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Acta Crystallogr Sect E Struct Rep Online. 2010 November 1; 66(Pt 11): o2707.
Published online 2010 October 2. doi:  10.1107/S1600536810038274
PMCID: PMC3009151

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

Abstract

In the title compound, C16H11FN2O4S, the mean planes of the bicyclic chromone system and of the benzene ring of the benzothia­diazine derivative make a dihedral angle of 54.28 (5)°. 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 a related structure, see: Mariya-al-Rashida et al. (2009 [triangle]);

An external file that holds a picture, illustration, etc.
Object name is e-66-o2707-scheme1.jpg

Experimental

Crystal data

  • C16H11FN2O4S
  • M r = 346.34
  • Orthorhombic, An external file that holds a picture, illustration, etc.
Object name is e-66-o2707-efi1.jpg
  • a = 7.0739 (3) Å
  • b = 8.2861 (4) Å
  • c = 25.0456 (12) Å
  • V = 1468.05 (12) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.26 mm−1
  • T = 296 K
  • 0.31 × 0.06 × 0.05 mm

Data collection

  • Bruker APEXII CCD area-detector diffractometer
  • 9538 measured reflections
  • 3453 independent reflections
  • 1993 reflections with I > 2σ(I)
  • R int = 0.056

Refinement

  • R[F 2 > 2σ(F 2)] = 0.052
  • wR(F 2) = 0.093
  • S = 0.97
  • 3453 reflections
  • 223 parameters
  • 3 restraints
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.23 e Å−3
  • Δρmin = −0.28 e Å−3
  • Absolute structure: Flack (1983 [triangle]), 1345 Friedel pairs
  • Flack parameter: 0.01 (9)

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/S1600536810038274/zq2060sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810038274/zq2060Isup2.hkl

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

Acknowledgments

The authors acknowledge the Higher Education Commission, Islamabad, Pakistan, for financial and GCU Lahore for technical support.

supplementary crystallographic information

Comment

The 1,2,4-benzothiadiazine-1,1-dioxide ring system has attained considerable importance in pharmaceutical and medicinal chemistry mainly due to the compounds such as chlorothiazide and diazoxide (Zhu et al., 2005; Kamal et al., 2007a). The sulfonamide group is an active pharmacophore which is responsible for many biological activities (Weisman & Brown, 1964). The crystal structure of the condensation product of 4-aminobenzenesulfonamide with 4-oxo-4H-1-benzopyran-3-carboxaldehyde has previously been reported (al-Rashida et al., 2009). Herein, we report the crystal structure of the condensation product of 2-aminobenzenesulfonamide with 6-fluoro-4-oxo-4H-1-benzopyran-3-carboxaldehyde.

In the molecule of the title compound (Fig. 1), the two rings of the chromone system (F1, O1, O4, C2—C10) are coplanar, making a dihedral angle of 0.55 (19)°. The carbon atom C11 deviates only by 0.034 (5) Å from the mean plane of the chromone. The phenyl ring (C12—C17) and the atoms N4, S1 and C11 are coplanar as well (rms deviation = 0.033) and make a dihedral angle of 54.28 (5)° with the mean plane of the 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 ethanol was slowly added to the stirred solution of 6-fluoro-4-oxo-4H-1-benzopyran-3-carboxaldehyde (1.0 mmol) containing a 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 81%, m.p. 472 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 molecule, 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

C16H11FN2O4SF(000) = 712
Mr = 346.34Dx = 1.567 Mg m3
Orthorhombic, P212121Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2abCell parameters from 1626 reflections
a = 7.0739 (3) Åθ = 3.3–22.0°
b = 8.2861 (4) ŵ = 0.26 mm1
c = 25.0456 (12) ÅT = 296 K
V = 1468.05 (12) Å3Needle, orange
Z = 40.31 × 0.06 × 0.05 mm

Data collection

Bruker APEXII CCD area-detector diffractometer1993 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.056
graphiteθmax = 28.3°, θmin = 3.0°
phi and ω scansh = −9→9
9538 measured reflectionsk = −10→10
3453 independent reflectionsl = −33→24

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.052H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.093w = 1/[σ2(Fo2) + (0.0318P)2] where P = (Fo2 + 2Fc2)/3
S = 0.97(Δ/σ)max < 0.001
3453 reflectionsΔρmax = 0.23 e Å3
223 parametersΔρmin = −0.28 e Å3
3 restraintsAbsolute structure: Flack (1983), 1345 Friedel pairs
Primary atom site location: structure-invariant direct methodsFlack parameter: 0.01 (9)

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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
S10.05991 (10)0.79823 (11)0.18441 (3)0.0371 (2)
O20.0424 (3)0.9692 (3)0.18575 (10)0.0520 (6)
O3−0.1066 (2)0.7017 (3)0.18043 (9)0.0481 (6)
N40.4758 (3)0.7352 (4)0.19622 (11)0.0431 (8)
H4A0.593 (4)0.736 (4)0.2026 (12)0.052*
N20.1714 (3)0.7397 (3)0.23806 (11)0.0315 (7)
H2A0.167 (4)0.634 (4)0.2387 (11)0.038*
C170.2141 (4)0.7419 (4)0.13334 (13)0.0342 (8)
C160.1469 (4)0.7134 (5)0.08251 (14)0.0469 (9)
H160.01940.72950.07530.056*
C150.2643 (5)0.6619 (4)0.04245 (14)0.0551 (10)
H150.21870.64460.00810.066*
C140.4523 (5)0.6364 (5)0.05458 (13)0.0499 (10)
H140.53350.60020.02790.060*
C130.5222 (4)0.6627 (4)0.10455 (13)0.0453 (10)
H130.64960.64400.11130.054*
C120.4050 (4)0.7178 (4)0.14604 (12)0.0338 (8)
C110.3657 (4)0.8018 (4)0.24047 (12)0.0334 (7)
H110.36290.91970.23740.040*
C30.4590 (4)0.7558 (4)0.29238 (12)0.0323 (8)
C40.6462 (4)0.8218 (4)0.30203 (12)0.0297 (7)
O40.7261 (3)0.9080 (3)0.26942 (8)0.0382 (6)
C100.7285 (4)0.7785 (4)0.35354 (12)0.0314 (7)
C50.9080 (4)0.8345 (4)0.36782 (12)0.0396 (9)
H50.97780.89980.34490.048*
C60.9767 (5)0.7904 (5)0.41614 (15)0.0516 (11)
F11.1503 (3)0.8486 (3)0.43125 (8)0.0783 (8)
C70.8798 (5)0.6941 (5)0.45116 (15)0.0598 (11)
H70.93140.66900.48430.072*
C80.7072 (5)0.6355 (4)0.43699 (13)0.0539 (10)
H80.64060.56700.45960.065*
C90.6331 (4)0.6803 (4)0.38801 (13)0.0401 (8)
O10.4555 (3)0.6203 (3)0.37625 (9)0.0471 (6)
C20.3784 (4)0.6620 (4)0.32923 (13)0.0429 (9)
H20.25840.62210.32170.051*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
S10.0215 (3)0.0401 (5)0.0498 (5)0.0054 (4)0.0011 (4)0.0013 (5)
O20.0419 (12)0.0430 (15)0.0711 (17)0.0132 (11)0.0049 (13)0.0072 (15)
O30.0186 (10)0.0601 (16)0.0658 (16)−0.0026 (10)−0.0003 (10)−0.0045 (14)
N40.0170 (12)0.075 (2)0.0377 (18)−0.0037 (14)0.0000 (11)−0.0042 (15)
N20.0221 (12)0.0295 (17)0.0430 (17)−0.0023 (11)0.0036 (11)0.0033 (13)
C170.0262 (15)0.038 (2)0.039 (2)0.0004 (14)0.0012 (13)0.0021 (16)
C160.0346 (16)0.060 (3)0.046 (2)0.0012 (18)−0.0116 (16)0.007 (2)
C150.056 (2)0.074 (3)0.035 (2)−0.007 (2)−0.0062 (19)0.000 (2)
C140.049 (2)0.063 (3)0.038 (2)−0.001 (2)0.0073 (18)−0.005 (2)
C130.0280 (17)0.063 (3)0.044 (2)−0.0004 (16)0.0028 (15)−0.002 (2)
C120.0215 (15)0.041 (2)0.039 (2)−0.0034 (14)−0.0012 (13)−0.0002 (18)
C110.0238 (14)0.038 (2)0.0387 (19)−0.0060 (15)0.0045 (13)0.0012 (17)
C30.0282 (14)0.035 (2)0.0341 (19)−0.0021 (15)0.0062 (14)−0.0030 (16)
C40.0302 (15)0.0255 (19)0.0332 (19)−0.0013 (14)0.0044 (13)−0.0031 (16)
O40.0351 (11)0.0418 (15)0.0376 (13)−0.0113 (11)0.0007 (10)0.0056 (11)
C100.0374 (16)0.026 (2)0.0307 (18)0.0027 (16)0.0000 (14)−0.0034 (16)
C50.0404 (19)0.039 (2)0.039 (2)−0.0019 (15)−0.0028 (15)−0.0014 (17)
C60.046 (2)0.060 (3)0.048 (2)0.000 (2)−0.0181 (18)−0.004 (2)
F10.0598 (13)0.108 (2)0.0671 (16)−0.0153 (13)−0.0323 (11)0.0078 (14)
C70.077 (3)0.062 (3)0.041 (2)−0.001 (2)−0.016 (2)0.006 (2)
C80.075 (3)0.051 (3)0.036 (2)−0.003 (2)0.0002 (19)0.0075 (19)
C90.0470 (18)0.036 (2)0.038 (2)−0.0005 (17)0.0016 (17)0.0016 (19)
O10.0512 (13)0.0521 (16)0.0381 (14)−0.0150 (13)−0.0022 (11)0.0119 (12)
C20.0349 (16)0.048 (3)0.045 (2)−0.0079 (16)0.0031 (16)−0.0028 (19)

Geometric parameters (Å, °)

S1—O21.422 (2)C11—C31.507 (4)
S1—O31.427 (2)C11—H110.9800
S1—N21.632 (3)C3—C21.335 (4)
S1—C171.745 (3)C3—C41.453 (4)
N4—C121.360 (4)C4—O41.224 (3)
N4—C111.463 (4)C4—C101.460 (4)
N4—H4A0.85 (3)C10—C91.364 (4)
N2—C111.469 (3)C10—C51.398 (4)
N2—H2A0.88 (3)C5—C61.354 (4)
C17—C161.379 (4)C5—H50.9300
C17—C121.402 (4)C6—C71.370 (5)
C16—C151.370 (5)C6—F11.373 (3)
C16—H160.9300C7—C81.361 (5)
C15—C141.380 (4)C7—H70.9300
C15—H150.9300C8—C91.385 (4)
C14—C131.363 (4)C8—H80.9300
C14—H140.9300C9—O11.383 (4)
C13—C121.406 (4)O1—C21.343 (3)
C13—H130.9300C2—H20.9300
O2—S1—O3119.19 (14)N2—C11—C3110.9 (2)
O2—S1—N2108.60 (15)N4—C11—H11109.1
O3—S1—N2106.84 (13)N2—C11—H11109.1
O2—S1—C17109.76 (14)C3—C11—H11109.1
O3—S1—C17108.36 (14)C2—C3—C4119.6 (3)
N2—S1—C17102.83 (13)C2—C3—C11123.8 (3)
C12—N4—C11122.9 (2)C4—C3—C11116.6 (3)
C12—N4—H4A122 (2)O4—C4—C3122.0 (3)
C11—N4—H4A112 (2)O4—C4—C10123.3 (3)
C11—N2—S1112.4 (2)C3—C4—C10114.7 (3)
C11—N2—H2A112.3 (19)C9—C10—C5119.0 (3)
S1—N2—H2A107.2 (19)C9—C10—C4120.5 (3)
C16—C17—C12121.1 (3)C5—C10—C4120.4 (3)
C16—C17—S1120.5 (2)C6—C5—C10117.7 (3)
C12—C17—S1118.3 (2)C6—C5—H5121.1
C15—C16—C17121.4 (3)C10—C5—H5121.1
C15—C16—H16119.3C5—C6—C7123.3 (3)
C17—C16—H16119.3C5—C6—F1118.2 (4)
C16—C15—C14118.0 (3)C7—C6—F1118.4 (3)
C16—C15—H15121.0C8—C7—C6119.3 (3)
C14—C15—H15121.0C8—C7—H7120.3
C13—C14—C15121.8 (3)C6—C7—H7120.3
C13—C14—H14119.1C7—C8—C9118.3 (3)
C15—C14—H14119.1C7—C8—H8120.8
C14—C13—C12121.1 (3)C9—C8—H8120.8
C14—C13—H13119.4C10—C9—O1121.9 (3)
C12—C13—H13119.4C10—C9—C8122.2 (3)
N4—C12—C17123.3 (3)O1—C9—C8115.8 (3)
N4—C12—C13120.0 (2)C2—O1—C9117.6 (3)
C17—C12—C13116.5 (3)C3—C2—O1125.6 (3)
N4—C11—N2109.6 (3)C3—C2—H2117.2
N4—C11—C3109.0 (2)O1—C2—H2117.2

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N4—H4A···O3i0.85 (3)2.21 (3)2.993 (3)153 (3)
N4—H4A···O40.85 (3)2.39 (3)2.924 (3)121 (3)
N2—H2A···O4ii0.88 (3)2.03 (3)2.848 (3)155 (3)
C2—H2···O2iii0.932.483.399 (4)168
C13—H13···O3i0.932.493.258 (3)140

Symmetry codes: (i) x+1, y, z; (ii) −x+1, y−1/2, −z+1/2; (iii) −x, y−1/2, −z+1/2.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: ZQ2060).

References

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