4-[2-(1-Acetyl-2-oxopropyl­idene)­hydrazino]-N-(pyrimidin-2-yl)benzene­sulfonamide

Priyanka Rai; Shalini Upadhyay; M Nethaji; K K Upadhyay

doi:10.1107/S1600536809018765

. 2009 May 23;65(Pt 6):o1397. doi: 10.1107/S1600536809018765

4-[2-(1-Acetyl-2-oxopropylidene)hydrazino]-N-(pyrimidin-2-yl)benzenesulfonamide

Priyanka Rai ^a, Shalini Upadhyay ^b, M Nethaji ^c, K K Upadhyay ^b,^*

PMCID: PMC2969759 PMID: 21583242

Abstract

In the title compound, C₁₅H₁₅N₅O₄S, the dihedral angle between the pyrimidine and benzene rings is 84.56 (2)°. Intramolecular hydrazine–carbonyl N—H⋯O and intermolecular sulfonamide–pyridimine N—H⋯N hydrogen bonds stabilize the molecular and crystal structures, respectively.

Related literature

For background to sulfa drugs and their derivatives, see: Abbate et al. (2004 ▶); Badr (2008 ▶); Gale et al. (2007 ▶); Hanafy et al. (2007 ▶); Novinson et al. (1976 ▶); Supuran et al. (2003 ▶). For the synthesis of the title compound, see: Goyal & Bhargava (1989 ▶).

Experimental

Crystal data

C₁₅H₁₅N₅O₄S
M _r = 361.38
Monoclinic,
a = 11.354 (3) Å
b = 5.7875 (13) Å
c = 25.974 (6) Å
β = 101.877 (4)°
V = 1670.3 (7) Å³
Z = 4
Mo Kα radiation
μ = 0.23 mm⁻¹
T = 293 K
0.24 × 0.22 × 0.20 mm

Data collection

Bruker SMART APEX diffractometer
Absorption correction: empirical (using intensity measurements) (SADABS; Bruker, 2005 ▶) T _min = 0.947, T _max = 0.957
17935 measured reflections
3999 independent reflections
3164 reflections with I > 2σ(I)
R _int = 0.027

Refinement

R[F ² > 2σ(F ²)] = 0.047
wR(F ²) = 0.135
S = 1.07
3999 reflections
228 parameters
H-atom parameters constrained
Δρ_max = 0.43 e Å⁻³
Δρ_min = −0.27 e Å⁻³

Data collection: APEX2 (Bruker, 2008 ▶); cell refinement: SAINT (Bruker, 2008 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809018765/tk2450sup1.cif

e-65-o1397-sup1.cif^{(19.1KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809018765/tk2450Isup2.hkl

e-65-o1397-Isup2.hkl^{(196KB, hkl)}

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
N2—H2A⋯O3	0.86	2.01	2.654 (2)	131
C15—H15⋯O4ⁱ	0.93	2.46	3.262 (3)	144

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Symmetry code: (i) Inline graphic .

Acknowledgments

KKU and SU are grateful to the UGC, New Delhi, for financial support.

supplementary crystallographic information

Comment

Sulfa drugs and their derivatives have attracted much attention due to their wide spectrum of applications as compounds with anti-bacterial (Badr, 2008), anti-fungal (Hanafy et al., 2007), anti-viral (Supuran et al., 2003), anti-malarial (Gale et al., 2007), and anti-cancer (Abbate et al., 2004) activities. Although the title compound (I) been reported in the literature (Goyal & Bhargava, 1989), its crystal structure was not reported. The molecule of (I), Fig. 1, is-non planar as seen in arrangement of the two aromatic moieties attached to sulfonamide, –NHSO₂-, group; the C1—S1—N1—C12 torsion angle is 68.66 (15)°. Within the molecule, there is a prominent intramolecular interaction between the hydrazo-N—H and the carbonyl-O3 atoms, Fig. 2 and Table 1. Intermolecular hydrogen bonds formed between centrosymmetrically related molecules involving the sulfonamide-N—H and the pyrimidine-N4 atoms lead to dimeric aggregates, Fig. 2 and Table 1.

Experimental

Compound (I) was synthesized using the literature procedure (Novinson et al., 1976) as follows. Sulfadiazine (2 mmol, 501 mg) and sodium nitrite (~4 mmol, 300 mg) were dissolved separately in conc. HCl (2 ml) and distilled water (10 ml), respectively, followed by their cooling on crushed ice. The cooled sodium nitrite solution was added to the sulfdiazine solution with constant stirring while maintaining ice-cold temperature. The resulting yellow solution was added to a mixture of acetyl acetone (2 mmol, 0.2 ml) and sodium acetate (~37 mmol, 3 g) in distilled water (15 ml) with continuous stirring. The stirring was continued for 2 h maintaining the temperature of the reaction vessel between 293–298 K. The resulting solids were filtered, washed with water, ethanol and finally, by diethyl ether. The crude product was recrystallized from a water–ethanol mixture (50% v/v) and dried in vacuo. Crystals of (I) were developed by layering its supersaturated solution in ethanol with diethylether and leaving for a few days.

Yield 78%. Spectroscopic anaylysis: ¹H NMR (DMSO-d₆, TMS, δ p.p.m.) 13.51 (1H, NH) 11.79 (1H, NH), 8.51–7.04 (7H, Ar—H), 2.54–2.42 (6H, CH₃). ¹³C NMR (DMSO-d₆, TMS, δ p.p.m.) 197.41, 196.40 (>C═O), 158.3, 156.8, 145.44 (>C═C<), 135.4, 135.3, 129.35, 115.73 (ArC), 31.18, 26.24 (CH₃).