N-(2-Chloro­phen­yl)-4-hydr­oxy-2H-1,2-benzothia­zine-3-carboxamide 1,1-dioxide

Waseeq Ahmad Siddiqui; Hamid Latif Siddiqui; Muhammad Azam; Masood Parvez; Umar Farooq Rizvi

doi:10.1107/S1600536809033972

. 2009 Aug 29;65(Pt 9):o2279–o2280. doi: 10.1107/S1600536809033972

N-(2-Chlorophenyl)-4-hydroxy-2H-1,2-benzothiazine-3-carboxamide 1,1-dioxide

Waseeq Ahmad Siddiqui ^a,^*, Hamid Latif Siddiqui ^b, Muhammad Azam ^c, Masood Parvez ^d, Umar Farooq Rizvi ^b

PMCID: PMC2969961 PMID: 21577673

Abstract

In the title compound, C₁₅H₁₁ClN₂O₄S, there are two independent molecules in the asymmetric unit, in which the heterocyclic thiazine rings in both molecules adopt half-chair conformations. The conformations about the C—C and C—N bonds in the central C—C—N—C chain in both molecules are all EZ. There are strong intramolecular O—H⋯O and N—H⋯N hydrogen bonds resulting in graph-set patterns S(6) and S(5) for the oxo and amino rings, in addition to intramolecular N—H⋯Cl interactions. In the crystal structure, molecules are linked by intermolecular O—H⋯O and N—H⋯O hydrogen bonds into chains along [100].

Related literature

For details of the synthesis, see: Siddiqui et al. (2008 ▶). For background to benzothiazine carboxamide derivatives as analgesic and anti-inflammatory agents, see: Myung et al. (2002 ▶); Shin et al. (2000 ▶); Banerjee & Sarkar (2002 ▶). For related structures, see: Siddiqui et al. (2006 ▶, 2007 ▶, 2008 ▶). Allen et al. (1987 ▶). For hydrogen-bond patterns and graph sets, see: Bernstein et al. (1994 ▶).

Experimental

Crystal data

C₁₅H₁₁ClN₂O₄S
M _r = 350.77
Monoclinic,
a = 10.077 (2) Å
b = 13.818 (3) Å
c = 21.426 (4) Å
β = 97.070 (13)°
V = 2960.8 (10) Å³
Z = 8
Mo Kα radiation
μ = 0.42 mm⁻¹
T = 200 K
0.16 × 0.14 × 0.12 mm

Data collection

Nonius KappaCCD diffractometer
Absorption correction: multi-scan (SORTAV; Blessing, 1997 ▶) T _min = 0.936, T _max = 0.951
12965 measured reflections
6732 independent reflections
5711 reflections with I > 2σ(I)
R _int = 0.031

Refinement

R[F ² > 2σ(F ²)] = 0.041
wR(F ²) = 0.101
S = 1.05
6732 reflections
433 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.33 e Å⁻³
Δρ_min = −0.39 e Å⁻³

Data collection: COLLECT (Hooft, 1998 ▶); cell refinement: DENZO (Otwinowski & Minor, 1997 ▶); data reduction: SCALEPACK (Otwinowski & Minor, 1997 ▶); 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: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809033972/lh2886sup1.cif

e-65-o2279-sup1.cif^{(27.5KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809033972/lh2886Isup2.hkl

e-65-o2279-Isup2.hkl^{(322.8KB, 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
O3—H3O⋯O4	0.83 (3)	1.89 (3)	2.612 (2)	144 (3)
O3—H3O⋯O4ⁱ	0.83 (3)	2.33 (3)	2.854 (2)	122 (2)
O7—H7O⋯O8	0.89 (3)	1.81 (3)	2.607 (2)	147 (2)
O7—H7O⋯O8ⁱⁱ	0.89 (3)	2.46 (3)	2.964 (2)	116 (2)
N1—H1N⋯O8ⁱⁱ	0.87 (2)	2.06 (2)	2.911 (2)	164 (2)
N2—H2N⋯N1	0.82 (2)	2.24 (2)	2.700 (2)	116 (2)
N2—H2N⋯Cl1	0.82 (2)	2.47 (2)	2.930 (2)	116 (2)
N3—H3N⋯O4ⁱ	0.89 (2)	2.07 (2)	2.912 (2)	157 (2)
N4—H4N⋯N3	0.88 (2)	2.23 (2)	2.692 (2)	113 (2)
N4—H4N⋯Cl2	0.88 (2)	2.41 (2)	2.934 (2)	119 (2)

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

supplementary crystallographic information

Comment

Benzothiazine carboxamide derivatives are important due to their role as analgesic and anti-inflammatory agents (Myung et al., 2002). These compounds belong to the oxicam class of non-steroidal anti-inflammatory drugs (NSAIDs) and are free from steroidal side-effects. However, these are ulcerogenic in behavior to varying degrees (Shin et al., 2000). Besides great therapeutic potential, these compounds are very motivating polyfunctional heterocycles by virtue of their dynamic structural features (Banerjee & Sarkar, 2002). The search for more effective anti-inflammatory agents has led us to the synthesis of new agents using readily available starting material following facile routes to yield several products (Siddiqui et al., 2006; Siddiqui et al., 2007). In continuation of this program, we required the title compound, (I), to act as a nucleus for a variety of biologically active 1,2-benzothiazine-1,1-dioxide derivatives. Herein, we report the crystal structure of the title compound.

There are two molecules and in the asymmetric unit of the title compound (Fig. 1); the molecules containing S1 and S2 are referred to as molecules A and B, respectively. The bond lengths and bond angles in both molecules of (I) are within normal ranges (Allen et al., 1987) and agree well with the corresponding bond lengths and bond angles of its N-methyl analogues (Siddiqui et al., 2008).

The heterocyclic thiazine rings in both molecules of (I) adopt half-chair conformations wherein S1 and N1 are displaced by 0.439 (4) and -0.291 (3) Å, respectively, from the plane defined by C5/C6/C7/C8 atoms in molecule A and S2 and N3 displaced by -0.463 (4) and 0.284 (4) Å, respectively, from the plane defined by C20/C21/C22/C23 atoms in the molecule B. The puckering parameters (Cremer & Pople, 1975) in molecules A and B are: Q = 0.477 (2) and 0.489 (2) Å, θ = 118.2 (2) and 117.7 (2)° and φ = 203.8 (3) and 202.9 (3)°, respectively. Similar conformations of the thiazine ring have been reported in the structures related to (I) (Siddiqui et al., 2008).

The conformations about the bonds C8–C9 and C9–N2 in molecule A and the bonds C23–C24 and C24–N4 in molecule B are all EZ, as determined by the strong intramolecular hydrogen bonds O3–H3O···O4 and N2–H2N···N1 in molecule A and O7–H7O···O8 and N4—H4N···N3 in molecule B resulting in graph set patterns S(6) and S(5) for the oxo and amino rings, respectively (Bernstein et al., 1994). The intramolecular hydrogen bonds of the types N–H···Cl and C–H···O are also present in both molecules which represent S(5) and S(6) motifs, respectively. The structure is stabilized by intermolecular hydrogen bonds of the types O–H···O and N–H···O (details of H-bonding geometry have been provided in Table 1 and depicted in Fig. 2). The central atoms N2/O4/C8/C9/C10 in molecule A and N4/O8/C23/C24/C25 in molecule B are individually planar with maximum deviations of atoms from the planes being 0.0086 (16) and 0.0127 (14) Å for C9 and N4, respectively.

Experimental

The method of preparation of the title compound has already been reported (Siddiqui et al., 2006; Siddiqui et al., 2007). Crystal of (I) suitable for X-ray crystallographic study were obtained by slow evaporation of its methanol solution at 313 K.