4-[(3-Formyl-4-hydroxy­phen­yl)diazen­yl]-N-(pyrimidin-2-yl)benzene­sulfonamide

Hoda El-Ghamry; Raafat Issa; Kamal El-Baradie; Keiko Isagai; Shigeyuki Masaoka; Ken Sakai

doi:10.1107/S1600536808024239

. 2008 Aug 6;64(Pt 9):o1673–o1674. doi: 10.1107/S1600536808024239

4-[(3-Formyl-4-hydroxyphenyl)diazenyl]-N-(pyrimidin-2-yl)benzenesulfonamide

Hoda El-Ghamry ^a,^*, Raafat Issa ^a, Kamal El-Baradie ^a, Keiko Isagai ^b, Shigeyuki Masaoka ^b, Ken Sakai ^b

PMCID: PMC2960714 PMID: 21201664

Abstract

The title molecule, C₁₇H₁₃N₅O₄S, has a trans configuration with respect to the diazenyl (azo) group. The pyrimidine ring and the terminal benzene ring are inclined at angles of 89.38 (4) and 1.6 (6)°, respectively, with respect to the central benzene ring. The conformation of the molecule is in part stabilized by an intramolecular O—H⋯O hydrogen bond. In the crystal structure, molecules related through inversion centers form hydrogen-bonded dimers involving the sulfonamide N—H group and the N atom of the pyrimidine ring.

Related literature

For related literature, see: Gaber et al. (2008 ▶ and references therein); Kakoti et al. (1993 ▶); La Roche & Co (1967a,b); Misra et al. (1998 ▶); Mubarak et al. (2007 ▶); Nagaraja et al. (2002 ▶); Santra & Lahiri (1997 ▶); Vaichulis (1977 ▶). For bond-length data, see: Allen et al. (1987 ▶).

Experimental

Crystal data

C₁₇H₁₃N₅O₄S
M _r = 383.39
Monoclinic,
a = 18.579 (2) Å
b = 5.7731 (7) Å
c = 17.372 (2) Å
β = 115.99 (1)°
V = 1674.73 Å³
Z = 4
Mo Kα radiation
μ = 0.23 mm⁻¹
T = 100 (2) K
0.30 × 0.20 × 0.10 mm

Data collection

Bruker SMART APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.934, T _max = 0.977
17304 measured reflections
3560 independent reflections
3277 reflections with I > 2σ(I)
R _int = 0.017

Refinement

R[F ² > 2σ(F ²)] = 0.034
wR(F ²) = 0.097
S = 1.05
3560 reflections
245 parameters
H-atom parameters constrained
Δρ_max = 0.42 e Å⁻³
Δρ_min = −0.37 e Å⁻³

Data collection: APEX2 (Bruker, 2006 ▶); cell refinement: SAINT (Bruker, 2004 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: KENX (Sakai, 2004 ▶); software used to prepare material for publication: SHELXL97, TEXSAN (Molecular Structure Corporation, 2001 ▶), KENX and ORTEPII (Johnson, 1976 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808024239/lh2668sup1.cif

e-64-o1673-sup1.cif^{(21.9KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808024239/lh2668Isup2.hkl

e-64-o1673-Isup2.hkl^{(174.6KB, 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
O2—H1⋯O1	0.84	1.90	2.6269 (17)	145
N3—H10⋯N5ⁱ	0.88	1.98	2.8574 (17)	179

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Symmetry code: (i) Inline graphic .

Acknowledgments

This work was supported by a Grant-in-Aid for Specially Promoted Research (No. 18002016) from the Ministry of Education, Culture, Sports, Science, and Technology of Japan. HE acknowledges the Egyptian Channel System for financial support to promote the joint research project between Tanta and Kyushu Universities.

supplementary crystallographic information

Comment

Sulfa-drugs are widely used in the treatment of infections, especially for patients intolerant to antibiotics (Nagaraja et al., 2002). The vast commercial success of these medical agents has made the chemistry of sulfonamides become a major area of research and an important branch of commercial importance in pharmaceutical sciences (Nagaraja et al., 2002). Heterocyclic azo compounds are also considered very important class of compounds. The importance of these compounds may stem from its biological activity and analytical investigations (Gaber et al., 2008). Also, it is well known that heterocyclic azo compounds have been used to establish the low oxidation states of different metal ions (Kakoti et al., 1993; Santra & Lahiri, 1997; Misra et al., 1998). What appears more important is that sulfonamide and azo-sulfonamide derivatives have been found to be biologically versatile anticancer (La Roche & Co, 1967a,b) and antitubercular (Vaichulis, 1977) drugs.

In the title compound (I), C₁₇H₁₃N₅O₄S, the two aromatic groups attached to the azo double bond are oriented in a trans fashion. All the bond lengths are found to be within the normal values (Allen et al., 1987). An intramolecular hydrogen bond is formed between the O—H (hydroxyl) group and the oxygen atom of the carbonyl group (O2—H1···O1; Table 1), stabilizing the coformation of the molecule. Moreover, the molecule is further correlated with an adjacent molecule through an inversion center, where the intermolecular interaction is stabilized with two hydrogen bonds formed between the N—H(sulfonamide) group and the nitrogen atom of pyrimidine ring, N3—H···N5ⁱ hydrogen bond [symmetry code: (i) 1 - x, 2 - y, 1 - z] (see Fig. 2 and Table 1). There is an unusually short intermolecular contact between the C (carbonyl) and the O (sulfonamide) atoms, i.e., C1···O3ⁱⁱ = 2.91 (2) Å [symmetry code: (ii) 2 - x, 1/2 + y, 3/2 - z]. Although the rotation about the C10—S1 bond axis is essentially allowed, the rotation at this geometry is fixed as a result of strong intermolecular hydrogen bonds formed at the peripheral pyrimidine attached to the sulfonamide unit. This must be the major cause of the short contact found for one of the sulfonamide oxygen atoms, i.e., O3.

The pyrimidine ring and both the central and terminal benzene rings are found to have a planar geometry (r.m.s deviations are 0.0136, 0.0106 and 0.0225 Å, respectively). Both the pyrimidine and the terminal phenyl rings are canted with respect to the central phenyl ring at angle of 89.38 (4) and 1.6 (6)°, respectively.

Experimental

Compound (I) was prepared by the previously reported method in the literature (Mubarak et al., 2007) in which 2.5 g m (0.01 mol) of sulfadiazine was dissolved in 25 ml of distilled water containing 2.5 ml (12M, 2.5 ml, 0.03 mol) of conc. HCl. The resulting solution was then cooled under stirring to 273 K. A cold solution containing 0.69 g m (0.01 mol) of sodium nitrite was drop wisely added to the previous solution to form the diazonium chloride. This solution was then added to a solution containing 1.06 ml of salicylaldehyde (0.01 mol) dissolved in 10 ml of water containing 0.4 g m (0.01 mol) of NaOH. The orange dye, which separated out, was kept in an ice bath under stirring for 30 minutes. The precipitate was then filtered off, washed by distilled water, and finally air_dried (yield: 80%). Analysis calculated for C₁₇H₁₃N₅O₄S: C, 53.26; H, 3.39; N, 18.27; S, 8.35% found: C, 53.44; H, 3.34; N, 18.38; S, 8.25%. IR (ν, cm^-1): 3424(w), 3358(w), 3082(w), 3041(w), 2944(w), 2814(w), 2727(w), 1652(s), 1621(m), 1581(s), 1496(s), 1443(s), 1410(s), 1384(m), 1339(s), 1305(m), 1289(s), 1269(m), 1206(m), 1166(s), 1154(s), 1141(w), 1001(m), 952(s), 902(m), 840(s), 797(s), 772(w), 750(s), 729(s), 669(s), 640(s), 606(s), 582(s), 564(s), 540(w), 531(w), 521(m), 509(m), 455(s), 432(m), 424(w), 403(m). A good crystal suitable for x-ray measurement was prepared by vapour diffusion method in which compound (I) was dissolved in the least possible amount of DMF and then the solution was left at room temperature in the presence of water pool outside. The outside water slowly diffused by vapour and gradually mixed with DMF of the dye. After 7 days, dark orange crystals suitable for X-ray diffraction analysis was separated out.