Hexaaqua­cobalt(II) bis­{[N-(4-meth­oxy-2-oxidobenzyl­idene)glycyl­glycinato]copper(II)} hexa­hydrate

Gan-Bing Yao; Jia-Xun Jiang; Li-Min Yuan; Xiao-Ming Ren

doi:10.1107/S1600536809040045

. 2009 Oct 7;65(Pt 11):m1316. doi: 10.1107/S1600536809040045

Hexaaquacobalt(II) bis{[N-(4-methoxy-2-oxidobenzylidene)glycylglycinato]copper(II)} hexahydrate

Gan-Bing Yao ^a,^*, Jia-Xun Jiang ^a, Li-Min Yuan ^a, Xiao-Ming Ren ^b

PMCID: PMC2971010 PMID: 21578079

Abstract

In the crystal structure of the title compound, [Co(H₂O)₆][Cu(C₁₂H₁₁N₂O₅)]₂·6H₂O, the Co^II atom is located on an inversion center and coordinated by six water molecules in a slightly distorted octahedral geometry. The Cu^II atom is chelated by the Schiff base ligand in a distorted CuN₂O₂ square-planar geometry. An extensive O—H⋯O hydrogen-bonding network is present in the crystal structure.

Related literature

For the magnetic properties of Schiff base complexes, see: Ion et al. (2009 ▶); Wu et al. (2007 ▶); Costes et al. (2006 ▶) and for their optical properties, see: Akine et al. (2008 ▶).

Experimental

Crystal data

[Co(H₂O)₆][Cu(C₁₂H₁₁N₂O₅)]₂·6H₂O
M _r = 928.66
Triclinic,
a = 7.834 (2) Å
b = 10.835 (3) Å
c = 11.474 (3) Å
α = 76.705 (4)°
β = 76.616 (5)°
γ = 81.085 (4)°
V = 916.7 (4) Å³
Z = 1
Mo Kα radiation
μ = 1.69 mm⁻¹
T = 296 K
0.35 × 0.30 × 0.25 mm

Data collection

Bruker SMART APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ▶) T _min = 0.561, T _max = 0.658
4773 measured reflections
3345 independent reflections
2801 reflections with I > 2σ(I)
R _int = 0.072

Refinement

R[F ² > 2σ(F ²)] = 0.042
wR(F ²) = 0.105
S = 1.01
3345 reflections
242 parameters
H-atom parameters constrained
Δρ_max = 0.59 e Å⁻³
Δρ_min = −0.73 e Å⁻³

Data collection: SMART (Bruker, 2002 ▶); cell refinement: SAINT-Plus (Bruker, 2003 ▶); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809040045/xu2621sup1.cif

e-65-m1316-sup1.cif^{(19.8KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809040045/xu2621Isup2.hkl

e-65-m1316-Isup2.hkl^{(164KB, hkl)}

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

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O6—H6A⋯O11	0.83	1.94	2.771 (4)	174
O6—H6B⋯O3ⁱ	0.84	1.93	2.765 (3)	169
O7—H7A⋯O9ⁱⁱ	0.83	1.95	2.757 (3)	165
O7—H7B⋯O10	0.81	1.94	2.723 (3)	162
O8—H8C⋯O2ⁱⁱⁱ	0.85	2.31	2.812 (3)	118
O9—H9A⋯O10	0.85	1.99	2.769 (4)	152
O9—H9B⋯O1	0.85	1.96	2.798 (3)	172
O10—H10C⋯O2^iv	0.85	2.02	2.783 (3)	149
O10—H10D⋯O4ⁱ	0.85	2.00	2.844 (4)	173
O11—H11A⋯O2^v	0.85	2.09	2.916 (3)	164
O11—H11B⋯O9	0.85	2.00	2.844 (4)	176

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) ; (v) .

Acknowledgments

This work was supported by Foundation of Key Laboratory of Environmental Material and Environmental Engineering of Jiangsu Province, China.

supplementary crystallographic information

Comment

In recent years, the design and synthesis of Schiff base complexes caused an increasing interest in coordination chemistry because they were potential optical, magnetic materials (Ion et al., 2009; Wu et al., 2007; Costes et al., 2006; Akine et al., 2008). Now, we present the synthesis and structure analysis of the title Schiff base complex derived from 4-methoxy-salicylaldehyde and glycylglycine.

The complex (I) crystallizes in the triclinic space group P1. The asymmetric unit consists of one [CuL]^- anion (L is a Schiff base derived from glycylglycine and 4-methoxy-salicylaldehyde), half Co(H₂O)₆²⁺ cation [Co(1), O(6), O(7), O(8)] and three uncoordinated aqua molecules [O(9), O(10), O(11)] in the complex (I) (Fig. 1). The deprotonated Schiff base is a triple negatively charged tetradentate chelate ligand, coordinating to the Cu(II) atom by one phenolate O atom [O(1)], one imine N atom [N(1)], one deprotonated amide N atom [N(2)] and one carboxylato O atom [O(3)]. [CuL]^- has approximately square-planar structure. The Cu(II) atom is in a slightly distorted square-planar environment with four donor atoms deviating from their mean plane by -0.0503 Å (N(1)), +0.0621 Å (N(2)), +0.0509 Å (O(1)) and -0.0494 Å (O(3)) (observed bond angles vary from 83.4 (1)° and 96.6 (1)°). The benzene ring [C(1)–C(6)] and the [O(1), C(1), C(6), C(7), N(1), Cu(1)] chelate ring are almost coplanar with a small dihedral angle of 0.1 (1)°, suggesting a large π-electron delocalization. The Co(II) atom lies on an inversion center and the coordination by six aqua ligands is slightly distorted octahedral. The six Co—O bonds in the structure are in the range of 2.075 (2) - 2.081 (2) Å. In the crystal structure, the [CuL]^- anions and [Co(H₂O)₆]²⁺ cations form well separated columns along the a-axis, which are further formed a three-dimensional network by hydrogen bonds (Table 1).

Experimental

Glycylglycine (5 mmol), 4-methoxy-salicylaldehyde (5 mmol) and LiOH (10 mmol) were dissolved in MeOH/H₂O (30 ml, v:v = 1:1) and refluxed for 30 min. Then Cu(ClO₄)₂.6H₂O (5 mmol) was added to the solution and the resulting solution was adjusted to 9–11 by 5 M NaOH solution. After stirring at room temperature for 1 h, CoCl₂.6H₂O (2.5 mmol) was added. A violet precipitate was obtained immediately. After stirring for another 30 min and then filtrated, the precipitate was recrystallized from water. The violet crystals suitable for X-ray diffraction were obtained after one week (yield 30% based on Cu(ClO₄)₂.6H₂O).