Di-μ-acetato-κ3 O,O′:O′;κ3 O:O,O′-bis­[(acetato-κ2 O,O′)bis­(5-nitro-1,10-phenanthroline-κ2 N,N′)cadmium]

Fenghua Cui; Shuxia Zhang

doi:10.1107/S1600536811032259

. 2011 Aug 17;67(Pt 9):m1247. doi: 10.1107/S1600536811032259

Di-μ-acetato-κ³ O,O′:O′;κ³ O:O,O′-bis[(acetato-κ² O,O′)bis(5-nitro-1,10-phenanthroline-κ² N,N′)cadmium]

Fenghua Cui ^a,^b, Shuxia Zhang ^a,^*

PMCID: PMC3200609 PMID: 22058861

Abstract

In the binuclear title compound, [Cd₂(C₂H₃O₂)₄(C₁₂H₇N₃O₂)₂], the Cd^II cations are linked by carboxylate O atoms into a four-membered Cd₂O₂ rhombic ring with a Cd⋯ Cd separation of 3.7515 (5) Å. Each Cd^II atom is seven-coordinated by a bidentate 5-nitro-1,10-phenanthroline (5-NO₂-phen) ligand and two bidentate acetate anions, one of which also acts as a bridge linking the two Cd atoms. The crystal packing is stabilized by π–π interactions between the phen rings of neighboring molecules, with centroid–centroid distances of 3.491 (2) (intramolecular) and 3.598 (2) Å (intermolecular).

Related literature

For related structures, see: Peng et al. (2008 ▶); Harvey et al. (2008 ▶); Kruszynski et al. (2009 ▶). For our studies on transition metal complexes with 1,10-phenanthroline (phen) and its derivatives and carboxylates, see: Xuan et al. (2007a ▶,b ▶, 2008 ▶). For their applications in organic transformations, molecular recognition and organization of molecular solids, see: Braga et al. (1998 ▶).

Experimental

Crystal data

[Cd₂(C₂H₃O₂)₄(C₁₂H₇N₃O₂)₂]
M _r = 911.39
Monoclinic,
a = 18.653 (3) Å
b = 11.2236 (16) Å
c = 15.510 (2) Å
β = 94.531 (2)°
V = 3236.9 (8) Å³
Z = 4
Mo Kα radiation
μ = 1.39 mm⁻¹
T = 298 K
0.45 × 0.30 × 0.27 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 1997 ▶) T _min = 0.573, T _max = 0.705
17895 measured reflections
5988 independent reflections
4970 reflections with I > 2σ(I)
R _int = 0.022

Refinement

R[F ² > 2σ(F ²)] = 0.025
wR(F ²) = 0.057
S = 1.02
5988 reflections
473 parameters
H-atom parameters constrained
Δρ_max = 0.53 e Å⁻³
Δρ_min = −0.36 e Å⁻³

Data collection: SMART (Bruker, 1997 ▶); cell refinement: SAINT (Bruker, 1997 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811032259/bg2418sup1.cif

e-67-m1247-sup1.cif^{(37.3KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811032259/bg2418Isup2.hkl

e-67-m1247-Isup2.hkl^{(293.1KB, hkl)}

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Selected bond lengths (Å).

Cd1—O6	2.324 (2)
Cd1—N2	2.372 (2)
Cd1—O9	2.378 (2)
Cd1—O7	2.390 (2)
Cd1—N1	2.403 (2)
Cd1—O5	2.423 (2)
Cd1—O8	2.429 (2)
Cd2—O12	2.238 (2)
Cd2—O9	2.300 (2)
Cd2—O8	2.365 (2)
Cd2—N4	2.394 (2)
Cd2—N5	2.435 (2)
Cd2—O11	2.527 (3)
Cd2—O10	2.590 (3)

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Acknowledgments

Financial support from the National Natural Science Foundation of Henan Educational Committee (2011 A150018) is gratefully acknowledged.

supplementary crystallographic information

Comment

The work presented here is a continuation of our studies on transition metal complexes with 1,10-phenanthroline (phen) and its derivatives and carboxylates (Xuan et al. 2007a, 2007b, 2008), due to their applications, for example in organic transformations, molecular recognition and organization of molecular solids (Braga et al. 1998). Among such compounds, a number of dinuclear cadmium(II) compounds with 1,10-phenanthroline (phen) or its derivatives and oxygen donor ligands have been synthesized and structurally characterized (Peng et al. 2008; Harvey et al. 2008; Kruszynski et al. 2009). Recently, we obtained the title cadmium(II) complex containing two different kinds of chelating ligands, by the reaction of cadmium acetate and 5-nitro-1,10-phenanthroline (5NO2phen) in methanol/water mixtures.

The crystal structure of the title compound consists of dimeric units, made up of two Cd cations, two 5NO2phen molecules and four acetate anions (Fig. 1). Two carboxylate groups of acetate anions act as bidentate, and two as monodentate bridging and bidentate chelating ligands. Each Cd atom, in a uncommon seven-coordination environment, is chelated by the two N atoms of 5NOphen and five carbonyl oxygen atoms of three acetate anions. One carboxylate group acts as bidentate, and two as monodentate bridging and bidentate chelating ligands. All coordinating groups are bonded unsymmetrically to the central atom. The Cd—O bridging interactions form a four-membered Cd₂O₂ quadrilateral with a Cd—Cd separation of 3.7515 (5) Å.

The dimer crystal structure is stabilized by π-π stacking interactions between adjacent phen rings, with a centroid-centroid distance between Cg1(N1/C7—C11) and Cg4 (C4—C7C11C12) is 3.491 (2) Å (Fig.2). Another intermoleclular π-π stacking interaction exists with a centroid-centroid distance of 3.598 (2) Å between Cg2 (N2/C1—C4/C13) and Cg3 (N4/C13—C16/C24)[symmetry code: - x, -y, 1 - z], which provide additional stabilization to the crystalline networks. There are no classical hydrogen bonding interactions present in the structure.

Experimental

A solution (6 ml) of methnol containing 5-nitro-1,10-phenanthroline (0.1130 g) was added slowly to a aqueous solution (10 ml) containing cadmium acetate dihydrate (0.1627 g). Block-like single crystals were obtained by slow evaporation of the mixture at room temperature after one month.