N-(4-Bromo­butano­yl)-N′-phen­ylthio­urea

Bohari M Yamin; Nur Eliyanti Ali Othman

doi:10.1107/S1600536811021684

. 2011 Jun 11;67(Pt 7):o1629. doi: 10.1107/S1600536811021684

N-(4-Bromobutanoyl)-N′-phenylthiourea

Bohari M Yamin ^a,^*, Nur Eliyanti Ali Othman ^a

PMCID: PMC3152046 PMID: 21837035

Abstract

The asymmetric unit of the title compound, C₁₁H₁₃Br₁N₂O₁S₁, consists of two independent molecules, which are linked by N—H⋯O hydrogen bonds, forming a dimer. Both molecules maintain the trans--cis configuration with respect to the position of the butanoyl groups and benzene rings against the thiono group across the C—N bonds. The molecule is stabilized by intramolecular N—H⋯O hydrogen bonds. Intermolecular N—H⋯S, C—H⋯S and C—H⋯π interactions also occur.

Related literature

For related structures of halocarbonyl thiourea derivatives, see: Othman et al. (2010 ▶); Yamin et al. (2011 ▶). For standard bond lengths, see: Allen et al. (1987 ▶).

Experimental

Crystal data

C₁₁H₁₃BrN₂OS
M _r = 301.20
Monoclinic,
a = 14.689 (3) Å
b = 10.349 (2) Å
c = 18.249 (4) Å
β = 111.220 (5)°
V = 2586.0 (10) Å³
Z = 8
Mo Kα radiation
μ = 3.32 mm⁻¹
T = 298 K
0.50 × 0.33 × 0.10 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2000 ▶) T _min = 0.287, T _max = 0.732
15722 measured reflections
5077 independent reflections
3076 reflections with I > 2/s(I)
R _int = 0.048

Refinement

R[F ² > 2σ(F ²)] = 0.058
wR(F ²) = 0.177
S = 1.01
5077 reflections
289 parameters
H-atom parameters constrained
Δρ_max = 0.89 e Å⁻³
Δρ_min = −0.75 e Å⁻³

Data collection: SMART (Bruker, 2000 ▶); cell refinement: SAINT (Bruker, 2000 ▶); data reduction: SAINT; 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: SHELXTL, PARST (Nardelli, 1995 ▶) and PLATON (Spek, 2009) ▶.

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811021684/dn2691sup1.cif

e-67-o1629-sup1.cif^{(29.4KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811021684/dn2691Isup2.hkl

e-67-o1629-Isup2.hkl^{(248.7KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811021684/dn2691Isup3.cml

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

Table 1. Hydrogen-bond geometry (Å, °).

Cg1 and Cg2 are the centroids of the C6–C11 and C17–C22 rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯O1	0.86	2.02	2.690 (6)	134
N4—H4⋯O2	0.86	2.03	2.687 (6)	133
N2—H2⋯O2	0.86	2.41	3.140 (5)	143
N4—H4⋯O1	0.86	2.33	3.049 (6)	142
N1—H1⋯S2ⁱ	0.86	2.53	3.386 (4)	173
C14—H14A⋯S2ⁱⁱ	0.97	2.78	3.711 (6)	160
N3—H3⋯S1ⁱⁱⁱ	0.86	2.59	3.445 (4)	176
C2—H2A⋯Cg2	0.97	2.69	3.405 (8)	131
C13—H13A⋯Cg1	0.97	2.83	3.708 (6)	150

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

Acknowledgments

The authors thank the Ministry of Higher Education of Malaysia and Universiti Kebangsaan Malaysia for the research grant UKM-ST-06-FRGS0114–2009 and an NSF scholarship from the Ministry of Science, Technology and Innovation to NEAO.

supplementary crystallographic information

Comment

The title compound (I) is similar to previously reported N-(4-chlorobutanoyl)-N'-phenyl thiourea (Yamin et al., 2011), except the chlorine atom is replaced by bromine atom. The asymmetric unit also consists of two independent molecules linked by N-H···O hydrogen bonds forming a pseudo dimer (Fig. 1).

Both molecules are not planar. The thiourea fragments (C4/N1/C5/S1/N2/C6), (C15/N3/C16/S2/N4/C17) and the benzene rings, (C6—C11) and (C17—C22) are each planar with maximum deviation of 0.055 (4)Å for N3 atom from the least square plane. The dihedral angles between the benzene ring and thiourea fragment in each molecule are 71.9 (2)° and 82.2 (3)° respectively and comparable to those in the N-(4-chlorobutanoyl)-N'-phenyl thiourea (72.98 (10)°, 81.47 (14)°). Both molecules maintain the trans-cis configuration with respect to the butanoyl and benzene ring against the thiono group across their C—N bonds respectively.

There are intramolecular hydrogen bonds, N2—H2···O1, N4—H4···O2 and C3—H3A···Br1 forming two pseudo-six membered rings, [O1···H2/N2/C5/N1/C4], [O2···H4/N4/C16/N3/C15] and a pseudo-five membered rings, [Br1···H3A/C3/C2/C1] respectively. In the crystal structure, the molecules are linked by N1—H1···S2, N3—H3···S1 and N4—H4···O1 intermolecular hydrogen bonds (symmetry codes as in Table 1) to form trimers which are then liked by the N4—H4···O1 and N2—H2···O2 intramolecular hydrogen bonds (Table 1). In addition, there are also C2—H2A..π and C13—H13A..π bonds with the centeroid benzene rings Cg2 (C17—C22)and Cg1 (C6—C11)respectively. All these interactions build up a complicated three dimensional network (Table 1).

Experimental

30 ml acetone solution of aniline (1.33 g, 14 mmol) was added into 30 ml acetone containing 4-bromobutanoyl chloride (2.60 g, 14 mmol) and ammonium thiocyanate (1.09 g, 14 mmol). The mixture was refluxed for 2 h. The solution was filtered and left to evaporate at room temperature. Colourless crytals were obtained after two days of slow evaporation. Yield 90%; m.p 392.3–393.2 K.