(1Z,2E)-N′-{1-[2-(4-Bromo­phen­yl)hydrazin-1-yl­idene]-1-chloro­propan-2-yl­idene}thio­phene-2-carbohydrazide

Fun, H.-K.; Chantrapromma, S.; Abdel-Aziz, H.A.

doi:10.1107/S1600536812017114

organic compounds

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ISSN: 2056-9890

Volume 68| Part 5| May 2012| Pages o1510-o1511

doi:10.1107/S1600536812017114

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(1Z,2E)-N′-{1-[2-(4-Bromophenyl)hydrazin-1-ylidene]-1-chloropropan-2-ylidene}thiophene-2-carbohydrazide

Hoong-Kun Fun,^a ^*‡ Suchada Chantrapromma ^b § and Hatem A. Abdel-Aziz ^c

^aX-ray Crystallography Unit, School of Physics, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia, ^bCrystal Materials Research Unit, Department of Chemistry, Faculty of Science, Prince of Songkla University, Hat-Yai, Songkhla 90112, Thailand, and ^cDepartment of Pharmaceutical Chemistry, College of Pharmacy, King Saud University, PO Box 2457, Riyadh 11451, Saudi Arabia
^*Correspondence e-mail: hkfun@usm.my

(Received 11 April 2012; accepted 18 April 2012; online 25 April 2012)

In the title compound, C₁₄H₁₂BrClN₄OS, the thienyl ring is disordered over two orientations with a site-occupancy ratio of 0.853 (2):0.147 (2). The molecule is roughly planar, with the dihedral angles between the thienyl and benzene rings being 6.24 (16) and 9.7 (11)° for the major and minor components, respectively. The central fragment is almost planar [r.m.s. deviation = 0.0275 (2) Å for the ten non-H atoms]. The mean plane through this middle unit makes a dihedral angle of 2.71 (7)° with the benzene ring, whereas these values are 4.46 (15) and 7.7 (11)° for the major and minor components of the thienyl ring, respectively. In the crystal, molecules are linked into dimers by pairs of N—H⋯O hydrogen bonds, forming R₂²(8) ring motifs. These dimers are arranged into sheets parallel to the ac plane.

Related literature

For bond-length data, see: Allen et al. (1987 ). For hydrogen-bond motifs, see: Bernstein et al. (1995 ). For background to and the biological activity of (1Z,2E)-N-(aryl)propanehydrazonoyl chlorides, see: Abdel-Aziz & Mekawey (2009 ); Abdel-Aziz et al. (2010 ). For a related structure, see: Abdel-Aziz et al. (2012 ). For the stability of the temperature controller, see: Cosier & Glazer (1986 ).

Experimental

Crystal data

C₁₄H₁₂BrClN₄OS
M_r = 399.79
Monoclinic, P 2₁ /c
a = 13.5502 (14) Å
b = 3.8932 (4) Å
c = 29.816 (3) Å
β = 103.075 (2)°
V = 1532.1 (3) Å³
Z = 4
Mo Kα radiation
μ = 3.00 mm⁻¹
T = 100 K
0.38 × 0.10 × 0.06 mm

Data collection

Bruker APEX Duo CCD area detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ) T_min = 0.399, T_max = 0.848
14314 measured reflections
4458 independent reflections
3378 reflections with I > 2σ(I)'
R_int = 0.037

Refinement

R[F² > 2σ(F²)] = 0.031
wR(F²) = 0.075
S = 1.05
4458 reflections
223 parameters
6 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.54 e Å⁻³
Δρ_min = −0.36 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N4—H1N4⋯O1ⁱ	0.92 (3)	2.03 (3)	2.938 (2)	168 (2)
N1—H1N1⋯Cl1	0.92 (2)	2.51 (2)	2.9246 (19)	107.7 (15)
Symmetry code: (i) -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/S1600536812017114/bq2351sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812017114/bq2351Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812017114/bq2351Isup3.cml

checkCIF report

Comment top

The synthesis of a new class of (1Z,2E)-N-(aryl)propanehydrazonoyl chlorides as analogs of the title compound have recently been reported. These derivatives were used as an economical and versatile synthetic approach for stereoselective synthesis of novel amidrazone derivatives possessing significant antifungal and antiviral potencies (AbdelAziz & Mekawey, 2009; Abdel-Aziz et al., 2010). As part of our ongoing research on the bioactivity of bis-hydrazones, the title compound (I) was synthesized for a comparable study of another analog (Abdel-Aziz et al., 2012). Herein we report the synthesis and crystal structure of the title compound.

In the molecule of (I) (Fig. 1), C₁₄H₉BrClN₄OS, the thienyl ring is disordered over two positions with the refined site-occupancy ratio of 0.853 (2): 0.147 (2). The molecule is essentially planar with the dihedral angles between the thienyl and benzene rings being 6.24 (16) and 9.7 (11)° for the major and minor components, rsepectively. The middle fragment is planar with an r.m.s. 0.0275 (2) Å for the ten non-H atoms (C7–C10/N1–N4/O1/Cl1). The mean plane through this middle bridge makes the dihedral angle of 2.71 (7) ° with the benzene ring whereas these values are 4.46 (15) and 7.7 (11)° for the major and minor components of the thienyl ring, respectively. An intramolecular N—H···Cl hydrogen bond (Table 1) generates an S(5) ring motif (Bernstein et al., 1995). The bond distances agree with the literature values (Allen et al., 1987) and comparable to the related structure (Abdel-Aziz et al., 2012).

In the crystal packing (Fig. 2), the molecules are linked into dimers by pairs of N—H···O hydrogen bonds forming the R²₂(8) ring motifs (Bernstein et al., 1995) and these dimers arranged into sheets parallel to the ac plane.

Related literature top

For bond-length data, see: Allen et al. (1987). For hydrogen-bond motifs, see: Bernstein et al. (1995). For background to and the biological activity of (1Z,2E)-N-(aryl)propanehydrazonoyl chlorides, see: Abdel-Aziz & Mekawey (2009); Abdel-Aziz et al. (2010). For a related structure, see: Abdel-Aziz et al. (2012). For the stability of the temperature controller, see: Cosier & Glazer (1986).

Experimental top

A mixture of thiophene-2-carbohydrazide (1.42 g, 10 mmol) and (Z)-N'-(4-bromophenyl)-2-oxopropanehydrazonoyl chloride (2.76 g, 10 mmol) in absolute ethanol (50 ml) was refluxed for 6 h. The reaction was then left to cool at room temperature. The solid formed was filtered off, washed with ethanol and recrystallized twice from EtOH to afford yellow needle-shaped title compound.

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 molecular structure of the title compound with 50% probability displacement ellipsoids and the atom-numbering scheme. Open bonds show the minor component.
	Fig. 2. The crystal packing of the title compound viewed along the b axis. Hydrogen bonds were shown as dash lines.

(1Z,2E)-N'-{1-[2-(4-Bromophenyl)hydrazin-1-ylidene]- 1-chloropropan-2-ylidene}thiophene-2-carbohydrazide top

Crystal data top

C₁₄H₁₂BrClN₄OS	F(000) = 800
M_r = 399.79	D_x = 1.733 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 4458 reflections
a = 13.5502 (14) Å	θ = 1.4–30.0°
b = 3.8932 (4) Å	µ = 3.00 mm⁻¹
c = 29.816 (3) Å	T = 100 K
β = 103.075 (2)°	Needle, yellow
V = 1532.1 (3) Å³	0.38 × 0.10 × 0.06 mm
Z = 4

Data collection top

Bruker APEX Duo CCD area detector diffractometer	4458 independent reflections
Radiation source: sealed tube	3378 reflections with I > 2σ(I)'
Graphite monochromator	R_int = 0.037
ϕ and ω scans	θ_max = 30.0°, θ_min = 1.4°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −19→19
T_min = 0.399, T_max = 0.848	k = −2→5
14314 measured reflections	l = −41→41

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)] = 0.031	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.075	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ²(F_o²) + (0.0313P)² + 0.3052P] where P = (F_o² + 2F_c²)/3
4458 reflections	(Δ/σ)_max = 0.001
223 parameters	Δρ_max = 0.54 e Å⁻³
6 restraints	Δρ_min = −0.36 e Å⁻³

Crystal data top

C₁₄H₁₂BrClN₄OS	V = 1532.1 (3) Å³
M_r = 399.79	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 13.5502 (14) Å	µ = 3.00 mm⁻¹
b = 3.8932 (4) Å	T = 100 K
c = 29.816 (3) Å	0.38 × 0.10 × 0.06 mm
β = 103.075 (2)°

Data collection top

Bruker APEX Duo CCD area detector diffractometer	4458 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2009)	3378 reflections with I > 2σ(I)'
T_min = 0.399, T_max = 0.848	R_int = 0.037
14314 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.031	6 restraints
wR(F²) = 0.075	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	Δρ_max = 0.54 e Å⁻³
4458 reflections	Δρ_min = −0.36 e Å⁻³
223 parameters

Special details top

Experimental. The crystal was placed in the cold stream of an Oxford Cryosystems Cobra open-flow nitrogen cryostat (Cosier & Glazer, 1986) operating at 100.0 (1) K.

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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)
Cl1	0.46435 (3)	0.69142 (13)	0.184855 (16)	0.01888 (11)
Br1	1.077635 (15)	0.50439 (6)	0.376036 (7)	0.02669 (7)
O1	0.38556 (10)	0.1793 (4)	−0.02052 (4)	0.0194 (3)
N1	0.66736 (13)	0.5947 (5)	0.24295 (6)	0.0197 (4)
N2	0.65558 (12)	0.4813 (4)	0.19957 (5)	0.0174 (3)
N3	0.47407 (12)	0.3945 (4)	0.09546 (5)	0.0158 (3)
N4	0.46842 (12)	0.2636 (5)	0.05229 (5)	0.0162 (3)
C1	0.84509 (14)	0.4225 (5)	0.25890 (7)	0.0176 (4)
H1A	0.8369	0.3350	0.2293	0.021*
C2	0.93831 (15)	0.4030 (5)	0.28961 (7)	0.0180 (4)
H2A	0.9929	0.3003	0.2808	0.022*
C3	0.95018 (14)	0.5373 (5)	0.33370 (7)	0.0171 (4)
C4	0.86974 (14)	0.6913 (5)	0.34736 (7)	0.0182 (4)
H4A	0.8786	0.7839	0.3768	0.022*
C5	0.77589 (14)	0.7069 (5)	0.31702 (7)	0.0174 (4)
H5A	0.7212	0.8057	0.3263	0.021*
C6	0.76335 (14)	0.5748 (5)	0.27276 (7)	0.0158 (4)
C7	0.57143 (14)	0.5059 (5)	0.17035 (6)	0.0165 (4)
C8	0.56220 (14)	0.3761 (5)	0.12343 (6)	0.0160 (4)
C9	0.65679 (14)	0.2370 (6)	0.11173 (7)	0.0204 (4)
H9A	0.6666	0.3445	0.0841	0.031*
H9B	0.6502	−0.0067	0.1071	0.031*
H9C	0.7139	0.2844	0.1365	0.031*
C10	0.38400 (13)	0.2968 (5)	0.01792 (6)	0.0151 (4)
C11	0.29185 (14)	0.4686 (5)	0.02516 (6)	0.0149 (4)
S1	0.26973 (5)	0.6374 (2)	0.07517 (3)	0.01674 (17)	0.854 (2)
C12	0.2069 (3)	0.5033 (13)	−0.01037 (15)	0.0204 (8)	0.854 (2)
H12A	0.2047	0.4293	−0.0402	0.024*	0.854 (2)
C13	0.1241 (3)	0.6605 (15)	0.00274 (13)	0.0175 (7)	0.854 (2)
H13B	0.0616	0.7008	−0.0171	0.021*	0.854 (2)
C14	0.1476 (2)	0.7459 (12)	0.04819 (11)	0.0174 (7)	0.854 (2)
H14B	0.1024	0.8517	0.0631	0.021*	0.854 (2)
S1X	0.2004 (5)	0.498 (2)	−0.02227 (19)	0.0144 (13)*	0.146 (2)
C12X	0.2653 (17)	0.592 (8)	0.0633 (8)	0.039 (8)*	0.146 (2)
H12B	0.3082	0.5916	0.0924	0.047*	0.146 (2)
C13X	0.1671 (17)	0.721 (8)	0.0541 (8)	0.0144 (13)*	0.15
H13A	0.1352	0.8097	0.0760	0.017*	0.146 (2)
C14X	0.125 (2)	0.698 (13)	0.0090 (9)	0.039 (8)*	0.15
H14A	0.0607	0.7818	−0.0042	0.047*	0.146 (2)
H1N4	0.5211 (19)	0.138 (7)	0.0459 (8)	0.035 (7)*
H1N1	0.6170 (15)	0.722 (6)	0.2508 (7)	0.013 (5)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0152 (2)	0.0249 (3)	0.0170 (2)	0.00090 (19)	0.00470 (17)	−0.0032 (2)
Br1	0.01893 (10)	0.03023 (13)	0.02601 (12)	0.00166 (9)	−0.00517 (8)	−0.00167 (10)
O1	0.0184 (6)	0.0270 (8)	0.0133 (7)	0.0001 (6)	0.0047 (5)	−0.0034 (6)
N1	0.0163 (8)	0.0294 (10)	0.0135 (8)	0.0020 (7)	0.0039 (6)	−0.0054 (7)
N2	0.0177 (8)	0.0221 (9)	0.0122 (7)	−0.0014 (7)	0.0033 (6)	−0.0019 (7)
N3	0.0172 (8)	0.0185 (8)	0.0119 (7)	−0.0016 (6)	0.0039 (6)	−0.0006 (7)
N4	0.0139 (7)	0.0230 (9)	0.0116 (7)	0.0012 (7)	0.0028 (6)	−0.0022 (7)
C1	0.0182 (9)	0.0219 (10)	0.0137 (9)	−0.0002 (7)	0.0060 (7)	−0.0019 (8)
C2	0.0159 (9)	0.0188 (10)	0.0200 (10)	−0.0006 (7)	0.0056 (8)	−0.0007 (8)
C3	0.0145 (8)	0.0174 (10)	0.0176 (9)	−0.0019 (7)	−0.0003 (7)	0.0021 (8)
C4	0.0220 (9)	0.0182 (10)	0.0138 (9)	−0.0004 (8)	0.0030 (7)	−0.0003 (8)
C5	0.0185 (9)	0.0195 (10)	0.0147 (9)	0.0016 (8)	0.0051 (7)	0.0003 (8)
C6	0.0150 (8)	0.0181 (10)	0.0142 (9)	−0.0011 (7)	0.0029 (7)	0.0011 (8)
C7	0.0150 (8)	0.0212 (10)	0.0146 (9)	−0.0018 (8)	0.0057 (7)	−0.0002 (8)
C8	0.0162 (9)	0.0182 (9)	0.0137 (9)	−0.0009 (7)	0.0039 (7)	0.0002 (8)
C9	0.0153 (8)	0.0298 (12)	0.0156 (9)	0.0026 (8)	0.0026 (7)	−0.0037 (9)
C10	0.0146 (8)	0.0174 (9)	0.0140 (9)	−0.0031 (7)	0.0043 (7)	0.0019 (8)
C11	0.0150 (8)	0.0169 (9)	0.0138 (9)	−0.0025 (7)	0.0051 (7)	0.0005 (8)
S1	0.0170 (3)	0.0194 (3)	0.0146 (4)	0.0011 (2)	0.0052 (2)	−0.0011 (3)
C12	0.0187 (14)	0.0260 (16)	0.0185 (19)	−0.0034 (11)	0.0082 (15)	−0.0041 (19)
C13	0.0126 (12)	0.0226 (19)	0.0167 (14)	−0.0015 (10)	0.0020 (9)	0.0031 (14)
C14	0.0143 (16)	0.0217 (15)	0.0170 (15)	0.0056 (13)	0.0048 (12)	0.0032 (12)

Geometric parameters (Å, º) top

Cl1—C7	1.7601 (19)	C8—C9	1.503 (3)
Br1—C3	1.8990 (19)	C9—H9A	0.9600
O1—C10	1.239 (2)	C9—H9B	0.9600
N1—N2	1.342 (2)	C9—H9C	0.9600
N1—C6	1.402 (2)	C10—C11	1.475 (3)
N1—H1N1	0.92 (2)	C11—C12X	1.36 (2)
N2—C7	1.272 (2)	C11—C12	1.383 (5)
N3—C8	1.295 (2)	C11—S1X	1.660 (6)
N3—N4	1.370 (2)	C11—S1	1.717 (2)
N4—C10	1.358 (2)	S1—C14	1.721 (2)
N4—H1N4	0.92 (3)	C12—C13	1.409 (5)
C1—C2	1.384 (3)	C12—H12A	0.9300
C1—C6	1.399 (3)	C13—C14	1.361 (4)
C1—H1A	0.9300	C13—H13B	0.9300
C2—C3	1.390 (3)	C14—H14B	0.9300
C2—H2A	0.9300	S1X—C14X	1.717 (19)
C3—C4	1.384 (3)	C12X—C13X	1.389 (18)
C4—C5	1.385 (3)	C12X—H12B	0.9300
C4—H4A	0.9300	C13X—C14X	1.339 (17)
C5—C6	1.391 (3)	C13X—H13A	0.9300
C5—H5A	0.9300	C14X—H14A	0.9300
C7—C8	1.466 (3)

N2—N1—C6	118.94 (16)	C8—C9—H9C	109.5
N2—N1—H1N1	119.5 (13)	H9A—C9—H9C	109.5
C6—N1—H1N1	120.4 (13)	H9B—C9—H9C	109.5
C7—N2—N1	121.87 (17)	O1—C10—N4	118.37 (17)
C8—N3—N4	115.57 (16)	O1—C10—C11	119.68 (17)
C10—N4—N3	122.12 (16)	N4—C10—C11	121.95 (17)
C10—N4—H1N4	117.1 (16)	C12X—C11—C12	105.9 (9)
N3—N4—H1N4	120.7 (16)	C12X—C11—C10	132.7 (9)
C2—C1—C6	119.53 (18)	C12—C11—C10	121.2 (2)
C2—C1—H1A	120.2	C12X—C11—S1X	113.6 (9)
C6—C1—H1A	120.2	C10—C11—S1X	113.6 (3)
C1—C2—C3	119.87 (18)	C12—C11—S1	110.5 (2)
C1—C2—H2A	120.1	C10—C11—S1	128.37 (14)
C3—C2—H2A	120.1	S1X—C11—S1	118.0 (3)
C4—C3—C2	120.75 (18)	C11—S1—C14	91.51 (15)
C4—C3—Br1	119.47 (15)	C11—C12—C13	114.0 (3)
C2—C3—Br1	119.78 (14)	C11—C12—H12A	123.0
C3—C4—C5	119.64 (18)	C13—C12—H12A	123.0
C3—C4—H4A	120.2	C14—C13—C12	111.2 (3)
C5—C4—H4A	120.2	C14—C13—H13B	124.4
C4—C5—C6	120.05 (17)	C12—C13—H13B	124.4
C4—C5—H5A	120.0	C13—C14—S1	112.9 (3)
C6—C5—H5A	120.0	C13—C14—H14B	123.6
C5—C6—C1	120.15 (18)	S1—C14—H14B	123.6
C5—C6—N1	118.55 (17)	C11—S1X—C14X	89.5 (9)
C1—C6—N1	121.30 (17)	C11—C12X—C13X	112.7 (16)
N2—C7—C8	119.82 (17)	C11—C12X—H12B	123.6
N2—C7—Cl1	121.57 (15)	C13X—C12X—H12B	123.6
C8—C7—Cl1	118.61 (14)	C14X—C13X—C12X	110 (2)
N3—C8—C7	117.55 (17)	C14X—C13X—H13A	124.9
N3—C8—C9	125.54 (17)	C12X—C13X—H13A	124.9
C7—C8—C9	116.89 (16)	C13X—C14X—S1X	113.8 (19)
C8—C9—H9A	109.5	C13X—C14X—H14A	123.1
C8—C9—H9B	109.5	S1X—C14X—H14A	123.1
H9A—C9—H9B	109.5

C6—N1—N2—C7	−176.96 (19)	N4—C10—C11—C12	179.3 (3)
C8—N3—N4—C10	−173.07 (18)	O1—C10—C11—S1X	−2.8 (4)
C6—C1—C2—C3	−0.6 (3)	N4—C10—C11—S1X	176.9 (3)
C1—C2—C3—C4	−0.1 (3)	O1—C10—C11—S1	177.55 (15)
C1—C2—C3—Br1	179.12 (15)	N4—C10—C11—S1	−2.7 (3)
C2—C3—C4—C5	1.1 (3)	C12X—C11—S1—C14	−32 (13)
Br1—C3—C4—C5	−178.13 (15)	C12—C11—S1—C14	0.7 (3)
C3—C4—C5—C6	−1.4 (3)	C10—C11—S1—C14	−177.4 (2)
C4—C5—C6—C1	0.7 (3)	S1X—C11—S1—C14	3.0 (4)
C4—C5—C6—N1	179.99 (19)	C12X—C11—C12—C13	2.2 (14)
C2—C1—C6—C5	0.3 (3)	C10—C11—C12—C13	177.5 (4)
C2—C1—C6—N1	−178.97 (19)	S1X—C11—C12—C13	−166 (4)
N2—N1—C6—C5	177.19 (18)	S1—C11—C12—C13	−0.8 (5)
N2—N1—C6—C1	−3.5 (3)	C11—C12—C13—C14	0.4 (7)
N1—N2—C7—C8	−179.62 (18)	C12—C13—C14—S1	0.1 (6)
N1—N2—C7—Cl1	0.1 (3)	C11—S1—C14—C13	−0.5 (4)
N4—N3—C8—C7	−178.66 (17)	C12X—C11—S1X—C14X	2 (2)
N4—N3—C8—C9	2.3 (3)	C12—C11—S1X—C14X	15 (4)
N2—C7—C8—N3	177.33 (19)	C10—C11—S1X—C14X	179.2 (19)
Cl1—C7—C8—N3	−2.4 (3)	S1—C11—S1X—C14X	−1.1 (19)
N2—C7—C8—C9	−3.5 (3)	C12—C11—C12X—C13X	−2 (3)
Cl1—C7—C8—C9	176.79 (15)	C10—C11—C12X—C13X	−176.9 (17)
N3—N4—C10—O1	178.17 (17)	S1X—C11—C12X—C13X	−1 (3)
N3—N4—C10—C11	−1.6 (3)	S1—C11—C12X—C13X	146 (15)
O1—C10—C11—C12X	173.4 (18)	C11—C12X—C13X—C14X	−2 (4)
N4—C10—C11—C12X	−6.8 (18)	C12X—C13X—C14X—S1X	4 (5)
O1—C10—C11—C12	−0.4 (4)	C11—S1X—C14X—C13X	−3 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N4—H1N4···O1ⁱ	0.92 (3)	2.03 (3)	2.938 (2)	168 (2)
N1—H1N1···Cl1	0.92 (2)	2.51 (2)	2.9246 (19)	107.7 (15)

Symmetry code: (i) −x+1, −y, −z.

Experimental details

Crystal data
Chemical formula	C₁₄H₁₂BrClN₄OS
M_r	399.79
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	100
a, b, c (Å)	13.5502 (14), 3.8932 (4), 29.816 (3)
β (°)	103.075 (2)
V (Å³)	1532.1 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	3.00
Crystal size (mm)	0.38 × 0.10 × 0.06

Data collection
Diffractometer	Bruker APEX Duo CCD area detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2009)
T_min, T_max	0.399, 0.848
No. of measured, independent and observed [I > 2σ(I)'] reflections	14314, 4458, 3378
R_int	0.037
(sin θ/λ)_max (Å⁻¹)	0.703

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.031, 0.075, 1.05
No. of reflections	4458
No. of parameters	223
No. of restraints	6
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.54, −0.36

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
N4—H1N4···O1ⁱ	0.92 (3)	2.03 (3)	2.938 (2)	168 (2)
N1—H1N1···Cl1	0.92 (2)	2.51 (2)	2.9246 (19)	107.7 (15)

Symmetry code: (i) −x+1, −y, −z.

Footnotes

‡Thomson Reuters ResearcherID: A-3561-2009.

§Thomson Reuters ResearcherID: A-5085-2009.

Acknowledgements

HAAA thanks the Deanship of Scientific Research and the Research Center, College of Pharmacy, King Saud University. HKF and SC thank the Universiti Sains Malaysia for the Research University Grant No. 1001/PFIZIK/811160.

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