Poly[[tetra­aquatetrakis­[μ3-5-(pyridine-4-carboxamido)­isophthalato]cobalt(II)digadolinium(III)] tetra­hydrate]

Yi-Fang Deng; Man-Sheng Chen; Chun-Hua Zhang; Dai-Zhi Kuang

doi:10.1107/S1600536811038074

. 2011 Sep 30;67(Pt 10):m1431–m1432. doi: 10.1107/S1600536811038074

Poly[[tetraaquatetrakis[μ₃-5-(pyridine-4-carboxamido)isophthalato]cobalt(II)digadolinium(III)] tetrahydrate]

Yi-Fang Deng ^a, Man-Sheng Chen ^a,^*, Chun-Hua Zhang ^a,^*, Dai-Zhi Kuang ^a

PMCID: PMC3201412 PMID: 22064912

Abstract

In the centrosymmetric polymeric title compound, {[CoGd₂(C₁₄H₈N₂O₅)₄(H₂O)₄]·4H₂O}_n, the Gd^III cation is coordinated by one water molecule and four pyridine-4-carboxamidoisophthalate (L) anions in a distorted square-antiprismatic arrangement, while the Co^II cation, located on an inversion center, is coordinated by two pyridyl-N atoms, two carboxylate-O atoms and two water molecules in a distorted octahedral geometry. The asymmetric unit contains two anionic L ligands: one bridges two Gd cations and one Co cation through two carboxyl groups and one pyridine-N atom; the other bridges two Gd cations and one Co cation through two carboxyl groups and the uncoordinated pyridine-N atom is hydrogen-bonded to the adjacent coordinated water molecule. Extensive O—H⋯O and N—H⋯O hydrogen bonds are present in the crystal structure.

Related literature

For related hetero-metallic complexes, see: Chen et al. (2011 ▶); Gu & Xue (2006 ▶); Liang et al. (2000 ▶); Prasad et al. (2007 ▶); Zhao et al. (2003 ▶, 2004 ▶).

Experimental

Crystal data

[CoGd₂(C₁₄H₈N₂O₅)₄(H₂O)₄]·4H₂O
M _r = 1654.45
Triclinic,
a = 10.1457 (14) Å
b = 10.8728 (15) Å
c = 13.7552 (19) Å
α = 79.123 (2)°
β = 78.844 (3)°
γ = 86.317 (2)°
V = 1461.3 (3) Å³
Z = 1
Mo Kα radiation
μ = 2.62 mm⁻¹
T = 293 K
0.20 × 0.16 × 0.10 mm

Data collection

Bruker SMART 1000 CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ▶) T _min = 0.622, T _max = 0.779
7307 measured reflections
5053 independent reflections
4462 reflections with I > 2σ(I)
R _int = 0.045

Refinement

R[F ² > 2σ(F ²)] = 0.031
wR(F ²) = 0.070
S = 1.00
5053 reflections
430 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 1.23 e Å⁻³
Δρ_min = −0.88 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; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811038074/xu5327sup1.cif

e-67-m1431-sup1.cif^{(31KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811038074/xu5327Isup2.hkl

e-67-m1431-Isup2.hkl^{(247.5KB, hkl)}

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

Table 1. Selected bond lengths (Å).

Co1—O1	2.083 (3)
Co1—O1W	2.178 (4)
Co1—N4ⁱ	2.159 (4)
Gd1—O2	2.246 (3)
Gd1—O2W	2.365 (3)
Gd1—O3ⁱⁱ	2.436 (3)
Gd1—O4ⁱⁱ	2.420 (3)
Gd1—O6	2.487 (3)
Gd1—O7	2.408 (3)
Gd1—O8ⁱⁱⁱ	2.475 (3)
Gd1—O9ⁱⁱⁱ	2.382 (3)

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

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O4W^iv	0.86	2.16	2.999 (6)	166
N3—H3⋯O4^v	0.86	2.15	2.942 (6)	152
O1W—H1WA⋯O6^vi	0.82	2.25	2.992 (5)	151
O1W—H1WB⋯O3W^vii	0.85	2.03	2.753 (6)	143
O2W—H2WA⋯O3W^viii	0.85	2.40	3.130 (6)	144
O2W—H2WB⋯N2ⁱ	0.85	1.92	2.676 (6)	147
O3W—H3WA⋯O3^vii	0.85	1.91	2.737 (6)	163
O3W—H3WB⋯O8ⁱⁱⁱ	0.85	1.97	2.781 (6)	160
O4W—H4WA⋯O9^ix	0.85	2.26	3.097 (6)	170
O4W—H4WB⋯O9^v	0.85	2.18	3.028 (6)	172

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

Acknowledgments

This work was supported by the Open Fund Project of Key Laboratories in Hunan Universities (11 K009) and the Science Foundation of Hengyang Normal University of China (10B67).

supplementary crystallographic information

Comment

The rational synthesis and investigation of 3d-4f or 4d-4f hetero-metallic complexes are challenge for chemists and have attracted increasing attention in last few years since the competitive reaction containing 3d-4f metal ions in conjunction with ligands often result in formation of a mixture of homometallic assemblies rather than hetero-metallic analogous (Liang et al., 2000; Zhao et al., 2003; Zhao et al., 2004; Gu et al., 2006; Prasad et al., 2007). So we have recently prepared a new lanthanide(III)-transition metal(II) coordination polymer, [GdCo_0.5(H₂O)₂(L)₂]_n.2nH₂O, (I) through hydrothermal condition.

In the title compound, the central Gd^III ion is eight-coordinated by seven O atoms from four ligands and one water molecule, which forming a distorted square antiprismatic geometry(Fig. 1). It is interesting that the carboxyl groups of two unique L^2- ligands exhibit the different coordination modes: one coordinated to two Gd^III and one Co^II atoms using its two carboxylate groups with µ₁-η¹:η¹-chelate and µ₂-η¹:η¹-bis-monodentate coordination modes while the pyridyl group is free of coordination, the other one coordinated to two Gd^III through the carboxylate groups with µ₁-η¹:η¹-chelate coordination mode and one Co^IIvia the pyridyl group. Based on the coordination modes of the carboxylate and pyridyl groups of L^2- ligands, a complicated three-dimensional network is formed (Fig. 2), which is similar to the complex {[LnCo_0.5(INAIP)₂(H₂O)₂].2H₂O}_n (Chen, et al. 2011).

Experimental

A mixture of 0.05 mmol Gd(NO₃)₃.6H₂O (21.8 mg. 0.05 mmol), H₂L (28.6 mg, 0.1 mmol), Co(OAc)₂.4H₂O (13.1 mg, 0.05 mmol), NaOH (6.0 mg, 0.15 mmol), MeOH (4 ml) and H₂O (6 ml) was heated in a 16 mL capacity Teflon-lined reaction vessel at 433 K for 4 days, the reaction mixture was cooled to room temperature over a period of 40 h. The product was collected by filtration, washed with H₂O and air-dried.