Supramolecular Architectures and Helical Water Chains in Cocrystals

Aug 20, 2004 - Guangdong Institute of Education, Guangzhou 510310, People's Republic of China. Received May 30, 2004. ABSTRACT: Melamine (MA) base ...
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Supramolecular Architectures and Helical Water Chains in Cocrystals of Melamine and Aromatic Carboxylic Acids Xiu-Lian Zhang†,‡ and Xiao-Ming Chen*,†

CRYSTAL GROWTH & DESIGN 2005 VOL. 5, NO. 2 617-622

School of Chemistry and Chemical Engineering, Sun Yat-Sen University, Guangzhou 510275, People’s Republic of China, and Department of Chemistry, Guangdong Institute of Education, Guangzhou 510310, People’s Republic of China Received May 30, 2004

ABSTRACT: Melamine (MA) base was crystallized with different aromatic carboxylic acids trimesicacid (TMA), terephthalic acid (TPA), and 3,5-dinitrobenzoic acid (DNBA), affording cocrystals of (MAH+)‚(DNBA-) (1), (MAH+)‚(TPA2-)0.5‚H2O (2), and (MAH+)‚(H2TMA-)‚3H2O (3). Meanwhile, crystallization of MA and trimellitic acid (H3BTA) in a 1:1 ratio in hot methanol solution led to esterification of one carboxylic group in H3BTA, resulting in cocrystals of (MAH+)‚(HBTA-M-)‚H2O (4). Extensive N-H‚‚‚O/N-H‚‚‚N hydrogen bonds are found in 1-4, featuring different hydrogen-bonding motifs. Compounds 1 and 2 have two-dimensional (2D) layers stabilized by strong N-H‚‚‚O/N-H‚‚‚N hydrogen bonds and weak C-H‚‚‚O hydrogen bonds. Compound 3 exhibits a thermally stable three-dimensional (3D) architecture formed by the stacking of 2D layers, featuring one-dimensional (1D) pores enclosing unusual helical water chains. In compound 4, three kinds of 1D chains are intersected to form a 3D structure consolidated by extensive hydrogen bonds including unusual triple hydrogen bonds between an HMA+ ion and a carboxylate group. Introduction Organic crystals built from acid-base complexes have received considerable attention in the predictable assembly of supramolecular architectures.1-4 One of the important ways is the use of self-organization of small molecules with N-H‚‚‚O, O-H‚‚‚O and other weak intermolecular interactions to create one-, two-, and three-dimensional (1D, 2D, and 3D) networks in crystalline solids.5,6 Recent studies have been focused on the host networks with space to create materials for molecular storage and catalysis.7-9 The melamine (MA) molecule has multiple hydrogen-bonded sites and is known to form hydrogen-bonded supramolecular architectures such as tape, sheet, rectangular net, and organic-inorganic sandwich type 3D network structures10-15 with barbituric acid, succinimide, cyanuric acid, 4,4′-bipyridyl, and nitrilotriacetic acid. So far, MA molecules form mostly hydrogen-bonded supramolecular tapes in the solid state, and the structures formed by hydrogen-bonding interactions of MA rarely exhibit cavities and channels.5 Aromatic acids attract our interest because of their importance in crystal engineering, which can form strong and directional hydrogen bonds,9 and the number of carboxylic groups and the different placement of the carboxylic groups on the aromatic ring may lead to variable hydrogen-bonding fashions and architectures. Therefore, combinations of different polycarboxylic acids with MA molecules may be expected to exhibit variable hydrogen-bonding modes and interesting networks. Herein, we report the structures of cocrystals of MA with aromatic carboxylic acids 3,5-dinitrobenzoic acid (DNBA), terephthalic acid (TPA), * To whom correspondence should be addressed. Fax: 86-2084112245. E-mail: [email protected]. † Sun Yat-Sen University. ‡ Guangdong Institute of Education.

Chart 1.

Structures of MA and the Aromatic Carboxylic Acids

trimesic acid (TMA), and trimellitic acid (BTA) (Chart 1), namely, (MAH+)‚(DNBA-) (1), (MAH+)‚(TPA2-)0.5‚ H2O (2), (MAH+)‚(H2TMA-)‚3H2O (3), and (MAH+)‚ (HBTA-M-)‚H2O (4). Aside from the extensive hydrogen bonds in different fashions in 1-4, unusual helical 1D chains of water molecules anchored by hydrogen-bonding interactions in channels of the supramolecular, porous organic host of 3 are also found. Experimental Section All materials were commercially available and used as received. The Fourier transform infrared spectra were recorded from KBr pellets between 400 and 4000 cm-1 on a Nicolet 5DX spectrometer. Elemental analyses were carried out with a Perkin-Elmer 240 elemental analyzer. Thermal gravimetric analyses (TGA) were performed under dinitrogen atmosphere

10.1021/cg0498251 CCC: $30.25 © 2005 American Chemical Society Published on Web 08/20/2004

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Table 1. Crystallographic Data and Structure Refinement Parameters formula Mr crystal color cryst size/mm3 cryst syst space group a (Å) b (Å) c (Å) R (°) β (°) γ (°) cell vol (Å3) Dcalcd (g cm-3) Z no. of data/params µ (mm-1) θ range (°) h range k range l range reflns collected unique reflns observed reflns R1 [I > 2σ(I)] wR2 [all] GOF

1

2

3

4

C10H10N8O6 338.24 colorless 0.17 × 0.12 × 0.10 triclinic P1 h 8.2068(8) 12.702(1) 13.373(1) 94.106(2) 99.216(2) 94.645(2) 1366.4(2) 0.822 2 4739/441 0.069 1.55-25.00 -9 to 9 -15 to 8 -15 to 15 6970 4739 3188 0.067 0.189 1.01

C7H11N6O3 227.20 colorless 0.36 × 0.32 × 0.19 monoclinic P21/c 6.7992(8) 20.156(2) 7.0861(8) 90 93.366(2) 90 969.5(2) 1.168 4 2236/189 0.094 2.02-28.22 -9 to 7 -26 to 18 -9 to 9 5979 2236 1864 0.042 0.124 1.05

C12H18N6O9 390.31 colorless 0.30 × 0.24 × 0.24 triclinic P1 h 6.928(2) 11.272(4) 11.678(4) 110.157(6) 103.151(6) 94.128(6) 822.3(5) 0.788 2 3560/304 0.068 1.93-28.22 -9 to 6 -14 to 14 -13 to 15 5037 3560 2506 0.063 0.171 1.10

C13H16N6O7 368.31 colorless 0.32 × 0.30 × 0.19 monoclinic P21/c 13.139(3) 8.164(2) 14.947(3) 90 93.80(3) 90 1599.8(6) 1.529 4 3051/236 0.126 1.55-26.00 -17 to 16 -9 to 10 -17 to 16 8205 3051 2769 0.053 0.161 1.03

using a Perkin-Elmer 7 thermogravimetric analyzer with a heating rate of 10 °C min-1. The cocrystals were prepared as follows. (MAH+)‚(DNBA-) (1). MA (0.063 g, 0.50 mmol) and DNBA (0.106 g, 0.5 mmol) were dissolved in hot EtOH/H2O (1:1) solution (20 mL). The solution was allowed to cool to room temperature and was evaporated in air for 4 days to give colorless crystals of 1 (0.140 g, 0.40 mmol; yield 67%). Anal. calcd for C10H10N8O6: C, 35.51; H, 2.98; N 33.11. Found: C, 35.41; H, 2.88; N, 33.22%. IR (KBr, cm-1): 3474, 3396, 3162, 3008, 2658, 2550, 1685, 1644, 1615, 1515, 1371, 1287. (MAH+)‚(TPA2-)0.5‚H2O (2). To a hot solution of MA (0.025 g, 0.20 mmol) in methanol (10 mL), a hot solution of TPA (0.033 g, 0.20 mmol) in methanol (10 mL) was added, and a white solid precipitated immediately. After filtration, the white solid was washed with methanol, dried under vacuum, and then dissolved with dimethylformamide. The resulting solution was evaporated in air for a week. Colorless crystals of 2 (0.031 g, 0.14 mmol, yield 67% based on MA) were isolated. Anal. calcd for C7H11N6O3: C, 37.00; H, 4.88; N, 36.97. Found: C, 37.20; H, 4.71; N, 36.82%. IR (KBr, cm-1): 3378, 3160, 1664, 1514, 1371, 1278, 1190. (MAH+)‚(H2TMA-)‚3H2O (3). A hot aqueous solution of MA (0.063 g, 0.50 mmol) was added in a hot aqueous solution of TMA (0.105 g, 0.50 mmol), and a white solid precipitated immediately. To the solution were added excess water (20 mL) and HNO3 (1 M, 2 mL) until the white solids were dissolved. The clear solution was allowed to cool to room temperature and evaporated in air for 2 days. Colorless platelike crystals of 1 were obtained (0.174 g, 0.45 mmol; yield 89%). Anal. calcd for C12H18N6O9: C, 36.92; H, 4.65; N, 21.24. Found: C, 36.91; H, 4.46; N, 22.14%. IR (KBr, cm-1): 3496, 3355, 3133, 1711, 1676, 1612, 1574, 1366, 1230, 1186. (MAH+)‚(HBTA-M-)‚H2O (4). To a solution of MA (0.025 g, 0.20 mmol) in methanol (10 mL), a solution of BTA (0.042 g, 0.20 mmol) in methanol (10 mL) was added. The reaction mixture was refluxed for 2 h and then allowed to cool to room temperature and filtered. The filtrate was then evaporated in air for a week. Colorless crystals of 2 were obtained in 70% yield (0.052 g, 0.14 mmol). Anal. calcd for C13H16N6O7: C, 42.38; H, 4.37; N, 21.82. Found: C, 42.20; H, 4.21; N, 22.82. IR (KBr, cm-1): 3378, 3160, 1664, 1514, 1371, 1278, 1190. X-ray Crystallography. The data were collected on a Bruker SMART Apex CCD Diffractometer, and the data reduction was performed using Bruker SAINT.16a The struc-

tures were solved with direct methods and refined by fullmatrix least-squares refinement on F2 with anisotropic displacement parameters for non-H atoms using SHELXTL.16b The hydrogen atoms of the water molecules and organic groups involving hydrogen bonding are located from the difference maps, and the other hydrogen atoms were generated geometrically (C-H, 0.96 Å; N-H, 0.90 Å) for 1-4. The structural plots were drawn using SHELXTL and Mercury.17

Results and Discussion Crystallizations of MA and different aromatic carboxylic acids were carried out in a 2:3 or 1:1 ratio, considering the number of hydrogen-bonding donor/ acceptor groups in each component. Crystal data and hydrogen bond metrics are listed in Tables 1-3. In the four structures, each MA is monoprotonated, leading to a slight enhancement of the internal angles at N7 [C15N7-C17 118.6(3)°] and N13 [C18-N13-C20 119.2(3)°] for 1, N6 [C1-N6-C3 118.5(1)°] for 2, N1 [C1-N1-C3 119.8(2)°] for 3, and N2 [C11-N2-C12 122.8(2)°] for 4, as compared with the neutral MA (116 and 117°).18 The schematic representations of the different types of hydrogen-bonding synthons observed in this work are summarized in Scheme 1. Almost in all cocrystals, the carboxylic protons are frequently transferred to aromatic nitrogen atoms of MA, furnishing a pair of N-H‚‚‚O hydrogen bonds with a graph set R22(8), as shown in Scheme 1III, which is one of the 24 most frequently observed bimolecular cyclic hydrogen-bonded synthons in organic crystal structures.19,20 With the coexistence of synthons III and other hydrogen-bonding patterns, the organic molecules are self-organized into various hydrogen-bonded molecular architectures (14). All of the amino hydrogen atoms of HMA+ participate in the hydrogen-bonding interactions in 1-4. Basepairing patterns synthon II (1-3) involving N-H‚‚‚N hydrogen bonds have been found in the crystal structures of many MA complexes.12-14 In the crystal structure of 1, the DNBA molecules are approximately coplanar with the MA molecules [dihe-

Cocrystals of Melamine and Aromatic Carboxylic Acids Table 2. Hydrogen Bond Metrics compound 1

2

3

4

D-H‚‚‚A (Å)

D‚‚‚A (Å)

H‚‚‚A (Å)

D-H‚‚‚A (Å)

N7-H7N‚‚‚O9a N8-H8A‚‚‚O1 N8-H8B‚‚‚O10b N9-H9B‚‚‚N12c N10-H10A‚‚‚O4d N13-H13N‚‚‚O2 N14-H14A‚‚‚O10e N14-H14B‚‚‚O1 N15-H15A‚‚‚O7f N16-H16B‚‚‚N6g N9-H9B‚‚‚N12h C6-H6‚‚‚O12i C13-H13‚‚‚O5j N1-H1A‚‚‚O1Wk N6-H6A‚‚‚O1 N5-H5A‚‚‚O1Wl N5-H5B‚‚‚O2 N1-H1B‚‚‚O2m N3-H3A‚‚‚N4n O1W-H1WA‚‚‚O2g O1W-H1WB‚‚‚O1l C6-H6‚‚‚N2o N3-H3A‚‚‚N4p N1-H1A‚‚‚O4 N6-H6A‚‚‚O5q O2W‚‚‚O4 N5-H5B‚‚‚O3 N1-H1A‚‚‚O4 N6-H6A‚‚‚O5q O6-H6‚‚‚N2 O2-H2‚‚‚O3r C6-H5C‚‚‚O2s N1-H1A‚‚‚O1W N1-H1B‚‚‚O5 N2-H2A‚‚‚O5 N2-H2A‚‚‚O6 N3-H3A‚‚‚O6 N5-H5B‚‚‚O6t N5-H5B‚‚‚O5t O1W-H1WA‚‚‚O2u N1-H1B‚‚‚N4v N4-H4A‚‚‚N1w N3-H3B‚‚‚O5x O1-H1C‚‚‚O6y N5-H5B‚‚‚O4 N5-H5C‚‚‚O4

2.654(3) 2.836(4) 2.762(4) 3.043(4) 3.059(3) 2.671(3) 2.800(4) 2.819(4) 2.878(4) 3.002(4) 3.043(4) 3.426(4) 3.382(4) 3.048(2) 2.711(2) 2.958(2) 2.808(2) 2.887(2) 3.053(2) 2.892(2) 2.730(2) 3.643(2) 2.879(3) 2.726(3) 2.912(4) 2.691(3) 2.879(3) 2.726(3) 2.912(4) 2.677(3) 2.609(3) 3.138(2) 2.683(3) 3.069(2) 2.790(2) 3.075(2) 3.041(2) 3.040(3) 3.035(2) 2.753(3) 3.329(2) 3.329(2) 3.332(2) 2.490(3) 2.941(2) 2.941(2)

1.81 2.11 1.91 2.18 2.72 1.82 1.99 1.96 2.44 2.15 2.18 2.56 2.50 2.17 1.73 2.14 1.85 2.07 2.23 2.05 1.84 2.68 1.79 1.84 2.02 1.86 1.79 1.84 2.02 1.87 1.71 2.29 1.81 2.39 1.95 2.33 2.22 2.17 2.43 1.92 2.64 2.62 2.43 1.66 2.65 2.63

169 142 174 176 105 175 155 176 112 171 176 156 158 166 176 151 178 158 173 161 169 164 166 176 168 155 166 176 168 172 170 151 162 132 155 141 152 163 125 166 135 136 174 167 100 101

Crystal Growth & Design, Vol. 5, No. 2, 2005 619 Table 3. Selected Bond Lengths and Angles Associated with the Helical Water Chain in 3 (D, Donor Atom; A, Acceptor Atom) D-H‚‚‚A

D‚‚‚A (Å)

H‚‚‚A (Å)

D-H‚‚‚A (°)

O3W-H3WB‚‚‚O1Wa O1Wa-H1WB‚‚‚O2W O2W-H2WA‚‚‚O3W N5-H5A‚‚‚O1Wa O1Wa-H1WA‚‚‚O1a N4-H4HG‚‚‚O2W O2W-H2WB‚‚‚O4 O3W-H3WA‚‚‚O5 N4-H4B‚‚‚O3W

2.803(2) 2.805(4) 2.828(4) 2.963(4) 2.772(2) 2.874(2) 2.690(2) 2.793(2) 2.903(2)

2.12 1.98 1.85 2.18 2.12 1.96 1.85 1.93 2.19

159 171 159 130 154 167 154 163 144

a

Symmetry codes: x, y, -1 + z.

Scheme 1.

Hydrogen Bond Synthons in 1-4

a x + 1, -y + 2, -z + 1. b x - 1, y, z - 1. c -x + 1, -y + 2, -z + 1. d -1 + x, 1 + y, z. e -x + 1, -y + 2, -z + 1. f -x + 1, -y + 1. g -x, -y + 1, -z + 1. h -x + 1, y, -1 + z. i 1 - x, 1 - y, -z. j -x + 1, -y + 1, -z + 1. k -x, y + 1/2, -z + 1/2. l x + 1, -y + 3/2, z + 1/2. m -x, -y + 2. n -x + 1. o -1 + x, 1.5 - y, -1/2 + z. p -y + 1, -z + 1. q x, y - 1, z - 1. r -x + 1, -y + 1, -z + 1. s 1 - x, 1 - y, 1 - z. t -x + 2, y + 1/2. u -z + 1/2, x + 1. v x, -y + 1/2, z + 1/2, x. w -y + 1/2, z - 1/2. x x, -y + 1/2, z - 1/2. y -x + 1, y + 1/2.

dral angle 10.4(2)°]. A pair of adjacent DNBA- anions form a pair of C-H‚‚‚O hydrogen bonds [synthon I; C‚‚‚O 3.382(2), 3.426(2) Å], similar to those observed in the DNBP-urea complex (DNBP ) 4,4′-dinitrobiphenyl).21 Meanwhile, two adjacent MAH+ ions are paired by two N-H‚‚‚N hydrogen bonds [synthon II, N‚‚‚N 3.002(4), 3.043(4) Å], similar to those observed in TMPsorbate, TMP-o-nitrobenzoate complexes (TMP ) trimethoprim).19 Such pairs of DNBA- and MAH+ ions are interconnected alternatively by two N-H‚‚‚O(C) hydrogen bonds [synthon III; N13‚‚‚O2 2.671(3), N14‚‚‚O1 2.819(4) Å] between the protonated aromatic/amino nitrogen atoms of MA and the carboxylate oxygen atoms, as well as two N-H‚‚‚O(N) hydrogen bonds [synthon V; N7‚‚‚O9 2.654(3), N8‚‚‚O10 2.762(4) Å]

between the protonated aromatic/amino nitrogen atoms of MA and the nitryl oxygen atoms to form an undulate chain running along the b-axis. Adjacent chains are hydrogen-bonded through the amino group to nitryl oxygen atoms [N14‚‚‚O10 2.800(4), N10‚‚‚O4 3.059(4) Å] and amino group to carboxylate oxygen atoms [N8‚‚‚O1 2.836(4), N15‚‚‚O7 2.878(4) Å] into a 2D grid (Figure 1). No significant void is found in the network of 1. There are strong π‚‚‚π stacking interactions [3.340(3) Å] between the DNBA molecules, which are found to consolidate the 3D structure in 1. The study of TGA

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Figure 1. Two-dimensional parquet framework of 1.

Figure 2. Hydrogen-bonded 2D net in 2 viewed along the b-axis.

suggests that the host framework of 1 remains stable below 250 °C. In the structure of 2, a pair of MAH+ ions is dimerized through two N-H‚‚‚N hydrogen bonds [synthon II, N‚‚‚N, 3.053(2) Å], similar to those found in 1. Two carboxylate groups of a TPA anion are each doubly hydrogen-bonded to an adjacent MAH+ ion [synthon III, N6‚‚‚O1 2.711(2), N5‚‚‚O2 2.808(2) Å], also similar to those found in 1, resulting in the formation of hydrogenbonded supramolecular undulated chains running along the b-axis (Figure 2). Furthermore, each MAH+ ion is associated by two hydrogen bonds [synthon IV, N1‚‚‚O2 2.887(2) Å, C6‚‚‚N2 3.643(2) Å] with a TPA2- anion from an adjacent chain, furnishing slightly undulated 2D layers parallel to the crystallographic (112) plane in the lattice. In the layer, there are small and irregular cavities, each accommodating a water molecule. The water molecule forms one donor hydrogen bond [O1W‚‚‚O1

Zhang and Chen

2.730(2) Å] to a carboxylate oxygen atom of TPA2- ion and two acceptor hydrogen bonds [N5‚‚‚O1W 2.958(2), N1‚‚‚O1W 3.048(2) Å] with two MAH+ ions. Finally, hydrogen bonds [O1W‚‚‚O2 2.892(2) Å] between the water molecules and TPA carboxylate groups and π-π stacking interactions [3.361(2) Å] between MA and TPA generate the 3D structure in the solid. Because of the offset stacking, no channel is found in the 3D structure of 2. The TGA measurement of 2 shows a weight loss of 8.1% in the temperature range 23-171 °C, which corresponds to the loss of lattice water molecules (theoretical value of 7.9%), and the host framework remains stable up to 202 °C. In 3, both MA and TMA molecules involve extensive hydrogen bonds. Each pair of MAH+ ions is doubly N-H‚‚‚N hydrogen bonded [synthon II, N‚‚‚N 2.879(3) Å] into a dimer, while each pair of H2TMA- ions is also associated by two O-H‚‚‚O bonds between a pair of carboxylate groups [syn and anti configurations, respectively, O‚‚‚O 2.609(3) Å] and two weak C-H‚‚‚O bonds [3.138(2) Å], giving rise to a new synthon VI (Scheme 1). Each H2TMA- anion utilizes another carboxylate group to form two N-H‚‚‚O hydrogen bonds with an MAH+ ion from an adjacent MAH+ dimer, resulting in hydrogen-bonded chains, which are further extended into a sheet parallel to the crystallographic (211) plane through double hydrogen bonds [N6‚‚‚O5 2.912(4), O6‚‚‚N2 2.677(3) Å] between each H2TMA- and MAH+ ion from neighboring chains. The honeycomb grid of 3 consists of two kinds of hourglass-shaped cavities, one composed of four MAH+ cations and two H2TMAanions, while another consists of two MAH+ cations and four H2TMA- anions. Each cavity is occupied by two water molecules: each of them accepts one hydrogen bond from the MAH+ and donates another one to a H2TMA- carboxyl group [N‚‚‚O 2.874(2), 2.903(2), 2.963(4), O‚‚‚O 2.690(2), 2.730(2), 2.793(3) Å] (Figure 3a). These sheets are stacked into a 3D structure exhibiting micropores (atom-to-atom distances 9.2 Å × 5.5 Å or 8.1 Å × 5.5 Å) in the lattice (Figure 3b) through the strong, offset π-π stacking interactions (ca. 3.37 Å) between TMA-TMA, TMA-MA, and MA-MA from adjacent layers, and pores occupy 18.7% of the crystal volume in 3. Interestingly, the water molecules are interconnected by a single hydrogen bond between two neighboring ones [synthon VII, O‚‚‚O 2.803(2)-2.828(4) Å] into helical chains; a pair of such 1:1 left- and right-handed helices exists in each channel running along the a-axis (Figure 3c). The formation of these helical water chains may apparently be attributed to the fact that the host layers are packed in an ABAB fashion with the channels formed with alternatively different neighboring cavities in the host of 3. Similar helical 1D water chains have recently been reported in the crystal structure of a dicopper(II) complex containing pentadentate Schiff base and p-hydroxycinnamate.22 Although the water molecules are hydrogen bonded to the organic framework in 3, the TGA study (Figure 4) shows a weight loss of 13.0% in the temperature range 23-175 °C, which is close to the theoretical value of 13.8% for the loss of water molecules, and the TGA curve implies that the host framework remains stable below 270 °C, upon removing the water molecules.

Cocrystals of Melamine and Aromatic Carboxylic Acids

Crystal Growth & Design, Vol. 5, No. 2, 2005 621

Figure 4. Thermogravimetric diagram of 3.

Figure 5. Water molecule-bridged chain of MA and BTA-M running along the a-axis (a), hydrogen-bonded helical HBTAM- chains (b), and HBTA-M-/MAH+ chains running along the b-axis (c), as well as a space-filling model of the 3D network in 4 (d). Figure 3. Views of the hydrogen-bonded sheet (a) and molecular packing showing micropores (b) viewed along the a-axis, as well as the left- and right-handed helical water chains (c) in 3.

The reaction of MA and BTA in 1:1 ratio under reflux somewhat unexpectedly led to regioselective esterification of the 1-carboxylic group of BTA in a high yield, resulting in the formation of 4. In 4, each MAH+ is

hydrogen bonded to a HBTA-M- [N2‚‚‚O5 2.790(2) Å], and such pairs of molecules are bridged by water molecules through hydrogen bond [O1W‚‚‚O2 2.753(3), N1‚‚‚O1W 2.683(3) Å] into an undulated 1D chain along the a-axis (Figure 5a). As the 1-carboxylate group [O(5)-C(3)-O(6)] is noncoplanar [twisted by 70.6(3)° to the phenyl plane]23 with the phenyl ring in HBTA-M-, it is singly hydrogen bonded to another carboxylic group

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from an adjacent HBTA-M- [synthon VIII, O1‚‚‚O6 2.491(3) Å], generating helical chains along the b-axis, as shown in Figure 5b. It is worthy of note that the 1-carboxylate group forms three hydrogen bonds with an adjacent MAH+ ion, including two N-H‚‚‚O [N1‚‚‚O5 3.069(2), N3‚‚‚O6 3.041(2) Å] and one N-H‚‚‚O [N2‚‚‚O5 2.790(2), N2‚‚‚O6 3.075(2) Å] tricentered hydrogen bonds (Scheme 1, IX). The carbonyl group of the 2-carboxylate accepts two hydrogen atoms of an amino group from another MAH+ ion [N5‚‚‚O4 2.941(2), H5B‚‚‚O4 2.650(3), H5C‚‚‚O4 2.634(2) Å]. Alternative connections through these hydrogen bonds, HBTA-M- and MAH+ ions [interplanar angle 54.2(2)°], are assembled into helical chains (Figure 5c). The three kinds of 1D chains are intersected to form the final 3D structure (Figure 5d). The lattice water molecule is hydrogen bonded to an amino group [N1‚‚‚O1W 2.683(3) Å] and a carbonyl group [O1W‚‚‚O2 2.753(3) Å] in a cavity of the hydrogenbonded network. No significant channel is observed. The TGA measurement shows a weight loss of 4.4% in the temperature range 23-81 °C, which is close the theoretical value of 4.8% for the loss of water molecules. The carboxylic acid decomposed in the temperature range 81-140 °C. Conclusion Upon self-recognition, four new MA-carboxylic acid cocrystals are formed, which exhibit interesting hydrogenbonding patterns and layer structures in common. The hydrogen-bonding patterns include the commonly observed synthons such as synthons II-V and VII, the less commonly observed synthons such as those involving C-H‚‚‚O(N) (synthons I and IV), and the most unusual synthon involving triple hydrogen bonds between a MAH+ ion and a carboxylate group (synthon IX). The results demonstrate that the main driving forces in the formation of the final 3D structures are hydrogenbonding and π-π stacking interactions. Aside from the frameworks of organic hosts, the most interesting feature is a thermal stable 1D porous structure observed in 3, which hosts unusual helical water chains. Acknowledgment. We thank the National Natural Science Foundation of China (Grant 20131020), Sun Yat-Sen University, and the Guangdong Institute of Education for supporting this work.

Zhang and Chen Supporting Information Available: Three X-ray crystallographic files in CIF format. This material is available free of charge via the Internet at http://pubs.acs.org.

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