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

Yi-Fang Deng; Man-Sheng Chen; Chun-Hua Zhang; Xue Nie

doi:10.1107/S1600536813014876

. 2013 Jun 8;69(Pt 7):m358–m359. doi: 10.1107/S1600536813014876

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

Yi-Fang Deng ^a, Man-Sheng Chen ^a, Chun-Hua Zhang ^a,^*, Xue Nie ^a

PMCID: PMC3772404 PMID: 24046547

Abstract

In the title compound, {[NiTb₂(C₁₄H₈N₂O₅)₄(H₂O)₄]·4H₂O}_n, the Tb^III ion is coordinated by one water molecule and seven O atoms from four 5-(pyridine-4-carboxamido)isophthalate (L) ligands in a distorted square-antiprismatic arrangement, while the Ni^II ion, lying on an inversion center, is six-coordinated in an octahedral geometry by two pyridine N atoms, two carboxylate O atoms and two water molecules. One L ligand bridges two Tb^III ions and one Ni^II ion through two carboxylate groups and one pyridine N atom. The other L ligand bridges two Tb^III ions and one Ni^II ion through two carboxylate groups, while the uncoordinating pyridine N atom is hydrogen bonded to an adjacent coordinating water molecule. Extensive O—H⋯O, N—H⋯O and O—H⋯N hydrogen bonds play an important role in stabilizing the crystal structure.

Related literature

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

Experimental

Crystal data

[NiTb₂(C₁₄H₈N₂O₅)₄(H₂O)₄]·4H₂O
M _r = 1657.57
Triclinic,
a = 10.2347 (12) Å
b = 10.8608 (13) Å
c = 13.7452 (17) Å
α = 79.053 (2)°
β = 78.745 (1)°
γ = 86.326 (2)°
V = 1470.7 (3) Å³
Z = 1
Mo Kα radiation
μ = 2.80 mm⁻¹
T = 293 K
0.22 × 0.16 × 0.08 mm

Data collection

Bruker APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ▶) T _min = 0.578, T _max = 0.807
7345 measured reflections
5088 independent reflections
4486 reflections with I > 2σ(I)
R _int = 0.045

Refinement

R[F ² > 2σ(F ²)] = 0.033
wR(F ²) = 0.074
S = 1.03
5088 reflections
434 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 1.24 e Å⁻³
Δρ_min = −0.85 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: XP in SHELXTL and DIAMOND (Brandenburg, 1999 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536813014876/hy2627sup1.cif

e-69-0m358-sup1.cif^{(30.9KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813014876/hy2627Isup2.hkl

e-69-0m358-Isup2.hkl^{(249.2KB, 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
N1—H1⋯O4W ⁱ	0.86	2.16	3.000 (6)	166
N3—H3⋯O4ⁱⁱ	0.86	2.17	2.958 (6)	153
O1W—H1WA⋯O6ⁱⁱⁱ	0.82	2.24	2.988 (4)	151
O1W—H1WB⋯O3W ^iv	0.85	2.04	2.763 (6)	143
O2W—H2WA⋯O3W ^v	0.85 (6)	2.47 (6)	3.117 (7)	134 (5)
O2W—H2WB⋯N2^vi	0.85	1.92	2.672 (6)	147
O3W—H3WC⋯O3^iv	0.85	1.92	2.736 (5)	159
O3W—H3WD⋯O8^vii	0.85	1.98	2.793 (5)	160
O4W—H4WA⋯O9^viii	0.85	2.25	3.088 (6)	170
O4W—H4WB⋯O9ⁱⁱ	0.85	2.19	3.034 (5)	172

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

Acknowledgments

This work was supported by the Open Fund Project of Key Laboratories in Hunan Universities (grant No. 11 K009) and the Hunan Provincial Natural Science Foundation of China (grant No.13 J J6069).

supplementary crystallographic information

Comment

The synthesis and investigation of d-f heterometallic complexes are challenge for chemists and have attracted increasing attention in last few years since the competitive reaction containing d-f metal ions in conjunction with ligands often result in the formation of a mixture of homometallic assemblies rather than heterometallic analogous (Gu & Xue, 2006; Liang et al., 2000; Prasad et al., 2007; Zhao et al., 2003, 2004;). We have recently prepared the title compound, a new transition metal(II)–lanthanide(III) coordination polymer, under hydrothermal conditions.

In the title compound, the Tb^III ion is eight-coordinated by seven O atoms from four 5-(pyridine-4-carboxamido)isophthalate (L) ligands and one water molecule, forming a distorted square-antiprismatic geometry (Fig. 1). It is interesting that the carboxylate groups of two unique L ligands exhibit different coordination modes: one coordinates to two Tb^III ions and one Ni^II ion 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 coordinates to two Tb^III ions through the carboxylate groups with µ₁-η¹:η¹-chelate coordination mode and to one Ni^II ion through the pyridyl group. Based on the coordination modes of the carboxylate and pyridyl groups, a complicated three-dimensional network is formed (Fig. 2), which is similar to the complexes {[LnCo_0.5(INAIP)₂(H₂O)₂].2H₂O}_n (Chen et al., 2011; Deng et al., 2011).

Experimental

A mixture of Tb(NO₃)₃.6H₂O (22.1 mg. 0.05 mmol), H₂L (28.7 mg, 0.1 mmol), NiSO₄.6H₂O (13.1 mg, 0.05 mmol), NaOH (6.0 mg, 0.15 mmol), EtOH (4 ml) and H₂O (6 ml) was heated in a 16 ml capacity Teflon-lined reaction vessel at 453 K for 3 days. The reaction mixture was cooled to room temperature over a period of 48 h. The product was collected by filtration, washed with H₂O and air-dried.