3-(6-Bromo-4-oxo-4H-chromen-3-yl)-3,4-dihydro-2H-1,2,4-benzothia­diazine-1,1-dione

Mariya al-Rashida; Saeed Ahmad Nagra; Islam Ullah Khan; George Kostakis; Ghulam Abbas

doi:10.1107/S1600536810044648

. 2010 Nov 6;66(Pt 12):o3081–o3082. doi: 10.1107/S1600536810044648

3-(6-Bromo-4-oxo-4H-chromen-3-yl)-3,4-dihydro-2H-1,2,4-benzothiadiazine-1,1-dione

Mariya al-Rashida ^a,^‡, Saeed Ahmad Nagra ^a, Islam Ullah Khan ^b, George Kostakis ^c, Ghulam Abbas ^a,^*

PMCID: PMC3011492 PMID: 21589389

Abstract

The molecular structure of the title compound, C₁₆H₁₁BrN₂O₄S, is very similar to that of the previously reported fluoro analogue [al-Rashida et al. (2010 ▶). Acta Cryst. E66, o2707]. The mean planes of the bicyclic chromone system and the benzene ring of the benzothiadiazine derivative make a dihedral angle of 58.23 (8)°. An intramolecular N—H⋯O hydrogen bond occurs. In the crystal, molecules are linked into layers by N—H⋯O and C—H⋯O hydrogen bonds, generating an infinite two-dimensional network.

Related literature

For background to the importance of the 1,2,4-benzothiadiazine-1,1-dioxide ring system in pharmaceutical and medicinal chemistry, see: Zhu et al. (2005 ▶); Kamal et al. (2007a ▶). For a survey on the antimicrobial activity of benzothiadiazine derivatives, see: Di Bella et al. (1983) ▶; Kamal et al. (2007a ▶,b ▶). The sulfonamide group is an active pharmacophore, see: Weisman & Brown (1964) ▶. For related structures, see: al-Rashida et al. (2009 ▶, 2010 ▶).

Experimental

Crystal data

C₁₆H₁₁BrN₂O₄S
M _r = 407.24
Monoclinic,
a = 7.0778 (4) Å
b = 8.6070 (6) Å
c = 25.6290 (16) Å
β = 94.607 (3)°
V = 1556.24 (17) Å³
Z = 4
Mo Kα radiation
μ = 2.80 mm⁻¹
T = 296 K
0.28 × 0.28 × 0.22 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2007 ▶) T _min = 0.475, T _max = 0.540
17309 measured reflections
3873 independent reflections
1969 reflections with I > 2σ(I)
R _int = 0.058

Refinement

R[F ² > 2σ(F ²)] = 0.046
wR(F ²) = 0.103
S = 0.98
3873 reflections
223 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.50 e Å⁻³
Δρ_min = −0.51 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 Mercury (Macrae et al., 2006 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810044648/zq2069sup1.cif

e-66-o3081-sup1.cif^{(25.7KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810044648/zq2069Isup2.hkl

e-66-o3081-Isup2.hkl^{(189.9KB, 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
N4—H4A⋯O4	0.79 (3)	2.59 (3)	2.987 (3)	113 (3)
N4—H4A⋯O3ⁱ	0.79 (3)	2.23 (3)	2.999 (3)	164 (3)
C13—H13⋯O3ⁱ	0.93	2.54 (1)	3.314 (4)	141 (1)
N2—H2A⋯O2	0.84 (2)	2.67 (3)	3.222 (4)	124 (2)
C2—H2⋯O2	0.93	2.41 (1)	3.330 (4)	169 (1)
N2—H2A⋯O4	0.84 (2)	2.12 (3)	2.903 (4)	154 (3)

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Symmetry code: (i) Inline graphic .

Acknowledgments

The authors acknowledge the Higher Education Commission (HEC), Islamabad, Pakistan, for financial and GCU, Lahore, for technical suppport.

supplementary crystallographic information

Comment

The 1,2,4-benzothiadiazine-1,1-dioxide ring system is of considerable importance in medicinal and pharmaceutical chemistry (Zhu et al., 2005; Kamal et al., 2007a). Novel products from reactions of 4- and 2-aminobenzenesulfonamide with 6-(un)substituted-4-oxo-4H-1-benzopyran-3-carboxaldehyde have already been reported by us (Mariya-al-Rashida et al., 2009, 2010). In continuation of our project, the crystal structure of the title compound is reported here (Fig. 1).

In the crystal structure, the two rings of the chromone system (Br1, O1, O4, C2—C10) are coplanar making a dihedral angle of 1.0 (2)°. The carbon atom C11 deviates from the mean plane of the chromone ring by 0.016 (4) Å. The phenyl ring (C12—C17) of the benzothiadiazine moiety and the atoms S1, N4 and C11 are almost planar as well (rms deviation = 0.007) and make a dihedral angle of 58.23 (8)° with the mean plane of the bicyclic chromone system. The crystal structure is stabilized by intra- and intermolecular N—H···O and C—H···O hydrogen bonds which link the molecules into an infinite two-dimensional network (Fig. 2).

Experimental

A solution of 2-aminobenzenesulfonamide (1.0 mmol) in 10 ml e thanol was slowly added to the stirred solution of 6-bromo-4-oxo-4H-1-benzopyran-3-carboxaldehyde (1.0 mmol) containing catalytic amount of p-toluene sulfonic acid (p-TsOH) and refluxed for 3 hrs. The resulting product was isolated by filtration, washed with ethanol, dried and recrystallized from hot ethanol and acetone (1:1) (yield 77%, m.p. 496 K).