Diversity in Supramolecular Solid-State Architecture Formed by Self

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Diversity in Supramolecular Solid-State Architecture Formed by SelfAssembly of 1-(diaminomethylene)thiourea and Aliphatic Dicarboxylic Acids Jan Janczak Cryst. Growth Des., Just Accepted Manuscript • DOI: 10.1021/acs.cgd.5b01049 • Publication Date (Web): 21 Sep 2015 Downloaded from http://pubs.acs.org on September 23, 2015

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Crystal Growth & Design

Diversity in Supramolecular Solid-State Architecture Formed by Self-Assembly of 1(diaminomethylene)thiourea and Aliphatic Dicarboxylic Acids Jan Janczak* Institute of Low Temperature and Structure Research, Polish Academy of Sciences, Okólna 2 str., P.O. Box 1410, 50-950 Wrocław, Poland KEYWORDS. 1-(diaminomethylene)thiourea; Aliphatic dicarboxylic acids; Crystal engineering; Acid-base supramolecular complexes; Hydrogen bond.

ABSTRACT

A family of supramolecular complexes of 1-(diaminomethylene)thiourea with aliphatic dicarboxylic acids, HOOC(CH2)nCOOH, with odd and even number of methylene groups in the carbon chain of the acids has been characterized. Using solvent-assisted and evaporation-based techniques, crystallization of 1-(diaminomethylene)thiourea with aliphatic dicarboxylic acids from water solutions yielding ionic supramolecular complexes with base to acid ratio of 2:1 or

ACS Paragon Plus Environment

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1:1. Malonic, succinic, adipic and sebacic acids with 1-(diaminomethylene)thiourea form supramolecular complexes of 2:1 ratio (1, 2, 4 and 8), whereas glutaric, pimelic, azelaic and suberic acids form supramolecular complexes of 1:1 ratio (3, 5, 6 and 7). Within all supramolecular complexes only one with adipic acid crystallizes as a hydrate containing water molecules of crystallization. In the hydrated crystal with adipic acid, the OH…O chains of water molecules interact with adipiate(2-) anions forming anionic layers, and the charge is compensated by 1-(diaminomethylene)thiouron-1-ium cations. The 2:1 supramolecular complexes further interact each other via NH…O hydrogen bonds forming two- or threedimensional supramolecular structure. Within 1:1 supramolecular complexes, the singly deprotonated aliphatic dicarboxylic acids are linked together via strong symmetrical O…H…O hydrogen

bonds

into

infinitive

chains.

The

chains

are

further

linked

by

1-

(diaminomethylene)thiouron-1-ium cations to form two- or three-dimensional hydrogen bonding network. Interaction between the 1-(diaminomethylene)thiouron-1-ium and the singly or doubly deprotonated aliphatic dicarboxylic acid units in solid of 1-8 supramolecular complexes were also analysed by vibrational spectroscopy.

INTRODUCTION Crystal engineering involving a combination of synthesis and structural analysis for the understanding of intermolecular interactions in the context in design of new solids has been rapidly extending research branch of material science over the past few decades.1-6 The accurate prediction of a structure and the physical and chemical properties of a product from the structures of the substrates remains the ultimate goal of the investigations.7,8 A productive strategy in the supramolecular synthesis and the crystal engineering is to build supramolecular structures from molecules containing complementary arrays of the hydrogen bonding sites.9-13


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The non-covalent interactions such as hydrogen bonding, π-stacking interactions and the van der Waals forces have been used in the self-assembly and design of a number of supramolecular architectures in solids like as layers, rosettes, roods, tapes, sheet and spheres.14-21 Among the self-assembly organisation forces, the hydrogen bond is the most important interaction for design of extending supramolecular solids due to its abundance, strength and specific relative and directional properties.22-24 The supramolecular synthon of recurring hydrogen-bonding pattern, reliable in numerous crystal structures is an effective approach for structural design and prediction.25,26 Supramolecular synthesis based on a combination of ionic and hydrogen bonds between organic base-acid adducts or salts yielding several kinds of self-assembly supramolecular frameworks in solids have been reported.27-35 Commercially available 2-imino-4-thiobiuret (Aldrich, CAS No. 2114-02-5) is, as has been shown by the X-ray single crystal analysis, its tatutomeric form of 1-(diaminomethylene)thiourea (Scheme 1).36 Both tautomers are useful in the crystal engineering as building blocks, since they contain hydrogen-bonding sites and can form

extended

hydrogen-bonding

networks

in

solids.

In

addition,

the

1-

(diaminomethylene)thiourea due to presence of basic N atom has been used to produce with organic or inorganic acids extended supramolecular frameworks in solids combined both ionic and hydrogen bonding interaction.37-48 H

H

H

H

N

N

N

N

H

H N

S

H (a)

H N

N H

H H

N

H

S

(b)

Scheme 1. 2-imino-4-thiobiuret (a) and its tautomeric form of 1-(diaminomethylene)thiourea (b).


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In the present work it has been examined the supramolecular architecture in solid formed by selfassembly of 1-(diaminomethylene)thiourea with some common aliphatic dicarboxylic acids: malonic, succinic, glutaric, adipic, pimelic, suberic, azelaic and sebacic (Scheme 2). In addition, this study is aimed how the increasing number of the methylene groups in the chain, odd-number or even-number of CH2 in diacids, are influenced on the composition and the topology of the supramolecular architecture of the formed crystals. even number of CH 2 O

odd number of CH2 O

O OH

O

OH

OH OH (b)

(a)

O O

O

O

OH OH

OH

OH

(d)

(c) O

O OH

O

O

OH OH

OH

(f)

(e)

O

O

O OH

OH

O

OH OH

(g)

(h)

Scheme 2. Aliphatic dicarboxylic acids: (a) malonic, (b) succinic, (c) glutaric, (d) adipic, (e) pimelic, (f) suberic, (g) azelaic and (h) sebacic.

EXPERIMENTAL SECTION Materials. 2-imino-4-thiobiuret (99%) and the aliphatic dicarboxylic acids: malonic (99%), succinic (≥99%), glutaric (99%), adipic (≥99%), pimelic (98%), suberic (98%), azelaic (98%) and sebacic (99%), which are anhydrous were purchased from Sigama-Aldrich and were used without further purification. Elemental analysis was carried out with a Perkin Elmer 240 elemental analyser.


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Synthesis: Commercially available 2-imino-4-thiobiuret (Aldrich, CAS No. 2114-02-05), which is in fact the tautomeric form 1-(diaminomethylene)thiourea and the respective aliphatic dicarboxylic acids (malonic, succinic, glutaric, adipic, pimelic, suberic, azelaic and sebacic) were added to hot water in a molar proportion of 2:1. When the solutions became homogeneous they were cooled slowly and kept at room temperature. After several days, transparent colourless crystals of the respective compounds 1-8 suitable for the X-ray single crystal measurements were formed. The crystals have been separated by filtration and dried in air. Bis(1-(diaminomethylene)thiouron-1-ium) malonate, (C2H7N4S)2(C3H2O4) (1): analysis: calculated for C7H16N8O4S2: C, 24.70; N, 32.92; O, 18.80; S, 18.84 and H, 4.74%. Found: C, 24.56; N, 33.08; O, 18.86; S, 18.80 and H, 4.72%. Bis(1-(diaminomethylene)thiouron-1-ium) succinate, (C2H7N4S)2(C4H4O4) (2): analysis: calculated for C8H18N8O4S2; C, 27.11; N, 31.62; O, 18.06; S, 18.09 and H, 5.12%. Found: C, 27.02; N, 31.70; O, 18.14; S, 18.02 and H, 5.02%. 1-(diaminomethylene)thiouron-1-ium hydrogenglutarate, (C2H7N4S)(C5H7O4) (3): analysis: calculated for C7H14N4O4S: C, 33.59; N, 22.39; O, 25.57; S, 12.81 and H, 5.64%. Found: C, 33.42; N, 22.44; O, 25.70; S, 12.72 and H, 5.72%. Bis(1-(diaminomethylene)thiouron-1-ium) adipiate dihydrate, (C2H7N4S)2C6H8O4×2H2O (4): analysis: calculated for C10H26N8O6S2: C, 28.70; N, 26.78; O, 22.94; S, 15.32 and H, 6.26%. Found: C, 28.56; N, 26.85; O, 22.98; S, 15.44 and H, 6.17%. 1-(diaminomethylene)thiouron-1-ium hydrogenpimelate, (C2H7N4S)(C7H11O4) (5): analysis: calculated for C9H18N4O4S: C, 38.84; N, 20.13; O, 22.99; S, 11.52 and H, 6.52%. Found: C, 38.62; N, 20.20; O, 23.14; S, 11.48 and H, 6.56%.


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1-(diaminomethylene)thiouron-1-ium hydrogensuberate, (C2H7N4S)(C8H13O4) (6): analysis: calculated for C10H20N4O4S: C, 41.08; N, 19.16; O, 21.89; S, 10.97 and H, 6.90%. Found: C, 40.88; N, 19.33; O, 21.98; S, 10.82 and H, 6.99%. 1-(diaminomethylene)thiouron-1-ium hydrogenazelate, (C2H7N4S)(C9H15O4) (7): analysis: calculated for C11H22N4O4S: C, 43.12; N, 18.29; O, 20.89; S, 10.46 and H, 7.24%. Found: C, 43.32; N, 18.12; O, 20.98; S, 10.36 and H, 7.22%. Bis(1-(diaminomethylene)thiouron-1-ium ) sebacate, (C2H7N4S)2(C10H16O4) (8): analysis: calculated for C14H30N8O4S2: C, 38.34; N, 25.55; O, 14.59; S, 14.62 and H, 6.90%. Found: C, 38.52; N, 25.66; O, 14.49; S, 10.52 and H, 6.81%. The deuterated analogues of the respective 1 - 8 salts were prepared by the usual reaction with heavy water. The respective protiated crystals were dissolved in heavy water, and left in the atmosphere saturated with heavy water for one-two weak, in order to avoid the contamination of the crystals and next this procedure was repeated twice. Single Crystal X-ray Diffraction. X-ray intensity data for the 1-8 crystals were collected using graphite monochromatic MoKα radiation on a four-circle κ geometry KUMA KM-4 diffractometer with a two-dimensional area CCD detector. The ω-scan technique with ∆ω = 1.0o for each image was used for data collection. Data collections were made using the CrysAlis CCD program.49 Integration, scaling of the reflections, correction for Lorenz and polarisation effects and absorption corrections were performed using the CrysAlis Red program.49 The structures were solved by the direct methods using SHELXS-97 and refined using SHELXL-97 program.50 The hydrogen atoms involving in the hydrogen bonds were located in difference Fourier maps and were refined. The hydrogen atoms joined to aromatic carbon atoms were introduced in their geometrical positions. The final difference Fourier maps showed no peaks of chemical


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significance. Details of the data collection parameters, crystallographic data and final agreement parameters are collected in Table 1. Visualisations of the structures were made with the Diamond 3.0 program.51 Selected geometrical parameters are listed in Table S1 (in Supporting Information) and the geometry of hydrogen bonding interactions is collected in Table S2-S9. The X-ray crystallographic information files (CIF) for 1-8 structures have been deposited with the Cambridge Crystallographic Data Center. CCDC numbers no. CCDC 1414303, 1414304, 1414305, 1414306, 1414307, 1414308, 1414309 and 1414310 for structures of 1-8. Powder X-ray Diffraction (PXRD). Powder X-ray diffraction patterns of the powdered protiated and deuterated 1-8 compounds were checked on

a PANanalytical X’Pert

diffractometer equipped with a Cu-Kα radiation source (λ=1.54182 Å). The diffraction data were recorded in the range of 5-45o at room temperature. The powder diffraction patterns of Hand D-compounds are included in supporting information (Figs. S1–S8). The obtained deuterated analogues crystallise, similar as H-compounds, in the same crystal systems with quite similar lattice parameters. Vibrational Spectra Measurements. The vibrational measurements of H-compound and its deuterated analogues were carried out at room temperature. The Fourier transform infrared spectrum was recorded from nujol mulls between 4000 and 400 cm-1 on a Bruker IFS 113 V FTIR spectrometer. Resolution was set up to 2 cm-1. The Fourier Transform Raman spectra for 1-8 were recorded on a FRA-106 attached to the Bruker 113 V FTIR spectrometer equipped with Ge detector cooled to liquid nitrogen temperature. Resolution was set up to 2 cm-1, signal/noise ratio was established by 32 scans. Nd3+ - YAG air-cooled diode pumped laser of power ca. 200 mW was used as an exciting source. The incident laser excitation was 1064 nm. The scattered light was collected at the angle of 180o in the region of 3600÷80 cm-1, resolution 2


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cm-1, 256 scans. Vibrational spectra for all compounds are included in supplementary (Figs S9S16). SHG measurements. Powder SHG measurements were carried out by the Kurtz−Perry method.52 Powdered samples of protiated and deuterated compound 1 and that of KDP with approximately the same particle size, were mounted between microscope glass slides and were excited by tunable fs laser pulses from the laser system consisting of a Quantronix Integra-C regenerative amplifier operating as an 800 nm pump and a Quantronix-Palitra-FS BIBO crystalbased optical parametric amplifier. Laser pulses provided by this system are of ~130 fs length and are operated at the repetition rate of 1 kHz. Measurements were conducted for two excitation wavelengths: 800 and 1064 nm. SHG photoluminescence was collected in a backscattering mode from three different places of the sample, by an Ocean Optics fiber coupled CCD spectrograph. The integrating time was 10000 ms and 2000 ms for samples and KDP, respectively.

RESULTS AND DISCUSSION Synthesis and preliminary characterization. Crystallizing 1-(diaminomethylene)thiourea with several aliphatic dicarboxylic acids different ionic supramolecular complexes have been obtained. Since the 1-(diaminomethylene)thiourea as an organic base contains one active site (acceptor H), therefore in synthesis with aliphatic dicarboxylic acids the molar proportion base/acid of 2:1 has been used. However, the observed stoichiometries of the obtained ionic supramolecular complexes are different. Compounds 1, 2, 4 and 8 crystallize with a 2:1 ratio of base to acid stoichiometry, while 3, 5, 6 and 7 had 1:1 stoichiometry. Dissolving starting components in a 1:1 molar ratio gave identical results. Within the obtained ionic supramolecular complexes only one in the case of 1-(diaminomethylene)thiourea with adipic acid gave hydrated


8

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crystals. The formation of ionic supramolecular complexes with different base/acid ratios can be explained by the component concentration changes during solvent evaporation.53,54 Recrystallizations of these 1-8 ionic supramolecular complexes in heavy water yield respective deuterated analogues. The PXRD patterns of protiated and deuterated complexes together with the calculated ones (Figs. S1-S8, in Supporting Information) confirm that the deuterated analogues crystallize, similar as H-compounds, in the same crystal systems with quite similar lattice parameters. Conformation of 1-(diaminomethylene)thiouron-1-ium cation and aliphatic dicarboxylate anions. The conformation of 1-(diaminomethylene)thiouron-1-ium cation in each of studied crystals is not strictly planar, but twisted. Both arms of the cation are oppositely rotated around the CN bonds involving the central N2 atom. The twisting angle of the cation in these crystals ranges from 1.6(1)o in 3 to 8.6(1)o in 2 (Table S1). The Cambridge Structural Data Base search for structures containing the 1-(diaminomethylene)thiouron-1-ium cation yield 22 structures,55 in

which

the

cation

exhibits

also

twisted

conformation

(Table

S10).

The

1-

(diaminomethylene)thiouron-1-ium cation twisting may differ from 1.4(1)o for perchlorate38 to 22.9(1)o for chloride37 and depends on the anions and is undoubtedly dependent on the hydrogen bonding system formed with the oppositely charged units. The gas-phase conformation of the 1(diaminomethylene)thiouron-1-ium cation as shown the DFT calculations is also twisted with a dihedral angle of 6.2o.37 The carbon chain of aliphatic dicarboxyalate anions is planar in all 1-8 crystals, but the carboxylate groups are not coplanar with the plane of the carbon chain. The dihedral angles between the carboxylate groups and the carbon chain plane in these 1-8 crystals are ranging from 2.3(1)o in succinate(2-) (2) to 84.9(1)o in malonate(2-) (1). In general the carboxylate groups of the aliphatic dicarboxylate ions are almost coplanar with the plane of the


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carbon chain in 2-8 crystals, while in crystal 1 the carboxylate group of malonate anion is almost perpendicular to the plane of the carbon chain (Table S1). Analysis of supramolecular structures: Bis(1-(diaminomethylene)thiouron-1-ium) malonate (1). Compound 1 crystallizes in the monoclinic non-centrosymmetric space group C2 with four molecules in the unit cell. Asymmetric unit of 1 consists of two 1-(diaminomethylene)thiouron-1-ium cations and two halves of double deprotonated malonate anions (Fig. 1a). The malonate(2-) anions have twofold symmetry axis with the central carbon atoms (C3/C6) located on a twofold axis, and link 1(diaminomethylene)thiouron-1-ium cations through NH…O hydrogen bonds with R22(8) or R22(10) graphs (Table S2). The R22(8) graph is formed by donation to the one carboxylate group from two amine groups of one 1-(diaminomethylene)thiouron-1-ium cation joined to C2, whereas the R22(10) graph is formed by donation to the two carboxylate groups of the second malonate(2-) anion from amine groups of the other 1-(diaminomethylene)thiouron-1-ium cation. Both hydrogen bonded cation-anion complexes are combined together via much weaker NH…S hydrogen bonds with a graph of R22(8) forming hydrogen bonding supramolecular complex (Fig. 1a). Because of its reduced electonegativity, the S atom should be a weaker hydrogen-bond acceptor than an O atom. Many theoretical and experimental investigations concerning with the stability of the NH…O and the NH…S hydrogen bonds have been reported, but no clear trend has emerged. Ab-initio energy calculations showed that a base pair linked by an NH…O hydrogen bond is more stable than that combined by an NH…S hydrogen bond.56 The importance of such interactions has been questioned,57 but the DH…S (D=donor) interactions are important in biological systems.58 In addition, the NH…S interactions have been utilised for design supramolecular arrangement of thiourea derivatives.59


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The formation of such NH…S interactions is favoured by the six-membered hydrogen-bonded ring with a graph of R22(8); the presence of C=S bond makes it some resonance-assisted stabilisation.60 Due to the almost perpendicular orientation of the carboxylate groups to the plane of the carbon chain of malonate(2-) anions the cation-anion hydrogen-bonded supramolecular complex is not planar. The solid-state supramolecular architecture in 1 is mainly, besides the ionic interaction, determined by the NH…O hydrogen bonds. The hydrogen bonds between the supramolecular 2:1 cation-anion complexes are formed between the imine and amine groups of the cation and the carboxylate groups of the malonate anions with graphs of R21(6), R22(8) and R22(10). The NH…O interactions in 1 lead to formation of pseudo two-dimensional layers parallel to (100) crystallographic plane (Fig. 1b), which is the cleavage plane of the crystals. Within the layer each malonate(2-) anion is surrounded by four 1-(diaminomethylene)thiouron1-ium cations and is involved as an acceptor into twelve NH…O hydrogen bonds (Table S2). Each oxygen atom of carboxylate groups of malonate(2-) anions acts as an acceptor in three hydrogen bonds. These layers are combined together through much weaker NH…S interaction (Fig. 1b) forming three-dimensional hydrogen bonding network (Fig. S9). Bis(1-(diaminomethylene)thiouron-1-ium) succinate (2). The compound 2 crystallizes in the centrosymmetric space group P21/c of the monoclinic system with two molecules per unit cell. The asymmetric unit contains one 1-(diaminomethylene)thiouron-1-ium cation and half of succinate(2-) anion. The succinate(2-) anion lies on the inversion center and interacts with two symmetrically equivalent 1-(diaminomethylene)thiouron-1-ium cations via almost linear NH…O hydrogen bonds (Table S3) with a graph of R22(8) forming 2:1 roughly planar supramolecular complex (Fig. 2a). The 2:1 hydrogen bonded via two R22(8) graphs supramolecular complexes related by two-fold screw axis interact each other via multiple


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NH…O hydrogen bonds with two pairs of R21(6) and one pair of R42(8) forming two dimensional layers aligned to (100) crystallographic plane (Fig. 2b). The (100) plane is the cleavage plane of the crystals, since the layers interact each other via much weaker NH…S hydrogen bonds. The NH…S hydrogen bonds are formed between each pairs of 1(diaminomethylene)thiouron-1-ium cations related by an inversion linking the 2D-layers into three-dimensional hydrogen bonded supramolecular network (Fig. S10). 1-(diaminomethylene)thiouron-1-ium hydrogenglutarate (3). The compound 3 crystallizes in the centrosymmetric space group P21/c of the monoclinic system with eight molecules per unit cell.

The

asymmetric

unit

of

3

contains

two

symmetry

independent

1-

(diaminomethylene)thiouron-1-ium cations and two symmetry independent singly deprotonated hydrogenglutarate(-) anions that are linked together via almost linear and strong symmetric O3…H3…O11

hydrogen

bond

with

O…O

distance

of

2.454(2)

Å.

The

1-

(diaminomethylene)thiouron-1-ium cations in interact with symmetric O…H…O hydrogenbonded hydrogenglutarate(-) anions via NH…O hydrogen bonds with R21(6) and R12(10) graphs forming almost planar 2:2 supramolecular complex (Fig. 3a). The R21(6) graph is formed by donation to the one oxygen atom (O4 or O12) of carboxylate groups from imine and amine linked to C2 or C12, whereas the R12(10) graph is formed by donation to the O atoms of both carboxylate groups of deprotonated hydrogenglutarate(-) anions from amine group of 1(diaminomethylene)thiouron-1-ium cations joined to C1 or C11. The translationally related strong O…H…O hydrogen-bonded singly deprotonated hydrogenglutarate(-) dimers interact each other via another strong symmetric O1…H2…O12i with O…O distance of 2.435(2) Å and its equivalents into chains parallel to [010] direction (Fig. 3b). The strong O…H…O hydrogenbonded hydrogenglutarate(-) chains interact with the 1-(diaminomethylene)thiouron-1-ium


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cations via NH…O hydrogen bonds with R21(6), R22(8), R32(10) and R12(10) graphs forming planar sheet located almost parallel to the (101) crystallographic plane (Fig. 3b), which is the cleavage plane of the crystals 3. Since between the sheets there are no any directional interaction like as hydrogen bonds, they are interact via van der Waals forces (Fig. S11). The distance between the average planes of the sheets is equal to 3.45(1) Å. Bis(1-(diaminomethylene)thiouron-1-ium) adipiate dihydrate (4). The compound 4 crystallizes in the centrosymmetric space group P21/c of the monoclinic system with two molecules per unit cell. The asymmetric unit contains one 1-(diaminomethylene)thiouron-1-ium cation, half double deprotonated adipiate anion and one water molecule. The adipiate(2-) anion lies on the inversion center and links two 1-(diaminomethylene)thiouron-1-ium cations via NH…O hydrogen bonds with R22(8) and R21(6) graphs forming 2:1 cation:anion supramolecular complex. The water molecule interacts with the 2:1 complex as a donor and as an acceptor via OH…O and NH…O hydrogen bonds forming 2:1:2 supramolecular complex (Fig. 4a). The water molecules related by a screw axis and translation along b-axis interact each other via OH…O hydrogen bonds with O…O distance of 2.866(2) Å forming chain along [010] direction. The OH…O hydrogen-bonded water chains interact with adipiate(2-) anions via OH…O hydrogen bonds forming two-dimensional anionic layer aligned to (100) crystallographic plane (Fig. 4b). The charge of anionic layers is compensated by the 1(diaminomethylene)thiouron-1-ium cations. The cations interact on both side of the anionic layer via NH…O hydrogen bonds (Table S5) with R22(8) and R21(6) graphs forming twodimensional hydrogen-bonded neutral supramolecular layer parallel to (100) crystallographic plane (Fig. 4c). Translation related along a-axis the neutral supramolecular layers interact each other via much weaker NH…S hydrogen bonds. The NH…S hydrogen bonds are formed


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between each pairs of 1-(diaminomethylene)thiouron-1-ium cations related by an inversion linking the neutral hydrogen-bonded supramolecular 2D-layers into three-dimensional hydrogen bonded supramolecular network (Fig. 4d). Since the NH…S hydrogen bonds between the layers parallel to (100) crystallographic plane that is the cleavage plane of the crystal are much weaker than the OH…O and NH…O hydrogen bonds interconnecting the units within the layers (Table S5). 1-(diaminomethylene)thiouron-1-ium hydrogenpimelate (5). The compound 5 crystallizes in the centrosymmetric space group of the triclinic system with two molecules per unit cell. The asymmetric unit contains 1-(diaminomethylene)thiouron-1-ium cation and singly deprotonated hydrogenpimelate anion linked together via almost linear NH…O hydrogen bonds (Table S6) with a graph of R22(8) as illustrated in Fig. 5a. However, the hydrogen atom of singly deprotonated hydrogenpimelate anion is disordered over two non-equivalent positions (H11 lies in 1h and H13 lies in 1c inversion centres). Both hydrogen’s form centrosymmetrical OH…O hydrogen bonds with O…O distances of 2.452(3) and 2.468(3) Å (Table S6) linking the pimelate anions into zig-zag chains (Fig. 5b). The OH…O hydrogen bonded anionic chains of hydrogenpimelate anions are interconnected by 1-(diaminomethylene)thiouron-1-ium cations NH…O hydrogen bonds with R22(8) to one chain and with R21(6) and R33(10) graphs to neighbouring forming almost planar two-dimensional supramolecular network (Fig.5b). In addition, within this planar two-dimensional supramolecular sheet much weaker NH…S hydrogen bonds between each inversion related pairs of 1-(diaminomethylene)thiouron-1-ium cations are formed. Translationally related hydrogen-bonded two-dimensional supramolecular sheets of 1-(diaminomethylene)thiouron-1-ium hydrogenpimelate are parallel each other and aligned almost parallel to the (33-5) crystallographic plane. This plane is the cleavage plane of


14

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the crystal, since between the planar hydrogen-bonded two-dimensional supramolecular sheets there are no any directional interaction, they are interact via van der Waals forces (Fig. S12). The distance between the average planes of the sheets is equal to 3.43(1) Å. 1-(diaminomethylene)thiouron-1-ium hydrogensuberate (6). The compound 6 crystallizes in the centrosymmetric space group P-1 of the triclinic system with two molecules per unit cell. The asymmetric unit contains 1-(diaminomethylene)thiouron-1-ium cation and singly deprotonated hydrogensuberate(-) anion linked together via almost linear NH…O hydrogen bonds (Table S7) with a graph of R22(8) as illustrated in Fig. 6a. The hydrogen atom of singly deprotonated hydrogensuberate anion is disordered over two non-equivalent positions (H2O lies in 1b and H4O lies in 1c inversion centres). Inversion related with translation occurrence hydrogensuberate anions are joined together via linear, strong symmetrical OH…O hydrogen bonds with O…O distances of 2.437(4) and 2.446(4) Å (Table S7) linking the hydrogensuberate anions into zig-zag chains (Fig. 6b). Two neighbouring zig-zag hydrogensuberate anionic chains related by an inversion are interconnected by 1-(diaminomethylene)thiouron-1-ium cations via NH…O hydrogen bonds with R22(8), R21(6) and R33(10) graphs forming pseudo two dimensional hydrogen-bonded supramolecular layer almost parallel to (311) crystallographic plane (Fig. 6b). Since the carboxylate groups of the hydrogensuberate anions are twisted (10.4(1)o and 13.8(1)o) in relation to the plane of the carbon chains, therefore the interacted 1(diaminomethylene)thiouron-1-ium cations with the chains are up and down from the average plane defined by the carbon atoms of hydrogensuberate anions forming the pseudo two dimensional hydrogen-bonded supramolecular layer (Fig. 6c). Neighbouring transitional related the hydrogen-bonded supramolecular layers are combined into three dimensional hydrogenbonded supramolecular network (Fig. 6d).


15


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Page 16 of 47

1-(diaminomethylene)thiouron-1-ium hydrogenazelate (7). The compound 7 crystallizes in the centrosymmetric space group P-1 of the triclinic system with two molecules per unit cell. The asymmetric unit contains 1-(diaminomethylene)thiouron-1-ium cation and singly deprotonated hydrogenazelate(-) anion interact together via NH…O hydrogen bonds (Table S8) with a graph of R21(6) as illustrated in Fig. 7a. The hydrogen atom of singly deprotonated hydrogenazelate(-) anion is disordered over two non-equivalent positions (H2 lies in 1h and H3 lies in 1c inversion centres). Inversion related hydrogenazelate(-) anions are interconnected by linear, strong symmetrical OH…O hydrogen bonds with O…O distances of 2.462(4) and 2.468(4) Å forming the zig-zag anionic chains (Fig. 7b). The charge of anionic chains is compensated by the 1(diaminomethylene)thiouron-1-ium cations. Each 1-(diaminomethylene)thiouron-1-ium cation interconnects neighbouring inversion related anionic zig-zag chains NH…O hydrogen bonds with a graph of R21(6) to the one anionic chain and with R21(6) and R33(10) to the other chain forming two dimensional hydrogen-bonded supramolecular sheet. In addition, the two dimensional hydrogen-bonded supramolecular network is stabilized by much weaker NH…S hydrogen bonds between each inversion related pairs of 1-(diaminomethylene)thiouron-1-ium cations forming layers almost parallel to (1-1 2) crystallographic plane (Fig. 7b). This plane is the cleavage plane of the crystal, since between the planar hydrogen-bonded two-dimensional supramolecular sheets there are no any directional interaction, they are interact via van der Waals forces (Fig. S13). The distance between the average planes of the sheets is equal to 3.46(1) Å. Bis(1-(diaminomethylene)thiouron-1-ium ) sebacate (8). Compound 8 crystallizes in the centrosymmetric space group C2/c of monoclinic system with four molecules in the unit cell. Asymmetric unit consists of 1-(diaminomethylene)thiouron-1-ium cation and half of double deprotonated sebacate anion (Fig. 8a). The sebacate(2-) anion lies on the inversion centre, and


16

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links two 1-(diaminomethylene)thiouron-1-ium cations through NH…O hydrogen bonds with a graph of R22(8) (Table S9) forming 2:1 supramolecular complex. Inversion related 2:1 complexes interact each other via weaker NH…S hydrogen bonds between each inversion related pairs of 1-(diaminomethylene)thiouron-1-ium cations forming infinitive chains (Fig. 8b). The chains related by inversion and translation are arranged into layers parallel to the (001) crystallographic plane (Fig. 8c). The chains belong to adjacent layers (along the c-axis) interact each other via NH…O hydrogen bonds with a graph of R21(6) forming a three-dimensional supramolecular network (Fig. S14). Some supramolecular features of 1-8. Aliphatic dicarboxylic acid functional groups are known to form robust intermolecular interactions with several organic N-bases forming different hydrogen bonding supramolecular complexes in solid.61-71 Using 1-(diaminomethylene)thiourea as an organic base for crystallization with aliphatic dicarboxylic acids depending on the deprotonation of one or both COOH groups yielding base-acid supramolecular complexes with 1:1 or 2:1 ratio. In studied supramolecular complexes 1-8 interaction between the 1(diaminomethylene)thiouron-1-ium cation and oppositely charged singly or doubly deprotonated aliphatic dicarboxylate anions may be realized in different modes as shown in Scheme 3.

Scheme 3. Supramolecular synthons between 1-(diaminomethylene)thiouron-1-ium cation and the deprotonated (COO-) and non-deprotonated (COOH) groups of aliphatic dicarboxylic acids.


17


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The R22(8) synthons I, II and III are formed only by deprotonated COO- group, whereas the R21(6) synthons IV, V and VI can be formed by both deprotonated (COO-) and non-deprotonated (COOH) groups. The R22(8) synthon is the most stable interaction motif in the studied supramolecular complexes in solid due to the strong geometrical complementarity between the base-acid units. Investigated supramolecular complexes contain aliphatic dicarboxylic acids with different number of CH2 groups between the terminal carboxylic groups, with odd number of CH2 (in 1, 3, 5 and 7) as well as with even number of CH2 (in 2, 4, 6 and 8). Depending on the deprotonation of aliphatic dicarboxylic acids, the 1-8 supramolecular complexes are fall into two groups: (1) singly deprotonated with base to acid ratio of 1:1 (supramolecular complexes 3, 5, 6 and 7) and (2) double deprotonated with the ratio of 2:1 base to acid (supramolecular complexes 1, 2, 4 and 8). Within supramolecular complexes of singly deprotonated acid three of them contain odd number of CH2 (in 3, 5 and 7) and in only in one the even number of CH2 groups is present (in 6), and the opposite relation is observed within complexes with both deprotonated carboxylic groups: one supramolecular complex with odd number of CH2 groups as in 1 and three with even number of CH2 groups as in 2, 4 and 8. Within the possible NH…O hydrogen bonding supramolecular motif R22(8), the synthon I formed by donation to COO- group from amine groups linked to the same C atom of 1-(diaminomethylene)thiouron-1-ium cation is observed in 1, 2, 3, 5 and 6 supramolecular complexes in solid. The other R22(8) motif (synthon II) is found only in the 1 and 4 supramolecular complexes in solid, while the synthon III is absent in all investigated complexes. The R21(6) motif formed by donation to the one O atom of COOH or

COO-

group

from

both

amine

groups

linked

to

the

same

C

atom

1-

(diaminomethylene)thiouron-1-ium cation (synthon IV) is present in the supramolecular structures of 1, 2, 3, 4, 5 and 7. The other R21(6) motif formed by donation to O atom from amine


18

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and imine groups is present in the supramolecular structure of 1 (synthon V), whereas the other R21(6) motif (synthon VI) is observed in the supramolecular structure of 2, 6, 7 and 8. Within the 1-8 supramolecular structures only in 7 the all three NH…O hydrogen bonding supramolecular R22(8) motifs (synthons I, II and III) are absent. In all supramolecular structures, except the structure 3, the 1-(diaminomethylene)thiouron-1-ium cations are interacted via much weaker NH…S hydrogen bonding supramolecular R22(8) motif. In these supramolecular structures, except the structure 1, this R22(8) motif is formed between the inversion related 1(diaminomethylene)thiouron-1-ium cations, in 1 the NH…S hydrogen bonding R22(8) motif is formed between both 1-(diaminomethylene)thiouron-1-ium cations in the unit. In all supramolecular structures with the base to acid ratio of 1:1 (3, 5, 6 and 7), the singly deprotonated aliphatic dicarboxylic acids are interacted via strong symmetrical O…H…O hydrogen bonds with O…O distances of ~2.44 Å forming infinitive chains. The O…H…O hydrogen bonds chains are running along the [010] direction in 3, along [1-12] in 5, along [-311] in 6 and along [111] in 7. In 5, 6 and 7 the O…H…O hydrogen bonded chains of singly deprotonated aliphatic dicarboxylic acids adopt a zig-zag form. Within the 1-8 supramolecular complexes only one is hydrated (4), in which the presence of water molecules are arranged into infinitive OH…O hydrogen bonds chains along b-axis. The OH…O hydrogen bonded chains of water molecules are interconnected via OH…O hydrogen bonds with adipiate(2-) units forming anionic 2D-layers parallel to (100) crystallographic plane. These anionic 2D-layers are combined together via NH…O hydrogen bonds by dimeric inversion related NH…S hydrogen bonded 1-(diaminomethylene)thiouron-1-ium cations into 3D supramolecular network. The dimensionality of the hydrogen bonding supramolecular network in 1-8 is 2D or 3D. The 2D supramolecular network is present in three 3, 5 and 7


19


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supramolecular structures and in the other dimensionality of the hydrogen bonding supramolecular network is 3D. Vibrational characterization of 1-8. In order to gain an insight into the structure and the nature of the interaction between the 1-(diaminomethylene)thiourea and aliphatic dicarboxylic acids in the crystalline form of supramolecular complexes 1-8, the vibrational spectra were measured and discussed with those of 1-(diaminomethylene)thiourea43 and aliphatic dicarboxylic acids.72-79 Assignment of the IR bands was supported by the spectra of their deuterated analogues. The infrared spectra (protiated and deuterated) and Raman spectra (protiated) of 1-8 complexes are included in the Supporting Information (Figs. S15-S22). Bands corresponding to the vibration of the functional groups were identified with the aid of infrared and Raman correlation charts.80,81 In solid form, most of aliphatic dicarboxylic acids appear as H-bonded chains, where the carboxyl groups of one molecule are H-bonded to the carboxyl groups of the neighbouring molecules, so that C=O groups act as acceptors and the OH groups act as donors.82-87 In the investigated supramolecular complexes with the composition of 2:1 (3, 5, 6 and 7) due to deprotonation of both carboxylic groups of the acids, the chains as in pure dicaraboxylic acids are absent, therefore in the vibrational spectra of these compounds the typical C=O and O−H vibrational bands are absent. The vibrational band of carboxylate group in double deprotonated acids are observed near 1600 cm-1 (νa(COO-) and near 1400 cm-1 (νs(COO-) (Fig. 9a). In supramolecular complexes of 1:1 ratio in solids (1, 2, 4 and 8), the chains of singly deprotonated aliphatic dicarboxylic acids are present. Within the chains the singly deprotonated dicarboxylic acids are linked by the strong and symmetrical O…H…O hydrogen bonds with O…O distances of ~2.44 Å. The strong O…H…O hydrogen bonds within the chains make the CO distances of both deprotonated and non-deprotonated carboxyl groups intermediate between the


20

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typical C(sp2)O single (~1.31Å ) and C(sp2)=O double (1.21 Å) bonds.88 Therefore the stretching vibrations of asymmetric and symmetric νa(COO-) and νs(COO-) in the supramolecular complexes 1, 2, 4 and 8 are shifted to a higher wavenumber (~1650 and ~1420 cm-1) in comparison to the complexes of doubly deprotonated complexes 3, 5, 6 and 7 (Fig. 9b). The medium-strong intensity bands in the spectral region of 3400-3100 cm-1 observed in the spectra of all 1-8 compounds are attributed to the asymmetric and symmetric stretching of the three NH2 groups of the 1-(diaminomethylene)thiouron-1-ium cation. These bands, as expected, are shifted in the IR spectra of deuterated analogues to the spectral region of 2550-2200 cm-1 (see respective figures in SI). Within the 1-8 supramolecular complexes only compound 4 contains water that in the IR spectrum is observed as a narrow band at ~3446 cm-1, which is shifted to 2595 in the spectrum of deuterated analogue (Fig. S18). The strong narrow band in the region of 1725-1710 cm-1 according to the literature89 is assigned to stretching of the imine group of the cation, which is shifted to ~1240 cm-1 in the spectrum of deuterated analogues. The ν(C=S) band of the 1-(diaminomethylene)thiouron-1-ium cation similar as in thiourea90 is observed at ~730 cm-1 in IR and at ~745 cm-1 in Raman spectra of the 1-8 supramolecular complexes. Interaction between the 1-(diaminomethylene)thiouron-1-ium and the singly or doubly deprotonated aliphatic dicarboxylic acid units in solid of 1-8 supramolecular complexes takes place between the imine and amine groups of 1-(diaminomethylene)thiouron-1-ium cations and the singly or doubly deprotonated carboxylic groups of the anions. This interaction results in medium and weak NH…O hydrogen bonds that reveal in the IR spectra as a broad band in the range of 3300-2500 cm-1, which is shifted to 2400-1800 cm-1 in the spectra of deuterated analogues. In addition, the broad band in the spectral region of 1500-1100 cm-1, which is overlapped with other bands, points on the presence of this type of the NH…O hydrogen


21


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bonds. In the salts of singly deprotonated dicarboxylic acids (3, 5, 6 and 7), besides the medium and weak NH…O hydrogen bonds, the strong and symmetrical O…H…O hydrogen bonds with O…O distances of ~2.44 Å are present. The IR stretching bands of the hydrogen bonded O−H units with strong O…H…O hydrogen bonds occur as a broad band in the spectral region below 1000 cm-1 (Fig. 10). The correlation between the O…O distances and the stretching frequency is used to classify and characterize the hydrogen bonds.91 Strong and very strong O…H…O hydrogen bonds are not only characterized by a decreasing wavenumber, but also by an increasing band width and an increasing integrated intensity of the stretching.92 The former is caused by the repeated combination of the stretching mode with the very low-frequent breaching mode of the hydrogen bond, the latter is a function of the attenuated principal O−H bond by increasing of the O…H bond strength that facilitates easier IR excitation. The potential energy surface of the O…H…O with increasing hydrogen bond strength change from double to single minimum at the O…O distance of ~ 2.44 Å as observed in the investigated supramolecular complexes 3, 5, 6 and 7.93 As a consequence, the hydrogen bonds show and increasing anharmonicity with increasing hydrogen bond strength.93 The strong anharmonicity of the broad band causes peculiar features like as anomalous deuteration shifts close to 1.0 as in deuterated analogues 3, 5, 6 and 7 (Figs. S17, S19, S20 and S21) instead of ~1.35 for the weak hydrogen bonds, observation of the IR absorption bands that are actually forbidden by normal mode analysis, and finally different resonance phenomena. The latter are observed in the spectra of 3, 5, 6 and 7 (Fig. 10b) in the form of enhanced combination of overtones and the gap within the broad absorption band that has been described in the literature as “Fermi resonance”, “Evans type transmission windows” or “Evans hole”91 or more recently as “antiresonance” or “Fano


22

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type” feature.94 The peculiar shape of the feature was also confirmed by the theoretical calculation.91 Nonlinear Optical Properties. As is known, only the noncentrosymmetric structures might have a second-order nonlinear optical effect.95-97 Within investigated supramolecular complexes only one crystallized in an acentric space group (C2 for 1). Therefore, the second-harmonic generation (SHG) measurements for protiated and deuterated samples of 1 were investigated. Approximate estimations were carried out at wavelengths of 800 and 1064 nm. The results obtained from powdered samples in the form of a pellet were compared with those obtained for KDP. The preliminary experimental results revealed that protiated and deuterated samples of 1 display of almost the same powder SHG efficiencies 0.22(1) times that of KDP (for both wavelengths 800 and 1064 nm).

CONCLUSIONS A new series of 1-(diaminomethylene)thiourea-based supramolecular complexes with a range of aliphatic acids were synthesised using solvent-assisted evaporation-based crystallization. Independent on the base/acid molar ratios used for crystallization the formed supramolecular complexes in solid have 2:1 ratio in the case of malonic, succinic, adipic and sebacic acids and 1:1 ratio in the case of glutaric, pimeleic, suberic and azelaic acids. Generally, the formation of supramolecular complexes with base to acid 2:1 ratio may be affected by geometrical compatibility between base and acid and by the NH…O hydrogen bonds with a graph of R22(8). Whereas the formation of supramolecular complexes with base to acid 1:1 ratio in solids is governed by strong and symmetrical O…H…O hydrogen bonds linking the singly deprotonated aliphatic

dicarboxylate(-)

anions

into

chains

that

interact


weaker

with

the

1-

23


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Page 24 of 47

(diaminomethylene)thiouron-1-ium cations. This work demonstrates a wide diversity supramolecular structures of 1-(diaminomethylene)thiourea with aliphatic dicarboxylic acids having a variety of the carbon chain lengths. This finding alone has a considerable conceptual and also practical value in the field crystal engineering suggesting importance of strong O…H…O hydrogen bonds as well as much weaker NH…O hydrogen bonds into formation of supramolecular architectures by self-assembly of 1-(diaminomethylene)thiourea with aliphatic dicarboxylic acids.


24

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(a)

(b)

Figure 1. View of supramolecular complex of 1 with the anisotropic displacement ellipsoids at the 50% probability level (a)

and the hydrogen-bonded viewed along [001] (b). Broken lines

represent NH…O (black) and NH…S hydrogen bonds (red).


25


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Page 26 of 47

(a)

(b)

Figure 2. View of supramolecular complex of 2 with the anisotropic displacement ellipsoids at the 50% probability level (a) and the hydrogen-bonded supramolecular structure viewed along [001] (b). Broken lines represent NH…O (black) and NH…S hydrogen bonds (red).


26

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(a)

(b) Figure 3. View of supramolecular complex of 3 with the anisotropic displacement ellipsoids at the 50%

probability level (a), the 2D hydrogen-bonded sheet (b). Broken lines represent NH…O (black) and OH…O hydrogen bonds (red). One of the OH…O hydrogen bonded chains is marked in red on the figure 3b. Symmetry code as in Table S4.


27


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Page 28 of 47

(a)

(b)

(c)


28

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(d) Figure 4. View of supramolecular complex of 4 with the anisotropic displacement ellipsoids at the 50%

probability level (a), the 2D OH…O hydrogen-bonded anionic layer viewed along a-axis (b), and the anionic layer interacted on both sides via NH…O hydrogen bonds with 1-(diaminomethylene)thiouron1-ium cations (c) and the packing viewed along b-axis (d). Broken lines represent NH…O and OH…O (black) and NH…S hydrogen bonds (red). Symmetry code as in Table S5.


29


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Page 30 of 47

(a)


probability level (a), the 2D NH…O and OH…O hydrogen-bonded layer viewed along [001] (b). Broken lines represent NH…O (black), and OH…O (red) and NH…S hydrogen bonds (blue). One of the OH…O hydrogen bonded zig-zag chains is marked in red on the figure 5b. Symmetry code as in Table S6.


30

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(a)

(b)

(c)


31


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Page 32 of 47

(d) Figure 6. View of supramolecular complex of 6 with the anisotropic displacement ellipsoids at the 50%

probability level (a), the 2D hydrogen-bonded layer (b and c) and the packing showing the stacking structure (d). Broken lines represent NH…O (black), and OH…O (red) and NH…S hydrogen bonds (blue). One of the OH…O hydrogen bonded zig-zag chains is marked in red on the b, c and d. Symmetry code as in Table S7.


32

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(a)


probability level (a), the 2D hydrogen-bonded sheet (b). Broken lines represent NH…O (black), and OH…O (red) and NH…S hydrogen bonds (blue). One of the OH…O hydrogen bonded zig-zag chains is marked in red on the Fig. b. Symmetry code as in Table S8.


33


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Page 34 of 47

(a)

(b)

(c) Figure 8. View of supramolecular complex of 8 with the anisotropic displacement ellipsoids at the 50%

probability level (a), two almost perpendicular hydrogen bonded chains (b) and the packing showing 3D supramolecular structure viewed along b-axis (c). Broken lines represent NH…O (black) and NH…S hydrogen bonds (blue). Symmetry code as in Table S9.


34

1 2 4 8

1800

1700

1600

1500

1400

1300

1200

1400

1300

1200

-1

Wavenumber [cm ]

(a)

Raman Intensity

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


Raman Intensity

Page 35 of 47

3 5 6 7

1800

1700

1600

1500

-1

Wavenumber [cm ]

(b) Figure 9. Raman spectra of doubly (a) and singly (b) deprotonated aliphatic dicarboxylic acids supramolecular complexes 1-8.


35


1

Transmittance

2

4 8

1000

900

800

700

600

500

600

500

-1

Wavenumber [cm ]

(a)

3 Transmittance

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 36 of 47

5 6 7

1000

900

800

700 -1

Wavenumber [cm ]

(b) Figure 10. IR spectra of doubly (a) and singly (b) deprotonated aliphatic dicarboxylic acids supramolecular complexes 1-8. The spectra of singly deprotonated acid compounds 3, 5, 6 and 7 show the “Evans hole” near 900 cm-1.


36

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Table 1. Crystal Data and Structure Refinement for Compounds 1-8.

1 Formula

2

3

4

5

C7H16N8O4S2 C8H18N8O4S2 C14H28N8O8S2 C10H26N8O6S2 C9H18N4O4S

6

7

8

C10H20N4O4S C11H22N4O4S C14H30N8O4S2

f.w.(g·mol–1) 340.4

354.44

500.56

418.51

278.33

292.36

306.39

438.58

Crystal system

monoclinic

monoclinic

monoclinic

monoclinic

triclinic

triclinic

triclinic

monoclinic

space group

C2 (No. 5)

P21/c (No.14)

P21/c (No.14)

P21/c (No.14)

P-1 (No. 2)

P-1 (No. 2)

P-1 (No. 2)

C2/c (No. 15)

a (Å)

26.119(2)

13.129(2)

10.381(2)

14.115(2)

5.4130(11)

4.0633(4)

5.3064(12)

22.814(1)

b (Å)

4.0778(2)

5.1895(8)

16.044(3)

4.888(1)

10.624(2)

11.8739(13)

9.9344(16)

9.1161(4)

c (Å)

15.4735(7)

11.809(2)

14.255(3)

14.301(2)

12.271(3)

15.4615(15)

14.382(2)

10.6126(4)

69.95(1)

69.99(1)

92.733(13)

84.72(2)

86.541(8)

99.956(16)

85.73(1)

89.414(8)

93.509(16)

α (º) 119.51(1)

β (º)

108.34(1)

108.60(3)

95.54(1)

γ (º)

107.504(4)

V (Å3)

1434.3(3)

763.71(21)

2250.2(8)

982.1(3)

659.4(2)

699.62(12)

744.0(2)

2104.94(15)

Z

4

2

4

2

2

2

2

4

Dcalc / Dobs 1.576 / 1.57 (g·cm–3)

1.541 / 1.54

1.478 / 1.47

1.415 / 1.41

1.402 /1.40

1.388 / 1.38

1.368 / 1.36

1.384 / 1.38

µ (mm–1)

0.381

0.295

0.315

0.259

0.248

0.237

0.291

Crystal (mm)

0.402

size 0.34 × 0.18 × 0.34 × 0.18 × 0.26 × 0.22 × 0.38 × 0.21 × 0.36 × 0.31 × 0.35 × 0.14 × 0.45 × 0.19 × 0.38 × 0.22 × 0.14 0.12 0.17 0.15 0.22 0.11 0.16 0.15

Radiation, λ (Å)

Mo Kα , 0.71073

Mo Kα , 0.71073

Mo Kα , 0.71073

Mo Kα , 0.71073

Mo Kα , 0.71073

Mo Kα , 0.71073

Mo Kα , 0.71073

Mo Kα , 0.71073

T (K)

295(2)

295(2)

295(2)

295(2)

295(2)

295(2)

295(2)

295(2)

θ range(o)

2.65 ÷ 28.50

3.27 ÷ 28.50

2.49 ÷ 29.16

2.86 ÷ 29.44

3.12 ÷ 29.45

2.78 ÷ 27.89

3.44 ÷ 28.90

2.96 ÷ 28.30

Tmin/Tmax

0.8783 / 0.9477

0.8837 / 0.9588

0.9301 / 0.9591

0.8992 / 0.9564

0.9201 / 0.9622

0.9218 / 0.9779

0.9043 / 0.9671

0.9033 / 0.9646

Refls collected/ unique/ observed

10195/ 3200/ 1890

9813/ 1952/ 1272

27729/ 5605/ 2944

12718/ 2554/ 1273

7754/ 3341/ 1778

9497/ 3334/ 1874

10001/ 3745/ 1961

13926/ 2728/ 1881

Rint

0.0583

0.0411

0.0562

0.0689

0.0285

0.0768

0.0921

0.0288


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Page 38 of 47

R[F2>2σ(F2)] 0.0431

0.0361

0.0432

0.0459

0.0480

0.0677

0.0655

0.0352

wR(F2) refls

0.0723

0.0448

0.0967

0.1111

0.1382

0.1405

0.0945

all 0.0803

Goodnessof-fit, S

1.000

1.000

1.000

1.002

1.051

1.004

1.016

1.001

Flack parameter

0.09(8)

−

−

−

−

−

−

−

+0.220;

+ 0.215;

+0.206;

+0.229;

+0.378;

+0.217;

+0.180;

-0.211

-0.228

-0.209

-0.265

-0.280

-0.248

-0.211

∆ρmax; ∆ρmin + 0.227; (e Å–3) -0.238

wR={Σ [w(Fo2–Fc2)2]/ΣwFo4}½; w–1=1/[σ2(Fo2) + (aP)2+bP] where a and b are 0.0284 and 0.3848 for 1, 0.0276 and 0.1871 for 2, 0.0038 and 0.0 for 3, 0.0350 and 0.1582 for 4, 0.0442 and 0.0 for 5, 0.0529 and 0.0 for 6, 0.0470 and 0.0 for 7, 0.0454 and 1.0557 for 8, and P = (Fo2 + 2Fc2)/3.

ASSOCIATED CONTENT Supporting Information. Selected geometrical parameters and hydrogen bonding tables for all compounds (1-8); twisting angle for 1-(diaminomethylene)thiouron-1-ium cation of the known salts; calculated and experimental PXRD diagrams for all compounds 1-8 (protiated H and

deuterated D); additional packing diagrams; IR and Raman spectra of 1-8 and the X-ray crystallographic information files (CIF) are available for compounds 1-8. This material is available free of charge via the Internet at http://pubs.acs.org. AUTHOR INFORMATION Corresponding Author *E-mail: [email protected]. Tel. +48 71 39 54 145. Fax: +48 71 34 410 29.

Notes The author declare no competing financial interest.


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For Table of Contests Use Only

Diversity in Supramolecular Solid-State Architecture Formed by Self-Assembly of 1(diaminomethylene)thiourea and Aliphatic Dicarboxylic Acids

Jan Janczak Institute of Low Temperature and Structure Research, Polish Academy of Sciences, Okólna 2 str., P.O. Box 1410, 50-950 Wrocław, Poland

A family of 1-(diaminomethylene)thiourea based supramolecular complexes with a range of aliphatic dicarboxylic acids, HOOC(CH2)nCOOH (n=1,2,...8), and base to acids 1:1 or 2:1 ratios was synthesised and structurally characterized. In supramolecular complexes of 1:1 ratio strong symmetrical O…H…O and weaker NH…O hydrogen bonds are present, whereas in supramolecular structures of 2:1 ratio only weaker NH…O hydrogen bonds are found.


47

Diversity in Supramolecular Solid-State Architecture Formed by Self

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