Chlorobis[N-ethoxycarbonyl-N'-(p-methoxyphenyl)thiourea-kS]copper(l)

Article abstract of DOI:10.1107/S0108270104028215

The synthesis and crystal structure of chlorobis[N-ethoxycarbonyl-N′- (p-methoxyphenyl)thiourea-κS]copp er(I) was discussed. The Cu¹ coordination environment was found to be trigonal planar, involving two S atoms and one Cl atom. The presence of intramolecular hydrogen bonds formed a cis conformation and promotes the stability of the complex. The results show that the existence of intramolecular hydrogen bonds in carbonylthiourea influences coordination properties and promotes the stability of the complex it forms.

Full text of DOI:10.1107/S0108270104028215

metal-organic compounds
Acta Crystallographica Section C
Crystal Structure
Communications
methoxyphenyl)thiourea, according to previous publications
(Jeannin et al., 1979). This reaction is similar to those reported
by Shen et al. (1997) and Zhang, Xian & Wei (2003).
ISSN 0108-2701
Chlorobis[N-ethoxycarbonyl-N0-(p-
methoxyphenyl)thiourea-jS]copper(I)
Bi-Quan Su,a* Liang Xian,b Hai-Bin Songc and Li Shenga
aSchool of Chemical and Biological Engineering, Lanzhou Jiaotong University,
Lanzhou, 730070, People's Republic of China, bState Key Laboratory for Oxo
Synthesis and Selective Oxidation, Lanzhou Institute of Chemical Physics,
Chinese Academy of Sciences, Lanzhou, 730000, People's Republic of China, and
cState Key Laboratory of Elemento-organic Chemistry, Nankai University, Tianjin,
300071, People's Republic of China
In the molecular structure of (I), the two acylthiourea
molecules adopt a cis conformation relative to the central CuI
ion (Fig. 1) because of the existence of intramolecular
hydrogen bonds between the Cl ion and the H atoms on
atoms N2 and N4 (Table 2). The CuI ion in (I) has trigonal
geometry, composed of two S atoms from two thiourea ligands
and one Cl ion (Table 1). These atoms are coplanar, the mean
Correspondence e-mail: subq@mail.lzjtu.cn
Received 13 October 2004
Accepted 2 November 2004
Online 30 November 2004
Ê
deviation from the least-squares plane being 0.0034 A.
The existence of intramolecular hydrogen bonds in
carbonylthiourea evidently in¯uences its coordination prop-
erties and promotes the stability of the complex it forms.
In cis-bis(N-benzoyl-N0-propylthiourea)dichloroplatinum(II)
(Bourne & Koch, 1993), the two ligand molecules bind to the
PtII ion via the S atoms only, the carbonyl O atoms being
locked into position by hydrogen bonds similar to those in the
free ligand. The same observation was reported for a CuI
complex by both Shen et al. (1997) and Zhang, Xian & Wei
(2003). By comparison, in N,N-disubstituted carbonylthiourea
complexes, the carbonyl O atom commonly participates in
The title copper(I) complex, [CuCl(C11H14N2O3S)2], was
synthesized by the redox reaction of cupric chloride with the
corresponding thiourea derivative as reducing agent. The CuI
coordination environment is trigonal planar, involving two S
atoms and one Cl atom. The presence of intramolecular
hydrogen bonds leads to the formation of a cis conformation
and promotes the stability of the complex.
Comment
Complexes of thiourea derivatives have been reported in
several papers (Guillon et al., 1996, 1998), and these
compounds have been widely used in organic synthesis,
such as in the metal-catalyzed asymmetric reduction of
carbonyl compounds and carbonylative cyclization of
o-hydroxyarylacetylenes (Touchard et al., 1997; Nan et al.,
2000). Of all the thiourea derivatives, the N-substituted-N0-
acylthiourea compounds have received the most attention,
because the existence of acyl and thiocarbonyl groups in these
complexes enhances the coordination ability of the ligands,
which readily form supramolecular structures via hydrogen
bonds. In our previous work (Zhang, Xian, Wei & Yu, 2003;
Zhang, Xian & Wei, 2003), a series of complexes with thiourea
derivatives was synthesized and characterized, and the coor-
dination behavior of the thiourea derivatives was discussed.
The preparation of the title complex, (I), and its crystal
structure are reported here.
In many syntheses of copper complexes, irreversible CuII/
CuI systems have been observed (Guillon et al., 1996, 1998)
and there are many reports of the reduction of CuII in the
presence of thione derivatives (Jeannin et al., 1979; Raper,
1985; Karagiannidis et al., 1990). For the synthesis of (I), the
cuprous complex was obtained by the redox reaction of cupric
ions with the thiourea ligand. The reducing agent in this
reaction is the thiourea ligand, viz. N-ethoxycarbonyl-N0-(p-
Figure 1
A view of the title compound showing the atomic labeling. Displacement
ellipsoids are drawn at the 50% probability level. Intramolecular
hydrogen bonds are indicated by dashed lines.
Acta Cryst. (2004). C60, m661±m662
DOI: 10.1107/S0108270104028215
# 2004 International Union of Crystallography m661

metal-organic compounds
Data collection
coordination with the central metal ion, for example, in the
PtII and CuII complexes (Koch et al., 1994; Richter et al., 1980).
This behavior is due to the absence of a thioamide H atom in
the N,N-disubstituted-carbonylthiourea ligands, which means
that no hydrogen bonds can form. This hypothesis is con®rmed
in (I), in which there are four intramolecular hydrogen bonds
in the molecule (Table 2). Acyl atoms O2 and O5 form
hydrogen bonds with the H atoms on atoms N1 and N3. Since
they are locked into a planar six-membered ring formed by
these hydrogen bonds, the acyl O atoms in the ligands cannot
take part in coordination with the CuI ion in the same way as
the S atoms.
Bruker SMART CCD area-detector
diffractometer
' and ! scans
Absorption correction: multi-scan
(SADABS; Bruker, 1998)
Tmin = 0.654, Tmax = 0.824
15 513 measured re¯ections
5690 independent re¯ections
3568 re¯ections with I > 2ꢅ(I)
Rint = 0.046
ꢃmax = 26.6ꢀ
h = 17 ! 16
k = 16 ! 10
l = 19 ! 18
Re®nement
Re®nement on F2
R[F2 > 2ꢅ(F2)] = 0.039
wR(F2) = 0.095
S = 1.04
5690 re¯ections
342 parameters
w = 1/[ꢅ2(F2o) + (0.0408P)2]
where P = (F2o + 2Fc2)/3
(Á/ꢅ)max = 0.001
3
Ê
Áꢆmax = 0.29 e A
3
Ê
0.47 e A
Áꢆmin
=
Absolute structure: Flack (1983),
2678 Friedel pairs
Flack parameter = 0.438 (16)
H atoms treated by a mixture of
independent and constrained
re®nement
Experimental
The N-ethoxycarbonyl-N0-(p-methoxyphenyl)thiourea ligand was
synthesized according to the method reported by Zhang, Xian & Wei
(2003). To an ethanol solution (30 ml) of the ligand (2 mmol) was
added an ethanol solution (10 ml) of cupric chloride (1 mmol). After
the solution had been stirred at room temperature for 2 h, the
mixture was ®ltered to obtain a white solid, which was then dried in
air (yield 34%). Single crystals of (I) were obtained after one week by
slow evaporation of a chloroform solution. Analysis calculated for
C22H28ClCuN4O6S2: C 43.45, H 4.61, N 9.22%; found: C 43.00, H 4.05,
N 8.89%. IR (KBr disc): ꢀ 3115 (vs), 1724 (vs), 1558 (s), 1530 (s), 1513
(vs), 1253 (vs), 1186 (s), 1040 (s), 834 (w), 769 (w), 684 (w), 521 (w).
1H NMR (benzene-d6): ꢁ 0.92 (3H, CH3), 3.19 (3H, ArOCH3), 5.00
(2H, CH2), 7.16 (4H, aryl H), 11.46 (1H, NH), 11.88 (1H, NH).
H atoms bonded to N atoms were found by difference Fourier
Ê
methods and the distances were restrained [NÐH = 0.87 (1) A].
H atoms bonded to C atoms were included in calculated positions
Ê
(CÐH = 0.93±0.97 A) using a riding model.
Data collection: SMART (Bruker, 1998); cell re®nement: SMART;
data reduction: SAINT (Bruker, 1998); program(s) used to solve
structure: SHELXS97 (Sheldrick, 1990); program(s) used to re®ne
structure: SHELXL97 (Sheldrick, 1997); molecular graphics:
SHELXTL (Bruker, 1998); software used to prepare material for
publication: SHELXTL.
Support for this work from the Foundation of Lanzhou
Jiaotong University (2004±5) is gratefully acknowledged.
Crystal data
[CuCl(C11H14N2O3S)2]
Mr = 607.59
Orthorhombic, Pna21
Mo Kꢂ radiation
Cell parameters from 949
re¯ections
Supplementary data for this paper are available from the IUCr electronic
archives (Reference: HJ1031). Services for accessing these data are
described at the back of the journal.
ꢃ = 2.5±23.4ꢀ
Ê
a = 13.648 (3) A
1
Ê
b = 13.254 (3) A
ꢄ = 1.08 mm
T = 293 (2) K
Ê
c = 15.358 (6) A
Ê
V = 2778.1 (13) A
3
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Block, colorless
0.26 Â 0.24 Â 0.18 mm
Z = 4
Dx = 1.453 Mg m
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Â
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ꢀ
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Â
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ꢀ
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N1ÐH1Á Á ÁO2
N2ÐH2Á Á ÁCl1
N3ÐH3Á Á ÁO5
N4ÐH4Á Á ÁCl1
0.87 (4)
0.87 (3)
0.87 (4)
0.87 (3)
1.99 (4)
2.31 (3)
2.01 (4)
2.31 (3)
2.670 (6)
3.175 (5)
2.682 (6)
3.174 (4)
134 (4)
176 (5)
133 (4)
172 (5)
ꢁ
m662 Bi-Quan Su et al. [CuCl(C11H14N2O3S)2]
Acta Cryst. (2004). C60, m661±m662