6-Bromo-3-{2-[2-(diphenyl­methyl­ene)hydrazin­yl]-1,3-thia­zol-5-yl}-2H-chromen-2-one chloro­form monosolvate

Arshad, A.; Osman, H.; Lam, C.K.; Hemamalini, M.; Fun, H.-K.

doi:10.1107/S1600536811012335

organic compounds

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ISSN: 2056-9890

Volume 67| Part 5| May 2011| Pages o1079-o1080

doi:10.1107/S1600536811012335

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6-Bromo-3-{2-[2-(diphenylmethylene)hydrazinyl]-1,3-thiazol-5-yl}-2H-chromen-2-one chloroform monosolvate

Afsheen Arshad,^a Hasnah Osman,^a ‡ Chan Kit Lam,^b Madhukar Hemamalini ^c and Hoong-Kun Fun ^c ^*§

^aSchool of Chemical Sciences, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia, ^bSchool of Pharmaceutical Sciences, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia, and ^cX-ray Crystallography Unit, School of Physics, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia
^*Correspondence e-mail: hkfun@usm.my

(Received 29 March 2011; accepted 2 April 2011; online 13 April 2011)

In the title compound, C₂₅H₁₆BrN₃O₂S·CHCl₃, the thiazole ring is approximately planar [maximum deviation = 0.002 (3) Å] and makes dihedral angles of 10.75 (14) and 87.75 (15)/2.80 (14)° with the pyran ring system and the two terminal phenyl rings, respectively. The solvent molecule is disordered over two sets of sites, with refined occupancies of 0.639 (7) and 0.361 (7). In the crystal, molecules are connected via pairs of weak C—H⋯O interactions, forming centrosymmetric dimers. An intramolecular C—H⋯O hydrogen bond generates an S(6) ring motif.

Related literature

For details and applications of coumarin derivatives, see: Siddiqui et al. (2009 ); Kamal et al. (2009 ); Kalkhambkar et al. (2007 ); Gursoy & Karali (2003 ). For the synthesis of benzophenone thiosemicarbazone and 6-bromo-3-(2-bromoacetyl)-2H-chromen-2-one, see: Yaragatti et al. (2010 ); Lobana et al. (2006 ). For graph-set notation, see: Bernstein et al. (1995 ).

Experimental

Crystal data

C₂₅H₁₆BrN₃O₂S·CHCl₃
M_r = 621.75
Triclinic, $[P \overline 1]$
a = 8.0774 (3) Å
b = 12.6782 (5) Å
c = 14.4396 (5) Å
α = 114.157 (2)°
β = 92.879 (2)°
γ = 100.384 (2)°
V = 1314.40 (8) Å³
Z = 2
Mo Kα radiation
μ = 1.98 mm⁻¹
T = 296 K
0.56 × 0.14 × 0.06 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009) T_min = 0.401, T_max = 0.891
21464 measured reflections
7663 independent reflections
3262 reflections with I > 2σ(I)
R_int = 0.041

Refinement

R[F² > 2σ(F²)] = 0.047
wR(F²) = 0.125
S = 1.00
7663 reflections
357 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.35 e Å⁻³
Δρ_min = −0.40 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C11—H11A⋯O2	0.93	2.32	2.868 (4)	117
C19—H19A⋯O2ⁱ	0.93	2.54	3.448 (4)	165
C26—H26B⋯O2ⁱⁱ	0.96	2.55	3.350 (5)	141
Symmetry codes: (i) -x+1, -y, -z+1; (ii) x+1, y, z.

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

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811012335/lh5227sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811012335/lh5227Isup2.hkl

checkCIF report

Comment top

The pharmacological properties of coumarin and thiazole rings impart special importance to them in synthetic chemistry. The thiazole incorporated coumarin derivatives exhibit anticonvulsant (Siddiqui et al., 2009), anticancer, antimicrobial (Kamal et al., 2009), analgesic and anti-inflammatory activities (Kalkhambkar et al., 2007). Some of these compounds are also reported to have activity against Mycobacterium tuberculosis (Gursoy et al., 2003). The title compound (I) is a new derivative of coumarin having thiazole moiety. We report herein its crystal structure.

The asymmetric unit of the title compound (Fig. 1) consists of one 6-bromo-3-(2-(2-(diphenylmethylene)hydrazinyl)thiazol-5-yl)-2H- chromen-2-one molecule and one chloroform solvent molecule. The thiazole (S1/N1/C10–C12) ring is approximately planar, with maximum deviation of 0.002 (3) Å for atom C10. The solvent molecule is disordered over two sets of sites, with an occupancy ratio of 0.639 (7): 0.361 (7). The central thiazole (S1/N1/C10–C12) ring makes dihedral angles of 10.75 (12) ° and 87.75 (15) and 2.80 (14)° with the pyran (O1/C3–C7) ring system and the two terminal phenyl (C14–C19/C20–C25) rings, respectively.

In the crystal structure, (Fig. 2), the molecules are connected via weak C19—H19A···O2ⁱ and C26—H26B···O2ⁱⁱ (Table 1) interactions. An intramolecular C11—H11A···O2 hydrogen bond generates an S(6) ring motif (Bernstein et al., 1995).

Related literature top

For details and applications of coumarin derivatives, see: Siddiqui et al. (2009); Kamal et al. (2009); Kalkhambkar et al. (2007); Gursoy & Karali (2003). For the synthetic procedure of benzophenone thiosemicarbazone and 6-bromo-3-(2-bromoacetyl)-2H-chromen-2-one, see: Yaragatti et al. (2010); Lobana et al. (2006). For graph-set notation, see: Bernstein et al. (1995).

Experimental top

Benzophenone thiosemicarbazone (Lobana et al., 2006) and 6-bromo-3-(2-bromoacetyl)-2H-chromen-2-one (Yaragatti et al., 2010) were synthesized as reported in the literature. A solution of 6-bromo-3-(2-bromoacetyl)-2H-chromen-2-one (2.5 mmol) and benzophenone thiosemicarbazone (2.5 mmol) in chloroform-ethanol (2:1) was refluxed for 1.5 hours. Precipitates formed were filtered and boiled with water containing sodium acetate. The title compound (I) was purified by recrystallization with ethanol-chloroform (1:3) as large brownish, yellow needle-like crystals.

Computing details top

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

Figures top

	Fig. 1. The asymmetric unit of the title compound, showing 30% probability displacement ellipsoids. The intramolecular hydrogen bond is shown as a dashed line. The open bonds represents disordered components.
	Fig. 2. The crystal packing of the title compound with hydrogen bonds shown as dashed lines.

6-Bromo-3-{2-[2-(diphenylmethylene)hydrazinyl]-1,3-thiazol-5-yl}- 2H-chromen-2-one chloroform monosolvate top

Crystal data top

C₂₅H₁₆BrN₃O₂S·CHCl₃	Z = 2
M_r = 621.75	F(000) = 624
Triclinic, P1	D_x = 1.571 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.0774 (3) Å	Cell parameters from 4500 reflections
b = 12.6782 (5) Å	θ = 2.9–29.6°
c = 14.4396 (5) Å	µ = 1.98 mm⁻¹
α = 114.157 (2)°	T = 296 K
β = 92.879 (2)°	Plate, yellow
γ = 100.384 (2)°	0.56 × 0.14 × 0.06 mm
V = 1314.40 (8) Å³

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	7663 independent reflections
Radiation source: fine-focus sealed tube	3262 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.041
ϕ and ω scans	θ_max = 30.1°, θ_min = 1.6°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −11→11
T_min = 0.401, T_max = 0.891	k = −17→17
21464 measured reflections	l = −20→20

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)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.125	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	w = 1/[σ²(F_o²) + (0.0487P)² + 0.0043P] where P = (F_o² + 2F_c²)/3
7663 reflections	(Δ/σ)_max = 0.001
357 parameters	Δρ_max = 0.35 e Å⁻³
0 restraints	Δρ_min = −0.40 e Å⁻³

Crystal data top

C₂₅H₁₆BrN₃O₂S·CHCl₃	γ = 100.384 (2)°
M_r = 621.75	V = 1314.40 (8) Å³
Triclinic, P1	Z = 2
a = 8.0774 (3) Å	Mo Kα radiation
b = 12.6782 (5) Å	µ = 1.98 mm⁻¹
c = 14.4396 (5) Å	T = 296 K
α = 114.157 (2)°	0.56 × 0.14 × 0.06 mm
β = 92.879 (2)°

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	7663 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2009)	3262 reflections with I > 2σ(I)
T_min = 0.401, T_max = 0.891	R_int = 0.041
21464 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.047	0 restraints
wR(F²) = 0.125	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	Δρ_max = 0.35 e Å⁻³
7663 reflections	Δρ_min = −0.40 e Å⁻³
357 parameters

Special details top

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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	Occ. (<1)
Br1	−0.38420 (5)	−0.63922 (3)	0.45724 (3)	0.09363 (18)
S1	0.38790 (9)	0.12055 (6)	0.50298 (6)	0.0610 (2)
O1	−0.1491 (2)	−0.32668 (16)	0.24872 (13)	0.0643 (5)
O2	0.0058 (3)	−0.17090 (17)	0.24065 (14)	0.0764 (6)
N1	0.2137 (3)	−0.03044 (18)	0.55842 (16)	0.0540 (5)
N2	0.3995 (3)	0.1301 (2)	0.69187 (19)	0.0651 (7)
N3	0.5130 (3)	0.23407 (18)	0.71595 (17)	0.0591 (6)
C1	−0.3766 (4)	−0.5695 (3)	0.2940 (2)	0.0740 (8)
H1A	−0.4596	−0.6386	0.2594	0.089*
C2	−0.3234 (4)	−0.4974 (2)	0.2462 (2)	0.0726 (8)
H2A	−0.3701	−0.5172	0.1795	0.087*
C3	−0.2001 (3)	−0.3959 (2)	0.2988 (2)	0.0568 (7)
C4	−0.0283 (3)	−0.2219 (2)	0.2938 (2)	0.0582 (7)
C5	0.0446 (3)	−0.1845 (2)	0.39995 (19)	0.0509 (6)
C6	−0.0045 (3)	−0.2545 (2)	0.44803 (19)	0.0540 (6)
H6A	0.0438	−0.2311	0.5152	0.065*
C7	−0.1285 (3)	−0.3632 (2)	0.39842 (19)	0.0529 (6)
C8	−0.1827 (4)	−0.4375 (2)	0.4461 (2)	0.0627 (7)
H8A	−0.1358	−0.4186	0.5126	0.075*
C9	−0.3070 (4)	−0.5392 (2)	0.3928 (2)	0.0651 (8)
C10	0.1692 (3)	−0.0710 (2)	0.45345 (19)	0.0505 (6)
C11	0.2498 (3)	−0.0017 (2)	0.4115 (2)	0.0580 (7)
H11A	0.2326	−0.0181	0.3423	0.070*
C12	0.3265 (3)	0.0681 (2)	0.5923 (2)	0.0540 (7)
C13	0.5912 (3)	0.2922 (2)	0.8078 (2)	0.0549 (6)
C14	0.5663 (4)	0.2503 (2)	0.8896 (2)	0.0569 (7)
C15	0.4327 (4)	0.2721 (3)	0.9451 (3)	0.0856 (10)
H15A	0.3585	0.3140	0.9318	0.103*
C16	0.4080 (5)	0.2325 (3)	1.0202 (3)	0.0930 (10)
H16A	0.3189	0.2494	1.0583	0.112*
C17	0.5125 (5)	0.1691 (3)	1.0390 (2)	0.0788 (9)
H17A	0.4941	0.1414	1.0889	0.095*
C18	0.6456 (4)	0.1458 (3)	0.9841 (2)	0.0775 (9)
H18A	0.7180	0.1026	0.9970	0.093*
C19	0.6724 (4)	0.1868 (2)	0.9093 (2)	0.0690 (8)
H19A	0.7630	0.1709	0.8723	0.083*
C20	0.7132 (3)	0.4042 (2)	0.8283 (2)	0.0567 (7)
C21	0.7536 (4)	0.4354 (2)	0.7496 (2)	0.0673 (8)
H21A	0.7037	0.3853	0.6828	0.081*
C22	0.8674 (4)	0.5400 (3)	0.7692 (3)	0.0784 (9)
H22A	0.8936	0.5599	0.7155	0.094*
C23	0.9421 (4)	0.6150 (3)	0.8679 (3)	0.0815 (9)
H23A	1.0189	0.6853	0.8811	0.098*
C24	0.9026 (4)	0.5853 (3)	0.9461 (3)	0.0789 (9)
H24A	0.9521	0.6361	1.0130	0.095*
C25	0.7901 (4)	0.4809 (2)	0.9271 (2)	0.0683 (8)
H25A	0.7654	0.4615	0.9812	0.082*
C26	0.9833 (5)	0.0897 (3)	0.2392 (3)	0.0975 (11)
H26A	0.9796	0.0622	0.2935	0.117*	0.372 (7)
H26B	0.9696	0.0357	0.2707	0.117*	0.628 (7)
Cl1A	0.8630 (12)	−0.0189 (3)	0.1341 (3)	0.136 (3)	0.372 (7)
Cl2A	1.1856 (9)	0.1392 (9)	0.2352 (8)	0.157 (3)	0.372 (7)
Cl3A	0.8588 (9)	0.2080 (4)	0.2724 (5)	0.0986 (14)	0.372 (7)
Cl1B	0.9957 (6)	0.0084 (4)	0.1053 (2)	0.1538 (16)	0.628 (7)
Cl2B	1.1788 (7)	0.1888 (3)	0.2910 (3)	0.1360 (14)	0.628 (7)
Cl3B	0.8225 (10)	0.1494 (8)	0.2524 (5)	0.213 (3)	0.628 (7)
H1N2	0.384 (4)	0.102 (3)	0.737 (2)	0.091 (11)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.1128 (3)	0.0744 (2)	0.0971 (3)	−0.0036 (2)	0.0211 (2)	0.0490 (2)
S1	0.0596 (5)	0.0589 (4)	0.0710 (5)	0.0057 (3)	0.0107 (4)	0.0367 (4)
O1	0.0655 (12)	0.0705 (12)	0.0572 (11)	0.0013 (10)	−0.0032 (9)	0.0344 (9)
O2	0.0841 (15)	0.0871 (13)	0.0646 (12)	−0.0019 (11)	0.0008 (10)	0.0483 (11)
N1	0.0526 (13)	0.0562 (12)	0.0549 (14)	0.0093 (11)	0.0099 (11)	0.0263 (11)
N2	0.0742 (17)	0.0621 (14)	0.0549 (16)	0.0001 (13)	0.0053 (13)	0.0272 (13)
N3	0.0565 (14)	0.0509 (12)	0.0676 (16)	0.0045 (11)	0.0083 (12)	0.0261 (11)
C1	0.073 (2)	0.0605 (17)	0.079 (2)	−0.0024 (15)	0.0021 (17)	0.0286 (16)
C2	0.071 (2)	0.0718 (18)	0.0674 (19)	0.0002 (17)	−0.0081 (16)	0.0311 (16)
C3	0.0519 (16)	0.0585 (15)	0.0644 (18)	0.0090 (14)	0.0076 (14)	0.0320 (14)
C4	0.0489 (17)	0.0678 (17)	0.0636 (18)	0.0086 (14)	0.0065 (14)	0.0356 (15)
C5	0.0444 (15)	0.0606 (15)	0.0518 (15)	0.0123 (13)	0.0079 (12)	0.0275 (13)
C6	0.0555 (16)	0.0586 (15)	0.0479 (15)	0.0086 (13)	0.0062 (12)	0.0244 (13)
C7	0.0537 (16)	0.0541 (14)	0.0518 (16)	0.0113 (13)	0.0104 (13)	0.0235 (12)
C8	0.0709 (19)	0.0566 (16)	0.0599 (17)	0.0080 (15)	0.0134 (15)	0.0262 (14)
C9	0.071 (2)	0.0552 (16)	0.072 (2)	0.0083 (15)	0.0191 (16)	0.0304 (15)
C10	0.0460 (15)	0.0539 (14)	0.0576 (17)	0.0125 (12)	0.0084 (12)	0.0289 (13)
C11	0.0575 (17)	0.0646 (16)	0.0598 (16)	0.0117 (13)	0.0091 (13)	0.0348 (14)
C12	0.0498 (16)	0.0543 (15)	0.0647 (18)	0.0134 (13)	0.0140 (14)	0.0304 (14)
C13	0.0546 (16)	0.0530 (14)	0.0573 (17)	0.0130 (13)	0.0086 (14)	0.0230 (13)
C14	0.0532 (17)	0.0545 (15)	0.0578 (17)	0.0042 (14)	0.0013 (14)	0.0225 (13)
C15	0.083 (2)	0.113 (3)	0.090 (2)	0.043 (2)	0.030 (2)	0.062 (2)
C16	0.090 (3)	0.124 (3)	0.089 (2)	0.040 (2)	0.037 (2)	0.060 (2)
C17	0.092 (3)	0.078 (2)	0.068 (2)	0.0045 (19)	0.0092 (19)	0.0389 (17)
C18	0.088 (3)	0.0714 (19)	0.083 (2)	0.0185 (18)	0.005 (2)	0.0433 (17)
C19	0.0654 (19)	0.0707 (18)	0.080 (2)	0.0171 (16)	0.0148 (16)	0.0398 (17)
C20	0.0539 (17)	0.0526 (15)	0.0653 (18)	0.0127 (13)	0.0068 (14)	0.0266 (14)
C21	0.069 (2)	0.0631 (17)	0.0687 (19)	0.0103 (15)	0.0092 (15)	0.0289 (15)
C22	0.079 (2)	0.0716 (19)	0.093 (2)	0.0081 (17)	0.0210 (19)	0.0460 (19)
C23	0.074 (2)	0.0603 (18)	0.107 (3)	0.0039 (16)	0.006 (2)	0.038 (2)
C24	0.071 (2)	0.0663 (19)	0.086 (2)	0.0033 (17)	−0.0089 (17)	0.0267 (18)
C25	0.073 (2)	0.0603 (17)	0.071 (2)	0.0127 (16)	0.0038 (16)	0.0290 (16)
C26	0.118 (3)	0.095 (2)	0.098 (3)	0.022 (2)	−0.002 (2)	0.063 (2)
Cl1A	0.211 (7)	0.0912 (19)	0.097 (3)	0.014 (3)	−0.030 (3)	0.0435 (17)
Cl2A	0.108 (4)	0.223 (8)	0.229 (8)	0.052 (5)	0.074 (5)	0.171 (7)
Cl3A	0.117 (3)	0.107 (2)	0.098 (2)	0.055 (2)	0.0259 (19)	0.055 (2)
Cl1B	0.160 (3)	0.148 (2)	0.1210 (18)	0.065 (2)	0.0162 (18)	0.0132 (15)
Cl2B	0.174 (3)	0.1110 (18)	0.128 (2)	−0.0059 (17)	−0.007 (2)	0.0741 (17)
Cl3B	0.280 (6)	0.332 (7)	0.185 (4)	0.231 (6)	0.132 (4)	0.190 (5)

Geometric parameters (Å, º) top

Br1—C9	1.898 (3)	C14—C19	1.370 (4)
S1—C11	1.716 (3)	C14—C15	1.377 (4)
S1—C12	1.732 (2)	C15—C16	1.379 (4)
O1—C3	1.372 (3)	C15—H15A	0.9300
O1—C4	1.379 (3)	C16—C17	1.353 (4)
O2—C4	1.202 (3)	C16—H16A	0.9300
N1—C12	1.295 (3)	C17—C18	1.371 (4)
N1—C10	1.390 (3)	C17—H17A	0.9300
N2—C12	1.362 (3)	C18—C19	1.387 (4)
N2—N3	1.363 (3)	C18—H18A	0.9300
N2—H1N2	0.87 (3)	C19—H19A	0.9300
N3—C13	1.284 (3)	C20—C21	1.382 (4)
C1—C9	1.375 (4)	C20—C25	1.387 (4)
C1—C2	1.378 (4)	C21—C22	1.383 (4)
C1—H1A	0.9300	C21—H21A	0.9300
C2—C3	1.373 (3)	C22—C23	1.378 (4)
C2—H2A	0.9300	C22—H22A	0.9300
C3—C7	1.384 (4)	C23—C24	1.364 (4)
C4—C5	1.461 (3)	C23—H23A	0.9300
C5—C6	1.353 (3)	C24—C25	1.378 (4)
C5—C10	1.473 (3)	C24—H24A	0.9300
C6—C7	1.428 (3)	C25—H25A	0.9300
C6—H6A	0.9300	C26—Cl3B	1.599 (7)
C7—C8	1.402 (3)	C26—Cl2A	1.655 (8)
C8—C9	1.381 (4)	C26—Cl1A	1.674 (5)
C8—H8A	0.9300	C26—Cl2B	1.740 (6)
C10—C11	1.354 (3)	C26—Cl1B	1.798 (5)
C11—H11A	0.9300	C26—Cl3A	1.869 (7)
C13—C20	1.483 (3)	C26—H26A	0.9800
C13—C14	1.488 (3)	C26—H26B	0.9601

C11—S1—C12	87.98 (13)	C16—C17—C18	119.8 (3)
C3—O1—C4	122.8 (2)	C16—C17—H17A	120.1
C12—N1—C10	109.2 (2)	C18—C17—H17A	120.1
C12—N2—N3	117.0 (2)	C17—C18—C19	120.0 (3)
C12—N2—H1N2	122 (2)	C17—C18—H18A	120.0
N3—N2—H1N2	120 (2)	C19—C18—H18A	120.0
C13—N3—N2	118.9 (2)	C14—C19—C18	120.4 (3)
C9—C1—C2	120.1 (3)	C14—C19—H19A	119.8
C9—C1—H1A	119.9	C18—C19—H19A	119.8
C2—C1—H1A	119.9	C21—C20—C25	118.1 (2)
C3—C2—C1	118.8 (3)	C21—C20—C13	121.0 (2)
C3—C2—H2A	120.6	C25—C20—C13	120.9 (2)
C1—C2—H2A	120.6	C20—C21—C22	120.8 (3)
O1—C3—C2	117.3 (2)	C20—C21—H21A	119.6
O1—C3—C7	120.5 (2)	C22—C21—H21A	119.6
C2—C3—C7	122.2 (2)	C23—C22—C21	120.2 (3)
O2—C4—O1	115.8 (2)	C23—C22—H22A	119.9
O2—C4—C5	126.9 (2)	C21—C22—H22A	119.9
O1—C4—C5	117.3 (2)	C24—C23—C22	119.5 (3)
C6—C5—C4	119.4 (2)	C24—C23—H23A	120.3
C6—C5—C10	120.9 (2)	C22—C23—H23A	120.3
C4—C5—C10	119.7 (2)	C23—C24—C25	120.6 (3)
C5—C6—C7	121.7 (2)	C23—C24—H24A	119.7
C5—C6—H6A	119.1	C25—C24—H24A	119.7
C7—C6—H6A	119.1	C24—C25—C20	120.8 (3)
C3—C7—C8	118.5 (2)	C24—C25—H25A	119.6
C3—C7—C6	118.3 (2)	C20—C25—H25A	119.6
C8—C7—C6	123.2 (2)	Cl3B—C26—Cl2A	132.4 (4)
C9—C8—C7	118.9 (3)	Cl3B—C26—Cl1A	85.1 (3)
C9—C8—H8A	120.5	Cl2A—C26—Cl1A	119.6 (4)
C7—C8—H8A	120.5	Cl3B—C26—Cl2B	115.0 (4)
C1—C9—C8	121.4 (2)	Cl2A—C26—Cl2B	27.3 (3)
C1—C9—Br1	119.3 (2)	Cl1A—C26—Cl2B	146.5 (4)
C8—C9—Br1	119.3 (2)	Cl3B—C26—Cl1B	110.0 (3)
C11—C10—N1	115.4 (2)	Cl2A—C26—Cl1B	79.3 (4)
C11—C10—C5	127.3 (2)	Cl1A—C26—Cl1B	40.7 (2)
N1—C10—C5	117.4 (2)	Cl2B—C26—Cl1B	105.8 (3)
C10—C11—S1	110.9 (2)	Cl3B—C26—Cl3A	20.7 (4)
C10—C11—H11A	124.6	Cl2A—C26—Cl3A	112.6 (4)
S1—C11—H11A	124.6	Cl1A—C26—Cl3A	102.1 (4)
N1—C12—N2	124.1 (2)	Cl2B—C26—Cl3A	94.4 (3)
N1—C12—S1	116.6 (2)	Cl1B—C26—Cl3A	116.5 (3)
N2—C12—S1	119.33 (19)	Cl3B—C26—H26A	101.7
N3—C13—C20	116.0 (2)	Cl2A—C26—H26A	107.3
N3—C13—C14	123.1 (2)	Cl1A—C26—H26A	107.3
C20—C13—C14	120.9 (2)	Cl2B—C26—H26A	95.1
C19—C14—C15	118.7 (3)	Cl1B—C26—H26A	129.1
C19—C14—C13	120.9 (3)	Cl3A—C26—H26A	107.3
C15—C14—C13	120.4 (3)	Cl3B—C26—H26B	108.6
C14—C15—C16	120.6 (3)	Cl2A—C26—H26B	112.0
C14—C15—H15A	119.7	Cl1A—C26—H26B	88.0
C16—C15—H15A	119.7	Cl2B—C26—H26B	108.5
C17—C16—C15	120.5 (3)	Cl1B—C26—H26B	108.8
C17—C16—H16A	119.8	Cl3A—C26—H26B	120.5
C15—C16—H16A	119.8	H26A—C26—H26B	20.9

C12—N2—N3—C13	−176.4 (2)	C12—S1—C11—C10	0.2 (2)
C9—C1—C2—C3	0.2 (5)	C10—N1—C12—N2	−178.7 (2)
C4—O1—C3—C2	179.0 (3)	C10—N1—C12—S1	0.3 (3)
C4—O1—C3—C7	−1.1 (4)	N3—N2—C12—N1	−178.3 (2)
C1—C2—C3—O1	179.5 (3)	N3—N2—C12—S1	2.8 (3)
C1—C2—C3—C7	−0.4 (5)	C11—S1—C12—N1	−0.3 (2)
C3—O1—C4—O2	179.1 (2)	C11—S1—C12—N2	178.7 (2)
C3—O1—C4—C5	−0.8 (4)	N2—N3—C13—C20	179.8 (2)
O2—C4—C5—C6	−178.0 (3)	N2—N3—C13—C14	1.1 (4)
O1—C4—C5—C6	1.9 (4)	N3—C13—C14—C19	94.4 (3)
O2—C4—C5—C10	2.5 (4)	C20—C13—C14—C19	−84.2 (3)
O1—C4—C5—C10	−177.6 (2)	N3—C13—C14—C15	−83.9 (4)
C4—C5—C6—C7	−1.2 (4)	C20—C13—C14—C15	97.5 (3)
C10—C5—C6—C7	178.3 (2)	C19—C14—C15—C16	1.1 (5)
O1—C3—C7—C8	−179.1 (2)	C13—C14—C15—C16	179.3 (3)
C2—C3—C7—C8	0.8 (4)	C14—C15—C16—C17	−1.5 (5)
O1—C3—C7—C6	1.8 (4)	C15—C16—C17—C18	1.1 (5)
C2—C3—C7—C6	−178.3 (3)	C16—C17—C18—C19	−0.3 (5)
C5—C6—C7—C3	−0.6 (4)	C15—C14—C19—C18	−0.3 (4)
C5—C6—C7—C8	−179.7 (3)	C13—C14—C19—C18	−178.5 (3)
C3—C7—C8—C9	−1.0 (4)	C17—C18—C19—C14	−0.1 (4)
C6—C7—C8—C9	178.1 (3)	N3—C13—C20—C21	−7.5 (4)
C2—C1—C9—C8	−0.4 (5)	C14—C13—C20—C21	171.2 (3)
C2—C1—C9—Br1	179.4 (2)	N3—C13—C20—C25	172.5 (3)
C7—C8—C9—C1	0.8 (4)	C14—C13—C20—C25	−8.8 (4)
C7—C8—C9—Br1	−179.0 (2)	C25—C20—C21—C22	0.0 (4)
C12—N1—C10—C11	−0.1 (3)	C13—C20—C21—C22	179.9 (3)
C12—N1—C10—C5	178.5 (2)	C20—C21—C22—C23	−0.1 (5)
C6—C5—C10—C11	168.7 (3)	C21—C22—C23—C24	−0.2 (5)
C4—C5—C10—C11	−11.8 (4)	C22—C23—C24—C25	0.5 (5)
C6—C5—C10—N1	−9.7 (4)	C23—C24—C25—C20	−0.7 (5)
C4—C5—C10—N1	169.8 (2)	C21—C20—C25—C24	0.4 (4)
N1—C10—C11—S1	−0.1 (3)	C13—C20—C25—C24	−179.6 (3)
C5—C10—C11—S1	−178.5 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C11—H11A···O2	0.93	2.32	2.868 (4)	117
C19—H19A···O2ⁱ	0.93	2.54	3.448 (4)	165
C26—H26B···O2ⁱⁱ	0.96	2.55	3.350 (5)	141

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

Experimental details

Crystal data
Chemical formula	C₂₅H₁₆BrN₃O₂S·CHCl₃
M_r	621.75
Crystal system, space group	Triclinic, P1
Temperature (K)	296
a, b, c (Å)	8.0774 (3), 12.6782 (5), 14.4396 (5)
α, β, γ (°)	114.157 (2), 92.879 (2), 100.384 (2)
V (Å³)	1314.40 (8)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	1.98
Crystal size (mm)	0.56 × 0.14 × 0.06

Data collection
Diffractometer	Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2009)
T_min, T_max	0.401, 0.891
No. of measured, independent and observed [I > 2σ(I)] reflections	21464, 7663, 3262
R_int	0.041
(sin θ/λ)_max (Å⁻¹)	0.705

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.047, 0.125, 1.00
No. of reflections	7663
No. of parameters	357
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.35, −0.40

Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C11—H11A···O2	0.93	2.32	2.868 (4)	117
C19—H19A···O2ⁱ	0.93	2.54	3.448 (4)	165
C26—H26B···O2ⁱⁱ	0.96	2.55	3.350 (5)	141

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

Footnotes

‡Additional correspondence author, e-mail: ohasnah@usm.my.

§Thomson Reuters ResearcherID: A-3561-2009.

Acknowledgements

AA, HO and CKL thank the Malaysian Government and Universiti Sains Malaysia (USM) for a grant [1001/PKimia/811133] to conduct this work. AA also thanks USM for a fellowship. HKF and MH thank the Malaysian Government and USM for the Research University grant No. 1001/PFIZIK/811160. MH also thanks USM for a post-doctoral research fellowship.

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