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Acta Crystallogr Sect E Struct Rep Online. 2009 October 1; 65(Pt 10): o2588.
Published online 2009 September 30. doi:  10.1107/S1600536809037799
PMCID: PMC2970184

A nonmerohedral twin of methyl 2-[meth­yl(methyl­sulfon­yl)amino]benzoate

Abstract

The asymmetric unit of the title compound, C10H13NO4S, comprises two crystallographically independent mol­ecules. The crystal structure is stabilized by weak inter­molecular C—H(...)O hydrogen bonds, which link mol­ecules along the b axis. The crystal is a nonmerohedral twin, the refined ratio of the twin components being 0.344 (2):0.656 (2).

Related literature

For standard values of bond lengths, see: Allen et al. (1987 [triangle]). For applications of benzothia­zine derivatives in organic synthesis, see: Shafiq et al. (2008 [triangle], 2009a [triangle],b [triangle]); Lombardino (1972 [triangle]); Arshad et al. (2008 [triangle]).

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Object name is e-65-o2588-scheme1.jpg

Experimental

Crystal data

  • C10H13NO4S
  • M r = 243.27
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-o2588-efi1.jpg
  • a = 8.7476 (4) Å
  • b = 10.2081 (4) Å
  • c = 13.8377 (7) Å
  • β = 108.347 (3)°
  • V = 1172.84 (9) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.27 mm−1
  • T = 296 K
  • 0.32 × 0.21 × 0.15 mm

Data collection

  • Bruker SMART APEXII CCD area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2005 [triangle]) T min = 0.917, T max = 0.960
  • 13537 measured reflections
  • 5720 independent reflections
  • 3842 reflections with I > 2σ(I)
  • R int = 0.041

Refinement

  • R[F 2 > 2σ(F 2)] = 0.043
  • wR(F 2) = 0.083
  • S = 0.99
  • 5720 reflections
  • 296 parameters
  • 1 restraint
  • H-atom parameters constrained
  • Δρmax = 0.20 e Å−3
  • Δρmin = −0.29 e Å−3
  • Absolute structure: Flack (1983), 2643 Friedel pairs
  • Flack parameter: 0.00 (8)

Data collection: APEX2 (Bruker, 2005 [triangle]); cell refinement: SAINT (Bruker, 2005 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809037799/lh2905sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809037799/lh2905Isup2.hkl

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

Acknowledgments

We thank the GC University, Lahore, for supporting this work.

supplementary crystallographic information

Comment

Our group is actively involved in the synthesis and characterization by X-ray studies of various benzothiazine derivatives (Shafiq et al., 2009a; Shafiq et al., 2009b; Shafiq et al., 2008; Arshad et al., 2008). The crystal structure of the title compound is reported here.

In the molecule of the title compound, (Fig. 1), intermolecular C—H···O interactions (Table 1) link neighbouring molecules along the b axis (Fig. 2). The crystal was a nonmerohedral twin with a refined BASF parameter ratio of 0.344 (2)/0.656 (2).

Experimental

The title compound was synthesized as reported earlier (Lombardino et al., 1972) and was recrystallized from a solution of Ethanol by slow evaporation at room temperature.

Refinement

All of the hydrogen atoms were positioned geometrically [C—H = 0.93–0.96 Å] and refined using a riding model approximation with Uiso (H) = 1.2 or 1.5 Ueq (C). A rotating group model was applied for the methyl groups. PLATON and intensity statistic indicate nonmerohedral twinning. Applying the twin instruction [TWIN -1 0 0 0 -1 0 1 0 1] with a BASF parameter in SHELXLTL (Sheldrick, 2008) of 0.365 (1) in SHELXTL (Sheldrick, 2008), the R1 value drops to 0.043 (0.1886 without TWIN instruction).

Figures

Fig. 1.
The molecular structure of the title compound, showing 30% probability displacement ellipsoids and the atomic numbering.
Fig. 2.
The crystal packing of the title compound, viewed down the c-axis, showing linking of the molecules through intermolecular C—H···O interactions along the b-axis. Intermolecular interactions are drawn as dashed lines.

Crystal data

C10H13NO4SF(000) = 512
Mr = 243.27Dx = 1.378 Mg m3
Monoclinic, P21Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ybCell parameters from 3745 reflections
a = 8.7476 (4) Åθ = 2.5–29.5°
b = 10.2081 (4) ŵ = 0.27 mm1
c = 13.8377 (7) ÅT = 296 K
β = 108.347 (3)°Block, colourless
V = 1172.84 (9) Å30.32 × 0.21 × 0.15 mm
Z = 4

Data collection

Bruker SMART APEXII CCD area-detector diffractometer5720 independent reflections
Radiation source: fine-focus sealed tube3842 reflections with I > 2σ(I)
graphiteRint = 0.041
[var phi] and ω scansθmax = 28.3°, θmin = 1.6°
Absorption correction: multi-scan (SADABS; Bruker, 2005)h = −11→11
Tmin = 0.917, Tmax = 0.960k = −13→13
13537 measured reflectionsl = −18→18

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.043H-atom parameters constrained
wR(F2) = 0.083w = 1/[σ2(Fo2) + (0.0315P)2] where P = (Fo2 + 2Fc2)/3
S = 0.99(Δ/σ)max < 0.001
5720 reflectionsΔρmax = 0.20 e Å3
296 parametersΔρmin = −0.29 e Å3
1 restraintAbsolute structure: Flack (1983), 2643 Friedel pairs
Primary atom site location: structure-invariant direct methodsFlack parameter: 0.00 (8)

Special details

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 > 2sigma(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)

xyzUiso*/Ueq
S110.34203 (10)1.01678 (10)−0.09098 (6)0.0492 (2)
O130.4796 (4)0.9599 (3)−0.1065 (2)0.0757 (9)
O110.3556 (4)0.8101 (3)0.1014 (3)0.0921 (12)
O120.1243 (4)0.7697 (2)0.1261 (2)0.0569 (8)
O140.1950 (3)0.9443 (3)−0.1159 (2)0.0631 (8)
N110.3887 (3)1.0581 (3)0.0270 (2)0.0460 (7)
C110.2621 (5)1.0872 (4)0.0698 (3)0.0440 (10)
C120.2224 (5)1.2160 (4)0.0785 (3)0.0569 (12)
H120.27871.28170.05750.068*
C130.1001 (6)1.2502 (4)0.1178 (4)0.0679 (14)
H130.07721.33770.12560.081*
C140.0131 (5)1.1521 (4)0.1450 (3)0.0551 (11)
H14−0.07311.17330.16780.066*
C150.0540 (4)1.0221 (5)0.1385 (3)0.0503 (8)
H15−0.00340.95660.15860.060*
C160.1787 (4)0.9889 (3)0.1025 (3)0.0431 (9)
C170.2342 (5)0.8487 (4)0.1083 (3)0.0491 (10)
C180.1680 (6)0.6327 (4)0.1398 (3)0.0737 (14)
H18A0.27230.62430.18980.111*
H18B0.17080.59660.07630.111*
H18C0.08990.58640.16230.111*
C190.5524 (5)1.0955 (5)0.0835 (3)0.0745 (14)
H19A0.58621.04950.14720.112*
H19B0.55671.18820.09600.112*
H19C0.62251.07370.04470.112*
C200.3003 (6)1.1605 (4)−0.1635 (3)0.0791 (15)
H20A0.22361.2121−0.14350.119*
H20B0.25671.1385−0.23430.119*
H20C0.39781.2098−0.15240.119*
S210.93347 (9)0.01388 (10)0.56230 (7)0.0483 (2)
O210.7083 (4)0.2046 (3)0.3383 (3)0.0857 (10)
O220.4802 (4)0.2520 (3)0.3686 (2)0.0646 (9)
O230.8215 (4)0.0862 (3)0.5968 (2)0.0686 (9)
O241.0850 (3)0.0697 (3)0.5679 (3)0.0782 (10)
N210.8462 (3)−0.0237 (2)0.4449 (2)0.0460 (7)
C210.6795 (4)−0.0606 (4)0.4145 (3)0.0395 (9)
C220.6397 (5)−0.1920 (4)0.4206 (3)0.0493 (10)
H220.7207−0.25440.44230.059*
C230.4821 (5)−0.2289 (4)0.3946 (3)0.0522 (11)
H230.4563−0.31710.39630.063*
C240.3619 (5)−0.1381 (4)0.3663 (3)0.0591 (11)
H240.2551−0.16400.35150.071*
C250.3989 (4)−0.0073 (4)0.3595 (3)0.0520 (10)
H250.31660.05440.34030.062*
C260.5591 (4)0.0328 (4)0.3811 (2)0.0402 (8)
C270.5960 (5)0.1720 (4)0.3634 (3)0.0488 (10)
C280.5045 (7)0.3895 (4)0.3499 (4)0.0806 (15)
H28A0.51860.39890.28420.121*
H28B0.59870.42130.40140.121*
H28C0.41230.43920.35180.121*
C290.9422 (6)−0.0656 (6)0.3808 (4)0.0864 (17)
H29A0.8828−0.04980.31060.130*
H29B0.9657−0.15740.39090.130*
H29C1.0411−0.01690.39890.130*
C300.9703 (5)−0.1321 (5)0.6318 (3)0.0742 (14)
H30A1.0313−0.11380.70130.111*
H30B1.0302−0.19070.60300.111*
H30C0.8697−0.17200.62930.111*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
S110.0494 (5)0.0530 (6)0.0502 (5)−0.0082 (6)0.0229 (4)−0.0054 (6)
O130.079 (2)0.082 (2)0.084 (2)0.0002 (16)0.0516 (19)−0.0212 (17)
O110.092 (3)0.0563 (18)0.157 (4)0.0362 (18)0.081 (3)0.038 (2)
O120.0624 (19)0.0402 (17)0.070 (2)−0.0011 (14)0.0241 (16)−0.0016 (13)
O140.0620 (18)0.0702 (18)0.0598 (17)−0.0278 (15)0.0230 (16)−0.0191 (14)
N110.0370 (16)0.0516 (18)0.0512 (17)−0.0085 (14)0.0165 (15)−0.0038 (12)
C110.045 (2)0.045 (2)0.041 (2)−0.0018 (19)0.0122 (18)−0.0017 (15)
C120.058 (3)0.041 (2)0.073 (3)−0.001 (2)0.023 (2)−0.007 (2)
C130.066 (3)0.056 (3)0.082 (4)0.012 (3)0.023 (3)−0.017 (2)
C140.050 (2)0.062 (3)0.058 (2)0.008 (2)0.024 (2)−0.010 (2)
C150.0497 (19)0.053 (2)0.054 (2)−0.003 (3)0.0241 (16)−0.002 (2)
C160.047 (2)0.042 (2)0.0415 (18)0.0067 (17)0.0166 (17)0.0016 (16)
C170.055 (3)0.050 (2)0.045 (2)0.013 (2)0.021 (2)0.0116 (18)
C180.091 (4)0.042 (2)0.087 (3)−0.002 (2)0.025 (3)0.010 (2)
C190.043 (2)0.106 (4)0.074 (3)−0.017 (2)0.018 (2)−0.035 (3)
C200.078 (4)0.077 (3)0.075 (3)−0.022 (3)0.013 (3)0.024 (3)
S210.0360 (5)0.0431 (5)0.0628 (5)−0.0009 (5)0.0111 (4)−0.0045 (6)
O210.071 (2)0.0638 (18)0.134 (3)−0.0058 (17)0.048 (2)0.026 (2)
O220.077 (2)0.0438 (17)0.080 (2)0.0108 (16)0.0350 (19)0.0115 (14)
O230.0614 (19)0.0662 (18)0.075 (2)0.0129 (16)0.0176 (16)−0.0248 (14)
O240.0447 (17)0.071 (2)0.107 (2)−0.0199 (14)0.0075 (17)−0.0016 (16)
N210.0432 (17)0.0425 (17)0.0579 (17)0.0006 (13)0.0240 (16)0.0025 (12)
C210.039 (2)0.041 (2)0.044 (2)−0.0028 (17)0.0205 (18)−0.0020 (15)
C220.059 (3)0.038 (2)0.048 (2)0.006 (2)0.014 (2)−0.0005 (16)
C230.054 (3)0.038 (2)0.065 (3)−0.006 (2)0.019 (2)−0.0047 (19)
C240.046 (2)0.058 (3)0.073 (3)−0.017 (2)0.017 (2)−0.009 (2)
C250.0394 (19)0.055 (3)0.059 (2)0.004 (2)0.0128 (17)0.003 (2)
C260.0406 (19)0.042 (2)0.0377 (16)−0.0059 (19)0.0124 (15)0.0013 (16)
C270.051 (3)0.047 (2)0.050 (2)−0.001 (2)0.020 (2)0.0028 (18)
C280.115 (4)0.041 (2)0.098 (3)0.012 (3)0.050 (3)0.015 (2)
C290.068 (3)0.109 (4)0.107 (4)−0.010 (3)0.061 (3)−0.026 (3)
C300.066 (3)0.080 (3)0.064 (3)0.007 (3)0.002 (2)0.014 (3)

Geometric parameters (Å, °)

S11—O131.412 (3)S21—O241.422 (3)
S11—O141.429 (3)S21—O231.424 (3)
S11—N111.609 (3)S21—N211.609 (3)
S11—C201.750 (4)S21—C301.748 (5)
O11—C171.166 (5)O21—C271.189 (4)
O12—C171.335 (5)O22—C271.320 (4)
O12—C181.446 (5)O22—C281.455 (5)
N11—C111.441 (5)N21—C211.435 (4)
N11—C191.450 (5)N21—C291.464 (5)
C11—C121.375 (5)C21—C261.388 (5)
C11—C161.398 (5)C21—C221.394 (5)
C12—C131.389 (6)C22—C231.364 (6)
C12—H120.9300C22—H220.9300
C13—C141.380 (6)C23—C241.363 (6)
C13—H130.9300C23—H230.9300
C14—C151.385 (6)C24—C251.383 (6)
C14—H140.9300C24—H240.9300
C15—C161.377 (5)C25—C261.399 (5)
C15—H150.9300C25—H250.9300
C16—C171.505 (5)C26—C271.495 (5)
C18—H18A0.9600C28—H28A0.9600
C18—H18B0.9600C28—H28B0.9600
C18—H18C0.9600C28—H28C0.9600
C19—H19A0.9600C29—H29A0.9600
C19—H19B0.9600C29—H29B0.9600
C19—H19C0.9600C29—H29C0.9600
C20—H20A0.9600C30—H30A0.9600
C20—H20B0.9600C30—H30B0.9600
C20—H20C0.9600C30—H30C0.9600
O13—S11—O14119.71 (18)O24—S21—O23120.1 (2)
O13—S11—N11107.81 (17)O24—S21—N21106.75 (18)
O14—S11—N11107.60 (15)O23—S21—N21107.73 (16)
O13—S11—C20106.9 (2)O24—S21—C30107.7 (2)
O14—S11—C20106.7 (2)O23—S21—C30106.6 (2)
N11—S11—C20107.6 (2)N21—S21—C30107.4 (2)
C17—O12—C18115.6 (3)C27—O22—C28115.4 (3)
C11—N11—C19118.7 (3)C21—N21—C29118.1 (3)
C11—N11—S11119.2 (2)C21—N21—S21118.3 (2)
C19—N11—S11120.5 (3)C29—N21—S21120.1 (3)
C12—C11—C16119.1 (4)C26—C21—C22120.2 (3)
C12—C11—N11118.8 (4)C26—C21—N21120.8 (3)
C16—C11—N11122.1 (3)C22—C21—N21119.0 (3)
C11—C12—C13121.4 (4)C23—C22—C21120.0 (4)
C11—C12—H12119.3C23—C22—H22120.0
C13—C12—H12119.3C21—C22—H22120.0
C14—C13—C12119.0 (4)C24—C23—C22120.8 (4)
C14—C13—H13120.5C24—C23—H23119.6
C12—C13—H13120.5C22—C23—H23119.6
C13—C14—C15120.1 (4)C23—C24—C25120.0 (4)
C13—C14—H14120.0C23—C24—H24120.0
C15—C14—H14120.0C25—C24—H24120.0
C16—C15—C14120.7 (4)C24—C25—C26120.5 (4)
C16—C15—H15119.7C24—C25—H25119.7
C14—C15—H15119.7C26—C25—H25119.7
C15—C16—C11119.6 (3)C21—C26—C25118.3 (4)
C15—C16—C17119.6 (4)C21—C26—C27121.8 (3)
C11—C16—C17120.5 (3)C25—C26—C27119.8 (4)
O11—C17—O12122.6 (4)O21—C27—O22124.2 (4)
O11—C17—C16127.2 (4)O21—C27—C26123.7 (4)
O12—C17—C16110.2 (3)O22—C27—C26111.7 (3)
O12—C18—H18A109.5O22—C28—H28A109.5
O12—C18—H18B109.5O22—C28—H28B109.5
H18A—C18—H18B109.5H28A—C28—H28B109.5
O12—C18—H18C109.5O22—C28—H28C109.5
H18A—C18—H18C109.5H28A—C28—H28C109.5
H18B—C18—H18C109.5H28B—C28—H28C109.5
N11—C19—H19A109.5N21—C29—H29A109.5
N11—C19—H19B109.5N21—C29—H29B109.5
H19A—C19—H19B109.5H29A—C29—H29B109.5
N11—C19—H19C109.5N21—C29—H29C109.5
H19A—C19—H19C109.5H29A—C29—H29C109.5
H19B—C19—H19C109.5H29B—C29—H29C109.5
S11—C20—H20A109.5S21—C30—H30A109.5
S11—C20—H20B109.5S21—C30—H30B109.5
H20A—C20—H20B109.5H30A—C30—H30B109.5
S11—C20—H20C109.5S21—C30—H30C109.5
H20A—C20—H20C109.5H30A—C30—H30C109.5
H20B—C20—H20C109.5H30B—C30—H30C109.5
O13—S11—N11—C11−164.2 (3)O24—S21—N21—C21−169.1 (3)
O14—S11—N11—C11−33.8 (3)O23—S21—N21—C21−38.9 (3)
C20—S11—N11—C1180.8 (3)C30—S21—N21—C2175.5 (3)
O13—S11—N11—C1930.1 (4)O24—S21—N21—C2932.8 (3)
O14—S11—N11—C19160.5 (3)O23—S21—N21—C29163.0 (3)
C20—S11—N11—C19−84.9 (4)C30—S21—N21—C29−82.6 (3)
C19—N11—C11—C1267.4 (5)C29—N21—C21—C26−111.5 (4)
S11—N11—C11—C12−98.6 (4)S21—N21—C21—C2689.9 (3)
C19—N11—C11—C16−112.7 (4)C29—N21—C21—C2269.5 (5)
S11—N11—C11—C1681.3 (4)S21—N21—C21—C22−89.1 (3)
C16—C11—C12—C13−0.8 (6)C26—C21—C22—C23−0.7 (6)
N11—C11—C12—C13179.1 (4)N21—C21—C22—C23178.3 (3)
C11—C12—C13—C14−2.5 (7)C21—C22—C23—C24−2.5 (7)
C12—C13—C14—C153.7 (7)C22—C23—C24—C252.7 (7)
C13—C14—C15—C16−1.7 (6)C23—C24—C25—C260.2 (6)
C14—C15—C16—C11−1.6 (5)C22—C21—C26—C253.5 (5)
C14—C15—C16—C17172.4 (3)N21—C21—C26—C25−175.5 (3)
C12—C11—C16—C152.8 (5)C22—C21—C26—C27−173.6 (3)
N11—C11—C16—C15−177.1 (3)N21—C21—C26—C277.4 (5)
C12—C11—C16—C17−171.1 (4)C24—C25—C26—C21−3.3 (5)
N11—C11—C16—C179.0 (5)C24—C25—C26—C27173.9 (4)
C18—O12—C17—O112.1 (6)C28—O22—C27—O21−5.3 (6)
C18—O12—C17—C16−176.3 (3)C28—O22—C27—C26−178.7 (4)
C15—C16—C17—O11−162.8 (4)C21—C26—C27—O2129.6 (6)
C11—C16—C17—O1111.2 (7)C25—C26—C27—O21−147.4 (4)
C15—C16—C17—O1215.5 (5)C21—C26—C27—O22−157.0 (3)
C11—C16—C17—O12−170.6 (3)C25—C26—C27—O2226.0 (5)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C13—H13···O14i0.932.583.248 (6)129
C20—H20C···O11ii0.962.293.240 (5)171
C22—H22···O24iii0.932.513.391 (5)159
C28—H28A···O13iv0.962.543.490 (6)169
C30—H30A···O14v0.962.553.512 (5)178
C30—H30B···O21iii0.962.423.181 (6)136

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: LH2905).

References

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