Methyl 4-hy­droxy-2-isopropyl-1,1-dioxo-2H-1,2-benzothia­zine-3-carboxyl­ate

Abstract

In the crystal structure of the title mol­ecule, C₁₃H₁₅NO₅S, the S and N atoms of the thia­zine ring exihibit the maximum deviations from the least-squares plane of 0.3008 (6) and 0.3280 (7) Å, respectively. The ring therefore adopts a half chair conformation. The thia­zine ring is twisted by an angle of 13.29 (7)° with respect to the aromatic ring. The isopropyl substituent is oriented at a dihedral angle of 53.2 (12)° with respect to the thia­zine ring. An intra­molecular O—H⋯O hydrogen bond occurs. Inter­molecular hydrogen bonding is observed in the crystal structure.

Related literature

For the synthetic procedure, see: Arshad et al. (2011 ▶). For the biological activity of related compounds, see: Lombardino et al. (1971 ▶); Vidal et al. (2006 ▶); Turck et al. (1996) ▶; Zia-ur-Rehman et al. (2006 ▶). For related structures, see: Arshad et al. (2008 ▶, 2009 ▶). For graph-set analysis, see Bernstein et al. (1995 ▶).

Experimental

Crystal data

• C₁₃H₁₅NO₅S

• M _r = 297.32

• Monoclinic,

• a = 11.3896 (6) Å

• b = 9.8421 (5) Å

• c = 12.7680 (7) Å

• β = 105.782 (1)°

• V = 1377.31 (13) ų

• Z = 4

• Mo Kα radiation

• μ = 0.25 mm⁻¹

• T = 100 K

• 0.43 × 0.27 × 0.27 mm

Data collection

• Siemens SMART 1K diffractometer with a Bruker APEXII detector

• Absorption correction: multi-scan (SADABS; Bruker 2001 ▶) T _min = 0.899, T _max = 0.949

• 16137 measured reflections

• 3380 independent reflections

• 2967 reflections with I > 2σ(I)

• R _int = 0.024

Refinement

• R[F ² > 2σ(F ²)] = 0.034

• wR(F ²) = 0.092

• S = 1.06

• 3380 reflections

• 187 parameters

• H atoms treated by a mixture of independent and constrained refinement

• Δρ_max = 0.43 e Å⁻³

• Δρ_min = −0.40 e Å⁻³

Data collection: APEX2 (Bruker, 2001 ▶); cell refinement: SAINT (Bruker, 2001 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶) and PLATON (Spek, 2009 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶) and PLATON.

Supplementary Material

Supplementary material file. DOI: 10.1107/S1600536811024573/im2299Isup3.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C4—H4⋯O2i	0.93	2.49	3.311 (2)	147
C3—H3⋯O2ii	0.93	2.46	3.370 (2)	165
C11—H11⋯O1iii	0.98	2.39	3.317 (2)	157
O3—H3O⋯O4	0.88 (2)	1.77 (2)	2.578 (2)	151 (2)

Symmetry codes: (i) ; (ii) ; (iii) .

supplementary crystallographic information

Comment

Benzothiazine 1,1-dioxide derivatives are the constituents of various drugs including Piroxicam and Meloxicam which are being used as non-steroidal anti-inflammatory drugs (NSAIDs) (Lombardino et al., 1971; Turck et al., 1996). Besides other biological activities (Zia-ur-Rehman et al., 2006) these type of molecules have found their applications as intermediates (Vidal et al., 2006). Our research group already reported the synthesis, biological activities (Arshad et al., 2011) and crystal structures (Arshad et al., 2008; 2009) of benzothiazine derivatives, II and III.

The title compound, I, is varied in structure with respect to III only concerning the alkyl group attached to the nitrogen atom of the thiazine ring. The characteristic intramolecular O—H···O hydrogen bond is observed in the structure of I as for II and III forming a six membered S¹₁(6) ring (C7/C8/C9/O4 H3O/O3) system (Bernstein, et al., 1995). The observed ring is inclined at dihedral angles of 18.9 (4)° and 16.1 (4)° with respect to the thiazine (C1/C6/C7/C8/N1/S1) and aromatic (C1/C2/C3/C4/C5/C6) rings. The isopropyl group is oriented at a dihedral angle of 53.2 (1)° relative to the thiazine ring. The dihedral angle between the thiazine and aromatic ring is 13.29 (7)°. Alongwith the O—H···O type hydrogen bonding interaction the molecule is connected to it's neighboring symmetry equivalents by additional weak C—H···O type interactions producing a three dimensional network (Fig. 2. Tab. 1).

Experimental

The synthesis of the titled compound has already been published (Arshad et al., 2011). Recrystallization from methanol under slow evaporation of the solvent leads to the formation of crystals suitable for structural analysis.

Refinement

Carbon bound H atoms were positioned geometrically with C—H = 0.93 Å and 0.98Å for aromatic and C11 carbon atoms, respectively, and were refined using a riding model with U_iso(H) = 1.2 U_eq(C). Similarly, H atoms of methyl groups were positioned geometrically with C—H = 0.96 Å and were refined using a riding model with U_iso(H) = 1.5 U_eq(C). The H atom of the hydroxyl group was located from the difference map with O–H= 0.88 (2)Å and was refined with U_iso(H) = 1.5 U_eq(O).

Figures

Fig. 1.

Ortep diagram for (I), thermal ellipsoids are drawn at the 50% probability level.

Fig. 2.

Unit cell packing for (I) showing hydrogen bonds as dashed lines. Hydrogen atoms not involved in hydrogen bonding interactions have been omitted.

Crystal data

C13H15NO5S	F(000) = 624
Mr = 297.32	Dx = 1.434 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 7059 reflections
a = 11.3896 (6) Å	θ = 2.7–28.4°
b = 9.8421 (5) Å	µ = 0.25 mm−1
c = 12.7680 (7) Å	T = 100 K
β = 105.782 (1)°	Needle, colorless
V = 1377.31 (13) Å3	0.43 × 0.27 × 0.27 mm
Z = 4

Data collection

Siemens SMART 1K diffractometer with a Bruker APEXII detector	3380 independent reflections
Radiation source: fine-focus sealed tube	2967 reflections with I > 2σ(I)
graphite	Rint = 0.024
φ and ω scans	θmax = 28.4°, θmin = 2.1°
Absorption correction: multi-scan (SADABS; Bruker 2001)	h = −15→15
Tmin = 0.899, Tmax = 0.949	k = −13→12
16137 measured reflections	l = −16→16

Refinement

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) = 0.092	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ2(Fo2) + (0.0464P)2 + 0.6953P] where P = (Fo2 + 2Fc2)/3
3380 reflections	(Δ/σ)max < 0.001
187 parameters	Δρmax = 0.43 e Å−3
0 restraints	Δρmin = −0.40 e Å−3

Special details

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'s 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 > 2σ(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 (Ų)

	x	y	z	Uiso*/Ueq
S1	0.45158 (3)	0.80155 (3)	0.24103 (3)	0.01449 (10)
O1	0.41963 (9)	0.73289 (10)	0.32827 (8)	0.0204 (2)
O2	0.46334 (9)	0.72358 (10)	0.14956 (8)	0.0208 (2)
O4	0.32490 (9)	1.14730 (11)	−0.03579 (8)	0.0239 (2)
O5	0.19108 (9)	1.00457 (10)	0.00818 (8)	0.0206 (2)
O3	0.54813 (10)	1.14548 (11)	0.08196 (9)	0.0235 (2)
N1	0.35223 (10)	0.92191 (11)	0.19471 (9)	0.0148 (2)
C1	0.58852 (11)	0.89070 (13)	0.29337 (10)	0.0144 (2)
C2	0.67716 (12)	0.84231 (14)	0.38274 (11)	0.0167 (3)
H2	0.6646	0.7626	0.4174	0.020*
C3	0.78531 (12)	0.91527 (15)	0.41972 (11)	0.0194 (3)
H3	0.8463	0.8834	0.4788	0.023*
C4	0.80243 (13)	1.03493 (15)	0.36896 (12)	0.0213 (3)
H4	0.8745	1.0835	0.3950	0.026*
C5	0.71319 (13)	1.08340 (15)	0.27951 (11)	0.0207 (3)
H5	0.7258	1.1639	0.2459	0.025*
C6	0.60455 (12)	1.01095 (14)	0.24018 (11)	0.0163 (3)
C7	0.50866 (12)	1.05859 (14)	0.14559 (11)	0.0171 (3)
C8	0.39091 (12)	1.01442 (13)	0.12351 (11)	0.0159 (3)
C9	0.30108 (12)	1.06172 (14)	0.02519 (11)	0.0180 (3)
C10	0.09884 (14)	1.05700 (17)	−0.08516 (12)	0.0271 (3)
H10A	0.0828	1.1505	−0.0728	0.041*
H10B	0.0252	1.0051	−0.0954	0.041*
H10C	0.1276	1.0500	−0.1490	0.041*
C11	0.28252 (12)	0.98889 (14)	0.26547 (11)	0.0181 (3)
H11	0.2354	1.0621	0.2214	0.022*
C13	0.36474 (14)	1.05728 (17)	0.36523 (12)	0.0258 (3)
H13A	0.4031	0.9894	0.4173	0.039*
H13B	0.3170	1.1166	0.3970	0.039*
H13C	0.4262	1.1091	0.3444	0.039*
C12	0.18920 (13)	0.89440 (17)	0.29256 (13)	0.0263 (3)
H12A	0.1452	0.8473	0.2280	0.039*
H12B	0.1332	0.9466	0.3205	0.039*
H12C	0.2303	0.8297	0.3464	0.039*
H3O	0.482 (2)	1.167 (2)	0.0300 (17)	0.039*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
S1	0.01430 (16)	0.01178 (16)	0.01607 (17)	0.00005 (11)	0.00187 (12)	0.00036 (11)
O1	0.0185 (5)	0.0178 (5)	0.0237 (5)	−0.0013 (4)	0.0035 (4)	0.0067 (4)
O2	0.0194 (5)	0.0180 (5)	0.0225 (5)	0.0020 (4)	0.0015 (4)	−0.0060 (4)
O4	0.0277 (5)	0.0229 (5)	0.0188 (5)	0.0008 (4)	0.0023 (4)	0.0069 (4)
O5	0.0186 (5)	0.0226 (5)	0.0176 (5)	0.0017 (4)	−0.0002 (4)	0.0023 (4)
O3	0.0259 (5)	0.0252 (5)	0.0178 (5)	−0.0055 (4)	0.0033 (4)	0.0078 (4)
N1	0.0158 (5)	0.0139 (5)	0.0145 (5)	0.0027 (4)	0.0041 (4)	0.0021 (4)
C1	0.0147 (6)	0.0149 (6)	0.0138 (6)	−0.0013 (5)	0.0043 (5)	−0.0027 (5)
C2	0.0189 (6)	0.0158 (6)	0.0157 (6)	0.0011 (5)	0.0055 (5)	0.0003 (5)
C3	0.0172 (6)	0.0237 (7)	0.0157 (6)	0.0019 (5)	0.0020 (5)	−0.0018 (5)
C4	0.0175 (6)	0.0252 (7)	0.0205 (7)	−0.0058 (5)	0.0042 (5)	−0.0036 (6)
C5	0.0225 (7)	0.0209 (7)	0.0190 (7)	−0.0056 (5)	0.0063 (5)	0.0019 (5)
C6	0.0179 (6)	0.0180 (6)	0.0134 (6)	−0.0011 (5)	0.0048 (5)	−0.0003 (5)
C7	0.0228 (7)	0.0153 (6)	0.0137 (6)	−0.0013 (5)	0.0054 (5)	0.0003 (5)
C8	0.0199 (6)	0.0142 (6)	0.0133 (6)	0.0006 (5)	0.0037 (5)	0.0007 (5)
C9	0.0214 (6)	0.0160 (6)	0.0161 (6)	0.0020 (5)	0.0040 (5)	−0.0008 (5)
C10	0.0232 (7)	0.0304 (8)	0.0220 (7)	0.0037 (6)	−0.0036 (6)	0.0038 (6)
C11	0.0191 (6)	0.0181 (6)	0.0182 (7)	0.0042 (5)	0.0072 (5)	0.0004 (5)
C13	0.0286 (8)	0.0290 (8)	0.0211 (7)	0.0014 (6)	0.0091 (6)	−0.0053 (6)
C12	0.0212 (7)	0.0291 (8)	0.0314 (8)	0.0017 (6)	0.0117 (6)	0.0037 (6)

Geometric parameters (Å, °)

S1—O1	1.4319 (10)	C4—H4	0.9300
S1—O2	1.4338 (10)	C5—C6	1.3978 (19)
S1—N1	1.6338 (11)	C5—H5	0.9300
S1—C1	1.7556 (13)	C6—C7	1.4675 (18)
O4—C9	1.2264 (17)	C7—C8	1.3644 (19)
O5—C9	1.3361 (17)	C8—C9	1.4632 (18)
O5—C10	1.4524 (16)	C10—H10A	0.9600
O3—C7	1.3387 (16)	C10—H10B	0.9600
O3—H3O	0.88 (2)	C10—H10C	0.9600
N1—C8	1.4378 (17)	C11—C13	1.518 (2)
N1—C11	1.5072 (16)	C11—C12	1.521 (2)
C1—C2	1.3862 (18)	C11—H11	0.9800
C1—C6	1.4009 (18)	C13—H13A	0.9600
C2—C3	1.3926 (19)	C13—H13B	0.9600
C2—H2	0.9300	C13—H13C	0.9600
C3—C4	1.383 (2)	C12—H12A	0.9600
C3—H3	0.9300	C12—H12B	0.9600
C4—C5	1.390 (2)	C12—H12C	0.9600
O1—S1—O2	118.74 (6)	C8—C7—C6	122.54 (12)
O1—S1—N1	109.04 (6)	C7—C8—N1	121.61 (12)
O2—S1—N1	107.59 (6)	C7—C8—C9	119.64 (12)
O1—S1—C1	109.10 (6)	N1—C8—C9	118.75 (11)
O2—S1—C1	107.90 (6)	O4—C9—O5	123.06 (12)
N1—S1—C1	103.39 (6)	O4—C9—C8	122.64 (13)
C9—O5—C10	114.88 (11)	O5—C9—C8	114.29 (12)
C7—O3—H3O	104.6 (14)	O5—C10—H10A	109.5
C8—N1—C11	113.82 (10)	O5—C10—H10B	109.5
C8—N1—S1	112.76 (9)	H10A—C10—H10B	109.5
C11—N1—S1	121.74 (9)	O5—C10—H10C	109.5
C2—C1—C6	121.84 (12)	H10A—C10—H10C	109.5
C2—C1—S1	120.95 (10)	H10B—C10—H10C	109.5
C6—C1—S1	117.20 (10)	N1—C11—C13	113.06 (11)
C1—C2—C3	118.74 (13)	N1—C11—C12	112.55 (11)
C1—C2—H2	120.6	C13—C11—C12	112.96 (12)
C3—C2—H2	120.6	N1—C11—H11	105.8
C4—C3—C2	120.30 (13)	C13—C11—H11	105.8
C4—C3—H3	119.8	C12—C11—H11	105.8
C2—C3—H3	119.8	C11—C13—H13A	109.5
C3—C4—C5	120.81 (13)	C11—C13—H13B	109.5
C3—C4—H4	119.6	H13A—C13—H13B	109.5
C5—C4—H4	119.6	C11—C13—H13C	109.5
C4—C5—C6	119.86 (13)	H13A—C13—H13C	109.5
C4—C5—H5	120.1	H13B—C13—H13C	109.5
C6—C5—H5	120.1	C11—C12—H12A	109.5
C5—C6—C1	118.43 (12)	C11—C12—H12B	109.5
C5—C6—C7	121.37 (12)	H12A—C12—H12B	109.5
C1—C6—C7	120.19 (12)	C11—C12—H12C	109.5
O3—C7—C8	123.48 (12)	H12A—C12—H12C	109.5
O3—C7—C6	113.95 (12)	H12B—C12—H12C	109.5
O1—S1—N1—C8	167.45 (9)	C5—C6—C7—O3	20.73 (19)
O2—S1—N1—C8	−62.53 (10)	C1—C6—C7—O3	−159.37 (12)
C1—S1—N1—C8	51.48 (10)	C5—C6—C7—C8	−161.14 (13)
O1—S1—N1—C11	26.69 (11)	C1—C6—C7—C8	18.8 (2)
O2—S1—N1—C11	156.70 (10)	O3—C7—C8—N1	−179.43 (12)
C1—S1—N1—C11	−89.28 (11)	C6—C7—C8—N1	2.6 (2)
O1—S1—C1—C2	31.83 (13)	O3—C7—C8—C9	0.6 (2)
O2—S1—C1—C2	−98.46 (12)	C6—C7—C8—C9	−177.37 (12)
N1—S1—C1—C2	147.76 (11)	C11—N1—C8—C7	102.87 (14)
O1—S1—C1—C6	−149.00 (10)	S1—N1—C8—C7	−41.11 (16)
O2—S1—C1—C6	80.71 (11)	C11—N1—C8—C9	−77.14 (15)
N1—S1—C1—C6	−33.07 (11)	S1—N1—C8—C9	138.88 (11)
C6—C1—C2—C3	−0.5 (2)	C10—O5—C9—O4	−3.37 (19)
S1—C1—C2—C3	178.64 (10)	C10—O5—C9—C8	176.14 (12)
C1—C2—C3—C4	1.1 (2)	C7—C8—C9—O4	−4.9 (2)
C2—C3—C4—C5	−0.9 (2)	N1—C8—C9—O4	175.11 (12)
C3—C4—C5—C6	0.1 (2)	C7—C8—C9—O5	175.59 (12)
C4—C5—C6—C1	0.5 (2)	N1—C8—C9—O5	−4.40 (18)
C4—C5—C6—C7	−179.64 (13)	C8—N1—C11—C13	−80.86 (14)
C2—C1—C6—C5	−0.3 (2)	S1—N1—C11—C13	59.52 (15)
S1—C1—C6—C5	−179.45 (10)	C8—N1—C11—C12	149.66 (12)
C2—C1—C6—C7	179.81 (12)	S1—N1—C11—C12	−69.95 (14)
S1—C1—C6—C7	0.65 (17)

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4···O2i	0.93	2.49	3.311 (2)	147
C3—H3···O2ii	0.93	2.46	3.370 (2)	165
C11—H11···O1iii	0.98	2.39	3.317 (2)	157
O3—H3O···O4	0.88 (2)	1.77 (2)	2.578 (2)	151 (2)

Symmetry codes: (i) −x+3/2, y+1/2, −z+1/2; (ii) x+1/2, −y+3/2, z+1/2; (iii) −x+1/2, y+1/2, −z+1/2.