3-Benzoyl-4-hydr­oxy-2-methyl-2H-1,2-benzothia­zine 1,1-dioxide

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

doi:10.1107/S1600536810011025

3-Benzoyl-4-hydroxy-2-methyl-2H-1,2-benzothiazine 1,1-dioxide

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

In the title molecule, C₁₆H₁₃NO₄S, the heterocyclic thiazine ring adopts a half-chair conformation with the S and N atoms displaced by 0.410 (3) and 0.299 (3) Å, respectively, on opposite sides of the mean plane formed by the remaining ring atoms. The crystal structure is stabilized by intermolecular hydrogen bonds of the types O—H

O and C—H

O; the former result in dimers lying about inversion centers and the latter form chains of molecules running along the c axis. In addition, intramolecular O—H

O links are present.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536810011025/jh2140sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536810011025/jh2140Isup2.hkl Contains datablock I

CCDC reference: 774376

checkCIF report

Key indicators

Single-crystal X-ray study
T = 173 K
Mean (C-C) = 0.002 Å
R factor = 0.041
wR factor = 0.113
Data-to-parameter ratio = 20.3

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT919_ALERT_3_B Reflection(s) # Likely Affected by the Beamstop           1

Alert level C
PLAT910_ALERT_3_C Missing # of FCF Reflections Below Th(Min) .....          1
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.600         32
PLAT913_ALERT_3_C Missing # of Very Strong Reflections in FCF ....          6
PLAT912_ALERT_4_C Missing # of FCF Reflections Above STh/L=  0.600         54
PLAT927_ALERT_1_C Reported and Calculated  wR2 * 100.0 Differ by .       0.15

Alert level G
PLAT154_ALERT_1_G The su's on the Cell Angles are Equal  (x 10000)        200 Deg.

   0 ALERT level A = In general: serious problem
   1 ALERT level B = Potentially serious problem
   5 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
   4 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

Oxicam, a class of non steroidal anti-inflammatory drugs (NSAIDs) consists of benzothiazine derivatives which are found to be potent anti-inflammatory and analgesic agents, e.g., piroxicam (Lombardino et al., 1971), droxicam (Soler, 1985), ampiroxicam (Carty et al., 1993), meloxicam (Turck et al., 1995), etc. In continuation of our research on potential biologically active benzothiazine compounds (Siddiqui et al., 2007; Ahmad, Siddiqui, Zia-ur-Rehman et al., 2010), we report the synthesis and crystal structure of the title compound in this article.

In the title compound (Fig. 1), the bond distances and angles agree with the cortresponding bond distances and angles reported in closely related compounds (Siddiqui et al., 2008; Ahmad, Siddiqui, Rizvi et al., 2010). The heterocyclic thiazine ring adopts half chair conformation with atoms S1 and N1 displaced by 0.410 (3) and 0.299 (3) Å on the opposite sides from the mean planes formed by the remaining ring atoms.

The structure is stabilized by intermolecular hydrogen bonds of the types O—H···O and C—H···O; the former result in dimers lying about inversion centers and the later form chains of molecules running along the c-axis (Tab. 1 and Fig. 2). In addition, intramolecular interactions of the types O—H···O and C—H···N are also present consolidating the crystal packing.

Related literature top

For 1,2-benzothiazine derivatives as anti-inflammatory drugs (NSAIDs), see: Lombardino et al. (1971); Soler (1985); Carty et al. (1993); Turck et al. (1995). For the synthesis of benzothiazine derivatives, see: Siddiqui et al. (2007); Ahmad, Siddiqui, Zia-ur-Rehman et al. (2010). For related structures, see: Siddiqui et al. (2008); Ahmad, Siddiqui, Rizvi et al. (2010).

Experimental top

An aqueous sodium hydroxide solution (1.33 g in 10 ml water) was slowly added to a solution of 3-benzoyl-4-hydroxy-2H-1,2-benzothiazine 1,1-dioxide (5.0 g, 16.6 mmole) in acetone (50 ml). Dimethylsulfate (4.03 g, 32 mmole) was added drop wise and the mixture was stirred for 30 minutes. The contents of the flask were acidified to pH 3.0 by the addition of 5% HCl. White precipitates of the title compound were formed which were collected and washed with excess distilled water. Crystals suitable for crystallographic study were grown from a solution of chloroform/methanol (4:1); yield = 3.5 g, 70%; m.p. = 420-421 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 plotted with the displacement ellipsoids at 50% probability level (Farrugia, 1997).
	Fig. 2. A part of the unit cell showing intermolecular and intrmolecular hydrogen bonds by dashed lines; the H-atoms not involved in H-bonds have been excluded for clarity.

3-Benzoyl-4-hydroxy-2-methyl-2H-1,2-benzothiazine 1,1-dioxide top

Crystal data top

C₁₆H₁₃NO₄S	Z = 2
M_r = 315.33	F(000) = 328
Triclinic, P1	D_x = 1.480 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.8342 (3) Å	Cell parameters from 3532 reflections
b = 9.9085 (3) Å	θ = 1.0–30.0°
c = 10.7234 (4) Å	µ = 0.25 mm⁻¹
α = 83.257 (2)°	T = 173 K
β = 79.481 (2)°	Block, pale-yellow
γ = 85.113 (2)°	0.12 × 0.10 × 0.08 mm
V = 707.50 (5) Å³

Data collection top

Nonius KappaCCD diffractometer	4080 independent reflections
Radiation source: fine-focus sealed tube	3665 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.022
ω and ϕ scans	θ_max = 30.1°, θ_min = 2.1°
Absorption correction: multi-scan (SORTAV; Blessing, 1997)	h = −9→9
T_min = 0.971, T_max = 0.981	k = −13→13
7177 measured reflections	l = −15→15

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)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.113	H-atom parameters constrained
S = 1.09	w = 1/[σ²(F_o²) + (0.0468P)² + 0.3608P] where P = (F_o² + 2F_c²)/3
4080 reflections	(Δ/σ)_max < 0.001
201 parameters	Δρ_max = 0.42 e Å⁻³
0 restraints	Δρ_min = −0.34 e Å⁻³

Crystal data top

C₁₆H₁₃NO₄S	γ = 85.113 (2)°
M_r = 315.33	V = 707.50 (5) Å³
Triclinic, P1	Z = 2
a = 6.8342 (3) Å	Mo Kα radiation
b = 9.9085 (3) Å	µ = 0.25 mm⁻¹
c = 10.7234 (4) Å	T = 173 K
α = 83.257 (2)°	0.12 × 0.10 × 0.08 mm
β = 79.481 (2)°

Data collection top

Nonius KappaCCD diffractometer	4080 independent reflections
Absorption correction: multi-scan (SORTAV; Blessing, 1997)	3665 reflections with I > 2σ(I)
T_min = 0.971, T_max = 0.981	R_int = 0.022
7177 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.041	0 restraints
wR(F²) = 0.113	H-atom parameters constrained
S = 1.09	Δρ_max = 0.42 e Å⁻³
4080 reflections	Δρ_min = −0.34 e Å⁻³
201 parameters

Special details top

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
S1	0.20282 (5)	0.24470 (3)	0.28051 (3)	0.02305 (10)
O1	−0.00548 (16)	0.28521 (10)	0.28975 (11)	0.0279 (2)
O2	0.29460 (19)	0.15793 (11)	0.18540 (11)	0.0339 (3)
O3	0.23671 (18)	0.47875 (11)	0.58638 (10)	0.0290 (2)
H3O	0.2333	0.5621	0.5604	0.044*
O4	0.24683 (18)	0.68733 (10)	0.42430 (10)	0.0303 (2)
N1	0.32262 (17)	0.38365 (11)	0.25903 (11)	0.0218 (2)
C1	0.2435 (2)	0.17087 (13)	0.43178 (14)	0.0230 (3)
C2	0.2400 (2)	0.03080 (14)	0.46264 (16)	0.0284 (3)
H2	0.2244	−0.0268	0.4008	0.034*
C3	0.2596 (2)	−0.02341 (15)	0.58521 (17)	0.0321 (3)
H3	0.2570	−0.1189	0.6078	0.039*
C4	0.2832 (2)	0.06112 (16)	0.67508 (16)	0.0325 (3)
H4	0.2965	0.0229	0.7588	0.039*
C5	0.2875 (2)	0.20118 (15)	0.64393 (14)	0.0279 (3)
H5	0.3035	0.2582	0.7062	0.033*
C6	0.2683 (2)	0.25797 (13)	0.52084 (13)	0.0228 (3)
C7	0.2650 (2)	0.40639 (13)	0.48734 (13)	0.0218 (2)
C8	0.2777 (2)	0.46608 (13)	0.36361 (13)	0.0205 (2)
C9	0.2466 (2)	0.61275 (13)	0.33796 (13)	0.0222 (2)
C10	0.5305 (2)	0.38032 (17)	0.19048 (16)	0.0336 (3)
H10A	0.5688	0.4736	0.1624	0.040*
H10B	0.5419	0.3296	0.1161	0.040*
H10C	0.6189	0.3356	0.2474	0.040*
C11	0.2056 (2)	0.67762 (13)	0.21160 (13)	0.0227 (3)
C12	0.0803 (2)	0.61998 (14)	0.14609 (14)	0.0254 (3)
H12	0.0330	0.5325	0.1758	0.030*
C13	0.0252 (2)	0.69159 (15)	0.03694 (14)	0.0283 (3)
H13	−0.0619	0.6535	−0.0071	0.034*
C14	0.0968 (3)	0.81858 (15)	−0.00811 (15)	0.0304 (3)
H14	0.0587	0.8668	−0.0828	0.036*
C15	0.2239 (3)	0.87500 (15)	0.05592 (15)	0.0309 (3)
H15	0.2752	0.9609	0.0240	0.037*
C16	0.2759 (2)	0.80577 (14)	0.16662 (14)	0.0270 (3)
H16	0.3595	0.8456	0.2119	0.032*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.02533 (17)	0.02010 (16)	0.02556 (17)	−0.00128 (11)	−0.00723 (12)	−0.00570 (11)
O1	0.0246 (5)	0.0277 (5)	0.0338 (6)	−0.0033 (4)	−0.0113 (4)	−0.0022 (4)
O2	0.0448 (7)	0.0258 (5)	0.0331 (6)	0.0001 (4)	−0.0074 (5)	−0.0127 (4)
O3	0.0404 (6)	0.0251 (5)	0.0231 (5)	0.0006 (4)	−0.0084 (4)	−0.0063 (4)
O4	0.0444 (6)	0.0224 (5)	0.0263 (5)	−0.0038 (4)	−0.0088 (4)	−0.0065 (4)
N1	0.0218 (5)	0.0210 (5)	0.0224 (5)	−0.0014 (4)	−0.0020 (4)	−0.0053 (4)
C1	0.0189 (6)	0.0221 (6)	0.0281 (7)	−0.0007 (4)	−0.0050 (5)	−0.0017 (5)
C2	0.0218 (6)	0.0220 (6)	0.0412 (8)	−0.0019 (5)	−0.0061 (6)	−0.0017 (5)
C3	0.0234 (7)	0.0245 (6)	0.0460 (9)	−0.0031 (5)	−0.0055 (6)	0.0068 (6)
C4	0.0278 (7)	0.0326 (7)	0.0337 (8)	−0.0019 (6)	−0.0045 (6)	0.0093 (6)
C5	0.0261 (7)	0.0311 (7)	0.0256 (7)	−0.0004 (5)	−0.0053 (5)	0.0012 (5)
C6	0.0194 (6)	0.0230 (6)	0.0254 (6)	−0.0004 (4)	−0.0040 (5)	−0.0010 (5)
C7	0.0212 (6)	0.0226 (6)	0.0226 (6)	−0.0010 (4)	−0.0054 (5)	−0.0038 (5)
C8	0.0209 (6)	0.0202 (5)	0.0211 (6)	−0.0011 (4)	−0.0041 (4)	−0.0042 (4)
C9	0.0227 (6)	0.0211 (6)	0.0234 (6)	−0.0033 (4)	−0.0039 (5)	−0.0032 (4)
C10	0.0259 (7)	0.0364 (8)	0.0373 (8)	−0.0034 (6)	0.0036 (6)	−0.0123 (6)
C11	0.0255 (6)	0.0200 (6)	0.0222 (6)	0.0002 (5)	−0.0033 (5)	−0.0033 (4)
C12	0.0278 (7)	0.0232 (6)	0.0258 (6)	−0.0021 (5)	−0.0054 (5)	−0.0036 (5)
C13	0.0319 (7)	0.0287 (7)	0.0261 (7)	−0.0005 (5)	−0.0093 (6)	−0.0046 (5)
C14	0.0391 (8)	0.0266 (7)	0.0249 (7)	0.0036 (6)	−0.0077 (6)	−0.0012 (5)
C15	0.0404 (8)	0.0216 (6)	0.0301 (7)	−0.0031 (5)	−0.0058 (6)	0.0005 (5)
C16	0.0312 (7)	0.0217 (6)	0.0294 (7)	−0.0034 (5)	−0.0070 (6)	−0.0036 (5)

Geometric parameters (Å, º) top

S1—O2	1.4329 (11)	C6—C7	1.4716 (18)
S1—O1	1.4346 (11)	C7—C8	1.3784 (19)
S1—N1	1.6333 (12)	C8—C9	1.4518 (18)
S1—C1	1.7593 (14)	C9—C11	1.4936 (19)
O3—C7	1.3265 (16)	C10—H10A	0.9800
O3—H3O	0.8400	C10—H10B	0.9800
O4—C9	1.2509 (16)	C10—H10C	0.9800
N1—C8	1.4373 (16)	C11—C12	1.3966 (19)
N1—C10	1.4753 (18)	C11—C16	1.3969 (19)
C1—C2	1.3896 (19)	C12—C13	1.391 (2)
C1—C6	1.4011 (19)	C12—H12	0.9500
C2—C3	1.386 (2)	C13—C14	1.390 (2)
C2—H2	0.9500	C13—H13	0.9500
C3—C4	1.388 (2)	C14—C15	1.389 (2)
C3—H3	0.9500	C14—H14	0.9500
C4—C5	1.390 (2)	C15—C16	1.388 (2)
C4—H4	0.9500	C15—H15	0.9500
C5—C6	1.3974 (19)	C16—H16	0.9500
C5—H5	0.9500

O2—S1—O1	118.95 (7)	C7—C8—N1	120.26 (11)
O2—S1—N1	108.49 (7)	C7—C8—C9	120.23 (12)
O1—S1—N1	107.25 (6)	N1—C8—C9	119.51 (12)
O2—S1—C1	109.77 (7)	O4—C9—C8	119.85 (12)
O1—S1—C1	107.98 (6)	O4—C9—C11	118.55 (12)
N1—S1—C1	103.26 (6)	C8—C9—C11	121.55 (12)
C7—O3—H3O	109.5	N1—C10—H10A	109.5
C8—N1—C10	116.02 (11)	N1—C10—H10B	109.5
C8—N1—S1	114.56 (9)	H10A—C10—H10B	109.5
C10—N1—S1	118.88 (9)	N1—C10—H10C	109.5
C2—C1—C6	121.72 (13)	H10A—C10—H10C	109.5
C2—C1—S1	120.23 (11)	H10B—C10—H10C	109.5
C6—C1—S1	117.96 (10)	C12—C11—C16	119.90 (13)
C3—C2—C1	118.87 (14)	C12—C11—C9	121.08 (12)
C3—C2—H2	120.6	C16—C11—C9	118.60 (12)
C1—C2—H2	120.6	C13—C12—C11	119.51 (13)
C2—C3—C4	120.34 (14)	C13—C12—H12	120.2
C2—C3—H3	119.8	C11—C12—H12	120.2
C4—C3—H3	119.8	C14—C13—C12	120.42 (14)
C3—C4—C5	120.73 (15)	C14—C13—H13	119.8
C3—C4—H4	119.6	C12—C13—H13	119.8
C5—C4—H4	119.6	C15—C14—C13	120.07 (14)
C4—C5—C6	119.87 (15)	C15—C14—H14	120.0
C4—C5—H5	120.1	C13—C14—H14	120.0
C6—C5—H5	120.1	C16—C15—C14	119.93 (14)
C5—C6—C1	118.46 (13)	C16—C15—H15	120.0
C5—C6—C7	120.69 (13)	C14—C15—H15	120.0
C1—C6—C7	120.79 (12)	C15—C16—C11	120.14 (14)
O3—C7—C8	122.43 (12)	C15—C16—H16	119.9
O3—C7—C6	114.62 (12)	C11—C16—H16	119.9
C8—C7—C6	122.84 (12)

O2—S1—N1—C8	−166.36 (9)	C1—C6—C7—C8	−13.2 (2)
O1—S1—N1—C8	63.98 (11)	O3—C7—C8—N1	175.55 (12)
C1—S1—N1—C8	−49.92 (11)	C6—C7—C8—N1	−8.6 (2)
O2—S1—N1—C10	−22.94 (13)	O3—C7—C8—C9	−4.2 (2)
O1—S1—N1—C10	−152.60 (11)	C6—C7—C8—C9	171.61 (12)
C1—S1—N1—C10	93.50 (12)	C10—N1—C8—C7	−100.95 (16)
O2—S1—C1—C2	−37.60 (14)	S1—N1—C8—C7	43.55 (16)
O1—S1—C1—C2	93.50 (12)	C10—N1—C8—C9	78.84 (16)
N1—S1—C1—C2	−153.13 (11)	S1—N1—C8—C9	−136.66 (11)
O2—S1—C1—C6	145.77 (11)	C7—C8—C9—O4	13.9 (2)
O1—S1—C1—C6	−83.13 (12)	N1—C8—C9—O4	−165.87 (13)
N1—S1—C1—C6	30.25 (12)	C7—C8—C9—C11	−163.55 (13)
C6—C1—C2—C3	0.6 (2)	N1—C8—C9—C11	16.66 (19)
S1—C1—C2—C3	−175.86 (11)	O4—C9—C11—C12	−137.23 (14)
C1—C2—C3—C4	−0.3 (2)	C8—C9—C11—C12	40.27 (19)
C2—C3—C4—C5	0.0 (2)	O4—C9—C11—C16	35.29 (19)
C3—C4—C5—C6	−0.1 (2)	C8—C9—C11—C16	−147.21 (14)
C4—C5—C6—C1	0.4 (2)	C16—C11—C12—C13	−0.6 (2)
C4—C5—C6—C7	177.71 (13)	C9—C11—C12—C13	171.87 (13)
C2—C1—C6—C5	−0.7 (2)	C11—C12—C13—C14	1.1 (2)
S1—C1—C6—C5	175.85 (10)	C12—C13—C14—C15	−0.1 (2)
C2—C1—C6—C7	−178.00 (13)	C13—C14—C15—C16	−1.4 (2)
S1—C1—C6—C7	−1.42 (18)	C14—C15—C16—C11	2.0 (2)
C5—C6—C7—O3	−14.30 (19)	C12—C11—C16—C15	−1.0 (2)
C1—C6—C7—O3	162.91 (13)	C9—C11—C16—C15	−173.59 (13)
C5—C6—C7—C8	169.55 (13)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3O···O4	0.84	1.80	2.5365 (15)	146
O3—H3O···O1ⁱ	0.84	2.56	3.0108 (15)	115
C3—H3···O1ⁱⁱ	0.95	2.50	3.2627 (18)	138
C12—H12···N1	0.95	2.59	3.0163 (18)	107

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

Experimental details

Crystal data
Chemical formula	C₁₆H₁₃NO₄S
M_r	315.33
Crystal system, space group	Triclinic, P1
Temperature (K)	173
a, b, c (Å)	6.8342 (3), 9.9085 (3), 10.7234 (4)
α, β, γ (°)	83.257 (2), 79.481 (2), 85.113 (2)
V (Å³)	707.50 (5)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.25
Crystal size (mm)	0.12 × 0.10 × 0.08

Data collection
Diffractometer	Nonius KappaCCD diffractometer
Absorption correction	Multi-scan (SORTAV; Blessing, 1997)
T_min, T_max	0.971, 0.981
No. of measured, independent and observed [I > 2σ(I)] reflections	7177, 4080, 3665
R_int	0.022
(sin θ/λ)_max (Å⁻¹)	0.706

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.041, 0.113, 1.09
No. of reflections	4080
No. of parameters	201
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.42, −0.34

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).