Poly[[di-μ3-nicotinato-μ3-oxalato-samarium(III)silver(I)] dihydrate]

Li-Cai Zhu; Zhen-Gang Zhao; Shu-Juan Yu

doi:10.1107/S1600536809032115

. 2009 Aug 19;65(Pt 9):m1105. doi: 10.1107/S1600536809032115

Poly[[di-μ₃-nicotinato-μ₃-oxalato-samarium(III)silver(I)] dihydrate]

Li-Cai Zhu ^a, Zhen-Gang Zhao ^b, Shu-Juan Yu ^b,^*

PMCID: PMC2969901 PMID: 21577452

Abstract

In the title three-dimensional heterometallic complex, {[AgSm(C₆H₄NO₂)₂(C₂O₄)]·2H₂O}_n, the Sm^III ion is eight-coordinated by four O atoms from four different nicotinate ligands and four O atoms from two different oxalate ligands. The three-coordinate Ag^I ion is bonded to two N atoms from two different nicotinate anions and one O atom from an oxalate anion. These metal coordination units are connected by bridging nicotinate and oxalate ligands, generating a three-dimensional network. The uncoordinated water molecules link the carboxylate groups via O—H⋯O hydrogen bonding. The crystal structure is further stabilized by hydrogen bonds between the water molecules.

Related literature

For theapplications of lanthanide–transition metal heterometallic complexes with bridging multifunctional organic ligands, see: Cheng et al. (2006 ▶); Kuang et al. (2007 ▶); Luo et al. (2007 ▶); Peng et al. (2008 ▶).

Experimental

Crystal data

[AgSm(C₆H₄NO₂)₂(C₂O₄)]·2H₂O
M _r = 626.49
Monoclinic,
a = 9.7145 (9) Å
b = 22.3444 (15) Å
c = 9.1726 (6) Å
β = 117.295 (1)°
V = 1769.4 (2) Å³
Z = 4
Mo Kα radiation
μ = 4.45 mm⁻¹
T = 296 K
0.23 × 0.20 × 0.19 mm

Data collection

Bruker APEXII area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.374, T _max = 0.429
8972 measured reflections
3171 independent reflections
2995 reflections with I > 2σ(I)
R _int = 0.027

Refinement

R[F ² > 2σ(F ²)] = 0.023
wR(F ²) = 0.052
S = 1.12
3171 reflections
254 parameters
H-atom parameters constrained
Δρ_max = 0.84 e Å⁻³
Δρ_min = −0.65 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: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809032115/pv2185sup1.cif

e-65-m1105-sup1.cif^{(19.1KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809032115/pv2185Isup2.hkl

e-65-m1105-Isup2.hkl^{(155.6KB, 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
O1W—H1W⋯O7ⁱ	0.86	2.10	2.960 (5)	175
O1W—H2W⋯O2W	0.86	2.06	2.892 (7)	161
O2W—H4W⋯O1Wⁱ	0.87	1.92	2.780 (7)	171

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Symmetry code: (i) Inline graphic .

Acknowledgments

The authors acknowledge 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 have generated much 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; Luo et al., 2007; Peng et al., 2008). As an extension of this research, we report here the structure of the title compound, a new heterometallic coordination polymer.

In the title compound (Fig. 1), there are one Sm^III ion, one Ag^I ion, two halves of oxalate ligand, two nicotinate ligands, and two lattice water molecules in the asymmetric unit. Each Sm^III ion is eight-coordinated by four O atoms from four different nicotinate ligands, and four O atoms of two different oxalate ligands. The Sm center can be described as having a bicapped trigonal prism coordination geometry. The three-coordinate Ag^I ion is bonded to two N atoms from two different nicotinate anions and one O atom from an oxalate anion. Thus the Ag^I ion is in a T-shaped configuration. These metal coordination units are connected by bridging nicotinate and oxalate ligands, generating a three-dimensional network (Fig. 2). The uncoordinated water molecules link the carboxylate groups by O—H···O hydrogen bonding (Table 1). The crystal structure is further stabilized by hydrogen bonds.

Experimental

A mixture of AgNO₃ (0.057 g, 0.33 mmol), Sm₂O₃ (0.116 g, 0.33 mmol), nicotinic acid (0.164 g, 1.33 mmol), oxalic acid (0.119 g, 1.33 mmol), H₂O (7 ml), and HClO₄ (0.257 mmol)(pH 2) was sealed in a 20 ml Teflon-lined reaction vessel at 443 K for 6 days then slowly cooled to room temperature. The product was collected by filtration, washed with water and air-dried. Colorless block crystals suitable for X-ray analysis were obtained.