metal-organic compounds
Acta Crystallographica Section C
Crystal Structure
morpholino-4-oxo-4,5-dihydro-1,3-thiazol-5-ylidene)methyl-
phenoxy]propene ligand, L, of the title compound, (I).
Communications
ISSN 0108-2701
catena-Poly[[cyclo-tetra-l-chloro-
tetracopper(I)]-bis{l-3-[(2-morpho-
lino-4-oxo-4,5-dihydro-1,3-thiazol-
5-ylidene)methylphenoxy]propene}-
2jN,10g2;1g2,20jN]
The Cu and Cl atoms in (I) form chair-like Cu4Cl4 cycles
(Fig. 1). Similar eight-membered rings have been reported in
the structures of 2CuCl(dibenzocyclooctatetraene) (Mak et
al., 1983), CuCl(allyl alcohol) (Zavalij et al., 1983), 2CuCl(1,5-
hexadien-3-ol) (Oliinik et al., 1987) and 2CuCl(C3H5Ð
N
CHÐR) (R = 2-furyl and phenyl; Filinchuk & Mys'kiv,
Evgeny Goreshnik,a* Volodymyr Karpyakb and Marian
Mys'kivb
1998). The ligand L acts as a bridge between two Cu4Cl4
cycles, being coordinated to atom Cu1 of one copper±chloride
cycle via ꢀ interaction with the C4 C5 bond of the allyl group
and to atom Cu2 from another inorganic fragment via the N
atom of the thiazole ring. Ligand L is essentially planar; the
benzene and thiazole aromatic rings, the non-H atoms of the
allyl group, and atom N1 of the morpholine ring are coplanar.
Each bridge actually consists of a pair of organic moieties
oriented in a `head-to-tail' manner (Fig. 2). The aromatic rings
within the bridge exhibit a stacking interaction with a parallel
a
Ï
Department of Inorganic Chemistry and Technology, Jozef Stefan Institute, Jamova
39, 1000 Ljubljana, Slovenia, and bDepartment of Chemistry, Ivan Franko National
University of L'viv, Kyryla and Mefodia Str. 8, 79005 L'viv, Ukraine
Correspondence e-mail: evgeny.goreshnik@ijs.si
Received 8 June 2005
Accepted 27 June 2005
Online 23 July 2005
Ê
mutual orientation and typical ring±ring distances of 3.6 A. In
Crystals of a new copper(I) ꢀ complex of composition
[Cu4Cl4(C17H18N2O3S)2]n have been obtained by alternating-
current electrochemical synthesis. In the crystal structure, the
Cu and Cl atoms form a chair-like Cu4Cl4 cyclic fragment. The
turn, each Cu4Cl4 ring is bonded to four ligands, resulting in
two such bridges which connect two neighboring inorganic
rings, thus forming in®nite zigzag organic±inorganic chains
oriented along the [111] direction. These chains are inter-
connected by weak interactions only.
organic ligand acts as a bridge, being connected via the C
C
bond of the allyl group to a Cu atom from one inorganic cycle
and via the N atom of the thiazole ring to a Cu atom of
another copper±chloride fragment. The geometry of the ꢀ
center indicates that the CuÐ(C C) interaction is moder-
ately effective.
The CuIÐ(C C) ꢀ interaction in (I) appears to be of
moderate effectiveness, as indicated by the slight elongation of
Ê
the C4 C5 bond [to 1.351 (8) A] compared with a free C
C
ꢀ
Ê
double bond (1.33 A). In addition, the value of 37.5 (3) for
the C4ÐCuÐC5 angle, being an important reference of
copper(I)±ole®n interaction ef®ciency, is comparable to the
value of 38.0 (8)ꢀ in C7H5N2S(C3H5)CuCl (Goreshnik et al.,
2002) with the same 2Cl + C C CuI atom arrangement. The
ꢀ-coordinated Cu-atom environment in (I) is essentially
planar (the sum of the ligand±copper±ligand angles is 359.9ꢀ),
which is likewise typical for effective ꢀ interaction. On the
other hand, the combination of a large inorganic fragment and
a large organic ligand hinders achievement of the most
suitable mutual orientation of the C C group and metal
center for effective CuÐ(C C) interaction. Consequently,
Comment
The catalytic properties of copper(I) halides and the possibi-
lity of their ole®n ꢀ-adduct separation were the basis for early
studies of the structural chemistry of copper(I) ꢀ complexes
(Herberhold, 1972). Such interest has led to the investigation
of metal adducts with aliphatic ole®n derivatives, whereas
copper(I) ꢀ complexes with heterocyclic ligands have been
poorly investigated. We have therefore focused on the struc-
tural investigation of copper(I) ꢀ complexes with the allyl
derivatives of heterocyclic compounds.
Our recent studies of these compounds have shown some
interesting peculiarities with respect to stereochemistry.
Sharply de®ned differences in three-dimensional structure are
observed between small monocyclic aromatic and non-
aromatic derivatives [such as morpholine (Goreshnik &
Mys'kiv, 2003) or aminopyridine (Goreshnik et al., 2005a)] on
the one hand, and between bicyclic aromatic compounds
[derivatives of benzotriazole (Goreshnik et al., 1999) or
benzimidazole (Goreshnik et al., 2000, 2002)] on the other. As
a logical extension of this chemistry, we chose to use more
voluminous heterocyclic derivatives, including the 3-[(2-
Figure 1
The ligand and copper±chloride rings in (I). [Symmetry codes: (J) x + 2,
y + 1, z; (K) x 1, y + 1, z + 1; (L) x + 1, y + 2, z + 1.]
m390 # 2005 International Union of Crystallography
DOI: 10.1107/S0108270105020299
Acta Cryst. (2005). C61, m390±m392
Goreshnik, Evgeny
