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Acta Crystallogr Sect E Struct Rep Online. 2008 July 1; 64(Pt 7): o1213–o1214.
Published online 2008 June 7. doi:  10.1107/S160053680801670X
PMCID: PMC2961640

N-Butyl-4-hydr­oxy-2-methyl-2H-1,2-benzothia­zine-3-carboxamide 1,1-dioxide

Abstract

The title compound, C14H18N2O4S, contains hydrogen-bonded dimeric pairs of mol­ecules arranged around inversion centers, forming 14-membered rings with an R 2 2(14) motif. The structure is stabilized by extensive intra­molecular inter­actions. The thia­zine ring adopts a half-chair conformation, with the S and N atoms displaced by −0.485 (3) and 0.296 (3) Å, respectively, from the plane formed by the remaining atoms of the ring.

Related literature

For related literature, see: Ahmad, Siddiqui, Ahmad et al. (2008 [triangle]); Ahmad, Siddiqui, Zia-ur-Rehman et al. (2008 [triangle]); Bernstein et al. (1994 [triangle]); Gupta et al. (1993 [triangle], 2002 [triangle]); Kojić-Prodić & Rużić-Toroš (1982 [triangle]); Lombardino (1971 [triangle]); Lombardino & Wiseman (1972 [triangle]); Rehman et al. (2005 [triangle], 2006 [triangle]); Sianesi et al. (1973 [triangle]); Siddiqui et al. (2008 [triangle]); Zinnes et al. (1982 [triangle]); Drebushchak et al. (2006 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-64-o1213-scheme1.jpg

Experimental

Crystal data

  • C14H18N2O4S
  • M r = 310.36
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-o1213-efi1.jpg
  • a = 10.233 (2) Å
  • b = 14.780 (4) Å
  • c = 10.365 (5) Å
  • β = 108.79 (2)°
  • V = 1484.1 (9) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.23 mm−1
  • T = 173 (2) K
  • 0.14 × 0.12 × 0.06 mm

Data collection

  • Nonius KappaCCD diffractometer
  • Absorption correction: multi-scan (SORTAV; Blessing, 1997 [triangle]) T min = 0.968, T max = 0.986
  • 12380 measured reflections
  • 3405 independent reflections
  • 2646 reflections with I > 2σ(I)
  • R int = 0.041

Refinement

  • R[F 2 > 2σ(F 2)] = 0.039
  • wR(F 2) = 0.100
  • S = 1.03
  • 3405 reflections
  • 198 parameters
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.30 e Å−3
  • Δρmin = −0.43 e Å−3

Data collection: COLLECT (Hooft, 1998 [triangle]); cell refinement: HKL DENZO (Otwinowski & Minor, 1997 [triangle]); data reduction: SCALEPACK (Otwinowski & Minor, 1997 [triangle]); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 [triangle]); software used to prepare material for publication: SHELXL97.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks Global, I. DOI: 10.1107/S160053680801670X/bh2176sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S160053680801670X/bh2176Isup2.hkl

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

supplementary crystallographic information

Comment

Several benzothiazine derivatives like piroxicam, sudoxicam (Lombardino & Wiseman, 1972; Rehman et al., 2005) and isoxicam (Zinnes et al., 1982) have been reported in the literature to be potential anti-inflammatory agents. Some of the derivatives of benzothiazines are found to be analgesic (Gupta et al., 2002), anti-cancer (Gupta et al., 1993) and exhibitors of central nervous system activity (Sianesi et al., 1973). We have reported anti-bacterial activities (Rehman et al., 2006) of a series of 1,2-benzothiazines. In continuation of our work on 1,2-benzothiazines 1,1-dioxides (Ahmad, Siddiqui, Ahmad, Irfan Ashiq & Tizzard, 2008; Ahmad, Siddiqui, Zia-ur-Rehman, Ashiq & Tizzard, 2008), we report in this paper the crystal structure of the title compound, (I), which was patented for Pfizer Inc. (Lombardino, 1971).

The structure of (I), (Fig. 1), contains dimeric pairs of molecules lying about inversion centers resulting from N2—H2N···O2 hydrogen bonds (Fig. 2). The 14-membered rings thus formed represent R22(14) motif in the graph set notation (Bernstein et al., 1994). Similar hydrogen-bonded dimers have been reported in structures related to the title compound (Siddiqui et al., 2008; Drebushchak et al., 2006; Kojić-Prodić & Rużić-Toroš, 1982). The structure is stabilized by extensive intramolecular interactions (Fig. 1 and Table 1). The thiazine ring in (I) adopts a half-chair conformation with atoms S1 and N1 displaced by -0.485 (3) and 0.296 (3) Å, respectively, from the plane formed by the remaining atoms of the ring.

Experimental

Methyl-4-hydroxy-2-methyl-2H-1,2-benzothiazine-3-carboxylate-1,1-dioxide (1.0 g, 3.72 mmoles) was dissolved in n-butyl amine (5 ml) in a test tube. The mixture was placed at room temperature for 7 days. Crystals of (I) suitable for crystallographic analysis were found, which were washed with MeOH.

Refinement

Though all the H atoms could be found in a difference map, the H atoms bonded to C atoms were included at geometrically idealized positions and refined in riding-model approximation with the following constraints: C—H distances were set to 0.95, 0.98 and 0.99 Å for aryl, methyl and methylene H atoms, respectively, and Uiso(H) = 1.2Ueq(C). H atoms bonded to N2 and O3 were taken from a difference map and were allowed to refine with Uiso = 1.2 times Ueq of the parent atom. The final difference map was free of any chemically significant features.

Figures

Fig. 1.
ORTEP-3 (Farrugia, 1997) drawing of (I) with displacement ellipsoids plotted at 50% probability level; intramolecular interactions have been indicated by dashed lines.
Fig. 2.
Unit cell packing of (I) showing hydrogen bonds with dashed lines; H atoms not involved in hydrogen bonds have been omitted.

Crystal data

C14H18N2O4SF000 = 656
Mr = 310.36Dx = 1.389 Mg m3
Monoclinic, P21/cMo Kα radiation λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 12380 reflections
a = 10.233 (2) Åθ = 3.4–27.6º
b = 14.780 (4) ŵ = 0.24 mm1
c = 10.365 (5) ÅT = 173 (2) K
β = 108.79 (2)ºPrism, colorless
V = 1484.1 (9) Å30.14 × 0.12 × 0.06 mm
Z = 4

Data collection

Nonius KappaCCD diffractometer3405 independent reflections
Radiation source: fine-focus sealed tube2646 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.041
T = 173(2) Kθmax = 27.6º
ω and [var phi] scansθmin = 3.4º
Absorption correction: Multi-scan(SORTAV; Blessing, 1997)h = −13→13
Tmin = 0.968, Tmax = 0.986k = −19→19
12380 measured reflectionsl = −13→13

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.039H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.100  w = 1/[σ2(Fo2) + (0.045P)2 + 0.606P] where P = (Fo2 + 2Fc2)/3
S = 1.03(Δ/σ)max = 0.001
3405 reflectionsΔρmax = 0.30 e Å3
198 parametersΔρmin = −0.43 e Å3
Primary atom site location: structure-invariant direct methodsExtinction correction: none

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

xyzUiso*/Ueq
S10.53051 (4)0.13868 (3)0.96872 (5)0.03033 (13)
O10.45310 (12)0.12905 (9)0.82760 (14)0.0384 (3)
O20.46724 (13)0.11547 (9)1.06916 (15)0.0400 (3)
O30.86081 (13)0.22923 (9)0.83438 (13)0.0336 (3)
H3O0.899 (2)0.1799 (16)0.816 (2)0.050*
O40.92527 (12)0.06200 (9)0.82242 (13)0.0356 (3)
N10.67274 (13)0.07980 (9)0.99855 (14)0.0265 (3)
N20.78434 (15)−0.04424 (10)0.86553 (16)0.0327 (3)
H2N0.714 (2)−0.0525 (14)0.894 (2)0.039*
C10.59359 (17)0.24980 (11)0.99677 (17)0.0283 (4)
C20.53309 (18)0.31325 (12)1.05849 (19)0.0342 (4)
H20.45870.29671.08970.041*
C30.58309 (19)0.40116 (12)1.07376 (19)0.0359 (4)
H30.54300.44551.11590.043*
C40.69144 (19)0.42436 (12)1.02763 (18)0.0349 (4)
H40.72350.48511.03630.042*
C50.75381 (17)0.36033 (12)0.96906 (18)0.0309 (4)
H50.82890.37720.93920.037*
C60.70664 (17)0.27103 (11)0.95385 (17)0.0276 (4)
C70.77716 (16)0.19970 (12)0.90287 (17)0.0272 (4)
C80.76003 (16)0.11021 (12)0.92283 (17)0.0269 (4)
C90.74832 (19)0.05636 (13)1.14249 (18)0.0355 (4)
H9A0.82060.01211.14570.043*
H9B0.68390.03051.18480.043*
H9C0.79050.11101.19210.043*
C100.82934 (17)0.04054 (12)0.86719 (17)0.0288 (4)
C110.8470 (2)−0.12047 (12)0.8176 (2)0.0385 (4)
H11A0.9478−0.11070.84300.046*
H11B0.8091−0.12380.71700.046*
C120.82004 (18)−0.20820 (12)0.8775 (2)0.0335 (4)
H12A0.7192−0.21890.84860.040*
H12B0.8537−0.20340.97810.040*
C130.88952 (19)−0.28900 (12)0.83487 (19)0.0339 (4)
H13A0.8496−0.29750.73510.041*
H13B0.9892−0.27610.85620.041*
C140.8724 (2)−0.37560 (13)0.9058 (2)0.0405 (5)
H14A0.9237−0.42450.87990.049*
H14B0.7743−0.39160.87870.049*
H14C0.9079−0.36681.00480.049*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
S10.0252 (2)0.0286 (2)0.0417 (3)−0.00243 (16)0.01704 (18)−0.00165 (18)
O10.0263 (6)0.0414 (8)0.0450 (8)−0.0039 (5)0.0078 (5)−0.0038 (6)
O20.0400 (7)0.0340 (7)0.0597 (9)−0.0031 (5)0.0352 (7)−0.0005 (6)
O30.0347 (7)0.0328 (7)0.0411 (7)−0.0041 (5)0.0232 (6)0.0015 (6)
O40.0316 (6)0.0379 (7)0.0455 (8)−0.0004 (5)0.0239 (6)0.0008 (6)
N10.0267 (7)0.0273 (7)0.0306 (8)−0.0003 (5)0.0160 (6)0.0018 (6)
N20.0306 (8)0.0311 (8)0.0433 (9)−0.0001 (6)0.0215 (7)−0.0031 (7)
C10.0269 (8)0.0267 (8)0.0330 (9)0.0003 (6)0.0121 (7)0.0023 (7)
C20.0317 (9)0.0342 (10)0.0404 (10)0.0042 (7)0.0167 (8)0.0028 (8)
C30.0400 (10)0.0296 (9)0.0393 (10)0.0073 (8)0.0142 (8)0.0019 (8)
C40.0407 (10)0.0269 (9)0.0353 (10)−0.0007 (7)0.0097 (8)0.0024 (7)
C50.0306 (9)0.0309 (9)0.0315 (9)−0.0027 (7)0.0104 (7)0.0040 (7)
C60.0255 (8)0.0307 (9)0.0267 (8)−0.0011 (7)0.0087 (7)0.0019 (7)
C70.0229 (8)0.0338 (9)0.0264 (8)−0.0028 (6)0.0098 (7)0.0014 (7)
C80.0234 (8)0.0318 (9)0.0282 (9)−0.0018 (6)0.0122 (7)0.0008 (7)
C90.0385 (10)0.0390 (10)0.0331 (10)−0.0019 (8)0.0171 (8)0.0021 (8)
C100.0245 (8)0.0345 (9)0.0290 (9)0.0006 (7)0.0107 (7)0.0003 (7)
C110.0432 (10)0.0326 (10)0.0502 (12)0.0037 (8)0.0294 (9)−0.0028 (8)
C120.0324 (9)0.0340 (10)0.0398 (10)0.0013 (7)0.0194 (8)−0.0026 (8)
C130.0329 (9)0.0348 (10)0.0367 (10)0.0015 (7)0.0152 (8)−0.0036 (8)
C140.0365 (10)0.0356 (10)0.0486 (12)−0.0003 (8)0.0128 (9)−0.0003 (9)

Geometric parameters (Å, °)

S1—O11.4286 (15)C5—C61.397 (2)
S1—O21.4335 (14)C5—H50.9500
S1—N11.6375 (14)C6—C71.469 (2)
S1—C11.7543 (18)C7—C81.359 (2)
O3—C71.349 (2)C8—C101.470 (2)
O3—H3O0.88 (2)C9—H9A0.9800
O4—C101.254 (2)C9—H9B0.9800
N1—C81.438 (2)C9—H9C0.9800
N1—C91.484 (2)C11—C121.501 (3)
N2—C101.333 (2)C11—H11A0.9900
N2—C111.460 (2)C11—H11B0.9900
N2—H2N0.87 (2)C12—C131.526 (2)
C1—C21.388 (2)C12—H12A0.9900
C1—C61.402 (2)C12—H12B0.9900
C2—C31.387 (3)C13—C141.514 (3)
C2—H20.9500C13—H13A0.9900
C3—C41.385 (3)C13—H13B0.9900
C3—H30.9500C14—H14A0.9800
C4—C51.386 (3)C14—H14B0.9800
C4—H40.9500C14—H14C0.9800
O1—S1—O2119.25 (9)C7—C8—C10121.34 (15)
O1—S1—N1107.84 (8)N1—C8—C10117.28 (14)
O2—S1—N1108.51 (8)N1—C9—H9A109.5
O1—S1—C1108.42 (8)N1—C9—H9B109.5
O2—S1—C1109.38 (8)H9A—C9—H9B109.5
N1—S1—C1102.07 (8)N1—C9—H9C109.5
C7—O3—H3O104.4 (15)H9A—C9—H9C109.5
C8—N1—C9114.06 (13)H9B—C9—H9C109.5
C8—N1—S1113.67 (11)O4—C10—N2122.76 (16)
C9—N1—S1117.24 (11)O4—C10—C8120.15 (15)
C10—N2—C11122.83 (15)N2—C10—C8117.08 (15)
C10—N2—H2N116.6 (14)N2—C11—C12111.55 (15)
C11—N2—H2N120.6 (14)N2—C11—H11A109.3
C2—C1—C6122.08 (16)C12—C11—H11A109.3
C2—C1—S1120.92 (13)N2—C11—H11B109.3
C6—C1—S1117.00 (13)C12—C11—H11B109.3
C3—C2—C1118.85 (16)H11A—C11—H11B108.0
C3—C2—H2120.6C11—C12—C13113.08 (14)
C1—C2—H2120.6C11—C12—H12A109.0
C4—C3—C2119.98 (17)C13—C12—H12A109.0
C4—C3—H3120.0C11—C12—H12B109.0
C2—C3—H3120.0C13—C12—H12B109.0
C3—C4—C5121.00 (17)H12A—C12—H12B107.8
C3—C4—H4119.5C14—C13—C12112.53 (15)
C5—C4—H4119.5C14—C13—H13A109.1
C4—C5—C6120.23 (16)C12—C13—H13A109.1
C4—C5—H5119.9C14—C13—H13B109.1
C6—C5—H5119.9C12—C13—H13B109.1
C5—C6—C1117.78 (16)H13A—C13—H13B107.8
C5—C6—C7121.80 (15)C13—C14—H14A109.5
C1—C6—C7120.31 (15)C13—C14—H14B109.5
O3—C7—C8122.01 (15)H14A—C14—H14B109.5
O3—C7—C6115.20 (15)C13—C14—H14C109.5
C8—C7—C6122.79 (15)H14A—C14—H14C109.5
C7—C8—N1121.38 (14)H14B—C14—H14C109.5
O1—S1—N1—C861.67 (13)S1—C1—C6—C7−6.9 (2)
O2—S1—N1—C8−167.86 (11)C5—C6—C7—O3−19.3 (2)
C1—S1—N1—C8−52.42 (13)C1—C6—C7—O3164.56 (15)
O1—S1—N1—C9−161.75 (12)C5—C6—C7—C8160.65 (16)
O2—S1—N1—C9−31.28 (14)C1—C6—C7—C8−15.5 (2)
C1—S1—N1—C984.16 (13)O3—C7—C8—N1178.67 (14)
O1—S1—C1—C2103.81 (15)C6—C7—C8—N1−1.3 (2)
O2—S1—C1—C2−27.73 (17)O3—C7—C8—C10−1.7 (3)
N1—S1—C1—C2−142.53 (15)C6—C7—C8—C10178.33 (15)
O1—S1—C1—C6−76.03 (15)C9—N1—C8—C7−98.65 (19)
O2—S1—C1—C6152.43 (13)S1—N1—C8—C739.3 (2)
N1—S1—C1—C637.63 (15)C9—N1—C8—C1081.71 (18)
C6—C1—C2—C32.3 (3)S1—N1—C8—C10−140.30 (13)
S1—C1—C2—C3−177.53 (14)C11—N2—C10—O43.1 (3)
C1—C2—C3—C40.1 (3)C11—N2—C10—C8−177.77 (16)
C2—C3—C4—C5−1.7 (3)C7—C8—C10—O413.4 (3)
C3—C4—C5—C60.9 (3)N1—C8—C10—O4−166.94 (15)
C4—C5—C6—C11.4 (2)C7—C8—C10—N2−165.76 (16)
C4—C5—C6—C7−174.82 (16)N1—C8—C10—N213.9 (2)
C2—C1—C6—C5−3.0 (3)C10—N2—C11—C12156.43 (17)
S1—C1—C6—C5176.82 (13)N2—C11—C12—C13−177.35 (16)
C2—C1—C6—C7173.25 (16)C11—C12—C13—C14174.83 (17)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O3—H3O···O40.88 (2)1.76 (2)2.572 (2)153 (2)
N2—H2N···O2i0.87 (2)2.21 (2)3.052 (2)161 (2)
N2—H2N···N10.87 (2)2.34 (2)2.753 (2)109 (2)
C9—H9B···O20.982.492.864 (2)102

Symmetry codes: (i) −x+1, −y, −z+2.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: BH2176).

References

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