3-(3-Chloro­benzo­yl)-4-hydr­oxy-2H-1,2-benzothia­zine 1,1-dioxide

Khalid, Z.; Siddiqui, H.L.; Ahmad, M.; Aslam, S.; Parvez, M.

doi:10.1107/S1600536810009761

3-(3-Chlorobenzoyl)-4-hydroxy-2H-1,2-benzothiazine 1,1-dioxide

Z. Khalid, H. L. Siddiqui, M. Ahmad, S. Aslam and M. Parvez

In the title compound, C₁₅H₁₀ClNO₄S, the heterocyclic thiazine ring adopts a half-chair conformation with the S and N atoms displaced by 0.476 (5) and 0.227 (5) Å, respectively, on opposite sides of the mean plane formed by the remaining ring atoms. The structure is stabilized by intermolecular N—H

O and C—H

O hydrogen bonds. In addition, intramolecular O—H

O and C—H

N interactions are also present.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536810009761/pk2231sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536810009761/pk2231Isup2.hkl Contains datablock I

CCDC reference: 774316

checkCIF report

Key indicators

Single-crystal X-ray study
T = 295 K
Mean (C-C) = 0.004 Å
R factor = 0.051
wR factor = 0.121
Data-to-parameter ratio = 16.0

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.600         42
PLAT913_ALERT_3_C Missing # of Very Strong Reflections in FCF ....          3
PLAT912_ALERT_4_C Missing # of FCF Reflections Above STh/L=  0.600         40
PLAT927_ALERT_1_C Reported and Calculated  wR2 * 100.0 Differ by .      -0.35

Alert level G
PLAT154_ALERT_1_G The su's on the Cell Angles are Equal  (x 10000)        300 Deg.

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   4 ALERT level C = Check and explain
   1 ALERT level G = General alerts; check

   2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 ALERT type 2 Indicator that the structure model may be wrong or deficient
   2 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

Comment top

1,2-Benzothiazine 1,1-dioxides represent a class of pharmaceutically important heterocyclic compounds that have received considerable attention because of their dynamic structural features and a wide range of biological activity, e.g., anti-inflammatory (Lombardino & Wiseman, 1972), analgesic (Gupta et al., 2002), anti-cancer (Gupta et al., 1993), anti-bacterial (Zia-ur-Rehman et al., 2006) and endothelin receptor antagonists (Berryman et al., 1998), etc. In continuation of our research on the synthesis of biologically active benzothiazine derivatives (Ahmad et al., 2010), we herein report the synthesis and crystal structure of the title compound.

The title molecule is presented in Fig. 1. The bond distances are as expected (Allen et al., 1987) and agree with the corresponding parameters reported in closely related compounds (Siddiqui et al., 2008). The heterocyclic thiazine ring adopts a half chair conformation with atoms S1 and N1 displaced by 0.476 (5) and 0.227 (5) Å , respectively, on the opposite sides from the mean plane formed by the remaining ring atoms.

The structure is stabilized by intermolecular hydrogen bonds of the types N—H···O and C—H···O. In addition, intramolecular interactions O3—H3O···O4 and C15—H15···N1 are also present consolidating the crystal packing; details are provided in Table 1.

Related literature top

For the biological activity of 1,2-benzothiazine derivatives, see: Ahmad et al. (2010); Lombardino & Wiseman, (1972); Gupta et al. (1993, 2002); Zia-ur-Rehman et al. (2006); Berryman et al. (1998). For comparative bond distances, see: Allen et al. (1987). For related structures, see: Siddiqui et al. (2008)

Experimental top

Sodium metal (4.83 g, 210 mmol) was dissolved in dry methanol (35 ml) and 2-[2-(3-chlorophenyl)-2-oxoethyl]-1,2-benzisothiazol-3(2H)-one 1,1-dioxide (10.07 g, 30 mmol) was added to it. The mixture was refluxed for 30 minutes. The contents of the flask were cooled to room temperature and pH was adjusted at 3.0 using 5% HCl. A pale yellow precipitate of the title compound was filtered and washed with cold methanol. Crystals suitable for crystallographic study were grown from a methanolic solution by slow evaporation at room temperature. Yield, 74%; m.p. 438-440 K.

Computing details top

Data collection: COLLECT (Hooft, 1998); cell refinement: DENZO (Otwinowski & Minor, 1997); data reduction: SCALEPACK (Otwinowski & Minor, 1997); 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); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

Fig. 1. The title molecule with the displacement ellipsoids plotted at 30% probability level (Farrugia, 1997).

3-(3-Chlorobenzoyl)-4-hydroxy-2H-1,2-benzothiazine 1,1-dioxide top

Crystal data top

C₁₅H₁₀ClNO₄S	Z = 2
M_r = 335.75	F(000) = 344
Triclinic, P1	D_x = 1.558 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 4.7151 (3) Å	Cell parameters from 1649 reflections
b = 12.2879 (8) Å	θ = 1.0–27.5°
c = 12.5809 (6) Å	µ = 0.43 mm⁻¹
α = 81.375 (3)°	T = 295 K
β = 84.463 (3)°	Block, yellow
γ = 85.608 (3)°	0.14 × 0.12 × 0.10 mm
V = 715.88 (7) Å³

Data collection top

Nonius KappaCCD diffractometer	3202 independent reflections
Radiation source: fine-focus sealed tube	2783 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.027
ω and ϕ scans	θ_max = 27.5°, θ_min = 1.6°
Absorption correction: multi-scan (SORTAV; Blessing, 1997)	h = −6→6
T_min = 0.942, T_max = 0.958	k = −15→15
4352 measured reflections	l = −16→16

Refinement top

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)] = 0.051	Hydrogen site location: difference Fourier map
wR(F²) = 0.121	H-atom parameters constrained
S = 1.09	w = 1/[σ²(F_o²) + (0.025P)² + 0.745P] where P = (F_o² + 2F_c²)/3
3202 reflections	(Δ/σ)_max < 0.001
200 parameters	Δρ_max = 0.45 e Å⁻³
0 restraints	Δρ_min = −0.36 e Å⁻³

Crystal data top

C₁₅H₁₀ClNO₄S	γ = 85.608 (3)°
M_r = 335.75	V = 715.88 (7) Å³
Triclinic, P1	Z = 2
a = 4.7151 (3) Å	Mo Kα radiation
b = 12.2879 (8) Å	µ = 0.43 mm⁻¹
c = 12.5809 (6) Å	T = 295 K
α = 81.375 (3)°	0.14 × 0.12 × 0.10 mm
β = 84.463 (3)°

Data collection top

Nonius KappaCCD diffractometer	3202 independent reflections
Absorption correction: multi-scan (SORTAV; Blessing, 1997)	2783 reflections with I > 2σ(I)
T_min = 0.942, T_max = 0.958	R_int = 0.027
4352 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.051	0 restraints
wR(F²) = 0.121	H-atom parameters constrained
S = 1.09	Δρ_max = 0.45 e Å⁻³
3202 reflections	Δρ_min = −0.36 e Å⁻³
200 parameters

Special details top

Experimental. IR (KBr) 3157, 1615, 1358, 1156 cm^-1, MS m/z: 335.2 [M⁺]. ¹H NMR (DMSO-d₆); 7.64 (t, 2H, J = 8.0 Hz, Ar—H), 7.75 (d, 2H, J = 8.0 Hz, Ar—H), 7.96 (d, 1H, J = 10.0 Hz, Ar—H), 7.96 (s, 1H, J = 16.4 Hz, Ar—H), 8.18 (t, 2H, J = 3.2 Hz, Ar—H).

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) top

	x	y	z	U_iso*/U_eq
Cl1	1.12832 (17)	−0.15369 (6)	0.14547 (7)	0.0618 (2)
S1	−0.00971 (13)	0.31098 (5)	0.38523 (5)	0.03988 (17)
O1	0.1096 (5)	0.34309 (18)	0.47468 (16)	0.0601 (6)
O2	−0.2260 (4)	0.23281 (16)	0.40650 (15)	0.0511 (5)
O3	−0.0663 (5)	0.30935 (17)	0.04835 (15)	0.0604 (6)
H3O	0.0372	0.2596	0.0257	0.073*
O4	0.3079 (4)	0.15059 (17)	0.05644 (14)	0.0553 (5)
N1	0.2456 (4)	0.26558 (18)	0.30655 (17)	0.0441 (5)
H1N	0.4144	0.2519	0.3277	0.053*
C1	−0.1507 (5)	0.4240 (2)	0.3008 (2)	0.0415 (5)
C2	−0.2846 (7)	0.5148 (2)	0.3434 (3)	0.0563 (7)
H2	−0.2815	0.5204	0.4162	0.068*
C3	−0.4223 (8)	0.5961 (3)	0.2754 (3)	0.0715 (10)
H3	−0.5125	0.6575	0.3025	0.086*
C4	−0.4271 (9)	0.5873 (3)	0.1678 (3)	0.0748 (10)
H4	−0.5241	0.6421	0.1233	0.090*
C5	−0.2904 (7)	0.4985 (3)	0.1253 (3)	0.0623 (8)
H5	−0.2926	0.4943	0.0522	0.075*
C6	−0.1488 (5)	0.4148 (2)	0.1915 (2)	0.0425 (5)
C7	−0.0006 (5)	0.3206 (2)	0.1462 (2)	0.0415 (5)
C8	0.1900 (5)	0.2482 (2)	0.20148 (19)	0.0386 (5)
C9	0.3263 (5)	0.1547 (2)	0.1542 (2)	0.0407 (5)
C10	0.4876 (5)	0.0619 (2)	0.21729 (19)	0.0394 (5)
C11	0.7101 (5)	0.0062 (2)	0.1617 (2)	0.0413 (5)
H11	0.7634	0.0309	0.0895	0.050*
C12	0.8495 (5)	−0.0854 (2)	0.2149 (2)	0.0435 (6)
C13	0.7712 (7)	−0.1251 (2)	0.3214 (2)	0.0553 (7)
H13	0.8680	−0.1870	0.3562	0.066*
C14	0.5477 (7)	−0.0714 (2)	0.3752 (2)	0.0589 (8)
H14	0.4910	−0.0984	0.4465	0.071*
C15	0.4057 (6)	0.0222 (2)	0.3248 (2)	0.0494 (6)
H15	0.2568	0.0583	0.3623	0.059*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0599 (4)	0.0588 (4)	0.0699 (5)	0.0225 (3)	−0.0186 (4)	−0.0246 (4)
S1	0.0367 (3)	0.0471 (3)	0.0379 (3)	0.0050 (2)	−0.0090 (2)	−0.0131 (2)
O1	0.0647 (13)	0.0721 (14)	0.0503 (11)	0.0158 (10)	−0.0234 (10)	−0.0297 (10)
O2	0.0417 (10)	0.0556 (11)	0.0526 (11)	−0.0028 (8)	−0.0053 (8)	0.0035 (9)
O3	0.0839 (15)	0.0576 (13)	0.0399 (10)	0.0222 (11)	−0.0180 (10)	−0.0126 (9)
O4	0.0659 (13)	0.0607 (12)	0.0395 (10)	0.0191 (10)	−0.0104 (9)	−0.0160 (8)
N1	0.0318 (10)	0.0567 (13)	0.0484 (12)	0.0085 (9)	−0.0125 (9)	−0.0226 (10)
C1	0.0394 (13)	0.0387 (12)	0.0480 (14)	0.0002 (10)	−0.0061 (10)	−0.0116 (10)
C2	0.0612 (18)	0.0490 (16)	0.0619 (17)	0.0089 (13)	−0.0079 (14)	−0.0232 (13)
C3	0.084 (2)	0.0411 (16)	0.089 (3)	0.0195 (15)	−0.0117 (19)	−0.0194 (15)
C4	0.095 (3)	0.0494 (18)	0.075 (2)	0.0278 (17)	−0.0176 (19)	−0.0025 (15)
C5	0.078 (2)	0.0501 (17)	0.0551 (17)	0.0170 (15)	−0.0116 (15)	−0.0028 (13)
C6	0.0442 (13)	0.0365 (12)	0.0466 (14)	0.0033 (10)	−0.0058 (11)	−0.0067 (10)
C7	0.0455 (13)	0.0409 (13)	0.0389 (12)	0.0028 (10)	−0.0068 (10)	−0.0092 (10)
C8	0.0358 (12)	0.0424 (13)	0.0390 (12)	0.0015 (10)	−0.0045 (9)	−0.0118 (10)
C9	0.0389 (12)	0.0435 (13)	0.0409 (13)	0.0001 (10)	−0.0036 (10)	−0.0109 (10)
C10	0.0428 (13)	0.0381 (12)	0.0385 (12)	−0.0001 (10)	−0.0051 (10)	−0.0094 (9)
C11	0.0445 (13)	0.0420 (13)	0.0387 (12)	0.0008 (10)	−0.0066 (10)	−0.0099 (10)
C12	0.0437 (13)	0.0426 (13)	0.0476 (14)	0.0028 (10)	−0.0130 (11)	−0.0140 (11)
C13	0.073 (2)	0.0411 (14)	0.0527 (16)	0.0030 (13)	−0.0202 (14)	−0.0049 (12)
C14	0.082 (2)	0.0514 (16)	0.0420 (15)	−0.0081 (15)	−0.0055 (14)	−0.0009 (12)
C15	0.0567 (16)	0.0492 (15)	0.0428 (14)	−0.0057 (12)	0.0035 (12)	−0.0122 (11)

Geometric parameters (Å, º) top

Cl1—C12	1.739 (3)	C4—H4	0.9300
S1—O1	1.4240 (18)	C5—C6	1.394 (4)
S1—O2	1.434 (2)	C5—H5	0.9300
S1—N1	1.604 (2)	C6—C7	1.467 (3)
S1—C1	1.747 (3)	C7—C8	1.377 (3)
O3—C7	1.327 (3)	C8—C9	1.451 (3)
O3—H3O	0.8200	C9—C10	1.491 (3)
O4—C9	1.250 (3)	C10—C15	1.395 (4)
N1—C8	1.422 (3)	C10—C11	1.396 (3)
N1—H1N	0.8600	C11—C12	1.376 (3)
C1—C2	1.391 (4)	C11—H11	0.9300
C1—C6	1.396 (3)	C12—C13	1.380 (4)
C2—C3	1.380 (4)	C13—C14	1.376 (4)
C2—H2	0.9300	C13—H13	0.9300
C3—C4	1.377 (5)	C14—C15	1.385 (4)
C3—H3	0.9300	C14—H14	0.9300
C4—C5	1.376 (4)	C15—H15	0.9300

O1—S1—O2	118.25 (13)	O3—C7—C8	122.4 (2)
O1—S1—N1	108.39 (12)	O3—C7—C6	115.1 (2)
O2—S1—N1	109.12 (12)	C8—C7—C6	122.6 (2)
O1—S1—C1	112.18 (12)	C7—C8—N1	118.7 (2)
O2—S1—C1	106.33 (11)	C7—C8—C9	120.5 (2)
N1—S1—C1	101.20 (12)	N1—C8—C9	120.8 (2)
C7—O3—H3O	109.5	O4—C9—C8	119.2 (2)
C8—N1—S1	119.34 (16)	O4—C9—C10	117.9 (2)
C8—N1—H1N	120.3	C8—C9—C10	122.9 (2)
S1—N1—H1N	120.3	C15—C10—C11	119.6 (2)
C2—C1—C6	121.6 (2)	C15—C10—C9	122.6 (2)
C2—C1—S1	120.7 (2)	C11—C10—C9	117.4 (2)
C6—C1—S1	117.43 (18)	C12—C11—C10	119.3 (2)
C3—C2—C1	118.6 (3)	C12—C11—H11	120.4
C3—C2—H2	120.7	C10—C11—H11	120.4
C1—C2—H2	120.7	C11—C12—C13	121.6 (2)
C4—C3—C2	120.6 (3)	C11—C12—Cl1	119.0 (2)
C4—C3—H3	119.7	C13—C12—Cl1	119.3 (2)
C2—C3—H3	119.7	C14—C13—C12	118.9 (3)
C5—C4—C3	120.9 (3)	C14—C13—H13	120.5
C5—C4—H4	119.6	C12—C13—H13	120.5
C3—C4—H4	119.6	C13—C14—C15	121.0 (3)
C4—C5—C6	120.2 (3)	C13—C14—H14	119.5
C4—C5—H5	119.9	C15—C14—H14	119.5
C6—C5—H5	119.9	C14—C15—C10	119.6 (3)
C5—C6—C1	118.2 (2)	C14—C15—H15	120.2
C5—C6—C7	120.3 (2)	C10—C15—H15	120.2
C1—C6—C7	121.5 (2)

O1—S1—N1—C8	−167.9 (2)	O3—C7—C8—N1	−179.3 (2)
O2—S1—N1—C8	62.0 (2)	C6—C7—C8—N1	−0.1 (4)
C1—S1—N1—C8	−49.8 (2)	O3—C7—C8—C9	−0.6 (4)
O1—S1—C1—C2	−35.9 (3)	C6—C7—C8—C9	178.6 (2)
O2—S1—C1—C2	94.9 (2)	S1—N1—C8—C7	36.5 (3)
N1—S1—C1—C2	−151.2 (2)	S1—N1—C8—C9	−142.2 (2)
O1—S1—C1—C6	150.4 (2)	C7—C8—C9—O4	12.1 (4)
O2—S1—C1—C6	−78.9 (2)	N1—C8—C9—O4	−169.2 (2)
N1—S1—C1—C6	35.0 (2)	C7—C8—C9—C10	−167.5 (2)
C6—C1—C2—C3	1.1 (5)	N1—C8—C9—C10	11.2 (4)
S1—C1—C2—C3	−172.4 (3)	O4—C9—C10—C15	−143.7 (3)
C1—C2—C3—C4	0.2 (5)	C8—C9—C10—C15	35.9 (4)
C2—C3—C4—C5	−1.3 (6)	O4—C9—C10—C11	29.3 (3)
C3—C4—C5—C6	1.2 (6)	C8—C9—C10—C11	−151.1 (2)
C4—C5—C6—C1	0.1 (5)	C15—C10—C11—C12	−1.6 (4)
C4—C5—C6—C7	−179.4 (3)	C9—C10—C11—C12	−174.8 (2)
C2—C1—C6—C5	−1.2 (4)	C10—C11—C12—C13	1.3 (4)
S1—C1—C6—C5	172.5 (2)	C10—C11—C12—Cl1	−179.47 (18)
C2—C1—C6—C7	178.3 (3)	C11—C12—C13—C14	0.2 (4)
S1—C1—C6—C7	−8.0 (3)	Cl1—C12—C13—C14	−179.1 (2)
C5—C6—C7—O3	−14.6 (4)	C12—C13—C14—C15	−1.3 (5)
C1—C6—C7—O3	165.9 (2)	C13—C14—C15—C10	0.9 (4)
C5—C6—C7—C8	166.2 (3)	C11—C10—C15—C14	0.5 (4)
C1—C6—C7—C8	−13.3 (4)	C9—C10—C15—C14	173.4 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O2ⁱ	0.86	2.03	2.872 (3)	168
O3—H3O···O4	0.82	1.80	2.525 (3)	146
C2—H2···O1ⁱⁱ	0.93	2.54	3.279 (3)	136
C14—H14···O2ⁱⁱⁱ	0.93	2.58	3.435 (3)	153
C15—H15···N1	0.93	2.54	3.009 (4)	112

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

Experimental details

Crystal data
Chemical formula	C₁₅H₁₀ClNO₄S
M_r	335.75
Crystal system, space group	Triclinic, P1
Temperature (K)	295
a, b, c (Å)	4.7151 (3), 12.2879 (8), 12.5809 (6)
α, β, γ (°)	81.375 (3), 84.463 (3), 85.608 (3)
V (Å³)	715.88 (7)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.43
Crystal size (mm)	0.14 × 0.12 × 0.10

Data collection
Diffractometer	Nonius KappaCCD diffractometer
Absorption correction	Multi-scan (SORTAV; Blessing, 1997)
T_min, T_max	0.942, 0.958
No. of measured, independent and observed [I > 2σ(I)] reflections	4352, 3202, 2783
R_int	0.027
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.051, 0.121, 1.09
No. of reflections	3202
No. of parameters	200
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.45, −0.36

Computer programs: COLLECT (Hooft, 1998), DENZO (Otwinowski & Minor, 1997), SCALEPACK (Otwinowski & Minor, 1997), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997).