Acta Cryst. (2010). E66, o2707 [ doi:10.1107/S1600536810038274 ]
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-HO and C-HO hydrogen bonds, generating an infinite two-dimensional network.
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).
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).
Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); 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).
![[Figure 1]](./zq2060fig1thm.gif)
| Fig. 1. The molecular structure of the title molecule, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. |
![[Figure 2]](./zq2060fig2thm.gif)
| Fig. 2. A packing diagram of the title compound showing hydrogen bonds as dashed lines. |
| C16H11FN2O4S | F(000) = 712 |
| Mr = 346.34 | Dx = 1.567 Mg m−3 |
| Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: P 2ac 2ab | Cell parameters from 1626 reflections |
| a = 7.0739 (3) Å | θ = 3.3–22.0° |
| b = 8.2861 (4) Å | µ = 0.26 mm−1 |
| c = 25.0456 (12) Å | T = 296 K |
| V = 1468.05 (12) Å3 | Needle, orange |
| Z = 4 | 0.31 × 0.06 × 0.05 mm |
| Bruker APEXII CCD area-detector diffractometer | 1993 reflections with I > 2σ(I) |
| Radiation source: fine-focus sealed tube | Rint = 0.056 |
| graphite | θmax = 28.3°, θmin = 3.0° |
| phi and ω scans | h = −9→9 |
| 9538 measured reflections | k = −10→10 |
| 3453 independent reflections | l = −33→24 |
| Refinement on F2 | Secondary atom site location: difference Fourier map |
| Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
| R[F2 > 2σ(F2)] = 0.052 | H atoms treated by a mixture of independent and constrained refinement |
| wR(F2) = 0.093 | w = 1/[σ2(Fo2) + (0.0318P)2] where P = (Fo2 + 2Fc2)/3 |
| S = 0.97 | (Δ/σ)max < 0.001 |
| 3453 reflections | Δρmax = 0.23 e Å−3 |
| 223 parameters | Δρmin = −0.28 e Å−3 |
| 3 restraints | Absolute structure: Flack (1983), 1345 Friedel pairs |
| Primary atom site location: structure-invariant direct methods | Flack parameter: 0.01 (9) |
| C16H11FN2O4S | V = 1468.05 (12) Å3 |
| Mr = 346.34 | Z = 4 |
| Orthorhombic, P212121 | Mo Kα radiation |
| a = 7.0739 (3) Å | µ = 0.26 mm−1 |
| b = 8.2861 (4) Å | T = 296 K |
| c = 25.0456 (12) Å | 0.31 × 0.06 × 0.05 mm |
| Bruker APEXII CCD area-detector diffractometer | 1993 reflections with I > 2σ(I) |
| 9538 measured reflections | Rint = 0.056 |
| 3453 independent reflections | θmax = 28.3° |
| R[F2 > 2σ(F2)] = 0.052 | H atoms treated by a mixture of independent and constrained refinement |
| wR(F2) = 0.093 | Δρmax = 0.23 e Å−3 |
| S = 0.97 | Δρmin = −0.28 e Å−3 |
| 3453 reflections | Absolute structure: Flack (1983), 1345 Friedel pairs |
| 223 parameters | Flack parameter: 0.01 (9) |
| 3 restraints |
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. |
| x | y | z | Uiso*/Ueq | ||
| S1 | 0.05991 (10) | 0.79823 (11) | 0.18441 (3) | 0.0371 (2) | |
| O2 | 0.0424 (3) | 0.9692 (3) | 0.18575 (10) | 0.0520 (6) | |
| O3 | −0.1066 (2) | 0.7017 (3) | 0.18043 (9) | 0.0481 (6) | |
| N4 | 0.4758 (3) | 0.7352 (4) | 0.19622 (11) | 0.0431 (8) | |
| H4A | 0.593 (4) | 0.736 (4) | 0.2026 (12) | 0.052* | |
| N2 | 0.1714 (3) | 0.7397 (3) | 0.23806 (11) | 0.0315 (7) | |
| H2A | 0.167 (4) | 0.634 (4) | 0.2387 (11) | 0.038* | |
| C17 | 0.2141 (4) | 0.7419 (4) | 0.13334 (13) | 0.0342 (8) | |
| C16 | 0.1469 (4) | 0.7134 (5) | 0.08251 (14) | 0.0469 (9) | |
| H16 | 0.0194 | 0.7295 | 0.0753 | 0.056* | |
| C15 | 0.2643 (5) | 0.6619 (4) | 0.04245 (14) | 0.0551 (10) | |
| H15 | 0.2187 | 0.6446 | 0.0081 | 0.066* | |
| C14 | 0.4523 (5) | 0.6364 (5) | 0.05458 (13) | 0.0499 (10) | |
| H14 | 0.5335 | 0.6002 | 0.0279 | 0.060* | |
| C13 | 0.5222 (4) | 0.6627 (4) | 0.10455 (13) | 0.0453 (10) | |
| H13 | 0.6496 | 0.6440 | 0.1113 | 0.054* | |
| C12 | 0.4050 (4) | 0.7178 (4) | 0.14604 (12) | 0.0338 (8) | |
| C11 | 0.3657 (4) | 0.8018 (4) | 0.24047 (12) | 0.0334 (7) | |
| H11 | 0.3629 | 0.9197 | 0.2374 | 0.040* | |
| C3 | 0.4590 (4) | 0.7558 (4) | 0.29238 (12) | 0.0323 (8) | |
| C4 | 0.6462 (4) | 0.8218 (4) | 0.30203 (12) | 0.0297 (7) | |
| O4 | 0.7261 (3) | 0.9080 (3) | 0.26942 (8) | 0.0382 (6) | |
| C10 | 0.7285 (4) | 0.7785 (4) | 0.35354 (12) | 0.0314 (7) | |
| C5 | 0.9080 (4) | 0.8345 (4) | 0.36782 (12) | 0.0396 (9) | |
| H5 | 0.9778 | 0.8998 | 0.3449 | 0.048* | |
| C6 | 0.9767 (5) | 0.7904 (5) | 0.41614 (15) | 0.0516 (11) | |
| F1 | 1.1503 (3) | 0.8486 (3) | 0.43125 (8) | 0.0783 (8) | |
| C7 | 0.8798 (5) | 0.6941 (5) | 0.45116 (15) | 0.0598 (11) | |
| H7 | 0.9314 | 0.6690 | 0.4843 | 0.072* | |
| C8 | 0.7072 (5) | 0.6355 (4) | 0.43699 (13) | 0.0539 (10) | |
| H8 | 0.6406 | 0.5670 | 0.4596 | 0.065* | |
| C9 | 0.6331 (4) | 0.6803 (4) | 0.38801 (13) | 0.0401 (8) | |
| O1 | 0.4555 (3) | 0.6203 (3) | 0.37625 (9) | 0.0471 (6) | |
| C2 | 0.3784 (4) | 0.6620 (4) | 0.32923 (13) | 0.0429 (9) | |
| H2 | 0.2584 | 0.6221 | 0.3217 | 0.051* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| S1 | 0.0215 (3) | 0.0401 (5) | 0.0498 (5) | 0.0054 (4) | 0.0011 (4) | 0.0013 (5) |
| O2 | 0.0419 (12) | 0.0430 (15) | 0.0711 (17) | 0.0132 (11) | 0.0049 (13) | 0.0072 (15) |
| O3 | 0.0186 (10) | 0.0601 (16) | 0.0658 (16) | −0.0026 (10) | −0.0003 (10) | −0.0045 (14) |
| N4 | 0.0170 (12) | 0.075 (2) | 0.0377 (18) | −0.0037 (14) | 0.0000 (11) | −0.0042 (15) |
| N2 | 0.0221 (12) | 0.0295 (17) | 0.0430 (17) | −0.0023 (11) | 0.0036 (11) | 0.0033 (13) |
| C17 | 0.0262 (15) | 0.038 (2) | 0.039 (2) | 0.0004 (14) | 0.0012 (13) | 0.0021 (16) |
| C16 | 0.0346 (16) | 0.060 (3) | 0.046 (2) | 0.0012 (18) | −0.0116 (16) | 0.007 (2) |
| C15 | 0.056 (2) | 0.074 (3) | 0.035 (2) | −0.007 (2) | −0.0062 (19) | 0.000 (2) |
| C14 | 0.049 (2) | 0.063 (3) | 0.038 (2) | −0.001 (2) | 0.0073 (18) | −0.005 (2) |
| C13 | 0.0280 (17) | 0.063 (3) | 0.044 (2) | −0.0004 (16) | 0.0028 (15) | −0.002 (2) |
| C12 | 0.0215 (15) | 0.041 (2) | 0.039 (2) | −0.0034 (14) | −0.0012 (13) | −0.0002 (18) |
| C11 | 0.0238 (14) | 0.038 (2) | 0.0387 (19) | −0.0060 (15) | 0.0045 (13) | 0.0012 (17) |
| C3 | 0.0282 (14) | 0.035 (2) | 0.0341 (19) | −0.0021 (15) | 0.0062 (14) | −0.0030 (16) |
| C4 | 0.0302 (15) | 0.0255 (19) | 0.0332 (19) | −0.0013 (14) | 0.0044 (13) | −0.0031 (16) |
| O4 | 0.0351 (11) | 0.0418 (15) | 0.0376 (13) | −0.0113 (11) | 0.0007 (10) | 0.0056 (11) |
| C10 | 0.0374 (16) | 0.026 (2) | 0.0307 (18) | 0.0027 (16) | 0.0000 (14) | −0.0034 (16) |
| C5 | 0.0404 (19) | 0.039 (2) | 0.039 (2) | −0.0019 (15) | −0.0028 (15) | −0.0014 (17) |
| C6 | 0.046 (2) | 0.060 (3) | 0.048 (2) | 0.000 (2) | −0.0181 (18) | −0.004 (2) |
| F1 | 0.0598 (13) | 0.108 (2) | 0.0671 (16) | −0.0153 (13) | −0.0323 (11) | 0.0078 (14) |
| C7 | 0.077 (3) | 0.062 (3) | 0.041 (2) | −0.001 (2) | −0.016 (2) | 0.006 (2) |
| C8 | 0.075 (3) | 0.051 (3) | 0.036 (2) | −0.003 (2) | 0.0002 (19) | 0.0075 (19) |
| C9 | 0.0470 (18) | 0.036 (2) | 0.038 (2) | −0.0005 (17) | 0.0016 (17) | 0.0016 (19) |
| O1 | 0.0512 (13) | 0.0521 (16) | 0.0381 (14) | −0.0150 (13) | −0.0022 (11) | 0.0119 (12) |
| C2 | 0.0349 (16) | 0.048 (3) | 0.045 (2) | −0.0079 (16) | 0.0031 (16) | −0.0028 (19) |
| S1—O2 | 1.422 (2) | C11—C3 | 1.507 (4) |
| S1—O3 | 1.427 (2) | C11—H11 | 0.9800 |
| S1—N2 | 1.632 (3) | C3—C2 | 1.335 (4) |
| S1—C17 | 1.745 (3) | C3—C4 | 1.453 (4) |
| N4—C12 | 1.360 (4) | C4—O4 | 1.224 (3) |
| N4—C11 | 1.463 (4) | C4—C10 | 1.460 (4) |
| N4—H4A | 0.85 (3) | C10—C9 | 1.364 (4) |
| N2—C11 | 1.469 (3) | C10—C5 | 1.398 (4) |
| N2—H2A | 0.88 (3) | C5—C6 | 1.354 (4) |
| C17—C16 | 1.379 (4) | C5—H5 | 0.9300 |
| C17—C12 | 1.402 (4) | C6—C7 | 1.370 (5) |
| C16—C15 | 1.370 (5) | C6—F1 | 1.373 (3) |
| C16—H16 | 0.9300 | C7—C8 | 1.361 (5) |
| C15—C14 | 1.380 (4) | C7—H7 | 0.9300 |
| C15—H15 | 0.9300 | C8—C9 | 1.385 (4) |
| C14—C13 | 1.363 (4) | C8—H8 | 0.9300 |
| C14—H14 | 0.9300 | C9—O1 | 1.383 (4) |
| C13—C12 | 1.406 (4) | O1—C2 | 1.343 (3) |
| C13—H13 | 0.9300 | C2—H2 | 0.9300 |
| O2—S1—O3 | 119.19 (14) | N2—C11—C3 | 110.9 (2) |
| O2—S1—N2 | 108.60 (15) | N4—C11—H11 | 109.1 |
| O3—S1—N2 | 106.84 (13) | N2—C11—H11 | 109.1 |
| O2—S1—C17 | 109.76 (14) | C3—C11—H11 | 109.1 |
| O3—S1—C17 | 108.36 (14) | C2—C3—C4 | 119.6 (3) |
| N2—S1—C17 | 102.83 (13) | C2—C3—C11 | 123.8 (3) |
| C12—N4—C11 | 122.9 (2) | C4—C3—C11 | 116.6 (3) |
| C12—N4—H4A | 122 (2) | O4—C4—C3 | 122.0 (3) |
| C11—N4—H4A | 112 (2) | O4—C4—C10 | 123.3 (3) |
| C11—N2—S1 | 112.4 (2) | C3—C4—C10 | 114.7 (3) |
| C11—N2—H2A | 112.3 (19) | C9—C10—C5 | 119.0 (3) |
| S1—N2—H2A | 107.2 (19) | C9—C10—C4 | 120.5 (3) |
| C16—C17—C12 | 121.1 (3) | C5—C10—C4 | 120.4 (3) |
| C16—C17—S1 | 120.5 (2) | C6—C5—C10 | 117.7 (3) |
| C12—C17—S1 | 118.3 (2) | C6—C5—H5 | 121.1 |
| C15—C16—C17 | 121.4 (3) | C10—C5—H5 | 121.1 |
| C15—C16—H16 | 119.3 | C5—C6—C7 | 123.3 (3) |
| C17—C16—H16 | 119.3 | C5—C6—F1 | 118.2 (4) |
| C16—C15—C14 | 118.0 (3) | C7—C6—F1 | 118.4 (3) |
| C16—C15—H15 | 121.0 | C8—C7—C6 | 119.3 (3) |
| C14—C15—H15 | 121.0 | C8—C7—H7 | 120.3 |
| C13—C14—C15 | 121.8 (3) | C6—C7—H7 | 120.3 |
| C13—C14—H14 | 119.1 | C7—C8—C9 | 118.3 (3) |
| C15—C14—H14 | 119.1 | C7—C8—H8 | 120.8 |
| C14—C13—C12 | 121.1 (3) | C9—C8—H8 | 120.8 |
| C14—C13—H13 | 119.4 | C10—C9—O1 | 121.9 (3) |
| C12—C13—H13 | 119.4 | C10—C9—C8 | 122.2 (3) |
| N4—C12—C17 | 123.3 (3) | O1—C9—C8 | 115.8 (3) |
| N4—C12—C13 | 120.0 (2) | C2—O1—C9 | 117.6 (3) |
| C17—C12—C13 | 116.5 (3) | C3—C2—O1 | 125.6 (3) |
| N4—C11—N2 | 109.6 (3) | C3—C2—H2 | 117.2 |
| N4—C11—C3 | 109.0 (2) | O1—C2—H2 | 117.2 |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N4—H4A···O3i | 0.85 (3) | 2.21 (3) | 2.993 (3) | 153 (3) |
| N4—H4A···O4 | 0.85 (3) | 2.39 (3) | 2.924 (3) | 121 (3) |
| N2—H2A···O4ii | 0.88 (3) | 2.03 (3) | 2.848 (3) | 155 (3) |
| C2—H2···O2iii | 0.93 | 2.48 | 3.399 (4) | 168 |
| C13—H13···O3i | 0.93 | 2.49 | 3.258 (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. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N4—H4A···O3i | 0.85 (3) | 2.21 (3) | 2.993 (3) | 153 (3) |
| N4—H4A···O4 | 0.85 (3) | 2.39 (3) | 2.924 (3) | 121 (3) |
| N2—H2A···O4ii | 0.88 (3) | 2.03 (3) | 2.848 (3) | 155 (3) |
| C2—H2···O2iii | 0.93 | 2.48 | 3.399 (4) | 168 |
| C13—H13···O3i | 0.93 | 2.49 | 3.258 (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. |
The authors acknowledge the Higher Education Commission, Islamabad, Pakistan, for financial and GCU Lahore for technical support.
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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).