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European	Journal	of	Chemistry	3	(1)	(2012)	37‐39	

European	Journal	of	Chemistry	
ISSN	2153‐2249	(Print)	/	ISSN	2153‐2257	(Online)		2012	EURJCHEM	

DOI:10.5155/eurjchem.3.1.37‐39.591	

	
	

	

	

European	Journal	of	Chemistry	
Journal	homepage:	www.eurjchem.com	

	 	 	

Crystal	and	molecular	structure	of		
bis(4‐bromo‐N‐(diethylcarbamothioyl)benzamido)nickel(II)		complex	

Gun	Binzeta,*,	Ulrich	Flörkeb,	Nevzat	Külcüc	and	Hakan	Arslanc	

a	Science	Education,	Faculty	of	Education,	Mersin	University,	Mersin,	TR‐33169,	Turkey	
b	Department	of	Chemistry,	University	of	Paderborn,	Paderborn,	D‐33098,	Germany		
c	Department	of	Chemistry,	Faculty	of	Arts	and	Science,	Mersin	University,	Mersin,	TR‐33343,	Turkey	

*Corresponding	author	at:	Science	Education,	Faculty	of	Education,	Mersin	University,	Mersin,	TR‐33169,	Turkey.		
Tel.:	+90.532.2701917;	fax:	+90.324.3610047.	E‐mail	address:	polatgun@gmail.com	(G.	Binzet).	

	
	

	 	

	 	 	
ARTICLE	INFORMATION	 	 ABSTRACT	
Received:	31	January	2012	
Received	in	revised	form:	06	February	2012	
Accepted:	06	February	2012	
Online:	31	March	2012	

KEYWORDS	

	 We	 report	 the	 synthesis	 of	 bis(4‐bromo‐N‐(diethylcarbamothioyl)benzamido)nickel(II)
complex	of	an	benzoylthiourea	derivative	formulated	as	C24H28Br2NiN4O2S2.	 	The	structure	of
compound	has	been	determined	by	single‐crystal	X‐ray	diffraction	analysis.	 It	 crystallizes	 in
the	 monoclinic	 space	 group,	 P21/c	 with	 unit	 cell	 dimensions	 of	 a	 =	 12.9099(17)	 Å,	 b	 =
15.264(2)	Å,	c	=	14.0287(19)	Å,	β	=	92.140(4)o	and	V	=	2762.5(6)	Å3.	 	In	this	compound,	the
nickel	 atom	 is	 coordinated	 by	 two	 sulphur	 and	 two	 oxygen	 atoms	 from	 two	 4‐bromo‐N‐
(diethylcarbamothioyl)benzamide	molecules	forming	an	distorted	square‐planar	geometry.		

Thiourea	
Benzamide	
Nickel	complex	
Benzoylthiourea	
Crystal	structure	
Single	crystal	X‐ray	diffraction	

	
1.	Introduction	
	

In	 recent	 years,	 there	 has	 been	 considerable	 interest	 in	
benzoylthiourea	compounds.	This	 is	due	 to	 the	 fact	 that	 these	
compounds	 have	 demonstrated	 remarkable	 pharmacological	
characteristics.	 Many	 benzoylthiourea	 compounds	 have	 been	
tested	for	their	in	vitro	activity	against	a	large	variety	of	tumor	
lines	 and	 have	 been	 found	 to	 be	 as	 effective	 or	 better	 than	
traditional	heavy	metal	anticancer	drugs	such	as	cis‐platin	[1].		
Some	 acylthiourea	 derivatives	 exhibit	 antiviral	 [2],	
antibacterial	 [3],	 antifungal	 [4],	 antihelmintic	 [5,6],	 herbicidal	
[7],		activities.	1,3‐Dialkyl	or	diaryl	thioureas	exhibit	significant	
antifungal	 activity	 against	 plant	 pathogens	 Pyricularia	 oryzae	
and	 Drechslera	 oryzae	 [8].	 Furthermore,	 thiourea	 and	 its	
derivatives	 are	 a	 well‐known	 class	 of	 excellent	 ligands	 for	
transition	 metals,	 which	 also	 exhibit	 redox	 activity	 with	
reducible	metal	ions	to	make	the	reaction	systems	complicated	
[9‐11].	Moreover,	 ion	 selective	 electrodes	 for	 Pb(II)	 based	 on	
benzoylthioureido	 derivatives	 as	 ionophores	 have	 been	
formulated	[12].	

Our	 group	 has	 studied	 the	 synthesis	 [13‐20],	 charac‐
terization,	crystal	structure	[21‐26],	 thermal	behavior	[26,	27]	
and	 antimicrobial	 activity	 [28,	 29]	 of	 some	 substitute	
benzoylthiourea	derivatives	and	 their	metal	complexes.	 In	 the	
present	work,	we	 report	 the	 crystal	 structure	of	bis(4‐bromo‐
N‐(diethylcarbamothioyl)benzamido)nickel(II)	complex.		
	
2.	Experimental	
	
2.1.	Instrumentation	
	

Melting	points	were	measured	on	an	Electrothermal	model	
9200	and	are	uncorrected.	Elemental	analyses	were	carried	out	

with	a	LECO	CHNS‐932	elemental	analyzer.	Fourier	 transform	
infrared	 spectra	 (FTIR)	were	 recorded	 in	 KBr	 pellets	 using	 a	
WinFirst	 Satellite	 FTIR	 spectrometer.	 1H	 NMR	 spectra	 were	
recorded	on	a	Bruker	DPX‐400	spectrometer	at	400	MHz	using	
CDCl3	 as	 the	 solvent,	 with	 tetramethylsilane	 as	 internal	
standard.	 The	 crystallographic	 data	 of	 bis(4‐bromo‐N‐
diethylcarbamothioyl)	 benzamido)nickel(II)	 complex	 were	
recorded	 on	 a	 Bruker	 AXS	 SMART‐APEX	 diffractometer	 using	
MoK	radiation	(	=	0.71073	Å)	at	T	=	120(2)	K.	The	structure	
was	 solved	 by	 direct	 methods	 and	 refined	 by	 least	 square	
cycles.	 The	 non‐hydrogen	 atoms	were	 refined	 anisotropically.	
All	calculations	were	performed	using	the	SHELXTL‐97	package	
[30].	 The	 crystallographic	 data	 for	 the	 complex	 are	 listed	 in	
Table	1.	
	
2.2.	Synthesis	of	bis(4‐bromo‐N‐(diethylcarbamothioyl)	
benzamido)nickel(II)	complex	
	

All	 chemicals	 were	 used	 as	 obtained	 from	 Merck	 and	
analytical‐grade	 solvents	 were	 used	 without	 further	
purification.	 The	 bis(4‐bromo‐N‐(diethylcarbamothioyl)benz‐
amido)nickel(II)	 complex	 was	 prepared	 according	 to	 the	
method	described	in	the	literature	[16]	(Scheme	1).		

4‐bromo‐N‐(diethylcarbamothioyl)benzamide	 was	 dissol‐
ved	 in	 methanol	 (30	 mL)	 and	 added	 dropwise	 to	 nickel(II)	
acetate,	 Ni(CH3COO)2,	 in	 methanol	 (30	 mL)	 in	 a	 1:2	 ratio	
(Metal:Ligand)	at	pH	>	7	and	the	mixture	was	stirred	for	30	min	
at	 room	 temperature.	 During	 the	 time,	 the	 color	 of	 the	 4‐
bromo‐N‐(diethylcarbamothioyl)benzamide	 is	 changed	 white	
to	 purple.	 The	 change	 in	 color	 was	 due	 to	 complete	 the	
reaction.	 The	 change	 in	 color	 was	 due	 to	 the	 interaction	 of	
NiCl2.6H2O	 with	 the	 4‐bromo‐N‐(diethylcarbamothioyl)	
benzamide.		



38	 Binzet	et	al.	/	European	Journal	of	Chemistry	3	(1)	(2012)	37‐39	
	
	

	
	

Scheme	1	
	
	
The	 solid	 complex	was	 filtered	 and	 recrystallized	 from	an	

ethanol:dichloromethane	 mixture	 (1:2)	 (Scheme	 1).	 Purple	
precipitate	was	formed	crystal	suitable	for	X‐ray	single	crystal	
diffraction.	

Bis(4‐bromo‐N‐(diethylcarbamothioyl)benzamido)	
nickel(II):	 Yield:	 82%.	 M.p.:	 248‐250	 oC.	 Anal.	 calcd.	 for	
C24H28Br2N4O2S2Ni:	C,	41.95;	H,	4.11;	N,	8.15.	Found:	C,	41.80;	H,	
4.05;	N,	8.16	%.	FT‐IR	(KBr,	cm‐1):	2974,	2932,	2868	(CH);	1581	
(CN),	 1492	 (C‐O),	 751	 (C‐Br).	 1H	 NMR	 (400	 MHz,	 CDCl3,	 δ,	
ppm):	 7.96	 (d,	 4H,	 Ar‐H),	 7.52	 (d,	 4H,	 Ar‐H),	 3.57	 (m,	 8H,	 N‐
CH2),	1.48	(m,	12H,‐CH3).	
	
Table	1.	Crystal	data	and	structure	refinement	for	the	title	compound.	
Empirical	formula		 C24H28Br2NiN4O2S2	
Formula	weight		 687.15	
Temperature / K		 120(2)	
Crystal	system	 Monoclinic	
Space	group		 P21/c	
a / Å,	b / Å,	c / Å		 12.9099(17),	15.264(2),	14.0287(19)
β°	 92.140(4)	
Volume / Å3		 2762.5(6)	
Z		 4	
ρcalc. / mg	mm‐3		 1.652	
μ / mm‐1		 3.775	
F(000)		 1384	
Crystal	size / mm3		 0.26	x	0.26	x	0.09	
2θ	range	for	data	collection		 1.58	to	27.88°	
Index	ranges		 ‐13	≤	h	≤	16,	‐18	≤	k	≤	20,	‐18	≤	l ≤	18
Reflections	collected		 22583	
Independent	reflections		 6579	[R(int)	=	0.0607]	
Data/restraints/parameters		 6579/4/324	
Goodness‐of‐fit	on	F2		 1.026	
Final	R	indexes	[I>2σ	(I)]		 R1	=	0.0503,	wR2	=	0.1146
Final	R	indexes	[all	data]		 R1	=	0.0901,	wR2	=	0.1301
Largest	diff.	peak/hole / e	Å‐3		 0.731	/	‐0.612	
	
3.	Results	and	discussion		

	
The	 reaction	 of	 nickel(II)	 acetate,	 Ni(CH3COO)2,	 with	 two	

equivalents	of	4‐bromo‐N‐(diethylcarbamothioyl)benzamide	in	
methanol	 produces	 the	 potentially	 bidentate	 molecule	 bis(4‐
bromo‐N‐(diethylcarbamothioyl)benzamido)nickel(II)	 complex	
high	yield	(Scheme	1),	as	an	air‐stable	purple	solid.	The	single	
crystals	of	nickel(II)	complex	were	grown	by	re‐crystallization	
from	 an	 ethanol	 :dichloromethane	 solution	 mixture	 (1:2)	 at	
ambient	temperature.		

The	 ORTEP	 drawing	 of	 complex	 is	 illustrated	 in	 Figure	 1	
and	some	selected	bond	lengths	and	angles	are	listed	in	Table	1	
and	Table	2.			

In	 this	 complex,	 the	 central	 Ni(II)	 atom	 is	 a	 cis‐complex	
with	 slightly	 distorted	 square	 planar	 coordination.	 In	 this	
complex	center	nickel	atom	coordinated	by	two	sulfur	and	two	
oxygen	atoms	from	two	ligands.	

The	bond	lengths	of	the	carbonyl	O1‐C6	1.263(5)	Å;	O2‐C18	
1.268(5)	Å	and	thiocarbonyl	S1‐C1	1.744(4)	Å;	S2‐C13	1.745(4)	
Å	 groups	 lie	 between	 those	 for	 double	 and	 single	 bonds.	 The	
same	 behavior	 is	 observed	 for	 C‐N	 bond	 lengths.	 C‐N	 bond	
lengths	for	the	investigated	complex	is	shorter	than	the	average	
single	C‐N	bond	length	of	1.48	Å,	being	C1‐N1	=	1.335(5)	Å,	C6‐

N1=	 1.325(6)	 Å,	 C1‐N2	 =	 1.334(6)	 Å,	 thus	 showing	 varying	
degrees	of	double	bond	character	[13‐27,33,34].	

Two	carbon	atoms	of	one	of	the	terminal	ethyl	groups	were	
modelled	 as	 disordered	 over	 two	 sites,	 the	 ratio	 of	 refined	
occupancies	 being	 0.5:0.5	 for	 C141/C151:	 C142/C152.	 The	
C141‐C151	 and	C141‐N4	 	bond	 lengths	were	 restrained	 to	be	
equal	 to	 the	 C142‐C152	 and	 C142‐N4	 bond	 lengths,	
respectively	with	an	effective	standard	deviation	of	0.003	Å.	H	
atoms	were	placed	in	calculated	positions	and	refined	as	riding,	
with	Uiso(H)	=	1.2Ueq	(	C)	or	1.5	Ueq	(methyl	C).	One	Br	atom	is	
disordered	 over	 two	 positions	 with	 a	 refined	 site‐occupancy	
ratio	of	0.509(5):0.491	(5).		
	

	
	
Figure	1.	A	perspective	view	of	the	title	compound,	with	atom‐numbering	
scheme.	
	

The	 crystal	 structure	 is	 stabilized	 by	weak	 C‐H…S	 and	 C‐
H…Br	hydrogen‐bonding	interactions	(Table	4).		
	
Table	2.	Bond	lengths	for	the	title	compound.		
Atom Atom Length,	Å	
Ni1	 O1	 1.852(3)	
Ni1 O2 1.854(3)	
Ni1 S1 2.1356(12)	
Ni1 S2 2.1405(12)	
Br2 C22 1.899(4)	
Br11 C10 1.980(6)	
S1 C1 1.744(4)	
S2 C13 1.745(4)	
O1	 C6	 1.263(5)	
O2	 C18	 1.268(5)	
N1	 C1	 1.335(5)	
N1 C6 1.325(6)	
N2 C1 1.334(6)	
N2 C2 1.466(6)	
N2 C4 1.487(5)	
N3 C13 1.345(5)	
N3 C18 1.314(5)	
N4 C13 1.322(6)	
N4	 C141	 1.519(8)	
	



Binzet	et	al.	/	European	Journal	of	Chemistry	3	(1)	(2012)	37‐39	 39	
 

Table	3.	Bond	angles	for	the	title	compound.		
Atom	 Atom	 Atom	 Angle,	o	
O1	 Ni1	 O2	 84.05(14)
O2	 Ni1	 S2	 93.39(10)
O1	 Ni1	 S2	 177.42(10)	
O2	 Ni1	 S1	 178.89(10)	
O1	 Ni1	 S1	 94.90(10)	
S1	 Ni1	 S2	 87.66(4)	
C1	 S1	 Ni1	 107.99(16)
C13	 S2	 Ni1	 105.87(17)
C6	 O1	 Ni1	 133.4(3)
C18	 O2	 Ni1	 131.9(3)
C6	 N1	 C1	 123.9(4)
C1	 N2	 C2	 124.3(4)
C1	 N2	 C4	 120.4(4)
C2	 N2	 C4	 115.3(4)	
C6	 N1	 C1	 123.9(4)
C1	 N2	 C2	 124.3(4)	
C1	 N2	 C4	 120.4(4)	
C2	 N2	 C4	 115.3(4)
N2	 C1	 N1	 115.6(4)
N2	 C1	 S1	 116.5(3)
N1	 C1	 S1	 127.9(4)
O1	 C6	 N1	 129.4(4)
O1	 C6	 C7	 114.8(5)
N1	 C6	 C7	 115.8(4)
N4	 C13	 N3	 115.6(4)	
N4	 C13	 S2	 116.5(3)	
N3	 C13	 S2	 127.8(4)	
C20	 C19	 C24	 119.8(4)	
C20	 C19	 C18	 119.1(4)
C24	 C19	 C18	 121.0(4)
	
	Table	4.	Hydrogen	bonds	for	the	title	compound.	
D	 H	 A	 d(D‐H),	Å	 d(H‐A),	Å	 d(D‐A),	Å D‐H‐A,	o
C(2)			 H(2B)			 S(1)				 0.99								 2.56				 2.965(5)							 105	
C(16)	 H(16A)	 S(2)	 0.99							 2.53				 2.951(6) 106
C(3)			 H(3A)	 Br(12)i	 0.98	 2.87				 3.633(6) 						 135
Symmetry	code:	i:	‐1+x,	1/2‐y,	‐1/2+z.	
	
4.	Conclusion	
	

In	 this	 work,	 bis(4‐bromo‐N‐(diethylcarbamothioyl)	
benzamido)nickel	(II)	complex	has	been	synthesized		according	
to	 the	 previous	 reports.	 The	 crystal	 of	 nickel(II)	 complex	 is	
suitable	 for	 	 	 	 	 X‐ray	 single	 crystal	 diffraction	 analysis.	 In	 this	
nickel	complex,	the	nickel	atom	is	coordinated	by	two	S	atoms	
and	two	O	atoms	from	two	4‐bromo‐N‐(diethylcarbamothioyl)	
benzamide	molecules.		
	
Acknowledgements	
	

This	 work	 was	 supported	 by	 Mersin	 University	 Research	
Fund	(Project	No:	BAP‐FBE‐KB(GB)‐2006‐1).	
	
Supplementary	material	
	

CCDC‐848930	contains	the	supplementary	crystallographic	
data	 for	 this	paper.	These	data	can	be	obtained	 free	of	charge	
via	 www.ccdc.cam.ac.uk/data_request/cif,	 or	 by	 e‐mailing	
data_request@ccdc.cam.ac.uk,	or	by	contacting	The	Cambridge	
Crystallographic	 Data	 Centre,	 12	 Union	 Road,	 Cambridge	 CB2	
1EZ,	UK;	fax:	+44(0)1223‐336033.	
	
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