Poly[[tetra­aqua-μ4-fumarato-di-μ3-fumarato-dineodymium(III)] trihydrate]

Hong-ren Chen; Tian-sheng Tang; Jin Wang; Pei-lian Liu; Zeng Zhuo

doi:10.1107/S1600536811046447

. 2011 Nov 9;67(Pt 12):m1717–m1718. doi: 10.1107/S1600536811046447

Poly[[tetraaqua-μ₄-fumarato-di-μ₃-fumarato-dineodymium(III)] trihydrate]

Hong-ren Chen ^a, Tian-sheng Tang ^a, Jin Wang ^a, Pei-lian Liu ^a, Zeng Zhuo ^a,^b,^*

PMCID: PMC3238635 PMID: 22199526

Abstract

The title coordination polymer, {[Nd₂(C₄H₂O₄)₃(H₂O)₄]·3H₂O}, was synthesized by the reaction of neodymium(III) nitrate hexahydrate with fumaric acid in a water–methanol (7:3) solution. The asymmetric unit comprises two Nd³⁺ cations, three fumarate dianions (L ²⁻), four aqua ligands and three uncoordinated water molecules. The carboxylate groups of the fumarate dianions exhibit different coordination modes. In one fumarate dianion, two carboxylate groups chelate two Nd³⁺ cations, while one of the O atoms is coordinated to another Nd³⁺ cation. Another fumarate dianion bridges three Nd³⁺ cations: one of the carboxylate groups chelates one Nd³⁺ cation, while the other carboxylate group bridges two Nd³⁺ cations in a monodentate mode. The third fumarate dianion bridges four Nd³⁺ cations, where one of the carboxylate groups chelates one Nd³⁺ cation and coordinates in a monodentate mode to a second Nd³⁺, while the second carboxylate groups bridges two Nd³⁺ cations in a monodentate mode and one O atom is coordinated to one Nd³⁺ cation. The Nd³⁺ cations are in a distorted tricapped–trigonal prismatic environment and coordinated by seven O atoms from the fumarate ligands and two O atoms from water molecules. The Nd³⁺ cations are linked by two carboxylate O atoms and two carboxylate groups, generating infinite Nd–O chains to form a three-dimensional framework. There are O—H⋯O and C—H⋯O hydrogen-bonding interactions between the coordinated and uncoordinated water molecules and carboxylate O atoms.

Related literature

For applications of metal complexes with carboxylato ligands, see: Eliseeva et al. (2010 ▶); Kim et al. (2001 ▶); Seki & Mori (2002 ▶).

Experimental

Crystal data

[Nd₂(C₄H₂O₄)₃(H₂O)₄]·3H₂O
M _r = 756.76
Monoclinic,
a = 9.5810 (9) Å
b = 14.8675 (15) Å
c = 14.9056 (14) Å
β = 91.538 (5)°
V = 2122.5 (4) Å³
Z = 4
Mo Kα radiation
μ = 4.93 mm⁻¹
T = 298 K
0.16 × 0.15 × 0.14 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.459, T _max = 0.501
24284 measured reflections
5150 independent reflections
4060 reflections with I > 2σ(I)
R _int = 0.052

Refinement

R[F ² > 2σ(F ²)] = 0.030
wR(F ²) = 0.075
S = 1.05
5150 reflections
306 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 1.36 e Å⁻³
Δρ_min = −0.89 e Å⁻³

Data collection: APEX2 (Bruker, 2008 ▶); cell refinement: SAINT (Bruker, 2008 ▶); 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 datablock(s) global, I. DOI: 10.1107/S1600536811046447/ez2264sup1.cif

e-67-m1717-sup1.cif^{(25.7KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811046447/ez2264Isup2.hkl

e-67-m1717-Isup2.hkl^{(243.4KB, 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
O2W—H2WA⋯O1	0.85	2.57	3.103 (13)	122
O2W—H2WA⋯O3	0.85	2.52	3.319 (13)	158
O2W—H2WB⋯O1Wⁱ	0.85	2.53	2.98 (2)	114
O3W—H3WD⋯O24ⁱ	0.85	2.07	2.896 (6)	165
O3W—H3WC⋯O1W	0.85	2.12	2.60 (2)	115
O3W—H3WC⋯O2W	0.85	2.08	2.911 (13)	165
O1W—H1WD⋯O2W	0.85	2.06	2.634 (19)	124
O1W—H1WC⋯O6ⁱⁱ	0.85	2.11	2.959 (17)	178
O8—H8C⋯O3Wⁱⁱⁱ	0.85	2.05	2.829 (5)	152
O8—H8B⋯O1^iv	0.85	1.91	2.745 (5)	169
O13—H13A⋯O3Wⁱⁱⁱ	0.85	2.14	2.938 (6)	157
O13—H13B⋯O25^v	0.82	2.02	2.787 (5)	157
O14—H14A⋯O12^vi	0.86 (6)	1.88 (6)	2.740 (5)	172 (6)
O14—H14B⋯O4ⁱⁱⁱ	0.75 (5)	2.04 (6)	2.776 (5)	166 (6)
O16—H16A⋯O27^vii	0.72	2.02	2.714 (5)	160
O16—H16C⋯O2^viii	0.85	2.07	2.915 (5)	171
C3—H3⋯O24^v	0.93	2.53	3.345 (6)	147
C8—H8⋯O12^iv	0.93	2.58	3.417 (6)	150

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

Acknowledgments

The authors gratefully acknowledge the support of the Department of Science and Technology, Guangdong Province (grant No. 2010 A020507001–76, 5300410, FIPL-05–003)

supplementary crystallographic information

Comment

Recently, many metal complexes of carboxylates and lanthanide complexes which display interesting properties have been reported: Mn dicarboxylate compounds present antiferromagnetic interactions (Kim et al., 2001), while Cu dicarboxylates have uniform micropores, high porosities and gas adsorption capacities (Seki et al., 2002). In addition, lanthanide complexes can be used as active materials in luminescent devices (Eliseeva et al., 2010). In this paper, we report the title complex, obtained by the reaction of neodymium(III) nitrate hexahydrate with fumaric acid in a water-methanol (7:3) solution.

The structure of the asymmetric unit of the title complex is shown in Fig. 1. It comprises two Nd³⁺ cations, three fumarate dianions (L^2-), four aqua ligands and three uncoordinated water molecules. The carboxylate groups of the fumarate dianion exhibit different coordination modes. In one fumarate dianion two carboxylate groups chelate with two Nd³⁺ cations, while one of the O atoms (O11) is coordinated with another Nd³⁺ cation. The second fumarate dianion bridges three Nd³⁺ cations, one of carboxylate groups chelating with one Nd³⁺ cation and the other carboxylate groups bridging two Nd³⁺ cations in monodentate mode. The third fumarate ligand bridges four Nd³⁺ cations, one of carboxylate groups chelating with one Nd³⁺ cation and one of carboxylate groups bridging two Nd³⁺ cations in monodentate mode, while one O atom (O3) is coordinated with a third Nd³⁺ cation. The Nd³⁺ cations are situated within a distorted tricapped trigonal prism and coordinated by seven O atoms from the fumarate dianion ligands and two O atom from water molecules. The Nd—O bond distances range from 2.387 (3) to 2.655 (3) Å. The O—Nd—O bond angles range from 73.4 (1) to 155.0 (1)°. The Nd³⁺ cations are linked by two carboxylate O atoms (O3 and O11) and two carboxylate groups (O5—C5—O6 and O26—C18—O27) to generate infinite neodymium-oxygen chains (Fig. 2). The chains are further connected by the ligands to form a three-dimensional framework. The crystal is stabilized by hydrogen bond interactions between the coordinated and uncoordinated water molecules and the carboxylate O atoms (Table 1).

Experimental

Fumaric acid (0.3 mmol, 0.035 g) and neodymium(III) nitrate hexahydrate(0.5 mmol, 0.22 g) were dissolved in a water-methanol(7:3) solution (10 ml). The mixture was transferred to a 20 ml Teflon-lined stainless steel autoclave, which was heated at 443 K for 96 h. The reactor was cooled to room temperature over a period of 24 h. Green crystals were obtained after filtration, washing with water and vacum drying.