Single-Crystal Structures and Typical Hydrogen-Bonding Motifs of

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Crystal Growth & Design

Single-crystal structures and typical hydrogenbonding motifs of supramolecular cocrystals containing 1,4-di(1H-imidazol-1-yl)benzene

Fanxing Meng, Yuhua Li, Xin Liu, Bao Li and Liyan Wang* State Key Laboratory of Supramolecular Structure and Materials, Jilin University, Changchun 130012, China

Abstract: Eight new supramolecular crystals of 1,4-di(1H-imidazol-1-yl)benzene (DIB) have been prepared using water, 4,4’-biphenol, terephthalic acid, isophthalic acid, succinic acid and 1,2,4,5-tetrafluoro-3,6-diiodobenzene. These materials were subsequently characterized by single crystal X-ray analysis. The results revealed that one-dimensional infinite chains were formed in these crystals through hydrogen bonding or halogen bonding interactions. The hydrogen atoms of the imidazole ring in DIB were found to be involved in three kinds of hydrogen-bonding ring motifs. These motifs could play an important role in the stabilization of the crystals and could therefore be beneficial to DIB in terms of its role as a good building block for supramolecular crystals.

ACS Paragon Plus Environment

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Introduction Crystal engineering involves the development of a thorough understanding of the interactions that occur between the molecules involved in crystal packing processes, and the subsequent application of this understanding to the preparation of crystals with specific physical and chemical properties.1-4 Since the concept of crystal engineering was first proposed 60 years ago,5 significant progress has been made towards the design and application of uniquely engineered crystals.6-7 Furthermore, in the field of design and synthesis, new synthons and crystals8 continue to be discovered on a regular basis and there have been numerous reports pertaining to the development of new synthons for the synthesis of specific crystals for specific purposes. For example, Desiraju et al.9 reported the design and preparation of a series of cocrystals of 4hydroxybenzamide and dicarboxylic acid using the corresponding amide-carboxylic acid as a synthon. With regard to its application, crystal engineering has been applied in pharmaceutical industry to improve the chemical and physical properties of drugs.10 For instance, Bernstein et al.11 reported the preparation of a cocrystal of 2-chloro-4-nitrobenzoic acid and nicotinamide. Furthermore, Nangia et al.12 used the synthon of carboxamide and pyridine N-oxide to synthesize a pharmaceutical cocrystal of barbital. Crystal engineering has also been used in several other areas, including for the rational construction of metal-organic-frameworks,13 which were subsequently used in gas storage,14-15 selective gas adsorption16-17 and catalysis.18 Hydrogen bond is an important driving force for supramolecular assemblies.19-20 Etter et al.1 developed empirical hydrogen-bond rules useful for determining preferred modes of hydrogen bonding. Pyridine and its derivatives are often used as hydrogen/halogen bond acceptors.21-22 For example, Biradha et al.23 prepared a series of 1,3,5-benzene-tri(3-pyridinyl)-carboxamide cocrystals with carboxylic acids through N-H···O hydrogen bonding interactions. In a separate


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study, Metrangolo et al.24 reported the preparation of cocrystals of pyridine derivatives via the formation of N···I halogen bonding interactions. Furthermore, Schultheiss et al.25 used pyridine and its amide derivatives to synthesize cocrystals with an N–H···O=C bond to the synthon, as well as N–H···N hydrogen bonding, O–H···N hydrogen bonding and N···I halogen bonding interactions. Imidazole and its derivatives can also be used as hydrogen/halogen bond acceptors in a similar manner to pyridine,26 as demonstrated by Ma et al.27 who reported the preparation of a cocrystal of 1,4-bis(imidazol-1-yl-methyl)benzene and C-methylcalix[4]resorcinarene via the formation of an O-H···N hydrogen bonding interaction to form a double-buckled chainlike polymer. Siebert et al.28 synthesized the cocrystals of several imidazole derivatives and dichloromethane, which all contained a N···Cl halogen bond. In addition, imidazole and its derivatives have been used as ligands in preparing metal-organic frameworks.29-31 In a separate study, Su et al.32 prepared a supramolecular cocrystal with 1,4-di(1H-imidazol-1-yl)benzene (DIB) and terephthalic acid. Based on these results, it was envisaged that DIB could be used as a predictable building block for the preparation of supramolecular cocrystals. In this study, we have prepared DIB crystals, as well as a series of cocrystals using DIB as hydrogen/halogen bond acceptor. The structures of DIB and several hydrogen-bonding/halogen-bonding donors are shown in Scheme 1. 4,4’-Biphenol (BP), terephthalic acid (TPA), isophthalic acid (IPA) and succinic acid (BDA) were selected as suitable candidates to investigate DIB’s ability to form hydrogen-bonding cocrystals with different donors.


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Scheme 1. Structures of 1,4-di(1H-imidazol-1-yl)benzene (DIB), 4,4'-biphenol (BP), butanedioic acid (BDA), terephthalic acid (TPA), isophthalic acid (IPA), and 1,4-diiodotetrafluorobenzene (DITFB).

Experimental DIB was synthesized according to the procedure previously published by Zhang.33 BP, TPA, IPA, BDA and 1,4-diiodotetrafluorobenzene (DITFB) were purchased from J&K (Beijing, China) and used without further purification. Single crystal X-ray data for all of crystals prepared in the current study were collected on an R-AXIS RAPID diffractometer (Rigaku, Japan). Preparation of a DIB crystal. DIB (10.5 mg, 0.05 mmol) was dissolved in chloroform (5 mL), and the resulting solution was allowed to evaporate at room temperature for several days to give crystal-1. Preparation of a crystal of DIB monohydrate. DIB (10.5 mg, 0.05 mmol) was dissolved in a 4:1 (v/v) mixture of methanol and water (5 mL), and the resulting solution was allowed to evaporate at room temperature for several days to give crystal-2. Preparation of a cocrystal of DIB and BP. DIB (10.5 mg, 0.05 mmol) and BP (9.3 mg, 0.05 mmol) were dissolved in acetone (5 mL), and the resulting solution was used to prepare the desired cocrystal by diffusion with pentane as the anti-solvent. Crystal-3 was obtained after several days.


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Preparation of a cocrystal of DIB and BDA. DIB (10.5 mg, 0.05 mmol) and BDA (5.9 mg, 0.05 mmol) were dissolved in methanol (5 mL), and the resulting solution was used to prepare the desired cocrystal by diffusion with pentane as the anti-solvent. Crystal-4 was obtained after several days. Preparation of a cocrystal of DIB and TPA. DIB (10.5 mg, 0.05 mmol) and TPA (8.3 mg, 0.05 mmol) were dissolved in acetone (5 mL), and the resulting mixture was used to prepare the desired cocrystal by diffusion with pentane as the anti-solvent. Crystal-5a was obtained after several days; DIB (10.5 mg, 0.05 mmol) and TPA (8.3 mg, 0.05 mmol) were dissolved in anhydrous methanol (5 mL), and the resulting solution was allowed to evaporate at room temperature for several days to give crystal-5b. Preparation of a cocrystal of DIB and IPA. DIB (10.5 mg, 0.05 mmol) and IPA (8.3 mg, 0.05 mmol) were dissolved in a 4:1 (v/v) mixture of acetone and water (5 mL), and the resulting solution was used to prepare the desired cocrystal by diffusion with pentane as the anti-solvent. Crystal-6 was obtained after several days. Preparation of a cocrystal of DIB and DITFB. DIB (10.5 mg, 0.05 mmol) and 1,2,4,5tetrafluoro-3,6-diiodobenzene (20.09 mg, 0.05 mmol) were dissolved in methanol (5 mL), and the resulting mixture was allowed to evaporate at room temperature for several days to give crystal-7.

Results and Discussion Eight different crystals were prepared in the current study and all of the associated crystallographic data are shown in Table 1.


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Table 1. Crystallographic data for crystal-1 to crystal-7.

Crystal

1

2

3

4

5a

5b

6

7

Sum

C12H10N4

C12H12N4O

C24H20N4O2

C16H16N4O4

C20H16N4O4

C20H16N4O4

C68H54N12O

C18H10F4I2N

16

4

formula Mr

210.24

228.26

396.44

328.33

376.37

376.37

1295.23

612.10

group

P2(1)/c

P2(1)/c

_ P1

_ P1

_ P1

P2(1)/n

_ P1

P2(1)/c

a (Å)

5.6072(11)

8.9092(18)

9.892(2)

4.9923(10)

7.1054(14)

5.2158(10)

7.563(3)

8.593(4)

b (Å)

7.3613(15)

18.421(4)

10.043(2)

7.9082(16)

9.834(2)

10.587(2)

11.686(4)

6.040(3)

c (Å)

12.010(2)

14.390(3)

10.989(2)

10.307(2)

12.691(3)

15.435(3)

17.136(9)

18.40(10)

α (°)

90

90

84.19(3)

109.52(3)

85.70(3)

90

104.99(18)

90

β (°)

90.89(3)

101.66(3)

79.26(3)

93.49(3)

88.25(3)

90.22(3)

93.587(18)

90.59(2)

γ (°)

90

90

63.72(3)

101.22(3)

77.93(3)

90

98.338(15)

90

Volume

495.67(16)

2312.9(8)

961.5(3)

372.70(3)

864.6(3)

852.3(3)

1439.5(11)

954.9(9)

Z

2

8

2

1

2

2

1

2

Dx

1.409

1.311

1.369

1.463

1.446

1.467

1.494

2.129

Rint

0.0508

0.0328

0.0298

0.0245

0.0312

0.0791

0.0293

0.0281

R1 [I >

0.0511

0.0538

0.0434

0.0471

0.0563

0.0511

0.0447

0.0235

0.1098

0.1545

0.1052

0.1366

0.1639

0.1285

0.1252

0.0536

1.049

1.023

1.018

1.094

0.963

1.068

0.974

1.140

993685

993695

993694

993089

993693

993692

993698

993707

Space

(g cm-3)

a

2σ(I)]c b

wR2 [I > 2σ(I)]

GOOF of F2 CCDC

a: R1 = ||Fo|–|Fc||/|Fo|. b: wR2 =

[w(Fo2–Fc2)2/w(Fo2)2]1/2.

Crystal-1. As shown in Figure 1A, DIB was found to exist in a trans-conformation in crystal1, which formed one-dimensional (1D) infinite chains via a hydrogen-bonding R22 (6) motif based on C-H···N hydrogen bonding interactions. An ‘edge to face’ C-H···π interaction was also observed between the DIB molecules in two adjacent chains, which was consistent with the


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findings of Bond reported in 2002.34 Figure 1B shows the simple herringbone packing structure resulting from the ‘edge to face’ C-H···π interaction.

Figure 1. Structure of crystal-1. (A) One-dimensional infinite chains and interaction between adjacent chains. Hydrogen-bonding motif is highlighted in a red box. (B). Simple herringbone packing. Color code: C, grey; H, white; N, blue. Crystal-2. As shown in Figure 2, the ratio of DIB and water was found to be 1:1 in crystal-2. When viewed along the c-axis, the molecules formed a winged-bean-like group composed of chain-a, chain-a’, chain-b and chain-b’. When viewed along the b-axis, as shown in Figure 3A, the molecules formed 1D infinite chains through O-H···N hydrogen bonding interactions between the DIB and water molecules. Furthermore, a hydrogen-bonding band formed between the adjacent infinite chains as a consequence of the interaction of the hydrogen-bonding R44 (10) and hydrogen-bonding R21 (7) motifs. Infinite chains with another conformation are shown in Figure 3B, which were formed by DIB and water through the O-H···N hydrogen bonding interactions, although the distance between the adjacent chains was found to be so large that there were no direct interactions between them. The DIB was found to exist in the cisconformation in the chains shown in Figure 3A and 3B. The two winged-bean-like groups were


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arranged in a parallel manner (Figure 3C). In two adjacent groups, there were C-H···π interactions between chain-b and chain-a’, and π···π interactions between chain-a and chain-a’. As shown in Figure 3D, two adjacent layers were arranged into antiparallel and interdigitated structures.

Figure 2. The winged-bean-like group of crystal-2.

Figure 3. Structure of crystal-2. (A) One-dimensional infinite chains and the interactions between the adjacent chains. The hydrogen-bonding motifs are highlighted in a red box. (B) One-


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dimensional infinite chains with another conformation. The four water molecules in blue circles belong to the chains in Figure 3A. (C) The packing structure of winged-bean-like groups. (D) The interdigitated layers. Color code: C, grey; H, white; N, blue; O, red. Crystal-3. Figure 4A shows that the ratio of DIB and BP was 1:1, and that the two molecules formed 1D infinite chains through O-H···N hydrogen bond, where the DIB existed in the transconformation. All of the infinite chains in crystal-3 were found to be the same. In terms of the interactions between the chains, the DIB molecules formed C-H···O hydrogen bonds with BP-1 and C-H···π interactions with BP-2 (Figure 4B). Furthermore, the DIB molecules formed CH···π interactions with BP-2 and π···π stacking interactions with BP-1 (Figure 4C).

Figure 4. Structure of crystal-3. (A) One-dimensional infinite chains. (B), (C) Interactions between adjacent chains. Color code: C, grey; H, white; N, blue; O, red.


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Crystal-4. As shown in Figure 5A, the ratio of DIB and BDA is 1:1. The two molecules formed infinite chains through hydrogen-bonding R22 (7) motifs composed of C-H···O and OH···N hydrogen bonding interactions, where DIB existed in the trans-conformation. Two different types of hydrogen-bonding motif, namely R21 (7) and R22 (10), formed between adjacent chains (Figure 5B). Furthermore, crystal-4 exhibited a clear layered structure, as shown in Figure 5C.

Figure 5. Structure of crystal-4. (A) One-dimensional infinite chains. (B) Interactions between adjacent chains. The hydrogen-bonding motifs have been highlighted in red boxes. (C) The layered structure. Color code: C, grey; H, white; N, blue; O, red. Crystal-5a and Crystal-5b. Two cocrystals with different crystal structures were obtained from DIB and TPA using two different processes, i.e. the system of DIB and TPA exhibits polymorphism. The ratio of DIB and TPA was found to be 1:1 in both crystals, with the DIB molecules existing in a trans-conformation.


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In crystal-5b, the DIB and TPA molecules in adjacent chains formed hydrogen-bonding R21 (7) motifs (Figure 6). Crystal-5b is similar to the crystal reported in Su’s study,32 and will therefore not be described in any further detail.

Figure 6. Hydrogen-bonding motifs in crystal-5b. Color code: C, grey; H, white; N, blue; O, red. The 1D infinite chains in crystal-5a existed in two different conformations. As shown in Figure 7A, the DIB and TPA molecules formed chain-a through O-H···N hydrogen bonding interactions, whilst chain-b was formed from a hydrogen-bonding R21 (7) motif through C-H···O and O-H···N hydrogen bonding interactions. Figure 7B shows the relative position of four chains as viewed along the direction of the chains. As shown in Figure 7C, there was a C-H···π interaction between each TPA molecule in chain-a and the imidazole ring moiety of each DIB molecule in chain-b. The DIB molecules in chain-a formed π···π stacking interactions with the imidazole ring moieties of the DIB molecules in chain-b. As shown in Figure 7D, the TPA in chain-a formed a hydrogen-bonding R21 (7) motif with a C-H···O hydrogen bonding interaction to the DIB in chain-b’. The TPA in chain-b’ formed a C-H···O hydrogen bond to the DIB in chain-a. Furthermore, C-H···π interactions formed between the DIB molecules in chain-b’ and the TPA molecules in chain-a. As shown in Figure 7E, there were hydrogen-bonding R22 (10) motifs between the TPA molecules in chain-b and chain-b’. C-H···π interactions were also


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observed between the benzene ring moiety of the TPA molecules in chain-b’ and the imidazole moieties in chain-b.

Figure 7. Structure of crystal-5a. (A) Two one-dimensional infinite chains with different conformations. (B) Relative positions of the adjacent chains with different conformations. (C) Interactions between chain-a and chain-b. (D) Interactions between chain-a and chain-b’. (E) Interactions between chain-b and chain-b’. All of the hydrogen-bonding motifs have been highlighted in red boxes. Color code: C, grey; H, white; N, blue; O, red.


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Crystal-6. The initial ratio of IPA and DIB added to the experiment to prepare crystal-6 was 1:1. However, the final ratio of IPA and DIB in the cocrystal was found to be 4:3. Following on from this result, we investigated the impact of adding different ratios of the two molecules, including 1:2, 1:3, 2:3 and 3:4, but all of these combinations resulted in a ratio of 4:3 in the cocrystal. The results imply that the formation of the 4:3 cocrystal could be energetically favored. The 1D infinite chains with the same conformation constitute crystal-6 (Figure 8A). Four molecules of IPA and two molecules of DIB formed a large ring, which then formed a chain with DIB-1 through a series of O-H···N hydrogen bonding interactions. IPA-1’ formed strong hydrogen-bonds not only with two DIB molecules but also with an IPA-2’ molecule. These molecules connected together in such a way that the expected alternating arrangement of DIB and IPA with 1:1 ratio was disrupted. Hydrogen-bonding R22 (7) motifs formed between DIB-2 and IPA-2’, as well as DIB-2’ and IPA-1’. As shown in Figure 8B, hydrogen-bonding R21 (7) motifs formed between the DIB-2 and IPA-2 units in the same chain, as well as between the IPA1’ and DIB-2 units in adjacent chains. Furthermore, the hydrogen bonding interactions between the IPA-1 and DIB-2 units were ionic hydrogen bonds.35 One of the imidazole groups of DIB-2 was found to be protonated and formed an N-H···O hydrogen bonding interaction to IPA-1. When viewed along the c-axis, a layered structure could be clearly observed. As shown in Figure 8C, a hydrogen-bonding R44 (10) motif was formed between the DIB-1 and IPA-1 units in the top layer, and the IPA-1’ and DIB-1 units in the bottom layer. A similar hydrogen-bonding R44 (10) motif was also found in crystal-4. Crystal-7. As shown in Figure 9A, the ratio of DIB and DITFB in crystal-7 was found to be 1:1, with the DIB molecules forming infinite chains with the DITFB molecules through N···I


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halogen bonding interactions. The DIB molecules existed in the trans-conformation, with crystal-7 forming a layered structure. Figure 9B shows a simplified drawing of two layers of crystal-7. Notably, the chains in the same layer projected in the same direction, whereas the directions of the chains in adjacent layers differed by about 35°. As shown in Figure 9C, hydrogen-bonding R21 (7) motifs formed between the two adjacent layers.

Figure 8. Structure of crystal-6. (A) A special hydrogen-bonding chain. (B) Interactions between adjacent chains. (C) Interactions between adjacent layers. The hydrogen-bonding motifs have been highlighted in red boxes. Color code: C, grey; H, white; N, blue; O, red.


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Figure 9. Structure of crystal-7. (A) One-dimensional halogen-bonding chain. (B) Simplified drawing of the layered structure. The DIB molecules and DITFB molecules in the top layers have been represented by blue and purple blocks, respectively. The molecules in the bottom layers have been represented by grey blocks. The dashed lines represent halogen bonds between molecules. (C) Hydrogen-bonding motifs between adjacent layers. The hydrogen-bonding motif has been highlighted in red box. Color code: C, grey; H, white; N, blue; I, purple; F, green. Typical hydrogen-bonding motifs. Three different kinds of motif were observed in the eight crystals prepared in the current study, including the R22 (7), R44 (10) and R21 (7) motifs. As shown in Figure 10A, the hydrogen and nitrogen atoms of the imidazole ring have been numbered with red text to make it easier to understand the following discussion. The H2 and N2 atoms of the DIB molecule can form a hydrogen-bonding R22 (7) motif with a carboxylic acid, and this type of bonding motif was observed in crystal-4, crystal-5a and crystal-6. This kind of motif has been reported in several pyridine derivatives, such as the cocrystals prepared by Clyburne et al.36 and Rao et al37 (Figure 10B). In the crystals formed in the current study, the molecules formed 1D infinite chains via a hydrogen-bonding R22 (7) motif consisting of O-H···N and C-H···O hydrogen bonding interactions.


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The H1 atom of the DIB molecule can form a hydrogen-bonding R44 (10) motif involving four molecules, and this motif was observed in crystal-5a and crystal-6 (Figure 11A). This motif has also been observed in the cocrystals of pyridine derivatives.38-39 For example, Müllen et al.39 reported that the cocrystal of 4,4-dipyridyl and 2,5-dihexylterephthalic acid contained a hydrogen-bonding R44 (10) motif (Figure 11B).

Figure 10. Hydrogen-bonding R 22 (7) motifs were found (A) in this article and (B) in the literature.37 The H1 and H3 atoms of DIB could form a hydrogen-bonding R21 (7) motif with the hydrogen bond acceptors in adjacent chains (Figure 12A). With the exception of crystal-1 and crystal-3, which formed one-component crystals, all of the other crystals prepared in this study contained a hydrogen-bonding R21 (7) motif. It is noteworthy that this motif has only been seen in only two of the 450 cocrystals of imidazole derivatives found in the CCDC, including the cocrystal of 1,4bis[(imidazol-1-yl)methyl]benzene and trans-3-hexenedioic acid40 and the cocrystal of 1,4bis((1H-imidazol-1-yl)methyl)cyclohexane(cis-1-imidazole) and succinic acid (Figure 12B).41 The R21 (7) motif has also been frequently observed in the cocrystals of numerous pyridine


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derivatives. For instance, the cocrystals of 4,4’-pyridine and fumaric acid37 and 4,4’-pyridine and 1,2,4,5-tetrafluoro-3,6-diiodobenzene42 have been reported to contain this kind of motif (Figure 12C). We found that there was a relationship between the formation of the hydrogen-bonding R21 (7) motif and the dihedral angle between the benzene and imidazole rings in DIB. Figure 13 shows the distribution of the dihedral angles of the cocrystals prepared in the current study. The DIB molecules in crystal-3 and the DIB-1 units in crystal-6 had dihedral angles of 33.70°, 41.01° and 33.75°, and did not form the hydrogen-bonding R21 (7) motif. In contrast, all of the DIB molecules with dihedral angles of less than 30° formed the hydrogen-bonding R21 (7) motif. Based on these results, we believe that the hydrogen-bonding R21 (7) motif will probably exist in cocrystals where the dihedral angle of the DIB is relatively small, which would benefit the close packing of the molecules.

Figure 11. The hydrogen-bonding R 44 (10) motif was found (A) in this article and (B) in the literature.39


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Figure 12. The hydrogen-bonding R 21 (7) motifs were found (A) in this article, (B) in cocrystals containing imidazole derivatives from the literature41 and (C) in the cocrystals containing pyridine derivatives from the literature.37

Figure 13. Histogram of the dihedral angles between benzene ring and imidazole ring in DIB.


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Conclusions We have prepared eight supramolecular crystals based on DIB. In all eight of these crystals, the molecules formed 1D infinite chains through hydrogen bonding or halogen bonding interactions. The DIB existed in the trans-conformation in the majority of the crystals. The hydrogen atoms of the imidazole ring also formed C-H···X hydrogen bonding interactions to give the hydrogen-bonding R 21 (7), R22 (7) and R44 (10) motifs. These motifs could play an important role in stabilizing the crystals and are also beneficial for the DIB in terms of making it a good building block of supramolecular crystals. Author Information *Tel.: +86-431-85168479; E-mail: [email protected]. Acknowledgments This work was supported by the National Basic Research Program of China [grant number 2013CB834503]. We would like to thank Prof. Zhan Shi (Jilin University, China) for his help with the characterization of the single crystals. References (1) Etter, M. C. Acc. Chem. Res. 1990, 23, 120. (2) Desiraju, G. R. Crystal Engineering: The Design of Organic Solids; Elsevier: Amsterdam, 1989. (3) Desiraju, G. R. Acc. Chem. Res. 2002, 35, 565. (4) Desiraju, G. R. J. Am. Chem. Soc. 2013, 135, 9952. (5) Pepinsky Phys. Rev. 1955, 100, 971. (6) Meng, X.; Qi, G.; Zhang, C.; Wang, K.; Zou, B.; Ma, Y. Chem. Commun. 2015, 51, 9320. (7) Yan, T.; Wang, K.; Tan, X.; Liu, J.; Liu, B.; Zou, B. J. Phys. Chem. C 2014, 118, 22960. (8) Desiraju, G. R. Angew. Chem., Int. Ed. 1995, 34, 2311. (9) Tothadi, S.; Desiraju, G. R. Cryst. Growth. Des. 2012, 12, 6188.


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(10) Fleischman, S. G.; Kuduva, S. S.; McMahon, J. A.; Moulton, B.; Walsh, R. D. B.; Rodriguez-Hornedo, N.; Zaworotko, M. J. Cryst. Growth. Des. 2003, 3, 909. (11) Lemmerer, A.; Esterhuysen, C.; Bernstein, J. J. Pharm. Sci. 2010, 99, 4054. (12) Reddy, L. S.; Babu, N. J.; Nangia, A. Chem. Commun. 2006, 1369. (13) Cao, R.; Sun, D.; Liang, Y.; Hong, M.; Tatsumi, K.; Shi, Q. Inorg. Chem. 2002, 41, 2087. (14) Caskey, S. R.; Wong-Foy, A. G.; Matzger, A. J. J. Am. Chem. Soc. 2008, 130, 10870. (15) Tranchemontagne, D. J.; Park, K. S.; Furukawa, H.; Eckert, J.; Knobler, C. B.; Yaghi, O. M. J. Phys. Chem. C 2012, 116, 13143. (16) Pan, L.; Olson, D. H.; Ciemnolonski, L. R.; Heddy, R.; Li, J. Angew. Chem., Int. Ed. 2006, 45, 616. (17) Pachfule, P.; Banerjee, R. Cryst. Growth. Des. 2011, 11, 5176. (18) Shultz, A. M.; Farha, O. K.; Hupp, J. T.; Nguyen, S. T. J. Am. Chem. Soc. 2009, 131, 4204. (19) Wang, Z. Q.; Wang, L. Y.; Zhang, X.; Shen, J. C.; Denzinger, S.; Ringsdorf, H. Macromol. Chem. Phys. 1997, 198, 573. (20) Mu, Z.; Shu, L.; Fuchs, H.; Mayor, M.; Chi, L. J. Am. Chem. Soc. 2008, 130, 10840. (21) Aakeroy, C. B.; Beatty, A. M.; Helfrich, B. A. Angew. Chem., Int. Ed. 2001, 40, 3240. (22) Nagarathinam, M.; Peedikakkal, A. M. P.; Vittal, J. J. Chem. Commun. 2008, 5277. (23) Rajput, L.; Biradha, K. J Mol Struct 2008, 876, 339. (24) Caronna, T.; Liantonio, R.; Logothetis, T. A.; Metrangolo, P.; Pilati, T.; Resnati, G. J. Am. Chem. Soc. 2004, 126, 4500. (25) Aakeroy, C. B.; Desper, J.; Fasulo, M.; Hussain, I.; Levin, B.; Schultheiss, N. CrystEngComm 2008, 10, 1816. (26) Chen, C.-L.; Goforth, A. M.; Smith, M. D.; Su, C.-Y.; zur Loye, H.-C. Inorg. Chem. 2005, 44, 8762. (27) Ma, B. Q.; Ferreira, L. F. V.; Coppens, P. Org Lett 2004, 6, 1087. (28) Weiss, A.; Pritzkow, H.; Siebert, W. Angew. Chem., Int. Ed. 2000, 39, 547. (29) Fan, L. M.; Zhang, X. T.; Sun, Z.; Zhang, W.; Ding, Y. S.; Fan, W. L.; Sun, L. M.; Zhao, X.; Lei, H. Cryst. Growth. Des. 2013, 13, 2462. (30) Hu, L. M.; Spencer, E. C.; Wang, G. B.; Yee, G.; Slebodnick, C.; Hanson, B. E. Inorg Chem Commun 2008, 11, 982. (31) Liu, Y. Y.; Ma, J. F.; Yang, J.; Ma, J. C.; Ping, G. J. CrystEngComm 2008, 10, 565. (32) Zhang, S. Y.; Tang, Y. R.; Mao, Z. H.; Li, M. L.; Lan, J. B.; Su, X. Y. Acta Crystallogr. E 2009, 65, O26. (33) Zhang, S. Y.; Yang, S. Y.; Lan, J. B.; Yang, S. J.; You, J. S. Chem. Commun. 2008, 6170. (34) Bond, A. D. Chem. Commun. 2002, 1664. (35) Meot-Ner, M. Chem. Rev. 2012, 112, PR22. (36) Dickie, D. A.; Schatte, G.; Jennings, M. C.; Jenkins, H. A.; Khoo, S. Y. L.; Clyburne, J. A. C. Inorg. Chem. 2006, 45, 1646.


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(37) Chatterjee, S.; Pedireddi, V. R.; Rao, C. N. R. Tetrahedron Lett. 1998, 39, 2843. (38) Najafpour, M. M.; Holynska, M.; Lis, T. Acta Crystallogr. E 2008, 64, O985. (39) Meiners, C.; Valiyaveettil, S.; Enkelmann, V.; Mullen, K. J. Mater. Chem. 1997, 7, 2367. (40) Aakeroy, C. B.; Desper, J.; Leonard, B.; Urbina, J. F. Cryst. Growth. Des. 2005, 5, 865. (41) Van Roey, P.; Bullion, K. A.; Osawa, Y.; Bowman, R. M.; Braun, D. G. Acta Crystallogr. C 1991, 47, 1015. (42) Walsh, R. B.; Padgett, C. W.; Metrangolo, P.; Resnati, G.; Hanks, T. W.; Pennington, W. T. Cryst. Growth. Des. 2001, 1, 165.


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For Table of Contents Use Only

Single-crystal structures and typical hydrogen-bonding motifs of supramolecular cocrystals containing 1,4-di(1H-imidazol-1-yl)benzene Fanxing Meng, Yuhua Li, Xin Liu, Bao Li and Liyan Wang*

Di(1H-imidazol-1-yl)benzene (DIB), as hydrogen-bonding acceptor, crystallized with several hydrogen-bonding donors. The X-ray analysis results revealed that one-dimensional infinite chains were formed in these cocrystals. The hydrogen atoms of the imidazole ring in DIB were found to be involved in three kinds of hydrogen-bonding ring motifs. These motifs could play an important role in the stabilization of the cocrystals.


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Single-Crystal Structures and Typical Hydrogen-Bonding Motifs of

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