6-Bromo-4-hydrazinyl­idene-1-methyl-3H-2λ6,1-benzothia­zine-2,2-dione

Muhammad Shafiq; Islam Ullah Khan; Muhammad Zia-ur-Rehman; Muhammad Nadeem Arshad; Abdullah M Asiri

doi:10.1107/S1600536811027930

. 2011 Jul 23;67(Pt 8):o2078. doi: 10.1107/S1600536811027930

6-Bromo-4-hydrazinylidene-1-methyl-3H-2λ⁶,1-benzothiazine-2,2-dione

Muhammad Shafiq ^a, Islam Ullah Khan ^a, Muhammad Zia-ur-Rehman ^b, Muhammad Nadeem Arshad ^c,^a,^*, Abdullah M Asiri ^d

PMCID: PMC3213521 PMID: 22091100

Abstract

In the title molecule, C₉H₁₀BrN₃O₂S, the thiazine ring has an envelope conformation with the S atom at the flap. The geometry around the S atom is distorted tetrahedral. In the crystal, inversion dimers linked by pairs of N—H⋯N hydrogen bonds occur, generating R ₂ ²(6) ring motifs. N—H⋯O hydrogen bonds and C—H⋯O interactions connect the dimers, forming a three-dimentional network structure.

Related literature

For the related structures of 6-bromo-1-methyl-1H-2,1-benzothiazin-4(3H)-one 2,2-dioxide and 6-bromo-1-ethyl-1H-2,1-benzothiazin-4(3H)-one 2,2-dioxide, see: Shafiq et al. (2009a ▶,b ▶), respectively. For the structures of other benzothiazine derivatives, see: Shafiq et al. (2011 ▶); Arshad et al. (2011 ▶). For graph-set notation, see: Bernstein et al. (1995 ▶). For puckering parameters, see: Cremer & Pople (1975 ▶).

Experimental

Crystal data

C₉H₁₀BrN₃O₂S
M _r = 304.17
Monoclinic,
a = 10.1483 (5) Å
b = 9.6375 (4) Å
c = 11.2118 (5) Å
β = 92.278 (2)°
V = 1095.69 (9) Å³
Z = 4
Mo Kα radiation
μ = 3.93 mm⁻¹
T = 296 K
0.21 × 0.09 × 0.07 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ▶) T _min = 0.492, T _max = 0.771
12176 measured reflections
2719 independent reflections
1972 reflections with I > 2σ(I)
R _int = 0.037

Refinement

R[F ² > 2σ(F ²)] = 0.032
wR(F ²) = 0.079
S = 1.01
2719 reflections
152 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.40 e Å⁻³
Δρ_min = −0.35 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) I, global. DOI: 10.1107/S1600536811027930/su2288sup1.cif

e-67-o2078-sup1.cif^{(16.7KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811027930/su2288Isup2.hkl

e-67-o2078-Isup2.hkl^{(130.8KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811027930/su2288Isup3.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
N3—H32⋯N2ⁱ	0.85 (4)	2.47 (4)	3.198 (4)	144 (3)
N3—H31⋯O1ⁱⁱ	0.90 (4)	2.38 (4)	3.252 (4)	162 (3)
C3—H3⋯O1ⁱⁱⁱ	0.93	2.45	3.323 (3)	156

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

Acknowledgments

The authors acknowledge the Higher Education Commission of Pakistan for providing a grant for the project to strengthen the Materials Chemistry Laboratory at GC University, Lahore, Pakistan.

supplementary crystallographic information

Comment

Continuing our research on the synthesis (Shafiq et al., 2011; Arshad et al., 2011) and crystal structure studies of benzothiazine derivatives (Shafiq et al., 2009a), we present herein the crystal structure of the title compound, (I).

The molecular structure of the title molecule, (I), is illustrated in Fig. 1. The structure differs to a similar published compound, 6-Bromo-1-methyl-1H-2,1-benzothiazin-4(3H)-one 2,2-dioxide (II) [Shafiq et al., 2009a], in that the carbonyl group in (II) has been replaced with a hydrazide moiety in (I). The bond lengths and angles in the title compound are similar to those of (II) and in 6-Bromo-1-ethyl-1H-2,1-benzothiazin-4(3H)-one 2,2-dioxide (III) (Shafiq et al., 2009b). In (I) atom Br1, attached to the planar aromatic ring (C1—C6), lies out of the plane by 0.0547 (3) Å, while in (II) and (III) the deviations are slightly greater, i.e. 0.064 (4) and 0.073 (4) Å, respectively. The thiazine ring, (C1/C6/C7/C8/S1/N1), has an envelope conformation with atom S1 as the flap [puckering parameters: Q (puckering amplitude) = 0.5873 (18) Å, θ = 124.31 (19) °, and φ = 185.9 (3) ° (Cromer & Pople, 1975)].

In the crystal structure of compound (I) the functional hydrazide group is involved in the formation of inversion dimers, through N3—H32···N2 hydrogen bonding, and generates a six-membered R₂²(6) ring motif (Bernstein et al., 1995). These dimers are further connected through N—H···O hydrogen bonds and weak C—H···O interactions to form a three dimensional network structure (Table 1, Fig. 2).

Experimental

A mixture of 1-methyl-2,2-dioxo-2,3-dihydro-1H-2λ⁶-benzo [c][1,2]thiazin-4-one (10.60 g; 50.0 mmoles), hydrazine hydrate (85%) (5.0 ml) and ethanol (200 ml) was reacted at 318 K using an ultrasound reaction bath for about 35 mins. After completion of the reaction, excess hydrazine and solvent were removed under vacuum. The crude product obtained was washed with water and dried; Yield: 74%. Suitable crystals were produced through recrystalization in methanol under slow evaporation.