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Acta Crystallographica Section E: Structure Reports Online logoLink to Acta Crystallographica Section E: Structure Reports Online
. 2012 May 5;68(Pt 6):o1663. doi: 10.1107/S1600536812019733

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

Muhammad Nadeem Arshad a,*, Islam Ullah Khan b, Muhammad Zia-ur-Rehman c, Waseem Ahmed d, Abdullah M Asiri e,‡
PMCID: PMC3379260  PMID: 22719458

Abstract

In the title compound, C14H17NO5S, the thia­zine ring adopts a half-chair conformation. The mol­ecule exhibits an intra­molecular O—H⋯O hydrogen bond, which forms a six-membered S(6) ring motif. The planes of the benzene and thia­zine rings are inclined at a dihedral angle of 15.30 (12)°.

Related literature  

For the synthesis, see: Arshad et al. (2011a ▶). For biological activity of related compounds, see: Zia-ur-Rehman et al. (2006 ▶). For related structures, see: Arshad et al. (2011b ▶, 2012 ▶); For graph-set notation, see: Bernstein et al. (1995 ▶). For puckering parameters, see: Cremer & Pople (1975 ▶).graphic file with name e-68-o1663-scheme1.jpg

Experimental  

Crystal data  

  • C14H17NO5S

  • M r = 311.35

  • Monoclinic, Inline graphic

  • a = 25.173 (7) Å

  • b = 9.280 (2) Å

  • c = 12.531 (3) Å

  • β = 91.741 (3)°

  • V = 2926.0 (13) Å3

  • Z = 8

  • Mo Kα radiation

  • μ = 0.24 mm−1

  • T = 100 K

  • 0.44 × 0.31 × 0.25 mm

Data collection  

  • Bruker SMART 1K diffractometer

  • Absorption correction: multi-scan (SADABS; Bruker, 2001 ▶) T min = 0.901, T max = 0.942

  • 12490 measured reflections

  • 3498 independent reflections

  • 3132 reflections with I > 2σ(I)

  • R int = 0.031

Refinement  

  • R[F 2 > 2σ(F 2)] = 0.070

  • wR(F 2) = 0.210

  • S = 1.10

  • 3498 reflections

  • 193 parameters

  • H-atom parameters constrained

  • Δρmax = 1.70 e Å−3

  • Δρmin = −0.49 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

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812019733/im2370sup1.cif

e-68-o1663-sup1.cif (23.1KB, cif)

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812019733/im2370Isup2.hkl

e-68-o1663-Isup2.hkl (171.6KB, hkl)

Supplementary material file. DOI: 10.1107/S1600536812019733/im2370Isup3.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
O1—H1O⋯O4 0.84 1.85 2.564 (4) 142
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Acknowledgments

The authors acknowledge support from the Higher Education Commission of Pakistan for providing fellowships to MNA (PIN # 042–120607-Ps2–183 and PIN # IRSIP-10-PS-2).

supplementary crystallographic information

Comment

Our research group already reported the synthesis and biological activities (Arshad et al., 2011a; Zia-ur-Rehman et al., 2006) of the title compound as well as the crystal structures of related compounds (Arshad et al., 2011b, 2012).

The title compound is the N-butyl derivative of methyl-4-hydroxy-1,1-dioxo-2H-1,2-benzothiazine-3-carboxylate. The methyl ester moiety attached to the thiazine ring shows an almost planar geometry with a root mean square (r. m. s.) deviation of 0.0034 (14) Å and is oriented at a dihedral angle of 11.4 (2)° and 10.5 (2)° with respect to the thiazine (C1/C6/C7/C8/N1/S1) and aromatic benzene (C1/C2/C3/C4/C5/C6) rings, respectively. The two fused rings in the molecule are inclined at 15.30 (12)°. The thiazine ring in the molecule adopts a half chair conformation which is in accordance with already published data. The r. m. s. deviation for the ring is 0.207 (2) Å. The molecule shows the formation of a six membered S11(6) ring motif (Bernstein, et al., 1995) by a O—H···O intramolecular hydrogen bonding interaction between the hydroxyl group in 4-position of the thiazine ring and the carbonyl oxygen atom of the methyl ester substituent. The resulting ring (C7/O1/H1O/O4/C9/C8) deviates from the least square plane with a r. m. s. deviation of 0.052 (4) Å. The maximum deviation is measured for O1 = 0.08 (2) Å and H1O = -0.08 (3) Å. The N-butyl moiety shows a maximum deviation of the thiazine ring of about 83.52 (11)° and it is anti with respect to the methyl ester.

Experimental

The synthesis of the title compound has already been published (Arshad et al., 2011a). Recrystallization has been performed from a methanolic solution by slow evaporation of the solvent.

Refinement

Carbon bound H-atoms were positioned in idealized positions with C—H = 0.95 Å, C—H = 0.99 Å and C—H = 0.98 Å for aromatic, methylene and methyl carbon atoms respectively, and were refined using a riding model with Uiso(H) = 1.2 Ueq(C) for aromatic and methylene and Uiso(H) = 1.5 Ueq(C) for methyl carbon atoms. The O–H hydrogen atom was located in the difference map and was refined with O–H= 0.84 (2) Å and Uiso(H) = 1.5 Ueq(O). Electron density synthesis with coefficients Fo—Fc: Highest peaks are 1.70 at 0.3972 0.1429 0.4219 [0.82 Å from N1] & 1.55 at 0.3978 0.1460 0.5612 [0.91 Å from S1] and deepest hole -0.49 at 0.3776 0.1772 0.4612 [0.59 A from S1]. A disorder of the thiazine ring could not be resolved.

The reflections 13 1 1, 1 3 1, -9 7 2 and 11 1 1 for which (Iobs)-(Icalc)/σW > 10 were omitted in the final refinement.

Figures

Fig. 1.

Fig. 1.

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ORTEP diagram of the molecular structure of (I) showing intramolecular O—H···O hydrogen bonding as a dashed line and thermal ellipsoids at the 50% probability level.

Crystal data

C14H17NO5S F(000) = 1312
Mr = 311.35 Dx = 1.414 Mg m−3
Monoclinic, C2/c Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc Cell parameters from 5544 reflections
a = 25.173 (7) Å θ = 2.3–28.4°
b = 9.280 (2) Å µ = 0.24 mm−1
c = 12.531 (3) Å T = 100 K
β = 91.741 (3)° Block, colorless
V = 2926.0 (13) Å3 0.44 × 0.31 × 0.25 mm
Z = 8
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Data collection

Bruker SMART 1K diffractometer 3498 independent reflections
Radiation source: fine-focus sealed tube 3132 reflections with I > 2σ(I)
Graphite monochromator Rint = 0.031
φ and ω scans θmax = 28.4°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 2001) h = −32→33
Tmin = 0.901, Tmax = 0.942 k = −12→12
12490 measured reflections l = −16→16
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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)] = 0.070 Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.210 H-atom parameters constrained
S = 1.10 w = 1/[σ2(Fo2) + (0.0839P)2 + 25.4705P] where P = (Fo2 + 2Fc2)/3
3498 reflections (Δ/σ)max < 0.001
193 parameters Δρmax = 1.70 e Å−3
0 restraints Δρmin = −0.49 e Å−3
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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.
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Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

x y z Uiso*/Ueq
S1 0.39425 (3) 0.14891 (9) 0.48843 (6) 0.0157 (2)
O1 0.28629 (10) 0.2661 (3) 0.23550 (19) 0.0204 (5)
H1O 0.3009 0.2796 0.1770 0.024*
O2 0.39702 (10) 0.3001 (3) 0.5114 (2) 0.0212 (5)
O3 0.42548 (10) 0.0508 (3) 0.55284 (19) 0.0218 (5)
O4 0.36673 (10) 0.3043 (3) 0.11802 (19) 0.0222 (5)
O5 0.44802 (10) 0.2584 (3) 0.19007 (19) 0.0202 (5)
N1 0.40931 (11) 0.1252 (3) 0.3631 (2) 0.0166 (6)
C1 0.32710 (13) 0.0977 (4) 0.4870 (3) 0.0164 (6)
C2 0.30543 (14) 0.0261 (4) 0.5729 (3) 0.0206 (7)
H2 0.3273 −0.0019 0.6325 0.025*
C3 0.25114 (15) −0.0039 (4) 0.5702 (3) 0.0231 (7)
H3 0.2358 −0.0522 0.6286 0.028*
C4 0.21938 (14) 0.0363 (4) 0.4828 (3) 0.0215 (7)
H4 0.1824 0.0160 0.4818 0.026*
C5 0.24152 (13) 0.1063 (4) 0.3964 (3) 0.0191 (7)
H5 0.2195 0.1339 0.3370 0.023*
C6 0.29595 (13) 0.1362 (4) 0.3967 (3) 0.0173 (6)
C7 0.32050 (13) 0.2003 (4) 0.3037 (3) 0.0171 (6)
C8 0.37370 (13) 0.1909 (4) 0.2873 (2) 0.0167 (6)
C9 0.39560 (13) 0.2557 (3) 0.1903 (3) 0.0169 (6)
C10 0.47078 (15) 0.3216 (5) 0.0957 (3) 0.0273 (8)
H10A 0.4646 0.2573 0.0346 0.041*
H10B 0.5091 0.3351 0.1081 0.041*
H10C 0.4540 0.4151 0.0809 0.041*
C11 0.43520 (13) −0.0124 (4) 0.3326 (3) 0.0182 (6)
H11A 0.4666 −0.0282 0.3805 0.022*
H11B 0.4480 −0.0028 0.2590 0.022*
C12 0.39938 (14) −0.1447 (4) 0.3374 (3) 0.0195 (7)
H12A 0.3675 −0.1300 0.2906 0.023*
H12B 0.3876 −0.1584 0.4114 0.023*
C13 0.42921 (15) −0.2787 (4) 0.3015 (3) 0.0227 (7)
H13A 0.4631 −0.2864 0.3432 0.027*
H13B 0.4378 −0.2683 0.2253 0.027*
C14 0.39715 (17) −0.4169 (4) 0.3160 (4) 0.0340 (9)
H14A 0.3861 −0.4238 0.3902 0.051*
H14B 0.4191 −0.5004 0.2989 0.051*
H14C 0.3656 −0.4149 0.2682 0.051*
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Atomic displacement parameters (Å2)

U11 U22 U33 U12 U13 U23
S1 0.0160 (4) 0.0161 (4) 0.0148 (4) 0.0010 (3) −0.0017 (3) −0.0007 (3)
O1 0.0192 (12) 0.0225 (12) 0.0192 (12) 0.0038 (9) −0.0023 (9) 0.0033 (9)
O2 0.0222 (12) 0.0166 (12) 0.0244 (12) −0.0010 (9) −0.0021 (9) −0.0047 (9)
O3 0.0210 (12) 0.0254 (13) 0.0188 (11) 0.0036 (10) −0.0032 (9) 0.0026 (9)
O4 0.0236 (13) 0.0227 (13) 0.0201 (12) 0.0006 (10) −0.0020 (9) 0.0049 (9)
O5 0.0202 (12) 0.0226 (12) 0.0176 (11) −0.0026 (9) 0.0000 (9) 0.0032 (9)
N1 0.0200 (14) 0.0180 (13) 0.0116 (12) 0.0010 (11) −0.0013 (10) 0.0003 (10)
C1 0.0149 (14) 0.0163 (15) 0.0180 (15) 0.0021 (12) −0.0008 (11) −0.0025 (12)
C2 0.0224 (17) 0.0195 (16) 0.0199 (16) 0.0047 (13) 0.0011 (12) 0.0014 (12)
C3 0.0277 (18) 0.0184 (16) 0.0235 (17) 0.0050 (14) 0.0066 (13) 0.0026 (13)
C4 0.0177 (16) 0.0179 (16) 0.0290 (18) −0.0012 (12) 0.0031 (13) −0.0043 (13)
C5 0.0173 (15) 0.0169 (15) 0.0232 (16) 0.0008 (12) −0.0005 (12) −0.0033 (12)
C6 0.0193 (16) 0.0151 (15) 0.0175 (15) 0.0026 (12) −0.0005 (11) −0.0023 (11)
C7 0.0205 (16) 0.0142 (15) 0.0164 (15) 0.0020 (12) −0.0037 (11) −0.0017 (11)
C8 0.0208 (16) 0.0149 (14) 0.0142 (14) 0.0000 (12) −0.0023 (11) 0.0006 (11)
C9 0.0199 (16) 0.0110 (14) 0.0197 (15) −0.0006 (11) −0.0008 (12) −0.0005 (11)
C10 0.0236 (18) 0.036 (2) 0.0225 (17) −0.0062 (16) 0.0038 (13) 0.0081 (15)
C11 0.0180 (15) 0.0179 (15) 0.0187 (15) 0.0017 (12) 0.0008 (11) 0.0009 (12)
C12 0.0215 (16) 0.0174 (16) 0.0196 (16) 0.0031 (12) −0.0002 (12) −0.0007 (12)
C13 0.0281 (18) 0.0206 (17) 0.0193 (16) 0.0060 (14) 0.0007 (13) −0.0014 (13)
C14 0.034 (2) 0.0225 (19) 0.046 (2) 0.0012 (16) −0.0062 (17) −0.0043 (17)
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Geometric parameters (Å, º)

S1—O2 1.433 (3) C5—H5 0.9500
S1—O3 1.435 (2) C6—C7 1.462 (5)
S1—N1 1.642 (3) C7—C8 1.364 (5)
S1—C1 1.756 (3) C8—C9 1.478 (5)
O1—C7 1.341 (4) C10—H10A 0.9800
O1—H1O 0.8400 C10—H10B 0.9800
O4—C9 1.230 (4) C10—H10C 0.9800
O5—C9 1.320 (4) C11—C12 1.526 (5)
O5—C10 1.453 (4) C11—H11A 0.9900
N1—C8 1.423 (4) C11—H11B 0.9900
N1—C11 1.489 (4) C12—C13 1.527 (5)
C1—C2 1.390 (5) C12—H12A 0.9900
C1—C6 1.404 (4) C12—H12B 0.9900
C2—C3 1.394 (5) C13—C14 1.528 (6)
C2—H2 0.9500 C13—H13A 0.9900
C3—C4 1.388 (5) C13—H13B 0.9900
C3—H3 0.9500 C14—H14A 0.9800
C4—C5 1.393 (5) C14—H14B 0.9800
C4—H4 0.9500 C14—H14C 0.9800
C5—C6 1.398 (5)
O2—S1—O3 119.06 (15) N1—C8—C9 118.7 (3)
O2—S1—N1 108.17 (15) O4—C9—O5 124.0 (3)
O3—S1—N1 108.32 (15) O4—C9—C8 121.9 (3)
O2—S1—C1 107.95 (15) O5—C9—C8 114.1 (3)
O3—S1—C1 110.17 (16) O5—C10—H10A 109.5
N1—S1—C1 101.78 (15) O5—C10—H10B 109.5
C7—O1—H1O 109.5 H10A—C10—H10B 109.5
C9—O5—C10 115.4 (3) O5—C10—H10C 109.5
C8—N1—C11 117.9 (3) H10A—C10—H10C 109.5
C8—N1—S1 114.9 (2) H10B—C10—H10C 109.5
C11—N1—S1 118.5 (2) N1—C11—C12 114.6 (3)
C2—C1—C6 121.6 (3) N1—C11—H11A 108.6
C2—C1—S1 121.5 (2) C12—C11—H11A 108.6
C6—C1—S1 117.0 (3) N1—C11—H11B 108.6
C1—C2—C3 119.0 (3) C12—C11—H11B 108.6
C1—C2—H2 120.5 H11A—C11—H11B 107.6
C3—C2—H2 120.5 C11—C12—C13 110.3 (3)
C4—C3—C2 120.4 (3) C11—C12—H12A 109.6
C4—C3—H3 119.8 C13—C12—H12A 109.6
C2—C3—H3 119.8 C11—C12—H12B 109.6
C3—C4—C5 120.3 (3) C13—C12—H12B 109.6
C3—C4—H4 119.9 H12A—C12—H12B 108.1
C5—C4—H4 119.9 C12—C13—C14 112.4 (3)
C4—C5—C6 120.4 (3) C12—C13—H13A 109.1
C4—C5—H5 119.8 C14—C13—H13A 109.1
C6—C5—H5 119.8 C12—C13—H13B 109.1
C5—C6—C1 118.3 (3) C14—C13—H13B 109.1
C5—C6—C7 121.1 (3) H13A—C13—H13B 107.8
C1—C6—C7 120.5 (3) C13—C14—H14A 109.5
O1—C7—C8 123.2 (3) C13—C14—H14B 109.5
O1—C7—C6 114.4 (3) H14A—C14—H14B 109.5
C8—C7—C6 122.3 (3) C13—C14—H14C 109.5
C7—C8—N1 121.9 (3) H14A—C14—H14C 109.5
C7—C8—C9 119.3 (3) H14B—C14—H14C 109.5
O2—S1—N1—C8 −63.0 (3) C5—C6—C7—O1 19.3 (5)
O3—S1—N1—C8 166.7 (2) C1—C6—C7—O1 −163.4 (3)
C1—S1—N1—C8 50.6 (3) C5—C6—C7—C8 −159.5 (3)
O2—S1—N1—C11 150.0 (2) C1—C6—C7—C8 17.9 (5)
O3—S1—N1—C11 19.7 (3) O1—C7—C8—N1 177.6 (3)
C1—S1—N1—C11 −96.5 (3) C6—C7—C8—N1 −3.8 (5)
O2—S1—C1—C2 −102.1 (3) O1—C7—C8—C9 0.1 (5)
O3—S1—C1—C2 29.5 (3) C6—C7—C8—C9 178.7 (3)
N1—S1—C1—C2 144.2 (3) C11—N1—C8—C7 112.4 (4)
O2—S1—C1—C6 76.0 (3) S1—N1—C8—C7 −34.9 (4)
O3—S1—C1—C6 −152.4 (2) C11—N1—C8—C9 −70.1 (4)
N1—S1—C1—C6 −37.7 (3) S1—N1—C8—C9 142.7 (3)
C6—C1—C2—C3 −2.0 (5) C10—O5—C9—O4 −1.1 (5)
S1—C1—C2—C3 176.0 (3) C10—O5—C9—C8 −179.9 (3)
C1—C2—C3—C4 0.4 (5) C7—C8—C9—O4 −8.0 (5)
C2—C3—C4—C5 0.4 (5) N1—C8—C9—O4 174.3 (3)
C3—C4—C5—C6 0.3 (5) C7—C8—C9—O5 170.8 (3)
C4—C5—C6—C1 −1.8 (5) N1—C8—C9—O5 −6.8 (4)
C4—C5—C6—C7 175.6 (3) C8—N1—C11—C12 −76.7 (4)
C2—C1—C6—C5 2.7 (5) S1—N1—C11—C12 69.3 (3)
S1—C1—C6—C5 −175.4 (3) N1—C11—C12—C13 178.3 (3)
C2—C1—C6—C7 −174.8 (3) C11—C12—C13—C14 174.0 (3)
S1—C1—C6—C7 7.1 (4)
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Hydrogen-bond geometry (Å, º)

D—H···A D—H H···A D···A D—H···A
O1—H1O···O4 0.84 1.85 2.564 (4) 142
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Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: IM2370).

References

  1. Arshad, M. N., Khan, I. U., Zia-ur-Rehman, M., Danish, M. & Holman, K. T. (2011b). Acta Cryst. E67, o3445. [DOI] [PMC free article] [PubMed]
  2. Arshad, M. N., Khan, I. U., Zia-ur-Rehman, M. & Shafiq, M. (2011a). Asian J. Chem. 23, o2801–2805.
  3. Arshad, M. N., Zia-ur-Rehman, M., Khan, I. U., Mustafa, G., Shafiq, M., Rafique, H. M. & Holman, K. T. (2012). Walailak J. Sci. Tech. 10 In the press.
  4. Barbour, L. J. (2001). J. Supramol. Chem. 1, 189–191.
  5. Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555–1573.
  6. Bruker (2001). SADABS, APEX2 and SAINT Bruker AXS Inc., Madison, Wisconsin, USA.
  7. Cremer, D. & Pople, J. A. (1975). J. Am. Chem. Soc. 97, 1354–1358.
  8. Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838.
  9. Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [DOI] [PubMed]
  10. Spek, A. L. (2009). Acta Cryst. D65, 148–155. [DOI] [PMC free article] [PubMed]
  11. Zia-ur-Rehman, M., Anwar, J., Ahmad, S. & Siddiqui, H. L. (2006). Chem. Pharm. Bull. 54, 1175–1178. [DOI] [PubMed]

Associated Data

This section collects any data citations, data availability statements, or supplementary materials included in this article.

Supplementary Materials

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812019733/im2370sup1.cif

e-68-o1663-sup1.cif (23.1KB, cif)

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812019733/im2370Isup2.hkl

e-68-o1663-Isup2.hkl (171.6KB, hkl)

Supplementary material file. DOI: 10.1107/S1600536812019733/im2370Isup3.cml

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

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography

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