4-Hy­droxy-2-methyl-1,1-dioxo-2H-1λ6,2- benzothia­zine-3-carb­oxy­lic acid hemihydrate

Aman, F.; Siddiqui, W.A.; Ashraf, A.; Tahir, M.N.

doi:10.1107/S1600536812004291

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 68| Part 3| March 2012| Pages o621-o622

doi:10.1107/S1600536812004291

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4-Hydroxy-2-methyl-1,1-dioxo-2H-1λ⁶,2- benzothiazine-3-carboxylic acid hemihydrate

Farhana Aman,^a Waseeq Ahmad Siddiqui,^a Adnan Ashraf ^a and M. Nawaz Tahir ^b ^*

^aUniversity of Sargodha, Department of Chemistry, Sargodha, Pakistan, and ^bUniversity of Sargodha, Department of Physics, Sargodha, Pakistan
^*Correspondence e-mail: dmntahir_uos@yahoo.com

(Received 30 January 2012; accepted 1 February 2012; online 4 February 2012)

In the title compound, C₁₀H₉NO₅S·0.5H₂O, two geometrically different organic molecules are present. The benzene rings and the carboxylate groups are oriented at dihedral angles of 13.44 (4) and 21.15 (18)°. In both molecules, an intramolecular O—H⋯O hydrogen bond generates an S(6) ring. In the crystal, both moleucles form inversion dimers linked by pairs of O—H⋯O hydrogen bonds to generate R₂²(8) loops. The dimers are consolidated into chains extending along [100] by bridging O—H⋯O hydrogen bonds from the water molecule. A weak C—H⋯O hydrogen bond also occurs.

Related literature

For background to non-steroidal anti-inflammatory drugs, see: Akram et al. (2008 ); Foye et al. (1995 ); Lombardino et al. (1971 , 1973 ); Siddiqui, Ahmad, Siddiqui et al. (2008 ); Siddiqui, Ahmad, Tariq et al. (2008 ). For a related structure, see: Golič & Leban (1987 ). For graph-set notation, see: Bernstein et al. (1995 ). For puckering parameters, see: Cremer & Pople (1975 ).

Experimental

Crystal data

C₁₀H₉NO₅S·0.5H₂O
M_r = 264.25
Triclinic, $[P \overline 1]$
a = 7.1837 (2) Å
b = 8.5847 (3) Å
c = 17.9814 (4) Å
α = 87.605 (1)°
β = 89.713 (2)°
γ = 87.174 (1)°
V = 1106.59 (6) Å³
Z = 4
Mo Kα radiation
μ = 0.31 mm⁻¹
T = 296 K
0.35 × 0.25 × 0.22 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.915, T_max = 0.938
15712 measured reflections
4317 independent reflections
3468 reflections with I > 2σ(I)
R_int = 0.028

Refinement

R[F² > 2σ(F²)] = 0.038
wR(F²) = 0.097
S = 1.03
4317 reflections
295 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.32 e Å⁻³
Δρ_min = −0.32 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯O2ⁱ	0.83 (2)	1.82 (2)	2.647 (2)	177 (2)
O3—H3⋯O2	0.88 (2)	1.76 (2)	2.558 (2)	150 (2)
O6—H6A⋯O11ⁱⁱ	0.89	1.70	2.5881 (17)	170
O8—H8A⋯O7	0.88	1.75	2.5675 (8)	154
O11—H11A⋯O4ⁱⁱⁱ	0.81 (3)	2.28 (3)	3.029 (2)	155 (3)
O11—H11B⋯O7ⁱⁱⁱ	0.84 (3)	2.06 (3)	2.8508 (18)	158 (3)
C10—H10B⋯O1^iv	0.96	2.50	3.3679 (16)	151
Symmetry codes: (i) -x+2, -y+2, -z+1; (ii) x, y+1, z; (iii) -x+1, -y+1, -z+1; (iv) -x+2, -y+1, -z+1.

Data collection: APEX2 (Bruker, 2009 ); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ) and PLATON (Spek, 2009 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ) and PLATON.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536812004291/hb6618sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812004291/hb6618Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812004291/hb6618Isup3.cml

checkCIF report

Comment top

Among non-steroidal anti-inflammatory drugs (NSAIDs) some of the agents who have proven clinical efficacy are the β-diketones such as phenylbutazone or derivatives of the carboxylic acid class like aspirin, indomethacin and flufenamic acid, (Lombardino et al., 1971). Piroxicam is the first member of the 'Oxicam' class of NSAIDs to serve as an effective anti-inflammatory agent and gain immediate popularity in the international market (Foye et al., 1995). The carboxylic acid derivative of piroxicam, 4-hydroxy-2-methyl-2H-1,2 benzothiazine-3-carboxylic acid 1,1-dioxide has shown satisfactory plasma half-life (Lombardino et al., 1973) for its application in human beings. Due to our interest in the synthesis of this type of molecules and their transition metal complexes (Siddiqui, Ahmad, Siddiqui et al., 2008; Siddiqui, Ahmad, Tariq et al., 2008; Akram et al., 2008), we have synthesized this molecule by a simple procedure. Herein, we report the crystal structure of (I), (Fig. 1).

The crystal structures of the reactant i.e (II) methyl 4-hydroxy-2-methyl-2H-1,2-benzothiazine-3-carboxylate-1,1-dioxide (Golič & Leban, 1987) has been published which is also related to (I).

The asymmetric unit of (I) consists of two molecules (A & B) of the acid moiety and a water molecule. In the molecule A, the benzene ring C (C4–C9) is planar with r. m. s. deviation of 0.0019 Å and oriented at a dihedral angle of 21.15 (18)° with the carboxylate group D (O1/C1/O2). The puckering parameters (Cremer & Pople, 1975) of the adjacent heterocyclic ring E (C2/C3/C4/C9/S1/N1) are Q = 0.5183 (15) Å, θ = 114.4 (2)° and ϕ = 204.0 (2)°. The molecule B differs from A as the benzene ring F (C14—C1) [r. m. s. deviation = 0.0063 Å] is oriented at a dihedral angle of 13.44 (4)° with its carboxylate moiety G (O6/C11/O7). Also the puckering parameters of its adjacent heterocyclic ring H (C12/C13/C14/C19/S2/N2) are Q = 0.5047 (7) Å, θ = 117.06 (10)° and ϕ = 205.52 (13)°. In both molecules there exist intramolecular H-bonding of O—H···O type (Table 1, Fig. 2) forming S(6) ring motif (Bernstein et al., 1995). The molecules are dimerized due to intermolecular H-bonding of O—H···O bonding (Table 1, Fig. 2) forming a conventional R₂²(8) ring motifs. The water molecules interlink the dimers from the CO₂ and SO₂ groups due to O—H···O bonding, where CO₂ and SO₂ are of molecule B and A, respectively. The molecules are stabilized in the form of one-dimensional polymeric chains along the [1 0 0] direction.

Related literature top

For background to non-steroidal anti-inflammatory drugs, see: Akram et al. (2008); Foye et al. (1995); Lombardino et al. (1971, 1973); Siddiqui, Ahmad, Siddiqui et al. (2008); Siddiqui, Ahmad, Tariq et al. (2008). For a related structure, see: Golič & Leban (1987). For graph-set notation, see: Bernstein et al. (1995). For puckering parameters, see: Cremer & Pople (1975).

Experimental top

A light yellow solution of 4-hydroxy-2-methyl-2H-1,2 benzothiazine-3-carboxylic acid 1,1 dioxide methyl ester (0.5 g, 1.86 mmol) was subjected to stirring with an excess of sodium hydroxide at room temperature for 24 h. The reaction mixture was then acidified with dilute HCl and the precipitates filtered, washed with cold distilled water (3×25 ml) and dried to get white product (0.4 g, 1.65 mmol, 89%). m.p 361–362 K.

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2009); software used to prepare material for publication: WinGX (Farrugia, 1999) and PLATON (Spek, 2009).

Figures top

	Fig. 1. View of the title compound with displacement ellipsoids drawn at the 50% probability level.
	Fig. 2. The partial packing, which shows that molecules form polymeric chains extending along the [100] direction.

4-Hydroxy-2-methyl-1,1-dioxo-2H-1λ⁶,2- benzothiazine-3-carboxylic acid hemihydrate top

Crystal data top

C₁₀H₉NO₅S·0.5H₂O	Z = 4
M_r = 264.25	F(000) = 548
Triclinic, P1	D_x = 1.586 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.1837 (2) Å	Cell parameters from 3468 reflections
b = 8.5847 (3) Å	θ = 2.3–26.0°
c = 17.9814 (4) Å	µ = 0.31 mm⁻¹
α = 87.605 (1)°	T = 296 K
β = 89.713 (2)°	Prism, light green
γ = 87.174 (1)°	0.35 × 0.25 × 0.22 mm
V = 1106.59 (6) Å³

Data collection top

Bruker Kappa APEXII CCD diffractometer	4317 independent reflections
Radiation source: fine-focus sealed tube	3468 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.028
Detector resolution: 8.00 pixels mm^-1	θ_max = 26.0°, θ_min = 2.3°
ω scans	h = −7→8
Absorption correction: multi-scan (SADABS; Bruker, 2005)	k = −9→10
T_min = 0.915, T_max = 0.938	l = −22→22
15712 measured reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.038	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.097	w = 1/[σ²(F_o²) + (0.0439P)² + 0.3985P] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max < 0.001
4317 reflections	Δρ_max = 0.32 e Å⁻³
295 parameters	Δρ_min = −0.32 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0115 (13)

Crystal data top

C₁₀H₉NO₅S·0.5H₂O	γ = 87.174 (1)°
M_r = 264.25	V = 1106.59 (6) Å³
Triclinic, P1	Z = 4
a = 7.1837 (2) Å	Mo Kα radiation
b = 8.5847 (3) Å	µ = 0.31 mm⁻¹
c = 17.9814 (4) Å	T = 296 K
α = 87.605 (1)°	0.35 × 0.25 × 0.22 mm
β = 89.713 (2)°

Data collection top

Bruker Kappa APEXII CCD diffractometer	4317 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	3468 reflections with I > 2σ(I)
T_min = 0.915, T_max = 0.938	R_int = 0.028
15712 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.038	0 restraints
wR(F²) = 0.097	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	Δρ_max = 0.32 e Å⁻³
4317 reflections	Δρ_min = −0.32 e Å⁻³
295 parameters

Special details top

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

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

	x	y	z	U_iso*/U_eq
S1	0.73268 (7)	0.47997 (5)	0.36202 (3)	0.0326 (2)
O1	1.0126 (2)	0.78588 (17)	0.48912 (8)	0.0460 (5)
O2	0.9190 (2)	0.99420 (16)	0.41728 (8)	0.0487 (5)
O3	0.7800 (2)	0.95223 (16)	0.28936 (8)	0.0429 (5)
O4	0.56659 (19)	0.53462 (17)	0.39886 (8)	0.0434 (5)
O5	0.7877 (2)	0.31809 (15)	0.36788 (8)	0.0433 (5)
N1	0.9045 (2)	0.57982 (17)	0.39058 (8)	0.0318 (5)
C1	0.9390 (3)	0.8508 (2)	0.42875 (11)	0.0374 (7)
C2	0.8833 (3)	0.7439 (2)	0.37332 (10)	0.0318 (6)
C3	0.8093 (3)	0.7998 (2)	0.30725 (10)	0.0318 (6)
C4	0.7527 (3)	0.6968 (2)	0.24926 (10)	0.0318 (6)
C5	0.7316 (3)	0.7497 (3)	0.17540 (11)	0.0396 (7)
C6	0.6781 (3)	0.6499 (3)	0.12229 (11)	0.0458 (8)
C7	0.6430 (3)	0.4970 (3)	0.14134 (12)	0.0462 (8)
C8	0.6621 (3)	0.4403 (3)	0.21428 (11)	0.0407 (7)
C9	0.7164 (3)	0.5410 (2)	0.26757 (10)	0.0328 (6)
C10	1.09513 (6)	0.50694 (9)	0.39024 (3)	0.0442 (7)
S2	0.34876 (5)	1.12692 (4)	0.12496 (2)	0.0377 (2)
O6	0.36746 (6)	1.17536 (7)	0.35142 (3)	0.0544 (6)
O7	0.37431 (6)	0.91858 (7)	0.37872 (3)	0.0550 (6)
O8	0.31763 (5)	0.73224 (5)	0.27403 (4)	0.0476 (5)
O9	0.54647 (5)	1.10602 (4)	0.13153 (2)	0.0479 (5)
O10	0.27227 (5)	1.25250 (4)	0.07867 (2)	0.0530 (6)
N2	0.26231 (5)	1.14344 (4)	0.20849 (2)	0.0361 (5)
C11	0.35007 (5)	1.03047 (5)	0.33412 (3)	0.0412 (7)
C12	0.29810 (5)	1.00779 (4)	0.25703 (2)	0.0352 (6)
C13	0.28734 (5)	0.86196 (5)	0.23138 (3)	0.0352 (6)
C14	0.24568 (5)	0.83233 (5)	0.15354 (3)	0.0363 (6)
C15	0.19471 (5)	0.68585 (5)	0.13242 (4)	0.0488 (8)
C16	0.1577 (3)	0.6612 (3)	0.05880 (15)	0.0585 (9)
C17	0.1707 (3)	0.7789 (3)	0.00546 (14)	0.0598 (9)
C18	0.2239 (3)	0.9247 (3)	0.02421 (12)	0.0511 (8)
C19	0.2620 (3)	0.9500 (2)	0.09812 (11)	0.0372 (6)
C20	0.0766 (3)	1.2219 (3)	0.21567 (13)	0.0530 (8)
O11	0.4465 (3)	0.2097 (2)	0.48986 (9)	0.0635 (7)
H1	1.038 (3)	0.854 (3)	0.5179 (13)	0.0552*
H3	0.816 (3)	1.001 (3)	0.3286 (13)	0.0514*
H5	0.75359	0.85293	0.16185	0.0475*
H6	0.66556	0.68614	0.07302	0.0549*
H7	0.60624	0.43125	0.10490	0.0554*
H8	0.63897	0.33706	0.22725	0.0488*
H10A	1.14009	0.50333	0.33994	0.0663*
H10B	1.09340	0.40282	0.41180	0.0663*
H10C	1.17576	0.56731	0.41874	0.0663*
H6A	0.39669	1.17567	0.39964	0.0652*
H8A	0.33841	0.76910	0.31793	0.0571*
H15	0.18570	0.60481	0.16802	0.0585*
H16	0.12344	0.56331	0.04515	0.0702*
H17	0.14353	0.76055	−0.04383	0.0717*
H18	0.23387	1.00439	−0.01205	0.0613*
H20A	0.05271	1.24259	0.26698	0.0795*
H20B	−0.01620	1.15579	0.19802	0.0795*
H20C	0.07219	1.31847	0.18667	0.0795*
H11A	0.453 (4)	0.294 (4)	0.5075 (17)	0.0762*
H11B	0.507 (4)	0.152 (3)	0.5209 (16)	0.0762*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0377 (3)	0.0276 (3)	0.0328 (3)	−0.0056 (2)	−0.0022 (2)	−0.0010 (2)
O1	0.0701 (10)	0.0310 (8)	0.0377 (8)	−0.0098 (7)	−0.0214 (7)	0.0008 (6)
O2	0.0744 (11)	0.0265 (8)	0.0457 (9)	−0.0063 (7)	−0.0213 (8)	−0.0001 (6)
O3	0.0589 (10)	0.0283 (8)	0.0412 (8)	−0.0037 (7)	−0.0138 (7)	0.0047 (6)
O4	0.0401 (8)	0.0479 (9)	0.0427 (8)	−0.0068 (7)	0.0066 (6)	−0.0051 (7)
O5	0.0575 (9)	0.0267 (8)	0.0456 (8)	−0.0047 (7)	−0.0087 (7)	0.0023 (6)
N1	0.0350 (9)	0.0247 (8)	0.0356 (9)	−0.0021 (7)	−0.0076 (7)	0.0014 (7)
C1	0.0440 (12)	0.0310 (12)	0.0374 (11)	−0.0070 (9)	−0.0078 (9)	0.0029 (9)
C2	0.0360 (10)	0.0255 (10)	0.0338 (10)	−0.0034 (8)	−0.0046 (8)	0.0020 (8)
C3	0.0327 (10)	0.0270 (10)	0.0357 (10)	−0.0028 (8)	−0.0009 (8)	0.0014 (8)
C4	0.0286 (10)	0.0338 (11)	0.0326 (10)	0.0005 (8)	−0.0021 (8)	0.0008 (8)
C5	0.0402 (11)	0.0423 (12)	0.0357 (11)	−0.0018 (9)	−0.0028 (9)	0.0048 (9)
C6	0.0468 (13)	0.0589 (15)	0.0311 (11)	0.0020 (11)	−0.0041 (9)	−0.0003 (10)
C7	0.0489 (13)	0.0524 (14)	0.0380 (12)	0.0010 (11)	−0.0087 (10)	−0.0138 (10)
C8	0.0424 (12)	0.0368 (12)	0.0435 (12)	−0.0008 (9)	−0.0056 (9)	−0.0090 (9)
C9	0.0308 (10)	0.0341 (11)	0.0334 (10)	0.0008 (8)	−0.0030 (8)	−0.0026 (8)
C10	0.0401 (12)	0.0345 (12)	0.0571 (14)	0.0004 (9)	−0.0016 (10)	0.0079 (10)
S2	0.0490 (3)	0.0330 (3)	0.0308 (3)	−0.0030 (2)	0.0016 (2)	0.0025 (2)
O6	0.0779 (12)	0.0512 (10)	0.0340 (8)	−0.0002 (8)	−0.0103 (8)	−0.0042 (7)
O7	0.0713 (11)	0.0566 (10)	0.0354 (8)	0.0034 (9)	−0.0033 (7)	0.0105 (8)
O8	0.0563 (10)	0.0377 (9)	0.0475 (9)	−0.0017 (7)	0.0050 (7)	0.0112 (7)
O9	0.0454 (9)	0.0476 (9)	0.0509 (9)	−0.0086 (7)	0.0081 (7)	0.0020 (7)
O10	0.0814 (12)	0.0390 (9)	0.0373 (8)	0.0008 (8)	−0.0052 (8)	0.0091 (7)
N2	0.0467 (10)	0.0312 (9)	0.0297 (9)	0.0020 (8)	0.0000 (7)	0.0009 (7)
C11	0.0430 (12)	0.0462 (13)	0.0336 (11)	0.0028 (10)	0.0028 (9)	0.0029 (10)
C12	0.0382 (11)	0.0363 (12)	0.0304 (10)	0.0015 (9)	0.0023 (8)	0.0038 (9)
C13	0.0328 (10)	0.0334 (11)	0.0384 (11)	0.0001 (9)	0.0048 (8)	0.0076 (9)
C14	0.0304 (10)	0.0345 (11)	0.0439 (11)	−0.0009 (9)	0.0043 (8)	−0.0032 (9)
C15	0.0429 (12)	0.0387 (13)	0.0653 (15)	−0.0065 (10)	0.0060 (11)	−0.0055 (11)
C16	0.0538 (15)	0.0506 (15)	0.0735 (18)	−0.0075 (12)	−0.0037 (12)	−0.0250 (14)
C17	0.0626 (16)	0.0646 (17)	0.0533 (15)	0.0035 (13)	−0.0080 (12)	−0.0242 (14)
C18	0.0618 (15)	0.0530 (15)	0.0384 (12)	0.0022 (12)	−0.0019 (10)	−0.0082 (11)
C19	0.0393 (11)	0.0346 (11)	0.0376 (11)	0.0021 (9)	0.0008 (9)	−0.0039 (9)
C20	0.0598 (15)	0.0465 (14)	0.0504 (14)	0.0160 (12)	0.0057 (11)	0.0017 (11)
O11	0.0951 (14)	0.0557 (12)	0.0398 (9)	0.0004 (11)	−0.0156 (9)	−0.0064 (8)

Geometric parameters (Å, º) top

S1—O4	1.4302 (15)	C4—C9	1.401 (2)
S1—O5	1.4257 (14)	C5—C6	1.378 (3)
S1—N1	1.6339 (15)	C6—C7	1.378 (4)
S1—C9	1.7590 (19)	C7—C8	1.385 (3)
S2—N2	1.6314 (5)	C8—C9	1.387 (3)
S2—O9	1.4276 (5)	C5—H5	0.9300
S2—O10	1.4241 (5)	C6—H6	0.9300
S2—C19	1.7566 (18)	C7—H7	0.9300
O1—C1	1.302 (2)	C8—H8	0.9300
O2—C1	1.241 (2)	C10—H10C	0.9600
O3—C3	1.341 (2)	C10—H10A	0.9600
O1—H1	0.83 (2)	C10—H10B	0.9600
O3—H3	0.88 (2)	C11—C12	1.4607 (6)
O6—C11	1.3067 (7)	C12—C13	1.3580 (6)
O7—C11	1.2315 (7)	C13—C14	1.4679 (7)
O8—C13	1.3349 (7)	C14—C19	1.3977 (19)
O6—H6A	0.8900	C14—C15	1.3951 (6)
O8—H8A	0.8800	C15—C16	1.379 (3)
O11—H11B	0.84 (3)	C16—C17	1.370 (4)
O11—H11A	0.81 (3)	C17—C18	1.382 (4)
N1—C10	1.4774 (15)	C18—C19	1.386 (3)
N1—C2	1.431 (2)	C15—H15	0.9300
N2—C12	1.4394 (5)	C16—H16	0.9300
N2—C20	1.472 (2)	C17—H17	0.9300
C1—C2	1.453 (3)	C18—H18	0.9300
C2—C3	1.363 (3)	C20—H20C	0.9600
C3—C4	1.467 (3)	C20—H20A	0.9600
C4—C5	1.392 (3)	C20—H20B	0.9600

O4—S1—O5	119.32 (9)	C7—C6—H6	120.00
O4—S1—N1	107.88 (8)	C6—C7—H7	120.00
O4—S1—C9	108.12 (9)	C8—C7—H7	120.00
O5—S1—N1	108.56 (8)	C9—C8—H8	121.00
O5—S1—C9	109.51 (9)	C7—C8—H8	121.00
N1—S1—C9	102.07 (9)	N1—C10—H10B	109.00
O9—S2—O10	119.03 (3)	N1—C10—H10C	109.00
O9—S2—N2	107.87 (3)	N1—C10—H10A	109.00
O9—S2—C19	108.08 (7)	H10A—C10—H10B	109.00
O10—S2—N2	108.36 (3)	H10B—C10—H10C	109.00
O10—S2—C19	109.87 (7)	H10A—C10—H10C	109.00
N2—S2—C19	102.34 (7)	O6—C11—O7	123.53 (5)
C1—O1—H1	109.6 (17)	O6—C11—C12	115.45 (4)
C3—O3—H3	105.2 (16)	O7—C11—C12	121.03 (4)
C11—O6—H6A	108.00	N2—C12—C11	118.50 (3)
C13—O8—H8A	103.00	N2—C12—C13	120.77 (4)
H11A—O11—H11B	102 (3)	C11—C12—C13	120.72 (4)
S1—N1—C2	114.15 (12)	C12—C13—C14	123.01 (4)
S1—N1—C10	118.74 (10)	O8—C13—C12	123.29 (5)
C2—N1—C10	117.70 (13)	O8—C13—C14	113.69 (4)
S2—N2—C20	117.81 (9)	C13—C14—C15	121.33 (5)
S2—N2—C12	113.99 (3)	C13—C14—C19	120.41 (8)
C12—N2—C20	115.64 (10)	C15—C14—C19	118.23 (9)
O1—C1—O2	123.45 (18)	C14—C15—C16	120.03 (12)
O1—C1—C2	115.62 (15)	C15—C16—C17	120.9 (2)
O2—C1—C2	120.91 (18)	C16—C17—C18	120.6 (2)
N1—C2—C1	118.39 (16)	C17—C18—C19	118.7 (2)
C1—C2—C3	120.37 (16)	S2—C19—C14	117.15 (13)
N1—C2—C3	121.22 (16)	S2—C19—C18	121.23 (16)
O3—C3—C4	113.89 (16)	C14—C19—C18	121.47 (17)
O3—C3—C2	123.67 (16)	C16—C15—H15	120.00
C2—C3—C4	122.44 (16)	C14—C15—H15	120.00
C3—C4—C5	121.78 (17)	C15—C16—H16	120.00
C5—C4—C9	118.12 (18)	C17—C16—H16	120.00
C3—C4—C9	120.10 (16)	C18—C17—H17	120.00
C4—C5—C6	120.3 (2)	C16—C17—H17	120.00
C5—C6—C7	120.8 (2)	C17—C18—H18	121.00
C6—C7—C8	120.6 (2)	C19—C18—H18	121.00
C7—C8—C9	118.5 (2)	N2—C20—H20B	109.00
C4—C9—C8	121.72 (18)	N2—C20—H20C	109.00
S1—C9—C4	117.15 (14)	N2—C20—H20A	109.00
S1—C9—C8	121.07 (15)	H20A—C20—H20C	109.00
C6—C5—H5	120.00	H20B—C20—H20C	109.00
C4—C5—H5	120.00	H20A—C20—H20B	109.00
C5—C6—H6	120.00

O4—S1—N1—C2	−61.72 (14)	C1—C2—C3—C4	179.38 (19)
O4—S1—N1—C10	152.50 (10)	O3—C3—C4—C9	−158.93 (19)
O5—S1—N1—C2	167.65 (13)	C2—C3—C4—C5	−160.1 (2)
O5—S1—N1—C10	21.87 (13)	C2—C3—C4—C9	20.5 (3)
C9—S1—N1—C2	52.05 (14)	O3—C3—C4—C5	20.4 (3)
C9—S1—N1—C10	−93.72 (12)	C3—C4—C5—C6	−179.9 (2)
O4—S1—C9—C4	78.31 (18)	C3—C4—C9—S1	2.5 (3)
O4—S1—C9—C8	−99.01 (19)	C3—C4—C9—C8	179.8 (2)
O5—S1—C9—C4	−150.19 (16)	C9—C4—C5—C6	−0.6 (3)
O5—S1—C9—C8	32.5 (2)	C5—C4—C9—C8	0.4 (3)
N1—S1—C9—C4	−35.29 (18)	C5—C4—C9—S1	−176.86 (16)
N1—S1—C9—C8	147.39 (18)	C4—C5—C6—C7	0.6 (3)
C19—S2—N2—C12	52.04 (8)	C5—C6—C7—C8	−0.5 (3)
C19—S2—N2—C20	−88.35 (13)	C6—C7—C8—C9	0.3 (3)
O9—S2—C19—C14	78.38 (14)	C7—C8—C9—S1	176.90 (17)
O9—S2—C19—C18	−97.21 (18)	C7—C8—C9—C4	−0.3 (3)
O10—S2—C19—C14	−150.27 (11)	O6—C11—C12—N2	−2.89 (5)
O10—S2—C19—C18	34.1 (2)	O6—C11—C12—C13	175.85 (4)
N2—S2—C19—C14	−35.32 (15)	O7—C11—C12—N2	176.85 (4)
N2—S2—C19—C18	149.09 (17)	O7—C11—C12—C13	−4.41 (6)
O10—S2—N2—C20	27.70 (12)	N2—C12—C13—O8	−179.45 (4)
O9—S2—N2—C12	−61.81 (4)	N2—C12—C13—C14	2.10 (6)
O9—S2—N2—C20	157.80 (11)	C11—C12—C13—O8	1.84 (6)
O10—S2—N2—C12	168.08 (3)	C11—C12—C13—C14	−176.62 (3)
S1—N1—C2—C1	140.26 (16)	O8—C13—C14—C15	15.95 (5)
S1—N1—C2—C3	−38.4 (2)	O8—C13—C14—C19	−162.03 (11)
C10—N1—C2—C1	−73.6 (2)	C12—C13—C14—C15	−165.46 (4)
C10—N1—C2—C3	107.7 (2)	C12—C13—C14—C19	16.56 (11)
S2—N2—C12—C11	138.41 (3)	C13—C14—C15—C16	−179.53 (11)
C20—N2—C12—C11	−80.31 (11)	C19—C14—C15—C16	−1.51 (15)
C20—N2—C12—C13	100.95 (11)	C13—C14—C19—S2	4.25 (18)
S2—N2—C12—C13	−40.33 (5)	C13—C14—C19—C18	179.83 (15)
O1—C1—C2—N1	3.0 (3)	C15—C14—C19—S2	−173.79 (8)
O1—C1—C2—C3	−178.26 (19)	C15—C14—C19—C18	1.8 (2)
O2—C1—C2—N1	−178.13 (18)	C14—C15—C16—C17	0.2 (2)
O2—C1—C2—C3	0.6 (3)	C15—C16—C17—C18	0.9 (3)
N1—C2—C3—O3	177.46 (18)	C16—C17—C18—C19	−0.7 (3)
N1—C2—C3—C4	−2.0 (3)	C17—C18—C19—S2	174.68 (17)
C1—C2—C3—O3	−1.2 (3)	C17—C18—C19—C14	−0.7 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O2ⁱ	0.83 (2)	1.82 (2)	2.647 (2)	177 (2)
O3—H3···O2	0.88 (2)	1.76 (2)	2.558 (2)	150 (2)
O6—H6A···O11ⁱⁱ	0.89	1.70	2.5881 (17)	170
O8—H8A···O7	0.88	1.75	2.5675 (8)	154
O11—H11A···O4ⁱⁱⁱ	0.81 (3)	2.28 (3)	3.029 (2)	155 (3)
O11—H11B···O7ⁱⁱⁱ	0.84 (3)	2.06 (3)	2.8508 (18)	158 (3)
C10—H10B···O1^iv	0.96	2.50	3.3679 (16)	151

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

Experimental details

Crystal data
Chemical formula	C₁₀H₉NO₅S·0.5H₂O
M_r	264.25
Crystal system, space group	Triclinic, P1
Temperature (K)	296
a, b, c (Å)	7.1837 (2), 8.5847 (3), 17.9814 (4)
α, β, γ (°)	87.605 (1), 89.713 (2), 87.174 (1)
V (Å³)	1106.59 (6)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.31
Crystal size (mm)	0.35 × 0.25 × 0.22

Data collection
Diffractometer	Bruker Kappa APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.915, 0.938
No. of measured, independent and observed [I > 2σ(I)] reflections	15712, 4317, 3468
R_int	0.028
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.038, 0.097, 1.03
No. of reflections	4317
No. of parameters	295
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.32, −0.32

Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2009), WinGX (Farrugia, 1999) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O2ⁱ	0.83 (2)	1.82 (2)	2.647 (2)	177 (2)
O3—H3···O2	0.88 (2)	1.76 (2)	2.558 (2)	150 (2)
O6—H6A···O11ⁱⁱ	0.89	1.70	2.5881 (17)	170
O8—H8A···O7	0.88	1.75	2.5675 (8)	154
O11—H11A···O4ⁱⁱⁱ	0.81 (3)	2.28 (3)	3.029 (2)	155 (3)
O11—H11B···O7ⁱⁱⁱ	0.84 (3)	2.06 (3)	2.8508 (18)	158 (3)
C10—H10B···O1^iv	0.96	2.50	3.3679 (16)	151

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

Acknowledgements

The authors acknowledge the provision of funds for the purchase of a diffractometer and encouragement by Dr Muhammad Akram Chaudhary, Vice Chancellor, University of Sargodha, Pakistan. The authors also acknowledge the technical support provided by Syed Muhammad Hussain Rizvi of Bana International, Karachi, Pakistan. WAS is thankful to the Higher Education Commission (HEC), Islamabad, Pakistan, for providing funds for this research work.

References

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