1-(4-Bromo­phen­yl)-3-butano­ylthio­urea

Sohail Saeed; Naghmana Rashid; Jerry P Jasinski; Ray J Butcher; Muhammad Shoaib

doi:10.1107/S1600536810050373

. 2010 Dec 8;67(Pt 1):o46. doi: 10.1107/S1600536810050373

1-(4-Bromophenyl)-3-butanoylthiourea

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

PMCID: PMC3050228 PMID: 21522755

Abstract

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,
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 ▶) 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[F ² > 2σ(F ²)] = 0.043
wR(F ²) = 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

Data collection: CrysAlis PRO (Oxford Diffraction, 2007 ▶); cell refinement: CrysAlis RED (Oxford Diffraction, 2007 ▶); 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 ▶).

Supplementary Material

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

e-67-00o46-sup1.cif^{(24.9KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810050373/im2247Isup2.hkl

e-67-00o46-Isup2.hkl^{(262.6KB, hkl)}

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

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

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) .

Acknowledgments

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

supplementary crystallographic information

Comment

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).

Experimental

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%).