Bis(4-sulfamoylanilinium) sulfate

B Ravikumar; S Pandiarajan; S Athimoolam

doi:10.1107/S1600536813007216

. 2013 Mar 28;69(Pt 4):o596. doi: 10.1107/S1600536813007216

Bis(4-sulfamoylanilinium) sulfate

B Ravikumar ^a, S Pandiarajan ^a, S Athimoolam ^b,^*

PMCID: PMC3629637 PMID: 23634124

Abstract

In the title salt, 2C₆H₉N₂O₂S⁺·SO₄ ²⁻, the sulfate S atom is situated on a crystallographic twofold axis (the symmetry of the anion is 2). The anion exerts intense libration, which is manifested by shortening of the observed sulfate S—O bonds, as well as by features in the electron-density map. The crystal structure is stabilized through a three-dimensional hydrogen-bonding network formed by strong N—H⋯O hydrogen bonds.

Related literature

For information about folate synthesis, see: Kent (2000 ▶). For related structures, see: Pandiarajan et al. (2011 ▶); Zaouali Zgolli et al. (2010 ▶). For correction of the S—O distances in the sulfate anion due to libration movement, see: Nardelli (1995 ▶). For TLS approximation, see: Schomaker & Trueblood (1968 ▶). For graph-set motifs, see: Etter et al. (1990 ▶). For the categorization of hydrogen bonds, see: Desiraju & Steiner (1999 ▶). graphic file with name e-69-0o596-scheme1.jpg

Experimental

Crystal data

2C₆H₉N₂O₂S⁺·SO₄ ²⁻
M _r = 442.48
Orthorhombic,
a = 9.6543 (6) Å
b = 9.7591 (11) Å
c = 18.579 (3) Å
V = 1750.5 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.48 mm⁻¹
T = 293 K
0.24 × 0.22 × 0.19 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer
18054 measured reflections
2054 independent reflections
1950 reflections with I > 2σ(I)
R _int = 0.025

Refinement

R[F ² > 2σ(F ²)] = 0.039
wR(F ²) = 0.104
S = 1.05
2054 reflections
131 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.69 e Å⁻³
Δρ_min = −0.51 e Å⁻³

Data collection: SMART (Bruker, 2001 ▶); cell refinement: SAINT (Bruker, 2001 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL/PC (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL/PC and JANA2006 (Petricek et al., 2006 ▶); molecular graphics: PLATON (Spek, 2009 ▶) and JANA2006; software used to prepare material for publication: SHELXTL/PC.

Supplementary Material

Click here for additional data file.^{(19.2KB, cif)}

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536813007216/fb2278sup1.cif

e-69-0o596-sup1.cif^{(19.2KB, cif)}

Click here for additional data file.^{(101.1KB, hkl)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813007216/fb2278Isup2.hkl

e-69-0o596-Isup2.hkl^{(101.1KB, hkl)}

Click here for additional data file.^{(6.6KB, cml)}

Supplementary material file. DOI: 10.1107/S1600536813007216/fb2278Isup3.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N⋯O22ⁱ	0.84 (2)	1.93 (2)	2.743 (3)	164 (3)
N1—H2N⋯O21ⁱⁱ	0.86 (2)	1.99 (2)	2.849 (3)	168 (3)
N2—H2B⋯O2ⁱⁱⁱ	0.89	2.30	3.043 (3)	141
N2—H2B⋯O1^iv	0.89	2.57	3.146 (2)	123
N2—H2A⋯O22^v	0.89	1.90	2.787 (3)	177
N2—H2C⋯O21^vi	0.89	2.06	2.900 (3)	158

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) ; (v) ; (vi) .

Acknowledgments

SPR and BRK thank the management of the Devanga Arts College for their support and encouragement and also extend their thanks to the University Grants Commission for the financial support of this work in the form of a Minor Research Project.

supplementary crystallographic information

Comment

Sulfonamides have been the first antibacterial drugs and paved the way for the antibiotic revolution in medicine. Sulfanilamides, which belong to sulfonamide drugs, act as competitive inhibitors for the enzyme dihydropteroate synthetase (DHPS). This enzyme is involved in the folate synthesis (Kent, 2000).

We have recently reported a nitrate complex of sulfanilamide (Pandiarajan et al., 2011). In continuation of our interest on the sulfanilamide complexes, the synthesis of the title compound and its title structure, bis(4-sulfamoylanilinium) sulfate, is described here.

In the title structure, the sulfate anion is situated in the special position on the twofold axis, thus the symmetry of this molecule is 2. The refinement has shown that the displacement ellipsoid of the sulfate atom O22 is extensively elongated while that of O21 has shown usual behaviour (Fig. 1). This is due to the libration movement as it is indicated by Figs. 2 and 3 which show the sections of the electron density maps (Petricek et al., 2006) through S2 and the atoms O21 and O22, respectively. Note the curved electron density pertinent to O22 (Fig. 3). The libration movement is also manifested by the values of the corrected S—O distances (Nardelli, 1995): The uncorrected values S2—O21 and S2—O22 are 1.475 (2) and 1.436 (2) Å, respectively, while the respective corrected values equal to 1.501 and 1.516 Å. The attempts to express the libration of the sulfate by TLS (Schomaker & Trueblood, 1968; JANA2006 (Petricek et al., 2006) failed in this case.

The geometric parameters of the cation in the title structure is in agreement with the reported structures of 4-sulfamoylanilinium nitrate (Pandiarajan et al., 2011) and 4-sulfamoylanilinium chloride (Zaouali Zgolli et al., 2010).

The crystal structure is stabilized through a three-dimensional hydrogen bonding network formed by strong N—H···O hydrogen bonds (Table 1, Fig. 4). (The nomenclature regarding the strength of the hydrogen bonds was taken from Desiraju & Steiner, 1999.) The sulfate oxygens as well as the oxygen O2 of the sulfonamyl group are the acceptors of these strong hydrogen bonds (Table 1) which are donated by the primary amine as well as by the ammonium groups. Among the N—H···O hydrogen bonds, one of the N—H···O hydrogen bonds is observed to be a bifurcated hydrogen bond, with one donor hydrogen (Table 1): N2—H2B···O2 (-x, -y+1, -z) and N2—H2B···O1 (x, -y+1, -z+1/2). All other hydrogen bonding interactions are cation-anion type. These hydrogen bonds are localized in layers parallel to (0 0 1) which are situated at z = 1/4 and z = 3/4. Hence, hydrophilic and hydrophobic regions alternate along c axis as a result of the arrangement of anions and the aromatic cationic parts.

Among the important graph set motifs pertinent to the hydrogen bonding in the structure can be named R₂²(16) (Etter et al., 1990): The cationic –NH₃ group is bonded to the O atom of the S═O group of another cation through the N2—H2B···O2ⁱⁱⁱ hydrogen bond (the symmetry code iii: -x, 1-y, 1-z). These bonds are involved in a ring motif R₂²(16) about the crystallographic inversion centre situated at the Wyckoff position 4a.

Among other graph-set motifs which can be discerned in this hydrogen bond pattern, C₄⁴(12) is worthwhile mentioning. This motif contains N2—H2A···O22^v—S2^v— O21^v···H2N^vii-N1^vii-H1N^vii···O22^viii-S2^viii-O21^viii··· H2C^ix-N2^ix··· where the symmetry codes are v : -1/2+x, 3/2-y, 1-z; vii : -x, 2-y, 1-z; viii : 1-x, 2-y, -1/2+z; ix : -x, 1+y, 1/2-z.

Experimental

The synthesis of the title compound was carried out by heating of the mixture of sulphanilamide (3.4 g) and sulfuric acid (0.5 ml of 98% concentration) in 20 ml of water as the stoichiometric ratio of 2:1 (at 60°C) under reflux for 1 h. Colourless prismatic crystals of bis(4-sulfamoylanilinium) sulfate suitable for single-crystal X-ray analysis with the approximate size of 1.6 cm × 0.8 cm × 0.3 cm were obtained by slow evaporation at room temperature. The measured sample was cut from a bigger crystal.