Journal of Molecular Structure 985 (2011) 361370

Contents lists available at ScienceDirect

Journal of Molecular Structure

journal homepage: www.elsevier.com/locate/molstruc

Hydrogen bonded binary molecular adducts derived from exobidentate N-donor ligand with dicarboxylic acids: Acid imidazole hydrogen-bonding interactions in neutral and ionic heterosynthons
Amal Cherian Kathalikkattil, Subin Damodaran, Kamal Kumar Bisht, Eringathodi Suresh
Analytical Science Discipline, Central Salt and Marine Chemicals Research Institute, Council of Scientic and Industrial Research (CSIR), G.B. Marg, Bhavnagar 364 002, Gujarat, India

a r t i c l e

i n f o

a b s t r a c t
Four new binary molecular compounds between a exible exobidentate N-heterocycle and a series of dicarboxylic acids have been synthesized. The N-donor 1,4-bis(imidazol-1-ylmethyl)benzene (bix) was reacted with exible and rigid dicarboxylic acids viz., cyclohexane-1,4-dicarboxylic acid (H2chdc), naphthalene-1,4-dicarboxylic acid (H2npdc) and 1H-pyrazole-3,5-dicarboxylic acid (H2pzdc), generating four binary molecular complexes. X-ray crystallographic investigation of the molecular adducts revealed the primary intermolecular interactions carboxylic acid amine (via OH N) as well as carboxylate protonated amine (via NH+ O) within the binary compounds, generating layered and twodimensional sheet type H-bonded networks involving secondary weak interactions (CH O) including the solvent of crystallization. Depending on the differences in pKa values of the selected base/acid (DpKa), diverse H-bonded supramolecular assemblies could be premeditated. This study demonstrates the Hbonding interactions between imidazole/imidazolium cation and carboxylic acid/carboxylate anion in providing sufcient driving force for the directed assembly of binary molecular complexes. In the twocomponent solid form of hetero synthons involving bix and dicarboxylic acid, only H2chdc exist as cocrystal with bix, while all the other three compounds crystallized exclusively as salt, in agreement with the DpKa values predicted for the formation of salts/cocrystals from the base and acid used in the synthesis of supramolecular solids. 2010 Elsevier B.V. All rights reserved.

Article history: Received 2 October 2010 Accepted 10 November 2010 Available online 16 November 2010 Keywords: Cocrystal Organic salt Supramolecular assembly Hydrogen bond Molecular adduct pKa values

1. Introduction Crystal engineering offers a rational approach to the design of materials with new compositions, properties and crystal structures. Much as an organic chemist employs the covalent bond in the design of target molecules, non-covalent bonds can be exploited in the design of supramolecular assemblies [1,2]. Such non-covalent interactions include hydrogen bonding, van der Waals, pp stacking, and electrostatic interactions. These kind of molecular interactions could be utilized in designing cocrystals, solvates, organic salts, polymorphs and pseudopolymorphs, etc. [37], out of which cocrystals are of widespread interest. Cocrystal [810], also referred to as molecular complex, is a homogeneous phase of two or more different components in a stoichiometric composition, and often relies on hydrogen bonded assemblies between neutral molecules. Strong and directional hydrogen bonds have been used in rational strategies to design binary/ternary cocrystals in crystal engineering, materials science,
Corresponding author. Tel.: +91 278 2567760x662/667 (ofce), +91 278 2565006 (residence), moblie: +91 9426910756; fax: +91 278 2567562. E-mail addresses: esuresh@csmcri.org, sureshe123@rediffmail.com (E. Suresh).
0022-2860/$ - see front matter 2010 Elsevier B.V. All rights reserved. doi:10.1016/j.molstruc.2010.11.022

hostguest inclusion compounds, and pharmaceutical solids [11]. Understanding of highly specic and mutually complementary non-covalent interactions between molecules is the basic aspect in molecular recognition, cocrystallization and supramolecular synthetic chemistry [12]. By the judicious choice of the supramolecular synthons with specic and directional non-covalent connectivity, multidimensional solid state assembly can be generated by the effective close packing of the discrete building blocks [1315]. Among all the non-bonded interactions, hydrogen bonding has proved to be the most useful and reliable because of its strength and directional properties [16]. Many molecular solids with novel properties have been prepared using hydrogen bonding as the main steering force [1719]. Molecular cocrystals have been known for a long time, still there is wide scope for further applications and structural studies in this eld. In recent years, many premeditated synthesis of binary and ternary cocrystals [2024] have been reported. Variety of cocrystals with multidimensional topology, based on hydrogen bonded networks can be achieved when a N-heterocycle moiety is allowed to interact with a suitable carboxylic acid [14,25]. The ability of carboxylic acids to readily aggregate through the dimer homosynthon have been observed traditionally in structural chemistry.

362

A.C. Kathalikkattil et al. / Journal of Molecular Structure 985 (2011) 361370

Conformationally exible ligand 4-bis(imidazol-1-ylmethyl)benzene (bix) has been proved as a suitable building block for designing the coordination polymers of various network topology. It has been employed to fabricate a large number of coordination polymers with a variety of structural diversity from low dimensional entities such as 1D helix, linear threads to high-dimensional supramolecular networks such as 3D interpenetrated networks, metal organic polyrotaxanes; brick-wall type networks, chiral and magnetic MetalOrganic Frameworks. These fascinating structures hold promising applications in the area of non linear optical properties, magnetic properties, gas adsorption ability and catalytic properties [2632]. Herein, we report synthesis, characterization by various physicochemical methods and a systematic structural examination of the cocrystal/salt resulted from cocrystallization between exobidentate N-heterocycle ligand 1,4-bis(imidazol-1-ylmethyl)benzene (bix) and a series of rigid and exible dicarboxylic ligands such as cyclohexane-1,4-dicarboxylic acid (H2chdc), naphthalene-1,4-dicarboxylic acid (H2npdc) and 1H-pyrazole-3,5-dicarboxylic acid (H2pzdc). The related primary intermolecular carboxylic acid amine (OH N)/carboxylate protonated amine (NH+ O) interactions and secondary weak molecular interactions including stacking have been investigated by crystallography on these binary cocrystals or organic salts in their supramolecular arrangement. 2. Experimental 2.1. Materials All the chemicals were purchased from Sigma Aldrich, USA and used without any further purication. All solvents were freshly puried by general distillation process and used as and when required. 2.2. IR, NMR, CHNS and TGA measurements IR spectra were recorded using KBr pellets on a PerkinElmer GX FTIR spectrometer. For each IR spectra 10 scans were recorded at 4 cm1 resolution. 1H NMR spectra for the compounds were recorded on Bruker AX 500 spectrometer (500 MHz) at temperature 25 C. 1H NMR Spectra was calibrated with respect to TMS and TMS was used as an internal reference for solvents such as d6-DMSO. Elemental analysis (CHNS estimation) was done by using the instrument PerkinElmer 2400 CHNS/O analyzer. All the TGA spectra were recorded on METTLER TOLEDO STAR SW 7.01. 2.3. X-ray crystallography The crystallographic data and details of data collection for all the four compounds are given in supplementary information (Table S1). In each case, a crystal of suitable size was selected from the mother liquor and then mounted on the tip of a glass ber and cemented using epoxy resin. Intensity data for all the six crystals were collected using Mo Ka (k = 0.71073 ) radiation on a Bruker SMART APEX diffractometer equipped with CCD area detector either at 293 K or at 100 K. The data integration and reduction were processed with SAINT [33] software. An empirical absorption correction was applied to the collected reections with SADABS [34]. The structures were solved by direct methods using SHELXTL [35] and were rened on F2 by the full-matrix least-squares technique using the SHELXL-97 [36] package. In all compounds all non-hydrogen atoms were rened anisotropically till convergence is reached. Hydrogen atoms attached to the ligand moieties are either located from the difference Fourier map or stereochemically xed. The diagrams of the crystal structures are generated using

programs ORTEP [37], Mercury 1.4.1 [38] or PLATON [39]. ORTEP diagrams of all four compounds are shown in Fig. 2, and structural drawings of the adducts for better understanding and clarity are incorporated in Supplementary material as Fig. S2. Relevant crystallographic data and selected bond lengths for the molecular adducts are given in Supplementary material as Tables S1 and S2 respectively. Hydrogen bonding interaction with symmetry code and pKa value data for all four compounds are listed in Table 1 and Table 2 respectively. 2.4. Synthesis of the N-donor ligand 1,4-Bis(imidazol-1-ylmethyl)benzene (bix) was synthesized by following a procedure reported by Abrahams et al. [40]. Re-crystallization of the crude product by dissolving in hot water and keeping at constant temperature 23 C yielded white crystalline material. The detailed synthetic procedure for the preparation of ligand bix and its proton NMR spectra is given in Supplementary data as S1 and Fig. S3 respectively. 2.4.1. 1H NMR data for bix d = 5.163(s, 4H; methylene), 6.885(s, 2H; imidazole), 7.715(s, 2H; imidazole), 7.231(s, 4H; aryl ring), 7.731(s, 2H; imidazole) CHN data for bix: calculated (%): C = 61.29; H = 5.15; N = 20.45. Observed (%): C = 60.3; H = 6.21; N = 19.63. IR spectral data: (mmax (cm1)) 3438(b), 3108(m), 2553(w), 2949(m), 1677(m), 1602(w), 1512(s), 1444(s), 1281(s), 1228(s), 1104(m), 1081(s), 1029(m), 919(s), 828(m), 767(m), 708 (m), 665(m). 2.5. Synthesis of molecular complexes 2.5.1. Bix:H2chdc (CC1) Bix (0.272 g, 1 mmol) and H2chdc (0.172 g, 1 mmol) was dissolved separately in 5 ml methanol each and mixed gradually with constant stirring at room temperature in 1 h duration. Five milliliters water was then added to this solution and continued stirring for another three more hours. The clear colorless solution obtained was kept at room temperature for 1 week to get crystals suitable

Fig. 1. NMR spectra of CC1, CC2, CC3, CC4 in d6-DMSO solvent. The spectra of bix and used dicarboxylic acids are also presented for assessment of signals.

A.C. Kathalikkattil et al. / Journal of Molecular Structure 985 (2011) 361370

363

Fig. 2. ORTEP diagrams a, b, c, and d for the compounds, CC1, CC2, CC3 and CC4 respectively (the thermal ellipsoids are drawn with 50% probability factor).

for crystallographic studies. Melting point: 195197 C. 1H NMR data for CC1: d = 1.3161.885 (multiplet, 10H, cyclohexane ring), 5.164 (s, 4H; methylene-bix), 6.888 (s, 2H; imidazole ring), 7.159(s, 2H; imidazole ring), 7.231(s, 4H; aryl ring), 7.736(s, 2H; imidazole ring) CHN data: Calculated values (%): C = 64.4; H = 6.4; N = 13.66. Observed values (%): C = 64.44; H = 5.98; N = 13.19. IR spectral data: (mmax (cm1)) 3135(s), 2952(s), 2859(s), 1695(m), 1513(s), 1441(s), 1397(w), 1296(s), 1083(s), 819(w), 741(w), 653(m), 615(s), 571(m), 491(s). CCDC number for the compound: CCDC 746435. 2.5.2. H2bix:(Hnpdc)26H2O (CC2) A solution containing bix (0.272 g, 1 mmol) in 5 ml methanol was added slowly to H2npdc (0.2162 g, 1 mmol) in 25 ml methanol and stirred at room temperature for 2 h. The light orange solution obtained was ltered and upon slow evaporation at room temperature yielded yellow micro-crystals. These micro-crystals were dissolved in methanol water mixture (15 ml and 5 ml respectively) with gentle warming. The solution was ltered and upon slow evaporation at room temperature yielded crystals suitable for Crystallographic studies. Melting point: 183185 C; 1H NMR data for CC2: d = 5.182 (s, 4H; methylene-bix), {7.223(s), 7.685(s), 8.121(s), 8.814(s), 4.373(s); 22H} CHN data: Calculated (%): C = 58.63; H = 5.45; N = 7.19. Observed (%): C = 59.97; H = 5.39; N = 6.92. IR spectral data: (mmax (cm1)) 3410(br), 3111(s), 1692(s), 1512 (m), 1448(w), 1395(w), 1227(m), 1082(m), 873(m), 824(m), 753(s), 658(m), 612(m), 537 (m). CCDC number for the compound: CCDC 746434. 2.5.3. H2bix:(Hpzdc)22H2O and H2bix:pzdc2H2O (CC3 and CC4) To a solution containing bix (0.272 g, 1 mmol) in 5 ml methanol was added 3,5-pyrazole dicarboxylic acid (0.1742 g, 1 mmol) dissolved in 5 ml ethanol with constant stirring. This was followed by slow addition of 5 ml water and the solution was stirred at room

temperature for 3 h to get clear solution. Slow evaporation of this ltered solution kept at room temperature gave microcrystalline material within a weeks time. Re-crystallization of this microcrystalline material by dissolving in hot water followed by slow evaporation resulted in two types of crystals with different morphology, viz., diamond and plate shapes named as CC3 and CC4 respectively. The optical snap-shots of CC3 and CC4 are given in Supplementary data Fig. S5. 2.5.3.1. Melting point (CC3). 230232 C, CHN (CC3): Calculated values (%): C = 49.14; H = 4.47; N = 19.11. Observed values (%): C = 50.02; H = 5.01; N = 18.98; 1H NMR data (CC3): d = 5.189 (s, 4H; methylene-bix); 6.969 (s), 7.071 (s), 7.252 (s), 7.874(s), (12H, aromatic) IR spectral data (CC3): (mmax(cm1))); 3424 (br), 3189(s), 3135(s), 3036(m), 1658(m), 1597(s), 1539(s), 1443(m), 1339(s), 1275(m), 1188(m), 858(m), 799(s), 765(m), 636(w), 527(w) CCDC number for CC3: CCDC 746437. 2.5.3.2. Melting point (CC4). 202205 C, CHN (CC4): Calculated values (%): C = 55.33; H = 4.89; N = 20.38. Observed values (%): C = 54.22; H = 5.32; N = 19.98. 2.5.3.3. NMR data (CC4). d = 5.180 (s, 4H; methylene-bix); 6.942 (s), 7.054 (s), 7.244 (s), 7.823 (s), (11H, aromatic) IR spectral data (CC4): (mmax (cm1)) 3421(br), 3188(s), 3136(s), 3103(s), 3037(m), 1652(m), 1597(s), 1542(m), 1445(m), 1340(s), 1275(m), 1188(m), 1102(s), 799(m), 763(s); 637(w), 522(w). CCDC number for CC4: CCDC 746436. 3. Results and discussion Reliability of the COOH Im and COO Him+ synthons in the presence of potential weak intermolecular interactions such as

364

A.C. Kathalikkattil et al. / Journal of Molecular Structure 985 (2011) 361370

Table 1 Hydrogen bonding interactions in CC1, CC2, CC3 and CC4. Compound CC1 DH A O(1)H(1C) N(2) C(3)H(3) O(2)2 C(4)H(4B) O(2)2
1

d(H A) () 1.70 2.56(4) 2.49(4)

d(D A) () 2.663(4) 3.287(5) 3.344(4)

\DHA () 172 134(3) 141(3)

Symmetry code: (1) 1 x, 1 y, z; (2) x, 1 y, z CC2 N(2)H(2A) O(2)1 O(3)H(3C) O(7)2 O(5)H(5C) O(6)3 O(5)H(5D) O(7)4 O(6)H(6C) O(5)4 O(6)H(6D) O(1)5 O(7)H(7C) O(2)6 O(7)H(7D) O(1)7 C(3)H(3) O(5)8 C(4)H(4B) O(4)9 C(13)H(13) O(4)10 C(14)H(14) O(6)11 C(16)H(16) O(2)10 1.71(5) 1.69(5) 1.89(5) 2.03(4) 1.97(3) 1.89(5) 1.89(4) 1.90(6) 2.33 2.46(3) 2.30(3) 2.58(3) 2.46(3) 2.668(3) 2.644(3) 2.805(4) 2.933(3) 2.828(4) 2.772(3) 2.735(3) 2.741(4) 3.184(4) 3.350(4) 2.918(4) 3.340(4) 3.026(4) 173(4) 167(4) 177(6) 172(4) 175(3) 173(4) 154(3) 171(5) 153 152(3) 120(3) 136(2) 119(2)

Symmetry code: (1) 1/2 + x, 3/2 y, 1/2 + z; (2) 1/2 x, 1/2 + y, 1/2 z; (3) 3/2 x, 1/2 + y, 1/2 z; (4) 1/2 + x, 1/2 y, 1/2 + z; (5) 1 x, 1 y, 1 z; (6) 1/2 x, 1/ 2 + y, 3/2 z; (7) 1 x, y, 1 z; (8) x, 1 y, 1 z; (9) 1/2 + x, 3/2 y, 1/2 + z; (10) x, y, z; (11) 1/2 + x, 1/2 y, 1/2 + z CC3 N(2)H(2C) N(3)1 O(2)H(2D) O(5)2 N(4)H(4C) O(4)3 O(5)H(5C) O(3)4 O(5)H(5D) O(3)5 C(1)H(1) O(1)4 C(3)H(3) O(4)6 C(6)H(6) O(1)4 C(7)H(7) O(3)6 1.73(6) 1.80 1.73(4) 1.65 2.16 2.41 2.29 2.47 2.57 2.816(5) 2.596(4) 2.688(5) 2.697(4) 2.886(4) 3.236(6) 3.056(5) 3.353(5) 3.465(5) 165(5) 163 163(3) 157 161 147 139 159 161

Symmetry code: (1) 1 + x, y, 1 + z; (2) x, y, 1 + z; (3) 1 x, y, z; (4) 1/2 + x, 1/2 y, 1/2 + z; (5) 1/2 + x, 1/2 y, 1/2 + z; (6) 2 x, y, 1 z CC4 N(2)H(2C) O(3)1 N(4)H(4C) O(2)2 N(5)H(5C) O(3)3 O(5)H(51) O(4)4 O(5)H(52) O(2)5 C(2)H(2) O(4)6 C(3)H(3) O(1)7 C(3)H(3) N(6)7 C(6)H(6) O(1)7 C(9)H(9) O(2)7 1.78(3) 1.44(4) 1.99(4) 1.98 1.99 2.56(4) 2.39(2) 2.34(2) 2.38(3) 2.38(3) 2.707(3) 2.562(3) 2.796(3) 2.845(3) 2.841(3) 3.317(4) 3.267(3) 3.100(3) 3.248(3) 3.359(3) 175(2) 176(3) 148(3) 173 163 138(3) 151.4(19) 135.6(18) 150(2) 171(2)

Symmetry code: (1) 1 + x, y, 1 + z; (2) x, y, z; (3) 2 x, 1 y, z; (4) 1 + x, y, z; (5)x, y, z; (6) 1 x, y, 1 z; (7) 1 x, 1 y, 1 z

Table 2 pKa values for the precursors of the salt/cocrystals. Salt/cocrystal former 1,4-Bis(imidazol-1-ylmethyl)benzene (base) trans-1,4-Cyclohexanedicarboxylic acid (CC1 precursor) 1,4-Naphthalenedicarboxylic acid (CC2 acid precursor) 1 H-pyrazole-3,5-dicarboxylic acid (CC3 and CC4 precursor) pK a 7.05 4.18 5.42 2.97 2.99 3.24

DpKa
2.87 1.63 4.08 10.04 3.81

p p stacking and interactions with solvent molecules has been exploited in the present investigation using ditopic N-donor ligand bix and dicarboxylic acids. The present system is chosen for a variety of reasons. (a) Ability of dicarboxylic acids to involve in O H N hydrogen bonding interaction with the imidazole nitrogens of the bix moiety. (b) Possibility to fabricate organic salts by the transfer of one or both protons from dicarboxylic acid to the imidazole nitrogens of the bix moiety, depending on DpKa values of the acid and bix used in the reaction via NH+ O interactions in the supramolecular assembly. When carboxylic acids interact with imidazole and closely related systems such as benzimidazole as a result of proton transfer, the solid-state outcome is often an

organic salt [4143]. Attempted reactions between bix with H2chdc and H2npdc resulted in CC1 and CC2 which are cocrystal and monocrboxylate salt of the corresponding acids. Two more molecular adducts (CC3 and CC4) were obtained from the same pot reaction between bix and H2pzdc with different acid/base stoichiometry. These adduct exhibit interesting combinations of acid to amine proton transfer. Characterization by various analytical methods such as CHN, NMR, IR and TGA has been carried out to establish the formation of the molecular adducts. Detailed structural investigations of all these four compounds revealed the molecular interactions in establishing the versatile supramolecular arrangement within the binary complexes. In this contribution, we have demonstrated the ability of carboxylic acid/carboxylate and amine/protonated amine functional groups exhibiting a variety of hydrogen bonding motifs involving two supramolecular hetero synthons and correlated the formation of the cocrystal/salt based on the DpKa values of the respective acid and base used in the reaction. Upon the basis of information extracted from the Cambridge Structural Database (CSD-2010 release) [44], when a carboxylic acid is allowed to react with a symmetric ditopic base such as bix, there are strong bias toward cocrystal formation, in preference to organic salts. Out of the ve total crystal structures retrieved from the CSD containing bix and carboxylic acid, four are cocrystals

A.C. Kathalikkattil et al. / Journal of Molecular Structure 985 (2011) 361370

365

involving dicarboxylic acid and the rest one is a 1:2 organic salt where the bix moiety is diprotonated due to the proton transfer from the sulphonic acid functionality and the carboxylic acid remains intact [45,46].

resonates at 7.7 ppm (singlet) remains almost intact even after adduct formation. The ratio of integral values for methylene proton to aromatic CH proton evidently indicates the stoichiometry bix:H2pzdc in CC3 and CC4 as 1:2 and 1:1 respectively. 5. Thermal analysis Thermogravimetric analysis for the compounds CC2, CC3, and CC4 which contains water molecules as solvent of crystallization was carried out on METTLER TOLEDO STAR SW 7.01 instrument under N2 ow in the temperature range 25400 C at a heating rate of 10 C/min. The observed data nds good match with the calculated ones and reveal that the salts CC2, CC3 and CC4 lose their lattice water nearby the boiling point of H2O and subsequently obtained anhydrous salts exhibit fairly thermal stability up to the temperatures as high as 250 C. In the case of CC2 a mass loss of 13.27% in the temperature range 30140 C (13.88% calculated value) corresponds to the loss of all lattice water molecules. The dehydrated compound remain intact up to 260 C temperature after that decomposition commences. For CC3 a weight loss of 5.24% between 100 and 220 C indicates the loss of two water molecules located in the lattice (calculated weight loss 6.14%). Decomposition of the CC3 starts at 270 C. In the case of CC4 a weight loss of 7.04% between 100 and 160 C corresponds to the removal of two water molecules in the lattice (calculated weight loss 8.37%). The adduct starts to decompose at 250 C. The TGA data for, CC2, CC3 and CC4 is given in Supplementary information (Fig. S4) which corroborate well with the structural data. 6. Crystal and molecular structure of bix:H2chdc (CC1) CC1 crystallizes in triclinic system with P-1 space group and the asymmetric unit of CC1 is composed of half a molecule each of bix and H2chdc as shown in Fig. 2a. In the 1:1 cocrystal no proton transfer has been occurred between the acid and the base which is reected in the bond distance involving C8 carboxylic acid group (C8O1 = 1.318(3) and C8O2 = 1.198(3) ) form the crystal structure (Table S2). Both bix and H2chdc molecules possesses center of symmetry at the mid-point of the phenyl and cyclohexane rings respectively. Expected primary OH N hydrogen bond is coined between the N-donor ligand and the exible dicarboxylic acid (from the OH group on the dicarboxylic acid with the imidazol-1-yl nitrogen atom) of the symmetrically disposed molecules from either side extending a one dimensional network oriented almost diagonal to ab-plane. This is further associated via CH p interaction between the imidazole ring of the symmetrically disposed bix and methyl hydrogen H4a (H4a Cg = 2.71 ) in the formation of two dimensional nets as depicted in Fig. 3a. Cocrystals incorporating bix with a series of both aliphatic and aromatic dicarboxylic acids is reported by Aakery et al. to understand the driving force for the directed assembly in a wide range of binary cocrystals shows similar pattern with OH N distance within the range reported in the present investigation [14]. In an attempt to understand the orientation and arrangement of the constituents within this cocrystal, secondary hydrogen-bonding interactions and packing mode have been analyzed in detail. Packing and hydrogen-bonding interactions of the cocrystal viewed down c-axis is given in Fig. 3b showing OH N hydrogen bonded layers of the cocrystal are oriented diagonal to ab-plane. In addition to the primary OH N interaction, secondary hydrogen bonding interaction involving H3 from the Imidazole ring and methylene hydrogen H4B from bix via bifurcated CH O contact with O2 of the carboxylic acid is also observed. Hence, the carbonyl oxygen O2 acting as an acceptor in a bifurcated CH O H-bonding to generate two-dimensional hydrogen bonded sheet like network

4. FTIR and proton NMR spectroscopic studies The adduct formation between bix and various dicarboxylic acids was explored by FTIR and proton NMR spectroscopy. 1H NMR Spectra for the constituents (bix and dicarboxylic acids) and the corresponding molecular adducts are shown in Fig. 1. High resolution proton NMR spectra of all adducts are also given in Supplementary data (Fig. S3). FTIR spectra of CC1 showed overtone bands ranging 18002500 cm1 indicating the presence of aromatic ring system supporting the presence of bix moiety in the adduct. Medium band at 1236 cm1 can be assigned to CN stretching of bix. Sharp peaks at 3135 and 1695 cm1 wavenumbers were assigned to OH and C@O stretching respectively from H2chdc. However, absence of the strong signal in the region around 3400 cm1 (for electron decient NH group) indicates the absence of proton transfer between acid and bix moieties in CC1. The supposition acquired from FTIR spectra are well supported by the 1H NMR data. The proton NMR spectra of CC1 in d6-DMSO shows no prominent change in chemical shifts of the constituents, i.e., the signals corresponding to bix and H2chdc moieties in CC1 appeared at the same positions that of the pure bix and pure H2chdc. This observation infers that the interaction between bix and H2chdc is very feeble and thus rules out the possibility of proton transfer as conrmed with the structural data. Moreover, integration of representative peaks suggests 1:1 stoichiometry of bix and H2chdc in the molecular adduct. The FTIR spectra of CC2 encompass a medium band at 3410 cm1 and a sharp bands at 1540 cm1 wavenumbers which can be attributed to NH stretch and bending vibrations of the electron decient heterocycles, apparently indicating bix is protonated in CC2. Peaks at 3111 cm1 and 1692 cm1 were assigned to OH stretch and C@O stretch of carboxylic acid (COOH) group respectively. Moreover, peak at 1620 cm1 along with shoulders around 1525 cm1 and 1570 cm1 can be attributed to the presence of carboxylate (COO) functionality inferring part of H2ndpc is in deprotonated form. In the 1H NMR spectra imidazole protons of bix were allocated at 7.71, 7.14 and 6.87 ppm; whereas in CC2 corresponding signals appeared downeld at 8.82, 8.12 and 7.67 ppm respectively. The considerable downeld shift of the imidazole protons clearly indicates the decrease in electron density on imidazole rings that suggest the proton transfer in adduct. Integration ratio of assigned peaks advocate 1:2 stoichiometry of bix and H2chdc in CC2. FTIR spectra of CC3 and CC4 include a medium band around 3425 cm1 and a sharp band at 1655 cm1. These two bands correspond to the NH stretch and bending in electron decient heterocycles signifying protonated bix in these molecular adducts. The sharp peaks at 3190 cm1 and 1658 cm1 observed for CC3 can be assigned to OH and C@O stretch of carboxylic acid (COOH) group respectively. The presence of carboxylate (COO) functionality can be inferred for both CC3 and CC4 by assigning peaks at 1600 cm1 (asym COO stretch) and 1540 cm1 (sym COO stretch) leading to the conclusion that CC3 and CC4 are molecular salts formed by the proton transfer between bix and H2pzdc. The proton NMR spectra of CC3 and CC4 are highly perturbed indicating strong interaction among the constituents. However, few protons particularly those are less likely to participate in hydrogen bonding are accountable when spectra was recorded for CC3 and CC4 in d6DMSO solvent. Thus methylene protons of bix resonating at 5.1 ppm (singlet) and the aromatic CH proton of H2pzdc that

366

A.C. Kathalikkattil et al. / Journal of Molecular Structure 985 (2011) 361370

Fig. 3. (a) Mercury diagram depicting the interaction between the bix and H2chdc in the formation of extended 2D supramolecular network in CC1; (b) packing diagram viewed down c-axis showing the diagonal orientation of the H-bonded cocrystal (bix-H2chdc) layer and the H-bonding interaction between these layers in the formation of two dimensional networks.

(Fig. 3b) linking the zigzag chain of heteromeric synthon between acid and bix. Details of all these pertinent hydrogen-bonding interactions with symmetry code is given in Table 1. In order to make effective OH N, CH O interactions with carboxylic acid the bix moiety has adopted the anti conformation in CC1. The mean plane angle between the symmetrically disposed imidazole moieties with the central phenyl ring is 80.05. Additional packing diagram with hydrogen bonding interaction viewed down b-axis for CC1 is given as Fig. S6 in Supplementary material. 7. Crystal and molecular structure of H2bix:(Hnpdc)26H2O (CC2) The asymmetric unit of CC2 consists of half portion of protonated bix moiety possessing center of symmetry at the mid-point of the aryl ring, one monoanionic 5-carboxynaphthalene-1-carboxylate (Hnpdc) along with three molecules of water as solvent of crystallization (Fig. 2b). N+H O interaction (N2 O2 = 2.668(3)) between the carboxylate oxygen O2 from Hnpdc and H2A of the protonated imidazole nitrogen from either side of the symmetrically disposed ditopic ligand create a trimeric supramolecular arrangement as shown in Fig. 4a.

The protonation of the imidazole nitrogen is reected in the 0 longer N2C3 bond (N2C3 = 1.331(4) A) compared to the free ligand [22]. The bond length of the carboxylate group indicate that carboxyl group0 involving C18 is 0 deprotonated (O(1) C(18) = 1.249(3) A, O(2)C(18) = 1.273(3) A) and C19 carboxyl 0 group is protonated (O(4)C(19) = 1.218(3) A , O(3)C(19) = 0 1.315(3) A) (Table S2) signifying the carboxylate ligand is in monoanionic from. The trimeric supramolecular units are oriented almost diagonal to ab-plane. The offset arrangement of the trimeric H-bonded moiety oriented along b-axis make effective stacking interaction between the protonated imidazole ring with the aryl ring of the Hnpdc with the stacking distance (3.678 and 3.436 ), between the centroids of the rings as depicted in Fig. 4b. It is interesting to note that all the three water molecules present in the asymmetric unit are involved in strong OH O hydrogen bonding interaction generating a zigzag one-dimensional water cluster involving O5 and O6 and a dangling water molecule O7 attached to O5 alternatively along b-axis as depicted in Fig. 4c. Thus, H6C from O6 is making contact with O5 and H5C from O5 is making contact with O6 with O O distances 2.828(4) and 2.805(4) and the corresponding OH O angles 175(3) and

A.C. Kathalikkattil et al. / Journal of Molecular Structure 985 (2011) 361370

367

trimeric species closer towards the stacking of the protonated imidazole ring with the phenyl moiety of the acid down b-axis. The binary salt aggregate via N+H O interaction regulate as supramolecular trimeric species is further involved in various inter and intramolecular OH O and CH O interactions with the one-dimensional water cluster in the formation of stable twodimensional hydrogen bonded network. Details of these various hydrogen-bonding interactions with symmetry code are given in Table 1.

8. Crystal and molecular structure of H2bix:(Hpzdc)22H2O (CC3) Re-crystallization of the microcrystalline material obtained by reaction between bix and H2pzdc dissolving in hot water followed by slow evaporation resulted in two types of crystals with different morphology (diamond shaped CC3 and plate shaped CC4 crystals, Fig. S5). Structure determination by X-ray diffraction methods revealed that the compound CC3 crystallized in monoclinic system with P21/n space group. The asymmetric unit of CC3 is composed of half a molecule of fully protonated bix moiety with the center of symmetry, one molecule of 5-carboxypyrazole-3-carboxylate in monoanionic form (Hpzdc) and water as solvent of crystallization with 1:2 ratio of H2bix and Hpzdc in the crystal lattice. As mentioned earlier the acidic component is monoanionic in CC3, in which one terminus remains as carboxylic acid (O(1) C(11) = 1.192(4) , O(2)C(11) = 1.326(4) while the other one exists as carboxylate (O(3)C(12) = 1.258(4) and O(4)C(12) = 1.238(4) ), which is obvious form the bond distances calculated from the X-ray diffraction studies. In the 1:2 salt imidazole nitrogen N2 of bix ligand is protonated which shows longer bond distance (N2C2 = 1.363(5) ) with the neighboring carbon. It is interesting to note that, the pyrazole monocarboxylates (Hpzdc) are associated as a centro-symmetric dimer by NH O interactions between the pyrazole hydrogen H4C and free carboxylate oxygen O4 (N4 O4 = 2.688(5) , \N4H4C O4 = 163(3)). Four pairs of such centro-symmetric dimers positioned at the corners of the rectangle are bridged via OH O interaction with four water molecules located at the center of the dimeric units generating rectangular grid (Fig. 5a) with dimensions 18.267 10.118 across the hydrogen bonded water molecules. Thus, water molecule O5 acts as both donor and acceptor in the OH O interaction in which H5C is making contact with the carboxylate oxygen O3 (O5 O3 = 2.697(4) , \O5H5C O3 = 157) and H2D of the carboxylic acid is involved in OH O interaction with O5 (O2 O5 = 2.596(4) , \O2H2D O5 = 163) from either side in the formation of the two dimensional rectangular grids which is translated along bc-plane. These two dimensional grids are further bridged via OH O hydrogen bonds from the water hydrogen H5D with carboxylate oxygen O3 of the adjacent 2-D grid layer down a-axis, generating a three dimensional hydrogen bonded network with through channels. It is remarkable that the protonated bix moiety is encapsulated within this channel by various hydrogen-bonding interactions as depicted in packing diagram viewed down a-axis Fig. 5b. Hence, the symmetrically disposed protonated imidazole nitrogen of the bix moiety is making N+ H N interaction (N(2) N(3) = 2.816(5) ; \N(2)H2C N(3) = 165(5)) with the pyrazole nitrogen of the carboxylate dimer at the corners of the hydrogen bonded rectangular grid by orienting almost diagonal to the rectangular channel. In addition to this N+H N interaction, CH O contacts do exist between imidazole hydrogens H1 and H3 from either ends of the symmetrically oriented H2bix as well as phenyl hydrogen H6 and H7 with the oxygen atoms of the carboxylate ligand O1, O4 and O1, O3 respectively in encapsulating the bix moiety strongly inside the rectangular cavity (Fig. S8). Details of all these pertinent hydrogen-bonding

Fig. 4. (a) Building blocks in CC2, H2bix and Hnpdc are linked via NH O interaction into a trimeric supermolecule; (b) stacking interaction between the protonated imidazole rings of the H2bix moiety and the aryl ring of the monocarboxylate Hnpdc anion in CC2; (c) hydrogen bonding interactions of the water molecules present in the asymmetric unit generating one-dimensional water cluster in CC2.

177(6) in building the zigzag water chain. The second hydrogen atom H5D from O5 further acts as a donor to attach the dangling water molecule O7 alternatively at a distance O5 O7 = 2.933(3) and \O5H5D O7 = 172(4) respectively. In an attempt to understand the interaction of the water cluster with the trimeric molecular adduct, we have analyzed the packing mode and hydrogen bonding interactions in detail. Packing diagram of the compound with various hydrogen-bonding interactions is depicted in Fig. S7. It is observed that the trimeric moiety is involved in various hydrogen-bonding interactions with the water cluster. Thus, the hydrogen atom H3C of the monoanionic carboxylic acid O3 of the symmetrically disposed trimeric supermolecule acts as a donor and is involved in OH O interaction with the dangling oxygen 0 of the water cluster O7 (O3 O7 = 2.644(3) A). H7C and H7D of the dangling water molecule O7 is involved in hydrogen bonding with the carboxylate oxygens of the acid O1 and O2 of the Hnpdc respectively. H6D which is not involved in the cluster formation is drawn in OH O contact with O1. Imidazole hydrogen H3 and the methylene hydrogen H4B is making intramolecular C H O contact with water oxygen O5 from the cluster and the carbonyl oxygen O4 of the acid moiety respectively. Hydrogen atoms H13, H14 and H16 of the naphthalene rings are involved in weak CH O interaction with O4, O6 and O2 respectively. The C H O contact between methylene hydrogen H4B of the bix moiety with the O4 of the acid described above is effective in bringing the

368

A.C. Kathalikkattil et al. / Journal of Molecular Structure 985 (2011) 361370

Fig. 5. (a) Ball and stick representations of the rectangular hydrogen bonded grids in which the H2bix moiety is encapsulated; (b) packing diagram of CC3 with various hydrogen bonding interaction viewed down a-axis showing the hydrogen bonded rectangular grids with encapsulation of the H2bix in the two dimensional network.

interactions with symmetry code is given in the Table 1. The driving force in the cavity containing supramolecular assembly is the dimeric association of the 5-carboxypyrazole-3-carboxylate in the formation of the rectangular grids with lattice water molecules and the association of the H2bix in the grids by N+H N and C H O interactions rather than the expected N+H O contacts between the heterosynthons. 9. Crystal and molecular structure of H2bix:pzdc2H2O (CC4)

system with P-1 space group and the crystal structure of the compound revealed that complete proton transfer has been occurred from the acid to the bix moiety resulting an 1:1 organic salt. The asymmetric unit of the salt is constituted by two half bix moieties both possessing a center of symmetry at the mid-point of the phenyl ring, one fully deprotonated dianionic pzdc moiety along with water as solvent of crystallization (Fig. 1d). The stoichiometry between the protonated bix to completely deprotonated acid is thus 1:1 in the unit cell. The deprotonation of the dicarboxylic acid is reected in the bond distances involving the carbon atoms C18 and C19 of the carboxylate group (O(1)C(18) = 1.230(3) , O(2) C(18) = 1.284(3) and O(3)C(19) = 1.259(3) , O(4) C(19) = 1.237(3) ) observed from the crystal structure. Slight difference in bond distance around protonated nitrogens N(2) and N(4) with the adjacent carbon atoms of different imidazole moiety in bix indicates the protonation of the imidazole nitrogen (Table S2). As depicted in Fig. 6a, both symmetrically protonated bix present in the asymmetric unit are placed alternatively between the completely deprotonated dianionic pzdc involving NH+ O (N2 O3 = 2.707(3) ; N4 O2 = 2.562(3) ) interaction with the carbonyl oxygen of the carboxylate group from either side generating a one dimensional hydrogen bonded inter-twined strands. Within the inter-twined strands effective p p stacking between the central phenyl rings of the bix moiety is observed (Cg Cg = 3.74 ). The carboxylate oxygen O3 is involved in a bifurcated NH O with the pyrazole hydrogen H5C (N(5) O(3) = 2.796(3) ) stabilising the inter-twined strands in the crystal lattice. Eventhough, both symmetrically disposed bix molecule present in the unit cell is anti conformation, it is observed that the mean plane involving the central phenyl ring with respect to the imidazole ring in the respective bix ligand shows slight variation (Mean plane between the phenyl ring C5 to C7 with imidazole ring N1C1C3N5 = 70.80 and C11 to C14 with N3 C10C12N4 = 74.80). This may be due to the self orientation of the exible bix moiety for making effective hydrogen bonding and weak p p stacking interaction between the phenyl rings within the strands while packing. In an attempt to understand other secondary hydrogen bonding interaction of these strands with the lattice water molecules and neighboring strands we have analyzed the packing mode and hydrogen bonding interactions in details. The crisscross p p stacked strands are oriented almost diagonal to bc-plane. The lattice water hydrogen acts as donors in strong OH O interaction with the terminal carboxylate oxygens O4 and O2 of the deprotonated dianionic 3,5-pyrazole dicarboxylate (pzdc). Intermolecular CH O and CH N interactions do exist between the carboxylate oxygen of the dicarboxylate ligand and the imidazole hydrogens of the bix moiety within the twined strands. Thus, imidazole hydrogens H2 and H3 are making contacts with carboxylate oxygens O4 and O1 respectively and H3 is making an additional contact with the pyrazole nitrogen N6. In addition to the above, phenyl hydrogen H6 is in contact with the carboxylate oxygen O6 in stabilization of the hydrogen bonded crisscross strands within the crystal lattice. The adjacent layered inter-twined double strands are bridged along c-axis via imidazole hydrogen H9 of the symmetrically disposed bix from either side to generate a two-dimensional hydrogen bonded network as depicted in Fig. 6b. Details of all these hydrogen-bonding interactions with symmetry codes are given in Table 1.

10. Prediction of salt vs cocrystal formation based on pKa values Re-crystallization of the micro-crystals obtained by the reaction of bix with and H2pzdc from hot water gave single crystals of CC4 with plate shaped morphology suitable for X-ray diffraction studies along with diamond shaped CC3. CC4 crystallized in triclinic The pKa values for the constituent acids and base used in the present investigation are obtained from different references and are listed in Table 2 [47]. Formation of salt/cocrystal from the reac-

A.C. Kathalikkattil et al. / Journal of Molecular Structure 985 (2011) 361370

369

Fig. 6. (a) Mercury diagram depicting the innite inter-twined N+H O hydrogen bonded strands between H2bix and pzdc with p p stacking of phenyl rings between the strands in CC4; (b) packing diagram with hydrogen-bonding interactions viewed down a-axis in CC4 showing the crisscross arrangement of the bix moiety in the two dimensional H-boned nets.

tion between an acid and base, primarily relay on ionization constants (pKa values). It is expected that, if the DpKa value [pKa (base)pKa(acid)] is greater than 2 or 3, a salt formation will take place [48]. According to Johnson and Rumon [49], a DpKa < 3.75 affords neutral COOH N interactions (cocrystal), whereas DpKa > 3.75 results in proton transfer (salt). However, more recently it has been reported that, even though DpKa values tend to be reliable indicators of salt formation when DpKa > 3, there is ambiguity in the DpKa range of 03. Specically, cocrystal formation is only expected when DpKa < 0, but a salt-cocrystal continuum can exist in the range 03.67. In the range 0 < DpKa < 3 experimental evidence shows that crystallization may result in a salt, cocrystal, or disordered solid form with partial proton transfer [50]. The calculated DpKa1 and DpKa2 values for CC1 are 2.87 and 1.63 respectively, which are well in agreement with the suggested criteria for cocrystal formation where a salt cocrystal continuum can exist in the range of DpKa value 03. In the case of CC2 DpKa value is 4.08, while for CC3 and CC4 DpKa1 and DpKa2 values are 10.04 and 3.81 respectively. CC2 exists as 1:2 salt of bix with monocarboxylate anion. In the case of CC3 and CC4 (which are obtained from the same pot) base/acid stoichiometry is 1:2 and 1:1 where the carboxylate group of the acid moiety exists in monoanionic and dianionic form respectively. Calculated DpKa values for the salts CC2, CC3 and CC4 clearly indicate salt formation when DpKa > 3 and the generalization of 0 < DpKa < 3 is valid fully in the prediction of cocrystal/salt formation in the present system.

11. Conclusion Cocrystals and ionic organic solids based on ditopic N-donor ligand bix with different dicarboxylic acids have been prepared and characterized by various physicochemical techniques. Single

crystal structures revealed the supramolecular hydrogen bonded network in the hetero synthons. The heteromeric acid base synthon, CC1 is a cocrystal between bix and H2chdc, which makes innite one-dimensional chains via OH N hydrogen-bonding and propagates into an innite two-dimensional sheet via secondary CH O, CH p interaction. In CC2, interaction between the protonated imidazole hydrogen of the symmetrically disposed bix ligand and the carboxylate oxygens of two different H2npdc via NH+ O, H-bonding results in a trimeric supramolecular assembly. The lattice water molecules, via OH O contacts generate innite one-dimensional water cluster, which connects the trimeric species in the two-dimensional supramolecular hydrogen bonded assembly involving week CH O contacts. Very exotic H-bonded motif is observed in the case of both CC3 and CC4 obtained from the same pot reaction. In the case of CC3, the monoanionic pyrazole dicarboxylate is associated as centro-symmetric dimers via NH O interaction, which is further involved in O H O contact with the lattice water molecule to create rectangular grid assembly, which is occupied by the centro-symmetric protonated bix moiety via various hydrogen-bonding interactions. CC4 is constituted by innite double stranded inter-twined N H+ O hydrogen bonded protonated bix with pyrazole dicarboxylate (pzdc) along with offset p stacking of phenyl rings between the double strands. These inter-twined double strands are interconnected via CH O contact in the formation of twodimensional hydrogen bonded assembly. Subtle interplay between the thermodynamic and the kinetic factors which control the crystallization process and balance between these factors is required for understanding the formation of the cocrystals/salts. In all the four molecular adducts observed supramolecular assemblies primarily possess COOH Im/COO Him+ interactions. This study also signies the importance of the synthesis of supramolecular assemblies of each molecular entity to unravel the many possible

370

A.C. Kathalikkattil et al. / Journal of Molecular Structure 985 (2011) 361370 [8] G.R. Desiraju, CrystEngComm (2003) 466. [9] D.J. Dunitz, CrystEngComm (2003) 506. [10] A. Jayasankar, A. Somwangthanaroj, Z.J. Shao, N.R. Hornedo, Pharm. Res. 23 (2006) 2381. [11] F.H. Allen, W.D.S. Motherwell, P.R. Raithby, G.P. Shields, R. Taylor, New J. Chem. 23 (1999) 25. [12] J.M. Lehn, Supramolecular Chemistry: Concepts and Perspectives, VCH, Weinheim, 1995. [13] T. Sugiyama, J. Meng, T. Matsuura, J. Mol. Struct. 611 (2002) 53. [14] C.B. Aakery, A.M. Beatty, B.A. Helfrich, J. Am. Chem. Soc. 124 (2002) 14425. [15] G.R. Desiraju, Angew. Chem., Int. Ed., Engl. 34 (1995) 2311. [16] C.B. Aakery, K.R. Seddon, Chem. Soc. Rev. 22 (1993) 397. [17] K.T. Holman, A.M. Pivovar, J.A. Swift, M.D. Ward, Acc. Chem. Res. 34 (2001) 107. [18] C.B. Aakery, A.M. Beatty, D.S. Leinen, Cryst. Growth Des. 1 (2001) 47. [19] K. Tanaka, K. Endo, Y. Aoyama, Chem. Lett. (1999) 887. [20] O. Almarsson, M.J. Zaworotko, Chem. Commun. (2004) 1889. [21] J. Xiao, M. Yang, J.W. Lauher, F.W. Fowler, Angew. Chem. Int. Ed. 39 (2000) 2132. [22] J.M. Lehn, M. Mascal, A. DeCian, J. Fischer, J. Chem. Soc., Chem. Commun. (1990) 479. [23] S. Shan, E. Batchelor, W. Jones, Tetrahedron Lett 43 (2002) 8721. [24] V.R. Pedireddi, S. Chatterjee, A. Ranganathan, C.N.R. Rao, J. Am. Chem. Soc. 119 (1997) 10867. [25] C.B. Aakery, D.J. Salmon, M.M. Smith, J. Desper, Cryst. Growth Des. 6 (2006) 1033. [26] B.F. Hoskins, R. Robson, D.A. Slizys, J. Am. Chem. Soc. 119 (1997) 2952. [27] L. Carlucci, G. Ciani, D.M. Proserpio, Cryst. Growth Des. 5 (2005) 37. [28] L. Carlucci, G. Ciani, D.M. Proserpio, L. Spadacini, CrystEngComm 6 (2004) 96. [29] M.H. Zeng, B. Wang, X.Y. Wang, W.X. Zhang, X.M. Chen, S. Gao, Inorg.Chem. 45 (2006) 7069. [30] B.F. Abrahams, F. Brendan, B.F. Hoskins, R. Robson, D.A. Slizys, CrystEngComm 4 (2002) 478. [31] L.L. Wen, D.B. Dang, C.Y. Duan, Z.Y. Li, Z.F. Tian, Q.J. Meng, Inorg.Chem. 44 (2005) 7161. [32] Z. Lu, L. Wen, Z. Ni, Y. Li, H. Zhu, Q. Meng, Cryst. Growth Des. 7 (2007) 268. [33] D.R. Trivedi, A. Ballabh, P. Dastidar, CrystEngComm 5 (2003) 358. [34] J. Overgaard, B. Schitt, F.K. Larsen, A.J. Schultz, J.C. MacDonald, B.B. Iversen, Angew Chem. Int. Ed. 38 (1999) 1239. [35] C.B. Aakery, D.P. Hughes, M. Nieuwenhuyzen, J. Am. Chem. Soc. 118 (1996) 10134. [36] F.A. Allen, Acta Crystallogr., Sect. B 58 (2002) 380. [37] C.B. Aakery, J. Desper, B. Leonard, J.F. Urbina, Cryst. Growth Des. 5 (2005) 865. [38] Y.-L. Peng, L.-H. Jia, Acta Cryst E65 (2009) o365. [39] G.M. Sheldrick, SAINT, 5.1 ed., Siemens Industrial Automation Inc., Madison, WI, 1995. [40] SADABS, Empirical Absorption Correction Program, University of Gttingen, Gttingen, Germany, 1997. [41] G.M. Sheldrick, SHELXTL Reference Manual: Version 5.1, Bruker AXS, Madison, WI, 1997. [42] G.M. Sheldrick, SHELXL-97: Program for Crystal Structure Renement, University of Gttingen, Gttingen, Germany, 1997. [43] A.L. Spek, J. Appl. Cryst. 36 (2003) 7. [44] L.J. Farrugia, J. Appl. Cryst. 30 (1997) 565. [45] C.F. Macrae, P.R. Edgington, P. McCabe, E. Pidcock, G.P. Shields, R. Taylor, M. Towler, J.V. Streek, J. Appl. Cryst. 39 (2006) 453. [46] B.F. Abrahams, B.F. Hoskins, R. Robson, D.A. Slizys, Acta Cryst. C54 (1998) 1666. [47] pKa Values for the Acids and Base were obtained either from pKa Data Compiled by R. Williams, <http://research.chem.psu.edu/brpgroup/pKa_compilation.pdf>, from the Merck Index or by using Scinder. [48] P.H. Stahl, C.G. Wermuth, Handbook of Pharmaceutical Salts: Properties, Selection, and Use International Union of Pure and Applied Chemistry, VHCA, Wiley-VCH, Weinheim, New York, 2002. [49] S.L. Johnson, K.A. Rumon, J. Phys. Chem. 69 (1965) 74. [50] B. Sarma, N.K. Nath, B.R. Bhogala, A. Nangia, Cryst. Growth Des. 9 (2009) 1546 (and references therein).

structural and molecular recognition features. The salient features of recognition patterns in terms of the pKa values of the constituents clearly indicates that the proposed rule for the cocrystal/salt formation is in well agreement considering the DpKa value. This information may be quite useful in further target-oriented supramolecular synthesis and also in many computational studies concerning intermolecular interactions including polymorph and crystal structure predictions. Studies pertinent to multi-component cocrystals/salts offer structural diversity, composition, and properties which will continue to attract attention from solid-state chemists and pharmaceutical scientists. Acknowledgments Authors gratefully acknowledge the Department of Science and Technology (DST), New Delhi, India (Grant No. SR/S1/IC-37/2006) and CSIR, India (Grant No. NWP-0010) for nancial support. ACK and KKB acknowledges DST (India) and CSIR for a SRF and JRF respectively. SD is thankful to Dr. Parimal Paul, CSMCRI, Bhavnagar for his M.Sc. dissertation work in analytical discipline. The authors are grateful to Mr. Hitesh Bhatt for recording NMR spectra, Mrs. Sheetal N. Patel for TGA data, Mr. Viral Vakani for microanalysis, Mr. Vinod Kumar Agrawal for IR data, and Dr. P. Paul for all-round analytical support. Appendix A. Supplementary material CCDC 746434 to 746437 contains the supplementary crystallographic data for compounds 14. These data can be obtained free of charge via http://www.ccdc.cam.ac.uk/conts/retrieving.html, or from the Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44 1223 336 033; or e-mail: deposit@ccdc.cam.ac.uk. Synthesis of bix; proton NMR spectra of all reported compounds; TGA plots for CC2, CC3 and CC4; optical images of CC3 and CC4, additional crystallographic diagrams; summary of crystallographic data and selected bond distances and angles for all compounds are given in supplementary material. Supplementary data associated with this article can be found, in the online version, at doi:10.1016/j.molstruc.2010.11.022. References
[1] J.A. Bis, O.L. McLaughlin, P. Vishweshwar, M.J. Zaworotko, Cryst. Growth Des. 6 (2006) 2648. [2] M. Du, Z.H. Zhang, X.J. Zhao, H. Cai, Cryst. Growth Des. 4 (2006) 14. [3] B. Sarma, L.S. Reddy, A. Nangia, Cryst. Growth Des. 8 (2008) 4546. [4] N.S. Goroff, S.M. Curtis, J.A. Webb, F.W. Fowler, J.W. Lauher, Org. Lett. 7 (2005) 1891. [5] L.Y. Park, D.G. Hamilton, E.A. McGehee, K.A. McMenimen, J. Am. Chem. Soc. 125 (2003) 10586. [6] S. Mohamed, D.A. Tocher, M. Vickers, P.G. Karamertzanis, S.L. Price, Cryst. Growth Des. 9 (2009) 2881. [7] W.W. Porter, S.C. Elie, A.J. Matzger, Cryst. Growth Des. 8 (2008) 14.