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Acta Crystallogr Sect E Struct Rep Online. 2010 December 1; 66(Pt 12): o3081–o3082.
Published online 2010 November 6. doi:  10.1107/S1600536810044648
PMCID: PMC3011492

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

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 [triangle]). 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 [triangle]); Kamal et al. (2007a [triangle]). For a survey on the anti­microbial activity of benzothia­diazine derivatives, see: Di Bella et al. (1983) [triangle]; Kamal et al. (2007a [triangle],b [triangle]). The sulfonamide group is an active pharmacophore, see: Weisman & Brown (1964) [triangle]. For related structures, see: al-Rashida et al. (2009 [triangle], 2010 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-66-o3081-scheme1.jpg

Experimental

Crystal data

  • C16H11BrN2O4S
  • M r = 407.24
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-o3081-efi1.jpg
  • 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 [triangle]) 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
  • Δρmax = 0.50 e Å−3
  • Δρmin = −0.51 e Å−3

Data collection: APEX2 (Bruker, 2007 [triangle]); cell refinement: SAINT (Bruker, 2007 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 [triangle]) and Mercury (Macrae et al., 2006 [triangle]); software used to prepare material for publication: publCIF (Westrip, 2010 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

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

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

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

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).

Refinement

The H atoms attached to N were located in a difference Fourier map and their coordinates were refined, with Uiso(H) = 1.2Ueq(N). The remaining H atoms were positioned geometrically with C-H = 0.93 and 0.98 Å for aromatic and methine H atoms, respectively, and constrained to ride on their parent atoms, with Uiso(H) = 1.2Ueq(C).

Figures

Fig. 1.
The molecular structure of the title compound with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.
Fig. 2.
A packing diagram of the title compound showing hydrogen bonds as dashed lines.

Crystal data

C16H11BrN2O4SF(000) = 816
Mr = 407.24Dx = 1.738 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 2932 reflections
a = 7.0778 (4) Åθ = 3.1–22.1°
b = 8.6070 (6) ŵ = 2.80 mm1
c = 25.6290 (16) ÅT = 296 K
β = 94.607 (3)°Needle, white
V = 1556.24 (17) Å30.28 × 0.28 × 0.22 mm
Z = 4

Data collection

Bruker APEXII CCD area-detector diffractometer3873 independent reflections
Radiation source: fine-focus sealed tube1969 reflections with I > 2σ(I)
graphiteRint = 0.058
phi and ω scansθmax = 28.4°, θmin = 1.6°
Absorption correction: multi-scan (SADABS; Bruker, 2007)h = −9→9
Tmin = 0.475, Tmax = 0.540k = −11→8
17309 measured reflectionsl = −34→34

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.046Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.103H atoms treated by a mixture of independent and constrained refinement
S = 0.98w = 1/[σ2(Fo2) + (0.0423P)2 + 0.1442P] where P = (Fo2 + 2Fc2)/3
3873 reflections(Δ/σ)max < 0.001
223 parametersΔρmax = 0.50 e Å3
2 restraintsΔρmin = −0.51 e Å3

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

xyzUiso*/Ueq
S11.22103 (10)0.73566 (10)0.31055 (3)0.0337 (2)
O21.2394 (3)0.5717 (3)0.30708 (9)0.0463 (6)
O31.3885 (3)0.8294 (3)0.31425 (9)0.0465 (6)
N21.0884 (3)0.7953 (3)0.25943 (10)0.0287 (6)
H2A1.085 (4)0.893 (3)0.2592 (12)0.034*
N40.8018 (3)0.7790 (4)0.30189 (10)0.0371 (7)
H4A0.690 (4)0.780 (4)0.3005 (13)0.045*
Br1−0.00741 (5)0.67254 (5)0.060030 (16)0.06277 (19)
C50.3194 (4)0.7029 (4)0.13029 (13)0.0350 (8)
H50.26220.62780.14980.042*
C60.2305 (5)0.7577 (4)0.08503 (13)0.0403 (9)
C70.3086 (5)0.8725 (4)0.05590 (14)0.0455 (9)
H70.24290.90990.02560.055*
C80.4824 (5)0.9304 (4)0.07182 (13)0.0424 (9)
H80.53741.00680.05230.051*
C90.5766 (4)0.8743 (4)0.11749 (12)0.0324 (8)
O10.7509 (3)0.9378 (3)0.13110 (8)0.0398 (6)
C100.4984 (4)0.7614 (4)0.14695 (12)0.0287 (7)
C40.6000 (4)0.7086 (4)0.19593 (12)0.0286 (8)
O40.5369 (3)0.6116 (3)0.22456 (9)0.0395 (6)
C30.7845 (4)0.7819 (4)0.20758 (12)0.0272 (7)
C20.8469 (4)0.8871 (4)0.17524 (12)0.0347 (8)
H20.96650.92910.18380.042*
C110.8977 (4)0.7310 (4)0.25680 (12)0.0289 (7)
H110.90660.61740.25680.035*
C120.8888 (4)0.7966 (4)0.35104 (12)0.0295 (8)
C130.7836 (4)0.8366 (4)0.39290 (13)0.0372 (8)
H130.65310.84940.38710.045*
C140.8682 (5)0.8573 (4)0.44190 (14)0.0431 (9)
H140.79420.88250.46910.052*
C161.1691 (5)0.8056 (4)0.41215 (13)0.0402 (9)
H161.29990.79640.41830.048*
C151.0631 (5)0.8417 (4)0.45229 (14)0.0445 (9)
H151.11960.85570.48600.053*
C171.0843 (4)0.7823 (4)0.36172 (12)0.0291 (8)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
S10.0158 (4)0.0421 (6)0.0427 (5)0.0059 (4)−0.0002 (4)−0.0004 (4)
O20.0393 (14)0.0381 (15)0.0622 (17)0.0148 (11)0.0081 (12)0.0055 (12)
O30.0160 (11)0.0624 (17)0.0608 (16)−0.0034 (11)0.0001 (11)−0.0038 (13)
N20.0172 (13)0.0291 (15)0.0393 (16)−0.0005 (12)0.0005 (12)0.0016 (14)
N40.0121 (12)0.070 (2)0.0293 (16)0.0004 (14)0.0002 (13)−0.0041 (14)
Br10.0358 (2)0.0836 (4)0.0653 (3)−0.0100 (2)−0.01830 (19)−0.0107 (2)
C50.0287 (17)0.035 (2)0.040 (2)−0.0072 (15)−0.0010 (16)−0.0056 (17)
C60.0290 (19)0.049 (2)0.040 (2)0.0009 (17)−0.0140 (16)−0.0148 (18)
C70.051 (2)0.046 (2)0.037 (2)−0.0006 (19)−0.0116 (18)0.0050 (18)
C80.047 (2)0.042 (2)0.036 (2)−0.0048 (18)−0.0029 (18)0.0077 (17)
C90.0332 (18)0.032 (2)0.0313 (19)−0.0038 (15)−0.0044 (15)−0.0040 (16)
O10.0367 (13)0.0447 (15)0.0367 (14)−0.0182 (11)−0.0056 (11)0.0071 (11)
C100.0283 (17)0.0265 (19)0.0309 (18)−0.0002 (14)0.0009 (15)−0.0027 (15)
C40.0250 (17)0.0269 (19)0.0338 (19)−0.0007 (14)0.0014 (15)−0.0058 (16)
O40.0347 (13)0.0426 (14)0.0406 (14)−0.0153 (11)−0.0015 (11)0.0104 (12)
C30.0219 (16)0.0315 (19)0.0286 (17)−0.0038 (14)0.0034 (14)−0.0041 (15)
C20.0283 (18)0.040 (2)0.035 (2)−0.0090 (16)−0.0022 (16)−0.0028 (17)
C110.0171 (15)0.0334 (19)0.0361 (19)−0.0019 (14)0.0027 (14)−0.0035 (15)
C120.0190 (15)0.038 (2)0.0303 (18)0.0018 (14)−0.0024 (14)−0.0023 (15)
C130.0213 (16)0.052 (2)0.038 (2)0.0039 (16)0.0010 (15)−0.0052 (18)
C140.039 (2)0.051 (2)0.039 (2)0.0055 (17)0.0017 (17)−0.0085 (18)
C160.0257 (18)0.048 (2)0.044 (2)0.0029 (16)−0.0094 (17)−0.0032 (18)
C150.044 (2)0.054 (3)0.033 (2)0.0006 (18)−0.0092 (17)−0.0068 (18)
C170.0167 (15)0.0338 (19)0.0363 (19)0.0029 (13)−0.0010 (14)−0.0017 (15)

Geometric parameters (Å, °)

S1—O21.421 (2)C9—C101.375 (4)
S1—O31.431 (2)O1—C21.345 (4)
S1—N21.632 (3)C10—C41.468 (4)
S1—C171.738 (3)C4—O41.219 (3)
N2—C111.456 (4)C4—C31.459 (4)
N2—H2A0.84 (2)C3—C21.327 (4)
N4—C121.365 (4)C3—C111.504 (4)
N4—C111.446 (4)C2—H20.9300
N4—H4A0.79 (3)C11—H110.9800
Br1—C61.900 (3)C12—C131.398 (4)
C5—C61.359 (4)C12—C171.394 (4)
C5—C101.398 (4)C13—C141.359 (4)
C5—H50.9300C13—H130.9300
C6—C71.380 (5)C14—C151.391 (5)
C7—C81.359 (5)C14—H140.9300
C7—H70.9300C16—C151.357 (5)
C8—C91.387 (4)C16—C171.395 (4)
C8—H80.9300C16—H160.9300
C9—O11.368 (4)C15—H150.9300
O2—S1—O3119.01 (14)O4—C4—C10123.3 (3)
O2—S1—N2108.16 (14)C3—C4—C10114.2 (3)
O3—S1—N2107.20 (14)C2—C3—C4120.3 (3)
O2—S1—C17109.63 (15)C2—C3—C11122.8 (3)
O3—S1—C17109.16 (14)C4—C3—C11117.0 (3)
N2—S1—C17102.36 (14)C3—C2—O1125.2 (3)
C11—N2—S1112.9 (2)C3—C2—H2117.4
C11—N2—H2A111 (2)O1—C2—H2117.4
S1—N2—H2A109 (2)N4—C11—N2110.3 (2)
C12—N4—C11124.3 (2)N4—C11—C3109.6 (2)
C12—N4—H4A115 (3)N2—C11—C3111.0 (3)
C11—N4—H4A120 (3)N4—C11—H11108.6
C6—C5—C10118.8 (3)N2—C11—H11108.6
C6—C5—H5120.6C3—C11—H11108.6
C10—C5—H5120.6N4—C12—C13120.5 (3)
C5—C6—C7122.2 (3)N4—C12—C17122.6 (3)
C5—C6—Br1119.4 (3)C13—C12—C17116.9 (3)
C7—C6—Br1118.5 (2)C14—C13—C12121.3 (3)
C8—C7—C6119.5 (3)C14—C13—H13119.4
C8—C7—H7120.3C12—C13—H13119.4
C6—C7—H7120.3C13—C14—C15121.4 (3)
C7—C8—C9119.2 (3)C13—C14—H14119.3
C7—C8—H8120.4C15—C14—H14119.3
C9—C8—H8120.4C15—C16—C17120.8 (3)
O1—C9—C10122.5 (3)C15—C16—H16119.6
O1—C9—C8116.0 (3)C17—C16—H16119.6
C10—C9—C8121.5 (3)C16—C15—C14118.5 (3)
C2—O1—C9118.0 (2)C16—C15—H15120.7
C9—C10—C5118.8 (3)C14—C15—H15120.7
C9—C10—C4119.8 (3)C16—C17—C12121.0 (3)
C5—C10—C4121.3 (3)C16—C17—S1120.5 (2)
O4—C4—C3122.5 (3)C12—C17—S1118.4 (2)
O2—S1—N2—C1161.9 (2)C9—O1—C2—C3−1.5 (5)
O3—S1—N2—C11−168.6 (2)C12—N4—C11—N2−35.8 (4)
C17—S1—N2—C11−53.8 (2)C12—N4—C11—C3−158.3 (3)
C10—C5—C6—C7−2.0 (5)S1—N2—C11—N461.6 (3)
C10—C5—C6—Br1177.0 (2)S1—N2—C11—C3−176.8 (2)
C5—C6—C7—C81.9 (5)C2—C3—C11—N4114.2 (3)
Br1—C6—C7—C8−177.2 (3)C4—C3—C11—N4−66.5 (3)
C6—C7—C8—C9−0.9 (5)C2—C3—C11—N2−7.9 (4)
C7—C8—C9—O1179.9 (3)C4—C3—C11—N2171.4 (2)
C7—C8—C9—C100.1 (5)C11—N4—C12—C13−177.1 (3)
C10—C9—O1—C2−0.4 (4)C11—N4—C12—C175.6 (5)
C8—C9—O1—C2179.7 (3)N4—C12—C13—C14−178.8 (3)
O1—C9—C10—C5179.9 (3)C17—C12—C13—C14−1.4 (5)
C8—C9—C10—C5−0.2 (5)C12—C13—C14—C150.9 (5)
O1—C9—C10—C42.1 (5)C17—C16—C15—C14−1.0 (5)
C8—C9—C10—C4−178.0 (3)C13—C14—C15—C160.3 (5)
C6—C5—C10—C91.2 (5)C15—C16—C17—C120.5 (5)
C6—C5—C10—C4179.0 (3)C15—C16—C17—S1−179.9 (3)
C9—C10—C4—O4178.2 (3)N4—C12—C17—C16178.0 (3)
C5—C10—C4—O40.5 (5)C13—C12—C17—C160.6 (5)
C9—C10—C4—C3−2.0 (4)N4—C12—C17—S1−1.6 (4)
C5—C10—C4—C3−179.7 (3)C13—C12—C17—S1−179.0 (2)
O4—C4—C3—C2−179.9 (3)O2—S1—C17—C1689.7 (3)
C10—C4—C3—C20.3 (4)O3—S1—C17—C16−42.3 (3)
O4—C4—C3—C110.8 (4)N2—S1—C17—C16−155.7 (3)
C10—C4—C3—C11−179.0 (3)O2—S1—C17—C12−90.7 (3)
C4—C3—C2—O11.4 (5)O3—S1—C17—C12137.3 (3)
C11—C3—C2—O1−179.3 (3)N2—S1—C17—C1224.0 (3)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N4—H4A···O40.79 (3)2.59 (3)2.987 (3)113 (3)
N4—H4A···O3i0.79 (3)2.23 (3)2.999 (3)164 (3)
C13—H13···O3i0.932.54 (1)3.314 (4)141 (1)
N2—H2A···O20.84 (2)2.67 (3)3.222 (4)124 (2)
C2—H2···O20.932.41 (1)3.330 (4)169 (1)
N2—H2A···O40.84 (2)2.12 (3)2.903 (4)154 (3)

Symmetry codes: (i) x−1, y, z.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: ZQ2069).

References

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