4-Sulfamoylanilinium nitrate

S Pandiarajan; S Balasubramanian; B Ravikumar; S Athimoolam

doi:10.1107/S1600536811038827

. 2011 Sep 30;67(Pt 10):o2788. doi: 10.1107/S1600536811038827

4-Sulfamoylanilinium nitrate

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

PMCID: PMC3201237 PMID: 22058822

Abstract

In the crystal structure of the title compound, C₆H₉N₂O₂S⁺·NO₃ ⁻, the cations and anions are connected by N—H⋯O hydrogen bonds into a three-dimensional network.

Related literature

For the biological importance of the title compound, see: Kent (2000 ▶). For related structures, see: Alléaume & Decap (1965a ▶,b ▶); Buttle et al. (1936 ▶); Chatterjee et al. (1981 ▶); Gelbrich et al. (2007 ▶, 2008 ▶); Gelmboldt et al. (2004 ▶); Hughes et al. (1999 ▶); O’Connell & Maslen (1967 ▶); O’Connor & Maslen (1965 ▶); Smith et al. (2001 ▶); Zaouali Zgolli et al. (2010 ▶). For the polymorphism of sulfanilamide, see: Burger (1973 ▶). For hydrogen-bond motifs, see: Etter et al. (1990 ▶).

Experimental

Crystal data

C₆H₉N₂O₂S⁺·NO₃ ⁻
M _r = 235.22
Monoclinic,
a = 14.1489 (19) Å
b = 8.1786 (11) Å
c = 8.6931 (12) Å
β = 107.129 (2)°
V = 961.3 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.34 mm⁻¹
T = 293 K
0.24 × 0.22 × 0.19 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer
4345 measured reflections
1694 independent reflections
1689 reflections with I > 2σ(I)
R _int = 0.017

Refinement

R[F ² > 2σ(F ²)] = 0.025
wR(F ²) = 0.061
S = 1.15
1694 reflections
157 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.17 e Å⁻³
Δρ_min = −0.25 e Å⁻³
Absolute structure: Flack (1983 ▶), 840 Friedel pairs
Flack parameter: 0.06 (5)

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; molecular graphics: PLATON (Spek, 2009 ▶); software used to prepare material for publication: SHELXTL/PC.

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811038827/bt5645sup1.cif

e-67-o2788-sup1.cif^{(15.5KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811038827/bt5645Isup2.hkl

e-67-o2788-Isup2.hkl^{(83.5KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811038827/bt5645Isup3.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—H1A⋯O2ⁱ	0.81 (3)	2.33 (3)	2.992 (2)	139 (2)
N1—H1B⋯O4ⁱⁱ	0.75 (3)	2.30 (3)	3.045 (3)	172 (3)
N2—H1N⋯O5ⁱⁱⁱ	0.93 (3)	2.01 (3)	2.866 (2)	151 (3)
N2—H2N⋯O1ⁱⁱⁱ	0.92 (2)	1.97 (2)	2.858 (2)	163 (2)
N2—H3N⋯O5^iv	0.83 (3)	1.95 (3)	2.770 (2)	171 (2)

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

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

Sulfanilamide, a sulfonamide antibacterial, acts as competitive inhibitor of the enzyme dihydropteroate synthetase (DHPS), an enzyme involved in folate synthesis which involves para-aminobenzoic acid (PABA). PABA is needed in enzymatic reactions that produce folic acid which acts as a coenzyme in the synthesis of purine, pyrimidine and other amino acids (Kent, 2000). Sulfonamide drugs were the first antimicrobial drugs, and paved the way for the antibiotic revolution in medicine. The antibacterial activity of sulfanilamide, was first investigated by Buttle (Buttle et al., 1936). The use of sulfanilamide was eclipsed by its prodrugs, the more effective sulfadrugs, shortly afterwards. From literature, it is observed that sulfadrugs are remarkably polymorphic. The polymorphs of sulfathiazole (Hughes et al., 1999) and sulfapyridine (Gelbrich et al., 2007) were already reported. The polymorphism of sulfanilamide was extensively investigated over a number of years (Burger, 1973). There are three well known polymorphs, usually represented as α, β and γ sulfanilamides (Alléaume & Decap, 1965a,b; O'Connor & Maslen, 1965; O'Connell & Maslen, 1967). Based on the above specifics, we are interested on the investigation of hydrogen bonding tendancy and its reactivity with different inorganic/organic acids.

The asymmetric part of the unit cell, contains a protonated sulfomylanilinium cation and a nitrate anion (Fig 1). The protonation on the one of the N sites is confirmed from C—N bond distance. The other geometrical parameters of the cation are in agreement with the reported structures of 4-homosulfanilamide hydrochloride (Chatterjee et al., 1981), 4-aminobenzenesulfonamide (Gelbrich et al., 2008), bis(4-Aminosulfonyl)benzeneammonium hexafluorosilicate (Gelmboldt et al.,2004), 4-sulfonamidoanilinium 3,5-dinitrosalicylate (Smith et al., 2001) and 4-sulfamoylanilinium chloride (Zaouali Zgolli et al., 2010).

The crystal structure is stabilized through intricate three dimensional hydrogen bonding network formed through N—H···O hydrogen bonds (Fig 2, Table 1). The N atom of the –NH₂ group of the cation is hydrogen bonded with O atom of the S=O group making a zigzag chain C(4) motif extending along c axis of the unit cell (Etter et al., 1990). Further, the N atom of the –NH₃ group of the cation is hydrogen bonded with another O atom of the S=O group making a head-to-tail like chain C(8) motif extending along diagonal of the ab-plane. Nitrate anions are sandwiched between these two chains leading to a unusual asymmetric ring R₅⁵(16) motif which involves four cation and one anion. Also, cations are linked through anion by two N—H···O hydrogen bonds [viz., N1—H1B···O4 (x, 1 - y, 1/2 + z) and N2—H3N···O5 (-1/2 + x, 3/2 - y, -1/2 + z)] forming a chain C₂²(12)motif extending along diagonal of the bc-plane.

Experimental

Colourless crystals of 4-sulfamoylanilinium nitrate suitable for single-crystal X-ray analysis were obtained by slow evaporation at room temperature from an aqeuous solution of sulphanilamide and nitric acid.