metal-organic compounds
ClÐCuÐCl lines deviate by 2.19 (6) and 2.58 (7)ꢁ from being
orthogonal to these equatorial planes for molecules A and B,
respectively.
Re®nement
Re®nement on F2
R[F2 > 2ꢅ(F2)] = 0.047
wR(F2) = 0.152
w = 1/[ꢅ2(Fo2) + (0.0958P)2
+ 0.0725P]
where P = (Fo2 + 2Fc2)/3
(Á/ꢅ)max < 0.001
In the two independent molecules, some differences are
observed with regard to the rotation of the phenyl and pyra-
zole rings about the Cn5ÐCn51 bond joining them, as shown
by the Nn1ÐCn5ÐCn51ÐCn52 (n = 1±4) torsion angles (see
Table 1).
S = 1.14
6079 re¯ections
432 parameters
H-atom parameters constrained
3
Ê
Áꢆmax = 0.41 e A
Áꢆmin =
Extinction correction: SHELXL97
3
Ê
0.65 e A
Extinction coef®cient: 0.0275 (12)
The orientation of the pyrazole ligands around the metal
ions is not the same in the two independent molecules, as
indicated by the ClÐCuÐNÐN torsion angles. The different
distortions of the ligands in molecules A and B can be
explained by the different packing interactions. These inter-
actions are of the CÐHÁ Á ÁCl and CÐHÁ Á ÁCg types (Cg are the
centroids of pyrazole rings Nn1/Nn2/Cn3/Cn4/Cn5, where n =
2 and 3). The geometry for these weak interactions is given in
Table 2.
Table 1
Selected geometric parameters (A, ).
ꢁ
Ê
Cu1ÐN12
Cu1ÐN22
Cu1ÐCl1
1.998 (2)
2.027 (2)
2.8174 (10)
Cu2ÐN42
Cu2ÐN32
Cu2ÐCl2
1.993 (2)
2.026 (2)
2.8226 (10)
N12ÐCu1ÐN22
N12ÐCu1ÐCl1
N22ÐCu1ÐCl1
87.39 (10)
88.90 (7)
88.1 (2)
N42ÐCu2ÐN32
N42ÐCu2ÐCl2
N32iÐCu2ÐCl2
90.10 (9)
88.92 (7)
92.35 (7)
Two intramolecular hydrogen bonds are observed in each
molecule, producing four ®ve-membered hydrogen-bonded
rings, incorporating the Cu atoms (see Fig. 1), which adopt the
following conformations: H11-envelope for ring I, twisted for
rings II and IV, and N31-half-chair for ring III. The puckering
parameters (Cremer & Pople, 1975) corresponding to the
CuÐNn2ÐNn1ÐHn1Á Á ÁCl (n = 1±4) atom sequences are q2 =
Cl1ÐCu1ÐN12ÐN11
N11ÐC15ÐC151ÐC152
Cl1ÐCu1ÐN22ÐN21
N21ÐC25ÐC251ÐC252
1.0 (2)
0.6 (4)
5.7 (2)
10.1 (5)
Cl2ÐCu2ÐN32ÐN31 15.8 (2)
N31ÐC35ÐC351ÐC352 148.2 (3)
Cl2ÐCu2ÐN42ÐN41
N41ÐC45ÐC451ÐC452
6.5 (2)
12.9 (4)
Symmetry code: (i) 1 x; y; 1 z.
ꢁ
0.11 (1) A and '2 = 65 (2) , q2 = 0.18 (1) A and '2 = 142 (1)ꢁ,
Table 2
Hydrogen-bonding geometry (A, ).
Ê
Ê
ꢁ
Ê
ꢁ
Ê
Ê
q2 = 0.28 (1) A and '2 = 19 (1) , and q2 = 0.19 (1) A and '2 =
144 (1)ꢁ for rings I, II, III and IV, respectively.
Cg2 and Cg3 are the centroids of the N21- and N31-containing pyrazole rings,
respectively.
The bond distances and angles in both molecules are in
good agreement with expected values (Allen et al., 1987).
DÐHÁ Á ÁA
DÐH
HÁ Á ÁA
DÁ Á ÁA
DÐHÁ Á ÁA
N11ÐH11Á Á ÁCl1
N21ÐH21Á Á ÁCl1
N31ÐH31Á Á ÁCl2
N41ÐH41Á Á ÁCl2
C14ÐH14Á Á ÁCl2i
C155ÐH155Á Á ÁCl2ii
C13ÐH13Á Á ÁCg3i
C455ÐH455Á Á ÁCg3iii
C456ÐH456Á Á ÁCg2iv
0.86
0.86
0.86
0.86
0.93
0.93
0.93
0.93
0.93
2.40
2.41
2.47
2.41
2.93
2.85
2.90
2.88
2.87
3.071 (2)
3.081 (3)
3.120 (3)
3.084 (2)
3.805 (3)
3.707 (4)
3.638 (5)
3.693 (6)
3.670 (5)
135
135
133
135
158
154
137
146
144
Experimental
The title compound was obtained by mixing hot ethanol solutions of
CuCl2Á2H2O and 5-phenylpyrazole in a 1:4 molar ratio. On cooling to
room temperature, a crystalline material began to separate. This
material was ®ltered off and washed three times with cold solvent and
dried in vacuo over phosphorus pentaoxide, giving single crystals of
the title compound suitable for X-ray analysis.
Symmetry codes: (i) x 1; y; z; (ii) x; 1 y; 1 z; (iii) 1 x; y; z; (iv) 1 x; y; z.
Crystal data
Ê
All H atoms were positioned geometrically (NÐH = 0.86 A and
Ê
CÐH = 0.93 A) and re®ned with a riding model. For the H atoms of
3
[CuCl2(C9H8N2)4]
Mr = 711.14
Triclinic, P1
a = 11.587 (4) A
b = 12.676 (3) A
Dm = 1.356 Mg m
Dm measured by ¯otation in tetralin
and iodomethane
the phenyl and pyrazole rings (except for the H atoms of the NÐH
groups), Uiso values were constrained to be 1.2Ueq of the carrier atom.
The H atoms of the NÐH groups were placed in calculated positions
and their Uiso values were re®ned.
Ê
Ê
Ê
Cu Kꢀ radiation
Cell parameters from 22
re¯ections
c = 13.352 (3) A
ꢀ = 81.54 (2)ꢁ
ꢁ = 72.71 (2)ꢁ
ꢂ = 68.29 (2)ꢁ
ꢃ = 23.0±31.9ꢁ
ꢄ = 2.60 mm
T = 293 (2) K
1
Data collection: MSC/AFC Diffractometer Control Software
(Molecular Structure Corporation, 1989); cell re®nement: MSC/AFC
Diffractometer Control Software; data reduction: TEXSAN (Mole-
cular Structure Corporation, 1989); program(s) used to solve struc-
ture: SHELXS86 (Sheldrick, 1990); program(s) used to re®ne
structure: SHELXL97 (Sheldrick, 1997); molecular graphics:
PLATON (Spek, 1998); software used to prepare material for
publication: PARST97 (Nardelli, 1996).
3
Ê
V = 1738.1 (9) A
Z = 2
Dx = 1.359 Mg m
Prism, blue
0.60 Â 0.50 Â 0.25 mm
3
Data collection
Rigaku AFC-5S diffractometer
! scans
Rint = 0.028
max = 67.5ꢁ
ꢃ
Absorption correction: analytical
(de Meulenaer & Tompa, 1965)
Tmin = 0.296, Tmax = 0.569
6374 measured re¯ections
6079 independent re¯ections
4962 re¯ections with I > 2ꢅ(I)
h = 13 ! 13
k = 15 ! 11
The authors are grateful to Agnieszka Rybarczyk-Pirek for
assistance with the X-ray experiments, and also thank
Professor K. Kostka and M. Strawiak for supplying the crys-
tals.
l = 15 ! 15
3 standard re¯ections
every 150 re¯ections
intensity decay: <2%
ꢀ
m116 Magdalena Maøecka et al.
[CuCl2(C9H8N2)4]
Acta Cryst. (2003). C59, m115±m117