Crystal Structures of Pyridine Sulfonamides and Sulfonic Acids

Article pubs.acs.org/crystal

Crystal Structures of Pyridine Sulfonamides and Sulfonic Acids Kalyanachakravarthi Akiri, Suryanarayan Cherukuvada, Soumendra Rana, and Ashwini Nangia* School of Chemistry, University of Hyderabad, Prof. C. R. Rao Road, Central University PO, Gachibowli, Hyderabad 500 046, India S Supporting Information *

ABSTRACT: Despite the widespread occurrence of pyridinesulfonic acid and pyridinesulfonamide functional groups in drugs and pharmaceuticals, and their use as ligands in metal−organic frameworks, a systematic structural study of their hydrogen bonding and molecular packing is lacking. We discuss crystal structures of 2-, 3-, and 4-pyridinesulfonic acids/amides in terms of N+−H···O− hydrogen bonds, N−H···O dimer/catemer synthons, and graph set notations. This model study provides a background for polymorph screening and solid form hunting of pharmacologically active sulfonamides.

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INTRODUCTION Sulfonamides (RSO2NH2) are a class of organosulfur compounds that are amide derivatives of sulfonic acids (RSO3H). Several molecules with the sulfonamide group are found to display a wide variety of pharmacological activities, such as hypoglycemic (Glycodiazine),1 antibacterial (Sulfanilamide),2 carbonic anhydrase inhibitor (Dorzolamide),3 and anticancer (Indisulam).4 Our group recently studied structural motifs in sulfonamide drugs Furosemide5,6 and Nimesulide.7 The ability of sulfonamides to form different intermolecular N−H···O hydrogen bonds makes them important in crystal engineering.6,8−10 A study of these molecules and their derivatives has advanced our understanding of which functionalities/molecular fragments favor polymorphism5,7,11−13 and cocrystal formation6,8−10 and their possible reasons. Heteroaromatic sulfonamides, such as pyridine sulfonamides (Scheme 1), are excellent ligands for metal−organic framework

Sulfadoxine and Sulfametopyrazine (respiratory, urinary tract, and malarial infections).24−26 In this background, it is somewhat surprising that crystal structures of model pyridine sulfonamides and sulfonic acids have not been analyzed in the literature. The recent CSD update27 (CCDC, ConQuest 1.14, ver. 5.33, November 2011 release, May 2012 update) contains crystal structures of 2- and 3-pyridine sulfonic acid,28,29 and among these the structure of 3-pyridine sulfonic acid has a high R factor of 0.115.29 There are no crystal structures of pyridine sulfonamides in the CSD. We report herein the X-ray crystal structure of 3-pyridinesulfonic acid with improved R-factor, and new crystal structures of 4-pyridinesulfonic acid, and 2-, 3-, and 4-pyridinesulfonamides.

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RESULTS AND DISCUSSION The synthesis of compounds was carried out according to reported procedures (see Experimental Section). We obtained their single crystals and discuss X-ray crystallographic details and intermolecular interactions and hydrogen bonding patterns in terms of supramolecular synthons30 and graph sets.31,32 All crystal structures contain auxiliary C−H···O hydrogen bonds. 2- and 3-Pyridinesulfonic Acid. Crystal structures of these two compounds are reported.28,29 We obtained the structure of 3-pyridinesulfonic acid in space group Pbca with improved R-factor of 0.0382 (reported 0.115).29 Crystallographic parameters are given in Table 1 and hydrogen bonds are in Table 2. Both 2- and 3-Py-SO3H isomers display a sheetlike structure of zwitterionic molecules. However, the sheets in the 2-Py isomer are formed of zigzag tapes (Figure 1a,b), whereas antiparallel tapes are present in the 3-Py isomer (Figure 1c,d). Zigzag tapes of N+−H···O− bonded glide-related 2-Py-SO3H molecules form a C(5) chain along the b-axis which extends into two-dimensional (2D) sheets through C(7) C−H···O chain and cyclic R44 (20) ring motif (Figure 1a). The antiparallel tapes of N+−H···O−

Scheme 1. Chemical Structure of Pyridinesulfonic Acid (Zwitterionic) and Pyridinesulfonamide

based functional polymers.14,15 Even in the absence of metal ions, certain pyridine sulfonamides act as adducts to generate resinous polymers that can remove dyes16 or mercury17 from aqueous solution. Both unsubstituted aromatic and heteroaromatic sulfonamides are effective inhibitors of carbonic anhydrase, an important enzyme in human physiology.18,19 The idea of polypharmacology of sulfonamides was advocated in a very recent paper by Winum et al.20 in which they showed that Pazopanib, a multitargeted tyrosine kinase inhibitor (a new antitumor drug), can act as a low nanomolar inhibitor of almost 15 different human carbonic anhydrase isoforms. There are several approved pyridine sulfonamide drugs, such as Sulfapyridine (antibacterial),21 Sulfamethazine (antimicrobial),22 Sulfadiazine (toxoplasmosis),23 © XXXX American Chemical Society

Received: June 4, 2012 Revised: July 29, 2012

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dx.doi.org/10.1021/cg3007603 | Cryst. Growth Des. XXXX, XXX, XXX−XXX

Crystal Growth & Design

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Table 1. Crystallographic Parameters of Pyridinesulfonic Acids and Pyridinesulfonamides

a

compound

3-pyridine sulfonic acida

4-pyridine sulfonic acid

2-pyridine sulfonamide



empirical formula formula weight crystal system space group ̅ T/K a (Å) b (Å) c (Å) α (°) β (°) γ (°) Z V/Å3 Dcalc/g cm−3 μ/mm−1 reflns collected unique reflns observed reflns R1 [I > 2σ(I)] wR2 [all] goodness-of-fit diffractometer

C5H5NO3S 159.16 orthorhombic Pbca 298(2) 7.1874(3) 11.4435(5) 14.9673(9) 90 90 90 8 1231.04(10) 1.718 0.461 3117 1255 1115 0.0382 0.0965 1.091 Oxford Xcalibur Gemini

C5H5NO3S 159.16 monoclinic P21/n 298(2) 5.4285(16) 15.583(5) 7.6802(19) 90 108.61(3) 90 4 615.7(3) 1.717 0.461 2411 1086 804 0.0540 0.1652 1.117 Oxford Xcalibur Gemini

C5H6N2O2S 158.18 monoclinic P21/c 298(2) 4.8946(3) 15.4818(8) 8.7607(5) 90 95.185(5) 90 4 661.14(6) 1.589 0.422 2659 1339 1131 0.0316 0.0865 1.061 Oxford Xcalibur Gemini

C5H6N2O2S 158.18 triclinic P1̅ 100(2) 4.9893(9) 7.0628(16) 9.7308(16) 108.250(2) 94.716(3) 96.499(3) 2 321.03(11) 1.636 0.435 3306 1247 1210 0.0297 0.0759 1.094 Bruker Smart Apex

C5H6N2O2S 158.18 triclinic P1̅ 298(2) 7.0259(4) 9.5404(8) 10.2794(9) 87.256(7) 79.631(6) 82.428(6) 4 671.66(9) 1.564 0.415 4626 2740 2134 0.0347 0.0862 1.050 Oxford Xcalibur Gemini

The reported crystal structure in ref 29 has high R-factor 0.115.

metabolic activity.33 X-ray crystal structures are reported for all the six pyridine carboxylic acids and amides,27 of which only two compounds are reported to be polymorphic. Nicotinamide exists as dimorphs34,35 and isonicotinamide (4-Py CONH2) is trimorphic.35,36 Interestingly, several nicotinic acid derivatives are polymorphic,37−40 and a zwitterionic polymorph is known in a trimorphic system.39 The parent nicotinic acid neither has polymorphs nor exists in a zwitterionic form in the solid-state.27 SPARC calculations41 (Table 3) show that pyridine carboxylic acids are weaker acids than pyridine sulfonic acids, and thus the latter exist as zwitterions whereas the carboxylic acids are in the un-ionized state. Even though experimental ΔpKa values of 2- and 3-pyridine carboxylic acids42,43 (Table 3) suggest that picolonic acid must be zwitterionic (ΔpKa > 3)39 and nicotinic acid is likely to be ionic, these compounds actually exist in an un-ionized form in the crystalline state. Picolinic acid is half zwitterionic, in that the hydrogen atom is located between the carboxylic oxygen and pyridine nitrogen with a positional disorder of 0.5 occupancy (Figure 6).44 The acid−pyridine synthon of isonicotinic acid is somewhat charged in nature since the carboxylic acid O−H is longer (1.07 Å) and the H atom is closer to pyridine N (1.51 Å)45 compared to that in nicotinic acid (O−H = 0.85 Å, H···N = 1.84 Å). Nicotinic acid is in an un-ionized form in the crystal structure.46 Nicotinamide and isonicotinamide are well studied in crystal engineering of model compounds and drugs, and numerous cocrystals of improved physicochemical properties are reported.6,35,47−52 Pyridine sulfonic acids/amides and carboxylic acids/amides are molecular analogues and display very different structural features and hydrogen bonding patterns by the change of functional group. Crystal structure analysis shows no real similarities in their packing motifs. Pyridinesulfonic acids display an N+−H···O− catemer, but the carboxylic acids contain dimer motifs. 2- and 3-Py sulfonic acids are sheet structures but 2-Py COOH has a crisscross packing (Figure 6) and 3-Py COOH is a tape structure (Figure 7).

bonded 3-Py-SO3H molecules in C(6) notation form cyclic synthons of R23(10) and R33(14) rings (Figure 1c). 4-Pyridinesulfonic Acid. It crystallized as a zwitterion in the space group P21/n. The crystal structure (Figure 2) displays intermolecular N+−H···O− interactions between molecules which translate via C(7) linear chains (Figure 2a) in a herringbone motif of phenyl rings. The intricate C−H···O interactions have R22(12), R44(14), and R44(20) network (Figure 2b). 2-Pyridinesulfonamide. It crystallized in the space group P21/c. Translation related molecules make antiparallel tapes of sulfonamide N−H···O catemer synthon in a C(4) chain along the a-axis (Figure 3a). These tapes make a helix down the a-axis through R22(10) N−H···N and C−H···O dimers between inversion-related molecules (Figure 3b). Successive helices connected through C−H···O interactions are arranged antiparallel in the structure (Figure 3c). 3-Pyridinesulfonamide. In the crystal structure (space group P1)̅ sulfonamide N−H···O and N−H···N dimers of R22(8) and R22(12) rings are present between inversion related molecules in a zigzag tape motif (Figure 4a) along the c-axis. These tapes extend into corrugated sheets through C−H···O dimers of R22(12) rings down the b-axis, which in turn propagate through C−H···O dimers of R22(10) rings along the a-axis (Figure 4b). 4-Pyridinesulfonamide. It crystallized in space group P1̅ with two molecules in the asymmetric unit (Z′ = 2). In the crystal structure, R22(8) sulfonamide dimer and R22(10) C−H···O dimer are present between the crystallographic unique molecules (shaded differently in Figure 5a). These symmetry independent molecules are connected by discrete N−H···N and N−H···O bonds. Corrugated sheets along the b-axis extend through N−H···N and N−H···O interactions (Figure 5b). Pyridine Carboxylic Acids. Pyridine carboxylic acids and amides are more extensively studied analogues of pyridine sulfonic acids and amides. 3-Pyridine carboxylic acid (nicotinic acid or vitamin B3, also called niacin) and its amide (nicotinamide or niacinamide) are important biomolecules vital for cellular and B



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Table 2. Hydrogen Bondsa in Crystal Structures interaction N1−H1A···O3 C1−H1···O1 C1−H1···O1 C1−H1···O3 C3−H3···O1 C4−H4···O2 C5−H5···O1 N1−H1A···O1 C2−H2···O1 C4−H4···O2 C1−H1···O3 C2−H2···O3 C5−H5···O2 N2−H2A···N1 N1−H2B···O1 C2−H2···O2 C2−H2···O2 C4−H4···O1 N2−H2A···N1 N1−H2B···O2 C1−H1···O1 C3−H3···O2 C1−H1···O1 C4−H4···O2 N2−H2A···N3 N2−H2B···O2 N4−H4A···N1 N4−H4B···O1 N4−H4B···N2 C2−H2···O1 C4−H4···O2 C9−H9···O4 C5−H5···O1 C9−H9···O4 C10−H10···O2

H···A (Å)

D···A (Å)

∠D−H···A (°)

3-Pyridinesulfonic Acid 1.91(4) 2.749(3) 170(3) 2.50 2.848(3) 102 2.68 3.179(3) 113 2.52 3.426(3) 160 2.57 3.192(3) 121 2.69 3.521(3) 144 2.38 3.267(3) 161 4-Pyridinesulfonic Acid 2.06(5) 2.772(5) 170(6) 2.60 2.938(4) 102 2.73 3.034(4) 100 2.45 3.219(5) 140 2.64 3.218(5) 130 2.63 3.273(5) 126 2-Pyridinesulfonamide 2.15(3) 2.957(2) 159(2) 2.19(2) 2.975(2) 153(2) 2.60 2.945(2) 102 2.56 3.277(2) 135 2.63 3.398(2) 141 3-Pyridinesulfonamide 2.18(3) 3.028(2) 167(2) 2.23(2) 2.987(2) 155(2) 2.57 2.942(2) 104 2.63 2.954(2) 100 2.43 3.226(2) 142 2.71 3.229(2) 115 4-Pyridinesulfonamide 2.04(3) 2.912(3) 173(2) 2.32(2) 3.071(3) 154(3) 2.16(3) 2.946(3) 172(3) 2.51(3) 2.973(3) 115(2) 2.60(3) 3.326(3) 144(2) 2.63 2.959(2) 101 2.64 2.957(2) 101 2.61 2.946(3) 102 2.53 3.264(3) 136 2.59 3.426(3) 150 2.51 3.351(3) 151

symmetry code 1 + x, y, z b 1/2 + x, 1/2 −y, −z 1/2 + x, 1/2 −y, −z 1/2 − x, 1/2 + y, z −x, 1/2 + y, 1/2 − z 3/2 − x, 1/2 + y, z −1 + x, y, −1 + z b b x, y, −1 + z x, y, 1 + z 1 − x, 1 − y, 1 − z

Figure 1. (a) Zigzag tapes of 2-pyridinesulfonic acid formed by N+− H···O− H bonds extend into (b) 2D sheets sustained by C−H···O interactions. (c) Antiparallel tapes of 3-pyridinesulfonic acid assemble to make (d) 2D sheets in the structure.

−x, 1 − y, 2 − z −1 + x, y, z b 1 − x, −y, 2 − z −x, 1/2 + y, 1/2 − z −x, 2 − y, 1 − z −x, 2 − y, −z b b 1 − x, 2 − y, 1 − z −x, 1 − y, −z 1 + x, y, z 1 − x, −y, −z −x, 1 − y, 1 − z −1 + x, y, −1 + z 1 − x, −y, 1 − z b b b −1 + x, y, z 1 − x, −y, 1 − z 1 − x, −y, −z

Figure 2. (a) Linear tapes of translation related molecules connected by N+−H···O− interactions form (b) C−H···O ring motifs in 4-pyridine sulfonic acid.

a N−H hydrogen atoms were refined in difference electron density maps. C−H hydrogens were fixed to the heavy atom. bIntramolecular hydrogen bond.

Picolinic acid (2-Py COOH) structure can be termed as halfzwitterionic (CCDC refcode PICOLA02)27 since the H atom is located in between the carboxylic O and pyridine N atoms, and the two C−O distances of carboxylic group are dissimilar (1.21, 1.28 Å).44 The hydrogen bonded acid molecules (O−H···H−O) make an angle of 58.2° with each other and propagate as zigzag tape (through N−H···H−N interactions) along the c-axis (Figure 6a), in a crisscross arrangement (Figure 6b). In the case of nicotinic acid46 (CCDC refcode NICOAC02),27 infinite tapes of acid−pyridine dimer synthon with R22(7) ring are arranged in an offset manner (Figure 7). The linear tapes of isonicotinic acid45 (CCDC refcode ISNICA)27 assemble via acid−pyridine R22(7) motif (Figure 8). In contrast, 4-pyridine sulfonic acid has a herringbone structure of different graph set pattern.

Figure 3. (a) Linear tapes of translation related molecules formed by N−H···O synthon of C(4) chain in 2-pyridine sulfonamide. (b) Inversion-related molecules are connected by R22(10) N−H···N and C−H···O dimers in a helix down the a-axis. (c) C−H···O interactions connect antiparallel helices. C



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Figure 4. (a) Zigzag tapes of inversion-related molecules formed by R22(8) sulfonamide dimer and R22(12) N−H···N dimer in 3-pyridinesulfonamide. (b) The tapes extend into corrugated sheets through C−H···O R22(12) dimers which are connected by C−H···O R22(10) dimers. Figure 6. (a) Acid dimer molecules formed by O−H···H−O interactions make a zigzag tape through N−H···H−N interactions along the c-axis in 2-Py COOH (picolinic acid). (b) Crisscross packing of molecules down the a-axis.

Figure 5. (a) N−H···N bonds connect the R22(8) sulfonamide dimer and R22(10) C−H···O dimer of symmetry independent molecules (shown in ball-stick and capped-stick styles for clarity) in 4-pyridinesulfonamide. (b) Crystallographic unique molecules form corrugated sheets along the b-axis through discrete N−H···N and N−H···O hydrogen bonds.

Figure 7. (a) Acid−pyridine R22(7) dimer synthon forms zigzag tapes in 3-Py COOH (nicotinic acid). (b) Stacking of aromatic rings in an offset geometry.

Pyridine Carboxamides. Amides are well-known to form R22(8) dimer and C(4) catemer N−H···O synthons,5,12,53,54 and pyridine sulfonamides and carboxamides follow this trend. The carboxamide NH has syn or anti geometry depending on whether the H atom is located on the same or opposite side of the CO bond.53 The syn-oriented N−H group generally forms a centrosymmetric N−H···O R22(8) dimer synthon and the anti N−H makes an N−H···O C(4) catemer in which neighboring molecules are related by a ∼5.1 Å translation. Nicotinamide (3-Py CONH2) and isonicotinamide (4-Py CONH2) are polymorphic: nicotinamide is dimorphic (one structure in space group P21/c with Z′ = 1 and the other in P2/n with Z′ = 4),34,35 and isonicotinamide is trimorphic (P21/c and Pbca structures with Z′ = 1, and P21/c structure with Z′ = 2).35,36 2-Py sulfonamide has a N−H···O catemer and adopts a helical

structure, but 2-Py CONH2 (picolinamide) has both carboxamide N−H···O R22(8) dimer and C(4) catemer motifs in 5.2 Å structure (Figure 9). 3-Py SO2NH2 has sulfonamide dimers in a corrugated sheet structure, whereas the carboxamide C(4) catemer of 3-Py CONH2 forms a sheet structure through syn N−H···N interactions (in nicotinamide Z′ = 1 polymorph, CCDC refcode NICOAM01)27 (Figure 10). 4-Py SO2NH2 has a corrugated sheet structure sustained by N−H···O dimers, whereas the layer structure of 4-Py CONH2 is assembled via N−H···O catemers (in isonicotinamide Z′ = 2 structure, CCDC refcode EHOWIH02) 27 (Figure 11a). The crystallographic unique molecules form an AABB motif (Figure 11b).

Table 3. Calculated and Experimental pKa Values calculated in SPARC41

a

experimental values

compound

base (pyridine N)

acid (O−H)

ΔpKa

base (pyridine N)

acid (O−H)

2-pyridine sulfonic acid 3-pyridine sulfonic acid 4-pyridine sulfonic acid 2-pyridine carboxylic acidb 3-pyridine carboxylic acidc 4-pyridine carboxylic acid

1.68 3.10 3.42 2.07 3.44 3.66

0.53 0.54 0.54 4.20 3.35 3.28

1.15 2.56 2.88 −2.13 0.09 0.38

a a a 5.29 4.90 a

a a a 1.04 2.18 a

ΔpKa

4.25 2.72

Not reported. bRef 42. cRef 43. D



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Figure 8. Linear tapes of acid−pyridine R22(7) dimer synthons extend into a sheet structure through C−H···O interactions in 4-Py COOH (isonicotinic acid).

Figure 11. (a) Antiparallel tapes formed by syn N−H···N interactions extend into sheets through anti N−H···O C(4) catemer motifs in 4-py CONH2 (isonicotinamide). (b) The crystallographic unique molecules (shown in ball-stick and capped-stick styles for clarity) form a bilayer along the a-axis.

Scheme 2. Preparation Methods for Pyridinesulfonic Acids and Amides

Figure 9. (a) Carboxamide syn N−H···O R22(8) dimers and anti N−H···O C(4) catemer motifs make 5.2 Å translation ribbons in 2-py CONH2 (picolinamide). (b) The ribbons are arranged in a zigzag manner along the a-axis.

sulfonamide crystal structures are compared with their carboxylic acid and amide counterparts. Their hydrogen bonding and crystal packing pattern is completely different, except for the sheet motifs in 3- and 4-pyridine sulfonamides and carboxamides. We did not observe polymorphism in this preliminary study with routine crystallization conditions. However, given the variable intermolecular hydrogen bond motifs, dimer/catemer synthons, and multiple Z′ structures, the appearance of new polymorphs is likely5,7,11−13 after more exhaustive experimentations.

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Figure 10. (a) Parallel catemers formed by carboxamide anti N−H···O bonds between glide related molecules make (b) 2D sheets along the b-axis through syn N−H···N interactions in 3-py CONH2 (nicotinamide).

EXPERIMENTAL SECTION

Materials and Methods. 4-Pyridinesulfonic acid and 2-, 3-, and 4-pyridinesulfonamides were synthesized as per reported procedures given below (Scheme 2). 3-Pyridinesulfonic acid was purchased from Sigma-Aldrich (Hyderabad, India). All other chemicals were of analytical or chromatographic grade. Synthesis and Crystallization. 3-Pyridinesulfonic Acid. The compound was obtained commercially (Sigma-Aldrich) and used without further purification. Twenty-five milligrams of the compound was dissolved in about 5 mL of warm EtOH and left for slow evaporation at room temperature. Colorless plate crystals were obtained after a few days upon solvent evaporation. 4-Pyridinesulfonic Acid. The compound was synthesized as reported by Evans et al.55 25 mg of the compound was dissolved in 6 mL of warm EtOH and left for slow evaporation at room temperature. Colorless block crystals were obtained after a few days upon solvent evaporation. 2-Py and 4-Pyridinesulfonamide. The compounds were synthesized as reported by Maślankiewicz et al.56 Single crystals of 2-Py isomer were obtained as reddish yellow plates when 25 mg of the compound was

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CONCLUSIONS We report the first crystal structures of 4-pyridinesulfonic acid, and 2-, 3-, and 4-pyridinesulfonamides. This structural study completes a model series of pyridinesulfonic acids and amides. All three pyridine sulfonic acids exist in zwitterionic form in the solid-state displaying an N+−H···O− catemer motif. 2- and 3-Pyridinesulfonic acids form sheet structures but the 4-Py isomer displays a herringbone structure. In pyridine sulfonamides, the 2-Py isomer contains N−H···O catemer whereas 3- and 4-Py isomers possess the dimer synthon, with the latter structure having Z′ = 2. The 3- and 4-Py sulfonamide isomers adopt a corrugated sheet structure sustained by sulfonamide N−H···O dimer synthon, whereas 2-Py isomer has a helical structure via the catemer synthon. The pyridine sulfonic acid and E



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crystallized from 6 mL of warm EtOH−water solvent mixture (1:1 v/v). In the case of 4-Py isomer, single crystals were brownish yellow plates when 25 mg of the compound was crystallized from 5 mL of warm water. 3-Pyridinesulfonamide. The compound was synthesized as reported by Karaman et al.57 25 mg of the compound was dissolved in 8 mL of warm acetone and left for slow evaporation at room temperature. Brownish yellow block crystals were obtained after a few days upon solvent evaporation. X-ray Crystallography. X-ray reflections for 3- and 4-pyridinesulfonic acids and 2- and 4-pyridinesulfonamides were collected at 298 K on Oxford Xcalibur Gemini Eos CCD diffractometer using Mo−Kα radiation (λ = 0.7107 Å). Data reduction was performed using CrysAlisPro (version 1.171.33.55)58 and OLEX2−1.059 was used to solve and refine the structures. X-ray reflections for 3-pyridine sulfonamide were collected at 100 K on Bruker SMART-APEX CCD diffractometer equipped with a graphite monochromator and Mo−Kα fine-focus sealed tube (λ = 0.71073 Å). Data reduction was performed using Bruker SAINT Software.60 Intensities were corrected for absorption using SADABS,61 and the structure was solved and refined using SHELX-97.62 All non-hydrogen atoms were refined anisotropically. Hydrogen atoms on heteroatoms were located from difference electron density maps and all C−H hydrogens were fixed geometrically. Hydrogen bond geometries were determined in Platon.63 X-Seed64 was used to prepare packing diagrams.

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ASSOCIATED CONTENT

S Supporting Information *

Crystallographic .cif files are available free of charge via the Internet at http://pubs.acs.org.

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AUTHOR INFORMATION

Corresponding Author

*E-mail: [email protected]. Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS K.A. and S.R. thank the CSIR, and S.C. thanks ICMR for fellowship. We thank the DST (SR/S2/JCB-06/2009) and CSIR (01(2410)/10/EMR-II) for research funding. DST (IRPHA) and UGC (PURSE grant) are thanked for providing instrumentation and infrastructure facilities.

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Article

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Crystal Structures of Pyridine Sulfonamides and Sulfonic Acids

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