (Figure 6). Diamondoid Nets 66-dia. These networks are the most numerous ones also in hydrogen-bonded interpenetrated systems (38 cases), though their % distribution is lower than expected (see above). They show an interpenetration degree Z ranging from 2 to 11. With Z > 2 (17 cases illustrated in Scheme 3), the interpenetration is generated by pure translational symmetry (Class Ia) in all but two cases (JUTGOU and QUSMEW, Z ) 4, Class IIIa). In the 2-fold interpenetrated net arrays, Class Ia (10 cases) and Class IIa (11 cases) are almost equally populated. Noncentrosymmetric space groups are observed in 13 cases, a result that can be of interest toward the achievement of acentric crystal structures with promising NLO properties, as appeared in recent years. The diamondoid net array with the highest interpenetration degree Z (11-fold, the current world record for 66-dia) is XEBTIH, a species that has been properly engineered using tetrahedral nodes and linear spacers in the ratio 1:2. In interpenetrated MOFs the current upper limit is represented by the 10-fold 66-dia network XISXAY, [Ag(dodecanedinitrile)2](NO3). Note that all the diamondoid nets of Class Ia show normal mode1a,2a,b of interpenetration except the four cases with Z ) 5 (GEJVEW, JADMAD, XUVBAR, XUVBEV) and one with Z ) 8 (the silane analogous of VOJFAB). Wuest and co-workers have reported that tetrakis[4-{(6oxopyrid-2-yl)ethynyl}phenyl]methane gives hydrogen-bonded frameworks containing carboxylic acids as guests. The bis(butyric acid) clathrate VOJFAB contains disordered guest molecules and is a 7-fold diamondoid net array. Note that the analogous silane species (not reported in CSD) is 8-fold interpenetrated (but non-normal,1a,2a,b that is, not along one of the 2-fold axes of the adamantane cage). The related species VOJFEF contains propionic acid guest molecules, which form direct hydrogen-bonds with the tecton thus preventing the possibility of an extended hydrogen-bonded network. It is worth mentioning the case of QUSMEW (a cyclic tetracarboxylic acid monohydrate, 4-fold 66-dia, Class IIIa). We have decided to not include guest water molecules in our topological analysis since they are often disordered or not well refined, but in this species the water molecules interestingly join the 66-dia nets in pairs, thus resulting in a completely different description of the supramolecular array, that is, a 2-fold Class IIa interpenetrated 6-c net array with the 48.67-msw topology (see below the 6-c WUQYOW). The substitution in TERRUD (N-acetyl-L-glutamic acid, 3-fold 66-dia) of a -COOH group by a -CONH2 one gives a species (AGLUAM10), which has the possibility of an additional NH · · · OdC hydrogen bond; neglecting this rather long new contact the net array remains 3-fold 66-dia, while taking it into account a unique single 6-c new net (44.611) results, with a lower HBRI of 8/6.


Crystal Growth & Design, Vol. 8, No. 2, 2008 527 Scheme 2

The structure of (+)-pinoresinol contains a 3-fold 66-dia array (FAFXUF). It was interesting to analyze also the structure of the racemic form NELRUR that exhibits a different local hydrogen-bond pattern producing a system of square layers of 44-sql topology. The molecular units are, in this case, flatter. Nitrilotriacetic acid (NTRTAC) is the second oldest example of recognized interpenetration (1967) but missing one subnet; it was classified as 2-fold instead of 3-fold. The oldest example (1947) is 2-fold β-quinol QUOLSO (vide infra). A number of 2-fold interpenetrated 66-dia net arrays show interesting features (see Scheme 4); some of them are discussed

Figure 6. Relationship between 66-dia (red) and 103-srs (blue) nets via ring synthon X observed in TIPKIM.

here, which change their topology by replacement of substituents not directly involved in the hydrogen-bond pattern. In FEWSAC the substitution of the two methyl groups by chlorine atoms leads to FEWRUV, exhibiting a different local hydrogen-bond pattern that contains a highly distorted single 65.8-cds network. The modification of the side chain -CH2-COOH in TAQXAL (2-fold 66-dia) has drastic effects: with a -CH2-CH2-COOH elongated side chain (BIYRIK) the hydrogen-bond pattern changes, and the array results in 63-hcb layers (HBRI ) 4/3). With a -CH2-CH2-CONH2 chain (CIRYUK) we obtain again 44-sql (HBRI ) 6/4), while with a -CH2-CH2-OH chain (DEFXOB) a 1D polymer is observed. Other 4-c nets. Many important 4-c nets, different from diamondoid nets, are observed. Collectively, their number is comparable with that of diamondoid nets (45 vs. 38 nets). We have the following net topologies: 14 of 65.8-cds, 11 of 42.84lvt, 5 of 64.82-nbo, 4 of 43.62.8-gis, 3 of 32.104-lcv, 3 of 66neb and 5 other nets with less common topologies. Curiously, some 4-c nets rather usual in other families of compounds, such as 42.84-pts, are here lacking.2d The numerous group of 65.8-cds nets (Scheme 5) shows a maximum Z value of 4 (BEQVUO, Class IIIa). The structure of 1,3-diamino-2,4,6-trinitrobenzene (DATNBZ) reveals a 2-fold 65.8-cds net array that remains unchanged also in the isomorphic 5-fluoro substituted species (BEWYOR). The high packing efficiency and crystal density observed for these compounds (and for related polynitro-organic compounds) were generally ascribed to efficient intermolecular packing arrangements, which



limit the amount of free space in the unit cells, while the possibility of interpenetration to fill voids was previously not considered. The interesting species 4-carboxamido-1-cubanecarboxylic acid (JUNQIS) gives a 2-fold 65.8-cds net array (erroneously classified by the authors as 64.82-nbo). Its bis(carboxamide) derivative (HIDTET) uses all its hydrogen-bond functionalities, so that each building block is linked to six other molecules resulting in a novel single 6-c net of topology (44.610.8). The 2-fold net observed for 2-aminoethene-1,1,2-tricarbonitrile (TAPZOA) was wrongly described as (non-“standard”) 103ths, while following their proposed simplification it is 103-utp. The structures of a series of p-alkylamido-substituted perbenzoic acids well illustrate the effects of the lengthening of an alkyl side chain: p-acetamidoperbenzoic acid (ZUHHIT) and p-propanamidoperbenzoic acid (ZUHHOZ) give 3-fold 65.8cds net arrays, but longer side chains (ZUHHUF, butanamido, and ZUHJAN, pentanamido) give simple almost flat 2D 44sql. Another numerous group of interpenetrated net arrays exhibits the 42.84-lvt topology (see Scheme 6). The lengthening of the molecular chain on passing from BOLNOF, 3,3′-(ethylenediimino)-bis(3-methyl-2-butanone oxime), to CEYSOO, 3,3′(trimethylenedi-imino)-bis(3-methyl-2-butanone oxime), does not alter the topology and Z (both are 2-fold 42.84-lvt), but only the Class, from Ia to IIa. A number of biimidazole and bipyrazole derivatives have been investigated because of their interesting hydrogen-bonded architectures (Scheme 6) that can be topologically described in different manners. While the parent 4,4′-biimidazole gives simple 2D 44-sql (KAMBEG) the methyl species 2,2′-dimethyl4,4′-biimidazole (LEBKUZ) is a 2-fold interpenetrated 64.82-

nbo array and the ethyl species 2,2′-diethyl-4,4′-biimidazole (LEBLAG) forms a single 3D 65.8-cds net. In spite of the different topologies, therefore, the “square-planar” local geometry of the nodes is always maintained. On choosing as an alternative node the ring synthon VI in LEBKUZ, a 2-fold 412.63-pcu net array is generated. Moreover, also the individual 5-membered rings of the molecule can also be selected as 3-c nodes leading to the 6.102-pcu-h (LEBKUZ) and 103-ths (LEBLAG) topologies, respectively. Also, the structure of the parent 4,4′-bipyrazole (UDAYIH) contains 2D 44-sql. The derivative 3,3′,5,5′-tetramethyl-4,4′bipyrazole is known in many fascinating forms, with or without clathrate molecules. There are three polymorphs of the guestfree species (UDAYUT, UDAYUT01, UDAYUT02) exhibiting different 3D networks, which are discussed later. Moreover, the tris(chloroform) clathrate (HUXMIW) is exceptional because it is a 4-fold interpenetrated 32.104-lcv array consisting of two nonequivalent pairs of net arrays (2 + 2 interpenetration, Class IIa + IIa). The methanol solvate species (HUXMUI) is of type AB since the methanol molecules (3:1 ligand/methanol) are included in the network as spacers: the resulting system shows again the 32.104-lcv topology but is 6-fold interpenetrated (Class IIIa). One of the older examples of well-characterized interpenetrated supramolecular assemblies via hydrogen-bond bridges was the family of rhombohedral β-quinol clathrates, all exhibiting the same structural type (see Figure 7). Also the guest free form (HYQUIN05) was claimed to possess this structure, which we have classified as 2-fold 64.82-nbo, using as nodes the whole molecules (the “standard” topology). However, here we have a classical case of possible alternative topological descriptions, that can seem more natural: assuming the hexagonal synthons



Scheme 5

V as nodes we obtain the 412.63-pcu topology, or, otherwise, a 3-c 6.102-pcu-h topology (pcu decorated by hexagons) can be envisaged using as nodes the -OH groups. Quinol, moreover, gives also the R- and γ-forms that are considered later.

A series of structural investigations were devoted to the characterization of supramolecular arrays based on 2,7dimethyltricyclo[4.3.1.13,8]undecane-syn-2,syn-7-diol and related species. These analyses are of great interest in the context of



crystal engineering: topological framework changes are observed upon variation of the clathrates and/or substituents. The clathrates show three different structural situations: (a) 2-fold interpenetrated 43.62.8-gis net array in BUXRIV/ BUXRIV10[(diol).benzene],LORQUE[(diol)4.CH3CN],LORQOY [(diol).CH2Cl2], POLFIF [(diol)4.CS2], QULKOX

Figure 7. On the left, the network observed in β-quinol HYQUIN05 showing the hexameric synthon V (Scheme I) that maps onto 412.63pcu. On the right, the three possible descriptions of a single net of the 2-fold β-quinol: “standard” 64.82-nbo (green) with the whole molecule as 4-c node, ring-synthon net 412.63-pcu (red) with the centres of the hexagonal synthon as 6-c nodes and 6.102-pcu-h (blue) when the oxygens of the -OH groups are considered as 3-c nodes.

[(diol)4.cyclohexane], QULLAK [(diol)4.CHCl3], VUSYEN [(diol)4.1,2-dichlorobenzene]; (b) single 64.82-qtz net in BUXREV/BUXREV10 [(diol).ethyl acetate], EDOLOY [(diol).t-butylcyclohexane], EDOLUE [(diol).cyclohexane], PAPSII [(diol).CCl4], PAPSOO [(diol).1,3dibromopropane], PAPSUU [(diol).o-xilene], POKVUG [(diol).dibromodifluoromethane], QULKUD [(diol)3.fluorocyclohexane], QULLEO [(diol)2.(CHCl3)], VUSYIR [(diol)3. 1,2-dichlorobenzene]; (c) 2D 44-sql in EQOPOP [(diol).propionic acid], EQOPUV [(diol).acetic acid], EQOQAC [(diol). 2-propanol], HIBGII [(diol).p-chlorophenol], HIBGOO [(diol).p-methoxyphenol], HIBGUU [(diol).p-hydroxythiophenol]. Also the guest-free species (SODVUC) is comprised of 2D 44-sql. Group (c) differs from the other two in that the clathrate molecules use their -OH functionalities to form direct hydrogen bonds with the diols that seem to prevent the formation of 3D architectures. In group (a) the 2-fold interpenetration is accompanied by a lower content of guest molecules with respect to group (b) single nets. For example, compare QULLAK (2fold 43.62.8-gis) and QULLEO (single 64.82-qtz), both CHCl3 clathrates but exhibiting (without guests) free voids of 13 and 26%, respectively, and a double amount of guests in the second


Figure 8. On top the network observed in acetamidine (CALVAM) showing the three possible alternative description: 4-c “standard” topology (green), 4-c rhombic ring synthon (red) and 3-c when the molecule is considered as two 3-c nodes (blue). Below the three nets gis (green), lvt (red), and lvt-a (blue) derived from the alternative descriptions.

one. A single gismondine network (43.62.8-gis) as observed in the 2-fold interpenetrated acetamidine (CALVAM) is shown in Figure 8. The structure of (+/-)1,2-bis(3,4-dimethoxyphenyl)-1,2ethanediol (HAGPUA) shows the unique case of a chiral 2-fold interpenetrated 64.82-qtz network. A drastic change is observed in the structure of the meso-form (TABJEL) that contains hydrogen-bonded 1D chains. The list of interpenetrated 4-c nets includes also some examples of quite unusual topology of great interest (Scheme 7). This is the case of 66-neb, a rather elusive topology that can be confused with 66-dia, first mentioned as ”net 9” by O’Keeffe and Brese17 during an enumeration of uninodal 4-c nets, and later observed and correctly described by Ermer and Eling18 in examining the hydrogen-bonded single supertetrahedral network of ethanolamine (JAKKEL).19 The comparison of 66-dia and 66-neb is shown in Figure 9; both nets have the same Schläfli Symbol 66 but different Vertex Symbols ([62.62.62.62.62.62]-dia; [6.6.6.62.62.62]-neb) and Coordination Sequences that differs from the third term (4,12,24,42 · · · dia; 4,12,27,50 · · · neb). The left column of Figure 9 shows a cut extracted from 66-dia, a double adamantane cage (14 carbon atoms), called diamantane or also congressane (D3d symmetry), while the right column illustrates the single cage of 66-neb. This is a hypothetical pentacyclotetradecane cage [66] named “isodiamantane” (D2 symmetry) by Ermer and Eling;18 it forms the natural tiling of 66-neb, while the 66-dia natural tiling is constructed of single [64] adamantane units.8 We have found here three examples of interpenetrated nets with this topology (RASBOD, JUKVOA, MIGRID) that was previously not seen by the authors (or confused with 66-dia). RASBOD (Type AB) is particularly noteworthy in that it is 8-fold interpenetrated of Class IIIa. The unusual topology (42.84)-uoc is observed in two cases. DASDIL contains two interpenetrated nets of the same topology but not symmetry related; that is, this is a rare case of (1 + 1) nonequivalent interpenetration.2e The molecule 17R-phenylandrost-5-ene-3β,17β-diol (CAXROI) gives a 3-fold (42.84)uoc net array, but the replacement of the phenyl with the benzyl group results in HAVFOZ which forms 2D 44-sql. Finally, compound 4-hydroxybenzaldehyde(4-nitrophenyl)hydrazone (ITUXIE) crystallizes with two independent mol-


ecules, each of which is an independent node; the array is a 2-fold binodal (65.8)(66)-sqc187 network.9 The same molecule with 1,4-dioxane solvate (ITUXEA) gives 2D 63-hcb layers using dioxane as spacer. Higher Connectivities. Here we briefly discuss interpenetrating networks with node connectivities >4, that is, in the range 5–8. These nets are rare (only 10 cases, see Scheme 7 for 5-c and Scheme 8 for the remainder), a feature that is peculiar of interpenetrating hydrogen-bonded networks, different from MOFs and inorganic frames where the 6-c primitive cubic 412.63-pcu (R-Po) topology is the second one after 66-dia (17.3% in MOFs and 18.8% in inorganic nets). There are five examples of 412.63-pcu net arrays, all 2-fold interpenetrated. In the pair UJOFEE, tetrakis(4-hydroxyphenyl)methane, and UJOFII, tetrakis(4-hydroxyphenyl)silane, the same arrays are observed, though they are not isomorphic. For UJOFII, one hydrogen-bond interaction was missed by the authors, with the consequence that the net was described as 4-c instead of 6-c 412.63-pcu. Wuest and co-workers have reported the structure of 3,3,9,9tetrakis(4-(2,6-diaminotriazen-4-yl)benzyl)-2,4,8,10tetraoxospiro[5.5]undecane (WUQYOW), which was incorrectly described as an 8-fold 66-dia (that should belong to Class IIIa, 4*2) because an important additional hydrogen-bond contact was neglected. Including these interactions the network becomes 6-c 2-fold interpenetrated of Class IIa and belongs to a new (48.67) topology that we name bp1. With all the hydrogen bonds this compound is the one with the highest HBRI (of 16/6 ) 2.666). WUCYUC is a different clathrate, isomorphic with WUQYOW. The nature of (48.67)-bp1 has suggested to us the possible existence of a whole new series of uninodal selfcatenated 6-c nets derived from interpenetrated 66-dia nets: when the parent n-fold 66-dia net arrays are of Class Ia, by connecting the 4-c nodes along the unique full interpenetration vector (FIV) we obtain single nets all having the same Schlafli Symbol (48.67) whichever the number of nets in the array (but topologically distinct by, e.g., Coordination Sequence). We can apply the same procedure to n-fold 66-dia net arrays of Class IIIa by connecting in this case the 4-c nodes along the translation interpenetration vector (TIV). Again we obtain (48.67) 6-c nets but now the array is interpenetrated of Class IIa (retaining the original nontranslational symmetry operation). This is what observed for WUQYOW [from 8-fold IIIa to 2-fold (48.67)-bp1] (see Figure 10) and for the previously mentioned QUSMEW [from 4-fold IIIa to 2-fold (48.67)-msw, when the solvate water molecule is considered]. The highest connectivity is present in the unique 8-c 2-fold interpenetrated species BAWJUF, which shows the (424.64)bcu topology. Mixed Nodes. Obviously, though not strictly necessarily, none of these species (13 cases) is of the type AA. Different molecular nodes, with different hydrogen-bonding requirements, favor the formation of mixed nodes networks. The most common ones are 3,4-c (see Scheme 9). It is noteworthy that four of the five new nets are in this group and that the net (83)2(85.10)bp2 has been recently observed as single net in a lead coordination polymer.20 Hydrogen-Bonded Nets and Interpenetration. Our results may provide new information for the rationalization of the phenomenon of interpenetration (class and degree) in networks based on similar tectons and exhibiting the same topology. Different Z values (or, at least, different classes) could, in principle, be produced in type AA species by one (or more) of the following factors: (a) effects of different guests; (b) atom



or group substitution in the node leading to variated dimensions of the tecton; (c) different length of side chains bearing the hydrogen-bond donors and/or acceptors. Examination of the networks listed in Table 1 reveals some

Figure 9. Two perpendicular views of the different cages made of 14 nodes observed in the uniform nets 66-dia and 66-neb.

interesting observations. The effect of changing the guest molecules has some influence in the family of 2-fold 66-dia nets assembled from 2,6-dimethylideneadamantane-1,3,5,7tetracarboxylic acid (see Scheme 4). While Z remains the same, some (VOBFAT, VOBFEX, VOBFIB) belong to Class IIa, with the two equivalent nets generated by an inversion center, others (VOBFOH, VOBFUN) belong to the same Class IIa but with a 2-fold axis as symmetry operation, and one (VOBGAU) is of Class Ia. On the other hand, guest substitution has different consequences in the family of 2-fold 66-dia networks INUJUW, INUKAD, and YINJOU: they represent a case of adaptive porosity and contain the tecton tetrakis(1,2-dihydro-2-oxo-5pyridyl)silane together with different carboxylic acids solvates that produce expansion/compression of the frames.21 All the net arrays belong to Class Ia and the change of guests implies a variation of the interpenetration vector (coincident with the c crystallographic axis). Curiously, the related species YINJUA, with Sn instead of Si and containing clathrate valeric acid, forms a different hydrogen-bond pattern resulting in a 6-c single 412.63pcu net. Substitution of the central atom in the node of VOJFAB (Si in place of C) leads to a greater Z value (from 7 to 8), as already mentioned. At difference from this case in the pair of net arrays XUVBAR/XUVBEV the replacement of C by Si at the nodes does not influence the degree of interpenetration (both are 5-fold 66-dia, Class Ia). It is of interest in the context of crystal engineering to compare the structure of β-quinol (HYQUIN05, see above and Figures 1 and 7 and Scheme 6) with that of the related linear diphenolic species 2,2′′,6,6′′-tetramethyl-4,4′′-terphenyldiol



(KAPVIH). The two species share the same 64.82-nbo topology, but the increased length of the tecton in KAPVIH causes a change of the interpenetration degree from 2- to 4-fold (both species are of Class Ia). The effect of side chains lengthening on interpenetration has been already observed in the pair BOLNOF/CEYSOO (see above and Scheme 6): both are 2-fold 42.84-lvt, but the Class passes from Ia to IIa. A major effect is observed in the pair methanetetracetic acid (GESTAZ) and methanetetrapropionic acid (JADMAD): both are 66-dia Class Ia, but the former is 3-fold while the latter is 5-fold interpenetrated. On the other hand, no effects on interpenetration are observed on comparing the 2-fold 66-dia net arrays, Class Ia, of 6-methylisocytosine-5-acetic acid (ZERMUE) and 6-methylisocytosine-5-propionic acid (ZERNEP), though they show somewhat different local hydrogen-bond patterns (see Scheme 4 bottom).

Figure 10. The generation of the new 6-c (48.67)-bp1 net from 4-fold interpenetrated 66-dia nets.

These observations show how difficult it is, given a certain topology, to predict the extent of the phenomenon of interpenetration, even when we compare two closely related species. Hydrogen-Bonded Nets and Crystal Engineering. Crystal engineering concerns the structural control of the outcoming architectures from a certain planned self-assembly process.22 However the arrays of type AA obtained from the self-assembly of organic molecules are difficult to control in their final result. A major control seems achievable when the deliberate building of type AB species (presumably nodes+spacers) is attempted using basic concepts that are the same for the construction of MOFs and of hydrogen-bonded arrays. A suitable building block of selected geometry is chosen as a node for a specific target network, together with proper spacer molecules to join the nodes. Unfortunately, this does not seem to be sufficient to obtain the target architecture. With type AA species, on the other hand, all the information on the resulting net should be embedded in the structure of the tecton, but the passage from tecton to synthon and then to the overall net is still far from being well understood.22 Conflicting factors for any strategy of this type are the concurrent possible alternatives arising from polymorphism and supramolecular isomerism (see below). Indeed, we probably prefer to ignore that there is a large variety of topologies associated with each selection of the (planned) building blocks, so that, for instance, we expect that tetrahedral nodes and linear spacers in the proper ratio should always result in superdiamond networks. The occurrence of alternative nets (see above the case of the 66-neb topology) is therefore usually overlooked. Factors orienting the topology of the assembly are poorly investigated. Moreover, the ambiguity associated with the possible control of the degree of interpenetration has already been described above. From the perspective of getting better insight we suggest that the unique possibility seems to investigate in a systematic fashion the self-assembly processes upon variation of the reaction conditions. At present we do not have true answers to questions like “why a certain topology?” and “why interpenetration?” As to the geometry of the tecton in orienting the topology of the resulting networks we have already shown (see above) that small changes in the molecule can have drastic topological



effects. Nevertheless, with a certain optimism, we can outline here some trends. (a) We observe that the local geometry may be “foreseen” by considering the structure of molecules. Thus the most frequent 4-c topologies can be divided in two classes looking at the local geometries at the node and comparing it with the ones for the idealized nets: tetrahedral (66-dia, 43.62.8-gis, 66neb) and rectangular (65.8-cds, 42.84-lvt, 64.82-nbo). Thus, in 66-dia nets there are tetrahedral molecular centers, and in nets with rectangular coordination there are planar molecules (often with conjugated π-electronic systems). We may expect with high probability that molecules with a rectangular hydrogen-bond environment will give one of the three possible rectangular nets. (b) Some relevance may be attributed to the fact that groups of networks with the same “standard” topologies can also be described in the same way using their “ring synthon nets”, as in the case of many molecular 42.84-lvt nets that contain 66dia “ring synthons nets”. Note that the “standard” and “ring synthon net” topologies are interrelated and match each other (Table 1); starting from the “standard” net one can anticipate possible topologies of “ring synthon nets”. (c) Another aspect that has been checked here concerns the substitution in a molecule of a bound group not directly involved in hydrogen-bonding with a different one of similar volume;

the exchange is not expected to influence the net topology. This is true, for example, in the pair BUXRIV/WOYLEB by replacement of a -CH2- moiety by a -S- atom (both net arrays are 2-fold 43.62.8-gis). On the other hand, in a family of aminophenols (ENANIQ/ENAMAD) the effect of substitution of a -CH2- group by an -S- atom shows a complete structural transformation from 2-fold 65.8-cds to a 2D 44-sql species. Hydrogen-Bonded Nets, Polymorphism, and Supramolecular Isomerism. In the self-assembly of hydrogen-bonded organic supramolecular arrays and in the crystal engineering strategies for the construction of specific networks we are continuously faced with the phenomena of polymorphism and supramolecular isomerism, that, together with the unpredictable event of interpenetration or other types of entanglements,1,2 can represent obstacles to our planning ability. Polymorphism appears when the same substance exhibits different crystal packing arrangements.23 Supramolecular isomerism, on the other hand, concerns the possible existence of more than one network superstructure for the same molecular building blocks; it has been introduced in the context of coordination polymers24 but applies as well to all other modular extended arrays. So, the former phenomenon deals with crystals, while the second one deals with networks and their topologies.



Table 2. True Polymorphs of Interpenetrated Nets Refcode

topology

SAYNAI01 (β tetragonal) SAYNAI (R orthorhombic) SAYMUB01 (orthorhombic) SAYMUB (monoclinic) UDAYUT02 (γ tetragonal) UDAYUT01(R monoclinic) UDAYUT (β hexagonal) KAPVIH (compound 1a) KAPVIH01 (compound 1b) BASVUM01(orange trigonal)

lig 3-f ths single srs 18-f hcb 3-f lcv 6-f cds single qtz single nbo 4-f sql layer nbo 2-f

BASVUM (yellow monocl.) HYQUIN02 (R) HYQUIN (γ) HYQUIN05 (β) APYRDN (R, RT) APYRDN01 (β, low T) a

C.P.a

crystallization

Y

from dichloromethane

Y

from DMSO

interconversion R interconverts to β at 368.8 K

Y

hydrothermal conditions from hot water from acetonitrile from ethyl acetate

Y

from ethyl acetate

yellow interconverts to orange in the range 25–125 °C

sql layer 4-c trinodal sql layer

N

γ and β spontaneously convert to R

nbo 2-f bp5 2-f bp4 2-f

N

sublimation sublimation or rapid evaporation at RT from ethyl ether n-octane (air free ethanol) acetonitrile at RT acetonitrile at 283 K

N

phase transition at 290 K

C.P. ) concomitant polymorphs.

Polymorphs can be always described also as supramolecular isomers but not vice versa. Supramolecular isomerism can apply therefore to nets of the same composition but with different topologies because of different guests (solvates or pseudopolymorphs). Moreover this phenomenon can include different independent isomeric nets that are found together in the same crystal, as observed in some MOFs.24b,c The analysis of polymorphism and supramolecular isomerism can be carried out using the network topological approach, that produces an useful categorization and creates opportunities for systematic structure–property studies. We have examined for all the interpenetrated hydrogenbonded nets the possible existence of polymorphs. The results are listed in Table 2. We can compare the polymorph structures considering the changes in topology/node connectivity, as a consequence of possible variations in the hydrogen-bond patterns. In the case of SAYNAI01/SAYNAI we pass from 3-fold interpenetrated 82.10-lig to a single 103-ths net; both topologies are 3-c and the local hydrogen-bond pattern remains almost the same, forming a ring synthon I that is flat in the former species while rather folded in the second one (“bowl shaped” according to the authors). The three polymorphs of 3,3′,5,5′-tetramethyl-4,4′-bipyrazolyl, UDAYUT01 (R form), UDAYUT (β form), and UDAYUT02 (γ form), give networks with the same connectivity (4-c) but different topologies: single 65.8-cds, single 64.82-qtz, and 6-fold 32.104-lcv (see Figure 11), respectively. The molecules form similar hydrogen bonds that result in “chain synthons” in the two former cases while in UDAYUT02, ring synthons II are present. The analysis of N-C-C-N torsion angles shows similar values in the R and β noninterpenetrated forms but quite different in the γ one. In the case of KAPVIH/KAPVIH01, we observe two 4-c networks: 4-fold 64.82-nbo in the former one vs 44-sql in the second one, that can be related to the formation of different synthons (ring synthon V and chain, respectively). On the other hand, in the pair BASVUM01/BASVUM the different topologies (2-fold 64.82-nbo vs. 44-sql) seem not to be related to different hydrogen-bond patterns but rather to more subtle factors, that is, to the relative orientations of adjacent molecules, as discussed by the authors. We have already discussed the structure of β-quinol in the guest-free HYQUIN05 (2-fold 64.82-nbo). Two polymorphs (R, HYQUIN02, and γ, HYQUIN) are also known. However,

Figure 11. On top, the network observed in UDAYUT02 (γ form) and in the bottom, the three possible alternative descriptions: 4-c “standard” topology 32.104-lcv (green), 3-c 103-srs rhombic ring synthon II (Scheme 1) (red) and 3-c 3.202-srs-a (blue) when the molecule is considered as two 3-c nodes.

though all the three species are 4-c, the nets are different: the topology of HYQUIN02 is a novel 3D trinodal net of topology (62.84)(62.84)(64.82) and HYQUIN gives 44-sql. Indeed, the same kind of hydrogen bonds are present but different synthons are formed in the three cases. All the above examples are of type AA, but there are also two cases of polymorphs that involve the assembly of different molecular building blocks. In the pair SAYMUB01/SAYMUB, of type AB (with only A nodes), both polymorphs are 3-c, but


only SAYMUB01 is 3D (the unique 18-fold 103-srs) while SAYMUB contains 2D 63-hcb layers that are 3-fold interpenetrated in a parallel fashion. Both show the same hydrogenbond pattern, with single bonds of the -COOH groups of the trimesic acid to the 4,4′-bispyridylethane spacers. The difference consists in the relative rotation about the hydrogen-bonds of the adjacent nodes, that is, the molecules of the acid give the three dihedral angles for C-C-OH · · · N that deviate considerably from 180° (150°-170°) only for the 3D derivative. Finally, we consider the case of APYRDN/APYRDN01, the R- and β-forms of 4-aminopyridin hemiperchlorate, respectively, that are both included in our list of interpenetrated nets. The two species are of type ABC, with three distinct nodes, that is, the 4-aminopyridin molecule, its protonated form and the perchlorate anion. In Scheme 9 we show only the APYRDN01 polymorph, the second one (APYRDN) differing only in the interactions of the perchlorate anion that uses three out of the four oxygen atoms for networking but gives a bifurcated H-bond. Thus the ClO4- anions are 4-c nodes in both polymorphs but originate different H-bonded patterns and different (3,4)-trinodal topologies with symbols: (4.6.83.10)(4.6.8)(6.82)bp5 for APYRDN and (83)(83)(86)-bp4 for APYRDN01. Both compounds can be alternatively described considering the resonance hydrogen-bond pyridine-pyridinium dimer as node. In summary, different polymorphs can be originated in some cases by variated hydrogen-bond patterns with different synthons, but can be observed also in the presence of almost identical hydrogen-bond patterns because of different spatial orientations of adjacent molecules (tectons), especially when these are not joined via the more rigid ring synthons. Given a certain environment of the nodes (tetrahedral, square-planar, etc.) we must remember that many alternative topologies are always possible. Preliminary examination of the interaction energies with the PIXEL method23b,c of three couples of polymorphs (SAYNAI/ 01, KAPVIH/01, BASVUM/01) shows that the contribution of the Coulumbic term (that include hydrogen bonds) is always on the same scale as the dispersion terms from the nearest molecules, indicating that the interpenetration phenomena cannot be distinguished on an energy basis. The dispersion interactions connect all the subnets into a single one. On the other hand, the different dimensionality 2D vs 3D can be appreciated. As to supramolecular isomerism, we can cite many examples that have been already mentioned, like the case of the family of clathrates of 2,7-dimethyltricyclo[4.3.1.13,8]undecane-syn2,syn-7-diol. We have above-described their distinct guestinduced topologies, as, for instance, in the pair QULLAK (2fold 43.62.8-gis) and QULLEO (single 64.82-qtz) containing CHCl3 solvated molecules in different amounts. Moreover, we can associate to the three just described guest-free polymorphs of 3,3′,5,5′-tetramethyl-4,4′-bipyrazolyl UDAYUT, UDAYUT01, and UDAYUT02, also the tris(chloroform) clathrate HUXMIW (2 + 2 interpenetrated 32.104-lcv) that can be considered a supramolecular isomer of all three. Conclusions The use of the TOPOS package for the analysis of interpenetrating 3D hydrogen-bonded networks in CSD has produced a comprehensive list of 122 distinct entangled architectures. Interpenetration was previously not seen in most (71%) of the listed species that exhibit a variety of topological types, some of which are unprecedented. The importance of describing the extended systems assembled with hydrogen-bonds in terms of the resulting overall array has been here emphasized to contrast

Baburin et al.

the attention often devoted only to the first molecular environments. The distribution of the topologies is rather different from what is observed in other classes of interpenetrated materials (such as coordination and inorganic networks). The results were analyzed to search for factors influencing the topologies, the degree of interpenetration, and the phenomena of polymorphism and supramolecular isomerism. Acknowledgment. L.C., G.C., and D.M.P. thank MIUR for financing the PRIN 2006–2007 “POLYM2006: Innovative experimental and theoretical methods for the study of crystal polymorphism: a multidisciplinary approach.”

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