Crystal structures of pyridine sulfonamides and sulfonic acids

Article abstract of DOI:10.1021/cg3007603

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.

Full text of DOI:10.1021/cg3007603

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 mole-
cular 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.
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.
INTRODUCTION
■
Sulfonamides (RSO2NH2) are a class of organosulfur com-
pounds 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 hydro-
gen 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.
RESULTS AND DISCUSSION
■
Heteroaromatic sulfonamides, such as pyridine sulfonamides
(Scheme 1), are excellent ligands for metal−organic framework
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 param-
eters 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
Received: June 4, 2012
Revised: July 29, 2012
© XXXX American Chemical Society
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Table 1. Crystallographic Parameters of Pyridinesulfonic Acids and Pyridinesulfonamides
a
compound
3-pyridine sulfonic acid
4-pyridine sulfonic acid
2-pyridine sulfonamide
3-pyridine sulfonamide
4-pyridine sulfonamide
empirical formula
formula weight
crystal system
space group
C5H5NO3S
C5H5NO3S
159.16
C5H6N2O2S
158.18
C5H6N2O2S
158.18
C5H6N2O2S
158.18
159.16
orthorhombic
monoclinic
P21/n
monoclinic
P21/c
triclinic
triclinic
Pbca
P1
̅
P1
̅
T
̅
/K
298(2)
298(2)
5.4285(16)
15.583(5)
7.6802(19)
90
298(2)
4.8946(3)
15.4818(8)
8.7607(5)
90
100(2)
298(2)
a (Å)
b (Å)
c (Å)
α (°)
β (°)
γ (°)
Z
7.1874(3)
4.9893(9)
7.0628(16)
9.7308(16)
108.250(2)
94.716(3)
96.499(3)
2
7.0259(4)
9.5404(8)
10.2794(9)
87.256(7)
79.631(6)
82.428(6)
4
11.4435(5)
14.9673(9)
90
90
108.61(3)
90
95.185(5)
90
90
8
4
4
V/Å3
1231.04(10)
615.7(3)
1.717
661.14(6)
1.589
321.03(11)
1.636
671.66(9)
1.564
D
calc/g cm−3
1.718
μ/mm−1
0.461
0.461
0.422
0.435
0.415
reflns collected
unique reflns
observed reflns
R1 [I > 2σ(I)]
wR2 [all]
3117
2411
2659
3306
4626
1255
1086
1339
1247
2740
1115
804
1131
1210
2134
0.0382
0.0540
0.0316
0.0297
0.0347
0.0965
0.1652
0.0865
0.0759
0.0862
goodness-of-fit
diffractometer
1.091
1.117
1.061
1.094
1.050
Oxford Xcalibur Gemini
Oxford Xcalibur Gemini
Oxford Xcalibur Gemini
Bruker Smart Apex
Oxford Xcalibur Gemini
a
The reported crystal structure in ref 29 has high R-factor 0.115.
bonded 3-Py-SO3H molecules in C(6) notation form cyclic
synthons of R23(10) and R33(14) rings (Figure 1c).
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
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 anti-
parallel in the structure (Figure 3c).
3-Pyridinesulfonamide. In the crystal structure (space
group P1) sulfonamide N−H···O and N−H···N dimers of R2(8)
̅
2
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 P1
̅
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
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).
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a
Table 2. Hydrogen Bonds in Crystal Structures
H···A
(Å)
∠D−H···A
(°)
interaction
D···A (Å)
symmetry code
3-Pyridinesulfonic Acid
1.91(4) 2.749(3) 170(3) 1 + x, y, z
N1−H1A···O3
C1−H1···O1
C1−H1···O1
C1−H1···O3
C3−H3···O1
C4−H4···O2
C5−H5···O1
2.50
2.68
2.52
2.57
2.69
2.38
2.848(3)
3.179(3)
3.426(3)
3.192(3)
3.521(3)
3.267(3)
102
113
160
121
144
161
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
4-Pyridinesulfonic Acid
N1−H1A···O1
C2−H2···O1
C4−H4···O2
C1−H1···O3
C2−H2···O3
C5−H5···O2
2.06(5) 2.772(5)
170(6) −1 + x, y, −1 + z
2.60
2.73
2.45
2.64
2.63
2.938(4)
3.034(4)
3.219(5)
3.218(5)
3.273(5)
102
100
140
130
126
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.
2-Pyridinesulfonamide
N2−H2A···N1
N1−H2B···O1
C2−H2···O2
C2−H2···O2
C4−H4···O1
2.15(3) 2.957(2)
2.19(2) 2.975(2)
159(2) −x, 1 − y, 2 − z
153(2) −1 + x, y, z
2.60
2.56
2.63
2.945(2)
3.277(2)
3.398(2)
102
135
141
b
1 − x, −y, 2 − z
−x, 1/2 + y, 1/2 − z
3-Pyridinesulfonamide
N2−H2A···N1
N1−H2B···O2
C1−H1···O1
C3−H3···O2
C1−H1···O1
C4−H4···O2
2.18(3) 3.028(2)
2.23(2) 2.987(2)
167(2) −x, 2 − y, 1 − z
155(2) −x, 2 − y, −z
2.57
2.63
2.43
2.71
2.942(2)
2.954(2)
3.226(2)
3.229(2)
104
100
142
115
b
b
1 − x, 2 − y, 1 − z
−x, 1 − y, −z
4-Pyridinesulfonamide
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
2.04(3) 2.912(3)
2.32(2) 3.071(3)
2.16(3) 2.946(3)
2.51(3) 2.973(3)
2.60(3) 3.326(3)
173(2) 1 + x, y, z
154(3) 1 − x, −y, −z
172(3) −x, 1 − y, 1 − z
115(2) −1 + x, y, −1 + z
144(2) 1 − x, −y, 1 − 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.
2.63
2.64
2.61
2.53
2.59
2.51
2.959(2)
2.957(2)
2.946(3)
3.264(3)
3.426(3)
3.351(3)
101
101
102
136
150
151
b
b
b
−1 + x, y, z
1 − x, −y, 1 − z
1 − x, −y, −z
a
N−H hydrogen atoms were refined in difference electron density
b
maps. C−H hydrogens were fixed to the heavy atom. Intramolecular
hydrogen bond.
Picolinic acid (2-Py COOH) structure can be termed as half-
zwitterionic (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)
2
Inversion-related molecules are connected by R2 (10) N−H···N and
C−H···O dimers in a helix down the a-axis. (c) C−H···O interactions
connect antiparallel helices.
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Figure 4. (a) Zigzag tapes of inversion-related molecules formed
2
2
by R2 (8) sulfonamide dimer and R2 (12) N−H···N dimer in
3-pyridinesulfonamide. (b) The tapes extend into corrugated sheets
through C−H···O R2 (12) dimers which are connected by C−H···O
R2 (10) dimers.
2
2
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.
2
Figure 5. (a) N−H···N bonds connect the R2 (8) sulfonamide
2
dimer and R2 (10) C−H···O dimer of symmetry independent mole-
cules (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.
2
Figure 7. (a) Acid−pyridine R2 (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 poly-
morphic: 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 carbox-
amide 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
experimental values
compound
base (pyridine N)
acid (O−H)
ΔpKa
base (pyridine N)
acid (O−H)
ΔpKa
2-pyridine sulfonic acid
3-pyridine sulfonic acid
4-pyridine sulfonic acid
2-pyridine carboxylic acid
3-pyridine carboxylic acid
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
a
a
a
a
2.88
a
a
b
c
−2.13
0.09
5.29
4.90
a
1.04
2.18
a
4.25
2.72
0.38
a
b
c
Not reported. Ref 42. Ref 43.
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2
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.
Figure 8. Linear tapes of acid−pyridine R2 (7) dimer synthons extend
into a sheet structure through C−H···O interactions in 4-Py COOH
(isonicotinic acid).
Scheme 2. Preparation Methods for Pyridinesulfonic Acids
and Amides
2
Figure 9. (a) Carboxamide syn N−H···O R2 (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.
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.
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 sulfona-
mides, 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
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 Masl
́
ankiewicz 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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Article
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-pyridine-
sulfonic 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 anisotropi-
cally. 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
* Supporting Information
Crystallographic .cif files are available free of charge via the
■
S
Internet at http://pubs.acs.org.
AUTHOR INFORMATION
Corresponding Author
*E-mail: ashwini.nangia@gmail.com.
■
Notes
The authors declare no competing financial interest.
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ACKNOWLEDGMENTS
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(37) Long, S.; Parkin, S.; Siegler, M. A.; Cammers, A.; Li, T. Cryst.
Growth Des. 2008, 8, 4006.
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.
(38) Long, S.; Li, T. Cryst. Growth Des. 2010, 10, 2465.
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