2-[2-(2-Bromo­phen­yl)-2-oxoeth­yl]-1λ6,2-benzothia­zole-1,1,3-trione

Sattar, N.; Siddiqui, H.L.; Siddiqui, W.A.; Akram, M.; Parvez, M.

doi:10.1107/S1600536812022428

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 68| Part 6| June 2012| Pages o1889-o1890

doi:10.1107/S1600536812022428

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2-[2-(2-Bromophenyl)-2-oxoethyl]-1λ⁶,2-benzothiazole-1,1,3-trione

Nazia Sattar,^a Hamid Latif Siddiqui,^a ^* Waseeq Ahmad Siddiqui,^b Muhammad Akram ^c and Masood Parvez ^d

^aInstitute of Chemistry, University of the Punjab, Lahore 54590, Pakistan, ^bDepartment of Chemistry, University of Sargodha, Sargodha 40100, Pakistan, ^cDepartment of Chemistry, Universiti Teknologi Malaysia, 81310 UTM Skudai Johor, Darul Ta'zim, Malaysia, and ^dDepartment of Chemistry, The University of Calgary, 2500 University Drive NW, Calgary, Alberta, Canada T2N 1N4
^*Correspondence e-mail: drhamidlatif@hotmail.com

(Received 9 May 2012; accepted 17 May 2012; online 26 May 2012)

The asymmetric unit of the title compound, C₁₅H₁₀BrNO₄S, contains two different conformers in which the benzisothiazole rings are essentially planar, with r.m.s. deviations of 0.012 and 0.017 Å. The mean planes of the benzene rings form dihedral angles 70.49 (13) and 72.79 (11)° with the benzisothiazole rings. The orientation of the Br atoms in the two conformers exhibit the most pronounced difference, with opposing orientations in the two molecules. The crystal structure is stabilized by π–π interactions between the benzene rings of the benzisothiazole moieties of one molecule and bromobenzene rings of the other molecule, with distances between the ring centroids of 3.599 (3) and 3.620 (3) Å, respectively. The crystal packing is further consolidated by pairs of weak intermolecular C—H⋯O hydrogen bonds, which form inversion dimers.

Related literature

For non-steroidal anti-inflammatory drugs (NSAIDs) and related compounds, see: Lombardino et al. (1971 ); Soler (1985 ); Carty et al. (1993 ); Turck et al. (1995 ); Blackham & Owen (1975 ); Singh et al. (2007 ); Vaccarino et al. (2007 ); Kapui et al. (2003 ). For related structures, see: Maliha et al. (2007 ); Siddiqui et al. (2007 ).

Experimental

Crystal data

C₁₅H₁₀BrNO₄S
M_r = 380.21
Triclinic, $[P \overline 1]$
a = 7.574 (2) Å
b = 13.903 (4) Å
c = 14.814 (4) Å
α = 110.574 (15)°
β = 96.936 (13)°
γ = 93.640 (14)°
V = 1440.3 (7) Å³
Z = 4
Mo Kα radiation
μ = 3.02 mm⁻¹
T = 123 K
0.18 × 0.18 × 0.16 mm

Data collection

Nonius KappaCCD diffractometer
Absorption correction: multi-scan (SORTAV; Blessing, 1997 ) T_min = 0.613, T_max = 0.644
12284 measured reflections
6541 independent reflections
5268 reflections with I > 2σ(I)
R_int = 0.042

Refinement

R[F² > 2σ(F²)] = 0.050
wR(F²) = 0.105
S = 1.12
6541 reflections
397 parameters
H-atom parameters constrained
Δρ_max = 0.81 e Å⁻³
Δρ_min = −1.04 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C14—H14⋯O1ⁱ	0.95	2.40	3.305 (5)	159
C17—H17⋯O5ⁱⁱ	0.95	2.43	3.225 (5)	141
C27—H27⋯O7ⁱⁱⁱ	0.95	2.29	3.164 (5)	153
Symmetry codes: (i) -x+2, -y+1, -z; (ii) -x+1, -y+1, -z+1; (iii) -x+2, -y, -z+1.

Data collection: COLLECT (Hooft, 1998 ); cell refinement: DENZO (Otwinowski & Minor, 1997 ); data reduction: SCALEPACK (Otwinowski & Minor, 1997); 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 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536812022428/pk2412sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812022428/pk2412Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812022428/pk2412Isup3.cml

checkCIF report

Comment top

Oxicam, a class of non-steroidal anti-inflammatory drugs (NSAIDs) consists of 1,2-benzothiazine 1,1-dioxide derivatives which are found to be potent anti-inflammatory and analgesic agents, e.g., Piroxicam (Lombardino et al., 1971), Droxicam (Soler, 1985), Ampiroxicam (Carty et al., 1993), Meloxicam (Turck et al., 1995) and Sudoxicam (Blackham & Owen, 1975) are the recent members of this class currently in use in the international market. Various derivatives are known to be cyclooxygenase-2 (COX-2) inhibitors (Singh et al., 2007), analgesic (Vaccarino et al., 2007) and human leucocyte elastase (HLE) inhibitors (Kapui et al., 2003). Earlier, we have reported the synthesis and crystal structures of some of the 1,2-benzothiazine derivatives (Maliha et al., 2007; Siddiqui et al., 2007). Herein, we report the synthesis and crystal structure of the title compound that has served as a precursor for the 1,2-benzothiazine derivative.

The asymmetric unit of the title compound contains two conformers (Fig. 1). In both molecules, the benzisothiazol rings S1/N1/C1–C7 and S2/N2/C16–C22 are essentially planar with rms deviations of fitted atoms being 0.017 Å and 0.012 Å, respectively, while the mean-planes of the benzene rings C10–C15 and C25–C30 form dihedral angles 70.49 (13)° and 72.79 (11)°, respectively, with the mean-planes of the benzisothiazol rings. The orientation of the Br atoms in the two conformers exhibit the most pronounced difference, with opposing orientations in the two molecules. The crystal structure is stabilized by π-π interactions between benzene rings (C1–C6) of benzisothiazol moieties in one molecule and bromobenzene rings (C25–C30) in the other molecule with distances between the ring centroids being 3.599 (3) Å and 3.620 (3) Å, respectively. The crystal packing is further consolidated by weak intermolecular C—H···O hydrogen bonds. The molecule containing S1 forms centrosymmetric dimers via C14—H14···O1 hydrogen bonding interactions. The other molecule also forms centrosymmetric dimers via C17—H17···O5 hydrogen bonds; the dimers are further extended along the b-axis via C27—H27···O7 hydrogen bonds (Fig. 2 and Tab. 1).

The bond distances and angles in the title compound (Fig. 1) agree very well with the corresponding bond distances and angles reported in closely related compounds (Maliha et al., 2007; Siddiqui et al., 2007).

Related literature top

For non-steroidal anti-inflammatory drugs (NSAIDs) and related compounds, see: Lombardino et al. (1971); Soler (1985); Carty et al. (1993); Turck et al. (1995); Blackham & Owen (1975); Singh et al. (2007); Vaccarino et al. (2007); Kapui et al. (2003). For related structures, see: Maliha et al. (2007); Siddiqui et al. (2007).

Experimental top

A mixture of 2-bromo-1-(2-bromophenyl)ethanone (2.0 g, 7.2 mmol) and sodium saccharin (1.76 g, 8.6 mmol) in dimethylformamide (15 ml) was stirred at 383 K for 3 h under anhydrous conditions. On completion of the reaction (as indicated by TLC), the contents of the flask were poured into crushed ice. The precipitates formed were filtered, washed with water, ice-cold ethanol and dried to give the reddish brown title product (1.94 g, 71%). Crystals were grown by slow evaporation of a solution in EtOAc and CHCl₃ (1:1) at room temperature; m.p. 395–397 K.

Computing details top

Data collection: COLLECT (Hooft, 1998); cell refinement: DENZO (Otwinowski & Minor, 1997); data reduction: SCALEPACK (Otwinowski & Minor, 1997); 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); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The asymmetric unit of the title compound. Displacement ellipsoids are drawn at the 50% probability level. H atoms are presented as small spheres of arbitrary radius.
	Fig. 2. A view of the C—H···O hydrogen bonds (dotted lines) in the crystal structure of the title compound. H atoms not participating in hydrogen-bonding were omitted to enhance clarity.

2-[2-(2-Bromophenyl)-2-oxoethyl]-1λ⁶,2-benzothiazole-1,1,3-trione top

Crystal data top

C₁₅H₁₀BrNO₄S	Z = 4
M_r = 380.21	F(000) = 760
Triclinic, P1	D_x = 1.753 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.574 (2) Å	Cell parameters from 6425 reflections
b = 13.903 (4) Å	θ = 1.0–27.5°
c = 14.814 (4) Å	µ = 3.02 mm⁻¹
α = 110.574 (15)°	T = 123 K
β = 96.936 (13)°	Prism, colorless
γ = 93.640 (14)°	0.18 × 0.18 × 0.16 mm
V = 1440.3 (7) Å³

Data collection top

Nonius KappaCCD diffractometer	6541 independent reflections
Radiation source: fine-focus sealed tube	5268 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.042
ω and ϕ scans	θ_max = 27.5°, θ_min = 1.5°
Absorption correction: multi-scan (SORTAV; Blessing, 1997)	h = −9→9
T_min = 0.613, T_max = 0.644	k = −18→18
12284 measured reflections	l = −19→19

Refinement top

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)] = 0.050	Hydrogen site location: difference Fourier map
wR(F²) = 0.105	H-atom parameters constrained
S = 1.12	w = 1/[σ²(F_o²) + 5.440P] where P = (F_o² + 2F_c²)/3
6541 reflections	(Δ/σ)_max < 0.001
397 parameters	Δρ_max = 0.81 e Å⁻³
0 restraints	Δρ_min = −1.04 e Å⁻³

Crystal data top

C₁₅H₁₀BrNO₄S	γ = 93.640 (14)°
M_r = 380.21	V = 1440.3 (7) Å³
Triclinic, P1	Z = 4
a = 7.574 (2) Å	Mo Kα radiation
b = 13.903 (4) Å	µ = 3.02 mm⁻¹
c = 14.814 (4) Å	T = 123 K
α = 110.574 (15)°	0.18 × 0.18 × 0.16 mm
β = 96.936 (13)°

Data collection top

Nonius KappaCCD diffractometer	6541 independent reflections
Absorption correction: multi-scan (SORTAV; Blessing, 1997)	5268 reflections with I > 2σ(I)
T_min = 0.613, T_max = 0.644	R_int = 0.042
12284 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.050	0 restraints
wR(F²) = 0.105	H-atom parameters constrained
S = 1.12	Δρ_max = 0.81 e Å⁻³
6541 reflections	Δρ_min = −1.04 e Å⁻³
397 parameters

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

	x	y	z	U_iso*/U_eq
Br1	0.36505 (6)	0.45967 (4)	0.15933 (3)	0.03241 (12)
Br2	0.91717 (7)	0.09057 (4)	0.66368 (3)	0.03844 (13)
S1	0.67803 (14)	0.13040 (8)	−0.09125 (7)	0.0234 (2)
S2	0.60738 (13)	0.34637 (7)	0.39090 (7)	0.02000 (19)
O1	0.8217 (4)	0.1917 (2)	−0.1062 (2)	0.0349 (7)
O2	0.5086 (4)	0.1188 (2)	−0.1509 (2)	0.0321 (7)
O3	0.6920 (4)	0.1327 (2)	0.1629 (2)	0.0283 (6)
O4	0.9038 (4)	0.3378 (2)	0.1237 (2)	0.0310 (7)
O5	0.5563 (4)	0.3780 (2)	0.4859 (2)	0.0283 (6)
O6	0.4665 (4)	0.3119 (2)	0.3092 (2)	0.0283 (6)
O7	1.0338 (4)	0.2269 (2)	0.3508 (2)	0.0260 (6)
O8	0.8207 (5)	0.2096 (2)	0.5384 (2)	0.0389 (8)
N1	0.6521 (5)	0.1750 (2)	0.0257 (2)	0.0215 (7)
N2	0.7478 (4)	0.2569 (2)	0.3791 (2)	0.0207 (7)
C1	0.7402 (5)	0.0120 (3)	−0.0868 (3)	0.0209 (8)
C2	0.7806 (5)	−0.0711 (3)	−0.1628 (3)	0.0250 (8)
H2	0.7750	−0.0703	−0.2270	0.030*
C3	0.8297 (5)	−0.1558 (3)	−0.1406 (3)	0.0277 (9)
H3	0.8576	−0.2148	−0.1908	0.033*
C4	0.8388 (5)	−0.1557 (3)	−0.0463 (3)	0.0261 (9)
H4	0.8734	−0.2146	−0.0332	0.031*
C5	0.7983 (5)	−0.0711 (3)	0.0290 (3)	0.0230 (8)
H5	0.8054	−0.0711	0.0934	0.028*
C6	0.7473 (5)	0.0133 (3)	0.0077 (3)	0.0208 (8)
C7	0.6977 (5)	0.1109 (3)	0.0771 (3)	0.0198 (8)
C8	0.5961 (5)	0.2769 (3)	0.0709 (3)	0.0213 (8)
H8A	0.5346	0.2778	0.1264	0.026*
H8B	0.5100	0.2916	0.0229	0.026*
C9	0.7555 (5)	0.3606 (3)	0.1071 (3)	0.0205 (8)
C10	0.7307 (5)	0.4707 (3)	0.1184 (3)	0.0215 (8)
C11	0.5795 (5)	0.5213 (3)	0.1368 (3)	0.0234 (8)
C12	0.5781 (6)	0.6246 (3)	0.1462 (3)	0.0305 (9)
H12	0.4728	0.6577	0.1583	0.037*
C13	0.7319 (7)	0.6784 (4)	0.1378 (4)	0.0384 (11)
H13	0.7330	0.7492	0.1453	0.046*
C14	0.8831 (7)	0.6296 (4)	0.1187 (4)	0.0386 (11)
H14	0.9878	0.6663	0.1118	0.046*
C15	0.8825 (6)	0.5280 (3)	0.1095 (3)	0.0290 (9)
H15	0.9880	0.4953	0.0967	0.035*
C16	0.7715 (5)	0.4356 (3)	0.3809 (3)	0.0181 (7)
C17	0.7503 (5)	0.5350 (3)	0.3834 (3)	0.0229 (8)
H17	0.6394	0.5629	0.3918	0.028*
C18	0.8992 (5)	0.5917 (3)	0.3730 (3)	0.0249 (8)
H18	0.8906	0.6597	0.3735	0.030*
C19	1.0615 (5)	0.5497 (3)	0.3619 (3)	0.0232 (8)
H19	1.1622	0.5905	0.3564	0.028*
C20	1.0793 (5)	0.4497 (3)	0.3586 (3)	0.0226 (8)
H20	1.1896	0.4213	0.3501	0.027*
C21	0.9302 (5)	0.3926 (3)	0.3681 (3)	0.0181 (7)
C22	0.9183 (5)	0.2841 (3)	0.3645 (3)	0.0197 (8)
C23	0.6895 (6)	0.1524 (3)	0.3720 (3)	0.0224 (8)
H23A	0.7401	0.1020	0.3186	0.027*
H23B	0.5574	0.1393	0.3561	0.027*
C24	0.7505 (5)	0.1370 (3)	0.4683 (3)	0.0204 (8)
C25	0.7189 (5)	0.0296 (3)	0.4674 (3)	0.0196 (8)
C26	0.7853 (5)	−0.0009 (3)	0.5443 (3)	0.0255 (9)
C27	0.7537 (6)	−0.1035 (4)	0.5369 (4)	0.0343 (11)
H27	0.8041	−0.1240	0.5883	0.041*
C28	0.6490 (7)	−0.1757 (4)	0.4549 (4)	0.0383 (12)
H28	0.6255	−0.2452	0.4508	0.046*
C29	0.5792 (6)	−0.1468 (3)	0.3795 (3)	0.0335 (10)
H29	0.5064	−0.1961	0.3236	0.040*
C30	0.6150 (5)	−0.0461 (3)	0.3851 (3)	0.0243 (8)
H30	0.5682	−0.0275	0.3319	0.029*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0246 (2)	0.0352 (2)	0.0418 (3)	0.01061 (18)	0.01351 (19)	0.0153 (2)
Br2	0.0388 (3)	0.0569 (3)	0.0219 (2)	0.0144 (2)	0.00103 (19)	0.0167 (2)
S1	0.0299 (5)	0.0228 (5)	0.0171 (4)	0.0017 (4)	0.0034 (4)	0.0071 (4)
S2	0.0177 (4)	0.0206 (5)	0.0245 (5)	0.0040 (4)	0.0070 (4)	0.0101 (4)
O1	0.048 (2)	0.0283 (16)	0.0300 (16)	−0.0069 (14)	0.0119 (15)	0.0128 (14)
O2	0.0371 (18)	0.0359 (17)	0.0229 (15)	0.0102 (14)	−0.0017 (13)	0.0111 (13)
O3	0.0403 (18)	0.0268 (15)	0.0198 (14)	0.0082 (13)	0.0104 (13)	0.0084 (12)
O4	0.0248 (16)	0.0288 (16)	0.0371 (17)	0.0087 (13)	0.0015 (13)	0.0092 (14)
O5	0.0278 (16)	0.0325 (16)	0.0313 (16)	0.0069 (13)	0.0172 (13)	0.0151 (13)
O6	0.0202 (14)	0.0290 (16)	0.0341 (16)	0.0009 (12)	0.0004 (12)	0.0111 (13)
O7	0.0233 (15)	0.0285 (15)	0.0328 (16)	0.0122 (12)	0.0074 (12)	0.0166 (13)
O8	0.059 (2)	0.0251 (16)	0.0254 (16)	−0.0119 (15)	−0.0055 (15)	0.0068 (13)
N1	0.0300 (18)	0.0185 (16)	0.0148 (15)	0.0028 (14)	0.0034 (14)	0.0044 (13)
N2	0.0239 (17)	0.0175 (16)	0.0249 (17)	0.0046 (13)	0.0076 (14)	0.0110 (14)
C1	0.0184 (19)	0.0199 (19)	0.0218 (19)	−0.0026 (15)	−0.0003 (15)	0.0061 (16)
C2	0.025 (2)	0.028 (2)	0.0169 (18)	−0.0004 (17)	0.0037 (16)	0.0019 (16)
C3	0.023 (2)	0.021 (2)	0.031 (2)	−0.0006 (16)	0.0070 (17)	−0.0009 (17)
C4	0.0187 (19)	0.022 (2)	0.035 (2)	0.0026 (16)	0.0054 (17)	0.0076 (18)
C5	0.023 (2)	0.0214 (19)	0.027 (2)	0.0023 (16)	0.0058 (16)	0.0105 (17)
C6	0.0180 (19)	0.0217 (19)	0.0202 (18)	−0.0023 (15)	0.0034 (15)	0.0052 (16)
C7	0.0206 (19)	0.0157 (18)	0.0222 (19)	−0.0009 (14)	0.0029 (15)	0.0065 (15)
C8	0.0207 (19)	0.0203 (19)	0.0217 (19)	0.0044 (15)	0.0010 (15)	0.0067 (16)
C9	0.024 (2)	0.0204 (19)	0.0158 (17)	0.0051 (15)	0.0028 (15)	0.0039 (15)
C10	0.022 (2)	0.024 (2)	0.0174 (18)	0.0013 (16)	0.0015 (15)	0.0072 (16)
C11	0.023 (2)	0.027 (2)	0.0204 (19)	0.0049 (16)	0.0032 (16)	0.0079 (16)
C12	0.036 (2)	0.026 (2)	0.028 (2)	0.0116 (19)	0.0030 (19)	0.0074 (18)
C13	0.046 (3)	0.023 (2)	0.045 (3)	0.004 (2)	0.001 (2)	0.012 (2)
C14	0.036 (3)	0.034 (3)	0.047 (3)	−0.008 (2)	0.003 (2)	0.019 (2)
C15	0.023 (2)	0.031 (2)	0.033 (2)	0.0036 (18)	0.0031 (18)	0.0122 (19)
C16	0.0201 (19)	0.0215 (19)	0.0129 (16)	0.0022 (15)	0.0024 (14)	0.0064 (15)
C17	0.024 (2)	0.023 (2)	0.0229 (19)	0.0068 (16)	0.0046 (16)	0.0084 (16)
C18	0.027 (2)	0.022 (2)	0.026 (2)	0.0015 (16)	0.0060 (17)	0.0087 (17)
C19	0.022 (2)	0.024 (2)	0.0216 (19)	−0.0064 (16)	0.0027 (16)	0.0085 (16)
C20	0.0170 (19)	0.029 (2)	0.0229 (19)	0.0040 (16)	0.0035 (15)	0.0101 (17)
C21	0.0193 (18)	0.0208 (18)	0.0149 (17)	0.0044 (15)	0.0045 (14)	0.0066 (15)
C22	0.0201 (19)	0.025 (2)	0.0159 (17)	0.0047 (15)	0.0016 (15)	0.0093 (15)
C23	0.029 (2)	0.0188 (19)	0.0212 (19)	−0.0011 (16)	0.0027 (16)	0.0097 (16)
C24	0.0211 (19)	0.0204 (19)	0.0224 (19)	0.0027 (15)	0.0052 (15)	0.0102 (16)
C25	0.0195 (19)	0.0214 (19)	0.0191 (18)	0.0043 (15)	0.0069 (15)	0.0070 (15)
C26	0.022 (2)	0.035 (2)	0.026 (2)	0.0116 (17)	0.0077 (16)	0.0154 (18)
C27	0.038 (3)	0.042 (3)	0.043 (3)	0.022 (2)	0.021 (2)	0.032 (2)
C28	0.047 (3)	0.026 (2)	0.056 (3)	0.015 (2)	0.033 (3)	0.022 (2)
C29	0.037 (3)	0.025 (2)	0.038 (3)	0.0022 (19)	0.018 (2)	0.007 (2)
C30	0.023 (2)	0.022 (2)	0.027 (2)	0.0052 (16)	0.0077 (17)	0.0073 (17)

Geometric parameters (Å, º) top

Br1—C11	1.908 (4)	C10—C15	1.403 (6)
Br2—C26	1.890 (4)	C11—C12	1.394 (6)
S1—O1	1.426 (3)	C12—C13	1.387 (7)
S1—O2	1.433 (3)	C12—H12	0.9500
S1—N1	1.664 (3)	C13—C14	1.377 (7)
S1—C1	1.762 (4)	C13—H13	0.9500
S2—O5	1.429 (3)	C14—C15	1.370 (6)
S2—O6	1.431 (3)	C14—H14	0.9500
S2—N2	1.664 (3)	C15—H15	0.9500
S2—C16	1.757 (4)	C16—C21	1.380 (5)
O3—C7	1.206 (5)	C16—C17	1.389 (5)
O4—C9	1.206 (5)	C17—C18	1.390 (5)
O7—C22	1.207 (4)	C17—H17	0.9500
O8—C24	1.200 (5)	C18—C19	1.397 (6)
N1—C7	1.395 (5)	C18—H18	0.9500
N1—C8	1.453 (5)	C19—C20	1.390 (5)
N2—C22	1.386 (5)	C19—H19	0.9500
N2—C23	1.455 (5)	C20—C21	1.388 (5)
C1—C2	1.382 (5)	C20—H20	0.9500
C1—C6	1.387 (5)	C21—C22	1.487 (5)
C2—C3	1.390 (6)	C23—C24	1.537 (5)
C2—H2	0.9500	C23—H23A	0.9900
C3—C4	1.389 (6)	C23—H23B	0.9900
C3—H3	0.9500	C24—C25	1.493 (5)
C4—C5	1.389 (6)	C25—C26	1.400 (5)
C4—H4	0.9500	C25—C30	1.405 (6)
C5—C6	1.383 (5)	C26—C27	1.394 (6)
C5—H5	0.9500	C27—C28	1.387 (7)
C6—C7	1.489 (5)	C27—H27	0.9500
C8—C9	1.525 (5)	C28—C29	1.373 (7)
C8—H8A	0.9900	C28—H28	0.9500
C8—H8B	0.9900	C29—C30	1.381 (6)
C9—C10	1.507 (5)	C29—H29	0.9500
C10—C11	1.387 (5)	C30—H30	0.9500

O1—S1—O2	116.92 (19)	C14—C13—C12	120.2 (4)
O1—S1—N1	109.81 (18)	C14—C13—H13	119.9
O2—S1—N1	109.41 (18)	C12—C13—H13	119.9
O1—S1—C1	112.50 (19)	C15—C14—C13	119.9 (4)
O2—S1—C1	112.67 (18)	C15—C14—H14	120.1
N1—S1—C1	92.85 (17)	C13—C14—H14	120.1
O5—S2—O6	117.20 (18)	C14—C15—C10	122.0 (4)
O5—S2—N2	109.94 (17)	C14—C15—H15	119.0
O6—S2—N2	109.76 (18)	C10—C15—H15	119.0
O5—S2—C16	112.41 (18)	C21—C16—C17	123.2 (3)
O6—S2—C16	112.30 (17)	C21—C16—S2	110.1 (3)
N2—S2—C16	92.44 (17)	C17—C16—S2	126.7 (3)
C7—N1—C8	123.3 (3)	C16—C17—C18	116.7 (4)
C7—N1—S1	115.4 (3)	C16—C17—H17	121.7
C8—N1—S1	121.2 (3)	C18—C17—H17	121.7
C22—N2—C23	121.7 (3)	C17—C18—C19	120.7 (4)
C22—N2—S2	115.7 (3)	C17—C18—H18	119.7
C23—N2—S2	122.2 (3)	C19—C18—H18	119.7
C2—C1—C6	123.1 (4)	C20—C19—C18	121.7 (4)
C2—C1—S1	127.2 (3)	C20—C19—H19	119.2
C6—C1—S1	109.6 (3)	C18—C19—H19	119.2
C1—C2—C3	116.5 (4)	C21—C20—C19	117.7 (4)
C1—C2—H2	121.7	C21—C20—H20	121.1
C3—C2—H2	121.7	C19—C20—H20	121.1
C4—C3—C2	121.3 (4)	C16—C21—C20	120.1 (3)
C4—C3—H3	119.4	C16—C21—C22	113.3 (3)
C2—C3—H3	119.4	C20—C21—C22	126.6 (3)
C3—C4—C5	121.1 (4)	O7—C22—N2	124.1 (4)
C3—C4—H4	119.5	O7—C22—C21	127.4 (4)
C5—C4—H4	119.5	N2—C22—C21	108.4 (3)
C6—C5—C4	118.3 (4)	N2—C23—C24	110.8 (3)
C6—C5—H5	120.9	N2—C23—H23A	109.5
C4—C5—H5	120.9	C24—C23—H23A	109.5
C5—C6—C1	119.7 (4)	N2—C23—H23B	109.5
C5—C6—C7	126.8 (4)	C24—C23—H23B	109.5
C1—C6—C7	113.5 (3)	H23A—C23—H23B	108.1
O3—C7—N1	124.0 (4)	O8—C24—C25	124.0 (4)
O3—C7—C6	127.5 (4)	O8—C24—C23	119.6 (3)
N1—C7—C6	108.4 (3)	C25—C24—C23	116.4 (3)
N1—C8—C9	111.4 (3)	C26—C25—C30	117.4 (4)
N1—C8—H8A	109.4	C26—C25—C24	124.0 (4)
C9—C8—H8A	109.4	C30—C25—C24	118.6 (3)
N1—C8—H8B	109.4	C27—C26—C25	120.6 (4)
C9—C8—H8B	109.4	C27—C26—Br2	115.6 (3)
H8A—C8—H8B	108.0	C25—C26—Br2	123.8 (3)
O4—C9—C10	119.6 (4)	C28—C27—C26	120.3 (4)
O4—C9—C8	119.7 (3)	C28—C27—H27	119.9
C10—C9—C8	120.6 (3)	C26—C27—H27	119.9
C11—C10—C15	117.1 (4)	C29—C28—C27	120.0 (4)
C11—C10—C9	128.4 (4)	C29—C28—H28	120.0
C15—C10—C9	114.5 (4)	C27—C28—H28	120.0
C10—C11—C12	121.6 (4)	C28—C29—C30	119.9 (4)
C10—C11—Br1	123.4 (3)	C28—C29—H29	120.0
C12—C11—Br1	114.8 (3)	C30—C29—H29	120.0
C13—C12—C11	119.3 (4)	C29—C30—C25	121.8 (4)
C13—C12—H12	120.4	C29—C30—H30	119.1
C11—C12—H12	120.4	C25—C30—H30	119.1

O1—S1—N1—C7	−111.1 (3)	Br1—C11—C12—C13	175.6 (3)
O2—S1—N1—C7	119.3 (3)	C11—C12—C13—C14	1.1 (7)
C1—S1—N1—C7	4.1 (3)	C12—C13—C14—C15	−1.1 (7)
O1—S1—N1—C8	65.3 (3)	C13—C14—C15—C10	0.4 (7)
O2—S1—N1—C8	−64.3 (3)	C11—C10—C15—C14	0.2 (6)
C1—S1—N1—C8	−179.6 (3)	C9—C10—C15—C14	−179.4 (4)
O5—S2—N2—C22	−116.7 (3)	O5—S2—C16—C21	113.1 (3)
O6—S2—N2—C22	113.0 (3)	O6—S2—C16—C21	−112.2 (3)
C16—S2—N2—C22	−1.8 (3)	N2—S2—C16—C21	0.3 (3)
O5—S2—N2—C23	70.9 (3)	O5—S2—C16—C17	−67.8 (4)
O6—S2—N2—C23	−59.4 (3)	O6—S2—C16—C17	66.9 (4)
C16—S2—N2—C23	−174.2 (3)	N2—S2—C16—C17	179.4 (3)
O1—S1—C1—C2	−69.0 (4)	C21—C16—C17—C18	−0.4 (6)
O2—S1—C1—C2	65.8 (4)	S2—C16—C17—C18	−179.4 (3)
N1—S1—C1—C2	178.2 (4)	C16—C17—C18—C19	−0.8 (6)
O1—S1—C1—C6	109.9 (3)	C17—C18—C19—C20	1.5 (6)
O2—S1—C1—C6	−115.4 (3)	C18—C19—C20—C21	−0.9 (6)
N1—S1—C1—C6	−2.9 (3)	C17—C16—C21—C20	1.0 (6)
C6—C1—C2—C3	0.1 (6)	S2—C16—C21—C20	−179.9 (3)
S1—C1—C2—C3	178.8 (3)	C17—C16—C21—C22	−178.0 (3)
C1—C2—C3—C4	−0.5 (6)	S2—C16—C21—C22	1.1 (4)
C2—C3—C4—C5	0.3 (6)	C19—C20—C21—C16	−0.3 (5)
C3—C4—C5—C6	0.4 (6)	C19—C20—C21—C22	178.6 (4)
C4—C5—C6—C1	−0.8 (6)	C23—N2—C22—O7	−4.5 (6)
C4—C5—C6—C7	179.7 (4)	S2—N2—C22—O7	−176.9 (3)
C2—C1—C6—C5	0.6 (6)	C23—N2—C22—C21	175.0 (3)
S1—C1—C6—C5	−178.3 (3)	S2—N2—C22—C21	2.6 (4)
C2—C1—C6—C7	−179.9 (4)	C16—C21—C22—O7	177.2 (4)
S1—C1—C6—C7	1.3 (4)	C20—C21—C22—O7	−1.7 (6)
C8—N1—C7—O3	1.4 (6)	C16—C21—C22—N2	−2.3 (4)
S1—N1—C7—O3	177.7 (3)	C20—C21—C22—N2	178.8 (4)
C8—N1—C7—C6	179.8 (3)	C22—N2—C23—C24	83.4 (4)
S1—N1—C7—C6	−3.9 (4)	S2—N2—C23—C24	−104.7 (3)
C5—C6—C7—O3	−0.7 (7)	N2—C23—C24—O8	6.4 (5)
C1—C6—C7—O3	179.8 (4)	N2—C23—C24—C25	−172.9 (3)
C5—C6—C7—N1	−179.0 (4)	O8—C24—C25—C26	−7.6 (6)
C1—C6—C7—N1	1.5 (4)	C23—C24—C25—C26	171.7 (4)
C7—N1—C8—C9	90.7 (4)	O8—C24—C25—C30	171.8 (4)
S1—N1—C8—C9	−85.4 (4)	C23—C24—C25—C30	−8.9 (5)
N1—C8—C9—O4	−22.3 (5)	C30—C25—C26—C27	2.2 (6)
N1—C8—C9—C10	155.1 (3)	C24—C25—C26—C27	−178.4 (4)
O4—C9—C10—C11	−155.3 (4)	C30—C25—C26—Br2	−176.7 (3)
C8—C9—C10—C11	27.3 (6)	C24—C25—C26—Br2	2.7 (5)
O4—C9—C10—C15	24.3 (5)	C25—C26—C27—C28	−2.9 (6)
C8—C9—C10—C15	−153.1 (4)	Br2—C26—C27—C28	176.0 (3)
C15—C10—C11—C12	−0.2 (6)	C26—C27—C28—C29	1.4 (6)
C9—C10—C11—C12	179.4 (4)	C27—C28—C29—C30	0.7 (6)
C15—C10—C11—Br1	−176.0 (3)	C28—C29—C30—C25	−1.4 (6)
C9—C10—C11—Br1	3.6 (6)	C26—C25—C30—C29	−0.1 (6)
C10—C11—C12—C13	−0.5 (6)	C24—C25—C30—C29	−179.5 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···O7ⁱ	0.95	2.56	3.238 (5)	129
C14—H14···O1ⁱⁱ	0.95	2.40	3.305 (5)	159
C17—H17···O5ⁱⁱⁱ	0.95	2.43	3.225 (5)	141
C27—H27···O7^iv	0.95	2.29	3.164 (5)	153
C30—H30···O2^v	0.95	2.51	3.251 (5)	135
C8—H8A···Br1	0.99	2.82	3.165 (4)	101
C23—H23A···O3	0.99	2.48	3.014 (5)	114

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

Experimental details

Crystal data
Chemical formula	C₁₅H₁₀BrNO₄S
M_r	380.21
Crystal system, space group	Triclinic, P1
Temperature (K)	123
a, b, c (Å)	7.574 (2), 13.903 (4), 14.814 (4)
α, β, γ (°)	110.574 (15), 96.936 (13), 93.640 (14)
V (Å³)	1440.3 (7)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	3.02
Crystal size (mm)	0.18 × 0.18 × 0.16

Data collection
Diffractometer	Nonius KappaCCD diffractometer
Absorption correction	Multi-scan (SORTAV; Blessing, 1997)
T_min, T_max	0.613, 0.644
No. of measured, independent and observed [I > 2σ(I)] reflections	12284, 6541, 5268
R_int	0.042
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.050, 0.105, 1.12
No. of reflections	6541
No. of parameters	397
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.81, −1.04

Computer programs: COLLECT (Hooft, 1998), DENZO (Otwinowski & Minor, 1997), SCALEPACK (Otwinowski & Minor, 1997), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C14—H14···O1ⁱ	0.95	2.40	3.305 (5)	158.5
C17—H17···O5ⁱⁱ	0.95	2.43	3.225 (5)	140.9
C27—H27···O7ⁱⁱⁱ	0.95	2.29	3.164 (5)	153.2

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

Acknowledgements

The authors are grateful to the Higher Education Commission, Pakistan, and the Institute of Chemistry, University of the Punjab, Lahore, Pakistan, for financial support.

References

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