Poly[dimethyl­ammonium [aquadi-μ2-oxalato-yttriate(III)] trihydrate]

Yao-Kang Lv; Li-Hua Gan; Liang Xu; Hao-Wen Zheng; Cao Liu

doi:10.1107/S1600536811019209

. 2011 Jun 4;67(Pt 7):m837–m838. doi: 10.1107/S1600536811019209

Poly[dimethylammonium [aquadi-μ₂-oxalato-yttriate(III)] trihydrate]

Yao-Kang Lv ^a, Li-Hua Gan ^a,^*, Liang Xu ^a, Hao-Wen Zheng ^a, Cao Liu ^a

PMCID: PMC3151934 PMID: 21836844

Abstract

The title complex, {(C₂H₈N)[Y(C₂O₄)₂(H₂O)]·3H₂O}_n, was obtained accidentally under hydrothermal conditions. The Y^III atom is chelated by four oxalate ligands and one water molecule resulting in a distorted tricapped trigonal–prismatic geometry. Each oxalate ligand bridges two Y^III atoms, thus generating a three-dimensional network with cavities in which the ammonium cations and lattice water molecules reside. Various O—H⋯O and N—H⋯O hydrogen-bonding interactions stabilize the crystal structure. The title complex is isotypic with the Eu and Dy analogues.

Related literature

For general background to the rational design and synthesis of metal-organic polymers, see: Lv et al. (2010 ▶, 2011 ▶). For related structures, see: Platel et al. (2009 ▶); Gao & Cui (2008 ▶); Deguenon et al. (1990 ▶). The structure of the isotypic Eu^III compound was reported by Yang et al. (2005 ▶), and that of the Dy^III compound by Ye & Lin (2010 ▶). For decomposition products obtained under hydrothermal conditions, see: Song et al. (2004 ▶).

Experimental

Crystal data

(C₂H₈N)[Y(C₂O₄)₂(H₂O)]·3H₂O
M _r = 383.11
Monoclinic,
a = 9.6008 (1) Å
b = 11.5422 (2) Å
c = 14.2886 (2) Å
β = 122.460 (1)°
V = 1336.00 (3) Å³
Z = 4
Mo Kα radiation
μ = 4.43 mm⁻¹
T = 293 K
0.31 × 0.20 × 0.19 mm

Data collection

Bruker APEXII area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.36, T _max = 0.43
11935 measured reflections
3040 independent reflections
2384 reflections with I > 2σ(I)
R _int = 0.044

Refinement

R[F ² > 2σ(F ²)] = 0.033
wR(F ²) = 0.082
S = 1.00
3040 reflections
207 parameters
13 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.70 e Å⁻³
Δρ_min = −0.58 e Å⁻³

Data collection: APEX2 (Bruker, 2006 ▶); cell refinement: SAINT (Bruker, 2006 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Brandenburg & Putz, 2004 ▶); software used to prepare material for publication: SHELXTL (Sheldrick, 2008 ▶).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811019209/wm2489sup1.cif

e-67-0m837-sup1.cif^{(20.4KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811019209/wm2489Isup2.hkl

e-67-0m837-Isup2.hkl^{(149.2KB, 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
O1W—H1WA⋯O2Wⁱ	0.83 (2)	1.93 (2)	2.742 (4)	167 (4)
O1W—H1WB⋯O2Wⁱⁱ	0.72 (2)	2.20 (2)	2.861 (4)	152 (4)
O2W—H2WA⋯O6ⁱⁱⁱ	0.81 (2)	2.38 (2)	3.143 (4)	158 (5)
O2W—H2WA⋯O7^iv	0.81 (2)	2.45 (5)	2.944 (4)	121 (5)
O2W—H2WB⋯O3W^v	0.79 (2)	2.38 (3)	2.963 (7)	131 (4)
O2W—H2WB⋯O4W	0.79 (2)	2.44 (3)	3.194 (6)	159 (5)
O3W—H3WA⋯O2	0.88 (2)	2.36 (7)	2.830 (5)	114 (6)
O3W—H3WB⋯O4W^iv	0.86 (2)	1.90 (3)	2.735 (6)	161 (6)
O4W—H4WA⋯O1^vi	0.82 (2)	2.13 (2)	2.943 (4)	172 (5)
O4W—H4WB⋯O3^vii	0.83 (2)	2.08 (3)	2.857 (4)	155 (6)
N1—H1A⋯O8^vi	0.90	2.00	2.869 (4)	163
N1—H1A⋯O1W^vi	0.90	2.54	3.107 (4)	122
N1—H1B⋯O3W	0.90	1.90	2.784 (6)	166

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

Acknowledgments

The present work was supported financially by the National Natural Science Foundation of China (No. 20973127) and Shanghai Nanotechnology Promotion Center (No. 0952nm00800).

supplementary crystallographic information

Comment

Rational design and synthesis of metal-organic polymers have attracted much attention in the field of supramolecular chemistry and crystal engineering (Lv et al., 2010; 2011). Oxalate, which usually represent one of the products of the degradation of some organic compounds, is one of the simplest multidentate organic ligands potentially able to bridge metal ions in a bidentate chelating manner (Deguenon et al., 1990). Herein, we report the synthesis and structure of a novel yttrium(III) complex, (C₂H₈N)[Y(C₂O₄)₂(H₂O)]^.3H₂O, (I).

Complex (I) is isotypic with its Eu(III) (Yang et al., 2005) and Dy(III) (Ye & Lin, 2010) analogues. As shown in Fig. 1, the Y^III atom is chelated by four oxalate ligands and one water molecule resulting in a distorted tricapped trigonal-prismatic coordination environment. The Y—O bond lengths fall in the range of 2.374 (2)-2.459 (2) Å, which is in agreement with comparable values reported elsewhere (Platel et al., 2009; Gao & Cui, 2008). Each oxalate ligand bridges two Y^III atoms, thus generating a three-dimensional network with cavities where the ammonium cations and lattice water molecules reside (Fig. 2). Furthermore, there are various hydrogen-bonding interactions (N—H···O and O—H···O), involving the lattice water molecules and the cations, which give rise to a tightly held network structure.

Experimental

A mixture of D-saccharic acid potassium salt (0.248 g, 1.0 mmol), Y(NO₃)₃^.6H₂O (0.191 g, 0.5 mmol) and N,N-dimethylformamide (20 ml) was stirred and heated at 373 K for 1 hour. The resulted colorless solution was kept at 293 K. Colorless block-shaped crystals of the title compound suitable for X-ray crystallographic study were obtained via slow evaporation within 2 weeks.

It is most likely that the oxalate ligands in this complex originates from the decomposition of the potassium salt of D-saccharic acid, and the protonated dimethylamine cations compensating the negative charge of the anionic network are believed to result from decomposition of the N,N-dimethylformamide solvent (Song et al., 2004; Ye & Lin, 2010).