catena-Poly[[[diaqua­terbium(III)]-tri-μ2-isonicotinato-κ6 O:O′] tris(perchlorate) monohydrate]

Xiao-Hui Huang; Wei-Bo Pan; Xiao-Hong Xu; Rong-Hua Zeng

doi:10.1107/S1600536808023623

. 2008 Jul 31;64(Pt 8):m1098–m1099. doi: 10.1107/S1600536808023623

catena-Poly[[[diaquaterbium(III)]-tri-μ₂-isonicotinato-κ⁶ O:O′] tris(perchlorate) monohydrate]

Xiao-Hui Huang ^a, Wei-Bo Pan ^a, Xiao-Hong Xu ^a, Rong-Hua Zeng ^a,^b,^*

PMCID: PMC2962002 PMID: 21203072

Abstract

In the title complex, {[Tb(C₆H₅NO₂)₃(H₂O)₂](ClO₄)₃·H₂O}_n, the Tb^III ion is coordinated by six O atoms from six isonicotinate (inic) ligands and two water molecules, displaying a bicapped trigonal-prismatic geometry. The inic ligands, which are protonated at the pyridine N atom, link the metal centres, forming a polymeric chain running parallel to the a axis. The chains are further assembled via intra- and intermolecular O—H⋯O and N—H⋯O hydrogen-bonding interactions into a three-dimensional supramolecular network involving the inic ligands, the water molecules and the perchlorate anions. One of the perchlorate ions is disordered over two sites with occupancies of 0.561 (17) and 0.439 (17).

Related literature

For related literature, see: Eddaoudi et al. (2001 ▶); Rizk et al. (2005 ▶).

Experimental

Crystal data

[Tb(C₆H₅NO₂)₃(H₂O)₂](ClO₄)₃·H₂O
M _r = 880.65
Triclinic,
a = 9.5270 (4) Å
b = 10.9508 (4) Å
c = 15.1309 (6) Å
α = 104.402 (2)°
β = 91.480 (2)°
γ = 111.159 (2)°
V = 1414.17 (10) Å³
Z = 2
Mo Kα radiation
μ = 2.88 mm⁻¹
T = 296 (2) K
0.20 × 0.18 × 0.15 mm

Data collection

Bruker APEXII area-detector diffractometer
Absorption correction: multi-scan (SADABS, Sheldrick, 1996 ▶) T _min = 0.566, T _max = 0.645
19700 measured reflections
6605 independent reflections
6206 reflections with I > 2σ(I)
R _int = 0.024

Refinement

R[F ² > 2σ(F ²)] = 0.021
wR(F ²) = 0.048
S = 1.04
6605 reflections
452 parameters
77 restraints
H-atom parameters constrained
Δρ_max = 0.94 e Å⁻³
Δρ_min = −0.79 e Å⁻³

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: APEX2; data reduction: SAINT (Bruker, 2004 ▶); 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: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808023623/rz2238sup1.cif

e-64-m1098-sup1.cif^{(25.6KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808023623/rz2238Isup2.hkl

e-64-m1098-Isup2.hkl^{(323.2KB, 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⋯O6ⁱ	0.86	2.15	2.949 (4)	154
N2—H2⋯O1Wⁱⁱ	0.86	1.91	2.756 (3)	166
N3—H3A⋯O5ⁱⁱⁱ	0.86	2.07	2.902 (3)	162
O1W—H1W⋯O4	0.84	2.48	3.054 (4)	127
O1W—H2W⋯O13	0.84	2.26	3.030 (3)	152
O2W—H4W⋯O3W^iv	0.84	2.20	2.920 (3)	145
O2W—H4W⋯O17	0.84	2.53	3.164 (2)	133
O2W—H3W⋯O11^v	0.83	2.23	2.959 (9)	147
O3W—H5W⋯O12	0.84	2.20	2.934 (9)	146
O3W—H6W⋯O11^vi	0.83	2.14	2.843 (9)	142

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

Acknowledgments

The authors acknowledge South China Normal University for supporting this work.

supplementary crystallographic information

Comment

The design, synthesis, characterization, and properties of supramolecular networks formed by using functionalized organic molecules as bridges between metal centres are of great interest (Rizk et al., 2005; Eddaoudi et al., 2001). As a building block, isonicotinic acid is an excellent candidate for the construction of supramolecular complexes. Recently, we obtained the title new coordination polymer, whise structure is reported here.

In the title compound, each Tb^III centre is coordinated by six oxygen donors of six inic ligands and two water molecules (Fig. 1), and exhibits a bicapped trigonal prismatic coordination geometry. The Tb^III ions are linked by inic ligands to form a polymeric chain in the a axis direction. The Tb···Tb separations between adjacent metal atoms are 4.318 (4) and 5.259 (5) Å. Intra- and intermolecular O—H···O and N—H···O hydrogen bonding interaction (Table 1) involving the inic ligands, the water molecules and the perchlorate ions assemble neighboring chains into a three-dimensional supramolecular network (Fig. 2).

Experimental

A mixture of Tb₄O₇ (0.189 g, 0.25 mmol), isonicotinic acid (0.135 g, 1.5 mmol) and water (10 ml) in the presence of HClO₄ (0.385 mmol) was stirred vigorously for 20 min and then sealed into a Teflon-lined stainless-steel autoclave (20 ml capacity). The autoclave was heated to and maintained at 433 K for 3 days, and then cooled to room temperature at 5 K h^-1 to obtain colourless block-shaped crystals of the title compound suitable for X-ray analysis.