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Acta Cryst. (2009). E65, o2998    [ doi:10.1107/S1600536809046029 ]

4-Hydroxy-N-(2,4,6-tribromophenyl)-2H-1,2-benzothiazine-3-carboxamide 1,1-dioxide

M. N. Arshad, M. Zia-ur-Rehman, I. U. Khan and M. Shafiq

Abstract top

In the title compound, C15H19Br3N2O4S, the thiazine ring adopts a distorted half-chair conformation. The enolic H atom is involved in an intramolecular O-H...O hydrogen bond, forming a six-membered ring. In the crystal, the molecules are linked into a three-dimensional network through intermolecular N-H...O, N-H...Br and O-H...Br hydrogen bonds.

Comment top

Owing to the applications of 1,2-benzothiazine 1,1-dioxides and their precursor intermediates as non-steroidal anti-inflammatory compounds (Turck et al., 1996), considerable attention has been given to their synthesis. As part of a research program synthesizing 1,2-benzothiazines (Zia-ur-Rehman et al., 2005), we herein report the crystal structure of the title compound, (I) (Scheme and figure 1).

The thiazine ring, involving two double bonds, exhibits a sofa conformation; with S1/C1/C6/C7 relatively planar and N1 showing significant departure from plane due to its pyramidal geometry. The enolic hydrogen on O4 is involved in intramolecular hydrogen bonding [O4—H4···O3] with the carbonyl oxygen at C9 giving rise to a six-membered hydrogen bond ring (Table 1). The C1—S1 [1.757 (5) Å] bond is shorter than a normal C—S single bond (1.81–2.55 Å) (Weast et al., 1984) due to partial double bond character and is in agreement with similar molecules (Kojić-Prodić & Rużić-Toroš, 1982). Each molecule is linked to its adjacent one through intermolecular N—H···Br forming a centrosymmetric dimer which is further linked to the next via O—H···Br hydrogen bonds giving rise to a zigzag chain along b (Figure 2). The title molecules are also linked to each other via N—H···O hydrogen bonds forming dimers along b which furthr links to the adjacent dimer through O—H···Br hydrogen bonds giving rise to a zigzag chain along b (Figure 3).

Related literature top

For the synthesis of related molecules, see: Kojić-Prodić & Rużić-Toroš (1982); Zia-ur-Rehman, Choudary & Ahmad (2005). For the applications of 1,2-benzothiazine 1,1-dioxides and their precursor intermediates as non-steroidal anti-inflammatory compounds, see: Turck et al. (1996). For bond-length data, see: Weast et al. (1984).

Experimental top

A mixture of methyl 4-hydroxy-2H-1,2-benzothiazine-3-carboxylate-1,1-dioxide (2.55 g; 10.0 mmoles), 2,3-dimethyl aniline (4.947 g; 15.0 mmoles) and xylene (25.0 ml) was refluxed under nitrogen atmosphere in a Soxhlet apparatus having Linde type 4Å molecular sieves. Three fourth of the xylene was then distilled off and the remaining contents were allowed to stand overnight at room temperature. Settled solids were filtered off, washed with diethyl ether and crystallized from ethanol. Yield: 82%.

Refinement top

All hydrogen atoms were identified in the difference map and subsequently fixed in ideal positions and treated as riding on their parent atoms. In the case of the methyl and hydroxyl H atoms the torsion angles were freely refined. The following distances were used: methyl C—H = 0.98Å, aromatic C—H = 0.95Å, hydroxyl O—H = 0.84Å. U(H) was set to 1.2Ueq of the parent atoms or 1.5Ueq for methyl groups.

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009) and Mercury (Macrae et al., 2006); software used to prepare material for publication: PLATON (Spek, 2009).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound, with displacement ellipsoids at the 50% probability level.
[Figure 2] Fig. 2. Perspective view of the three-dimensional crystal packing showing N—H···Br and O—H···Br hydrogen-bonded interactions (dashed lines). H atoms not involved in hydrogen bonding have been omitted for clarity.
[Figure 3] Fig. 3. Another perspective view of the three-dimensional crystal packing showing N—H···O and O—H···Br hydrogen-bonded interactions (dashed lines). H atoms not involved in hydrogen bonding have been omitted for clarity.
4-Hydroxy-N-(2,4,6-tribromophenyl)-2H-1,2-benzothiazine-3- carboxamide 1,1-dioxide top
Crystal data top
C15H9Br3N2O4SZ = 2
Mr = 553.03F(000) = 532
Triclinic, P1Dx = 2.159 Mg m−3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 7.5082 (4) ÅCell parameters from 5092 reflections
b = 8.7486 (6) Åθ = 2.3–24.2°
c = 13.0669 (9) ŵ = 7.26 mm−1
α = 83.618 (2)°T = 296 K
β = 86.280 (2)°Needle, light yellow
γ = 87.684 (2)°0.18 × 0.16 × 0.11 mm
V = 850.72 (9) Å3
Data collection top
Bruker APEXII CCD area-detector
diffractometer		3794 independent reflections
Radiation source: fine-focus sealed tube2599 reflections with I > 2σ(I)
graphiteRint = 0.031
φ and ω scansθmax = 27.6°, θmin = 1.6°
Absorption correction: multi-scan
(SADABS; Sheldrick, 2007)		h = −9→9
Tmin = 0.355, Tmax = 0.502k = −11→11
16515 measured reflectionsl = −16→16
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.043Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.116H-atom parameters constrained
S = 1.01 w = 1/[σ2(Fo2) + (0.049P)2 + 2.0189P]
where P = (Fo2 + 2Fc2)/3
3794 reflections(Δ/σ)max < 0.001
227 parametersΔρmax = 1.16 e Å−3
0 restraintsΔρmin = −0.63 e Å−3
Crystal data top
C15H9Br3N2O4Sγ = 87.684 (2)°
Mr = 553.03V = 850.72 (9) Å3
Triclinic, P1Z = 2
a = 7.5082 (4) ÅMo Kα radiation
b = 8.7486 (6) ŵ = 7.26 mm−1
c = 13.0669 (9) ÅT = 296 K
α = 83.618 (2)°0.18 × 0.16 × 0.11 mm
β = 86.280 (2)°
Data collection top
Bruker APEXII CCD area-detector
diffractometer		3794 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2007)		2599 reflections with I > 2σ(I)
Tmin = 0.355, Tmax = 0.502Rint = 0.031
16515 measured reflectionsθmax = 27.6°
Refinement top
R[F2 > 2σ(F2)] = 0.043H-atom parameters constrained
wR(F2) = 0.116Δρmax = 1.16 e Å−3
S = 1.01Δρmin = −0.63 e Å−3
3794 reflectionsAbsolute structure: ?
227 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
Special details top

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 (Å2) top
xyzUiso*/Ueq
Br10.82014 (8)0.13368 (9)0.54929 (5)0.0701 (2)
Br20.30934 (9)0.34516 (6)0.26785 (4)0.0603 (2)
Br30.17498 (9)0.43843 (7)0.68227 (5)0.0629 (2)
C10.8054 (6)0.2197 (6)1.0575 (4)0.0373 (11)
C20.8789 (7)0.2424 (6)1.1475 (4)0.0462 (12)
H20.90240.34121.16170.055*
C30.9184 (8)0.1144 (8)1.2182 (5)0.0591 (15)
H30.96410.12861.28080.071*
C40.8905 (7)−0.0287 (8)1.1956 (5)0.0625 (17)
H4A0.9211−0.11271.24190.075*
C50.8152 (6)−0.0538 (6)1.1026 (4)0.0454 (12)
H50.7971−0.15331.08780.055*
C60.7687 (6)0.0711 (5)1.0339 (4)0.0360 (10)
C70.6899 (6)0.0507 (5)0.9372 (4)0.0364 (10)
C80.6194 (6)0.1678 (5)0.8750 (4)0.0354 (10)
C90.5696 (6)0.1459 (6)0.7707 (4)0.0382 (11)
C100.4863 (6)0.2808 (5)0.6055 (4)0.0361 (10)
C110.5909 (6)0.2214 (5)0.5271 (4)0.0392 (11)
C120.5352 (7)0.2323 (6)0.4267 (4)0.0430 (12)
H120.60340.18740.37530.052*
C130.3776 (7)0.3105 (5)0.4054 (4)0.0383 (11)
C140.2718 (7)0.3729 (5)0.4799 (4)0.0421 (12)
H140.16550.42590.46380.050*
C150.3259 (6)0.3557 (5)0.5797 (4)0.0401 (11)
N10.6041 (5)0.3207 (4)0.9051 (3)0.0383 (9)
H10.51180.37980.89310.046*
N20.5404 (6)0.2763 (5)0.7070 (3)0.0430 (10)
H2A0.55600.36270.73030.052*
O20.9238 (5)0.3836 (4)0.8929 (3)0.0500 (9)
O30.5570 (5)0.0166 (4)0.7438 (3)0.0492 (9)
O40.6955 (5)−0.0922 (4)0.9118 (3)0.0470 (9)
H40.6471−0.09400.85750.070*
O1A0.7151 (5)0.5147 (4)1.0094 (3)0.0481 (9)
S10.77172 (16)0.37606 (13)0.96331 (10)0.0381 (3)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Br10.0467 (3)0.1064 (6)0.0550 (4)0.0271 (3)−0.0078 (3)−0.0070 (3)
Br20.0949 (5)0.0455 (3)0.0440 (3)0.0073 (3)−0.0311 (3)−0.0082 (2)
Br30.0685 (4)0.0635 (4)0.0548 (4)0.0185 (3)0.0116 (3)−0.0145 (3)
C10.032 (2)0.046 (3)0.034 (3)0.0044 (19)−0.0033 (19)−0.005 (2)
C20.048 (3)0.052 (3)0.041 (3)−0.002 (2)−0.008 (2)−0.011 (2)
C30.051 (3)0.085 (5)0.044 (3)−0.008 (3)−0.007 (3)−0.018 (3)
C40.043 (3)0.067 (4)0.070 (4)−0.005 (3)−0.004 (3)0.024 (3)
C50.038 (3)0.050 (3)0.047 (3)−0.003 (2)−0.003 (2)0.005 (2)
C60.029 (2)0.042 (3)0.037 (3)0.0009 (19)0.0021 (19)−0.006 (2)
C70.035 (2)0.037 (3)0.038 (3)0.0014 (19)0.002 (2)−0.007 (2)
C80.036 (2)0.037 (3)0.035 (3)0.0008 (19)−0.0050 (19)−0.013 (2)
C90.039 (3)0.041 (3)0.035 (3)0.003 (2)−0.004 (2)−0.009 (2)
C100.043 (3)0.034 (2)0.033 (3)−0.002 (2)−0.007 (2)−0.006 (2)
C110.043 (3)0.038 (3)0.037 (3)0.004 (2)−0.007 (2)−0.005 (2)
C120.050 (3)0.042 (3)0.038 (3)0.003 (2)0.002 (2)−0.010 (2)
C130.047 (3)0.030 (2)0.039 (3)−0.001 (2)−0.011 (2)−0.006 (2)
C140.044 (3)0.037 (3)0.046 (3)0.005 (2)−0.010 (2)−0.004 (2)
C150.043 (3)0.035 (3)0.042 (3)0.000 (2)0.005 (2)−0.009 (2)
N10.040 (2)0.037 (2)0.041 (2)0.0094 (17)−0.0127 (17)−0.0113 (18)
N20.062 (3)0.036 (2)0.033 (2)0.0022 (19)−0.0145 (19)−0.0089 (18)
O20.048 (2)0.050 (2)0.050 (2)0.0003 (16)0.0008 (17)0.0019 (17)
O30.067 (2)0.041 (2)0.042 (2)−0.0016 (17)−0.0091 (17)−0.0152 (17)
O40.056 (2)0.041 (2)0.047 (2)−0.0037 (16)0.0011 (17)−0.0202 (16)
O1A0.053 (2)0.045 (2)0.052 (2)0.0170 (16)−0.0234 (17)−0.0265 (17)
S10.0404 (6)0.0357 (6)0.0399 (7)0.0042 (5)−0.0088 (5)−0.0094 (5)
Geometric parameters (Å, °) top
Br1—C111.882 (5)C8—C91.471 (6)
Br2—C131.890 (5)C9—O31.230 (6)
Br3—C151.886 (5)C9—N21.355 (6)
C1—C21.368 (7)C10—C111.385 (7)
C1—C61.411 (7)C10—C151.391 (7)
C1—S11.757 (5)C10—N21.408 (6)
C2—C31.405 (8)C11—C121.395 (7)
C2—H20.9300C12—C131.371 (7)
C3—C41.345 (9)C12—H120.9300
C3—H30.9300C13—C141.363 (7)
C4—C51.415 (8)C14—C151.381 (7)
C4—H4A0.9300C14—H140.9300
C5—C61.383 (7)N1—S11.628 (4)
C5—H50.9300N1—H10.8600
C6—C71.461 (7)N2—H2A0.8600
C7—O41.328 (5)O2—S11.418 (4)
C7—C81.348 (7)O4—H40.8200
C8—N11.435 (6)O1A—S11.450 (3)
C2—C1—C6121.6 (5)C15—C10—N2119.5 (4)
C2—C1—S1119.9 (4)C10—C11—C12121.3 (4)
C6—C1—S1118.2 (4)C10—C11—Br1121.5 (4)
C1—C2—C3119.1 (5)C12—C11—Br1117.1 (4)
C1—C2—H2120.4C13—C12—C11118.6 (4)
C3—C2—H2120.4C13—C12—H12120.7
C4—C3—C2120.2 (6)C11—C12—H12120.7
C4—C3—H3119.9C14—C13—C12122.0 (5)
C2—C3—H3119.9C14—C13—Br2118.1 (4)
C3—C4—C5121.2 (6)C12—C13—Br2119.8 (4)
C3—C4—H4A119.4C13—C14—C15118.5 (4)
C5—C4—H4A119.4C13—C14—H14120.7
C6—C5—C4119.4 (5)C15—C14—H14120.7
C6—C5—H5120.3C14—C15—C10122.1 (4)
C4—C5—H5120.3C14—C15—Br3117.9 (4)
C5—C6—C1118.3 (5)C10—C15—Br3120.0 (4)
C5—C6—C7121.3 (5)C8—N1—S1116.2 (3)
C1—C6—C7120.4 (4)C8—N1—H1121.9
O4—C7—C8120.9 (4)S1—N1—H1121.9
O4—C7—C6115.6 (4)C9—N2—C10124.8 (4)
C8—C7—C6123.4 (4)C9—N2—H2A117.6
C7—C8—N1120.9 (4)C10—N2—H2A117.6
C7—C8—C9121.2 (4)C7—O4—H4109.5
N1—C8—C9117.7 (4)O2—S1—O1A117.6 (2)
O3—C9—N2122.8 (4)O2—S1—N1108.5 (2)
O3—C9—C8121.5 (4)O1A—S1—N1107.9 (2)
N2—C9—C8115.8 (4)O2—S1—C1108.0 (2)
C11—C10—C15117.4 (4)O1A—S1—C1111.6 (2)
C11—C10—N2123.0 (4)N1—S1—C1101.9 (2)
C6—C1—C2—C3−0.1 (7)C10—C11—C12—C133.3 (7)
S1—C1—C2—C3−174.8 (4)Br1—C11—C12—C13−172.9 (4)
C1—C2—C3—C42.5 (8)C11—C12—C13—C14−2.3 (8)
C2—C3—C4—C5−2.3 (9)C11—C12—C13—Br2173.8 (4)
C3—C4—C5—C6−0.3 (8)C12—C13—C14—C15−0.2 (8)
C4—C5—C6—C12.6 (7)Br2—C13—C14—C15−176.4 (4)
C4—C5—C6—C7−179.7 (5)C13—C14—C15—C101.8 (7)
C2—C1—C6—C5−2.4 (7)C13—C14—C15—Br3−178.5 (4)
S1—C1—C6—C5172.3 (3)C11—C10—C15—C14−0.8 (7)
C2—C1—C6—C7179.9 (4)N2—C10—C15—C14175.5 (4)
S1—C1—C6—C7−5.3 (6)C11—C10—C15—Br3179.5 (4)
C5—C6—C7—O4−11.4 (6)N2—C10—C15—Br3−4.2 (6)
C1—C6—C7—O4166.2 (4)C7—C8—N1—S140.0 (6)
C5—C6—C7—C8170.3 (5)C9—C8—N1—S1−135.0 (4)
C1—C6—C7—C8−12.1 (7)O3—C9—N2—C102.5 (7)
O4—C7—C8—N1176.5 (4)C8—C9—N2—C10−178.0 (4)
C6—C7—C8—N1−5.3 (7)C11—C10—N2—C9−64.1 (7)
O4—C7—C8—C9−8.7 (7)C15—C10—N2—C9119.8 (5)
C6—C7—C8—C9169.5 (4)C8—N1—S1—O265.2 (4)
C7—C8—C9—O314.5 (7)C8—N1—S1—O1A−166.3 (3)
N1—C8—C9—O3−170.5 (4)C8—N1—S1—C1−48.6 (4)
C7—C8—C9—N2−165.0 (4)C2—C1—S1—O293.0 (4)
N1—C8—C9—N210.0 (6)C6—C1—S1—O2−81.8 (4)
C15—C10—C11—C12−1.8 (7)C2—C1—S1—O1A−37.8 (5)
N2—C10—C11—C12−178.0 (5)C6—C1—S1—O1A147.4 (4)
C15—C10—C11—Br1174.3 (4)C2—C1—S1—N1−152.7 (4)
N2—C10—C11—Br1−1.9 (7)C6—C1—S1—N132.4 (4)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O4—H4···O30.821.832.561 (5)147
N1—H1···O1Ai0.862.292.966 (5)136
N2—H2A···Br2ii0.862.793.597 (4)157
O4—H4···Br2iii0.822.883.403 (3)124
Symmetry codes: (i) −x+1, −y+1, −z+2; (ii) −x+1, −y+1, −z+1; (iii) −x+1, −y, −z+1.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O4—H4···O30.821.832.561 (5)147
N1—H1···O1Ai0.862.292.966 (5)136
N2—H2A···Br2ii0.862.793.597 (4)157
O4—H4···Br2iii0.822.883.403 (3)124
Symmetry codes: (i) −x+1, −y+1, −z+2; (ii) −x+1, −y+1, −z+1; (iii) −x+1, −y, −z+1.
Acknowledgements top

The authors are grateful to the Higher Education Commission of Pakistan for a grant.

references
References top

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