Conformation-Directed Hydrogen-Bonding in meta-Substituted

Article pubs.acs.org/crystal

Conformation-Directed Hydrogen-Bonding in meta-Substituted Aromatic Ureadicarboxylic Acid: A Conformationally Flexible U‑Shaped Building Block Shugo Hisamatsu,† Hyuma Masu,‡ Masahiro Takahashi,† Keiki Kishikawa,† and Shigeo Kohmoto*,† †

Department of Applied Chemistry and Biotechnology, Graduate School of Engineering, Chiba University, 1-33 Yayoi-cho, Inage-ku, Chiba 263-8522, Japan ‡ Chemical Analysis Center, Chiba University, 1-33 Yayoi-cho, Inage-ku, Chiba 263-8522, Japan S Supporting Information *

ABSTRACT: Crystal structures of U-shaped aromatic ureadicarboxylic acid possessing two carboxy moieties at meta-positions of phenyl rings were investigated. It afforded cocrystals with dipyridyl derivatives. In addition to the U-shaped conformation obtained by recrystallization from methanol, another three types of U-shaped conformations were found in the crystal structure of the cocrystals. The direction of Hbonding was fixed based on the relative geometry of two carboxy moieties in the resulting conformations. Depending on these conformations, triple helices with one-dimensional water channels, infinite cross-belt, and step-like structures were generated via H-bonding between the carboxy and the pyridyl moieties. Methanol solvate was obtained for the cocrystal with 1,4-di(pyridine-4-yl)benzene which showed different U-shaped conformation of urea dicarboxylic acid from that involved in the cocrystal free of methanol.

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INTRODUCTION Stacked assemblies of aromatic molecules are of current interest in various technological fields.1 We are interested in a simple folding unit easily available for the building of folded architectures which can be applied to the piling of aromatics in a folding way. Assembling of the molecules possessing two H-bonding donor sites with the counter molecules possessing two H-bonding acceptor sites affords cocystals2 often with zigzag3 and seldom with triply helical H-bonding networks.4 Cocrystallization with rigid folding building blocks could create an infinite folded H-bonding network. Folded architectures like foldamers5 of zigzag and helix can be derived supramolecularly by this assembling. As folding linkages to afford zigzag-type aromatic foldamers, urea,6 guanidine,7 and imide8 linkers were employed and π-stacked foldamers were synthesized. Recently, we have developed U-shaped aromatic ureadicarboxylic acids as folded building blocks and demonstrated their usefulness for crystal engineering.9 Urea derivatives functionalized with Hbonding donor or acceptor like pyridyl or carboxy group can form cocrystals with their H-bonding partners with directional properties.10 In these urea derivatives, urea NH groups are utilized for the creation of H-bonding among them. They have extended molecular structures. In contrast, substitution with methyl groups at urea nitrogen atoms changes the conformation of urea from a linear (trans,trans-conformation) to a desirable U-shaped cis,cis-conformation.6a,f,11 They were powerful building blocks, especially for the formation of triple helices with rod-shaped dipyridyl derivatives. The dipyridyl derivatives are H-bonded with carboxy moieties at both ends of the rods to © 2013 American Chemical Society

give a helical structure. An assembling of helices results in the construction of a triple helix in cocrystals. Regardless of the length of the dipyridyl derivatives, triple helices can be furnished. The important point in this designing is the choice of the proper angle between the directions of two H-bonding for the creation of a helical array. Therefore, the location of two carboxy moieties in the U-shaped dicarboxylic acid is crucial. They determine the folding angle of the H-bonding network. In our previous report, we employed urea dicarboxylic acid possessing two carboxy moieties at the para-positions. The angle between the two directions of H-bonding created by the two carboxy moieties is appropriate for the construction of triple helices by the aforementioned assembling. Owing to the nature of the para-substitution, the relative location of two carboxy moieties is uniquely defined in its U-shaped conformation. In contrast, three relative locations of two carboxy moieties are possible in the meta-substituted urea dicarboxylic acid 1 in its U-shaped conformation because of its asymmetrical nature. Figure 1a shows these three geometrical relations of two carboxy moieties of 1 (type A, B, and C). For comparison, the conformation of the corresponding psubstituted dicarboxylic acid is shown together with them. In addition to these geometrical relations, three and four relative orientations of carboxy groups are possible for type A and B, and C, respectively. Therefore, total of 10 conformations can be Received: December 27, 2012 Revised: April 26, 2013 Published: April 26, 2013 2327

dx.doi.org/10.1021/cg301878r | Cryst. Growth Des. 2013, 13, 2327−2334

Crystal Growth & Design

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refluxed for 18 h. After the reaction, most of methanol was removed by evaporation and neutralized with aqueous 1 M HCl solution. The precipitate formed was filtered off and dried to give 1 (135 mg, 84%). Single crystals of 1 were obtained by recrystallization from methanol/ water as colorless prisms. Mp 255−258 °C; IR (KBr) 3071 (w), 2925 (w), 1720 (s), 1709 (s), 1585 (s), 1449 (s), 1249 (s) cm−1; 1H NMR (300 MHz, (CD3)2CO) δ 7.57 (dt, J = 7.5, 1.5 Hz, 2H), 7.12 (t, J = 1.8 Hz, 2H, 7.20 (t, J = 7.8 Hz, 2H), 7.15 (dt, J = 8.4, 1.5 Hz, 2H), 3.22 (s, 6H), 13C NMR (75 MHz, DMSO-d6) δ 167.5, 160.3, 145.8, 132.1, 129.8, 129.7, 126.11, 126.06, 39.3; HRMS(ESI) calcd for C17H17N2O5 [MH]+ 329.1132, found 329.1131. 1,4-Di(pyridine-4-yl)benzene 4 12 and 2,6-di(pyridine-4-yl)anthracene 513 were prepared according to the reported methods. Preparation of Cocrystals. Cocrystals were prepared by recrystallization of 1 and pyridyl derivatives at room temperature with a vapor diffusion method. For cocrystals, 1·2·(H2O)3, 1·3, and 1·4·CH3OH, the vessel containing a sample (3−10 mg) dissolved in 3−6 mL of methanol was placed in a jar in which water to be vaporized was added. After the sample stood for several days, the corresponding cocrystals were obtained. Replacement of methanol to ethanol afforded 1·4. Cocrystal 1·5 was obtained from ethanol/ chloroform with diffusion of hexane vapor. X-ray Crystallography. X-ray diffraction data for the crystals were measured on Bruker ApexII CCD diffractometer with graphite monochromated MoKα (λ = 0.71073 Ǻ ). Data collections were carried out at low temperature. All structures were solved by direct methods SHELXS-97,16 and the non-hydrogen atoms were refined anisotropically against F2, with full-matrix least-squares methods SHELXL-97.14 As for refinement, the hydrogen atoms of water molecules were excluded from the structure. All hydrogen atoms except that in water molecules were positioned geometrically and refined as riding. Other details of refinements of the crystal structures are described in Supporting Information.

Figure 1. Three possible geometrical relations of two carboxy moieties in meta-substituted ureadicarboxylic acid 1. (a) Comparison with parasubstituted one. (b) Three possible orientations of carboxy moieties in type A and type B geometrical relations. Subclassified conformations of type C are omitted from the figure because of the absence of the crystal structure corresponding to this in our experiments.

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generated. The type of the conformation was classified based on the relative positions of the two hydroxy groups of the carboxy moieties, inward−inward, inward−outward, and outward−outward, respectively. On the basis of this classification, type A and type B were subclassified as type A1−A3 and type B1B3, respectively. They are shown in Figure 1b. We are curious about the effect of the substitution pattern of two carboxy moieties on the assembling. If the diacid 1 takes type A3 conformation, we can expect possible construction of triple helices with dipyridyl derivatives as we observed in the case of para-substituted urea dicarboxylic acid. This is because of the similarity in the geometrical relation between the two carboxys in 1 to that in the para-substituted one. The appropriate angle for a helical array can be generated between the directions of two H-bonding in the cocrystal of 1. On the contrary, it is difficult to create helical arrays with other conformations due to the wrong directional relationships between the two H-bonding sites. The linearly arrayed assembly can be expected with type B conformation owing to the almost opposite positions of two carboxy groups.

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RESULTS AND DISCUSSION Single crystals of 1 were obtained by recrystallization from MeOH/H2O. Cocrystals were prepared by recrystallization of 1 with the corresponding dipyridine derivatives 2−5 (Figure 2).

EXPERIMENTAL SECTION

Figure 2. Chemical structures of dipyridyl derivatives for cocrystal formation.

Materials and Methods. All the reagents and solvents employed were commercially available and used as received without further purification. 1H and 13C NMR spectra were recorded for samples in CDCl3 with Me4Si as an internal standard. Synthesis. 3,3′-(Carbonylbis(methylazanediyl)dibenzoic Acid (1). The compound was prepared by saponification of diethyl 3,3′(carbonylbis(methylazanediyl)dibenzoate which was prepared by the coupling of ethyl 4-aminobenzoate with CDI (carbonyldiimidazole) followed by methylation with methyl iodide. Saponification was carried out in the following way. To a methanol solution (18 mL) of the diethyl dibenzoate (243 mg, 0.68 mmol) was added a solution of KOH (382 mg, 6.80 mmol) in water (2.0 mL), and the resulting mixture was

Cocrystals 1·2·(H2O)2, 1·3, and 1·4·CH3OH were obtained from methanol with diffusion of water vapor. Changing the recrystallization solvent from methanol to ethanol solvent free cocrystal 1·4 was obtained. Cocrystal 1·5 was obtained from ethanol/chloroform with diffusion of hexane vapor. Table 1 shows crystallographic data for urea dicarboxylic acid 1 and its cocrystals with the dipyridyl derivatives. Figure 3 shows the molecular structure and a packing diagram. The urea 1 adopts 2328


C17H16N2O5·C24H16H2 monoclinic C2/c 7.3667(7) 12.4342(12) 35.712(3) 90 93.8750(10) 90 3263.8(5) 1.345 4 173 0.059 0.1601

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C17H16N2O5·C16H12N2 monoclinic C2/c 7.53910(10) 15.3606(2) 23.5185(3) 90 90.7238(4) 90 2723.34(6) 1.367 4 173 0.0345 0.0979 C17H16N2O5·C16H12N2·CH3OH orthorhombic Pna21 27.693(2) 6.5838(5) 16.1466(12) 90 90 90 2943.9(4) 1.337 4 173 0.0447 0.1219 C17H16N2O5·C12H10N2 monoclinic C2/c 10.8373(11) 13.6735(14) 16.8579(17) 90 95.2820(10) 90 2487.5(4) 1.363 4 173 0.0390 0.1048 C17H16N2O5·C10H8N2·3H2O monoclinic P21/c 19.489(3) 9.2758(12) 14.632(2) 90 90.964(2) 90 2644.8(6) 1.337 4 173 0.073 0.1946 C17H16N2O5 monoclinic P21/c 8.7385(6) 14.9729(11) 12.6024(9) 90 102.1520(10) 90 1612.0(2) 1.353 4 173 0.0464 0.1120 formula crystal system space group a (Å) b (Å) c (Å) α (°) β (°) γ (°) V (Å3) Dc (Mg m−3) Z T (K) R1, [I > 2σ(I)] wR2 [I > 2σ(I)]

1·4·CH3OH 1·3 1·2·(H2O)3 1 compound

Table 1. Crystallographic Data for Ureadicarboxylic Acid 1 and Its Cocrystals with Dipyridyl Derivatives 2−5

1·4

1·5


Figure 3. Single crystal X-ray structure of 1. (a) ORTEP diagram and (b) packing diagram in which H-bonds and CH/O interactions are indicated with blue and green dotted lines, respectively. The O···O and C···O atomic distances are indicated in Å.

type A1 conformation. Four molecules of 1 are included in the unit cell. These four molecules interacted with each other via H-bonding and CH/O interactions. In the case of the psubstituted one, catemeric type H-bonding was created among carboxy moieties. The double catemeric H-bonding network afforded an infinite rod-like structure.9a In contrast, no such Hbonding between carboxy groups is observed in the crystal structure of 1. There exists H-bonding between the urea carbonyl and the hydroxyl of the carboxy group. The urea carbonyl is H-bonded with two neighboring hydroxyl moieties with the O···O atomic distances of 2.65 and 2.66 Å. The CH/O interactions are observed between the carbonyl oxygen atoms of the carboxy groups and the phenyl hydrogen atoms. The C···O atomic distances are 3.30 and 3.50 Å. Pyridine derivatives are reliable H-bonding acceptors for carboxylic acids, and many examples have been reported.3c,4a,15 Moreover, the combination of dicarboxylic acids and dipyridyl derivatives can afford extended H-bonding networks.16 In order to prepare triple helices in cocrystals, it is required to take type A3 conformation which is different from the conformation (type A1) in its crystalline state. However, a slight modification, rotations of carboxy groups, can adjust its conformation suitable for the formation of triple helices. Therefore, it is reasonable to consider that the helical H-bonding network can be created by cocrystallization with bipyridyl derivatives. Figure 4 shows the single crystal X-ray structure of the cocrystal of 1 with 2 (1·2·(H2O)3). Similar to 2329



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helical strands resulted in the formation of triple helices. Unlike the triple helices of the p-substituted one with 2 which we reported recently,9a cocrystal 1·2·(H2O)3 involved 1D water channels (Figure 4b). Because of the slight difference in the direction of H-bonding in 1 compared with that in the psubstituted one, the closest packing is difficult for 1·2·(H2O)3. As a result, extra space is created as a narrow channel which is suitable to settle a 1D array of water molecules (Figure 4c). Water trimer units are repeatedly H-bonded to furnish infinite 1D chain of water molecules in the channels. Urea carbonyl oxygen atoms are H-bonded with water molecules. Thermogravimetric (TG) and differential scanning calorimetric (DSC) analyses of 1·2·(H2O)3 were carried out. Weight loss was started from about 175 °C, and about 25% of weight loss was observed by TG. This corresponds to the loss of three water molecules and decarbonation of two carboxy groups (Figure S8). In analogy, we tried to prepare water channels by the creation of triple helices in the cocrystals of 1 with extended dipyridyl derivatives 3, 4, and 5. In our previous results on the cocrystal formation of the p-substituted ureadicarboxylic acid with dipyridyl derivatives 2, 3, and 5, we obtained triple helices for all of them. However, a different H-bonding network was created for m-substituted ureadicaboxylic acid 1 with them. Figure 5 shows packing diagram of cocrystal 1·3. It has A3 type conformation similar to that of 1·2·(H2O)3. A zigzag network is created by H-bonding and CH/O interaction between the carboxy and the pyridyl moieties with the N···O and C···O atomic distances of 2.65 and 3.15 Å, respectively. They are indicated by blue and green lines, respectively (Figure 5a). Figure 5b,c shows zigzag H-bonding networks viewed from the direction of the crystallographic a-axis and b-axis, respectively. One of the pyridyl moiety of 3 is H-bonded with the upper carboxy group of the neighboring urea, while the other pyridyl moiety is H-bonded with the lower carboxy group of the neighboring urea at the opposite side. The way of H-bonding is different from that observed in the triple helix formation in the cocrystals of the p-substituted ureadicarboxylic acid with dipyridyl derivatives even though the same type A3 conformation is involved in its crystal structure. This is easily visualized in the side-view of its packing (Figure 5d). The network looks like an infinite cross belt. Another type of conformation of 1 was found in the cocrystal of 1 with 4. In this case, pseudopolymorphism was observed depending on recrystallization solvents. When recrystallization was carried out from methanol/water, methanol molecules are included in the cocrystals 1·4·CH3OH in a ratio of 1:1:1 (1:4:CH3OH). Figure 6 shows its crystal structure. Instead of type A geometrical relation of two carboxy groups, type B3 conformation exists in the cocrystal. H-bonding among carboxy and pyridyl groups creates infinite steps. Figure 6a,b shows the stacking of steps viewed along the crystallographic a- and c-axes, respectively. The columns of two adjacent stacked steps are crossed with an angle of ca. 70°; the angle between the planes of the phenylene of two neighboring 4. Intermolecular CH/O interactions between the adjacent crossed steps are presented in Figure 6c together with H-bonding and π−π interactions. The urea carbonyl oxygen atom is interacted with three hydrogen atoms of neighboring 4 with the C···O atomic distances of 3.18, 3.30, and 3.48 Å. The columns of stacked steps are crossed alternately to create channels in which methanol molecules are included (Figure 6d).

Figure 4. Single crystal X-ray structure of cocyrstal 1·2·(H2O)3. (a) An H-bonded helical array in which the O···N atomic distances are indicated in Å. (b) Water channels (circled in red) created by triple helices of 1·2·(H2O)3 presented by space-filling model. Each helical strand is colored differently. Water molecules in the channels are omitted for clarity. (c) The H-bonded array of water molecules in the channel.

the cocrystal of the p-substituted one with 2, carboxy and pyridyl groups are H-bonded in a ratio 1:1 which was also confirmed by 1H NMR analysis of the cocrystals. Recently, much attention has been paid for crystals of acid−base pairs whether they are cocrystals or salts.17 Generally, depending on their acidities and basicities, the pairs afford either cocrystals based on H-bonding or salts. In the case of cocrystals, a nonequivalence of the C−O bonds in carboxylic function corroborates its formulation as a COOH group with retention of proton.18 Cocrystal 1·2·(H2O)3 showed apparently different lengths of two sets of C−O bonds for carboxylic functions, 1.208 and 1.303 Å, and 1.212 and 1.316 Å. The results indicate that cocrystals based on H-bonding were formulated for 1·2·(H2O)3. According to Etter H-bonding rule of strongest donor to strongest acceptor,19 the strongest carboxy donor Hbonds to the strongest acceptor urea oxygen atom in the crystal structure of 1, while in the cocrystals the best acceptor is the pyridine nitrogen atom. Consequently, H-bonding changes to make molecular cocrystals. A portion of the resulting helical Hbonding network is presented in Figure 4a. Assembling of the 2330



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Figure 6. Packing diagram of cocrystal 1·4·CH3OH. Stacking of steplike structure viewed along the crystallographic (a) a-axis and (b) caxis. (c) Intermolecular interactions, H-bonding, CH/O, and π−π interactions, indicated by blue, green, and orange lines, respectively. Their atomic distances, the N···O, C···O, and C···C are indicated in Å, respectively. (d) Methanol channels viewed along the crystallographic b-axis in which methanol molecules are colored green. Methanol molecules are omitted for clarity in (a−c).

Figure 5. Crystal structure of cocrystal 1·3. (a) Sandwiching of 3 by 1 via H-bonding. Space-filling model presentation of zigzag H-bonding network viewed along the crystallographic (b) a-axis and (c) b-axis, respectively, in which compound 3 is colored green. (d) Side-view of the network from the direction of [101] face showing an infinite crossbelt structure. H-bonding and CH/O interactions are indicated by blue and green lines, and the N···O and C···O atomic distances for those interactions are indicated in Å, respectively.

(2.57 Å). The angles created between the planes of the benzene ring of 1 and the neighboring pyridine ring of 4 to be Hbonded are 17 and 50° for 1·4·CH3OH and 1·4, respectively. This indicates that the H-bonding network of 1·4 is much more twisted than that of 1·4·CH3OH. In order to examine the effect of the length of dipyridyl derivatives on the crystal packing of cocrystals, 1 was recrystallized with 5 which possessed an anthracene moiety as a spacer. Cocrystal 1·5 was obtained by recrystallization from EtOH/CHCl3/hexane. Type B3 geometrical relation of two carboxy groups was also found in the cocrystal. However, unlike cocrystal 1·4 which included methanol molecules, no inclusion of them was observed. Figure 9 shows its crystal structure. The two carboxy groups of 1 direct H-bonding with the pyridyl moieties in almost the opposite direction. The stacking of twisted steps of H-bonding networks is presented in Figure 9a,b viewed along the crystallographic c- and b-axes, respectively. Figure 9c shows intermolecular CH/O interactions among adjacent steps indicated by green lines together with H-bonding within the step indicated by blue lines. Depending on the structure of dipyridyl derivatives, we found four U-shaped conformations of ureadicarboxylic acid 1 in the crystal structure of 1 and its cocrystals with dipyridyl derivatives. Figure 10 summarizes these four conformations of 1 for comparison. Torsion angles between the two phenyl rings are indicated in parentheses. Arrows indicate the direction of H-bonding with a pyridine ring. The crystal structure involves type A1 conformation in which two hydroxyl groups located inward. Type A3 conformation with two outward hydroxyl

Methanol free cocrystal 1·4 was obtained by recrystallization from ethanol/water. Unlike the cocrystals from methanol/ water, no solvent (ethanol) molecule was included in the cocrystal. Type B1 was observed for its U-shaped conformation. Dipyridyl derivative 4 was H-bonded by two molecules of 1 as in the case of cocrystal 1·4·CH3OH but in a different manner. Figure 7a,b shows packing diagrams of 1·4 viewed along the crystallographic b- and c-axes, respectively. Unlike the crystal structure of 1·4·CH3OH, stacking of dipyridyl derivative 4 is not efficient in 1·4. In contrast to the formation of a linear step via H-bonding in 1·4·CH3OH, a zigzag step is created in the case of 1·4. Intermolecular interactions between the steps, the CH/O and CH/π interactions together with H-bonding are presented in Figure 7c. For comparison, the superimposed image of the way of Hbonding of dipyridyl derivative 4 with two molecules of 1 in both cocrystals is shown in Figure 8 in which the structures of 1·4·CH3OH and 1·4 are colored yellow and green, respectively. The direction of H-bonding is different because of the difference of their conformations. Instead of the linear Hbonding network in 1·4·CH3OH, a zigzag H-bonding network is created in 1·4. The H-bonding distance between the oxygen atom of the carboxy and the nitrogen atom of the pyridyl is 2.64 Å in 1·4, which is slightly longer than that of 1·4·CH3OH 2331



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Figure 9. Packing diagram of cocrystal 1·5. Arrays of twisted steps viewed along the crystallographic (a) c-axis and (b) b-axis. (c) Intermolecular CH/O interactions among adjacent steps indicated by green lines together with H-bonding within the step indicated by blue lines. Their C···O and N···O atomic distances are indicated in Ǻ , respectively.

Figure 7. Crystal structure of cocrystal 1·4. Packing diagrams of 1·4 presented in space-filling model viewed along the crystallographic (a) b- and (b) c-axes, respectively. (c) H-bonding, CH/O, and CH/π interactions indicated by blue, green, and orange dotted lines with the O···N, O···C, and the ring centroid···carbon distances in Ǻ , respectively.

Figure 10. Comparison of the conformations of 1 (top views) found in (a) its crystal structure from methanol/water and in cocrystals (b) 1·2·(H2O)3, (c) 1·3, (d) 1·4·CH3OH, (e) 1·4, and (f) 1·5. Torsion angles between the two phenyl rings are indicated in parentheses. Arrows indicate the direction of H-bonding.

rings can range from 38° to 58°, which indicates the flexible nature of the U-shaped uradicarboxylic acids. Because of this flexibility and its U-shaped nature owing to the N-methylated urea linkage, ureadicarboxylic acid 1 can adopt multiple Ushaped conformations. We explored CSD search on the structure of dicarboxylic acids in which two meta-substituted benzoic acid moieties were connected with a linker consisting of three atom unit lengths. The only example relevant to the present study is dicarboxylic acid in which two meta-substituted benzoic acid moieties are connected with a sulfoneimide linkage.20 This sulfoneimide derivative afforded three solvate crystals. Two of them have folded and the other has extended molecular structure depending on the conformation of the sulfoneimide linkage. The former two folded structures have

Figure 8. Superimposed image of the way of H-bonding of 4 in both cocrystals in which the structures of 1·4·CH3OH and 1·4 are colored orange and green, respectively.

groups is responsible for the crystal structures of cocrystals 1·2·(H2O)3 and 1·3. In contrast, type B orientation of carboxy groups is facilitated in cocrystals 1·4·(CH3OH), 1·4, and 1·5. Methanol solvate was obtained with 4. The U-shaped conformation of 1 in cocrystal 1·4·(CH3OH) is type B3. However, recrystallization from ethanol gave cocrystal 1·4 in which two hydroxyl groups take outward positions (type B1). Cocrystal 1·5 shows type B3 conformation. It is interesting that different types of folding architectures can be created from the same building block. Torsion angles between the two phenyl 2332



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type C geometrical relationship of two carboxy groups according to our classification. Our N-methylated urea linkage is significant since all the cocrystals showed a U-shaped molecular structure of the diacid, but this is not the case for the diacid with a sulfoneimide linkage.

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CONCLUSION An introduction of asymmetric character by meta-substitution to the U-shaped conformation of N-alkylated aromatic ureadicarboxylic acids resulted in the generation of another three U-shaped conformations in cocrystals with dipyridyl derivatives in addition to the original U-shaped conformation observed in its crystal structure. This is a remarkable difference to the corresponding para-substituted one in which a single conformation was reported in cocrystals. This conformational flexibility is beneficial for the construction of a variety of folding architectures in crystal engineering. Folding building blocks with two H-bonding sites are capable of fabricating columns in a folding way in which captured functional guest molecules can be piled up. This can provide a unique way of functionalized cocrystals.

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ASSOCIATED CONTENT

S Supporting Information *

The crystallographic information files (CIF) and crystal data of 1 and cocrystals, 1·2·(H2O)3, 1·3, 1·4·CH3OH, 1·4, and 1·5, comparison of the powder XRD pattern of bulk crystals and the theoretical pattern generated from the single crystal structure of 1·4, TG and DSC curves of 1·2(H2O)3, and reflectance IR spectra of 1, 1·2(H2O)3, and 1·4, are available free of charge via the Internet at http://pubs.acs.org.

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AUTHOR INFORMATION

Corresponding Author

*Phone: +81-43-290-3420. Fax: +81-290-3422. E-mail: [email protected]. Notes

The authors declare no competing financial interest.

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REFERENCES

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Conformation-Directed Hydrogen-Bonding in meta-Substituted

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