Tetra­kis(1,10-phenanthroline)bis­(μ-pyridine-2,6-dicarboxyl­ato)(pyridine-2,6-di­carboxyl­ato)dicopper(II)terbium(III) nitrate tetra­hydrate

Wei Zhang

doi:10.1107/S1600536812031686

. 2012 Jul 18;68(Pt 8):m1084–m1085. doi: 10.1107/S1600536812031686

Tetrakis(1,10-phenanthroline)bis(μ-pyridine-2,6-dicarboxylato)(pyridine-2,6-dicarboxylato)dicopper(II)terbium(III) nitrate tetrahydrate

Wei Zhang ^a,^*

PMCID: PMC3414140 PMID: 22904747

Abstract

The asymmetric unit of the title compound, [Cu₂Tb(C₇H₃NO₄)₃(C₁₂H₈N₂)₄]NO₃·4H₂O, consists of one-half of the C ₂-symmetric trinuclear coordination cation, one-half of the C ₂-symmetric nitrate anion and two water molecules. In the coordination cation, the Cu^II atom is coordinated by four N atoms from two 1,10-phenanthroline ligands and two O atoms from a bridging–chelating carboxylate group of the pyridine-2,6-dicarboxylate anion, completing a distorted N₄O₂ octahedral coordination environment. The Tb^III atom, located on a twofold rotation axis, is nine-coordinated by three tridentate pyridine-2,6-dicarboxylate anions forming an N₃O₆ donor set. The intramolecular Cu⋯Tb distance of 5.0592 (11) Å indicates weak interactions between the Cu^II and Tb^III atoms. The coordination cations, nitrate anions and water molecules are connected via O—H⋯O hydrogen bonds into layers parallel to the (001) plane. Moreover, there are extensive π–π stacking interactions [centroid–centroid distances = 4.332 (7) and 3.878 (5) Å] between the phenanthroline ligands and between phenanthroline and pyridine-2,6-dicarboxylate ligands.

Related literature

For the photophysical properties of lanthanide(III) coordination compounds, see: Jüstel et al. (1998 ▶). For the Cu—O, Cu—N, Tb—O and Tb—N bond lengths in previously reported dinuclear copper(II)–terbium(III) coordination compounds, see: Sun et al. (2010 ▶); Yang et al. (2006 ▶).

Experimental

Crystal data

[Cu₂Tb(C₇H₃NO₄)₃(C₁₂H₈N₂)₄]NO₃·4H₂O
M _r = 1636.20
Monoclinic,
a = 17.058 (4) Å
b = 19.574 (5) Å
c = 19.927 (5) Å
β = 97.289 (4)°
V = 6599 (3) Å³
Z = 4
Mo Kα radiation
μ = 1.78 mm⁻¹
T = 296 K
0.19 × 0.17 × 0.15 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2008 ▶) T _min = 0.728, T _max = 0.776
17945 measured reflections
6454 independent reflections
4952 reflections with I > 2σ(I)
R _int = 0.029

Refinement

R[F ² > 2σ(F ²)] = 0.041
wR(F ²) = 0.134
S = 1.04
6454 reflections
479 parameters
27 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.88 e Å⁻³
Δρ_min = −1.09 e Å⁻³

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

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812031686/gk2483sup1.cif

e-68-m1084-sup1.cif^{(37KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812031686/gk2483Isup2.hkl

e-68-m1084-Isup2.hkl^{(316KB, hkl)}

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

Table 1. Selected bond lengths (Å).

Tb1—O5	2.374 (3)
Tb1—O3	2.422 (4)
Tb1—N6	2.450 (5)
Tb1—O1	2.489 (3)
Tb1—N5	2.542 (4)
Cu1—N3	2.011 (4)
Cu1—N1	2.019 (4)
Cu1—N2	2.027 (4)
Cu1—O2	2.038 (4)
Cu1—N4	2.195 (4)
Cu1—O1	2.667 (3)

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H1WB⋯O2	0.85 (2)	2.16 (2)	2.979 (7)	162 (4)
O2W—H2WB⋯O4	0.84 (2)	1.87 (3)	2.705 (9)	174 (11)
O2W—H2WA⋯O7	0.86 (2)	1.84 (2)	2.675 (14)	164 (10)
O1W—H1WA⋯O2W ⁱ	0.91 (2)	1.93 (2)	2.827 (12)	171 (10)

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Symmetry code: (i) Inline graphic .

supplementary crystallographic information

Comment

The lanthanide(III) coordination compounds have received much attention in recent years owing to their interesting structures, photophysical properties (Jüstel et al., 1998) and potential applications. In this article, we report the structure of a novel copper(II)–terbium(III) coordination compound obtained by hydrothermal method using the pyridine-2,6-dicarboxylate and 1,10-phenanthroline ligands, {[Cu^II(C₁₂H₈N₂)₂]₂[Tb^III(C₇H₃NO₄)₃]}NO₃.4H₂O (Fig. 1). In the coordination cation {[Cu^II(C₁₂H₈N₂)₂]₂[Tb^III(C₇H₃NO₄)₃]}⁺, the Cu^II atom is coordinated by four N atoms from two 1,10-phenanthroline ligands and two O atoms from one pyridine-2,6-dicarboxylate completing distorted CuN₄O₂ octahedral coordination environment. The Tb^III atom located on a two-fold rotation axis is nine-coordinated by three tridentate 2,6-pyridinedicarboxylate anions forming N₃O₆ donor set. The shortest distance of Cu···Tb is 5.0592 (11) Å, which indicates there are weak interactions between Cu^II and Tb^III ions. The details of bond lengths are given in Table 1. These bond lengths of Cu—O, Cu—N, Tb—O and Tb—N type fall in the typical range observed in previously reported copper(II)–terbium(III) coordination compounds (Sun et al., 2010; Yang et al., 2006). The coordination cations {[Cu^II(C₁₂H₈N₂)₂]₂[Tb^III(C₇H₃NO₄)₃]}⁺, nitrate anions and water molecules are connected via O—H···O hydrogen bonds into layered structure parallel to (001) (Fig. 2). In addition, there are extensive π–π stacking interactions between the phenanthroline ligands and between phenanthroline and pyridinedicarboxylate ligands. The hydrogen bonds and π–π stacking interactions play a crucial role in stability of the crystal structure.

Experimental

All chemicals were of reagent grade quality obtained from commercial sources and used without further purification. The compound was obtained by using hydrothermal method in a 50 ml Teflon-lined autoclave. The mixture of 0.17 g CuCl₂.2H₂O, 0.27 g Tb(NO₃)₃.6H₂O, 0.17 g pyridine-2,6-dicarboxylic acid, 0.16 g 1,10-phenanthroline and 20 ml H₂O was stirred for half an hour, and transferred into a Teflon-lined stainless steel autoclave (50 ml), then treated at 433 K for 6 d. After the mixture was slowly cooled to room temperature, blue block crystals suitable for X-ray structure determination were obtained. The chemical composition of the title compound was confirmed by elemental analysis. The C, H, and N elements analysis were performed on a PerkinElmer 2400II elemental analyzer. Anal. calcd for the title compound: C, 50.65; H, 3.02; N,10.27%. Found: C, 51.22; H, 3.65; N, 9.89%. The results well support the formula of the compound based on the single-crystal X-ray analysis.