Poly[[tetra­aqua­(μ4-imidazole-4,5-dicarboxyl­ato)(μ3-imidazole-4,5-dicarboxyl­ato)-μ3-sulfato-μ2-sulfato-cobalt(II)digadolinium(III)] monohydrate]

Li-Cai Zhu

doi:10.1107/S160053681104726X

. 2011 Nov 12;67(Pt 12):m1741–m1742. doi: 10.1107/S160053681104726X

Poly[[tetraaqua(μ₄-imidazole-4,5-dicarboxylato)(μ₃-imidazole-4,5-dicarboxylato)-μ₃-sulfato-μ₂-sulfato-cobalt(II)digadolinium(III)] monohydrate]

Li-Cai Zhu ^a,^*

PMCID: PMC3238650 PMID: 22199541

Abstract

The asymmetric unit of the title compound, {[CoGd₂(C₅H₂N₂O₄)₂(SO₄)₂(H₂O)₄]·H₂O}_n, contains one Co^II ion, two Gd^III ions, two imidazole-4,5-dicarboxylate ligands, two SO₄ ²⁻ anions, four coordinated water molecules and one uncoordinated water molecule. The Co^II ion is six-coordinated by two O atoms from two coordinated water molecules, as well as two O atoms and two N atoms from two imidazole-4,5-dicarboxylate ligands, giving a slightly distorted octahedral geometry. Both Gd^III ions are eight-coordinated in a distorted bicapped trigonal–prismatic geometry. One Gd^III ion is coordinated by four O atoms from two imidazole-4,5-dicarboxylate ligands, three O atoms from three SO₄ ²⁻ anions and a water O atom; the other Gd^III ion is bonded to five O atoms from three imidazole-4,5-dicarboxylate ligands, two O atoms from two SO₄ ²⁻ anions as well as a water O atom. These metal coordination units are connected by bridging imidazole-4,5-dicarboxylate and sulfate ligands, generating a heterometallic layer parallel to the ac plane. The layers are stacked along the b axis via N—H⋯O, O—H⋯O, and C—H⋯O hydrogen-bonding interactions, generating a three-dimensional framework.

Related literature

For applications of lanthanide–transition metal heterometallic complexes with bridging multifunctional organic ligands, see: Cheng et al. (2006 ▶); Kuang et al. (2007 ▶); Sun et al. (2006 ▶); Zhu et al. (2010 ▶).

Experimental

Crystal data

[CoGd₂(C₅H₂N₂O₄)₂(SO₄)₂(H₂O)₄]·H₂O
M _r = 963.82
Triclinic,
a = 9.0916 (5) Å
b = 10.7714 (6) Å
c = 12.9736 (7) Å
α = 93.119 (1)°
β = 96.416 (1)°
γ = 108.840 (1)°
V = 1189.35 (11) Å³
Z = 2
Mo Kα radiation
μ = 6.48 mm⁻¹
T = 296 K
0.20 × 0.18 × 0.15 mm

Data collection

Bruker APEXII area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.284, T _max = 0.378
6174 measured reflections
4208 independent reflections
3790 reflections with I > 2σ(I)
R _int = 0.016

Refinement

R[F ² > 2σ(F ²)] = 0.022
wR(F ²) = 0.054
S = 1.02
4208 reflections
397 parameters
17 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.79 e Å⁻³
Δρ_min = −0.81 e Å⁻³

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: SAINT (Bruker, 2004 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: XP in SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S160053681104726X/hp2018sup1.cif

e-67-m1741-sup1.cif^{(25.1KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S160053681104726X/hp2018Isup2.hkl

e-67-m1741-Isup2.hkl^{(206.2KB, 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
N1—H1⋯O1ⁱ	0.87 (4)	1.96 (4)	2.820 (5)	172 (5)
O1W—H1W⋯O5Wⁱⁱ	0.81 (4)	1.95 (3)	2.745 (5)	169 (6)
N3—H2⋯O14ⁱⁱⁱ	0.87 (3)	1.93 (3)	2.787 (4)	169 (4)
O2W—H3W⋯O1ⁱ	0.80 (3)	2.09 (4)	2.878 (5)	171 (5)
O2W—H4W⋯O14ⁱ	0.81 (4)	2.04 (4)	2.842 (5)	172 (5)
O2W—H4W⋯O15ⁱ	0.81 (4)	2.52 (4)	3.035 (5)	123 (4)
O3W—H5W⋯O12^iv	0.82 (3)	1.95 (4)	2.734 (4)	162 (5)
O3W—H6W⋯O14^v	0.83 (3)	2.41 (4)	2.919 (4)	120 (3)
O4W—H7W⋯O3^vi	0.82 (3)	2.49 (3)	3.306 (6)	174 (6)
O4W—H8W⋯O5Wⁱⁱⁱ	0.82 (5)	1.89 (5)	2.700 (6)	175 (6)
O5W—H9W⋯O12^v	0.85 (4)	1.99 (4)	2.797 (6)	161 (5)
O5W—H10W⋯O1ⁱ	0.85 (5)	1.93 (5)	2.728 (5)	157 (6)
C3—H3⋯O3^vii	0.93	2.44	3.193 (5)	138

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

Acknowledgments

The author acknowledges South China Normal University for supporting this work.

supplementary crystallographic information

Comment

In the past few years, lanthanide-transition metal heterometallic complexs with bridging multifunctionnal organic ligands are of increasing interest, not only because of their impressive topological structures, but also due to their versatile applications in ion exchange, magnetism, bimetallic catalysis and luminescent probe(Cheng et al., 2006; Kuang et al., 2007; Sun et al., 2006; Zhu et al., 2010). As an extension of this research, the structure of the title compound, a new heterometallic coordination polymer, (I), has been determined which is presented in this artcle.

The asymmetric unite of the title compound (Fig. 1), contains one Co^II ion, two Gd^III ions, two imidazole-4, 5-dicarboxylate ligands, two SO₄^2- anions, four coordinated water molecules and one uncoordinated water molecule. The Co^II ion is six-coordinated with two O atoms from two coordinated water molecules, two O atoms and two N atoms from two imidazole-4, 5-dicarboxylate ligands, giving a slightly distorted octahedral geometry. Both Gd^III ions are eight-coordinated in a bicapped trigonal prismatic coordination geometry. One Gd^III ion is coordinated by four O atoms from two imidazole-4,5-dicarboxylate ligands, three O atoms from three SO₄^2- anions and one water molecule; the other Gd^III ion is bonded to five O atoms from three imidazole-4, 5-dicarboxylate ligands, two O atoms from two SO₄^2- anions as well as one coordinated water molecule. These metal coordination units are connected by bridging imidazole-4, 5-dicarboxylate and sulfate ligands, generating a two-dimensional heterometallic layer. The two-dimensional layers are stacked along b axis via N—H···O, O—H···O, and C—H···O hydrogen-bonding interactions to generate the three-dimensional framework(Table 1 and Fig. 2).

Experimental

A mixture of CoSO₄.7H₂O(0.141 g, 0.5 mmol), Gd₂O₃(0.09 g, 0.25 mmol), imidazole-4,5-dicarboxylic acid (0.156 g, 1 mmol), and H₂O(7 ml) was sealed in a 20 ml Teflon-lined reaction vessel at 443 K for 5 days then slowly cooled to room temperature. The product was collected by filtration, washed with water and air-dried. Red block crystals suitable for X-ray analysis were obtained.