N′-[(E)-1-(4-Bromo­phen­yl)ethyl­idene]-4-hy­droxy-2-methyl-1,1-dioxo-2H-1,2-benzothia­zine-3-carbohydrazide

Naveed Ahmad; Muhammad Zia-ur-Rehman; Hamid Latif Siddiqui; Muhammad Nadeem Arshad; Abdullah M Asiri

doi:10.1107/S1600536811035641

. 2011 Sep 14;67(Pt 10):o2613. doi: 10.1107/S1600536811035641

N′-[(E)-1-(4-Bromophenyl)ethylidene]-4-hydroxy-2-methyl-1,1-dioxo-2H-1,2-benzothiazine-3-carbohydrazide

Naveed Ahmad ^a, Muhammad Zia-ur-Rehman ^b,^*, Hamid Latif Siddiqui ^a, Muhammad Nadeem Arshad ^c, Abdullah M Asiri ^d

PMCID: PMC3201552 PMID: 22064647

Abstract

The six-membered heterocycle in the title compound, C₁₈H₁₆BrN₃O₄S, adopts a sofa conformation. Intramolecular N—H⋯N and O—H⋯O hydrogen bonds stabilize the molecular conformation by forming a five- and a six-membered ring, respectively. The crystal packing is stabilized by intermolecular C—H⋯O hydrogen bonds.

Related literature

For general background, see: Zia-ur-Rehman et al. (2009 ▶). For synthesis details, see: Ahmad et al. (2011 ▶). For graph-set notation of hydrogen-bond motifs, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C₁₈H₁₆BrN₃O₄S
M _r = 450.31
Monoclinic,
a = 14.692 (2) Å
b = 16.562 (2) Å
c = 7.5254 (10) Å
β = 104.820 (1)°
V = 1770.2 (4) Å³
Z = 4
Mo Kα radiation
μ = 2.47 mm⁻¹
T = 173 K
0.48 × 0.36 × 0.11 mm

Data collection

Siemens SMART diffractometer equipped with a Bruker KappaCCD APEXII
Absorption correction: multi-scan (SADABS; Bruker, 2001 ▶) T _min = 0.383, T _max = 0.773
21408 measured reflections
4490 independent reflections
3600 reflections with I > 2σ(I)
R _int = 0.034

Refinement

R[F ² > 2σ(F ²)] = 0.029
wR(F ²) = 0.070
S = 1.03
4490 reflections
292 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.44 e Å⁻³
Δρ_min = −0.40 e Å⁻³

Data collection: SMART (Bruker, 2001 ▶); cell refinement: SAINT (Bruker, 2001 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: PLATON (Spek, 2009 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶) and X-SEED (Barbour, 2001 ▶).

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811035641/bt5633sup1.cif

e-67-o2613-sup1.cif^{(21.1KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811035641/bt5633Isup2.hkl

e-67-o2613-Isup2.hkl^{(215.5KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811035641/bt5633Isup3.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
C17—H17C⋯O2ⁱ	0.95 (3)	2.38 (3)	3.275 (2)	158 (2)
C17—H17A⋯O4ⁱⁱ	0.95 (3)	2.54 (3)	3.479 (2)	171 (2)
N2—H2N⋯N1	0.84 (3)	2.24 (3)	2.690 (2)	114 (2)
O1—H1O⋯O4	0.82 (3)	1.86 (3)	2.5979 (18)	148 (3)

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

Acknowledgments

NA is grateful to the Higher Education Commission of Pakistan for the award of an HEC indigenous scholarship.

supplementary crystallographic information

Comment

In continuation of our on-going research on various biologically active benzothiazine derivatives (Zia-ur-Rehman et al., 2009; Ahmad et al., 2011) synthesis and crystal structure of the title molecule (I) is reported here.

In the crystal structure of the title compound (I), two fused rings (benzene & thiazine) are twisted with a dihedral angle of 13.61 (10)° while the later (C1/C6/C7/C8/N1/S1) adopts half chair conformation [Nitrogen (0.3564 (10)Å and sulfur (-0.3114 (9) Å) atoms show maximum deviation from the least square plane]. The bromophenyl ring (C11—C16) is oriented almost at the same dihedral angle that measures 27.93 (7)° and 26.23 (8)° with respect to the thiazine and aromatic ring (C1—C6). Intramolecular hydrogen bonding through O—H···O and N—H···N interactions gives rise to two different rings S₁¹(6) A and S₁¹(5) B respectively (Figure 1). Rings generated from intramolecular hydrogen bondings are fused and twisted at dihedral angle of 5.01 (82)Å and both are inclined at 22.00 (47)Å and 18.83 (27)Å with respect to the thiazine ring. Molecules of the title compound (I) are involved in symmetry related C—H···O weak interactions which form inversion dimers and give rise to the formation of a twelve membered ring R₂²(12) (Bernstein et al., 1995). The dimers are further linked through another C—H···O interaction generating from N-methyl hydrogen and sulfone oxygen atoms giving rise to two dimensional polymeric network along bc plane (Figure 2., Table 1).

Experimental

A mixture of 4-hydroxy-2H-1,2-benzothiazine-3-carbohydrazide 1,1-dioxide (2.0 mmol), 4-bromo acetophenone (2.0 mmol), ortho phosphoric acid (2 drops) and methanol (50 ml) was refluxed for a period of seven hours. The content was cooled to 5°C in an ice bath, filtered and the solids were washed with cold methanol to get the pure compound. The product was crystallized from ethanol to get the suitable crystals. Yield: 82%.