Poly[[dodeca­aqua­hexa­kis­(μ2-pyridine-2,5-dicarboxyl­ato)tricopper(II)diytterbium(III)] dihydrate]

Fwu Ming Shen; Shie Fu Lush

doi:10.1107/S1600536811007446

. 2011 Mar 9;67(Pt 4):m406–m407. doi: 10.1107/S1600536811007446

Poly[[dodecaaquahexakis(μ₂-pyridine-2,5-dicarboxylato)tricopper(II)diytterbium(III)] dihydrate]

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

PMCID: PMC3099879 PMID: 21753939

Abstract

The asymmetric unit of the title heterometallic coordination polymer, {[Cu₃Yb₂(C₇H₃NO₄)₆(H₂O)₁₂]·2H₂O}_n, contains one Yb^III and two Cu^II atoms. The Cu^II atom that is located on an inversion center is N,O-chelated by two pyridine-2,5-dicarboxylate (pdc) anions in a square-planar geometry; the Cu atom located on a general position is N,O-chelated by two pdc anions in the basal plane and is further coordinated by a water O atom at the apical position in a distorted square-pyramidal geometry. The Yb(III) atom is eight coordinated in a distorted square-antiprismatic geometry formed by three carboxylate O atoms from three pdc anions and five water molecules. The pdc anions bridge adjacent Yb(III) and Cu(III) atoms, forming a three-dimensional polymeric structure. The crystal structure contains extensive O—H⋯O hydrogen bonds. π–π stacking is present in the crystal structure, the shortest centroid–centroid distance between parallel pyridine rings of adjacent molecules being 3.646 (3) Å.

Related literature

For general background to the use of pdc as a ligand in rare earth transition metal complexes, see: Huang et al. (2008 ▶). For related structures, see: Wei et al. (2005 ▶); Wen et al. (2007 ▶).

Experimental

Crystal data

[Cu₃Yb₂(C₇H₃NO₄)₆(H₂O)₁₂]·2H₂O
M _r = 1815.58
Triclinic,
a = 7.3486 (4) Å
b = 13.5417 (7) Å
c = 15.1244 (8) Å
α = 72.534 (1)°
β = 76.330 (1)°
γ = 80.166 (1)°
V = 1386.89 (13) Å³
Z = 1
Mo Kα radiation
μ = 4.59 mm⁻¹
T = 295 K
0.13 × 0.08 × 0.05 mm

Data collection

Bruker SMART 1000 CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ▶) T _min = 0.739, T _max = 0.973
14910 measured reflections
6624 independent reflections
6010 reflections with I > 2σ(I)
R _int = 0.044

Refinement

R[F ² > 2σ(F ²)] = 0.049
wR(F ²) = 0.083
S = 1.23
6624 reflections
421 parameters
H-atom parameters constrained
Δρ_max = 1.01 e Å⁻³
Δρ_min = −1.68 e Å⁻³

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

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811007446/xu5166sup1.cif

e-67-0m406-sup1.cif^{(29.6KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811007446/xu5166Isup2.hkl

e-67-0m406-Isup2.hkl^{(324.2KB, hkl)}

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

Table 1. Selected bond lengths (Å).

Yb1—O2	2.299 (5)
Yb1—O3	2.272 (4)
Yb1—O4	2.411 (4)
Yb1—O5	2.278 (4)
Yb1—O6	2.364 (4)
Yb1—O7	2.447 (3)
Yb1—O13	2.364 (4)
Yb1—O15	2.281 (4)
Cu1—N1	1.975 (4)
Cu1—N2ⁱ	1.955 (4)
Cu1—O1	2.372 (4)
Cu1—O8	1.964 (3)
Cu1—O11ⁱ	1.943 (3)
Cu2—N3	1.967 (4)
Cu2—O17	1.931 (4)

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Symmetry code: (i) Inline graphic .

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1A⋯O17ⁱⁱ	0.82	2.50	3.072 (5)	128
O1—H1A⋯O18ⁱⁱ	0.82	2.06	2.865 (6)	166
O1—H1B⋯O9ⁱⁱⁱ	0.82	2.02	2.840 (6)	173
O2—H2A⋯O10^iv	0.82	2.48	2.988 (7)	121
O2—H2B⋯O19	0.82	1.83	2.644 (8)	173
O3—H3A⋯O16	0.82	1.91	2.572 (6)	137
O3—H3B⋯O10ⁱⁱⁱ	0.82	1.91	2.695 (6)	159
O4—H4A⋯O9ⁱⁱⁱ	0.82	1.87	2.670 (6)	165
O4—H4B⋯O14^v	0.82	1.98	2.774 (6)	163
O5—H5A⋯O14	0.82	1.85	2.586 (6)	148
O5—H5B⋯O8	0.82	2.06	2.717 (6)	137
O6—H6A⋯O1^vi	0.82	2.09	2.826 (6)	149
O6—H6B⋯O4^vi	0.82	2.15	2.936 (6)	160
O19—H19A⋯O20^vii	0.82	2.06	2.816 (8)	152
O19—H19B⋯O12^viii	0.82	2.15	2.965 (7)	171
O20—H20A⋯O13^v	0.82	2.55	3.174 (7)	134
O20—H20B⋯O16	0.82	2.15	2.957 (9)	166

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

Acknowledgments

This work was supported financially by Yuanpei University, Taiwan.

supplementary crystallographic information

Comment

Many studies concering the use of pdc as a ligand toward transition metal (Wen et al., 2007) and /or rare earth transition metal (Wei et al., 2005; Huang et al., 2008) have shown that a great variety of polymeric structures can be obtained as a result of the differnet coordination modes of the pdc ligands.

The asymmetric unit of the title heterometallic coordination polymer, [Cu₃Yb₂(C₇H₃NO₄)₆(H₂O)₁₂.4H₂O]_n,contains one Yb^III and two Cu^II atoms, three pyridine-2,5-dicarboxylate (pdc) anions and six water molecules. One Cu^II atom is located on an located on an inversion center and is N,O-chelated by two pdc anions in the equatorial plane with square-planar geometry; the other Cu atom is N,O-chelated by two pdc anions in the coordination basal plane and coordinated by a carboxyl O atom at the apical position with a distorted square-pyramidal geometry [Cu—O = 2.374 (4) Å in the apical direction]. The Yb atom is eight coordinated with a distorted square-antiprismatic geometry formed by three carboxylate O atoms from three pdc anions and five water molecules (selected bond lengths are given in Table 1). The pdy anions bridge adjacent Yb and Cu atoms to form the three dimensional polymeric structure (Fig. 1).

The crystal structure contains the extensive O—H···O and weak C—H···O hydrogen bonds (Fig. 2 and Table 2). π-π stackings are present in the crystal structure, the shortest centroids distance between parallel pyridine rings is 3.646 (3) Å [Cg6^iiv···Cg6 (N1/C1—C5)] [symmetry code: (iiv) -x, 2 - y, -z].

Experimental

A mixture of ytterbium chloride hexahydrate (0.2438 g, 0.25 mmol), copper acetate hydrate (0.050 g, 0.25 mmol), pyridine-2,5-dicarboxylic acid (0.0418 g, 0.25 mmol,) and 10 ml H₂O were put in a 23-ml Teflon liner reactor and heated at 418 K in oven for 48 h. The resulting solution was slowly cooled to room temperature. The blue transparent single crystals of the title complex were obtained in 34.26% yield (based on Yb).