2-[(E)-({4-[(4,6-Dimethyl­pyrimidin-2-yl)sulfamo­yl]phen­yl}iminio)meth­yl]-6-hy­droxy­phenolate

M Nawaz Tahir; Abdul Haleem Khan; Mohammad S Iqbal; Hazoor Ahmad Shad; Muhammad Yaqub

doi:10.1107/S1600536812034757

. 2012 Aug 11;68(Pt 9):o2687. doi: 10.1107/S1600536812034757

2-[(E)-({4-[(4,6-Dimethylpyrimidin-2-yl)sulfamoyl]phenyl}iminio)methyl]-6-hydroxyphenolate

M Nawaz Tahir ^a,^*, Abdul Haleem Khan ^b, Mohammad S Iqbal ^c, Hazoor Ahmad Shad ^d, Muhammad Yaqub ^e

PMCID: PMC3435708 PMID: 22969579

Abstract

The title compound, C₁₉H₁₈N₄O₄S, exists as a zwitterion in the solid state, with nominal proton transfer from a phenol group to the imine N atom. The 2,3-dihydroxybenzaldehyde fragment is oriented at a dihedral angle of 35.51 (11)° to the adajacent aniline group and makes a dihedral angle of 76.99 (6)° with the 4,6-dimethylpyrimidin-2-amine group. Intramolecular O—H⋯O and N—H⋯O hydrogen bonds close S(5) and S(6) rings, respectively; the same O atom accepts both bonds. In the crystal, polymeric chains along [001] are formed from molecules joined end-to-end by N—H⋯O and O—H⋯N hydrogen bonds; these feature R ₂ ³(6) loops. The polymeric chains are linked by C—H⋯O interactions and there are π–π interactions between the pyrimidine rings with a centroid–centroid distance of 3.446 (2) Å.

Related literature

For related structures, see: Chohan et al. (2008 ▶); Shad et al. (2009 ▶); Tahir et al. (2012 ▶). For graph-set notation, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C₁₉H₁₈N₄O₄S
M _r = 398.43
Orthorhombic,
a = 24.7506 (12) Å
b = 12.1689 (6) Å
c = 12.8408 (5) Å
V = 3867.5 (3) Å³
Z = 8
Mo Kα radiation
μ = 0.20 mm⁻¹
T = 296 K
0.34 × 0.28 × 0.15 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T _min = 0.935, T _max = 0.971
16627 measured reflections
3796 independent reflections
1778 reflections with I > 2σ(I)
R _int = 0.069

Refinement

R[F ² > 2σ(F ²)] = 0.054
wR(F ²) = 0.151
S = 1.01
3796 reflections
259 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.21 e Å⁻³
Δρ_min = −0.28 e Å⁻³

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); 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 ▶) and PLATON (Spek, 2009 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶) and PLATON.

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812034757/hb6908sup1.cif

e-68-o2687-sup1.cif^{(27.3KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812034757/hb6908Isup2.hkl

e-68-o2687-Isup2.hkl^{(182.4KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536812034757/hb6908Isup3.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—H1⋯O1	0.78 (4)	1.88 (4)	2.569 (5)	148 (4)
O2—H2⋯O1	0.82	2.34	2.768 (5)	113
O2—H2⋯N3ⁱ	0.82	2.16	2.862 (5)	144
N2—H2A⋯O1ⁱⁱ	0.86	1.94	2.790 (4)	172
C18—H18A⋯O4ⁱⁱⁱ	0.96	2.52	3.469 (5)	171

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

Acknowledgments

The authors acknowledge the provision of funds for the purchase of the diffractometer and encouragement by Dr Muhammad Akram Chaudhary, Vice Chancellor, University of Sargodha, Pakistan.

supplementary crystallographic information

Comment

We have reported the crystal structure of 4-{[(E)-(2,3-dihydroxyphenyl) methylidene]amino}-N-(5-methyl-1,2-oxazol-3-yl)benzenesulfonamide (Tahir et al., 2012) and the title compound (I), (Fig. 1) has also been synthesized for the biological studies and forming different metal complexes.

The crystal structures of 4-(5-chloro-2-hydroxybenzylideneamino)-N- (4,6-dimethylpyrimidin-2-yl)benzenesulfonamide (Chohan et al., 2008) and 4-[(5-bromo-2-hydroxybenzylidene)amino]-N-(4,6-dimethylpyrimidin- 2-yl)benzenesulfonamide–4-bromo-2-[(E)-({4-[(4,6-dimethylpyrimidin-2-yl) sulfamoyl]phenyl}iminio)methyl]phenolate (Shad et al., 2009) have been published which are related to the title compound.

In (I) the parts of 2,3-dihydroxybenzaldehyde A (C1—C7/O1/O2), annilinic group B (C8—C13/N1) and 4,6-dimethylpyrimidin-2-amine C (C14—C19/N2/N3/N4) are planar with r.m.s. deviation of 0.0105, 0.0070 and 0.0216 Å, respectively. The dihedral angle between A/B, A/C and B/C is 35.51 (11)°, 76.99 (6)° and 88.92 (6)°, respectively. The sulfonyl group D (O3/S1/O4) is of course planar. The dihedral angle between A/D, B/D and C/D is 62.20 (13)°, 47.66 (17)° and 50.34 (15)°, respectively. In (I), S(5) and S(6) ring motif (Bernstein et al., 1995) are present due to H-bondings of O—H···O and N—H···O types, respectively (Table 1, Fig. 1). The molecules are interlinked from end to end due to H-bondings of N—H···O and O—H···O types (Table 1, Fig. 2). Due to these bondings R₂³(6) loops are also formed. The molecules are interlinked in the form of polymeric chains along the c-axis. The polymeric chains are also interlinked due to C–H···O bondings (Table 1, Fig. 2), Where CH is of methyl group and O-atom is of sulfonyl group. There exist π–π interaction between Cg1···Cg1ⁱ [i = 1 - x, y, 1/2 - z] at a distance of 3.446 (2) Å, where Cg1 is the centroid of pyrimidin ring (C14—C17/N3/N4).

Experimental

Equimolar quantities of 4-amino-N-(4,6-dimethylpyrimidin-2-yl) benzenesulfonamide (Sulfamethazine) and 2,3-dihydroxybenzaldehyde were refluxed in methanol along with few drops of acetic acid as catalyst for 3 h. The solution was kept at room temperature which afforded dark red plates after four days upon slow evaporation of the solvent.