Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270107059173/gz3109sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270107059173/gz3109Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270107059173/gz3109IIsup3.hkl |
CCDC references: 677209; 677210
For related literature, see: Banerjee & Sarkar (2002); Bernstein et al. (1994); Bhatt et al. (2005); Bordner et al. (1984, 1989); Chiesi-Villa, Rizzoli, Amari, Delcanale, Redenti & Ventura (1998); Cremer & Pople (1975); Drebushchak et al. (2006); Fabiola et al. (1998); Hammen et al. (1989); Hirai et al. (1997); Katzung (1994); Khalil et al. (2000); Kojić-Prodić & Rużić-Toroš (1982); Lombardino & Wiseman (1972); Luger et al. (1996); Myung et al. (2002); Reck et al. (1988); Siddiqui (2007); Siddiqui et al. (2006a, 2006b); Yaltirik et al. (2001).
A mixture of methyl 4-hydroxy-2-methyl-2H-1,2-benzothiazine-3-carboxylate-1,1-dioxide (67.3 g, 250 mmol) and o- or p-chloroaniline (35.7 g, 280 mmol) in xylene (250 ml) was refluxed for 4–12 h in a Soxhlet apparatus having Linde type A4 molecular sieves. Half of the xylene was then distilled off and the remaining contents were allowed to stand overnight at room temperature. The precipitates obtained were filtered, washed with hexane and dried at room temperature to obtain the crystalline products, (I) and (II), respectively. The products were crystallized from CHCl3 solutions by slow evaporation at 313 K.
Analysis for (I): IR (neat, νmax, cm-1): NH 3325 (s), CO 1742 (m), SO2 1380 and 1155; 1H NMR (300 MHz, CDCl3, δ, p.p.m.): 2.75 (s, 3H, CH3), 7.26–7.30 (d, J = 6.8 Hz, 2H), 7.31–7.45 (d, J = 7.5 Hz, 2H), 7.69–7.73 (m, 2H), 7.76–7.88 (d, J = 6.8 Hz, 1H), 7.90–8.06 (d, J = 7.5 Hz, 1H), 8.21 (s, 1H, NH); 13C NMR (δ, p.p.m.): 167.5, 157.3, 136.1, 134.7, 133.4, 132.6, 130.2, 129.1, 128.7, 126.2, 124.3, 121.7, 120.5, 118.3, 111.5, 42.3. Yield: 84.9 g (233 mmol, 93%); m.p. 457–459 K.
Analysis for (II): IR (neat, νmax, cm-1): NH 3337 (s), CO 1744 (m), SO2 1341 and 1156; 1H NMR (300 MHz, CDCl3, δ, p.p.m.): 2.94 (s, 3H, CH3), 7.30–7.31 (d, J = 6.7 Hz, 2H), 7.34–7.58 (d, J = 7.6 Hz, 2H), 7.70–7.75 (m, 2H), 7.76–7.90 (d, J = 6.9 Hz, 1H), 7.91–8.07 (d, J = 7.6 Hz, 1H), 8.38 (s, 1H, NH); 13C NMR (δ, p.p.m.): 166.6, 158.2, 135.0, 134.3, 133.2, 132.5, 130.5, 129.2, 128.5, 126.8, 124.8, 121.8, 120.6, 118.0, 111.6, 40.1. Yield: 87.5 g (240 mmol, 96%); m.p. 496–498 K.
For both structures, H atoms bonded to C atoms were included in the refinements in geometrically idealized positions, with C—H = 0.98 and 0.95 Å for methyl and phenyl H, respectively, and with Uiso(H) = 1.2Ueq(C). H atoms bonded to N and O atoms were allowed to refine, with Uiso(H) = 1.2Ueq(parent). The final difference maps were free of chemically significant features.
For both compounds, data collection: COLLECT (Nonius, 1998); cell refinement: HKL DENZO (Otwinowski & Minor, 1997); data reduction: SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SAPI91 (Fan, 1991); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).
C16H13ClN2O4S | F(000) = 752 |
Mr = 364.79 | Dx = 1.518 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 6588 reflections |
a = 7.750 (2) Å | θ = 2.9–27.5° |
b = 28.588 (7) Å | µ = 0.39 mm−1 |
c = 7.519 (1) Å | T = 173 K |
β = 106.630 (12)° | Block, colourless |
V = 1596.2 (6) Å3 | 0.22 × 0.20 × 0.11 mm |
Z = 4 |
Nonius KappaCCD diffractometer | 3610 independent reflections |
Radiation source: fine-focus sealed tube | 3003 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.027 |
ω and ϕ scans | θmax = 27.5°, θmin = 2.9° |
Absorption correction: multi-scan (SORTAV; Blessing, 1997) | h = −10→10 |
Tmin = 0.918, Tmax = 0.958 | k = −36→36 |
6588 measured reflections | l = −9→9 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.034 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.090 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.03 | w = 1/[σ2(Fo2) + (0.038P)2 + 0.84P] where P = (Fo2 + 2Fc2)/3 |
3610 reflections | (Δ/σ)max = 0.001 |
226 parameters | Δρmax = 0.30 e Å−3 |
0 restraints | Δρmin = −0.37 e Å−3 |
C16H13ClN2O4S | V = 1596.2 (6) Å3 |
Mr = 364.79 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 7.750 (2) Å | µ = 0.39 mm−1 |
b = 28.588 (7) Å | T = 173 K |
c = 7.519 (1) Å | 0.22 × 0.20 × 0.11 mm |
β = 106.630 (12)° |
Nonius KappaCCD diffractometer | 3610 independent reflections |
Absorption correction: multi-scan (SORTAV; Blessing, 1997) | 3003 reflections with I > 2σ(I) |
Tmin = 0.918, Tmax = 0.958 | Rint = 0.027 |
6588 measured reflections |
R[F2 > 2σ(F2)] = 0.034 | 0 restraints |
wR(F2) = 0.090 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.03 | Δρmax = 0.30 e Å−3 |
3610 reflections | Δρmin = −0.37 e Å−3 |
226 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
Cl1 | −0.03713 (5) | 0.513339 (14) | 0.25279 (6) | 0.02656 (12) | |
S1 | 0.27132 (5) | 0.335291 (13) | 0.26331 (6) | 0.02365 (12) | |
O1 | 0.78698 (15) | 0.39971 (4) | 0.43168 (17) | 0.0259 (3) | |
H1O | 0.766 (3) | 0.4296 (9) | 0.412 (3) | 0.045 (6)* | |
O2 | 0.11188 (16) | 0.31509 (4) | 0.2904 (2) | 0.0353 (3) | |
O3 | 0.28768 (17) | 0.33967 (4) | 0.07914 (17) | 0.0307 (3) | |
O4 | 0.62421 (15) | 0.47823 (4) | 0.34834 (16) | 0.0256 (3) | |
N1 | 0.29741 (17) | 0.38784 (5) | 0.35629 (19) | 0.0216 (3) | |
N2 | 0.31632 (19) | 0.47767 (5) | 0.23880 (19) | 0.0217 (3) | |
H2N | 0.225 (3) | 0.4605 (7) | 0.230 (3) | 0.034 (6)* | |
C1 | 0.4624 (2) | 0.30573 (6) | 0.4002 (2) | 0.0229 (3) | |
C2 | 0.4546 (2) | 0.25848 (6) | 0.4404 (3) | 0.0289 (4) | |
H2 | 0.3439 | 0.2419 | 0.4034 | 0.035* | |
C3 | 0.6130 (3) | 0.23615 (6) | 0.5360 (3) | 0.0333 (4) | |
H3 | 0.6106 | 0.2039 | 0.5651 | 0.040* | |
C4 | 0.7735 (3) | 0.26019 (7) | 0.5893 (3) | 0.0341 (4) | |
H4 | 0.8809 | 0.2442 | 0.6526 | 0.041* | |
C5 | 0.7802 (2) | 0.30753 (6) | 0.5516 (2) | 0.0289 (4) | |
H5 | 0.8916 | 0.3238 | 0.5899 | 0.035* | |
C6 | 0.6233 (2) | 0.33131 (5) | 0.4573 (2) | 0.0216 (3) | |
C7 | 0.6242 (2) | 0.38170 (6) | 0.4184 (2) | 0.0203 (3) | |
C8 | 0.4715 (2) | 0.40792 (5) | 0.3681 (2) | 0.0197 (3) | |
C9 | 0.4778 (2) | 0.45735 (5) | 0.3193 (2) | 0.0196 (3) | |
C10 | 0.2379 (2) | 0.39382 (7) | 0.5254 (3) | 0.0308 (4) | |
H10A | 0.2523 | 0.4266 | 0.5648 | 0.037* | |
H10B | 0.3111 | 0.3739 | 0.6248 | 0.037* | |
H10C | 0.1110 | 0.3849 | 0.4985 | 0.037* | |
C11 | 0.2843 (2) | 0.52450 (5) | 0.1801 (2) | 0.0202 (3) | |
C12 | 0.1188 (2) | 0.54476 (6) | 0.1741 (2) | 0.0214 (3) | |
C13 | 0.0742 (2) | 0.58932 (6) | 0.1055 (2) | 0.0286 (4) | |
H13 | −0.0400 | 0.6023 | 0.1006 | 0.034* | |
C14 | 0.1977 (3) | 0.61507 (6) | 0.0438 (3) | 0.0338 (4) | |
H14 | 0.1683 | 0.6457 | −0.0039 | 0.041* | |
C15 | 0.3640 (3) | 0.59591 (6) | 0.0520 (2) | 0.0304 (4) | |
H15 | 0.4493 | 0.6138 | 0.0121 | 0.036* | |
C16 | 0.4073 (2) | 0.55074 (6) | 0.1180 (2) | 0.0251 (3) | |
H16 | 0.5208 | 0.5377 | 0.1208 | 0.030* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl1 | 0.0232 (2) | 0.0261 (2) | 0.0314 (2) | 0.00171 (16) | 0.00939 (16) | 0.00061 (16) |
S1 | 0.0187 (2) | 0.0158 (2) | 0.0334 (2) | −0.00090 (15) | 0.00256 (16) | −0.00131 (16) |
O1 | 0.0149 (5) | 0.0243 (6) | 0.0374 (7) | −0.0001 (5) | 0.0057 (5) | 0.0024 (5) |
O2 | 0.0213 (6) | 0.0224 (6) | 0.0601 (9) | −0.0061 (5) | 0.0084 (6) | −0.0008 (6) |
O3 | 0.0315 (7) | 0.0258 (7) | 0.0298 (6) | 0.0030 (5) | 0.0010 (5) | −0.0036 (5) |
O4 | 0.0191 (5) | 0.0216 (6) | 0.0350 (6) | −0.0036 (5) | 0.0059 (5) | 0.0019 (5) |
N1 | 0.0150 (6) | 0.0175 (6) | 0.0318 (7) | −0.0013 (5) | 0.0061 (5) | −0.0020 (5) |
N2 | 0.0188 (7) | 0.0150 (6) | 0.0300 (7) | −0.0007 (5) | 0.0048 (6) | −0.0004 (5) |
C1 | 0.0227 (8) | 0.0194 (8) | 0.0273 (8) | 0.0036 (6) | 0.0084 (6) | 0.0016 (6) |
C2 | 0.0317 (9) | 0.0194 (8) | 0.0379 (10) | 0.0007 (7) | 0.0134 (8) | 0.0025 (7) |
C3 | 0.0411 (10) | 0.0212 (8) | 0.0416 (10) | 0.0103 (8) | 0.0181 (9) | 0.0096 (8) |
C4 | 0.0332 (10) | 0.0322 (10) | 0.0372 (10) | 0.0155 (8) | 0.0105 (8) | 0.0101 (8) |
C5 | 0.0230 (8) | 0.0304 (9) | 0.0325 (9) | 0.0065 (7) | 0.0067 (7) | 0.0037 (7) |
C6 | 0.0213 (8) | 0.0203 (8) | 0.0236 (8) | 0.0045 (6) | 0.0072 (6) | 0.0007 (6) |
C7 | 0.0181 (7) | 0.0205 (8) | 0.0225 (7) | −0.0009 (6) | 0.0063 (6) | −0.0011 (6) |
C8 | 0.0160 (7) | 0.0169 (7) | 0.0260 (8) | −0.0007 (6) | 0.0056 (6) | −0.0015 (6) |
C9 | 0.0192 (7) | 0.0191 (8) | 0.0206 (7) | 0.0002 (6) | 0.0059 (6) | −0.0028 (6) |
C10 | 0.0237 (8) | 0.0330 (10) | 0.0396 (10) | −0.0028 (7) | 0.0155 (7) | −0.0057 (8) |
C11 | 0.0245 (8) | 0.0153 (7) | 0.0191 (7) | 0.0002 (6) | 0.0033 (6) | −0.0014 (6) |
C12 | 0.0232 (8) | 0.0202 (8) | 0.0200 (7) | −0.0001 (6) | 0.0048 (6) | −0.0015 (6) |
C13 | 0.0310 (9) | 0.0252 (9) | 0.0278 (8) | 0.0087 (7) | 0.0054 (7) | 0.0023 (7) |
C14 | 0.0428 (11) | 0.0217 (9) | 0.0351 (9) | 0.0049 (8) | 0.0085 (8) | 0.0086 (7) |
C15 | 0.0369 (10) | 0.0257 (9) | 0.0296 (9) | −0.0041 (8) | 0.0110 (8) | 0.0049 (7) |
C16 | 0.0274 (8) | 0.0228 (8) | 0.0247 (8) | 0.0005 (7) | 0.0072 (7) | 0.0009 (7) |
Cl1—C12 | 1.7395 (17) | C4—H4 | 0.9500 |
S1—O2 | 1.4302 (13) | C5—C6 | 1.396 (2) |
S1—O3 | 1.4317 (14) | C5—H5 | 0.9500 |
S1—N1 | 1.6448 (14) | C6—C7 | 1.470 (2) |
S1—C1 | 1.7589 (17) | C7—C8 | 1.360 (2) |
O1—C7 | 1.340 (2) | C8—C9 | 1.464 (2) |
O1—H1O | 0.87 (2) | C10—H10A | 0.9800 |
O4—C9 | 1.245 (2) | C10—H10B | 0.9800 |
N1—C8 | 1.445 (2) | C10—H10C | 0.9800 |
N1—C10 | 1.482 (2) | C11—C16 | 1.394 (2) |
N2—C9 | 1.355 (2) | C11—C12 | 1.396 (2) |
N2—C11 | 1.409 (2) | C12—C13 | 1.381 (2) |
N2—H2N | 0.85 (2) | C13—C14 | 1.388 (3) |
C1—C2 | 1.389 (2) | C13—H13 | 0.9500 |
C1—C6 | 1.402 (2) | C14—C15 | 1.385 (3) |
C2—C3 | 1.388 (3) | C14—H14 | 0.9500 |
C2—H2 | 0.9500 | C15—C16 | 1.389 (2) |
C3—C4 | 1.377 (3) | C15—H15 | 0.9500 |
C3—H3 | 0.9500 | C16—H16 | 0.9500 |
C4—C5 | 1.387 (3) | ||
O2—S1—O3 | 119.48 (8) | O1—C7—C6 | 114.83 (13) |
O2—S1—N1 | 108.32 (8) | C8—C7—C6 | 122.82 (14) |
O3—S1—N1 | 107.29 (7) | C7—C8—N1 | 121.39 (14) |
O2—S1—C1 | 109.86 (8) | C7—C8—C9 | 120.86 (14) |
O3—S1—C1 | 108.37 (8) | N1—C8—C9 | 117.73 (13) |
N1—S1—C1 | 102.10 (7) | O4—C9—N2 | 123.49 (15) |
C7—O1—H1O | 104.0 (15) | O4—C9—C8 | 120.84 (14) |
C8—N1—C10 | 114.57 (13) | N2—C9—C8 | 115.65 (13) |
C8—N1—S1 | 112.82 (10) | N1—C10—H10A | 109.5 |
C10—N1—S1 | 116.09 (11) | N1—C10—H10B | 109.5 |
C9—N2—C11 | 127.19 (14) | H10A—C10—H10B | 109.5 |
C9—N2—H2N | 115.4 (14) | N1—C10—H10C | 109.5 |
C11—N2—H2N | 117.3 (14) | H10A—C10—H10C | 109.5 |
C2—C1—C6 | 122.02 (15) | H10B—C10—H10C | 109.5 |
C2—C1—S1 | 120.85 (13) | C16—C11—C12 | 118.42 (15) |
C6—C1—S1 | 117.04 (12) | C16—C11—N2 | 122.68 (14) |
C3—C2—C1 | 118.24 (17) | C12—C11—N2 | 118.81 (14) |
C3—C2—H2 | 120.9 | C13—C12—C11 | 121.59 (15) |
C1—C2—H2 | 120.9 | C13—C12—Cl1 | 118.67 (13) |
C4—C3—C2 | 120.83 (17) | C11—C12—Cl1 | 119.74 (12) |
C4—C3—H3 | 119.6 | C12—C13—C14 | 119.43 (16) |
C2—C3—H3 | 119.6 | C12—C13—H13 | 120.3 |
C3—C4—C5 | 120.75 (16) | C14—C13—H13 | 120.3 |
C3—C4—H4 | 119.6 | C15—C14—C13 | 119.80 (16) |
C5—C4—H4 | 119.6 | C15—C14—H14 | 120.1 |
C4—C5—C6 | 120.06 (17) | C13—C14—H14 | 120.1 |
C4—C5—H5 | 120.0 | C14—C15—C16 | 120.66 (17) |
C6—C5—H5 | 120.0 | C14—C15—H15 | 119.7 |
C5—C6—C1 | 118.06 (15) | C16—C15—H15 | 119.7 |
C5—C6—C7 | 121.65 (15) | C15—C16—C11 | 120.07 (16) |
C1—C6—C7 | 120.29 (14) | C15—C16—H16 | 120.0 |
O1—C7—C8 | 122.33 (15) | C11—C16—H16 | 120.0 |
O2—S1—N1—C8 | 169.01 (11) | O1—C7—C8—N1 | −179.44 (14) |
O3—S1—N1—C8 | −60.74 (12) | C6—C7—C8—N1 | 2.3 (2) |
C1—S1—N1—C8 | 53.10 (13) | O1—C7—C8—C9 | 2.1 (2) |
O2—S1—N1—C10 | 33.91 (14) | C6—C7—C8—C9 | −176.08 (14) |
O3—S1—N1—C10 | 164.16 (11) | C10—N1—C8—C7 | 95.02 (18) |
C1—S1—N1—C10 | −82.00 (13) | S1—N1—C8—C7 | −40.79 (19) |
O2—S1—C1—C2 | 31.19 (17) | C10—N1—C8—C9 | −86.52 (17) |
O3—S1—C1—C2 | −100.97 (15) | S1—N1—C8—C9 | 137.67 (12) |
N1—S1—C1—C2 | 145.98 (14) | C11—N2—C9—O4 | −1.9 (3) |
O2—S1—C1—C6 | −152.18 (13) | C11—N2—C9—C8 | 179.43 (14) |
O3—S1—C1—C6 | 75.66 (14) | C7—C8—C9—O4 | −10.5 (2) |
N1—S1—C1—C6 | −37.39 (15) | N1—C8—C9—O4 | 170.98 (14) |
C6—C1—C2—C3 | −1.7 (3) | C7—C8—C9—N2 | 168.20 (15) |
S1—C1—C2—C3 | 174.78 (14) | N1—C8—C9—N2 | −10.3 (2) |
C1—C2—C3—C4 | −0.1 (3) | C9—N2—C11—C16 | 30.3 (2) |
C2—C3—C4—C5 | 1.2 (3) | C9—N2—C11—C12 | −153.27 (15) |
C3—C4—C5—C6 | −0.5 (3) | C16—C11—C12—C13 | 1.2 (2) |
C4—C5—C6—C1 | −1.2 (3) | N2—C11—C12—C13 | −175.34 (15) |
C4—C5—C6—C7 | 178.64 (16) | C16—C11—C12—Cl1 | −179.29 (12) |
C2—C1—C6—C5 | 2.3 (2) | N2—C11—C12—Cl1 | 4.2 (2) |
S1—C1—C6—C5 | −174.26 (13) | C11—C12—C13—C14 | −1.1 (3) |
C2—C1—C6—C7 | −177.52 (15) | Cl1—C12—C13—C14 | 179.37 (13) |
S1—C1—C6—C7 | 5.9 (2) | C12—C13—C14—C15 | −0.1 (3) |
C5—C6—C7—O1 | 17.7 (2) | C13—C14—C15—C16 | 1.3 (3) |
C1—C6—C7—O1 | −162.40 (14) | C14—C15—C16—C11 | −1.2 (3) |
C5—C6—C7—C8 | −163.91 (16) | C12—C11—C16—C15 | 0.0 (2) |
C1—C6—C7—C8 | 15.9 (2) | N2—C11—C16—C15 | 176.37 (15) |
D—H···A | D—H | H···A | D···A | D—H···A |
C10—H10C···O1i | 0.98 | 2.45 | 3.366 (2) | 155 |
C4—H4···O2ii | 0.95 | 2.47 | 3.395 (2) | 165 |
O1—H1O···O4 | 0.87 (2) | 1.75 (2) | 2.563 (2) | 153 (2) |
N2—H2N···N1 | 0.85 (2) | 2.29 (2) | 2.733 (2) | 113 (2) |
N2—H2N···Cl1 | 0.85 (2) | 2.58 (2) | 2.953 (2) | 108 (2) |
C16—H16···O4 | 0.95 | 2.38 | 2.908 (2) | 115 |
Symmetry codes: (i) x−1, y, z; (ii) x+1, −y+1/2, z+1/2. |
C16H13ClN2O4S | Z = 2 |
Mr = 364.79 | F(000) = 376 |
Triclinic, P1 | Dx = 1.538 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 7.970 (5) Å | Cell parameters from 6690 reflections |
b = 10.945 (6) Å | θ = 3.7–27.4° |
c = 11.133 (7) Å | µ = 0.40 mm−1 |
α = 60.61 (3)° | T = 173 K |
β = 69.81 (3)° | Prism, colourless |
γ = 86.32 (2)° | 0.14 × 0.10 × 0.04 mm |
V = 787.6 (8) Å3 |
Nonius KappaCCD diffractometer | 3595 independent reflections |
Radiation source: fine-focus sealed tube | 2197 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.057 |
ω and ϕ scans | θmax = 27.4°, θmin = 3.7° |
Absorption correction: multi-scan (SORTAV; Blessing, 1997) | h = −10→10 |
Tmin = 0.946, Tmax = 0.984 | k = −14→14 |
6690 measured reflections | l = −14→14 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.050 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.127 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.02 | w = 1/[σ2(Fo2) + (0.0555P)2 + 0.159P] where P = (Fo2 + 2Fc2)/3 |
3595 reflections | (Δ/σ)max < 0.001 |
224 parameters | Δρmax = 0.34 e Å−3 |
0 restraints | Δρmin = −0.37 e Å−3 |
C16H13ClN2O4S | γ = 86.32 (2)° |
Mr = 364.79 | V = 787.6 (8) Å3 |
Triclinic, P1 | Z = 2 |
a = 7.970 (5) Å | Mo Kα radiation |
b = 10.945 (6) Å | µ = 0.40 mm−1 |
c = 11.133 (7) Å | T = 173 K |
α = 60.61 (3)° | 0.14 × 0.10 × 0.04 mm |
β = 69.81 (3)° |
Nonius KappaCCD diffractometer | 3595 independent reflections |
Absorption correction: multi-scan (SORTAV; Blessing, 1997) | 2197 reflections with I > 2σ(I) |
Tmin = 0.946, Tmax = 0.984 | Rint = 0.057 |
6690 measured reflections |
R[F2 > 2σ(F2)] = 0.050 | 0 restraints |
wR(F2) = 0.127 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.02 | Δρmax = 0.34 e Å−3 |
3595 reflections | Δρmin = −0.37 e Å−3 |
224 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
Cl1 | 0.95427 (10) | 0.37261 (9) | −0.07737 (9) | 0.0386 (2) | |
S1 | −0.27432 (9) | 0.38747 (7) | 0.55333 (8) | 0.0240 (2) | |
O1 | −0.2725 (3) | 0.0481 (2) | 0.4711 (2) | 0.0306 (5) | |
H1O | −0.164 (4) | 0.062 (3) | 0.405 (3) | 0.037* | |
O2 | −0.2654 (3) | 0.4552 (2) | 0.6335 (2) | 0.0310 (5) | |
O3 | −0.2889 (3) | 0.4703 (2) | 0.4114 (2) | 0.0289 (5) | |
O4 | 0.0601 (3) | 0.1388 (2) | 0.3081 (2) | 0.0307 (5) | |
N1 | −0.0952 (3) | 0.3061 (2) | 0.5333 (2) | 0.0230 (5) | |
N2 | 0.2034 (3) | 0.3078 (3) | 0.3169 (3) | 0.0261 (6) | |
H2N | 0.181 (4) | 0.354 (3) | 0.357 (3) | 0.031* | |
C1 | −0.4473 (4) | 0.2440 (3) | 0.6657 (3) | 0.0237 (6) | |
C2 | −0.5967 (4) | 0.2417 (3) | 0.7776 (3) | 0.0290 (7) | |
H2 | −0.6073 | 0.3174 | 0.7976 | 0.035* | |
C3 | −0.7307 (4) | 0.1266 (3) | 0.8600 (3) | 0.0338 (7) | |
H3 | −0.8331 | 0.1222 | 0.9383 | 0.041* | |
C4 | −0.7147 (4) | 0.0181 (3) | 0.8277 (4) | 0.0360 (8) | |
H4 | −0.8083 | −0.0590 | 0.8829 | 0.043* | |
C5 | −0.5657 (4) | 0.0203 (3) | 0.7172 (3) | 0.0294 (7) | |
H5 | −0.5575 | −0.0551 | 0.6969 | 0.035* | |
C6 | −0.4261 (4) | 0.1326 (3) | 0.6345 (3) | 0.0235 (6) | |
C7 | −0.2605 (4) | 0.1344 (3) | 0.5219 (3) | 0.0229 (6) | |
C8 | −0.1046 (4) | 0.2176 (3) | 0.4723 (3) | 0.0223 (6) | |
C9 | 0.0580 (4) | 0.2182 (3) | 0.3591 (3) | 0.0244 (6) | |
C10 | −0.0320 (4) | 0.2388 (3) | 0.6594 (3) | 0.0323 (7) | |
H10A | 0.0875 | 0.2106 | 0.6286 | 0.039* | |
H10B | −0.1168 | 0.1551 | 0.7411 | 0.039* | |
H10C | −0.0249 | 0.3061 | 0.6920 | 0.039* | |
C11 | 0.3801 (4) | 0.3180 (3) | 0.2226 (3) | 0.0241 (6) | |
C12 | 0.4168 (4) | 0.3063 (3) | 0.0971 (3) | 0.0275 (7) | |
H12 | 0.3206 | 0.2873 | 0.0743 | 0.033* | |
C13 | 0.5929 (4) | 0.3225 (3) | 0.0061 (3) | 0.0293 (7) | |
H13 | 0.6184 | 0.3145 | −0.0794 | 0.035* | |
C14 | 0.7324 (4) | 0.3504 (3) | 0.0398 (3) | 0.0269 (7) | |
C15 | 0.6982 (4) | 0.3623 (3) | 0.1642 (3) | 0.0262 (7) | |
H15 | 0.7947 | 0.3818 | 0.1864 | 0.031* | |
C16 | 0.5228 (4) | 0.3457 (3) | 0.2548 (3) | 0.0265 (7) | |
H16 | 0.4982 | 0.3532 | 0.3406 | 0.032* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl1 | 0.0269 (4) | 0.0440 (5) | 0.0411 (5) | −0.0007 (4) | −0.0013 (4) | −0.0251 (4) |
S1 | 0.0242 (4) | 0.0221 (4) | 0.0269 (4) | 0.0019 (3) | −0.0063 (3) | −0.0149 (3) |
O1 | 0.0294 (12) | 0.0333 (13) | 0.0385 (13) | 0.0029 (10) | −0.0105 (10) | −0.0256 (11) |
O2 | 0.0301 (11) | 0.0324 (12) | 0.0361 (12) | 0.0000 (9) | −0.0040 (10) | −0.0260 (11) |
O3 | 0.0337 (12) | 0.0236 (11) | 0.0245 (11) | 0.0040 (9) | −0.0093 (10) | −0.0093 (10) |
O4 | 0.0319 (12) | 0.0341 (12) | 0.0360 (12) | 0.0038 (9) | −0.0099 (10) | −0.0260 (11) |
N1 | 0.0250 (13) | 0.0240 (13) | 0.0250 (13) | 0.0031 (10) | −0.0104 (11) | −0.0150 (11) |
N2 | 0.0239 (13) | 0.0305 (15) | 0.0306 (15) | 0.0037 (11) | −0.0052 (11) | −0.0230 (13) |
C1 | 0.0214 (15) | 0.0234 (16) | 0.0266 (16) | 0.0025 (12) | −0.0098 (13) | −0.0119 (14) |
C2 | 0.0286 (17) | 0.0283 (17) | 0.0311 (17) | 0.0068 (13) | −0.0115 (14) | −0.0155 (15) |
C3 | 0.0248 (16) | 0.0307 (18) | 0.0328 (18) | 0.0030 (14) | −0.0035 (14) | −0.0110 (16) |
C4 | 0.0262 (17) | 0.0268 (18) | 0.045 (2) | −0.0008 (13) | −0.0083 (15) | −0.0134 (16) |
C5 | 0.0278 (17) | 0.0259 (17) | 0.0381 (18) | 0.0046 (13) | −0.0159 (15) | −0.0161 (15) |
C6 | 0.0234 (15) | 0.0221 (16) | 0.0258 (16) | 0.0020 (12) | −0.0113 (13) | −0.0107 (14) |
C7 | 0.0264 (15) | 0.0224 (16) | 0.0262 (16) | 0.0031 (12) | −0.0112 (13) | −0.0157 (14) |
C8 | 0.0257 (15) | 0.0226 (16) | 0.0246 (15) | 0.0050 (12) | −0.0110 (13) | −0.0151 (13) |
C9 | 0.0245 (15) | 0.0262 (16) | 0.0281 (16) | 0.0064 (12) | −0.0124 (13) | −0.0160 (14) |
C10 | 0.0339 (17) | 0.0401 (19) | 0.0329 (18) | 0.0068 (14) | −0.0177 (15) | −0.0220 (16) |
C11 | 0.0264 (16) | 0.0186 (16) | 0.0254 (16) | 0.0050 (12) | −0.0086 (13) | −0.0104 (14) |
C12 | 0.0273 (16) | 0.0294 (18) | 0.0289 (17) | 0.0042 (13) | −0.0132 (14) | −0.0148 (15) |
C13 | 0.0332 (18) | 0.0305 (18) | 0.0249 (16) | 0.0030 (14) | −0.0093 (14) | −0.0149 (15) |
C14 | 0.0243 (15) | 0.0225 (16) | 0.0278 (16) | 0.0018 (12) | −0.0038 (13) | −0.0118 (14) |
C15 | 0.0258 (16) | 0.0252 (16) | 0.0298 (17) | 0.0031 (12) | −0.0124 (14) | −0.0139 (14) |
C16 | 0.0297 (16) | 0.0242 (16) | 0.0276 (16) | 0.0058 (13) | −0.0126 (14) | −0.0133 (14) |
Cl1—C14 | 1.744 (3) | C4—H4 | 0.9500 |
S1—O3 | 1.428 (2) | C5—C6 | 1.398 (4) |
S1—O2 | 1.433 (2) | C5—H5 | 0.9500 |
S1—N1 | 1.641 (2) | C6—C7 | 1.466 (4) |
S1—C1 | 1.758 (3) | C7—C8 | 1.362 (4) |
O1—C7 | 1.340 (3) | C8—C9 | 1.461 (4) |
O1—H1O | 0.88 (3) | C10—H10A | 0.9800 |
O4—C9 | 1.247 (3) | C10—H10B | 0.9800 |
N1—C8 | 1.448 (3) | C10—H10C | 0.9800 |
N1—C10 | 1.481 (4) | C11—C12 | 1.393 (4) |
N2—C9 | 1.358 (3) | C11—C16 | 1.396 (4) |
N2—C11 | 1.408 (4) | C12—C13 | 1.380 (4) |
N2—H2N | 0.80 (3) | C12—H12 | 0.9500 |
C1—C2 | 1.385 (4) | C13—C14 | 1.383 (4) |
C1—C6 | 1.409 (4) | C13—H13 | 0.9500 |
C2—C3 | 1.390 (4) | C14—C15 | 1.386 (4) |
C2—H2 | 0.9500 | C15—C16 | 1.373 (4) |
C3—C4 | 1.386 (4) | C15—H15 | 0.9500 |
C3—H3 | 0.9500 | C16—H16 | 0.9500 |
C4—C5 | 1.375 (4) | ||
O3—S1—O2 | 119.26 (13) | O1—C7—C6 | 115.4 (2) |
O3—S1—N1 | 107.63 (12) | C8—C7—C6 | 122.5 (2) |
O2—S1—N1 | 108.11 (12) | C7—C8—N1 | 120.5 (2) |
O3—S1—C1 | 109.37 (13) | C7—C8—C9 | 121.4 (2) |
O2—S1—C1 | 109.62 (13) | N1—C8—C9 | 118.1 (2) |
N1—S1—C1 | 101.34 (13) | O4—C9—N2 | 123.5 (3) |
C7—O1—H1O | 104.1 (19) | O4—C9—C8 | 120.8 (2) |
C8—N1—C10 | 114.3 (2) | N2—C9—C8 | 115.7 (2) |
C8—N1—S1 | 112.17 (17) | N1—C10—H10A | 109.5 |
C10—N1—S1 | 116.54 (18) | N1—C10—H10B | 109.5 |
C9—N2—C11 | 127.1 (2) | H10A—C10—H10B | 109.5 |
C9—N2—H2N | 112 (2) | N1—C10—H10C | 109.5 |
C11—N2—H2N | 121 (2) | H10A—C10—H10C | 109.5 |
C2—C1—C6 | 122.1 (3) | H10B—C10—H10C | 109.5 |
C2—C1—S1 | 121.7 (2) | C12—C11—C16 | 119.4 (3) |
C6—C1—S1 | 116.2 (2) | C12—C11—N2 | 122.7 (2) |
C1—C2—C3 | 118.8 (3) | C16—C11—N2 | 117.9 (2) |
C1—C2—H2 | 120.6 | C13—C12—C11 | 119.9 (2) |
C3—C2—H2 | 120.6 | C13—C12—H12 | 120.0 |
C4—C3—C2 | 119.9 (3) | C11—C12—H12 | 120.0 |
C4—C3—H3 | 120.0 | C12—C13—C14 | 119.8 (3) |
C2—C3—H3 | 120.0 | C12—C13—H13 | 120.1 |
C5—C4—C3 | 121.1 (3) | C14—C13—H13 | 120.1 |
C5—C4—H4 | 119.4 | C13—C14—C15 | 121.0 (3) |
C3—C4—H4 | 119.4 | C13—C14—Cl1 | 119.3 (2) |
C4—C5—C6 | 120.5 (3) | C15—C14—Cl1 | 119.7 (2) |
C4—C5—H5 | 119.7 | C16—C15—C14 | 119.1 (2) |
C6—C5—H5 | 119.7 | C16—C15—H15 | 120.5 |
C5—C6—C1 | 117.5 (3) | C14—C15—H15 | 120.5 |
C5—C6—C7 | 122.0 (2) | C15—C16—C11 | 120.8 (3) |
C1—C6—C7 | 120.4 (2) | C15—C16—H16 | 119.6 |
O1—C7—C8 | 122.0 (2) | C11—C16—H16 | 119.6 |
O3—S1—N1—C8 | −58.3 (2) | O1—C7—C8—N1 | −178.0 (2) |
O2—S1—N1—C8 | 171.67 (18) | C6—C7—C8—N1 | 1.8 (4) |
C1—S1—N1—C8 | 56.5 (2) | O1—C7—C8—C9 | 0.7 (4) |
O3—S1—N1—C10 | 167.31 (19) | C6—C7—C8—C9 | −179.5 (3) |
O2—S1—N1—C10 | 37.3 (2) | C10—N1—C8—C7 | 92.2 (3) |
C1—S1—N1—C10 | −77.9 (2) | S1—N1—C8—C7 | −43.2 (3) |
O3—S1—C1—C2 | −104.7 (2) | C10—N1—C8—C9 | −86.5 (3) |
O2—S1—C1—C2 | 27.7 (3) | S1—N1—C8—C9 | 138.0 (2) |
N1—S1—C1—C2 | 141.8 (2) | C11—N2—C9—O4 | −6.2 (5) |
O3—S1—C1—C6 | 74.7 (2) | C11—N2—C9—C8 | 172.7 (3) |
O2—S1—C1—C6 | −152.8 (2) | C7—C8—C9—O4 | −2.3 (4) |
N1—S1—C1—C6 | −38.8 (2) | N1—C8—C9—O4 | 176.4 (2) |
C6—C1—C2—C3 | −1.0 (4) | C7—C8—C9—N2 | 178.7 (3) |
S1—C1—C2—C3 | 178.4 (2) | N1—C8—C9—N2 | −2.5 (4) |
C1—C2—C3—C4 | −1.1 (4) | C9—N2—C11—C12 | 39.1 (4) |
C2—C3—C4—C5 | 1.6 (5) | C9—N2—C11—C16 | −143.1 (3) |
C3—C4—C5—C6 | 0.1 (4) | C16—C11—C12—C13 | −0.1 (4) |
C4—C5—C6—C1 | −2.0 (4) | N2—C11—C12—C13 | 177.6 (3) |
C4—C5—C6—C7 | 176.2 (3) | C11—C12—C13—C14 | −0.1 (4) |
C2—C1—C6—C5 | 2.5 (4) | C12—C13—C14—C15 | 0.1 (4) |
S1—C1—C6—C5 | −176.9 (2) | C12—C13—C14—Cl1 | −179.3 (2) |
C2—C1—C6—C7 | −175.8 (3) | C13—C14—C15—C16 | 0.2 (4) |
S1—C1—C6—C7 | 4.8 (3) | Cl1—C14—C15—C16 | 179.5 (2) |
C5—C6—C7—O1 | 19.9 (4) | C14—C15—C16—C11 | −0.4 (4) |
C1—C6—C7—O1 | −161.9 (2) | C12—C11—C16—C15 | 0.4 (4) |
C5—C6—C7—C8 | −160.0 (3) | N2—C11—C16—C15 | −177.5 (3) |
C1—C6—C7—C8 | 18.3 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1O···O4 | 0.88 (3) | 1.74 (3) | 2.560 (3) | 153 (3) |
N2—H2N···N1 | 0.80 (3) | 2.27 (3) | 2.734 (4) | 118 (3) |
N2—H2N···O2i | 0.80 (3) | 2.30 (3) | 3.006 (3) | 148 (3) |
C13—H13···O2ii | 0.95 | 2.60 | 3.414 (4) | 144 |
C12—H12···O4 | 0.95 | 2.51 | 2.966 (4) | 110 |
Symmetry codes: (i) −x, −y+1, −z+1; (ii) x+1, y, z−1. |
Experimental details
(I) | (II) | |
Crystal data | ||
Chemical formula | C16H13ClN2O4S | C16H13ClN2O4S |
Mr | 364.79 | 364.79 |
Crystal system, space group | Monoclinic, P21/c | Triclinic, P1 |
Temperature (K) | 173 | 173 |
a, b, c (Å) | 7.750 (2), 28.588 (7), 7.519 (1) | 7.970 (5), 10.945 (6), 11.133 (7) |
α, β, γ (°) | 90, 106.630 (12), 90 | 60.61 (3), 69.81 (3), 86.32 (2) |
V (Å3) | 1596.2 (6) | 787.6 (8) |
Z | 4 | 2 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.39 | 0.40 |
Crystal size (mm) | 0.22 × 0.20 × 0.11 | 0.14 × 0.10 × 0.04 |
Data collection | ||
Diffractometer | Nonius KappaCCD diffractometer | Nonius KappaCCD diffractometer |
Absorption correction | Multi-scan (SORTAV; Blessing, 1997) | Multi-scan (SORTAV; Blessing, 1997) |
Tmin, Tmax | 0.918, 0.958 | 0.946, 0.984 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 6588, 3610, 3003 | 6690, 3595, 2197 |
Rint | 0.027 | 0.057 |
(sin θ/λ)max (Å−1) | 0.649 | 0.648 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.034, 0.090, 1.03 | 0.050, 0.127, 1.02 |
No. of reflections | 3610 | 3595 |
No. of parameters | 226 | 224 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.30, −0.37 | 0.34, −0.37 |
Computer programs: COLLECT (Nonius, 1998), HKL DENZO (Otwinowski & Minor, 1997), SCALEPACK (Otwinowski & Minor, 1997), SAPI91 (Fan, 1991), SHELXL97 (Sheldrick, 1997), ORTEPII (Johnson, 1976).
Cl1—C12 | 1.7395 (17) | O4—C9 | 1.245 (2) |
S1—O2 | 1.4302 (13) | N1—C8 | 1.445 (2) |
S1—O3 | 1.4317 (14) | N1—C10 | 1.482 (2) |
S1—N1 | 1.6448 (14) | N2—C9 | 1.355 (2) |
S1—C1 | 1.7589 (17) | N2—C11 | 1.409 (2) |
O1—C7 | 1.340 (2) | ||
O2—S1—O3 | 119.48 (8) | N1—S1—C1 | 102.10 (7) |
O2—S1—N1 | 108.32 (8) | C8—N1—C10 | 114.57 (13) |
O3—S1—N1 | 107.29 (7) | C8—N1—S1 | 112.82 (10) |
O2—S1—C1 | 109.86 (8) | C10—N1—S1 | 116.09 (11) |
O3—S1—C1 | 108.37 (8) | C9—N2—C11 | 127.19 (14) |
D—H···A | D—H | H···A | D···A | D—H···A |
C10—H10C···O1i | 0.98 | 2.45 | 3.366 (2) | 155 |
C4—H4···O2ii | 0.95 | 2.47 | 3.395 (2) | 165 |
O1—H1O···O4 | 0.87 (2) | 1.75 (2) | 2.563 (2) | 153 (2) |
N2—H2N···N1 | 0.85 (2) | 2.29 (2) | 2.733 (2) | 113 (2) |
N2—H2N···Cl1 | 0.85 (2) | 2.58 (2) | 2.953 (2) | 108 (2) |
C16—H16···O4 | 0.95 | 2.38 | 2.908 (2) | 115 |
Symmetry codes: (i) x−1, y, z; (ii) x+1, −y+1/2, z+1/2. |
Cl1—C14 | 1.744 (3) | O4—C9 | 1.247 (3) |
S1—O3 | 1.428 (2) | N1—C8 | 1.448 (3) |
S1—O2 | 1.433 (2) | N1—C10 | 1.481 (4) |
S1—N1 | 1.641 (2) | N2—C9 | 1.358 (3) |
S1—C1 | 1.758 (3) | N2—C11 | 1.408 (4) |
O1—C7 | 1.340 (3) | ||
O3—S1—O2 | 119.26 (13) | N1—S1—C1 | 101.34 (13) |
O3—S1—N1 | 107.63 (12) | C8—N1—C10 | 114.3 (2) |
O2—S1—N1 | 108.11 (12) | C8—N1—S1 | 112.17 (17) |
O3—S1—C1 | 109.37 (13) | C10—N1—S1 | 116.54 (18) |
O2—S1—C1 | 109.62 (13) | C9—N2—C11 | 127.1 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1O···O4 | 0.88 (3) | 1.74 (3) | 2.560 (3) | 153 (3) |
N2—H2N···N1 | 0.80 (3) | 2.27 (3) | 2.734 (4) | 118 (3) |
N2—H2N···O2i | 0.80 (3) | 2.30 (3) | 3.006 (3) | 148 (3) |
C13—H13···O2ii | 0.95 | 2.60 | 3.414 (4) | 144 |
C12—H12···O4 | 0.95 | 2.51 | 2.966 (4) | 110 |
Symmetry codes: (i) −x, −y+1, −z+1; (ii) x+1, y, z−1. |
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In recent years, there has been a rapid growth in the literature dealing with 1,2-benzothiazine-3-carboxamide 1,1-dioxide derivatives, due to their importance as analgesic and anti-inflammatory agents belonging to oxicams, a new class of non-steroidal anti-inflammatory drugs (NSAIDs) (Lombardino & Wiseman, 1972; Hirai et al., 1997; Khalil et al., 2000; Yaltirik et al., 2001; Myung et al., 2002). These drugs are free from steroidal side-effects, although they have little effect on the progression of bone and cartilage destruction (Katzung, 1994). The search for more effective anti-inflammatory agents has led to the exploration of a wide variety of compounds that may inhibit cartilage destruction associated with NSAIDs, or at least reduce their severity. Besides great therapeutic potential, these are very motivating polyfunctional heterocyclic molecules by virtue of their dynamic structural features, including different tautomeric forms and their possible polymorphism (Banerjee & Sarkar, 2002). The crystal structures of piroxicam (an oxicam, 4-hydroxy-2-methyl-N-2-pyridyl-2H-1,2-benzothiazine-3-carboxamide 1,1-dioxide) and a wide variety of its derivatives have been reported (Kojić-Prodić & Rużić-Toroš, 1982; Reck et al., 1988; Drebushchak et al., 2006; Bordner et al., 1984; Bhatt et al., 2005; Hammen et al., 1989; Bordner et al., 1989; Chiesi-Villa et al., 1998). The structures of a few derivatives of meloxicam (a 5-methyl-2-thiazolyl analogue of piroxicam) have also been reported (Fabiola et al., 1998; Luger et al., 1996). In continuation of our research in this important area (Siddiqui et al., 2006a,b, 2007), we have synthesized analogues of piroxicam and meloxicam wherein the pyridyl ring of the former and 5-methoxy-2-thiazolyl group of the latter have been replaced by a chlorophenyl ring. A new facile procedure has been adopted that leads to an excellent yield and product purity. In this paper, we report the structures of the 2-chloro- and 4-chlorophenyl derivatives of the title compound, (I) and (II), respectively.
The structure of (I) contains independent molecules separated by normal van der Waals distances (Fig. 1). The heterocyclic thiazine ring in (I) adopts a half-chair conformation, with atoms S1 and N1 displaced by -0.468 (3) and 0.328 (3) Å, respectively, from the plane defined by atoms C1/C6/C7/C8; the puckering parameters (Cremer & Pople, 1975) are Q = 0.522 (1) Å, θ = 117.8 (2)° and ϕ = 204.3 (2)°. Similar conformations of the thiazine ring have been reported in the above-mentioned structures of piroxicams and meloxicams. The conformations about the bonds C8—C9 and C9—N2 in (I) are both EZ, as determined by the intramolecular hydrogen bonds O1—H1O···O4 and N2—H2N···N1, resulting in graph-set patterns S(6) and S(5), respectively (Bernstein et al., 1994). The intramolecular hydrogen bonds N2—H2N···Cl1 and C16—H16···O4 also represent S(5) and S(6) motifs, respectively; details of the hydrogen-bonding geometry are given in Table 2. In the structures of oxicams, EZ and ZZ conformations about the corresponding bonds have been reported previously, depending on the environment of the drug molecules. In (I), the methyl C10 and O3 groups are axial, while atoms O1 and O2 are equatorial to the thiazine ring. Atoms N2/O4/C8/C9/C11 in (I) are essentially planar, with the maximum deviation from the plane being 0.0077 (11) Å for atom N2; the plane is inclined at 27.18 (6)° to the plane of the 2-chlorophenyl ring.
The structure of (II) (Fig. 3) contains dimeric pairs of molecules lying about inversion centres resulting from N2—H2N···O2 hydrogen bonds, thus forming 14-membered rings that can be best described in the graph-set notation as R22(14) (Bernstein et al., 1994) (Fig. 4); the structure of (I) is devoid of any such intermolecular interactions. However, similar hydrogen-bonded dimers have been reported in piroxicams (Kojić-Prodić & Rużić-Toroš, 1982; Drebushchak et al., 2006). The structure of (II) is also stabilized by extensive intramolecular interactions involving hydrogen bonds: N2—H2N···N1, O1—H1O···O4 and C12—H12···O4, representing S(5), S(6) and S(6) motifs, respectively; details of the hydrogen-bonding geometry are given in Table 4. The thiazine ring in (II) also adopts a half-chair conformation, with atoms S1 and N1 displaced by -0.485 (5) and 0.358 (5) Å, respectively, from the plane formed by atoms C1/C6/C7/C8. The values of the puckering parameters in (II) are Q = 0.556 (2) Å, θ = 117.0 (3)° and ϕ = 205.1 (4)°, and these are close to the corresponding values observed in (I) and other related compounds. The conformations about the bonds C8—C9 and C9—N2 in (II) are also both EZ, due to the strong intramolecular hydrogen bonds O1—H1O···O4 and N2—H2N···N1. Intramolecular hydrogen bonds N2—H2N···Cl1 and C16—H16···O4 also represent S(5) and S(6) motifs, respectively (Table 4). The methyl C10 and O3 groups in (II) are axial, while atoms O1 and O2 are equatorial to the thiazine ring. Atoms N2/O4/C8/C9/C11 are essentially planar, with the maximum deviation from the plane being 0.053 (2) Å for atom N2. However, the chlorophenyl ring in (II) is inclined at 33.0 (2)° to the plane formed by atoms N2/O4/C8/C9/C11.
The molecular dimensions in the two structures are unexceptional and agree with the reported values for the corresponding dimensions for oxicams.