1-(4-Bromo­phen­yl)-3-butano­ylthio­urea

Saeed, S.; Rashid, N.; Jasinski, J.P.; Butcher, R.J.; Shoaib, M.

doi:10.1107/S1600536810050373

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 67| Part 1| January 2011| Page o46

https://doi.org/10.1107/S1600536810050373

Open

access

1-(4-Bromophenyl)-3-butanoylthiourea

Sohail Saeed,^a ^* Naghmana Rashid,^a Jerry P. Jasinski,^b Ray J. Butcher ^c and Muhammad Shoaib ^d

^aDepartment of Chemistry, Research Complex, Allama Iqbal Open University, Islamabad, Pakistan, ^bDepartment of Chemistry, Keene State College, 229 Main Street, Keene, NH 03435-2001, USA, ^cDepartment of Chemistry, Howard University, 525 College Street NW, Washington, DC 20059, USA, and ^dNational Engineering & Scientific Commission, PO Box 2801, Islamabad, Pakistan
^*Correspondence e-mail: sohail262001@yahoo.com

(Received 8 November 2010; accepted 1 December 2010; online 8 December 2010)

In the title compound, C₁₁H₁₃BrN₂OS, there are two independent molecules (A and B) in the asymmetric unit. The dihedral angle between the mean planes of the benzene ring and the carbamothioyl group is 63.66 (molecule A) and 80.3 (0)° (molecule B). The butanamide group in molecule A is disordered [0.532 (6) and 0.468 (6) occupancy]. The carbamothioyl group is twisted by 63.6 (6) (molecule A) and 80.3 (0)° (molecule B) from the respective benzene ring. A strong intramolecular N—H⋯O hydrogen bond occurs in each molecule. The crystal packing is stabilized by weak intermolecular N—H⋯O and N—H⋯S hydrogen-bond interactions, the latter forming an infinite co-operative hydrogen-bonded two-dimensional network along [110].

Related literature

For general background to the chemistry of thiourea derivatives, see: Zhang et al. (2004 ); For related structures, see: Saeed et al. (2008a ,b , 2009 ). For an epoxy resin curing agent, see: Saeed et al. (2009). For bond-length data, see: Allen et al. (1987 ).

Experimental

Crystal data

C₁₁H₁₃BrN₂OS
M_r = 301.20
Triclinic, $[P \overline 1]$
a = 6.1746 (3) Å
b = 10.7883 (4) Å
c = 19.6450 (8) Å
α = 87.719 (3)°
β = 81.557 (4)°
γ = 76.047 (4)°
V = 1256.23 (9) Å³
Z = 4
Mo Kα radiation
μ = 3.42 mm⁻¹
T = 123 K
0.53 × 0.24 × 0.11 mm

Data collection

Oxford Diffraction Xcalibur Ruby Gemini diffractometer
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2007 $[Oxford Diffraction (2007). CrysAlis PRO and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, England.]$ ) T_min = 0.187, T_max = 1.000
13276 measured reflections
5362 independent reflections
3535 reflections with I > 2σ(I)
R_int = 0.054

Refinement

R[F² > 2σ(F²)] = 0.043
wR(F²) = 0.095
S = 0.92
5362 reflections
307 parameters
18 restraints
H-atom parameters constrained
Δρ_max = 0.83 e Å⁻³
Δρ_min = −0.74 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1A—H1AA⋯O1A	0.88	1.97	2.666 (5)	135
N1A—H1AA⋯O1Aⁱ	0.88	2.36	3.083 (6)	140
N2A—H2AB⋯S1Aⁱⁱ	0.88	2.54	3.382 (4)	160
N1B—H1BA⋯O1B	0.88	1.98	2.662 (4)	134
N2B—H2BB⋯S1Bⁱⁱⁱ	0.88	2.50	3.370 (3)	169
Symmetry codes: (i) -x+1, -y+1, -z; (ii) -x+1, -y, -z; (iii) -x+1, -y+1, -z+1.

Data collection: CrysAlis PRO (Oxford Diffraction, 2007 $[Oxford Diffraction (2007). CrysAlis PRO and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, England.]$ ); cell refinement: CrysAlis RED (Oxford Diffraction, 2007 $[Oxford Diffraction (2007). CrysAlis PRO and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, England.]$ ); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536810050373/im2247sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810050373/im2247Isup2.hkl

checkCIF report

Comment top

The background to this study has been set in our previous work on the structural chemistry of N, N'-disubstituted thiourea (Saeed et al., 2008a,b). Herein, as a continuation of these studies, the structure of the title compound, (I), C₁₁H₁₃BrN₂OS, is described. With two molecules in the asymmetric unit, the dihedral angle between the mean planes of the benzene ring and carbamothioyl group is 63.66° (A) Fig. 1) and 80.3 (0)° (B) (Fig. 2), respectively. The butanamide group in A is disordered (0.532 (6) & 0.4686 occupancy). The carbamothioyl group is twisted by 63.6 (6)° (A) and 80.3 (0)° (B) from the mean plane of the respective benzene ring. Bond distances and angles are in normal ranges (Allen et al. , 1987). Crystal packing is stabilized by strong intramolecular N—H···O and weak intermolecular N—H···O and N—H···S hydrogen bond interactions, the latter forming an infinite cooperative hydrogen bonded 2-D network along 110. (Fig. 3).

Related literature top

For general background to the chemistry of thiourea derivatives, see: Zhang et al. (2004); For related structures, see: Saeed et al. (2008a,b, 2009). For an epoxy resin curing agent, see: Saeed et al. (2009). For bond-length data, see: Allen et al. (1987).

Experimental top

A solution of butanoyl chloride (0.01 mol) in anhydrous acetone (75 ml) and 3% tetrabutylammonium bromide (TBAB) as a phase-transfer catalyst (PTC) in anhydrous acetone was added dropwise to a suspension of dry potassium thiocyanate (0.01 mol) in acetone (50 ml) and the reaction mixture was refluxed for 50 min. After cooling to room temperature, a solution of p-bromoaniline (0.01 mol) in anhydrous acetone (25 ml) was added dropwise and the resulting mixture refluxed for 3 h. Hydrochloric acid (0.1 N, 300 ml) was added, and the solution was filtered. The solid product was washed with water and purified by re-crystallization from ethyl acetate (yield: 92%).

Structure description top

For general background to the chemistry of thiourea derivatives, see: Zhang et al. (2004); For related structures, see: Saeed et al. (2008a,b, 2009). For an epoxy resin curing agent, see: Saeed et al. (2009). For bond-length data, see: Allen et al. (1987).

Computing details top

Data collection: CrysAlis PRO (Oxford Diffraction, 2007); cell refinement: CrysAlis RED (Oxford Diffraction, 2007); data reduction: CrysAlis RED (Oxford Diffraction, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: PLATON (Spek, 2009).

Figures top

	Fig. 1. Molecular structure of C₁₁H₁₃BrN₂OS, (A) showing the atom labeling scheme and 50% probability displacement ellipsoids. Dashed lined indicate intramolecular N—H···O hydrogen bonding. Only the predominate butanamide component (0.532 (6) occupancy) is displayed.
	Fig. 2. Molecular structure of C₁₁H₁₃BrN₂OS, (B) showing the atom labeling scheme and 50% probability displacement ellipsoids. Dashed lined indicate intramolecular N—H···O hydrogen bonding.
	Fig. 3. Packing diagram of the title compound viewed down the c axis. Dashed lines indicate strong N—H···O, weak N—H···O and N—H···S hydrogen bonds and are also displaying an R₂²(8) graph set motif betwen adjacent A–B molecules.

1-(4-Bromophenyl)-3-butanoylthiourea top

Crystal data top

C₁₁H₁₃BrN₂OS	Z = 4
M_r = 301.20	F(000) = 608
Triclinic, P1	D_x = 1.593 Mg m⁻³
Hall symbol: -P 1	Melting point: 409 K
a = 6.1746 (3) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.7883 (4) Å	Cell parameters from 6019 reflections
c = 19.6450 (8) Å	θ = 5.1–28.4°
α = 87.719 (3)°	µ = 3.42 mm⁻¹
β = 81.557 (4)°	T = 123 K
γ = 76.047 (4)°	Prism, colorless
V = 1256.23 (9) Å³	0.53 × 0.24 × 0.11 mm

Data collection top

Oxford Diffraction Xcalibur Ruby Gemini diffractometer	5362 independent reflections
Radiation source: Enhance (Mo) X-ray Source	3535 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.054
Detector resolution: 10.5081 pixels mm^-1	θ_max = 28.5°, θ_min = 5.1°
ω scans	h = −8→8
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2007)	k = −13→14
T_min = 0.187, T_max = 1.000	l = −24→26
13276 measured reflections

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)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.095	H-atom parameters constrained
S = 0.92	w = 1/[σ²(F_o²) + (0.0504P)²] where P = (F_o² + 2F_c²)/3
5362 reflections	(Δ/σ)_max = 0.001
307 parameters	Δρ_max = 0.83 e Å⁻³
18 restraints	Δρ_min = −0.74 e Å⁻³

Crystal data top

C₁₁H₁₃BrN₂OS	γ = 76.047 (4)°
M_r = 301.20	V = 1256.23 (9) Å³
Triclinic, P1	Z = 4
a = 6.1746 (3) Å	Mo Kα radiation
b = 10.7883 (4) Å	µ = 3.42 mm⁻¹
c = 19.6450 (8) Å	T = 123 K
α = 87.719 (3)°	0.53 × 0.24 × 0.11 mm
β = 81.557 (4)°

Data collection top

Oxford Diffraction Xcalibur Ruby Gemini diffractometer	5362 independent reflections
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2007)	3535 reflections with I > 2σ(I)
T_min = 0.187, T_max = 1.000	R_int = 0.054
13276 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.043	18 restraints
wR(F²) = 0.095	H-atom parameters constrained
S = 0.92	Δρ_max = 0.83 e Å⁻³
5362 reflections	Δρ_min = −0.74 e Å⁻³
307 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	Occ. (<1)
Br1A	1.12197 (6)	0.33692 (3)	0.30413 (2)	0.02775 (12)
S1A	0.6977 (2)	0.04500 (13)	0.07060 (6)	0.0486 (3)
O1A	0.3799 (6)	0.4183 (4)	−0.03038 (17)	0.0751 (13)
N1A	0.6368 (5)	0.2974 (4)	0.06119 (16)	0.0360 (8)
H1AA	0.5835	0.3690	0.0398	0.043*
N2A	0.4761 (6)	0.2029 (4)	−0.01539 (17)	0.0454 (10)	0.468 (6)
H2AB	0.4692	0.1311	−0.0337	0.054*	0.468 (6)
N2C	0.4761 (6)	0.2029 (4)	−0.01539 (17)	0.0454 (10)	0.532 (6)
H2CA	0.4577	0.1312	−0.0308	0.054*	0.532 (6)
C1A	0.7542 (6)	0.3041 (4)	0.11839 (19)	0.0267 (9)
C2A	0.9809 (6)	0.2465 (4)	0.11540 (19)	0.0276 (9)
H2AA	1.0608	0.1997	0.0758	0.033*
C3A	1.0908 (6)	0.2578 (4)	0.17075 (19)	0.0256 (9)
H3AA	1.2470	0.2195	0.1694	0.031*
C4A	0.9692 (6)	0.3256 (3)	0.22803 (19)	0.0239 (8)
C5A	0.7432 (6)	0.3813 (3)	0.23116 (19)	0.0252 (9)
H5AA	0.6621	0.4271	0.2710	0.030*
C6A	0.6355 (6)	0.3701 (3)	0.1759 (2)	0.0264 (9)
H6AA	0.4791	0.4080	0.1775	0.032*
C7A	0.6030 (6)	0.1894 (5)	0.0382 (2)	0.0380 (11)
C8A	0.359 (8)	0.3127 (6)	−0.044 (2)	0.066 (3)	0.468 (6)
C9A	0.1864 (14)	0.2620 (8)	−0.0861 (4)	0.0248 (13)	0.468 (6)
H9AA	0.2727	0.2012	−0.1225	0.030*	0.468 (6)
H9AB	0.0892	0.2179	−0.0543	0.030*	0.468 (6)
C10A	0.047 (4)	0.375 (3)	−0.1171 (9)	0.045 (3)	0.468 (6)
H10A	0.1473	0.4270	−0.1415	0.054*	0.468 (6)
H10B	−0.0541	0.4286	−0.0799	0.054*	0.468 (6)
C11A	−0.095 (6)	0.340 (4)	−0.1676 (15)	0.044 (5)	0.468 (6)
H11A	−0.1511	0.4151	−0.1954	0.066*	0.468 (6)
H11B	−0.2221	0.3113	−0.1419	0.066*	0.468 (6)
H11C	−0.0014	0.2714	−0.1977	0.066*	0.468 (6)
C8C	0.375 (7)	0.3120 (5)	−0.0481 (19)	0.066 (3)	0.532 (6)
C9C	0.2633 (12)	0.3155 (7)	−0.1089 (4)	0.0248 (13)	0.532 (6)
H9CA	0.2977	0.2288	−0.1287	0.030*	0.532 (6)
H9CB	0.3200	0.3727	−0.1441	0.030*	0.532 (6)
C10C	0.008 (4)	0.364 (2)	−0.0892 (8)	0.045 (3)	0.532 (6)
H10C	−0.0407	0.3218	−0.0460	0.054*	0.532 (6)
H10D	−0.0280	0.4570	−0.0809	0.054*	0.532 (6)
C11C	−0.119 (5)	0.338 (3)	−0.1444 (11)	0.044 (5)	0.532 (6)
H11D	−0.2794	0.3790	−0.1325	0.066*	0.532 (6)
H11E	−0.1006	0.2454	−0.1484	0.066*	0.532 (6)
H11F	−0.0604	0.3718	−0.1885	0.066*	0.532 (6)
Br1B	0.29893 (6)	−0.08278 (4)	0.22800 (2)	0.03337 (13)
S1B	0.40894 (16)	0.38143 (8)	0.43013 (5)	0.0282 (2)
O1B	0.9939 (4)	0.1368 (2)	0.52752 (12)	0.0214 (5)
N1B	0.7056 (5)	0.1586 (3)	0.43688 (15)	0.0199 (7)
H1BA	0.8214	0.1106	0.4543	0.024*
N2B	0.7405 (5)	0.3202 (3)	0.50548 (14)	0.0214 (7)
H2BB	0.6938	0.4015	0.5166	0.026*
C1B	0.6082 (5)	0.1031 (3)	0.38714 (17)	0.0170 (8)
C2B	0.7103 (6)	0.0919 (3)	0.31965 (18)	0.0199 (8)
H2BA	0.8430	0.1217	0.3062	0.024*
C3B	0.6197 (6)	0.0373 (3)	0.27136 (19)	0.0223 (8)
H3BA	0.6885	0.0297	0.2247	0.027*
C4B	0.4275 (6)	−0.0060 (3)	0.29247 (19)	0.0214 (8)
C5B	0.3250 (6)	0.0038 (3)	0.35972 (19)	0.0222 (8)
H5BA	0.1928	−0.0266	0.3732	0.027*
C6B	0.4171 (6)	0.0584 (3)	0.40740 (19)	0.0217 (8)
H6BA	0.3489	0.0652	0.4541	0.026*
C7B	0.6293 (6)	0.2788 (3)	0.45781 (17)	0.0196 (8)
C8B	0.9147 (5)	0.2507 (3)	0.53771 (17)	0.0188 (8)
C9B	0.9965 (6)	0.3278 (3)	0.58645 (19)	0.0227 (8)
H9BA	0.8748	0.3570	0.6252	0.027*
H9BB	1.0303	0.4045	0.5620	0.027*
C10B	1.2057 (6)	0.2531 (3)	0.6150 (2)	0.0286 (9)
H10E	1.3226	0.2162	0.5763	0.034*
H10F	1.1680	0.1817	0.6437	0.034*
C11B	1.2993 (7)	0.3366 (4)	0.6579 (2)	0.0366 (10)
H11G	1.4383	0.2862	0.6732	0.055*
H11H	1.1881	0.3682	0.6981	0.055*
H11I	1.3319	0.4090	0.6301	0.055*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1A	0.0310 (2)	0.0221 (2)	0.0329 (2)	−0.00409 (16)	−0.01694 (17)	−0.00039 (17)
S1A	0.0591 (8)	0.0681 (8)	0.0314 (6)	−0.0304 (7)	−0.0239 (5)	0.0060 (6)
O1A	0.079 (3)	0.080 (3)	0.047 (2)	0.038 (2)	−0.039 (2)	−0.024 (2)
N1A	0.0339 (19)	0.055 (2)	0.0200 (18)	−0.0100 (17)	−0.0101 (15)	0.0062 (17)
N2A	0.033 (2)	0.071 (3)	0.026 (2)	0.0062 (19)	−0.0118 (16)	−0.0179 (19)
N2C	0.033 (2)	0.071 (3)	0.026 (2)	0.0062 (19)	−0.0118 (16)	−0.0179 (19)
C1A	0.030 (2)	0.035 (2)	0.017 (2)	−0.0117 (18)	−0.0078 (16)	0.0106 (17)
C2A	0.028 (2)	0.038 (2)	0.018 (2)	−0.0102 (18)	−0.0037 (16)	0.0027 (18)
C3A	0.0193 (19)	0.030 (2)	0.029 (2)	−0.0085 (17)	−0.0036 (16)	0.0036 (18)
C4A	0.030 (2)	0.0193 (19)	0.029 (2)	−0.0116 (17)	−0.0162 (17)	0.0082 (16)
C5A	0.027 (2)	0.0217 (19)	0.028 (2)	−0.0061 (17)	−0.0066 (17)	−0.0009 (16)
C6A	0.021 (2)	0.025 (2)	0.034 (2)	−0.0037 (16)	−0.0096 (17)	0.0024 (18)
C7A	0.024 (2)	0.070 (3)	0.020 (2)	−0.010 (2)	−0.0043 (17)	−0.003 (2)
C8A	0.050 (5)	0.091 (4)	0.038 (4)	0.037 (3)	−0.022 (4)	−0.034 (3)
C9A	0.032 (4)	0.025 (3)	0.022 (3)	−0.014 (2)	−0.007 (3)	−0.002 (3)
C10A	0.033 (8)	0.056 (6)	0.049 (11)	−0.013 (4)	−0.010 (8)	−0.004 (10)
C11A	0.036 (6)	0.049 (3)	0.055 (15)	−0.014 (4)	−0.024 (9)	0.009 (10)
C8C	0.050 (5)	0.091 (4)	0.038 (4)	0.037 (3)	−0.022 (4)	−0.034 (3)
C9C	0.032 (4)	0.025 (3)	0.022 (3)	−0.014 (2)	−0.007 (3)	−0.002 (3)
C10C	0.033 (8)	0.056 (6)	0.049 (11)	−0.013 (4)	−0.010 (8)	−0.004 (10)
C11C	0.036 (6)	0.049 (3)	0.055 (15)	−0.014 (4)	−0.024 (9)	0.009 (10)
Br1B	0.0354 (2)	0.0344 (2)	0.0352 (3)	−0.01105 (19)	−0.01454 (18)	−0.00672 (19)
S1B	0.0362 (6)	0.0152 (5)	0.0327 (6)	0.0040 (4)	−0.0195 (4)	−0.0041 (4)
O1B	0.0235 (13)	0.0133 (12)	0.0262 (14)	−0.0003 (11)	−0.0065 (11)	−0.0011 (11)
N1B	0.0211 (15)	0.0125 (15)	0.0247 (17)	0.0024 (12)	−0.0080 (13)	−0.0045 (13)
N2B	0.0286 (17)	0.0113 (14)	0.0233 (17)	0.0020 (13)	−0.0105 (13)	−0.0025 (13)
C1B	0.0212 (18)	0.0084 (16)	0.021 (2)	0.0001 (14)	−0.0076 (15)	0.0001 (14)
C2B	0.0202 (18)	0.0138 (17)	0.026 (2)	−0.0039 (15)	−0.0037 (15)	0.0014 (15)
C3B	0.026 (2)	0.0197 (19)	0.0192 (19)	−0.0004 (16)	−0.0036 (15)	−0.0008 (15)
C4B	0.027 (2)	0.0111 (17)	0.028 (2)	−0.0042 (15)	−0.0118 (16)	−0.0013 (15)
C5B	0.0173 (18)	0.0152 (18)	0.033 (2)	−0.0018 (15)	−0.0053 (16)	0.0019 (16)
C6B	0.0193 (19)	0.0188 (18)	0.023 (2)	0.0026 (15)	−0.0012 (15)	−0.0010 (16)
C7B	0.026 (2)	0.0151 (18)	0.0185 (19)	−0.0039 (16)	−0.0065 (16)	0.0019 (15)
C8B	0.0199 (18)	0.0179 (18)	0.0180 (19)	−0.0033 (16)	−0.0037 (15)	0.0029 (15)
C9B	0.0237 (19)	0.0149 (18)	0.028 (2)	0.0022 (15)	−0.0087 (16)	−0.0027 (15)
C10B	0.030 (2)	0.0149 (19)	0.041 (2)	0.0011 (16)	−0.0171 (18)	−0.0005 (17)
C11B	0.031 (2)	0.023 (2)	0.058 (3)	−0.0008 (18)	−0.022 (2)	−0.005 (2)

Geometric parameters (Å, º) top

Br1A—C4A	1.904 (3)	C10C—H10C	0.9900
S1A—C7A	1.663 (5)	C10C—H10D	0.9900
O1A—C8C	1.220 (4)	C11C—H11D	0.9800
O1A—C8A	1.220 (4)	C11C—H11E	0.9800
N1A—C7A	1.338 (5)	C11C—H11F	0.9800
N1A—C1A	1.437 (4)	Br1B—C4B	1.902 (3)
N1A—H1AA	0.8800	S1B—C7B	1.678 (3)
N2A—C8A	1.376 (4)	O1B—C8B	1.221 (3)
N2A—C7A	1.385 (5)	N1B—C7B	1.328 (4)
N2A—H2AB	0.8800	N1B—C1B	1.438 (4)
C1A—C6A	1.374 (5)	N1B—H1BA	0.8800
C1A—C2A	1.382 (5)	N2B—C8B	1.376 (4)
C2A—C3A	1.387 (5)	N2B—C7B	1.386 (4)
C2A—H2AA	0.9500	N2B—H2BB	0.8800
C3A—C4A	1.385 (5)	C1B—C2B	1.378 (5)
C3A—H3AA	0.9500	C1B—C6B	1.380 (5)
C4A—C5A	1.373 (5)	C2B—C3B	1.385 (5)
C5A—C6A	1.377 (5)	C2B—H2BA	0.9500
C5A—H5AA	0.9500	C3B—C4B	1.381 (5)
C6A—H6AA	0.9500	C3B—H3BA	0.9500
C8A—C9A	1.644 (14)	C4B—C5B	1.375 (5)
C9A—C10A	1.48 (3)	C5B—C6B	1.382 (5)
C9A—H9AA	0.9900	C5B—H5BA	0.9500
C9A—H9AB	0.9900	C6B—H6BA	0.9500
C10A—C11A	1.53 (5)	C8B—C9B	1.508 (4)
C10A—H10A	0.9900	C9B—C10B	1.518 (5)
C10A—H10B	0.9900	C9B—H9BA	0.9900
C11A—H11A	0.9800	C9B—H9BB	0.9900
C11A—H11B	0.9800	C10B—C11B	1.521 (5)
C11A—H11C	0.9800	C10B—H10E	0.9900
C8C—C9C	1.459 (11)	C10B—H10F	0.9900
C9C—C10C	1.53 (2)	C11B—H11G	0.9800
C9C—H9CA	0.9900	C11B—H11H	0.9800
C9C—H9CB	0.9900	C11B—H11I	0.9800
C10C—C11C	1.50 (4)

C8C—O1A—C8A	5 (6)	H10C—C10C—H10D	107.9
C7A—N1A—C1A	124.4 (4)	C10C—C11C—H11D	109.5
C7A—N1A—H1AA	117.8	C10C—C11C—H11E	109.5
C1A—N1A—H1AA	117.8	H11D—C11C—H11E	109.5
C8A—N2A—C7A	129.2 (5)	C10C—C11C—H11F	109.5
C8A—N2A—H2AB	115.4	H11D—C11C—H11F	109.5
C7A—N2A—H2AB	115.4	H11E—C11C—H11F	109.5
C6A—C1A—C2A	120.9 (3)	C7B—N1B—C1B	123.1 (3)
C6A—C1A—N1A	118.3 (3)	C7B—N1B—H1BA	118.4
C2A—C1A—N1A	120.8 (3)	C1B—N1B—H1BA	118.4
C1A—C2A—C3A	119.4 (3)	C8B—N2B—C7B	128.4 (3)
C1A—C2A—H2AA	120.3	C8B—N2B—H2BB	115.8
C3A—C2A—H2AA	120.3	C7B—N2B—H2BB	115.8
C4A—C3A—C2A	118.9 (3)	C2B—C1B—C6B	120.4 (3)
C4A—C3A—H3AA	120.5	C2B—C1B—N1B	119.6 (3)
C2A—C3A—H3AA	120.5	C6B—C1B—N1B	120.0 (3)
C5A—C4A—C3A	121.5 (3)	C1B—C2B—C3B	120.2 (3)
C5A—C4A—Br1A	120.3 (3)	C1B—C2B—H2BA	119.9
C3A—C4A—Br1A	118.2 (3)	C3B—C2B—H2BA	119.9
C4A—C5A—C6A	119.2 (3)	C4B—C3B—C2B	118.6 (3)
C4A—C5A—H5AA	120.4	C4B—C3B—H3BA	120.7
C6A—C5A—H5AA	120.4	C2B—C3B—H3BA	120.7
C1A—C6A—C5A	120.0 (3)	C5B—C4B—C3B	121.8 (3)
C1A—C6A—H6AA	120.0	C5B—C4B—Br1B	118.3 (3)
C5A—C6A—H6AA	120.0	C3B—C4B—Br1B	120.0 (3)
N1A—C7A—N2A	116.0 (4)	C4B—C5B—C6B	119.0 (3)
N1A—C7A—S1A	124.5 (3)	C4B—C5B—H5BA	120.5
N2A—C7A—S1A	119.5 (3)	C6B—C5B—H5BA	120.5
O1A—C8A—N2A	122.2 (5)	C1B—C6B—C5B	120.0 (3)
O1A—C8A—C9A	133.9 (10)	C1B—C6B—H6BA	120.0
N2A—C8A—C9A	103.4 (6)	C5B—C6B—H6BA	120.0
C10A—C9A—C8A	107.3 (12)	N1B—C7B—N2B	117.1 (3)
C10A—C9A—H9AA	110.3	N1B—C7B—S1B	124.1 (3)
C8A—C9A—H9AA	110.3	N2B—C7B—S1B	118.9 (2)
C10A—C9A—H9AB	110.3	O1B—C8B—N2B	122.5 (3)
C8A—C9A—H9AB	110.3	O1B—C8B—C9B	123.6 (3)
H9AA—C9A—H9AB	108.5	N2B—C8B—C9B	113.9 (3)
C9A—C10A—C11A	113 (2)	C8B—C9B—C10B	112.9 (3)
C9A—C10A—H10A	109.0	C8B—C9B—H9BA	109.0
C11A—C10A—H10A	109.0	C10B—C9B—H9BA	109.0
C9A—C10A—H10B	109.0	C8B—C9B—H9BB	109.0
C11A—C10A—H10B	109.0	C10B—C9B—H9BB	109.0
H10A—C10A—H10B	107.8	H9BA—C9B—H9BB	107.8
O1A—C8C—C9C	112.4 (6)	C9B—C10B—C11B	111.9 (3)
C8C—C9C—C10C	110 (2)	C9B—C10B—H10E	109.2
C8C—C9C—H9CA	109.7	C11B—C10B—H10E	109.2
C10C—C9C—H9CA	109.7	C9B—C10B—H10F	109.2
C8C—C9C—H9CB	109.7	C11B—C10B—H10F	109.2
C10C—C9C—H9CB	109.7	H10E—C10B—H10F	107.9
H9CA—C9C—H9CB	108.2	C10B—C11B—H11G	109.5
C11C—C10C—C9C	111.9 (16)	C10B—C11B—H11H	109.5
C11C—C10C—H10C	109.2	H11G—C11B—H11H	109.5
C9C—C10C—H10C	109.2	C10B—C11B—H11I	109.5
C11C—C10C—H10D	109.2	H11G—C11B—H11I	109.5
C9C—C10C—H10D	109.2	H11H—C11B—H11I	109.5

C7A—N1A—C1A—C6A	−115.5 (4)	O1A—C8C—C9C—C10C	−74 (4)
C7A—N1A—C1A—C2A	65.0 (5)	C8C—C9C—C10C—C11C	−165.1 (18)
C6A—C1A—C2A—C3A	−1.3 (6)	C7B—N1B—C1B—C2B	100.1 (4)
N1A—C1A—C2A—C3A	178.2 (3)	C7B—N1B—C1B—C6B	−81.5 (4)
C1A—C2A—C3A—C4A	0.7 (5)	C6B—C1B—C2B—C3B	0.9 (5)
C2A—C3A—C4A—C5A	0.2 (5)	N1B—C1B—C2B—C3B	179.2 (3)
C2A—C3A—C4A—Br1A	178.8 (3)	C1B—C2B—C3B—C4B	−0.4 (5)
C3A—C4A—C5A—C6A	−0.4 (6)	C2B—C3B—C4B—C5B	0.0 (5)
Br1A—C4A—C5A—C6A	−179.0 (3)	C2B—C3B—C4B—Br1B	−179.5 (2)
C2A—C1A—C6A—C5A	1.1 (6)	C3B—C4B—C5B—C6B	0.0 (5)
N1A—C1A—C6A—C5A	−178.5 (3)	Br1B—C4B—C5B—C6B	179.5 (2)
C4A—C5A—C6A—C1A	−0.2 (5)	C2B—C1B—C6B—C5B	−1.0 (5)
C1A—N1A—C7A—N2A	176.9 (3)	N1B—C1B—C6B—C5B	−179.3 (3)
C1A—N1A—C7A—S1A	−1.9 (5)	C4B—C5B—C6B—C1B	0.5 (5)
C8A—N2A—C7A—N1A	−8 (3)	C1B—N1B—C7B—N2B	−179.4 (3)
C8A—N2A—C7A—S1A	171 (3)	C1B—N1B—C7B—S1B	0.7 (5)
C8C—O1A—C8A—N2A	85 (4)	C8B—N2B—C7B—N1B	−4.1 (5)
C8C—O1A—C8A—C9A	−104 (7)	C8B—N2B—C7B—S1B	175.8 (3)
C7A—N2A—C8A—O1A	11 (7)	C7B—N2B—C8B—O1B	−0.8 (6)
C7A—N2A—C8A—C9A	−162.5 (8)	C7B—N2B—C8B—C9B	179.5 (3)
O1A—C8A—C9A—C10A	6 (7)	O1B—C8B—C9B—C10B	6.9 (5)
N2A—C8A—C9A—C10A	178 (3)	N2B—C8B—C9B—C10B	−173.3 (3)
C8A—C9A—C10A—C11A	171 (3)	C8B—C9B—C10B—C11B	174.0 (3)
C8A—O1A—C8C—C9C	98 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1A—H1AA···O1A	0.88	1.97	2.666 (5)	135
N1A—H1AA···O1Aⁱ	0.88	2.36	3.083 (6)	140
N2A—H2AB···S1Aⁱⁱ	0.88	2.54	3.382 (4)	160
N1B—H1BA···O1B	0.88	1.98	2.662 (4)	134
N2B—H2BB···S1Bⁱⁱⁱ	0.88	2.50	3.370 (3)	169

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

Experimental details

Crystal data
Chemical formula	C₁₁H₁₃BrN₂OS
M_r	301.20
Crystal system, space group	Triclinic, P1
Temperature (K)	123
a, b, c (Å)	6.1746 (3), 10.7883 (4), 19.6450 (8)
α, β, γ (°)	87.719 (3), 81.557 (4), 76.047 (4)
V (Å³)	1256.23 (9)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	3.42
Crystal size (mm)	0.53 × 0.24 × 0.11

Data collection
Diffractometer	Oxford Diffraction Xcalibur Ruby Gemini
Absorption correction	Multi-scan (CrysAlis RED; Oxford Diffraction, 2007)
T_min, T_max	0.187, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	13276, 5362, 3535
R_int	0.054
(sin θ/λ)_max (Å⁻¹)	0.672

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.095, 0.92
No. of reflections	5362
No. of parameters	307
No. of restraints	18
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.83, −0.74

Computer programs: CrysAlis PRO (Oxford Diffraction, 2007), CrysAlis RED (Oxford Diffraction, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1A—H1AA···O1A	0.88	1.97	2.666 (5)	134.6
N1A—H1AA···O1Aⁱ	0.88	2.36	3.083 (6)	140.0
N2A—H2AB···S1Aⁱⁱ	0.88	2.54	3.382 (4)	159.5
N1B—H1BA···O1B	0.88	1.98	2.662 (4)	133.6
N2B—H2BB···S1Bⁱⁱⁱ	0.88	2.50	3.370 (3)	168.7

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

Acknowledgements

RJB acknowledges the NSF MRI program (grant No. CHE-0619278) for funds to purchase an X-ray diffractometer.

References

Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19. CSD CrossRef Web of Science Google Scholar
Oxford Diffraction (2007). CrysAlis PRO and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, England. Google Scholar
Saeed, S., Bhatti, M. H., Tahir, M. K. & Jones, P. G. (2008a). Acta Cryst. E64, o1369. Web of Science CSD CrossRef IUCr Journals Google Scholar
Saeed, S., Bhatti, M. H., Yunus, U. & Jones, P. G. (2008b). Acta Cryst. E64, o1566. Web of Science CSD CrossRef IUCr Journals Google Scholar
Saeed, S., Rashid, N., Tahir, A. & Jones, P. G. (2009). Acta Cryst. E65, o1870–o1871. Web of Science CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Zhang, Y.-M., Wei, T.-B., Xian, L. & &Gao, L.-M. (2004). Phosphorus Sulphur Silicon Relat. Elem. 179, 2007–2013. Web of Science CrossRef CAS Google Scholar