Di-μ-chromato-κ4 O:O′-bis­[bis­(phenan­throline-κ2 N,N′)cadmium(II)] dihydrate

Hai-Xing Liu; Fang-Fang Jian; Jing Wang

doi:10.1107/S160053680900823X

. 2009 Mar 14;65(Pt 4):m392–m393. doi: 10.1107/S160053680900823X

Di-μ-chromato-κ⁴ O:O′-bis[bis(phenanthroline-κ² N,N′)cadmium(II)] dihydrate

Hai-Xing Liu ^a, Fang-Fang Jian ^a,^*, Jing Wang ^b

PMCID: PMC2968914 PMID: 21582341

Abstract

In the title compound, [Cd₂Cr₂O₈(C₁₂H₈N₂)₄]·2H₂O, which was obtained by hydrothermal reaction of CdCO₃ and phenanthroline with K₂CrO₄ at 393 K, two distorted Cd(N₄O₂) octahedra are linked through μ₂-bridging chromate anions, forming a centrosymmetric tetranuclear eight-membered ring complex. The water molecules link the chromate O atoms via intermolecular O—H⋯O hydrogen bonds. These aggregates pack to a three-dimensional network through weak intermolecular C—H⋯O and C—H⋯π hydrogen-bonding contacts.

Related literature

For the properties of multimetallic complexes, see: Costisor et al. (2001 ▶). For the structures of heterometallic macrocyclic rings, see: Larsen et al. (2003 ▶); Timco et al. (2005 ▶). For related structures, see: Dai et al. (2002 ▶); Chaudhuri et al. (1988 ▶); Yoshikawa et al. (2002 ▶).

Experimental

Crystal data

[Cd₂Cr₂O₈(C₁₂H₈N₂)₄]·2H₂O
M _r = 1213.65
Monoclinic,
a = 11.2303 (13) Å
b = 13.6892 (16) Å
c = 14.5352 (19) Å
β = 91.928 (1)°
V = 2233.3 (5) Å³
Z = 2
Mo Kα radiation
μ = 1.48 mm⁻¹
T = 298 K
0.13 × 0.08 × 0.05 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 1997 ▶) T _min = 0.830, T _max = 0.930
11590 measured reflections
3922 independent reflections
2145 reflections with I > 2σ(I)
R _int = 0.096

Refinement

R[F ² > 2σ(F ²)] = 0.045
wR(F ²) = 0.065
S = 0.86
3922 reflections
316 parameters
H-atom parameters constrained
Δρ_max = 0.50 e Å⁻³
Δρ_min = −0.52 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: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053680900823X/si2157sup1.cif

e-65-0m392-sup1.cif^{(25.8KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S160053680900823X/si2157Isup2.hkl

e-65-0m392-Isup2.hkl^{(192.3KB, hkl)}

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

Table 1. Selected geometric parameters (Å, °).

Cd1—O2	2.215 (4)
Cd1—O1	2.226 (4)
Cd1—N2	2.370 (5)
Cd1—N1	2.376 (5)
Cd1—N4	2.394 (5)
Cd1—N3	2.397 (5)
O1—Cr1	1.660 (4)
O2—Cr1ⁱ	1.683 (4)
O3—Cr1	1.638 (4)
O4—Cr1	1.619 (4)

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Symmetry code: (i) Inline graphic .

Table 2. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O5—H5A⋯O2ⁱⁱ	0.85	2.13	2.849 (6)	142
O5—H5B⋯O4ⁱⁱⁱ	0.85	2.40	3.122 (6)	144
C2—H2⋯O3^iv	0.93	2.49	3.274 (7)	142
C3—H3⋯O3ⁱⁱⁱ	0.93	2.50	3.352 (8)	153
C9—H9⋯O3^v	0.93	2.48	3.391 (7)	168
C10—H10⋯O3	0.93	2.55	3.478 (7)	175
C12—H12⋯O4ⁱⁱ	0.93	2.58	3.423 (7)	151
C20—H20⋯O5^vi	0.93	2.49	3.344 (8)	152
C23—H23⋯Cg1^vii	0.93	2.61	3.509 (7)	164

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Symmetry codes: (ii) Inline graphic ; (iii) ; (iv) ; (v) ; (vi) ; (vii) . Cg1 is the centroid of atoms N1,C1–C5.

supplementary crystallographic information

Comment

In recent decades, research on multimetallic complexes has grown in modern inorganic chemistry, because of searching for new materials, exhibiting exciting magnetic properties, electrical and optical properties (Costisor et al., 2001). But the heterometallic systems are rare because of the difficult synthesis. In contrast to the heterometallic macrocylic ring structures reported (Larsen et al., 2003 & Timco et al., 2005), we describe the synthesis and structure of the title compound, which represents a centrosymmetric heterobinuclear eight-membered ring system.

The title structure (Fig. 1) has a centrosymmetric eight-membered ring, build up of [Cd(phenanthroline)₂]²⁺, [CrO₄]^2- units and two free water molecules. Each Cd atom is coordinated with four N atoms from phenanthroline ligands and two O atoms, presenting a distorted octahedral geometry. The Cr atoms are tetrahedrally coordinated. Two distorted Cd(N₄O₂) octahedra are linked through bridging chromate anions to form the centrosymmetric tetranuclear eight-membered ring complex. The mean Cd—O, Cr—O and Cd—N bond lengths are similar to the values reported (Dai et al., 2002, Chaudhuri et al., 1988, Yoshikawa et al., 2002). The Cr1ⁱ—O2—Cd1, O1—Cr1—O2, O2—Cd1—O1 angles are 133.1 (2)°, 109.40 (18)°, and 97.47 (13)°, respectively. Other selected geometrical parameters are given in Table 1. The dihedral angle between the phenanthroline ligands is 89.00 (1)°. The free water molecules link the chromate oxygen atoms via intermolecular O—H···O hydrogen bonds. The intermolecular C—H···O hydrogen bonds and the C—H···π interactions (Table 2) cause the crystal packing to be energetically preferable and generate a three-dimensional network as shown in Fig. 2.

Experimental

All commercially obtained reagent-grade chemicals were used without further purication. CdCO₃ (3.40 g, 2.00 mmol) was dissolved in water and methanol (2:1 v/v, 30 ml), mixed with phenanthroline (6.00 g, 3.00 mmol). After stirring for 0.5 h, K₂CrO₄ (1.94 g, 1.00 mmol) was added to the mixture. The hydrothermal reaction was conducted at 393 K for 4 h. The yellow prism crystals were collected, after cooling and filtering (yield 1.20 g). Analysis calculated for C₄₈H₃₆Cd₂Cr₂N₈O₁₀: C 47.46, H 2.97, N 9.22%; found: C 47.44, H 3.03, N 9.20%.