Two centrosymmetric dinuclear phenanthroline-copper(II) complexes with 3,5-dichloro-2-hy-droxy-benzoic acid and 5-chloro-2-hy-droxy-benzoic acid

Article abstract of DOI:10.1107/S0108270112004532

The title compounds, bis-(μ3,5-dichloro-2-oxidobenzoato)-³ O ¹,O ²:O ²;³ O ²:O ¹,O ²-bis-[(3,5-dichloro-2-hy-droxy-benzoic acid-O ¹)(1,10-phenanthroline-² N,N′)copper(II)], [Cu2(C7H2Cl2O3)2(C7H4Cl2O3)2(C12H8N2)2], (I), and bis-(-5-chloro-2- oxidobenzoato)-³ O ¹,O ²:O ¹; ³ O ¹:O ¹,O ²-bis-[(5-chloro-2-hy- droxy-benzoic acid-O ¹)(1,10-phenanthroline-² N,N′)copper(II)] ethanol monosolvate, [Cu₂(C₇H ₃ClO₃)₂(C₇H₅ClO ₃)₂(C1₂H₈N₂) ₂]·C₂H₆O, (II), contain centrosymmetric dinuclear complex mol-ecules in which Cu²⁺ cations are surrounded by a chelating 1,10-phenanthroline ligand, a chelating 3,5-dichloro-2-oxidoben- zoate or 5-chloro-2-oxidobenzoate an-ionic ligand and a monodentate 3,5-dichloro-2-hydroxybenzoic acid or 5-chloro-2-hy-droxybenzoic acid ligand. The chelating benzoate ligand also bridges to the other Cu²⁺ ion in the molecule, but the O atom involved in the bridge is different in the two complexes, being the phenolate O atom in (I) and a carboxylate O atom in (II). The bridge completes a 4+1+1 axially elongated tetragonal-bipy-ram-idal arrangement about each Cu²⁺ cation. The complex mol-ecules of both compounds are linked into one-dimensional supra-molecular chains through O - H...O hydrogen bonds.

Full text of DOI:10.1107/S0108270112004532

metal-organic compounds
Acta Crystallographica Section C
Crystal Structure
Communications
complex with 1,10-phenanthroline is able to induce the
formation of free radicals which in turn degrade DNAunder in
vitro conditions. The mechanism of action of this complex is
derived from the potential intercalation of planar phenan-
throline into DNA and the in situ generation of free radicals,
predominantly hydroxy radicals mediated by the presence of
copper (Sigman, 1986; Sigman et al., 1993). In these aspects,
copper complexes with the chelating 1,10-phenanthroline
ligand can be used as anticancer agents (Tardito & Marchio,
2009; Tisato et al., 2010).
ISSN 0108-2701
Two centrosymmetric dinuclear
phenanthroline–copper(II) complexes
with 3,5-dichloro-2-hydroxybenzoic
acid and 5-chloro-2-hydroxybenzoic
acid
a
b
b
´
´
´
´
Jan Moncol, * Klaudia Jomova and Maria Porubska
aDepartment of Inorganic Chemistry, Faculty of Chemical and Food Technology,
Slovak Technical University, SK-812 37 Bratislava, Slovakia, and bFaculty of Natural
Sciences, Constantine the Philosopher University in Nitra, SK-949 74 Nitra, Slovakia
Correspondence e-mail: jan.moncol@stuba.sk
Received 25 November 2011
Accepted 2 February 2012
Online 29 February 2012
The title compounds, bis(ꢀ-3,5-dichloro-2-oxidobenzoato)-
ꢁ3O1,O2:O2;ꢁ3O2:O1,O2-bis[(3,5-dichloro-2-hydroxybenzoic
acid-ꢁO1)(1,10-phenanthroline-ꢁ2N,N0)copper(II)], [Cu2(C7-
H2Cl2O3)2(C7H4Cl2O3)2(C12H8N2)2], (I), and bis(ꢀ-5-chloro-
2-oxidobenzoato)-ꢁ3O1,O2:O1;ꢁ3O1:O1,O2-bis[(5-chloro-2-hy-
droxybenzoicacid-ꢁO1)(1,10-phenanthroline-ꢁ2N,N0)copper(II)]
ethanol monosolvate, [Cu2(C7H3ClO3)2(C7H5ClO3)2(C12H8-
N2)2]ꢀC2H6O, (II), contain centrosymmetric dinuclear complex
molecules in which Cu2+ cations are surrounded by a chelating
1,10-phenanthroline ligand, a chelating 3,5-dichloro-2-oxidoben-
zoate or 5-chloro-2-oxidobenzoate anionic ligand and a mono-
dentate 3,5-dichloro-2-hydroxybenzoic acid or 5-chloro-2-
hydroxybenzoic acid ligand. The chelating benzoate ligand also
bridges to the other Cu2+ ion in the molecule, but the O atom
involved in the bridge is different in the two complexes, being the
phenolate O atom in (I) and a carboxylate O atom in (II). The
bridge completes a 4+1+1 axially elongated tetragonal–bipyram-
idal arrangement about each Cu2+ cation. The complex
molecules of both compounds are linked into one-dimensional
supramolecular chains through O—Hꢀ ꢀ ꢀO hydrogen bonds.
Salicylic acid (2-hydroxybenzoic acid; salH2) and its
substituted derivatives can be coordinated as neutral mol-
ecular ligands or as anionic ligands with deprotonated
carboxylic acid (salHꢁ) or deprotonated carboxylic acid and
hydroxy groups (sal2ꢁ). These ligands may coordinate in a
chelating and/or bridging fashion. In view of these properties,
in this preliminary contribution, we directed our attention to
the preparation and structural characterization of potentially
bioactive copper(II)–1,10-phenanthroline complexes with
anions of two derivatives of salicylic acid.
The structure of bis(ꢀ-3,5-dichloro-2-oxidobenzoato)bis-
[(3,5-dichloro-2-hydroxybenzoic acid)(1,10-phenanthroline)-
copper(II)], (I) (Fig. 1), exhibits a centrosymmetric dinuclear
molecular structure. Two Cu atoms are organized in a dimeric
unit via the bridging O atoms of the phenolate groups of 3,5-
dichloro-2-oxidobenzoate anions [O3 and O3i; symmetry
code: (i) ꢁx + 1, ꢁy + 1, ꢁz + 1]. Each Cu atom in the dimeric
unit is hexacoordinated (Table 1) in an axially stretched
tetragonal–bipyramidal geometry by the phenolate and
carboxylate O atoms, O3 and O1, respectively, of the chelating
bridging 3,5-dichloro-2-oxidobenzoate anion and the two N
atoms of the 1,10-phenanthroline ligand, which complete the
equatorial plane, while the axial positions are occupied by the
Comment
Many copper complexes with a variety of organic chelating
ligands have been shown to possess biological activities,
including anti-inflammatory and anticonvulsant properties
(Lemoine et al., 2002), cytotoxicity and antiviral activity
(Ranford et al., 1993). Several copper(II) complexes acting as
proteasome inhibitors capable of inducing programmed cell
death (apoptosis) have been prepared and characterized. In
these complexes, the metal ion is coordinated to heteroatomic
neutral ligands such as the 1,10-phenanthroline ligand
(Marzano et al., 2009). It has been reported that the copper
Acta Cryst. (2012). C68, m85–m89
doi:10.1107/S0108270112004532
# 2012 International Union of Crystallography m85

metal-organic compounds
Figure 2
Figure 1
A perspective view of (II), showing the atom-numbering scheme.
Displacement ellipsoids are drawn at the 30% probability level. The thin
dashed lines indicate hydrogen bonds. [Symmetry code: (i) ꢁx + 1, ꢁy + 1,
ꢁz + 1.]
A perspective view of (I), showing the atom-numbering scheme.
Displacement ellipsoids are drawn at the 30% probability level. Both
positions of the disordered hydroxyphenyl group (O6/O7) are shown. The
thin dashed lines indicate intramolecular hydrogen bonds. [Symmetry
code: (i) ꢁx + 1, ꢁy + 1, ꢁz + 1.]
through bridging phenolate or carboxylate O atoms. The
appearance of different binding modes of the bridging sal2ꢁ
ligands could be attributed to the almost identical energy of
both structural configurations. More insight into this
phenomenon might be obtained from theoretical calculations.
phenolate O atom from the second symmetry-related bridging
3,5-dichloro-2-oxidobenzoate anion and the carboxylic acid O
atom, O4, of the monodentate 3,5-dichloro-2-hydroxybenzoic
acid ligand. This complex represents the first example of a
dinuclear complex of sal2ꢁ in which the phenolate O atom is
both bridging and chelating. Interestingly, a three-atom car-
boxylate bridging ligand (Cu—O—C—O—Cu) in a dimeric
copper(II) sal2ꢁ complex was reported recently by Weng et al.
(2007).
i
˚
The Cu1ꢀ ꢀ ꢀCu1 distance of 3.3456 (5) A for (I), which has
bridging phenolate O atoms, is close to the range of 3.15–
2ꢁ
˚
3.31 A found in dinuclear copper(II) sal complexes with
bridging phenolate O atoms (Lemoine et al., 1999, 2000, 2002;
Fan et al., 2005; Hu et al., 2007; Nie et al., 2010; Palanisami et
al., 2006; Geraghty et al., 1999; Wang & Okabe, 2004). On the
other hand, dinuclear complex (II) has a longer Cu1ꢀ ꢀ ꢀCu1i
The crystal structure of bis(ꢀ-5-chloro-2-oxidobenzoato)-
bis[(5-chloro-2-hydroxybenzoic acid)(1,10-phenanthroline)-
copper(II)] ethanol monosolvate, (II) (Fig. 2), consists of
centrosymmetric dinuclear complex molecules and disordered
ethanol solvent molecules (see Experimental). The structure
of the dinuclear complex and the coordination geometry
(Table 3) of the Cu2+ ions in (II) are very similar to those in
(I), with the exception that the bridges between the Cu2+ ions
involve the carboxylate O atom, O1, of the chelating bridging
5-chloro-2-oxidobenzoate anion, instead of the phenolate O
atom. The axial Cu1—O1i [symmetry code: (i) ꢁx + 1, ꢁy + 1,
˚
distance of 3.5709 (5) A. We note that the Cuꢀ ꢀ ꢀCu distance in
the dimeric complex with a three-atom bridging sal2ꢁ ligand
2+
˚
has been reported to be 4.93 A (Wen et al., 2007). The Cu
ions in both (I) and (II) are coordinated by six donor atoms
and they represent the first two examples of copper(II) sal2ꢁ
complexes with coordinated salicylic acid as a ligand; all other
known dimeric copper(II) sal2ꢁ complexes are coordinated by
five atoms (two pyridine N atoms of 1,10-phenanthroline or
2,20-bipyridine and three O atoms of phenolate and
carboxylate groups of sal2ꢁ bridging anionic ligands or their
derivatives). The Cu atoms in monomeric copper(II) sal2ꢁ
complexes have a square-planar coordination environment
formed by two pyridine N atoms and two O atoms of sal2ꢁ
anions (Zhang et al., 2007a,b) or a square-pyramidal coordi-
nation environment formed by the same atoms in a square
plane with additional O or N atoms in the apical position from
another ligand such as water (Gao et al., 2009; Zhang et al.,
2008; Yu et al., 2009) or pyridine (Wen et al., 2007), respec-
˚
ꢁz + 1] bond of 2.984 (2) A involving this bridging O atom is
i
about 0.27 A longer than the Cu1—O3 bond in (I), although it
˚
is in the range found for copper(II) complexes with tetra-
gonal–bipyramidal coordination around the Cu2+ ion (Melnik,
Kabesova, Koman et al., 1998; Melnik, Kabesova, Macaskova
et al., 1998) possessing Jahn–Teller distortions (Gazo et al.,
1976).
The molecular structures of (I) and (II) revealed the exis-
tence of two alternative coordination modes of sal2ꢁ anions
ꢂ
m86 Moncol et al. [Cu2(C7H2Cl2O3)2(C7H4Cl2O3)2(C12H8N2)2] and an analogue
Acta Cryst. (2012). C68, m85–m89

metal-organic compounds
Figure 3
The crystal structure of (I). H atoms of the aromatic rings have been
omitted for clarity. The thin dashed lines indicate hydrogen bonds.
[Symmetry code: (i) ꢁx + 2, ꢁy + 1, ꢁz + 1.]
Figure 4
The crystal structure of (II). H atoms of the aromatic rings and ethyl
groups have been omitted for clarity. The thin dashed lines indicate
hydrogen bonds. [Symmetry code: (i) ꢁx + 2, ꢁy + 1, ꢁz + 1.]
tively. In the known complexes, the distances between the Cu
atom and the O atom from axially coordinated bridging sal2ꢁ
˚
ligands in dinuclear complexes are in the range of 2.28–2.65 A,
but the Cu—Lax (ax is axial) bond distances in monomeric
5-chloro-2-oxidobenzoate anion of a neighbouring molecule.
The disordered uncoordinated ethanol solvent molecules of
(II) are connected through an O1S—H1Sꢀ ꢀ ꢀO6 hydrogen
bond to the hydroxy O atom of a monodentate 5-chloro-2-
hydroxybenzoic acid ligand. The crystal structure of (II) is
observed also to have a short Cl2ꢀ ꢀ ꢀCl2iii contact (Desiraju,
1995) [symmetry code: (iii) ꢁx + 3, ꢁy + 1, ꢁz], with an
˚
complexes are in a narrower range (2.26–2.35 A).
The aromatic rings of the benzoate, benzoic acid and 1,10-
phenanthroline ligands of both complexes are stacked (Figs. 1
and 2) and ꢂ–ꢂ stacking interactions (Janiak, 2000) are
observed between the benzene ring of the sal2ꢁ anion and the
benzene ring of the salicylic acid ligand. The distances
between the planes of the two benzene rings are in the range
˚
interatomic distance of 3.2569 (14) A.
In this contribution, we report the crystal structures of two
copper(II)–1,10-phenanthroline complexes with derivatives of
salicylic acid. The structural study revealed dinuclear
complexes with hexacoordination around the Cu atom.
Further work on the biological activity of the prepared
complexes is in progress.
˚
˚
3.34–3.68 A for (I) and 3.27–3.84 A for (II) (Table 5). Further
ꢂ–ꢂ stacking interactions (Janiak, 2000) are observed between
the benzene ring of the sal2ꢁ anion and adjacent aromatic
rings of 1,10-phenanthroline ligands at (ꢁx + 1, ꢁy + 1, ꢁz + 1),
with the separation between the planes of the aromatic rings in
˚
˚
the range 3.16–3.99 A for (I) and 3.24–3.70 A for (II) (Table 5).
Experimental
˚
The centroid–centroid distances in (I) are 3.732 (2) A
The title copper complexes were prepared in a similar manner to
methods described previously by Ranford et al. (1993). To the royal-
blue solution formed from copper(II) acetate hydrate (0.200 g,
1 mmol) and 1,10-phenanthroline (0.182 g, 1.00 mmol) in ethanol
(40 ml) was added 3,5-dichloro-2-hydroxybenzoic acid (0.207 g,
1 mmol) for (I) or 5-chloro-2-hydroxybenzoic acid (0.173 g, 1 mmol)
for (II). The resulting mixture was stirred for 4 d and the green
products were filtered off and washed with ethanol. The green
filtrates were left to stand at room temperature for about two weeks
giving crystals suitable for X-ray analysis. The compositions of the
main product and the corresponding crystals obtained from the green
filtrates were checked with IR measurements and were found to be
identical.
between the benzene ring (C14–C19) of the 3,5-dichloro-2-
oxidobenzoate anion and the benzene ring (C21–C26) of the
˚
3,5-dichloro-2-hydroxybenzoic acid molecule, and 3.837 (2) A
between the C14–C19 benzene ring and the benzene ring (C4–
C7/C11/C12) of the 1,10-phenanthroline ligand in the mol-
ecule at (ꢁx + 1, ꢁy + 1, ꢁz + 1). The centroid–centroid
˚
distances in (II) are 3.8030 (13) A between the benzene ring
(C14–C19) of the 5-chloro-2-oxidobenzoate anion and the
benzene ring (C21–C26) of the 5-chloro-2-hydroxybenzoic
˚
acid molecule, and 3.5754 (13) A between the C14–C19
benzene ring and the N2/C6–C10 pyridine ring of the 1,10-
phenanthroline ligand in the molecule at (ꢁx + 1, ꢁy + 1,
ꢁz + 1).
The crystal packing in (I) and (II) is shown in Figs. 3 and 4,
respectively. The complex molecules of both compounds are
connected into one-dimensional supramolecular chains
through O5—H5Oꢀ ꢀ ꢀO2ii hydrogen bonds [Tables 2 and 4;
symmetry code: (ii) ꢁx + 2, ꢁy + 1, ꢁz + 1] between the
carboxylic acid H atom of a monodentate 3,5-dichloro-2-hy-
droxybenzoic acid ligand or a 5-chloro-2-hydroxybenzoic acid
ligand and the uncoordinated O atom of the carboxylate
group of a chelating 3,5-dichloro-2-oxidobenzoate or a
Compound (I)
Crystal data
[Cu2(C7H2Cl2O3)2(C7H4Cl2O3)2-
(C12H8N2)2]
Mr = 1311.48
ꢄ = 99.045 (2)ꢃ
ꢅ = 106.753 (2)ꢃ
V = 1264.44 (5) A
Z = 1
Mo Kꢃ radiation
ꢀ = 1.33 mmꢁ1
T = 293 K
0.43 ꢄ 0.14 ꢄ 0.05 mm
3
˚
Triclinic, P1
a = 9.2295 (2) A
b = 11.6047 (3) A
˚
˚
˚
c = 12.9863 (3) A
ꢃ = 102.423 (2)ꢃ
ꢂ
Acta Cryst. (2012). C68, m85–m89
Moncol et al.
[Cu2(C7H2Cl2O3)2(C7H4Cl2O3)2(C12H8N2)2] and an analogue m87

metal-organic compounds
Table 1
Selected bond lengths (A) for (I).
Table 3
Selected bond lengths (A) for (II).
˚
˚
Cu1—O3
Cu1—O1
Cu1—N2
1.881 (2)
1.906 (2)
1.990 (3)
Cu1—N1
Cu1—O4
Cu1—O3i
2.011 (3)
2.585 (3)
2.716 (3)
Cu1—O3
Cu1—O1
Cu1—N1
1.880 (1)
1.904 (1)
2.001 (2)
Cu1—N2
Cu1—O4
Cu1—O1i
2.005 (2)
2.582 (2)
2.984 (2)
Symmetry code: (i) ꢁx þ 1; ꢁy þ 1; ꢁz þ 1.
Symmetry code: (i) ꢁx þ 1; ꢁy þ 1; ꢁz þ 1.
Table 4
Hydrogen-bond geometry (A, ) for (II).
Table 2
Hydrogen-bond geometry (A, ) for (I).
ꢃ
˚
ꢃ
˚
D—Hꢀ ꢀ ꢀA
D—H
Hꢀ ꢀ ꢀA
Dꢀ ꢀ ꢀA
D—Hꢀ ꢀ ꢀA
D—Hꢀ ꢀ ꢀA
D—H
Hꢀ ꢀ ꢀA
Dꢀ ꢀ ꢀA
D—Hꢀ ꢀ ꢀA
O5—H5Oꢀ ꢀ ꢀO2ii
O6—H6Oꢀ ꢀ ꢀO4
O1S—H1Sꢀ ꢀ ꢀO6
0.82
0.82
0.82
1.67
1.83
2.03
2.472 (2)
2.560 (2)
2.811 (7)
165
147
159
O5—H5Oꢀ ꢀ ꢀO2ii
O6—H6Oꢀ ꢀ ꢀO4
O7—H7Oꢀ ꢀ ꢀO5
0.82
0.82
0.82
1.69
1.85
1.73
2.489 (3)
2.577 (5)
2.460 (14)
166
147
147
Symmetry code: (ii) ꢁx þ 2; ꢁy þ 1; ꢁz þ 1.
Symmetry code: (ii) ꢁx þ 2; ꢁy þ 1; ꢁz þ 1.
Table 5
ꢃ
˚
Geometrical parameters (A, ) for ꢂ–ꢂ stacking interactions.
Data collection
Oxford Diffraction Gemini R CCD
diffractometer
Absorption correction: analytical
(CrysAlis RED; Agilent, 2011)
Tmin = 0.598, Tmax = 0.936
31426 measured reflections
5150 independent reflections
3886 reflections with I > 2ꢆ(I)
Rint = 0.050
Complex
Cg–Cga
<(plane1–plane2)b
(I)c
3.73
3.84
3.80
3.58
7.6
16.9
11.7
9.2
(I)d
(II)e
(II)f
Refinement
Notes: (a) centroid–centroid distance; (b) the angle between the planes of the aromatic
rings; (c) 3,5-dichloro-2-oxidobenzoate–3,5-dichloro-2-hydroxybenzoic acid; (d) 3,5-di-
chloro-2-oxidobenzoate–1,10-phenanthroline (Cg is the centroid of the phenanthro-
line benzene ring); (e) 5-chloro-2-oxidobenzoate–5-chloro-2-hydroxybenzoic acid; (f)
5-chloro-2-oxidobenzoate–1,10-phenanthroline (Cg is the centroid of a phenanthroline
pyridine ring).
R[F2 > 2ꢆ(F2)] = 0.053
wR(F2) = 0.160
S = 1.08
5150 reflections
363 parameters
1 restraint
H-atom parameteꢁrs3 constrained
˚
Áꢇmax = 0.62 e A
ꢁ3
˚
Áꢇmin = ꢁ0.85 e A
the atoms at each end of these bonds were restrained to be similar
(SIMU and DELU instructions in SHELXL97; Sheldrick, 2008).
The ethanol solvent molecule of (II) is disordered around an
inversion centre. Distance restraints of 1.43 (1), 1.54 (1) and
Compound (II)
Crystal data
[Cu2(C7H3ClO3)2(C7H5ClO3)2-
(C12H8N2)2]ꢀC2H6O
Mr = 1219.78
ꢄ = 77.056 (2)ꢃ
ꢅ = 83.897 (2)ꢃ
V = 1238.39 (5) A
˚
2.38 (2) A were applied to the O1S—C1S, C1S—C2S and O1Sꢀ ꢀ ꢀC2S
distances, respectively, while the displacement parameters of the
solvent atoms were restrained to be similar (SIMU and DELU
commands in SHELXL97).
3
˚
Triclinic, P1
a = 7.9153 (2) A
Z = 1
˚
Mo Kꢃ radiation
ꢀ = 1.15 mmꢁ1
T = 293 K
0.35 ꢄ 0.24 ꢄ 0.06 mm
˚
b = 11.1877 (3) A
The aromatic and methylene H atoms were positioned with C—H =
˚
c = 15.0623 (3) A
˚
0.93 and 0.97 A, respectively, and constrained to ride on their parent
atoms with Uiso(H) = 1.2Ueq(C). The methyl H atoms were positioned
ꢃ = 72.456 (2)ꢃ
˚
with C—H = 0.98 A and constrained to ride on their parent atoms
with Uiso(H) = 1.5Ueq(C). The hydroxy/carboxylic acid H atoms were
Data collection
Oxford Diffraction Gemini R CCD
diffractometer
Absorption correction: analytical
(CrysAlis RED; Agilent, 2011)
Tmin = 0.689, Tmax = 0.934
20410 measured reflections
5017 independent reflections
4055 reflections with I > 2ꢆ(I)
Rint = 0.017
˚
positioned with O—H = 0.82 A and constrained to ride on their
parent atoms with Uiso(H) = 1.5Ueq(C) using the AFIX 147 instruc-
tion for the nondisordered O—H group and AFIX 83 for the disor-
dered O—H groups.
For both compounds, data collection: CrysAlis CCD (Agilent,
2011); cell refinement: CrysAlis RED (Agilent, 2011); data reduction:
CrysAlis RED. Program(s) used to solve structure: SIR97 (Altomare
et al., 1999) for (I); SHELXS97 (Sheldrick, 2008) for (II). For both
compounds, program(s) used to refine structure: SHELXL97 (Shel-
drick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008);
software used to prepare material for publication: publCIF (Westrip,
2010).
Refinement
R[F2 > 2ꢆ(F2)] = 0.032
wR(F2) = 0.096
S = 1.06
5017 reflections
363 parameters
16 restraints
H-atom parameteꢁrs3 constrained
˚
Áꢇmax = 0.33 e A
ꢁ3
˚
Áꢇmin = ꢁ0.30 e A
The 3,5-dichloro-2-hydroxybenzoic acid ligand of (I) has orienta-
tional disorder of the hydroxy group (O6/O7) and the site-occupation
factors of the disordered parts are 0.807 (8) and 0.193 (8), respec-
tively. The C—O distances involving these disordered hydroxy groups
The authors thank the Slovak Ministry of Education
(VEGA projects 1/0856/11 and 1/0562/10), APVV (project No.
0202-10) and APVV–VVCE (project No. 0004-07) for finan-
cial support.
˚
were restrained to 1.350 (1) A, while the displacement parameters of
ꢂ
m88 Moncol et al. [Cu2(C7H2Cl2O3)2(C7H4Cl2O3)2(C12H8N2)2] and an analogue
Acta Cryst. (2012). C68, m85–m89

metal-organic compounds
Marzano, C., Pellei, M., Tisato, F. & Santini, C. (2009). Anticancer Agents Med.
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Melnik, M., Kabesova, M., Koman, M., Macaskova, L., Garaj, J., Holloway,
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Melnik, M., Kabesova, M., Macaskova, L. & Holloway, C. E. (1998). J. Coord.
Chem. 45, 31–145.
Supplementary data for this paper are available from the IUCr electronic
archives (Reference: SF3164). Services for accessing these data are
described at the back of the journal.
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ꢂ
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[Cu2(C7H2Cl2O3)2(C7H4Cl2O3)2(C12H8N2)2] and an analogue m89