Gu ¨n Binzet,aUlrich Flo ¨rke,bNevzat Ku ¨lcu ¨aand Hakan
aDepartment of Chemistry, Faculty of Arts and Science, Mersin University, Mersin,
TR 33343, Turkey,bDepartment of Chemistry, University of Paderborn, Paderborn
D-33098, Germany,cDepartment of Natural Sciences, Fayetteville State University,
Fayetteville, NC 28301, USA, anddDepartment of Chemistry, Faculty of Pharmacy,
Mersin University, Mersin, TR 33169, Turkey
Correspondence e-mail: email@example.com
Received 26 January 2009; accepted 28 January 2009
Key indicators: single-crystal X-ray study; T = 120 K; mean ?(C–C) = 0.005 A ˚;
R factor = 0.043; wR factor = 0.094; data-to-parameter ratio = 22.0.
The synthesis of the title compound, C14H19BrN2OS, involves
the reaction of 4-bromobenzoyl chloride with potassium
thiocyanate in acetone followed by condensation of the
resulting 4-bromobenzoyl isothiocyanate with di-n-propyl-
amine. Typical thiourea carbonyl and thiocarbonyl double
bonds, as well as shortened C—N bonds, are observed in the
title compound. The short C—N bond lengths in the centre of
the molecule reveal the effects of resonance in this part of the
molecule. The asymmetric unit of the title compound contains
two crystallographically independent molecules, A and B.
There is very little difference between the bond lengths and
angles of these molecules. In molecule B, one di-n-propyl
group is twisted in a ?antiperiplanar conformation with C—
C—C—H = ?179.1 (3)?and the other adopts a ?synclinal
conformation with C—C—C—H = ?56.7 (4)?; in molecule A
the two di-n-propyl groups are twisted in + and ?anti-
periplanar conformations, with C—C—C—H = ?179.9 (3)
and 178.2 (3)?, respectively. In the crystal, the molecules are
linked into dimeric pairs via pairs of N—H???S hydrogen
For synthesis, see: O¨zer et al. (2009); Mansurog ˘lu et al. (2008);
Ug ˘ur et al. (2006); Arslan et al. (2003b, 2006), and references
therein. For general background, see: Koch (2001); El
Aamrani et al. (1998, 1999); Arslan et al. (2006, 2007a,b). For
related compounds, see: Khawar Rauf et al. (2009a,b,c,d);
Arslan et al. (2003a, 2004). For bond-length data, see: Allen et
a = 21.104 (3) A˚
b = 9.6940 (12) A˚
c = 16.208 (2) A˚
? = 108.956 (3)?
V = 3135.9 (7) A˚3
Z = 8
Mo K? radiation
? = 2.75 mm?1
T = 120 (2) K
0.48 ? 0.18 ? 0.17 mm
Bruker SMART APEX
Absorption correction: multi-scan
(SADABS; Sheldrick, 2004)
Tmin= 0.352, Tmax= 0.652
27091 measured reflections
7470 independent reflections
4686 reflections with I > 2?(I)
R[F2> 2?(F2)] = 0.043
wR(F2) = 0.094
S = 0.97
H atoms treated by a mixture of
independent and constrained
??max= 1.70 e A˚?3
??min= ?0.71 e A˚?3
Hydrogen-bond geometry (A˚,?).
Data collection: SMART (Bruker, 2002); cell refinement: SAINT
(Bruker, 2002); data reduction: SAINT; program(s) used to solve
structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine
SHELXTL (Sheldrick, 2008); software used to prepare material for
This work was supported by Mersin University Research
Fund [Project Nos. BAP-ECZ-F-TBB-(HA) 2004-3 and BAP-
FEF-KB-(NK) 2006-3]. This study is part of the PhD thesis of
Supplementary data and figures for this paper are available from the
IUCr electronic archives (Reference: AT2717).
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.
Arslan, H., Flo ¨rke, U. & Ku ¨lcu ¨, N. (2003a). Acta Cryst. E59, o641–o642.
Arslan, H., Flo ¨rke, U. & Ku ¨lcu ¨, N. (2004). Turk. J. Chem. 28, 673–678.
Arslan, H., Flo ¨rke, U. & Ku ¨lcu ¨, N. (2007a). Spectrochim. Acta A, 67, 936–943.
Binzet et al.
Acta Cryst. (2009). E65, o452–o453
Acta Crystallographica Section E
Arslan,H., Flo ¨rke,U., Ku ¨lcu ¨, N.& Binzet, G.(2007b). Spectrochim. Acta A, 68,
Arslan, H., Ku ¨lcu ¨, N. & Flo ¨rke, U. (2003b). Transition Met. Chem. 28, 816–819.
Arslan, H., Ku ¨lcu ¨, N. & Flo ¨rke, U. (2006). Spectrochim. Acta A, 64, 1065–1071.
Bruker (2002). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin,
El Aamrani, F. Z., Kumar, A., Beyer, L., Cortina, J. L. & Sastre, A. M. (1998).
Solvent Extr. Ion Exch. 16, 1389–1406.
El Aamrani, F. Z., Kumar, A., Cortina, J. L. & Sastre, A. M. (1999). Anal.
Chim. Acta, 382, 205–231.
Khawar Rauf, M., Bolte, M. & Anwar, S. (2009a). Acta Cryst. E65, o249.
Khawar Rauf, M., Bolte, M. & Badshah, A. (2009b). Acta Cryst. E65, o143.
Khawar Rauf, M., Bolte, M. & Badshah, A. (2009c). Acta Cryst. E65, o240.
Khawar Rauf, M., Bolte, M. & Rauf, A. (2009d). Acta Cryst. E65, o234.
Koch, K. R. (2001). Coord. Chem. Rev. 216, 473–488.
Mansurog ˘lu, D. S., Arslan, H., Flo ¨rke, U. & Ku ¨lcu ¨, N. (2008). J. Coord. Chem.
O¨zer, C. K., Arslan, H., VanDerveer, D. & Binzet, G. (2009). J. Coord. Chem.
Sheldrick, G. M. (2004). SADABS. University of Go ¨ttingen, Germany.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
Ug ˘ur, D., Arslan, H. & Ku ¨lcu ¨, N. (2006). Russ. J. Coord. Chem. 32, 669–675.
Acta Cryst. (2009). E65, o452–o453 Binzet et al.
Acta Cryst. (2009). E65, o452-o453 [ doi:10.1107/S1600536809003511 ]
G. Binzet, U. Flörke, N. Külcü and H. Arslan
Thiourea derivative ligands and their metal complexes have been one of the highlights in coordination chemistry. The
thiourea ligands which contain carbonyl and thiocarbonyl groups are used as reactant for extraction of some transition metal
ions (Koch, 2001; El Aamrani et al., 1998, 1999). The structures of thiourea derivatives and its metal complexes have been
determined during the last years. The title compound derivative acts as a bidentate ligand coordinating through the S atom
and the O atom.
The similar structures of these derivatives palladium, nickel, cobalt, and copper complexes and ligands have been de-
termined in previous studies (Özer et al., 2009; Arslan et al., 2003b, 2006; Mansuroğlu et al., 2008; Uğur et al., 2006).
The title compound, 4-bromo-N-(di-n-propylcarbamothioyl)benzamide, (I), is another example of our newly synthesized
thiourea derivatives that contains both aryl and alkyl groups.
The molecular structure of the title compound is depicted in Fig. 1. The asymmetric unit of the title compound contains
two crystallographically independent molecules A (atom numbering 1xx) and B (2xx). There is very little difference between
the bond lengths and angles of these molecules.
The typical thiourea carbonyl and thiocarbonyl double bonds as well as shortened C—N bond lengths are ob-
served in the title compound. These bond lengths in the title compound are comparable to those of related struc-
tures; 1-(4-chlorobenzoyl)-3-(2,4,6-trichlorophenyl)thiourea (Khawar Rauf et al., 2009b), 1-(3-chlorophenyl)-3-(2,6-
dichlorobenzoyl)thiourea (Khawar Rauf et al., 2009d), 1-(3-chlorobenzoyl)-3-(2,3-dimethylphenyl)thiourea (Khawar Rauf
et al., 2009c), 1-(2,6-dichlorobenzoyl)-3-(2,3,5,6-tetrachlorophenyl)thiourea (Khawar Rauf et al., 2009a), N'-(4-chloroben-
zoyl)-N,N-diphenylthiourea (Arslan et al., 2003a), 1-(2-chloro-benzoyl)-3-p-tolyl-thiourea (Arslan et al., 2004), N,N-di-
methyl-N-(2-chlorobenzoyl)thiourea (Arslan et al., 2006), o-ethylbenzoylthiocarbamate (Arslan et al., 2007a), 2-chloro-N-
(diethylcarbamothioyl)benzamide (Arslan et al., 2007b). The other bond lengths in (I) show normal values (Allen et al.,
The conformation of the title molecule with respect to the thiocarbonyl and carbonyl moieties is twisted, as re-
flected by the C101—N11—C108—O1, C108—N11—C101—S1, C108—N11—C101—N12, C201—N21—C208—O2,
C208—N21—C201—S2, and C208—N21—C201—N22 torsion angles of 11.9 (5), 110.7 (3), -69.6 (4), -13.6 (5), -
109.6 (3), and 70.5 (4)°, respectively. In addition, the difference in the torsion angles can be attributed to the different con-
formations of the two independent molecules.
The two di-n-propyl groups in independent molecules A (atom numbering 1xx) are twisted in a + and - antiperiplanar
conformation with -179.9 (3)° and 178.2 (3)°. In the independent molecule B (atom numbering 2xx), one di-n-propyl group is
twisted in a - antiperiplanar conformation with -179.1 (3)° and the other di-n-propyl group adopts a - synclinal conformation
with -56.7 (4)°.
The phenyl rings and central thiourea S1—N11—N12—C101 [largest dev. 0.002 (3) Å for C101] and
S2—N21—N22—C201 [largest dev. -0.001 (3) Å for C201] fragments are each essentially planar. The dihedral angle
between the 4-bromophenyl ring and the plane S1/N11/N12/C101 is 84.88 (15)°, and the dihedral angle between the 4-bro-
mophenyl ring and the plane S2/N21/N22/C201 is 82.53 (16)°.
The molecules of title compound are linked by paired N—H···S hydrogen bonds into centrosymmetric dimers. Details
of the symmetry codes and hydrogen bonding are given in Table 1 and Fig. 2.
The title compound was prepared with a procedure similar to that reported in the literature (Arslan et al., 2003b; Özer et
al., 2009). A solution of 4-bromobenzoyl chloride (0.01 mol) in acetone (50 ml) was added dropwise to a suspension of
potassium thiocyanate (0.01 mol) in acetone (30 ml) (Fig. 3). The reaction mixture was heated under reflux for 30 min,
and then cooled to room temperature. A solution of di-n-propylamine (0.01 mol) in acetone (10 ml) was added and the
resulting mixture was stirred for 2 h. Hydrochloric acid (0.1 N, 300 ml) was added to the solution, which was then filtered.
The solid product was washed with water and purifed by recrystallization from an ethanol–dichloromethane mixture (1:2).
Anal. Calcd. for C14H19N2OSBr: C, 48.9; H, 5.6; N, 8.2. Found: C, 48.7; H, 5.4; N, 8.4%.
H atoms were clearly identified in difference syntheses. H atoms attached to nitrogens were located from a difference Fourier
map and refined freely. The rest H atoms refined at idealized positions riding on the C atoms with C—H = 0.95–0.99 Å,
and Uiso(H) = 1.5Ueq(C) for methyl H atoms and 1.2Ueq(C) for other H atoms.
All CH3 H atoms were allowed to rotate but not to tip. For C203 and C204 neither anisotropic refinement nor split
model provided successful results, so an isotropic model was used that gave sensible geometries but some electron density
Fig. 1. The molecular structure of (I). Displacement ellipsoids are drawn at the 50% probabil-