Binding Modes of Nonspherical Anions to N-Alkylammonium

Article pubs.acs.org/crystal

Binding Modes of Nonspherical Anions to N‑Alkylammonium Resorcinarenes in the Solid State N. Kodiah Beyeh,† Mario Cetina,†,‡ and Kari Rissanen*,† †

Department of Chemistry, NanoScience Center, University of Jyväskylä, P.O. Box 35, 40014 Jyväskylä, Finland Department of Applied Chemistry, Faculty of Textile Technology, University of Zagreb, Prilaz baruna Filipovića 28a, 10000 Zagreb, Croatia

‡

S Supporting Information *

ABSTRACT: A series of hydrogen bond stabilized Nalkylammonium resorcinarene salts with nitrate, triflate, and picrate as the counteranions were synthesized and characterized with 1H NMR and electrospray ionization (ESI) mass spectrometry. Together with electrostatic interactions, the binding of the anions with several hydrogen bond donor sites proceeds through a complex array of intra- and intermolecular hydrogen bonds, evidenced by single crystal X-ray diffraction analysis. These N-alkyl ammonium resorcinarenes bind the larger nonspherical anions into deformed cavitand-like structures and enforce a transformation of the resorcinarene conformation from almost symmetrical to extremely distorted.

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INTRODUCTION Molecular recognition and crystal engineering using multiple interactions, such as electrostatic forces, hydrogen bonding, cation···π interaction, C−H···π and π···π interactions, is a constantly growing field of research.1 Multiple hydrogen-bond interactions are widely used in the design of self-assembled structures capable of molecular encapsulation.2 The intramolecular hydrogen bonds are responsible for the concave nature of resorcinarenes and hence enhance their ability to act as receptors for several guest molecules. Alongside the intramolecular interactions, intermolecular hydrogen bonds are responsible for the construction of several complicated selfassembled structures involving resorcinarenes and a variety of ionic and neutral guests leading to 1:1 inclusion complexes,3 dimeric,4 hexameric,5 and tubular6 assemblies. Anions are very important in many biological processes. For example, many enzyme substrates and cofactors are anionic in nature.7 Anion binding and recognition are demanding considering the larger size of the anions when compared to the isoelectronic cations, higher sensitivity to pH, and wider range of geometry modulation and solvation ability.8 There is a multitude of reports on noncovalent anion binding and their applications as sensors and templates.7−9 Furthermore, there are several studies on the utilization of hydrogen bonding to anions in the synthesis and shuttling motions of interlocked systems.10 The combination of electrostatic and hydrogen bond interactions capabilities in a receptor will enhance very effectively its recognition ability toward anions.11 Mannich condensation of resorcinarenes with primary amines resulting in the corresponding tetrabenzoxazines is well-known.12 Cleaving the tetrabenzoxazines by mineral acids under refluxing conditions leads to the formation of N© 2012 American Chemical Society

alkylammonium resorcinarene halides [organic salt molecules]. A strong circular intramolecular hydrogen bonded anion seam (···NR2H2+···X−···NR2H2+···X−···)2 is created between the ammonium moieties and the small spherical halide anions manifesting very strong anion binding and leading to extended cavitand-like structures.13,14 Chloride and bromide anions are strongly bound by virtue of their size, electronic nature, and hydrogen bond acceptor affinity. The chloride anion is optimal in size and hydrogen bonding acceptor capability, clearly surpassing the binding of the bromide anion. Actually, when the N-alkylammonium resorcinarene tetrabromide is treated with 4 mol of tetramethylammoniun chloride, a complete conversion to the corresponding N-alkylammonium resorcinarene tetrachloride is observed, and yet both of them exhibit the same cavitand-like conformation of the resorcinarene.13,14 Here we describe the synthesis, mass spectrometric, and single crystal Xray diffraction study of several N-alkylammonium resorcinarene tetracations with large nonspherical nitrate (trigonal planar), picrate (aromatic planar), and triflate (ellipsoidal) anions bound to the resorcinarene core by electrostatic and hydrogen bond interactions. Contrary to the halide anions, these nonspherical anions possess several hydrogen bond acceptor sites and manifest a complex array of intra- and intermolecular hydrogen bonds resulting in twisted cavitand-like structures possessing cavities suited for binding neutral molecules through C−H··· π and hydrogen bonding interactions. Received: June 21, 2012 Revised: August 2, 2012 Published: August 20, 2012 4919

dx.doi.org/10.1021/cg3008409 | Cryst. Growth Des. 2012, 12, 4919−4926

Crystal Growth & Design

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X-ray Crystallography. Four crystal structures were obtained with two of them representing the same compound with different encapsulated guests. These structures are the first examples of N-alkylammonium resorcinarene salts utilizing larger and nonspherical anions. Depending on the nature and length of the upper rim chain (substituent R in Scheme 1) and size of the solvent molecule(s) used for crystallization, two different types of complexes are observed, either self-included dimers or host−guest complexes. The picrate 3a·4H·4Pic crystallizes with two crystallographically independent molecules (designated as A and B), eight picrate anions, three n-butanol and chloroform molecules, and one water molecule in the asymmetric unit (Figure 1). In this structure, various intermolecular interactions form two self-included dimers: one A:A dimer (Figure 1a,b) and one B:B dimer (Figure 1c). The dimers are primarily held together via C−H···O hydrogen bonds between the molecules (Supporting Information, Table S1). Furthermore, picrates serve as a bridge between the adjacent molecules and also participate in the dimer formation via N−H···O, O−H···O, and C−H···O hydrogen bonds. Finally, four C−H···π interactions between the propyl chain and the resorcinarene phenyl rings also facilitate the A dimer formation, while in the B dimer, there are only three similar C− H···π interactions. The cations are self-included so deeply that the nitrogen atoms of both dimers (viz. in A:A and in B:B) are placed almost in the same plane. Thus, the self-included propyl groups are not directed to the bottom of the cavity of the dimer counterpart as in the case of the other salts with spherical anions.14 Instead they are folded and form a hook-like conformation (Figure 1c). As a result the hydrogen bonding to the anions and the deep self-inclusion of the propyl chains influence the conformation of the upper rim of the resorcinarene core. The upper rim is widely open with very long N···N distances and is quite unsymmetrical (Supporting Information, Figure S8). The difference in the distances between the opposite

RESULTS AND DISCUSSION Synthesis. Cleavage of the parent tetrabenzoxazines14 by refluxing in the presence of picric acid in n-butanol gave the picrate ammonium resorcinarene salts 3·4H·4Pic with yields of up to 75% (Scheme 1). An alternative approach to synthesize Scheme 1. Synthesis of the N-Alkylammonium Resorcinarene Picrate, Nitrate, and Triflate Salts

the nonspherical resorcinarene salts is through anion exchange from the chloride salt13,14 with either silver nitrate (AgNO3) or silver triflate (AgOTf) giving the corresponding nitrates, 4·4H·4NO3, and triflates, 5·4H·4OTf (Scheme 1). The 1H NMR in DMSO-d6 reveals that the picrate, triflate, and nitrate salts are nearly as symmetrical as the corresponding halide salts13,14 in solution (see Supporting Information).

Figure 1. The X-ray structure of 3a·4H·4Pic. Capped-stick (a) and CPK (b) representation of the A molecule. (c) Capped-stick representation of the self-included dimer of the B molecule. Atoms of one self-included propyl group are presented in CPK style and the picrate anions are omitted for clarity. (d) CPK plot of the self-included dimer. The anions are presented in capped-stick style. 4920



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Table 1. Geometrical Parameters Defining Conformation of the Resorcinarene Core core conformation Cg···Cga distance (Å)

3a·4H·4Pic

4b·4H·4NO3·MeOH

4b·4H·4NO3·MeCN

5b·4H·3OTf·Cl

C1−C6/C15−C20

6.44 6.46 7.18 7.17

6.17

6.98 6.86 6.75 6.89

6.81

C8−C13/C22−C27 N···N distance (Å) N30···N34 N32···N36 a

7.41

11.82 11.87 13.90 13.89

6.18 11.60

9.61 8.96 8.57 9.56

6.91

10.28 9.93

Cg is centroid of the phenyl ring.

nitrogen atoms is ca. 2 Å (Table 1). This large difference in the N···N distances, viz. the asymmetry of the upper rim, when compared to the corresponding highly symmetrical acetonitrile complex of the chloride salt13a (N···N distances from 8.34 to 8.55 Å), is quite surprising and makes the picrate highly asymmetrical. It is worth noting that the chloride analogue14 of 3a also crystallizes with two independent salt molecules in the asymmetric unit, but it forms a host−guest complex with dichloromethane molecules in a 1:2 ratio. The upper rim of the corresponding 3a bromide salt,14 which also forms self-included dimer, is almost symmetrical with the difference between opposite N···N distances of 0.16 Å, while the distance between phenyl ring centroids differs only by 0.05 Å. Each ammonium nitrogen atom within the dimer is linked to the picrate anions by two N−H···O hydrogen bonds (Figure 1a; Supporting Information, Table S1). Furthermore, all nitrogen atoms in both dimers are additionally linked to either four butanol molecules or to two butanol and two water molecules. The picrates are displaced outside the dimer and their exact positions are fixed by an additional O−H···O and N−H···O hydrogen bonds. The picrate anions do not show any orientation around the resorcinarene skeleton, and some of the picrates are almost parallel to the plane defined by the resorcinarene nitrogen atoms while some are almost perpendicular to it. Additionally, the picrates directly link the self-included dimers via O−H···O, N−H···O, and C−H···O hydrogen bonds. Two C−H···π interactions between the cations and the resorcinarene phenyl rings, one C−H···π interaction between the butanol molecule and the picrate and four π···π interactions between phenyl rings of the picrates also participate in the supramolecular aggregation of 3a·4H·4Pic. Butanol and chloroform molecules as well as crystal lattice water are either hydrogen bonded to the dimer or fill the voids, resulting in a highly compact network of self-assembled cationic dimers, anions, and solvent molecules (Figure 2). In the structure of the cyclohexyl analogue 4b with nitrate anions, 4b·4H·4NO3, the self-included dimer formation is not possible due to the sterically bulky cyclohexyl groups. Crystallizing 4b·4H·4NO3 from two different solvents led to two clathrate complexes. The 4b·4H·4NO3·MeOH crystallizes with two methanol and two water molecules in the asymmetric unit. This complex was obtained via crystallization from wet methanol. When a mixture of dichloromethane, acetonitrile, and butanol was used for crystallization, the nitrate crystallized as an acetonitrile solvate with two independent salt molecules (designated as A and B), eight nitrates and five acetonitrile molecules in the asymmetric unit (4b·4H·4NO3·MeCN). The resorcinarene core in 4b·4H·4NO3·MeCN shows slight

Figure 2. CPK plot of 3a·4H·4Pic, showing the parallel arrangement of the dimers and highly compact network of self-assembled dimers, anions, and solvent molecules. A and B independent cations are presented in green and blue, respectively.

distortion, whereas in 4b·4H·4NO3·MeOH, it is extremely distorted, with the difference of ca. 1.2 Å (Table 1) between phenyl ring centroids and a difference of ca. 5.4 Å between the opposite nitrogen atoms. Such a large deviation from symmetry has not been observed in any of the studied N-alkylammonium resorcinarene halide salts.13a,14 The upper rim o f the resor cinarene core in 4b·4H·4NO3·MeOH reflects the extreme distortion (Figure 3), being much larger than in 4b·4H·4NO3·MeCN (Supporting Information, Figure S9). The location of the nitrogen atoms are quite different in 4b·4H·4NO 3 ·MeCN compared to 4b·4H·4NO3·MeOH. This can only be explained by the fact that the nitrates are positioned in a different manner. Indeed, the three nitrates in 4b·4H·4NO3·MeOH are strongly hydrogen-bonded to the resorcinarene nitrogens by N−H···O hydrogen bonds (Figure 3, Supporting Information, Table S2). One nitrate is positioned slightly outside the resorcinarene core but so close that it is still hydrogen-bonded to the salt molecule by N−H···O hydrogen bond and to the water molecule. In the acetonitrile complex 4b·4H·4NO3·MeCN, one nitrate is positioned completely outside the resorcinarene core (Supporting Information, Figure S9) and is hydrogen-bonded to the salt molecule A only by one O−H···O hydrogen bond and to the salt molecule B by one O−H···O and one C−H···O hydrogen bond (Supporting Information, Table S3). In 4b·4H·4NO3·MeOH a water molecule is positioned in the plane of the nitrogen atoms between two nitrates and the alkyl chain of the nitrogen atom and is possibly responsible for such a large deviation from the symmetry of regular resorcinarene core (Figure 3a). The methanol molecule sits almost in the middle of the cavity, and its position is locked by N−H···O and O−H···O hydrogen bonds as well as by C−H···π interaction (Supporting Information, Table S2). The second methanol and 4921



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Figure 3. (a) Capped-stick representation of 4b·4H·4NO3·MeOH (side view). The included MeOH and H2O molecule are presented in CPK style. (b) CPK plot (from the top) of 4b·4H·4NO3·MeOH showing extremely distorted conformation of the resorcinarene core and the position of the nitrates. Included solvent molecules are omitted for clarity.

Figure 4. A partial view of the packing of 4b·4H·4NO3·MeOH, showing two-dimensional sheets formed by O−H···O, N−H···O, and C−H···O hydrogen bonds between salt molecules, nitrates, and solvent molecules. Included solvent molecules are presented in CPK style.

Figure 5. The X-ray structure of 4b·4H·4NO3·MeCN. (a) Capped-stick representation (side view) and (b) CPK plot (top view). (c) A partial packing view showing rows of salt molecules with included acetonitrile molecules (in CPK style) and the intricate array of hydrogen bonds between the salt molecules. Hydrogen atoms in salt molecules are omitted for clarity.

In the structure of 4b·4H·4NO3·MeCN, one acetonitrile molecule is placed between the plane of the resorcinarene hydroxyl groups and nitrogen atoms and is linked to one nitrogen atom and one nitrate by N−H···N(MeCN) and C(MeCN)−H···O(NO3−) hydrogen bonds, respectively (Figure 5; Supporting Information, Table S3). Acetonitrile molecules are positioned so far away from the electron rich phenyl rings that C−H···π interactions are not formed. The

water molecules links the adjacent salt molecules through weak O···H−C hydrogen bonds (O2···H38A, 2.66 Å), hence forming two-dimensional sheets (Figure 4), which are further extended to a three-dimensional network by C−H···O hydrogen bonds between the cyclohexyl ring atom and one adjacent nitrate (H52B···O109, 2.60 Å). In addition, there is one C−H···π interaction between the cations. 4922



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Figure 6. The X-ray structure of 5b·4H·3OTf·Cl. (a) Capped-stick representation showing the position of the chloroform molecules inside the cavity. (b) CPK plot showing the orientation of the cyclohexyl rings and the position of the anions. One of the triflate positions is actually occupied with 85% of OTf and 15% of the Cl, but for the sake of clarity of discussion, it is treated here as a full occupancy triflate.

second acetonitrile molecule in each cavity is placed in the plane of cyclohexyl rings of both cations, and they connect the cations in head-to-tail chains, while a fifth is beside the salt molecule B. These chains are linked either directly or via nitrates and acetonitrile molecules (Figure 5c), thus forming a three-dimensional network. No suitable crystal was obtained for the tetratriflate salt molecule 5·4H·4OTf. An incomplete anion exchange from the tetrachloride using silver triflate resulted in a 3:1 triflate/ chloride salt, 5b·4H·3OTf·Cl, and single crystal of this compound was obtained. As a consequence of the larger sterical demand of the cyclohexyl groups and the triflate anions, 5b·4H·3OTf·Cl also crystallizes as a host−guest complex with two chloroform molecules sitting inside the cavity (Figure 6). It is interesting to note that the sterically demanding cyclohexyl rings and inclusion of the chloroform molecule in the cavity had no influence on the conformation of the resorcinarene skeleton when compared to the previously published similar host−guest complexes14 as N···N and Cg···Cg distances are almost equal (Table 1; Supporting Information, Figure S10). The sulfonate moieties of the three triflate anions are intramolecularly hydrogen bonded in between the ammonium moieties. The trifluoromethyl moieties of the two triflates reside in between the three cyclohexyl groups, while the third trifluoromethyl group is pushed away from the upper rim by the second included CHCl3 molecule (Figure 6b; Supporting Information, Table S4). The hydrogen atoms of three ammonium groups are oriented in a circular manner, linking them with the triflates and the chloride via N−H···O and N− H···Cl hydrogen bonds, to a modulated circular (NR2H2+···OTf−···NR2H2+···Cl−···NR2H2+···OTf − ···NR2H2+···OTf −···) seam. The hydrogen atom of one ammonium group is hydrogen bonded to the triflate which is outside of the cation−anion seam. This triflate bridges two cations and forms a hydrogenbonded chain which is extended in the opposite direction via O−H···O, N−H···O, and C−H···O hydrogen bonds between two cations. Hydrogen bonding chains are parallel to the c axis. On the other side, the chloride anion equally bridges two cations in the opposite direction via O−H···Cl, N−H···Cl, and C−H···Cl hydrogen bonds (Figure 7). The cyclohexyl rings have a slightly different orientation toward the resorcinarene core and are displayed in a propellerlike fashion (Figure 6b). Chloroform molecules fill up the cavity with a host/guest ratio of 1:2. They sit on top of each other inside the cavity and are rotated and localized to a staggered orientation in order to minimize the steric repulsion

Figure 7. Partial packing view of 5b·4H·3OTf·Cl, showing hydrogenbonded chains of the tetracations, chlorides, and triflates. Chloroform molecules are presented in CPK style. Hydrogen atoms are omitted for clarity.

between them. The lower CHCl3 molecule is situated at the bottom of the cavity in a position that enables C−H···π interaction (Supporting Information, Table S4) with the resorcinarene skeleton. The second chloroform molecule is placed above the cation−anion seam, along with the cyclohexyl rings (Figure 6a), and is linked to the triflate and the cation which is above it by C−H···O(OTf) and C−H···Cl(CHCl3) hydrogen bonds. Mass Spectrometry. The N-alkyl ammonium resorcinarene salts can be easily ionized in the gas phase by ESI mass spectrometry.14,15 The spectra were dominated with signals corresponding to singly and doubly charged species. For the picrate and nitrate salts, signals corresponding to the compound incorporating a maximum of two anions were observed (see Supporting Information). The high vacuum of the mass spectrometer, low concentrations, and weak interactions between the components explain the difficulty in observing signals corresponding to structures containing all four anions. However, with the triflate salts, all four of the anions were observed as either sodium or potassium adducts, or in some cases as both sodium and potassium adducts with the metals providing the extra charge (Figure 8). An increase in the sample cone voltage results in an intense gas phase fragmentation with signals appearing at repetitive distances corresponding to the loss of an amine moiety. Intramolecular 4923



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one nitrate is positioned outside the resorcinarene core and has to be compensated by a large conformational adaptation, while in 4b·4H·4NO3·MeOH, inclusion of the water molecule resulted in severely distorted conformation of the resorcinarene core. The intra- and intermolecular interactions established within and between the cations and guest molecules, as well as between the guest molecules and the anions, are the most significant factors in determining the final structures of these compounds. In 3a·4H·4Pic, the only X-ray crystallographic example of a self-included dimer with nonspherical anions, the highly distorted conformation is a consequence of few different types of intermolecular interactions which participate in the dimer formation and is clearly different when compared to the structures with spherical chloride and bromide anions. The three nonspherical anions used had different positions and impact the final structure of resorcinarenes. One picrate in 3a·4H·4Pic directly participates in A and B dimer formation, while the other picrates are slightly outside the dimers. In 4b·4H·4NO3·MeCN, one nitrate is positioned outside the resorcinarene core, while the presence of one chloride in 5b·4H·3OTf·Cl possibly caused unexpected symmetrical conformation of the resorcinarene core. It is not surprising that because of strong hydrogen bonds involved among cations, anions, and solvent molecules, the supramolecular structures of all of these four complexes consist of three-dimensional networks. These findings highlight the importance of the concerted effects of electrostatic and hydrogen bonding interactions in anion binding and recognition processes.

Figure 8. ESI mass spectrum of 5a·4H·4OTf showing both singly and doubly charged species with a systematic fragmentation pattern resulting from the loss of amine moieties. Inset shows the calculated and experimental isotope pattern of selected signals.

hydrogen bonding between one of the OH groups on a resorcinarene ring and the amine nitrogen supports a 1,4elimination of an amine moiety proceeding through a sixmember transition state structure.14

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CONCLUSIONS The synthesis of several N-alkylammonium resorcinarene salts with polydentate trigonal planar, aromatic planar, and ellipsoidal anions lead to symmetrical and unsymmetrical cavitand-like structures, which in the solid state exhibit a complex network of strong intra- and intermolecular hydrogen bonds involving the ammonium nitrogens, the hydroxyl groups of the resorcinarene, the anions, and solvent molecules. The prepared picrate, nitrate, and triflate salts are relatively symmetrical in solution as seen from their relatively simple 1 H NMR spectra. These compounds can be easily ionized in the gas phase and show typical fragmentation patterns as a result of loss of amine moieties. The reported N-alkylammonium resorcinarene salts are the first examples of self-included dimers or host−guest complexes utilizing nonspherical and relatively large anions. Single crystal X-ray crystallographic study reveals that the conformation of the resorcinarene core will vary greatly due to the nature and structure of the anion and the included solvent molecules. Marked conformational differences were observed when compared to corresponding salts with smaller and spherical chloride or bromide anions. Variations from almost symmetrical (5b·4H·3OTf·Cl) to extremely distorted (4b·4H·4NO3·MeOH) were detected. The results show that the anion as well as the included solvent molecules have a crucial role in the control of the conformation of the resorcinarene skeleton. The dominating role of hydrogen bonding supports the conformational change of the Nalkylammonium resorcinarene salts in general and is mainly responsible for maintaining most of the positions of the large anions between adjacent ammonium cations in the salt molecule. Any strong disturbance in the hydrogen bonding, yet being based on sterical demand or other factors, has a drastic impact on the conformation of resorcinarene core. In the case of the two nitrate structures, distortion of the upper rim of the resorcinarene in 4b·4H·4NO3·MeCN can be a consequence of the fact that charge distribution is not equal as

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EXPERIMENTAL SECTION

Preparative Methods. Compounds 1 and 2 were synthesized according to reported procedures.13,14 The syntheses of compounds 3−5 are described in the Supporting Information. All materials were commercial and used as such unless otherwise mentioned. Melting points were determined with a Mettler Toledo FP62 capillary melting point apparatus and are uncorrected. 1H and 13C NMR spectra were recorded on Bruker Avance DRX 500 (500 MHz for 1H and 126 MHz for 13C) spectrometer. The mass spectrometric studies were performed with a micromass LCT ESI-TOF instrument. X-ray Crystallography. Single crystals were grown by either slow evaporation from solvent mixtures or by diffusion methods in the following solvent mixtures: 3a·4H·4Pic from butanol/chloroform; 4b·4H·4NO3·MeOH from wet methanol; 4b·4H·4NO3·MeCN from acetonitrile/dichloromethane/butanol; 5b·4H·3OTf·Cl from chloroform. In spite of many attempts the crystal quality for 3a·4H·4Pic and 5b·4H·3OTf·Cl remained poor. Data were collected on a BrukerNonius Kappa Apex II diffractometer using graphite-monochromated Cu Kα radiation (λ = 1.54184 Å) for 3a·4H·4Pic, 4b·4H·4NO3·MeCN and 5b·4H·3OTf·Cl and Mo Kα radiation (λ = 0.71073 Å) for 4b·4H·4NO3·MeOH at 123.0(1) K. COLLECT16 software was used for the data collection and DENZO-SMN17 was used for the data processing. The intensities were corrected for absorption using the multiscan absorption correction method.18 The crystal structures of 3a·4H·4Pic and 5b·4H·3OTf·Cl were solved by SUPERFLIP19 program, while SIR97 20 was used for structure solution of 4b·4H·4NO3·MeOH and 4b·4H·4NO3·MeCN. All non-hydrogen atoms were refined anisotropically by full-matrix least-squares calculations based on F2.21 All hydrogen atoms in cations, picrates, butanol, chloroform, methanol, and acetonitrile molecules were included in calculated positions as riding atoms, with SHELXL9721 defaults. Structures of 3a·4H·4Pic, 4b·4H·4NO3 ·MeCN, and 5b·4H·3OTf·Cl contain solvent-accessible voids with a small amount of solvent molecule(s) used for crystallization. As they could not be modeled satisfactorily, data were treated with the SQUEEZE routine in PLATON.22 High final R values for 3a·4H·4Pic and 5b·4H·3OTf·Cl are due to the weak diffraction power of the crystals and the many 4924



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Table 2. X-ray Crystallographic Data for Self-Inclusion and Host−Guest Complexes Described in This Paper 4b·4H·4NO3·MeCN

5b·4H·3OTf·Cl

C167H211Cl9N32O76 4201.73 triclinic P1̅

C66H108N8O24 1397.6 monoclinic P21/c

C138H207N21O40 2800.25 triclinic P1̅

C68.85H98Cl7.15F8.55N4O16.55S2.85 1753.8 monoclinic C2/c

15.635(2) 19.086(2) 34.414(4) 102.069(6) 95.145(6) 96.104(6) 9919(2) 2 1.407 2.015 2.46−63.53 122171 31484/0.1879 13815 31484/244/2595 1.027 0.1438/0.2250 0.3655/0.4294 1.898/−1.065

19.0473(3) 14.0303(2) 26.9299(5) 90 96.5600(10) 90 7149.6(2) 4 1.298 0.099 1.52−25 46492 12586/0.0653 8133 12586/1179/904 0.932 0.0805/0.1308 0.1622/0.2031 1.009/−0.729

18.8851(6) 21.7869(6) 21.9992(7) 100.1500(10) 107.610(2) 111.825(2) 7570.7(4) 2 1.228 0.749 2.31−63.31 64681 23725/0.0992 15077 23725/79/1867 0.997 0.0933/0.1296 0.2676/0.3007 1.590/−0.703

33.4470(9) 24.8056(9) 25.2165(8) 90 128.9170(10) 90 16278.1(9) 8 1.431 3.687 2.51−63.43 58807 13188/0.1142 8437 13188/61/1001 1.043 0.1367/0.1747 0.4190/0.4653 2.078/−2.034

3a·4H·4Pic formula formula weight crystal system space group unit cell dimensions a (Å) b (Å) c (Å) α (°) β (°) γ (°) V (Å3) Z Dcalc/g cm−3 absorption coeff μ/mm−1 θ range (°) collected reflections no. independent refln no./RInt reflections no. I ≥ 2σ(I) data/restraints/parameters goodness-of-fit on F2, S R [I ≥ 2σ(I)]/R [all data] wR [I ≥ 2σ(I)]/wR [all data] max/min el. dens/e Å−3

4b·4H·4NO3·MeOH

restraints used in the final refinements. Details of crystal data, data collection, and refinement parameters are given in Table 2 and additional experimental details of structure solution and refinement in Supporting Information. PLATON22 and Mercury23 programs were used for structure analysis and drawings preparation, respectively. CCDC 829592−829595 contain the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac. uk/data_request/cif.

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ASSOCIATED CONTENT

S Supporting Information *

Synthetic procedures, analytical data of compounds 3−5, the CPK plots, hydrogen bonding geometries for the X-ray structures and the additional experimental details for X-ray crystallography described in this paper. This material is available free of charge via the Internet at http://pubs.acs.org.

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AUTHOR INFORMATION

Corresponding Author

*Fax: +358 14 260 2501; tel: +358 50 562 3721; e-mail: kari.t. rissanen@jyu.fi. Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS The authors gratefully acknowledge the financial support from the Academy of Finland (K.R., Project Nos. 130629, 122350, 140718), the University of Jyväskylä and the Ministry of Science, Education and Sports of the Republic of Croatia (M.C., Project No. 119-1193079-3069).

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Binding Modes of Nonspherical Anions to N-Alkylammonium

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