Poly[[octa­aqua­tetra­kis­(μ3-pyridine-2,5-dicarboxyl­ato)copper(II)diytterbium(III)] monohydrate]

Shie Fu Lush; Fwu Ming Shen

doi:10.1107/S1600536811014048

. 2011 Apr 22;67(Pt 5):m615–m616. doi: 10.1107/S1600536811014048

Poly[[octaaquatetrakis(μ₃-pyridine-2,5-dicarboxylato)copper(II)diytterbium(III)] monohydrate]

Shie Fu Lush ^a, Fwu Ming Shen ^b,^*

PMCID: PMC3089069 PMID: 21754330

Abstract

The asymmetric unit of the title heterometallic polymeric coordination compound, {[CuYb₂(C₇H₃NO₄)₄(H₂O)₈]·H₂O}_n, contains one Cu^II cation located on an inversion center, a Yb^III cation, two pyridine-2,5-dicarboxylate (pda) anions, four coordination water molecules a disordered lattice water molecule, which is half-occupied and is located close to an inversion center. The Cu^II cation is N,O-chelated by two pda anions in the coordination basal plane and further coordinated by two carboxyl O atoms at the apical positions, with an elongated octahedral geometry. The Yb^III atom is eight-coordinated in a distorted square-antiprismatic geometry formed by two carboxylate O atoms from two pda anions, and is N,O-chelated by one pda anion and four coordinated water molecules. The pda anions bridge adjacent Yb and Cu cations, forming a three-dimensional polymeric structure. The crystal structure features extensive O—H⋯O hydrogen bonds. π–π stacking is observed between parallel pyridine rings, the centroid–centroid distance being 3.843 (4) Å.

Related literature

For related structures, see: Bai et al. (2008 ▶); Chi et al. (2009 ▶); Wang et al. (2009 ▶); Yue et al. (2007 ▶); Zhang et al. (2006 ▶). For structures in which the Cu atom displays an elongated octahedral geometry with a longer Cu—O bond, see: Chuang et al. (2008 ▶); Ghosh et al. (2004 ▶).

Experimental

Crystal data

[CuYb₂(C₇H₃NO₄)₄(H₂O)₈]·H₂O
M _r = 1232.19
Triclinic,
a = 7.7120 (5) Å
b = 9.2713 (6) Å
c = 13.2452 (9) Å
α = 75.529 (1)°
β = 76.216 (1)°
γ = 78.117 (1)°
V = 879.73 (10) Å³
Z = 1
Mo Kα radiation
μ = 5.98 mm⁻¹
T = 294 K
0.15 × 0.15 × 0.03 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ▶) T _min = 0.646, T _max = 0.984
7620 measured reflections
3150 independent reflections
3010 reflections with I > 2σ(I)
R _int = 0.036

Refinement

R[F ² > 2σ(F ²)] = 0.044
wR(F ²) = 0.095
S = 1.18
3150 reflections
271 parameters
H-atom parameters constrained
Δρ_max = 2.78 e Å⁻³
Δρ_min = −2.60 e Å⁻³

Data collection: SMART (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: PLATON (Spek, 2009 ▶); software used to prepare material for publication: PLATON.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811014048/xu5183sup1.cif

e-67-0m615-sup1.cif^{(23.9KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811014048/xu5183Isup2.hkl

e-67-0m615-Isup2.hkl^{(154.5KB, hkl)}

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

Table 1. Selected bond lengths (Å).

Yb1—N1	2.495 (7)
Yb1—O1	2.365 (6)
Yb1—O2	2.254 (7)
Yb1—O3	2.330 (8)
Yb1—O4	2.346 (7)
Yb1—O5	2.297 (5)
Yb1—O8ⁱ	2.297 (6)
Yb1—O9	2.334 (8)
Cu1—N2	1.985 (7)
Cu1—O7ⁱⁱ	2.641 (6)
Cu1—O11	1.944 (6)

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Symmetry codes: (i) Inline graphic ; (ii) .

Table 2. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1A⋯O12ⁱⁱⁱ	0.81	1.96	2.757 (9)	165
O1—H1B⋯O11^iv	0.82	2.02	2.782 (9)	153
O2—H2A⋯O10	0.88	1.88	2.670 (11)	149
O2—H2B⋯O5^v	0.82	1.87	2.667 (9)	163
O3—H3A⋯O7ⁱ	0.84	1.82	2.607 (9)	155
O3—H3B⋯O13	0.82	1.95	2.73 (2)	159
O4—H4A⋯O10^vi	0.82	1.95	2.760 (10)	167
O4—H4B⋯O6^vii	0.82	1.98	2.802 (9)	179
O13—H13A⋯O10	0.87	2.20	3.03 (2)	161
O13—H13B⋯O12ⁱ	0.85	1.96	2.81 (2)	177

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

Acknowledgments

This work was supported financially by Yuanpei University, Taiwan.

supplementary crystallographic information

Comment

In recent year, many studies select pyridine-2,5-dicarboxylic acid as a bridging ligand, because it offers both N– and O-donors. Thus, the carboxylate group can bond to the lanthanide, while the nitrogen atom can bond to transition metal ions, allowing the possibility of 3 d-4f heterometallic coordination polymers (Zhang et al., 2006; Yue et al., 2007; Bai et al., 2008; Chi et al., 2009; Wang et al., 2009).

Herein, we successfully prepared a heterometallic coordination polymer, [CuYb₂(C₇H₃NO₄)₄(H₂O)₈.H₂O]_n, from a hydrothermal reaction. Fig. 1 shows the structure unit of the title complex, which contains one Cu^II and two Yb^III atoms, four pda ligands, eight coordinating and one non-coordinating water molecules. The Yb^III center is eight-coordinated [YbNO₃(H₂O)₄] in a slightly distorted square-antiprismatic geometry formed by two carboxylate O atoms from two pda anions, N,O-chelated by one pda anion and four coordinated water molecules. One Cu^II atom is N,O-chelated by two pda anions in the coordination basal plane and coordinated by two carboxyl O atoms at the apical position with an elongated octahedral geometry (selected bond lengths are given in Table 1) (Ghosh et al.,2004; Chuang et al., 2008). The molecular structure contains both Cu and Yb atoms, with pda ligands bridging the six coordinate Cu^II centers and eight coordinate Yb^III centers to form a three-dimensional net structure.

The crystal structure contains the extensive O—H···O (shown as Fig. 2 and Table 2). π···π stackings are present in the crystal structure, the shortest centroid distance between parallel pyridine rings Cg5^iv···Cg5((N2/C8—C12) is 3.843 (4) Å, respectively [symmetry code:(iv)=-X, 2-Y,2-Z].

Experimental

A solution of Cu(OAc)₂.H₂O (0.0205 g, 0.10 mmol), Yb₂O₃ (0.0199 g, 0.050 mmol) and 2,5-pyridinedicarboxylic acid (0.0343 g, 0.20 mmol) were mixed in 10 ml deionized water. After stirring half an hour, the mixture was placed in 23 ml Teflon-lined reactor. After heating for four days at 418 K, the mixture was cooling to room-temperature. Green block-like crystals were isolated in 42% yield (based on Yb).