4-[(E)-4-Bromo­benzyl­ideneamino]-3-[1-(4-isobutyl­phen­yl)eth­yl]-1H-1,2,4-triazole-5(4H)-thione

Fun, H.-K.; Jebas, S.R.; Sujith, K.V.; Kalluraya, B.

doi:10.1107/S1600536809018030

organic compounds

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ISSN: 2056-9890

Volume 65| Part 6| June 2009| Pages o1340-o1341

doi:10.1107/S1600536809018030

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4-[(E)-4-Bromobenzylideneamino]-3-[1-(4-isobutylphenyl)ethyl]-1H-1,2,4-triazole-5(4H)-thione

Hoong-Kun Fun,^a ^*‡ Samuel Robinson Jebas,^a § K. V. Sujith ^b and Balakrishna Kalluraya ^b

^aX-ray Crystallography Unit, School of Physics, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia, and ^bDepartment of studies in Chemistry, Mangalore University, Mangalagangotri, Mangalore 574 199, India
^*Correspondence e-mail: hkfun@usm.my

(Received 28 April 2009; accepted 13 May 2009; online 20 May 2009)

In the title compound, C₂₁H₂₃BrN₄S, the 4-bromobenzylidene group is disordered over two orientations with occupancies of 0.504 (5) and 0.496 (5). One of the methyl groups of the isobutyl unit is disordered over two sites with occupancies of 0.751 (19) and 0.249 (19). The benzene rings of the isobutylphenyl and bromophenyl (major disorder component) groups form dihedral angles of 71.63 (11) and 21.8 (3)°, respectively, with the triazole ring. In the crystal, centrosymmetrically related molecules exist as centrosymmetric N—H⋯S hydrogen-bonded dimers.

Related literature

For the pharmaceutical applications of triazole derivatives, see: Al-Soud et al. (2003 ); Almasirad et al. (2004 ); Amir & Shikha (2004 ); Demirbas et al. (2004 ); Holla et al. (2003 ); Kawashima et al. (1987 ); Zitouni et al. (2005 ); Walczak et al. (2004 ); For bond-length data, see: Allen et al. (1987 ). For related structures, see: Fun et al. (2008a ,b ). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986 ).

Experimental

Crystal data

C₂₁H₂₃BrN₄S
M_r = 443.40
Triclinic, $[P \overline 1]$
a = 5.5791 (2) Å
b = 11.3052 (3) Å
c = 17.3688 (4) Å
α = 75.421 (1)°
β = 86.614 (1)°
γ = 79.616 (1)°
V = 1042.75 (5) Å³
Z = 2
Mo Kα radiation
μ = 2.08 mm⁻¹
T = 100 K
0.27 × 0.17 × 0.05 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.602, T_max = 0.908
26698 measured reflections
8529 independent reflections
5907 reflections with I > 2σ(I)
R_int = 0.029

Refinement

R[F² > 2σ(F²)] = 0.052
wR(F²) = 0.141
S = 1.05
8529 reflections
331 parameters
44 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.67 e Å⁻³
Δρ_min = −0.83 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N1⋯S1ⁱ	0.91 (4)	2.35 (4)	3.2582 (18)	175 (4)
Symmetry code: (i) -x+3, -y+1, -z+1.

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); 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/S1600536809018030/ci2795sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809018030/ci2795Isup2.hkl

checkCIF report

Comment top

Some degree of respectability has been bestowed on 1,2,4-triazole derivatives due to their antibacterial, antifungal (Zitouni et al., 2005), antitubercular (Walczak et al., 2004), anticancer (Holla et al., 2003), antitumor (Al-Soud et al., 2003), anticonvulsant (Almasirad et al., 2004), anti-inflammatory, and analgesic properties (Amir & Shikha, 2004). Certain 1,2,4-triazoles also find applications in the preparation of photographic plates, polymers, and as analytical agents (Kawashima et al., 1987). Similarly Schiff base derivatives of 1,2,4-triazol-5-ones have been found to possess antitumor activity (Demirbas et al., 2004). In our earlier studies, we have reported the crystal structure of heterocyclic compounds containing both the ibuprofen and 1,2,4- triazole fragments (Fun et al., 2008a,b). Prompted by these observations and in continuation of our interest in the synthesis of chemically and biologically important heterocycles, we synthesized the title compound and report here its crystal structure.

Bond lengths (Allen et al., 1987) and angles are normal. The (4-bromophenyl)methylidene group is disordered over two orientations. The C11-C16 benzene ring forms a dihedral angle of 71.63 (11)° with the triazole ring (N1-N3/C8/C9). The dihedral angle between the C1A-C6A and N1-N3/C8/C9 rings is 21.8 (3)°.

The crystal packing (Fig 2) is consolidated by intermolecular N—H···S hygrogen bonds. These hydrogen bonds link centrosymmetrically related molecules into dimers.

Related literature top

For the pharmaceutical applications of triazole derivatives, see: Al-Soud et al. (2003); Almasirad et al. (2004); Amir & Shikha (2004); Demirbas et al. (2004); Holla et al. (2003); Kawashima et al. (1987); Zitouni et al. (2005); Walczak et al. (2004); For bond-length data, see: Allen et al. (1987). For related structures, see: Fun et al. (2008a,b). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986).

Experimental top

The title Schiff base compound was obtained by refluxing 4-amino-5-[1-(4-isobutylphenyl)ethyl]-4H-1,2,4-triazole-3-thiol (0.01 mol) and 4-bromobenzaldehyde (0.01 mol) in ethanol (50 ml) with 3 drops of concentrated sulfuric acid for 3 h. The solid product obtained was collected by filtration, washed with ethanol and dried. It was then recrystallized using ethanol. Single crystals suitable for X-ray analysis were obtained by slow evaporation of an ethanol solution.

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); 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, showing 50% probability displacement ellipsoids and the atom-numbering scheme. Both disorder components are shown.
	Fig. 2. The crystal packing of the title compound, viewed along the b axis. Dashed lines indicate N—H···S hydrogen bonds. Only major disorder components are shown. For clarity, H atoms not involved in hydrogen bonding have been removed.

4-[(E)-4-Bromobenzylideneamino]-3-[1-(4-isobutylphenyl)ethyl]- 1H-1,2,4-triazole-5(4H)-thione top

Crystal data top

C₂₁H₂₃BrN₄S	Z = 2
M_r = 443.40	F(000) = 456
Triclinic, P1	D_x = 1.412 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 5.5791 (2) Å	Cell parameters from 9940 reflections
b = 11.3052 (3) Å	θ = 2.7–33.0°
c = 17.3688 (4) Å	µ = 2.08 mm⁻¹
α = 75.421 (1)°	T = 100 K
β = 86.614 (1)°	Plate, colourless
γ = 79.616 (1)°	0.27 × 0.17 × 0.05 mm
V = 1042.75 (5) Å³

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	8529 independent reflections
Radiation source: fine-focus sealed tube	5907 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.029
ϕ and ω scans	θ_max = 34.2°, θ_min = 2.4°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −8→8
T_min = 0.602, T_max = 0.908	k = −17→17
26698 measured reflections	l = −27→27

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)] = 0.052	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.141	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ²(F_o²) + (0.0732P)² + 0.4173P] where P = (F_o² + 2F_c²)/3
8529 reflections	(Δ/σ)_max = 0.001
331 parameters	Δρ_max = 0.67 e Å⁻³
44 restraints	Δρ_min = −0.83 e Å⁻³

Crystal data top

C₂₁H₂₃BrN₄S	γ = 79.616 (1)°
M_r = 443.40	V = 1042.75 (5) Å³
Triclinic, P1	Z = 2
a = 5.5791 (2) Å	Mo Kα radiation
b = 11.3052 (3) Å	µ = 2.08 mm⁻¹
c = 17.3688 (4) Å	T = 100 K
α = 75.421 (1)°	0.27 × 0.17 × 0.05 mm
β = 86.614 (1)°

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	8529 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	5907 reflections with I > 2σ(I)
T_min = 0.602, T_max = 0.908	R_int = 0.029
26698 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.052	44 restraints
wR(F²) = 0.141	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	Δρ_max = 0.67 e Å⁻³
8529 reflections	Δρ_min = −0.83 e Å⁻³
331 parameters

Special details top

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

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	Occ. (<1)
S1	1.28609 (9)	0.34264 (4)	0.51104 (3)	0.01997 (11)
N1	1.3036 (3)	0.56195 (15)	0.40486 (11)	0.0218 (3)
N2	1.1990 (3)	0.64191 (15)	0.33670 (10)	0.0210 (3)
N3	1.0344 (3)	0.47201 (14)	0.37298 (10)	0.0179 (3)
N4	0.8770 (3)	0.39601 (15)	0.36230 (10)	0.0207 (3)
Br1A	0.3846 (3)	−0.10655 (16)	0.32563 (14)	0.0250 (2)	0.504 (5)
C1A	0.6489 (11)	0.2199 (4)	0.3123 (3)	0.0230 (10)	0.504 (5)
H1A	0.6584	0.2931	0.2740	0.028*	0.504 (5)
C2A	0.5425 (10)	0.1269 (4)	0.2937 (3)	0.0257 (10)	0.504 (5)
H2A	0.4850	0.1376	0.2428	0.031*	0.504 (5)
C3A	0.524 (3)	0.0185 (11)	0.3521 (7)	0.023 (2)	0.504 (5)
C4A	0.6099 (8)	0.0001 (3)	0.4279 (2)	0.0222 (9)	0.504 (5)
H4A	0.5976	−0.0728	0.4661	0.027*	0.504 (5)
C5A	0.7157 (8)	0.0922 (3)	0.4464 (2)	0.0200 (8)	0.504 (5)
H5A	0.7704	0.0804	0.4977	0.024*	0.504 (5)
C6A	0.7418 (14)	0.2021 (7)	0.3895 (4)	0.0140 (13)	0.504 (5)
C7A	0.9410 (9)	0.2829 (4)	0.3857 (3)	0.0164 (8)	0.504 (5)
H7A	1.1007	0.2478	0.4003	0.020*	0.504 (5)
Br1B	0.3266 (4)	−0.0828 (2)	0.32652 (14)	0.0315 (3)	0.496 (5)
C1B	0.5581 (10)	0.2422 (5)	0.3354 (4)	0.0251 (10)	0.496 (5)
H1B	0.4996	0.3270	0.3207	0.030*	0.496 (5)
C2B	0.4229 (9)	0.1591 (4)	0.3211 (3)	0.0259 (10)	0.496 (5)
H2B	0.2742	0.1874	0.2955	0.031*	0.496 (5)
C3B	0.511 (2)	0.0331 (10)	0.3453 (7)	0.019 (2)	0.496 (5)
C4B	0.7310 (8)	−0.0122 (4)	0.3842 (3)	0.0227 (9)	0.496 (5)
H4B	0.7865	−0.0972	0.4007	0.027*	0.496 (5)
C5B	0.8665 (7)	0.0715 (3)	0.3982 (2)	0.0205 (9)	0.496 (5)
H5B	1.0132	0.0433	0.4250	0.025*	0.496 (5)
C6B	0.7815 (16)	0.1976 (8)	0.3717 (4)	0.0177 (15)	0.496 (5)
C7B	0.8642 (10)	0.2913 (4)	0.4107 (3)	0.0195 (9)	0.496 (5)
H7B	0.9015	0.2734	0.4643	0.023*	0.496 (5)
C8	1.2086 (4)	0.45804 (17)	0.42984 (11)	0.0183 (3)
C9	1.0332 (4)	0.58544 (17)	0.31907 (12)	0.0186 (3)
C10	0.8618 (4)	0.63522 (17)	0.25106 (11)	0.0182 (3)
H10	0.6956	0.6424	0.2732	0.022*
C11	0.8818 (3)	0.55032 (17)	0.19481 (11)	0.0182 (3)
C12	0.6815 (4)	0.55549 (18)	0.14931 (12)	0.0202 (4)
H12	0.5389	0.6103	0.1541	0.024*
C13	0.6911 (4)	0.48005 (19)	0.09682 (12)	0.0231 (4)
H13	0.5545	0.4853	0.0671	0.028*
C14	0.9017 (4)	0.39637 (18)	0.08781 (12)	0.0216 (4)
C15	1.1011 (4)	0.3927 (2)	0.13315 (14)	0.0248 (4)
H15	1.2441	0.3382	0.1283	0.030*
C16	1.0928 (4)	0.46833 (19)	0.18572 (13)	0.0236 (4)
H16	1.2299	0.4639	0.2150	0.028*
C17	0.9038 (5)	0.3124 (2)	0.03308 (14)	0.0269 (4)
H17A	1.0714	0.2834	0.0194	0.032*
H17B	0.8221	0.3598	−0.0157	0.032*
C18	0.7800 (5)	0.1999 (2)	0.06865 (16)	0.0336 (5)
H18A	0.6260	0.2265	0.0946	0.040*	0.751 (19)
H18B	0.6190	0.2385	0.0806	0.040*	0.249 (19)
C19	0.9578 (16)	0.1074 (4)	0.1326 (3)	0.0482 (17)	0.751 (19)
H19A	0.8860	0.0355	0.1564	0.072*	0.751 (19)
H19B	0.9859	0.1477	0.1729	0.072*	0.751 (19)
H19C	1.1099	0.0828	0.1074	0.072*	0.751 (19)
C19A	0.833 (5)	0.1155 (12)	0.1451 (7)	0.045 (4)	0.249 (19)
H19D	0.6845	0.1088	0.1756	0.068*	0.249 (19)
H19E	0.9431	0.1459	0.1728	0.068*	0.249 (19)
H19F	0.9065	0.0353	0.1380	0.068*	0.249 (19)
C20	0.7304 (6)	0.1367 (3)	0.0047 (2)	0.0443 (7)
H20A	0.6351	0.1960	−0.0366	0.066*
H20B	0.6427	0.0703	0.0278	0.066*
H20C	0.8823	0.1040	−0.0174	0.066*
C21	0.9022 (5)	0.76614 (19)	0.20644 (14)	0.0282 (4)
H21A	0.8821	0.8187	0.2428	0.042*
H21B	0.7857	0.7995	0.1646	0.042*
H21C	1.0640	0.7620	0.1840	0.042*
H1N1	1.424 (7)	0.584 (4)	0.429 (2)	0.058 (10)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0262 (2)	0.01396 (19)	0.0200 (2)	−0.00712 (16)	−0.00585 (17)	−0.00092 (16)
N1	0.0275 (8)	0.0159 (7)	0.0224 (8)	−0.0096 (6)	−0.0078 (7)	0.0004 (6)
N2	0.0268 (8)	0.0164 (7)	0.0200 (8)	−0.0085 (6)	−0.0040 (6)	−0.0006 (6)
N3	0.0230 (7)	0.0137 (7)	0.0179 (7)	−0.0067 (6)	−0.0035 (6)	−0.0022 (5)
N4	0.0228 (8)	0.0146 (7)	0.0244 (8)	−0.0080 (6)	−0.0057 (6)	0.0001 (6)
Br1A	0.0305 (6)	0.0176 (4)	0.0322 (3)	−0.0109 (3)	−0.0032 (4)	−0.0103 (3)
C1A	0.032 (3)	0.019 (2)	0.018 (2)	−0.0129 (19)	−0.0069 (18)	0.0021 (15)
C2A	0.035 (3)	0.0224 (19)	0.023 (2)	−0.0130 (18)	−0.0103 (19)	−0.0035 (16)
C3A	0.026 (4)	0.011 (2)	0.030 (4)	−0.004 (2)	0.005 (3)	−0.001 (2)
C4A	0.033 (2)	0.0124 (15)	0.0231 (19)	−0.0097 (14)	−0.0019 (17)	−0.0024 (13)
C5A	0.029 (2)	0.0126 (15)	0.0186 (17)	−0.0080 (13)	−0.0031 (14)	−0.0011 (13)
C6A	0.023 (3)	0.0115 (19)	0.009 (3)	−0.0039 (17)	−0.003 (2)	−0.0036 (19)
C7A	0.021 (2)	0.0120 (16)	0.017 (2)	−0.0037 (15)	−0.0023 (16)	−0.0046 (15)
Br1B	0.0392 (8)	0.0315 (8)	0.0318 (3)	−0.0229 (5)	−0.0061 (6)	−0.0093 (5)
C1B	0.022 (2)	0.021 (2)	0.033 (3)	−0.0042 (18)	−0.008 (2)	−0.0075 (19)
C2B	0.022 (2)	0.027 (2)	0.033 (2)	−0.0072 (17)	−0.0047 (18)	−0.0108 (18)
C3B	0.026 (4)	0.022 (4)	0.017 (3)	−0.014 (3)	−0.006 (2)	−0.010 (3)
C4B	0.027 (2)	0.0158 (17)	0.027 (2)	−0.0086 (14)	−0.0062 (17)	−0.0043 (15)
C5B	0.0243 (18)	0.0125 (15)	0.025 (2)	−0.0066 (13)	−0.0076 (15)	−0.0015 (13)
C6B	0.029 (3)	0.015 (2)	0.012 (3)	−0.0049 (19)	0.003 (2)	−0.009 (2)
C7B	0.025 (2)	0.0170 (19)	0.017 (2)	−0.0063 (17)	−0.0018 (17)	−0.0023 (16)
C8	0.0234 (9)	0.0144 (7)	0.0178 (8)	−0.0060 (6)	−0.0032 (7)	−0.0027 (6)
C9	0.0238 (9)	0.0130 (7)	0.0187 (8)	−0.0062 (6)	−0.0014 (7)	−0.0011 (6)
C10	0.0219 (8)	0.0130 (7)	0.0188 (8)	−0.0040 (6)	−0.0035 (7)	−0.0006 (6)
C11	0.0196 (8)	0.0144 (7)	0.0191 (8)	−0.0051 (6)	−0.0027 (6)	0.0004 (6)
C12	0.0208 (8)	0.0159 (8)	0.0228 (9)	0.0005 (6)	−0.0046 (7)	−0.0044 (7)
C13	0.0260 (9)	0.0210 (9)	0.0215 (9)	−0.0051 (7)	−0.0066 (7)	−0.0020 (7)
C14	0.0273 (9)	0.0173 (8)	0.0206 (9)	−0.0076 (7)	0.0028 (7)	−0.0032 (7)
C15	0.0192 (9)	0.0219 (9)	0.0329 (11)	−0.0015 (7)	0.0022 (8)	−0.0081 (8)
C16	0.0182 (8)	0.0233 (9)	0.0299 (10)	−0.0040 (7)	−0.0021 (7)	−0.0071 (8)
C17	0.0367 (11)	0.0202 (9)	0.0252 (10)	−0.0054 (8)	0.0016 (9)	−0.0082 (8)
C18	0.0443 (13)	0.0196 (10)	0.0392 (13)	−0.0108 (9)	0.0066 (11)	−0.0091 (9)
C19	0.064 (4)	0.0223 (16)	0.052 (2)	−0.0045 (18)	−0.012 (2)	0.0026 (15)
C19A	0.058 (6)	0.035 (5)	0.045 (5)	−0.015 (4)	0.010 (4)	−0.011 (4)
C20	0.0526 (17)	0.0268 (12)	0.0591 (18)	−0.0079 (11)	−0.0076 (14)	−0.0186 (12)
C21	0.0406 (12)	0.0167 (9)	0.0258 (10)	−0.0076 (8)	−0.0073 (9)	0.0011 (7)

Geometric parameters (Å, º) top

S1—C8	1.6794 (19)	C9—C10	1.494 (3)
N1—C8	1.338 (2)	C10—C11	1.520 (3)
N1—N2	1.383 (2)	C10—C21	1.538 (3)
N1—H1N1	0.91 (4)	C10—H10	0.98
N2—C9	1.305 (2)	C11—C16	1.389 (3)
N3—C9	1.384 (2)	C11—C12	1.391 (3)
N3—N4	1.384 (2)	C12—C13	1.389 (3)
N3—C8	1.387 (2)	C12—H12	0.93
N4—C7A	1.232 (5)	C13—C14	1.398 (3)
N4—C7B	1.279 (5)	C13—H13	0.93
Br1A—C3A	1.891 (13)	C14—C15	1.389 (3)
C1A—C2A	1.408 (5)	C14—C17	1.501 (3)
C1A—C6A	1.419 (7)	C15—C16	1.393 (3)
C1A—H1A	0.93	C15—H15	0.93
C2A—C3A	1.397 (11)	C16—H16	0.93
C2A—H2A	0.93	C17—C18	1.533 (3)
C3A—C4A	1.381 (11)	C17—H17A	0.97
C4A—C5A	1.395 (5)	C17—H17B	0.97
C4A—H4A	0.93	C18—C19A	1.438 (12)
C5A—C6A	1.405 (8)	C18—C20	1.526 (4)
C5A—H5A	0.93	C18—C19	1.576 (5)
C6A—C7A	1.549 (8)	C18—H18A	0.98
C7A—H7A	0.93	C18—H18B	0.96
Br1B—C3B	1.903 (10)	C19—H19A	0.96
C1B—C2B	1.381 (6)	C19—H19B	0.96
C1B—C6B	1.383 (9)	C19—H19C	0.96
C1B—H1B	0.93	C19A—H19D	0.96
C2B—C3B	1.385 (10)	C19A—H19E	0.96
C2B—H2B	0.93	C19A—H19F	0.96
C3B—C4B	1.386 (10)	C20—H20A	0.96
C4B—C5B	1.386 (5)	C20—H20B	0.96
C4B—H4B	0.93	C20—H20C	0.96
C5B—C6B	1.386 (9)	C21—H21A	0.96
C5B—H5B	0.93	C21—H21B	0.96
C6B—C7B	1.538 (9)	C21—H21C	0.96
C7B—H7B	0.93

C8—N1—N2	114.19 (16)	C21—C10—H10	107.6
C8—N1—H1N1	126 (2)	C16—C11—C12	118.05 (18)
N2—N1—H1N1	120 (2)	C16—C11—C10	123.04 (17)
C9—N2—N1	104.04 (15)	C12—C11—C10	118.90 (17)
C9—N3—N4	119.15 (15)	C13—C12—C11	121.08 (19)
C9—N3—C8	108.45 (15)	C13—C12—H12	119.5
N4—N3—C8	132.40 (15)	C11—C12—H12	119.5
C7A—N4—N3	118.1 (3)	C12—C13—C14	121.30 (18)
C7B—N4—N3	122.6 (3)	C12—C13—H13	119.3
C2A—C1A—C6A	120.1 (5)	C14—C13—H13	119.3
C2A—C1A—H1A	119.9	C15—C14—C13	117.07 (19)
C6A—C1A—H1A	119.9	C15—C14—C17	122.7 (2)
C3A—C2A—C1A	119.6 (6)	C13—C14—C17	120.17 (19)
C3A—C2A—H2A	120.2	C14—C15—C16	121.89 (19)
C1A—C2A—H2A	120.2	C14—C15—H15	119.1
C4A—C3A—C2A	121.2 (9)	C16—C15—H15	119.1
C4A—C3A—Br1A	119.7 (7)	C11—C16—C15	120.60 (19)
C2A—C3A—Br1A	119.1 (7)	C11—C16—H16	119.7
C3A—C4A—C5A	119.2 (6)	C15—C16—H16	119.7
C3A—C4A—H4A	120.4	C14—C17—C18	113.68 (19)
C5A—C4A—H4A	120.4	C14—C17—H17A	108.8
C4A—C5A—C6A	121.8 (4)	C18—C17—H17A	108.8
C4A—C5A—H5A	119.1	C14—C17—H17B	108.8
C6A—C5A—H5A	119.1	C18—C17—H17B	108.8
C5A—C6A—C1A	118.1 (6)	H17A—C17—H17B	107.7
C5A—C6A—C7A	127.4 (6)	C19A—C18—C20	113.6 (6)
C1A—C6A—C7A	109.9 (5)	C19A—C18—C17	125.0 (8)
N4—C7A—C6A	116.6 (5)	C20—C18—C17	111.2 (2)
N4—C7A—H7A	121.7	C20—C18—C19	110.1 (3)
C6A—C7A—H7A	121.7	C17—C18—C19	107.0 (3)
C2B—C1B—C6B	119.2 (5)	C19A—C18—H18A	83.7
C2B—C1B—H1B	120.4	C20—C18—H18A	109.5
C6B—C1B—H1B	120.4	C17—C18—H18A	109.5
C1B—C2B—C3B	119.3 (5)	C19—C18—H18A	109.5
C1B—C2B—H2B	120.3	C19A—C18—H18B	98.3
C3B—C2B—H2B	120.3	C20—C18—H18B	101.9
C2B—C3B—C4B	121.8 (7)	C17—C18—H18B	102.0
C2B—C3B—Br1B	119.9 (6)	C19—C18—H18B	124.2
C4B—C3B—Br1B	118.3 (7)	C18—C19—H19A	109.5
C5B—C4B—C3B	118.7 (5)	C18—C19—H19B	109.5
C5B—C4B—H4B	120.6	H19A—C19—H19B	109.5
C3B—C4B—H4B	120.6	C18—C19—H19C	109.5
C6B—C5B—C4B	119.4 (5)	H19A—C19—H19C	109.5
C6B—C5B—H5B	120.3	H19B—C19—H19C	109.5
C4B—C5B—H5B	120.3	C18—C19A—H19D	109.5
C1B—C6B—C5B	121.5 (7)	C18—C19A—H19E	109.5
C1B—C6B—C7B	112.5 (6)	H19D—C19A—H19E	109.5
C5B—C6B—C7B	121.0 (6)	C18—C19A—H19F	109.5
N4—C7B—C6B	113.6 (5)	H19D—C19A—H19F	109.5
N4—C7B—H7B	123.2	H19E—C19A—H19F	109.5
C6B—C7B—H7B	123.2	C18—C20—H20A	109.5
N1—C8—N3	102.67 (15)	C18—C20—H20B	109.5
N1—C8—S1	127.12 (15)	H20A—C20—H20B	109.5
N3—C8—S1	130.21 (14)	C18—C20—H20C	109.5
N2—C9—N3	110.62 (17)	H20A—C20—H20C	109.5
N2—C9—C10	125.50 (16)	H20B—C20—H20C	109.5
N3—C9—C10	123.88 (16)	C10—C21—H21A	109.5
C9—C10—C11	112.76 (16)	C10—C21—H21B	109.5
C9—C10—C21	109.82 (16)	H21A—C21—H21B	109.5
C11—C10—C21	111.13 (17)	C10—C21—H21C	109.5
C9—C10—H10	107.6	H21A—C21—H21C	109.5
C11—C10—H10	107.6	H21B—C21—H21C	109.5

C8—N1—N2—C9	0.1 (2)	N2—N1—C8—S1	−178.50 (16)
C9—N3—N4—C7A	149.7 (3)	C9—N3—C8—N1	−1.7 (2)
C8—N3—N4—C7A	−29.4 (4)	N4—N3—C8—N1	177.6 (2)
C9—N3—N4—C7B	−178.4 (4)	C9—N3—C8—S1	177.80 (17)
C8—N3—N4—C7B	2.4 (5)	N4—N3—C8—S1	−2.9 (3)
C6A—C1A—C2A—C3A	1.5 (12)	N1—N2—C9—N3	−1.2 (2)
C1A—C2A—C3A—C4A	−0.6 (17)	N1—N2—C9—C10	178.08 (19)
C1A—C2A—C3A—Br1A	−179.1 (7)	N4—N3—C9—N2	−177.49 (17)
C2A—C3A—C4A—C5A	0.6 (16)	C8—N3—C9—N2	1.9 (2)
Br1A—C3A—C4A—C5A	179.0 (6)	N4—N3—C9—C10	3.2 (3)
C3A—C4A—C5A—C6A	−1.4 (11)	C8—N3—C9—C10	−177.41 (19)
C4A—C5A—C6A—C1A	2.2 (9)	N2—C9—C10—C11	122.2 (2)
C4A—C5A—C6A—C7A	−150.8 (6)	N3—C9—C10—C11	−58.6 (3)
C2A—C1A—C6A—C5A	−2.3 (10)	N2—C9—C10—C21	−2.3 (3)
C2A—C1A—C6A—C7A	155.2 (6)	N3—C9—C10—C21	176.8 (2)
C7B—N4—C7A—C6A	60.1 (8)	C9—C10—C11—C16	−26.2 (3)
N3—N4—C7A—C6A	167.3 (4)	C21—C10—C11—C16	97.6 (2)
C5A—C6A—C7A—N4	−143.9 (6)	C9—C10—C11—C12	154.71 (18)
C1A—C6A—C7A—N4	61.2 (8)	C21—C10—C11—C12	−81.5 (2)
C6B—C1B—C2B—C3B	1.6 (11)	C16—C11—C12—C13	0.6 (3)
C1B—C2B—C3B—C4B	0.6 (16)	C10—C11—C12—C13	179.79 (18)
C1B—C2B—C3B—Br1B	179.7 (7)	C11—C12—C13—C14	0.0 (3)
C2B—C3B—C4B—C5B	−0.8 (15)	C12—C13—C14—C15	−0.4 (3)
Br1B—C3B—C4B—C5B	180.0 (6)	C12—C13—C14—C17	177.59 (19)
C3B—C4B—C5B—C6B	−1.1 (10)	C13—C14—C15—C16	0.3 (3)
C2B—C1B—C6B—C5B	−3.7 (10)	C17—C14—C15—C16	−177.7 (2)
C2B—C1B—C6B—C7B	−158.9 (6)	C12—C11—C16—C15	−0.8 (3)
C4B—C5B—C6B—C1B	3.4 (9)	C10—C11—C16—C15	−179.91 (19)
C4B—C5B—C6B—C7B	156.6 (6)	C14—C15—C16—C11	0.3 (3)
C7A—N4—C7B—C6B	−63.2 (8)	C15—C14—C17—C18	99.4 (3)
N3—N4—C7B—C6B	−152.4 (4)	C13—C14—C17—C18	−78.5 (3)
C1B—C6B—C7B—N4	−57.0 (8)	C14—C17—C18—C19A	−51.5 (11)
C5B—C6B—C7B—N4	147.5 (6)	C14—C17—C18—C20	165.7 (2)
N2—N1—C8—N3	1.0 (2)	C14—C17—C18—C19	−74.0 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N1···S1ⁱ	0.91 (4)	2.35 (4)	3.2582 (18)	175 (4)

Symmetry code: (i) −x+3, −y+1, −z+1.

Experimental details

Crystal data
Chemical formula	C₂₁H₂₃BrN₄S
M_r	443.40
Crystal system, space group	Triclinic, P1
Temperature (K)	100
a, b, c (Å)	5.5791 (2), 11.3052 (3), 17.3688 (4)
α, β, γ (°)	75.421 (1), 86.614 (1), 79.616 (1)
V (Å³)	1042.75 (5)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	2.08
Crystal size (mm)	0.27 × 0.17 × 0.05

Data collection
Diffractometer	Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.602, 0.908
No. of measured, independent and observed [I > 2σ(I)] reflections	26698, 8529, 5907
R_int	0.029
(sin θ/λ)_max (Å⁻¹)	0.791

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.052, 0.141, 1.05
No. of reflections	8529
No. of parameters	331
No. of restraints	44
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.67, −0.83

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), 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
N1—H1N1···S1ⁱ	0.91 (4)	2.35 (4)	3.2582 (18)	175 (4)

Symmetry code: (i) −x+3, −y+1, −z+1.

Footnotes

‡Thomson Reuters Researcher ID: A-3561-2009.

§Thomson Reuters Researcher ID: A-5473-2009. Permanent address: Department of Physics, Karunya University, Karunya Nagar, Coimbatore 641 114, India.

Acknowledgements

HKF and SRJ thank the Malaysian Government and Universiti Sains Malaysia for the Science Fund grant No. 305/PFIZIK/613312. SRJ thanks Universiti Sains Malaysia for a post–doctoral research fellowship. HKF also thanks Universiti Sains Malaysia for the Research University Golden Goose grant No. 1001/PFIZIK/811012.

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