N-(X-Chloro­phen­yl)-4-hydr­oxy-2-methyl-2H-1,2-benzothia­zine-3-carboxamide 1,1-dioxide (with X = 2 and 4)

The structures of N-(2-chloro­phenyl)-4-hydroxy-2-methyl-2H-1,2-benzo­thia­zine-3-carboxamide 1,1-dioxide and N-(4-chloro­phenyl)-4-hydroxy-2-methyl-2H-1,2-benzo­thia­zine-3-carboxamide 1,1-dioxide, both C₁₆H₁₃ClN₂O₄S, are stabilized by extensive intra­molecular hydrogen bonds. The 4-chloro derivative forms dimeric pairs of mol­ecules lying about inversion centres as a result of inter­molecular N—H...O hydrogen bonds, forming 14-membered rings representing an R₂²(14) motif; the 2-chloro derivative is devoid of any such inter­molecular hydrogen bonds. The heterocyclic thia­zine rings in both structures adopt half-chair conformations.

S1. Comment

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.

Related literature

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).

S2. Experimental

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, ν_max, 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, ν_max, 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.

S3. Refinement

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 U_iso(H) = 1.2U_eq(C). H atoms bonded to N and O atoms were allowed to refine, with U_iso(H) = 1.2U_eq(parent). The final difference maps were free of chemically significant features.

Computing details

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).

Figures

Fig. 1. A drawing of (I), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii. Fig. 2. The unit-cell packing of (I), showing the inter- and intramolecular interactions as dashed lines. Only H atoms involved in the hydrogen bonds are shown. Fig. 3. A drawing of (II), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii. Fig. 4. The unit-cell packing of (II), showing the inter- and intramolecular interactions as dashed lines. Only H atoms involved in the hydrogen bonds are shown.

(I) N-(2-chlorophenyl)-4-hydroxy-2-methyl-2H-1,2-benzothiazine-3-carboxamide 1,1-dioxide

Crystal data

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) Å^3	0.22 × 0.20 × 0.11 mm
Z = 4

Data collection

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

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.090	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ^2(Fo^2) + (0.038P)^2 + 0.84P] where P = (Fo^2 + 2Fc^2)/3
3610 reflections	(Δ/σ)max = 0.001
226 parameters	Δρmax = 0.30 e Å^−3
0 restraints	Δρmin = −0.37 e Å^−3

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.

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

	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*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

Geometric parameters (Å, º)

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)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C10—H10C···O1^i	0.98	2.45	3.366 (2)	155
C4—H4···O2^ii	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.

(II) N-(2-chlorophenyl)-4-hydroxy-2-methyl-2H-1,2-benzothiazine-3-carboxamide 1,1-dioxide

Crystal data

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) Å^3

Data collection

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

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.050	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.127	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ^2(Fo^2) + (0.0555P)^2 + 0.159P] where P = (Fo^2 + 2Fc^2)/3
3595 reflections	(Δ/σ)max < 0.001
224 parameters	Δρmax = 0.34 e Å^−3
0 restraints	Δρmin = −0.37 e Å^−3

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.

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

	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*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

Geometric parameters (Å, º)

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)

Hydrogen-bond geometry (Å, º)

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···O2^i	0.80 (3)	2.30 (3)	3.006 (3)	148 (3)
C13—H13···O2^ii	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.