Bis(2,2'-bipyridyl-κN,N')bis-(2-hydroxy-benzoato)-κO;κO,O-cadmium(II) methanol solvate.

Abstract

The title compound, [Cd(C(7)H(5)O(3))(2)(C(10)H(8)N(2))(2)]·CH(3)OH, contains one monomeric seven-coordinate cadmium complex and one methanol solvate mol-ecule. The Cd(II) atom is coordinated to two 2,2'-bipyridyl ligands via the N atoms and to two salicylate anions (Hsal(-)) via the carboxyl-ate O atoms, which act as monodentate ligand for the one and bidentate ligand for the second. The Cd(II) atom exhibits a {6 + 1} environment, approximately described as a distorted capped octa-hedron with the apical positions occupied by one of the two N atoms belonging to one bipyridyl ligand and one of the two carboxyl-ate O atoms from the monodentate Hsal(-) ligand. Two intra-molecular six-membered hydrogen-bonded rings are present, generated from inter-actions between the carboxyl-ate and hydr-oxy groups of the salicylate ligands. There is one inter-molecular hydrogen-bonding inter-action involving the methanol solvent mol-ecule and the carboxyl-ate group from the monodentate Hsal(-) ligand. The crystal packing is governed by π-π stacking inter-actions [centroid-centroid distance = 3.783 (4) Å] which occur between bipyridyl ligands, by C-H⋯O and C-H⋯π inter-actions and by numerous van der Waals contacts.

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Bis(2,20 0 0-bipyridyl-j2N,N0 0 0)bis(2-hydroxy-
benzoato)-jO1;j2O1,O10 0 0-cadmium(II)
methanol solvate
Rymel Benrabah, Bernard Viossat, Alain Tomas and
Pascale Lemoine*
Laboratoire de Cristallographie et RMN Biologiques, UMR 8015 CNRS, Faculte ´ des
Sciences Pharmaceutiques et Biologiques de Paris Descartes, 4, avenue de
l’Observatoire 75270 Paris Cedex 06, France
Correspondence e-mail: pascale.lemoine@parisdescartes.fr
Received 17 November 2009; accepted 18 December 2009
Key indicators: single-crystal X-ray study; T = 293 K; mean ?(C–C) = 0.008 A ˚;
R factor = 0.048; wR factor = 0.138; data-to-parameter ratio = 21.6.
The
contains one monomeric seven-coordinate cadmium complex
and one methanol solvate molecule. The CdIIatom is
coordinated to two 2,20-bipyridyl ligands via the N atoms
and to two salicylate anions (Hsal?) via the carboxylate O
atoms, which act as monodentate ligand for the one and
bidentateligandforthesecond.TheCdIIatomexhibitsa{6+1}
environment, approximately described as a distorted capped
octahedron with the apical positions occupied by one of the
two N atoms belonging to one bipyridyl ligand and one of the
two carboxylate O atoms from the monodentate Hsal?ligand.
Two intramolecular six-membered hydrogen-bonded rings are
present, generated from interactions between the carboxylate
and hydroxy groups of the salicylate ligands. There is one
intermolecular hydrogen-bonding interaction involving the
methanol solvent molecule and the carboxylate group from
the monodentate Hsal?ligand. The crystal packing is
governed by ?–? stacking interactions [centroid–centroid
distance = 3.783 (4) A˚] which occur between bipyridyl ligands,
by C—H???O and C—H???? interactions and by numerous
van der Waals contacts.
title compound,[Cd(C7H5O3)2(C10H8N2)2]?CH3OH,
Related literature
For related structures, see: Lemoine et al. (2004); Mazurier et
al. (2000);Tomas et al. (2006); Turner et al. (1982). For the anti-
inflammatory properties of zinc complexes, see: Sorensen
(2002 and references therein).
Experimental
Crystal data
[Cd(C7H5O3)2(C10H8N2)2]?CH4O
Mr= 731.03
Triclinic, P1
a = 9.115 (4) A˚
b = 12.189 (2) A˚
c = 14.883 (2) A˚
? = 97.64 (1)?
? = 92.30 (3)?
? = 101.00 (3)?
V = 1605.1 (8) A˚3
Z = 2
Mo K? radiation
? = 0.74 mm?1
T = 293 K
0.40 ? 0.18 ? 0.13 mm
Data collection
Enraf–Nonius CAD-4
diffractometer
9433 measured reflections
9117 independent reflections
4943 reflections with I > 2?(I)
Rint= 0.040
3 standard reflections every 60 min
intensity decay: none
Refinement
R[F2> 2?(F2)] = 0.048
wR(F2) = 0.138
S = 0.97
9117 reflections
423 parameters
H-atom parameters constrained
??max= 0.37 e A˚?3
??min= ?0.85 e A˚?3
Table 1
Hydrogen-bond geometry (A˚,?).
D—H???A
O3—H3???O1
O13—H13???O11
O61—H61???O12
C23—H23???O61i
C43—H43???O12ii
C45—H45???O13iii
C15—H15???Cg1iv
C47—H47???Cg2v
C62—H62A???Cg1vi
Symmetry codes: (i) x;y ? 1;z; (ii) ?x þ 1;?y þ 1;?z þ 1; (iii) x þ 1;y;z; (iv)
?x;?y þ 1;?z þ 2; (v) ?x þ 1;?y þ 1;?z þ 2; (vi) x þ 1;y þ 1;z. Cg1 and Cg2 are
the centroids of the C2–C7 and C12–C17 rings, respectively.
D—HH???AD???AD—H???A
0.82
0.82
0.82
0.93
0.93
0.93
0.93
0.93
0.96
1.82
1.78
1.98
2.57
2.43
2.47
2.81
2.79
2.94
2.545 (7)
2.505 (4)
2.802 (6)
3.429 (8)
3.356 (6)
3.370 (6)
3.620 (6)
3.589 (6)
3.858 (8)
147
147
177
154
172
163
147
145
160
Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994); cell
refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms &
Wocadlo, 1995); program(s) used to solve structure: SIR92 (Altomare
et al., 1994); program(s) used to refine structure: SHELXL97 (Shel-
drick, 2008); molecular graphics: CAMERON (Watkin et al., 1996);
software used to prepare material for publication: WinGX (Farrugia,
1999).
Supplementary data and figures for this paper are available from the
IUCr electronic archives (Reference: DN2517).
metal-organic compounds
m156
Rymel et al.
doi:10.1107/S1600536809054610
Acta Cryst. (2010). E66, m156–m157
Acta Crystallographica Section E
Structure Reports
Online
ISSN 1600-5368

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Kristallogr. New Cryst. Struct. 221, 517–519.
Turner, R. W., Rodesiler, P. F. & Amma, P. E. L. (1982). Inorg. Chim. Acta, 66,
L13–L15
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metal-organic compounds
Acta Cryst. (2010). E66, m156–m157Rymel et al.
? [Cd(C7H5O3)2(C10H8N2)2]?CH4O
m157

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supplementary materials

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supplementary materials
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Acta Cryst. (2010). E66, m156-m157 [ doi:10.1107/S1600536809054610 ]
Bis(2,2'-bipyridyl-2N,N')bis(2-hydroxybenzoato)- O1;2O1,O1'-cadmium(II) methanol solvate
R. Benrabah, B. Viossat, A. Tomas and P. Lemoine
Comment
Recently
phenanthroline)cadmium(II) complex (Tomas et al., 2006) as an extension of an ongoing crystal structure investigation
of non-steroidal anti-inflammatory drug zinc carboxylate complexes. Zinc is an essential metalloelement required by all
cells for activation of a large number of Zn-dependent enzymes (Sorenson, 2002 and references therein). Various zinc
carboxylates exhibit favorable anti-inflammatory, analgesic and antipyretic properties. In previous work, we have synthes-
ized and structurally characterized two ternary complexes of Zn(II) with 3,5-diisopropylsalicylate and 1,10-phenanthroline
or 2,9-dimethyl-1,10-phenanthroline (Lemoine et al., 2004). Anticonvulsant and rotorod toxicity activities of these com-
plexes were determined to examine structure-anticonvulsant and structure-hypnotic activities of these Zn(II) non- steroidal
antiinflammatory agent complexes. Since zinc and cadmium belong to the same group 12 of the periodic system of elements,
following this work, we report in this paper the synthesis and the structure of the bis(2,2'-bipyridyl- κ2N,N')(salicylato-
κ2O,O')(salicylato-κO)cadmium(II) methanol solvate.
we described the crystal structure of bis(3,5-diisopropylsalicylato)(2,9-dimethyl-1,10-
The title compound contains one monomeric seven- coordinate cadmium complex and one methanol solvate molecule.
CdII is coordinate-covalently bonded to two 2,2'-bipyridyl bidendate ligands via N21 and N30 or N41 and N50 atoms and
to two salicylate (Hsal-) anionic ligands, one of which is monodentate via O11 atom and the other is bidentate via O1 and
O2 atoms (Fig. 1). Therefore, the cadmium atom exhibits a {6 + 1} environment, approximately described as a distorted
capped octahedron. According to this description, the Cd atom lies 0.127 (2) Å out of the basal plane [O1, N30, N41, N50]
with the apical positions occupied by N21 and O11. The O2 atom caps the triangular face formed by O1, N21 and N50.
This very irregular geometry is imposed by the small bite angles of one salicylate [O1—Cd—O2, 50.7 (2)°] and the two
bipyridyl [N21—Cd—N30, 69.0 (1) °; N41—Cd—N50, 69.3 (1) °] bidentate ligands, mainly due to the rigidity of these
chelate molecules. The Cd—N bond lengths are very similar [average 2.367 (4) Å] and comparable with distances found
in other bipyridine containing Cd complexes (Turner et al., 1982). The distances between Cd and the oxygen atoms are the
following: d(Cd—O1) = 2.391 (5) Å and d(Cd—O2) = 2.685 (5) Å for the first salicylate ligand and d(Cd—O11) = 2.305 (3)
Å for the second ligand. The longer Cd—O2 distance is comparable to that described in the bis(salicylato)(2,2'-bipyridyl)
(dimethylformamide)cadmium(II) (Mazurier et al., 2000) in a (6 + 1) environment (2.667 Å). The bond lengths and angles
of the complexed salicylate ligands and 2,2'-bipyridyl are normal. The chelation of CdII by the Hsal- ligand leads to planar
ring, P1 (O1/C1/O2/Cd) with the maximum deviation of 0.026 (4) Å for C1 atom. The phenyl mean planes P2 [C2—C7]
and P3 [C12—C17] [maximum deviation of 0.003 (4) Å for C7] in the salicylate ligands make a dihedral 70.5 (2) °. The
bipyridyl ligands are essentially planar (maximum deviation of 0.067 (5) Å for C48) and the CdII atom is displaced from
the least-squares planes P4 [N21/C22- C29/N30/C31—C32] by 0.139 (5) Å and from P5 [N41/C42- C49/N50/C51—C52]
by 0.251 (5) Å. The dihedral angles between planes P4 and P5 is 82.1 (1) °.
The hydroxy H3 (or H13) atom attached to O3 (or O13) is involved in intramolecular via O1 (or O11) atom (Table 1)
thus contributing to planarity of the rings [O1 C1 C2 C3 O3 H3 and O11 C11 C12 C13 O13 H13] (maximum deviation

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supplementary materials
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of 0.022 (2) Å for H3). There is one intermolecular hydrogen bonding interaction involving the solvate methanol molecule
and the carboxylate O12 atom (Table 1).
Moreover, the packing is governed by π - π stacking interactions which occur between bipyridyl ligands [N21/C22—C25/
C32 and N30/C26—C29/C31] through inversion centre at (1/2, 1/2, 1/2) with a centroid-to-centroid distance of 3.783 (4) Å,
an average spacing of 3.50 Å with an offset of 22.1°. In addition, there are three C—H···O interactions (Table 1) and three C–
H···Cg(π-ring) interactions (Table 1, Cg1 being the centroid of the ring C2 to C7 and Cg2 the centroid of the ring C12 to C17).
Experimental
The cadmium(II) salicylate [CdII(Sal)2] was prepared by reaction of Cd(NO3)2.4H2O with NaSal after neutralizing HSal by
a NaOH solution. An amount of 0.387 g of CdII(Sal)2 (1 mmole) and 0.313 g of 2,2'-bipyridyl (2 mmole) were dissolved
in 20 ml of methanol. The solution was stirred at 60°C under reflux conditions for one hour to give the complex. Single
crystals were obtained by slow evaporation of this solution at room temperature (293 K).
Refinement
All H atoms were positioned geometrically and refined using a riding model with distances C—H = 0.96 Å (CH3) with
Uiso(H) = 1.5 times Ueq(C) or 0.93 Å (CH phenyl) with Uiso(H) = 1.2 times Ueq(C); O—H = 0.82 Å (O3, O13 and O61)
with Uiso(H) = 1.2 times Ueq(O).
Figures
Fig. 1. Molecular view of the solvate methanol complex showing atomic numbering and
O—H–O hydrogen bonds in dotted lines. Displacements ellipsoïds are drawn at the 30%
probability level.
Bis(2,2'-bipyridyl-κ2N,N')bis(2-hydroxybenzoato)- κO1;κ2O1,O1'-cadmium(II) methanol solvate
Crystal data
[Cd(C7H5O3)2(C10H8N2)2]·CH4O
Mr = 731.03
Z = 2
F(000) = 744
Dx = 1.513 Mg m−3
Dm = 1.53 (2) Mg m−3
Dm measured by flotation (CCl4/CH2Cl2)
Mo Kα radiation, λ = 0.71073 Å
Cell parameters from 25 reflections
θ = 1.7–8.9°
µ = 0.74 mm−1
Triclinic, P1
Hall symbol: -P 1
a = 9.115 (4) Å
b = 12.189 (2) Å
c = 14.883 (2) Å