Methyl 2-(but-3-en­yl)-4-hy­droxy-1,1-dioxo-2H-1λ⁶,2-benzothia­zine-3-carboxyl­ate

Abstract

In the title compound, C₁₄H₁₅NO₅S, the thia­zine ring adopts a sofa conformation and an intra­molecular O—H⋯O hydrogen bond forms an S(6) ring. In the crystal, molecules are linked viaC—H⋯O inter­actions.

Related literature  

For the synthesis, see: Arshad et al. (2011b ▶); Zia-ur-Rehman, et al. (2006 ▶). For related structures, see: Arshad et al. (2011a ▶, 2012 ▶). For graph-set notation, see: Bernstein et al. (1995 ▶).

Experimental  

Crystal data  

• C₁₄H₁₅NO₅S

• M _r = 309.33

• Orthorhombic,

• a = 25.265 (8) Å

• b = 8.929 (3) Å

• c = 12.584 (4) Å

• V = 2839.0 (15) ų

• Z = 8

• Mo Kα radiation

• μ = 0.25 mm⁻¹

• T = 100 K

• 0.41 × 0.36 × 0.19 mm

Data collection  

• Bruker SMART 1K diffractometer

• Absorption correction: multi-scan (SADABS; Bruker, 2001 ▶) T _min = 0.905, T _max = 0.954

• 22868 measured reflections

• 3445 independent reflections

• 2643 reflections with I > 2σ(I)

• R _int = 0.081

Refinement  

• R[F ² > 2σ(F ²)] = 0.042

• wR(F ²) = 0.109

• S = 1.05

• 3445 reflections

• 194 parameters

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

• Δρ_max = 0.33 e Å⁻³

• Δρ_min = −0.52 e Å⁻³

Data collection: SMART (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: PLATON (Spek, 2009 ▶) and X-SEED (Barbour 2001 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶) and PLATON.

Supplementary Material

Supplementary material file. DOI: 10.1107/S1600536812022908/bt5926Isup3.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	0.95	2.52	3.269 (2)	136
O1—H1O⋯O4	0.84 (3)	1.81 (3)	2.577 (2)	151 (3)

Symmetry code: (i) .

supplementary crystallographic information

Comment

Herein we report the crystal structure of the title compound in continuation of our research on the synthesis (Arshad et al., 2011b), biological activities (Zia-ur-Rehman et al., 2006) and crystal structures (Arshad et al., 2011a, 2012) of thiazine related heterocyles.

The title compound is the N-3-butenyl derivative of methyl-4-hydroxy-2H-1,2-benzothiazine-3-carboxylate 1,1-dioxide. The planar methyl ester moiety (r.m.s deviation 0.008Å) is oriented at dihedral angles of 11.39 (10)° and 16.97 (11)° with respect to the thiazine (C1/C6/C7/C8/N1/S1) and benzene (C1/C2/C3/C4/C5/C6) rings. The thiazine ring adopts a sofa conformation and is inclined at 17.27 (12)° with respect to the benzene ring. A six membered (C7/O1/H1O/O4/C9/C8) ring with graph set notation S¹₁(6) (Bernstein et al., 1995) is formed through an O—H···O intramolecular hydrogen bond. The crystal structure is stabilized by weak C—H···O interactions (Tab. 1).

Experimental

The synthesis of the titled compound has been published (Arshad et al., 2011a). The title compound was recrystallized from ethylacetate under slow evaporation of the solvent.

Refinement

The H-atoms bonded to C were positioned with idealized geometry with C—H ranging from 0.95 Å to = 0.99Å and refined using a riding model with U_iso(H) = 1.5 U_eq(C) for methyl and U_iso(H) = 1.2 U_eq(C) for the remaining H atoms. The coordinates of the H atom bonded to O were refined with U_iso(H) 1.5U_eq(O).

Figures

Fig. 1.

Molecular structure of the title compound with displacement ellipsoids drawn at the 50% probability.

Crystal data

C14H15NO5S	F(000) = 1296
Mr = 309.33	Dx = 1.447 Mg m−3
Orthorhombic, Pbcn	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2n 2ab	Cell parameters from 4741 reflections
a = 25.265 (8) Å	θ = 2.4–27.3°
b = 8.929 (3) Å	µ = 0.25 mm−1
c = 12.584 (4) Å	T = 100 K
V = 2839.0 (15) Å3	Block, colorless
Z = 8	0.41 × 0.36 × 0.19 mm

Data collection

Bruker SMART 1K diffractometer	3445 independent reflections
Radiation source: fine-focus sealed tube	2643 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.081
φ and ω scans	θmax = 28.3°, θmin = 2.4°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −33→32
Tmin = 0.905, Tmax = 0.954	k = −11→11
22868 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)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.109	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ2(Fo2) + (0.0432P)2 + 1.393P] where P = (Fo2 + 2Fc2)/3
3445 reflections	(Δ/σ)max = 0.001
194 parameters	Δρmax = 0.33 e Å−3
0 restraints	Δρmin = −0.52 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.

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 (Ų)

	x	y	z	Uiso*/Ueq
S1	0.383769 (17)	0.36570 (5)	0.46460 (3)	0.01998 (13)
O1	0.28657 (5)	0.22258 (15)	0.20949 (10)	0.0233 (3)
O2	0.38708 (5)	0.20923 (14)	0.48963 (10)	0.0237 (3)
O3	0.41184 (5)	0.47125 (15)	0.52964 (10)	0.0252 (3)
O4	0.37180 (5)	0.18207 (15)	0.10068 (10)	0.0242 (3)
O5	0.44900 (5)	0.25535 (14)	0.17283 (10)	0.0218 (3)
N1	0.40302 (6)	0.38813 (17)	0.34120 (11)	0.0193 (3)
C1	0.31660 (7)	0.4152 (2)	0.45726 (14)	0.0206 (4)
C2	0.29195 (7)	0.4945 (2)	0.53786 (14)	0.0234 (4)
H2	0.3113	0.5258	0.5987	0.028*
C3	0.23838 (7)	0.5274 (2)	0.52817 (15)	0.0260 (4)
H3	0.2210	0.5839	0.5819	0.031*
C4	0.21024 (7)	0.4782 (2)	0.44037 (15)	0.0256 (4)
H4	0.1734	0.4989	0.4354	0.031*
C5	0.23497 (7)	0.3991 (2)	0.35976 (15)	0.0233 (4)
H5	0.2151	0.3656	0.3003	0.028*
C6	0.28911 (7)	0.36857 (19)	0.36578 (14)	0.0194 (4)
C7	0.31751 (7)	0.29795 (19)	0.27785 (14)	0.0198 (4)
C8	0.37096 (7)	0.3116 (2)	0.26458 (14)	0.0190 (4)
C9	0.39673 (7)	0.2439 (2)	0.17199 (14)	0.0202 (4)
C10	0.47565 (8)	0.1946 (2)	0.08044 (15)	0.0271 (4)
H10A	0.4664	0.0886	0.0725	0.041*
H10B	0.5140	0.2044	0.0894	0.041*
H10C	0.4645	0.2496	0.0169	0.041*
C11	0.42697 (7)	0.5340 (2)	0.30952 (15)	0.0228 (4)
H11A	0.4436	0.5221	0.2387	0.027*
H11B	0.4554	0.5591	0.3606	0.027*
C12	0.38804 (8)	0.6648 (2)	0.30478 (16)	0.0272 (4)
H12A	0.3576	0.6377	0.2591	0.033*
H12B	0.3745	0.6864	0.3770	0.033*
C13	0.41478 (8)	0.8014 (2)	0.26092 (17)	0.0316 (5)
H13	0.4245	0.8001	0.1880	0.038*
C14	0.42573 (8)	0.9223 (2)	0.31568 (17)	0.0306 (5)
H14A	0.4166	0.9276	0.3888	0.037*
H14B	0.4428	1.0045	0.2823	0.037*
H1O	0.3066 (11)	0.199 (3)	0.159 (2)	0.046*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
S1	0.0183 (2)	0.0232 (2)	0.0185 (2)	−0.00070 (17)	−0.00184 (16)	−0.00094 (17)
O1	0.0193 (6)	0.0285 (7)	0.0221 (7)	−0.0037 (5)	−0.0026 (5)	−0.0032 (5)
O2	0.0240 (7)	0.0246 (7)	0.0227 (7)	0.0010 (5)	−0.0039 (5)	0.0011 (5)
O3	0.0231 (7)	0.0310 (7)	0.0217 (7)	−0.0030 (5)	−0.0018 (5)	−0.0041 (6)
O4	0.0211 (6)	0.0284 (7)	0.0230 (7)	−0.0001 (5)	−0.0031 (5)	−0.0043 (6)
O5	0.0174 (6)	0.0261 (7)	0.0219 (6)	0.0018 (5)	−0.0002 (5)	−0.0021 (5)
N1	0.0171 (7)	0.0230 (8)	0.0178 (7)	−0.0020 (6)	−0.0010 (6)	−0.0018 (6)
C1	0.0194 (8)	0.0202 (9)	0.0221 (9)	−0.0026 (7)	0.0016 (7)	0.0027 (7)
C2	0.0250 (9)	0.0250 (10)	0.0201 (9)	−0.0023 (8)	0.0012 (7)	−0.0004 (7)
C3	0.0264 (9)	0.0256 (10)	0.0260 (10)	0.0012 (8)	0.0076 (7)	0.0014 (8)
C4	0.0193 (9)	0.0278 (10)	0.0297 (10)	0.0015 (7)	0.0036 (7)	0.0062 (8)
C5	0.0192 (9)	0.0267 (10)	0.0241 (9)	−0.0029 (7)	−0.0001 (7)	0.0043 (8)
C6	0.0189 (8)	0.0187 (9)	0.0205 (9)	−0.0026 (7)	0.0001 (7)	0.0028 (7)
C7	0.0200 (8)	0.0194 (9)	0.0198 (9)	−0.0010 (7)	−0.0022 (7)	0.0018 (7)
C8	0.0186 (8)	0.0194 (8)	0.0189 (9)	−0.0013 (7)	−0.0025 (7)	−0.0004 (7)
C9	0.0196 (9)	0.0196 (9)	0.0213 (9)	0.0006 (7)	−0.0008 (7)	0.0027 (7)
C10	0.0241 (9)	0.0319 (11)	0.0253 (10)	0.0034 (8)	0.0040 (8)	−0.0036 (8)
C11	0.0210 (9)	0.0243 (10)	0.0230 (9)	−0.0048 (7)	0.0010 (7)	−0.0020 (8)
C12	0.0281 (10)	0.0249 (10)	0.0286 (10)	−0.0031 (8)	−0.0032 (8)	−0.0006 (8)
C13	0.0398 (12)	0.0307 (11)	0.0242 (10)	−0.0041 (9)	−0.0020 (9)	0.0037 (9)
C14	0.0343 (11)	0.0261 (10)	0.0313 (11)	−0.0013 (8)	−0.0053 (8)	0.0042 (9)

Geometric parameters (Å, º)

S1—O2	1.4346 (14)	C5—C6	1.397 (2)
S1—O3	1.4356 (13)	C5—H5	0.9500
S1—N1	1.6396 (16)	C6—C7	1.462 (2)
S1—C1	1.7561 (19)	C7—C8	1.366 (2)
O1—C7	1.343 (2)	C8—C9	1.465 (3)
O1—H1O	0.84 (3)	C10—H10A	0.9800
O4—C9	1.227 (2)	C10—H10B	0.9800
O5—C9	1.325 (2)	C10—H10C	0.9800
O5—C10	1.449 (2)	C11—C12	1.528 (3)
N1—C8	1.433 (2)	C11—H11A	0.9900
N1—C11	1.490 (2)	C11—H11B	0.9900
C1—C2	1.385 (3)	C12—C13	1.499 (3)
C1—C6	1.407 (2)	C12—H12A	0.9900
C2—C3	1.391 (3)	C12—H12B	0.9900
C2—H2	0.9500	C13—C14	1.310 (3)
C3—C4	1.386 (3)	C13—H13	0.9500
C3—H3	0.9500	C14—H14A	0.9500
C4—C5	1.385 (3)	C14—H14B	0.9500
C4—H4	0.9500
O2—S1—O3	119.04 (8)	C8—C7—C6	122.63 (16)
O2—S1—N1	108.04 (8)	C7—C8—N1	121.29 (16)
O3—S1—N1	108.25 (8)	C7—C8—C9	119.96 (16)
O2—S1—C1	108.24 (8)	N1—C8—C9	118.73 (15)
O3—S1—C1	110.00 (8)	O4—C9—O5	123.51 (17)
N1—S1—C1	101.90 (8)	O4—C9—C8	122.61 (16)
C7—O1—H1O	104.9 (18)	O5—C9—C8	113.87 (15)
C9—O5—C10	115.33 (14)	O5—C10—H10A	109.5
C8—N1—C11	117.79 (14)	O5—C10—H10B	109.5
C8—N1—S1	114.29 (12)	H10A—C10—H10B	109.5
C11—N1—S1	118.72 (12)	O5—C10—H10C	109.5
C2—C1—C6	121.90 (17)	H10A—C10—H10C	109.5
C2—C1—S1	121.65 (14)	H10B—C10—H10C	109.5
C6—C1—S1	116.46 (13)	N1—C11—C12	114.66 (15)
C1—C2—C3	118.80 (17)	N1—C11—H11A	108.6
C1—C2—H2	120.6	C12—C11—H11A	108.6
C3—C2—H2	120.6	N1—C11—H11B	108.6
C4—C3—C2	120.14 (17)	C12—C11—H11B	108.6
C4—C3—H3	119.9	H11A—C11—H11B	107.6
C2—C3—H3	119.9	C13—C12—C11	110.25 (17)
C5—C4—C3	120.96 (17)	C13—C12—H12A	109.6
C5—C4—H4	119.5	C11—C12—H12A	109.6
C3—C4—H4	119.5	C13—C12—H12B	109.6
C4—C5—C6	120.12 (18)	C11—C12—H12B	109.6
C4—C5—H5	119.9	H12A—C12—H12B	108.1
C6—C5—H5	119.9	C14—C13—C12	124.9 (2)
C5—C6—C1	118.02 (17)	C14—C13—H13	117.6
C5—C6—C7	121.60 (16)	C12—C13—H13	117.6
C1—C6—C7	120.29 (16)	C13—C14—H14A	120.0
O1—C7—C8	122.81 (16)	C13—C14—H14B	120.0
O1—C7—C6	114.53 (15)	H14A—C14—H14B	120.0
O2—S1—N1—C8	61.69 (14)	C5—C6—C7—O1	−20.8 (2)
O3—S1—N1—C8	−168.15 (12)	C1—C6—C7—O1	162.66 (16)
C1—S1—N1—C8	−52.19 (14)	C5—C6—C7—C8	157.21 (18)
O2—S1—N1—C11	−152.15 (12)	C1—C6—C7—C8	−19.3 (3)
O3—S1—N1—C11	−21.99 (15)	O1—C7—C8—N1	−177.64 (15)
C1—S1—N1—C11	93.96 (14)	C6—C7—C8—N1	4.5 (3)
O2—S1—C1—C2	104.25 (16)	O1—C7—C8—C9	0.7 (3)
O3—S1—C1—C2	−27.34 (18)	C6—C7—C8—C9	−177.14 (16)
N1—S1—C1—C2	−142.01 (15)	C11—N1—C8—C7	−110.93 (19)
O2—S1—C1—C6	−75.07 (15)	S1—N1—C8—C7	35.6 (2)
O3—S1—C1—C6	153.34 (13)	C11—N1—C8—C9	70.7 (2)
N1—S1—C1—C6	38.67 (15)	S1—N1—C8—C9	−142.81 (14)
C6—C1—C2—C3	0.6 (3)	C10—O5—C9—O4	2.4 (3)
S1—C1—C2—C3	−178.67 (14)	C10—O5—C9—C8	−177.74 (15)
C1—C2—C3—C4	1.6 (3)	C7—C8—C9—O4	4.8 (3)
C2—C3—C4—C5	−1.7 (3)	N1—C8—C9—O4	−176.84 (16)
C3—C4—C5—C6	−0.3 (3)	C7—C8—C9—O5	−175.05 (16)
C4—C5—C6—C1	2.4 (3)	N1—C8—C9—O5	3.3 (2)
C4—C5—C6—C7	−174.17 (17)	C8—N1—C11—C12	74.1 (2)
C2—C1—C6—C5	−2.6 (3)	S1—N1—C11—C12	−70.88 (19)
S1—C1—C6—C5	176.72 (14)	N1—C11—C12—C13	−173.83 (15)
C2—C1—C6—C7	174.05 (17)	C11—C12—C13—C14	−111.0 (2)
S1—C1—C6—C7	−6.6 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4···O2i	0.95	2.52	3.269 (2)	136
O1—H1O···O4	0.84 (3)	1.81 (3)	2.577 (2)	151 (3)

Symmetry code: (i) −x+1/2, y+1/2, z.