catena-Poly[[[tetra­aqua­lanthanum(III)]-di-μ-isonicotinato-κ4 O:O′] chloride]

Jin-He Zhao

doi:10.1107/S1600536812027778

. 2012 Jun 27;68(Pt 7):m972. doi: 10.1107/S1600536812027778

catena-Poly[[[tetraaqualanthanum(III)]-di-μ-isonicotinato-κ⁴ O:O′] chloride]

Jin-He Zhao ^a,^*

PMCID: PMC3393223 PMID: 22807791

Abstract

In the title compound, {[La(C₆H₄NO₂)₂(H₂O)₄]Cl}_n, the La^III atom lies on a twofold rotation axis and is eight-coordinated by four O atoms from four isonicotinate ligands and four water molecules in a distorted square-antiprismatic coodination environment. Adjacent La^III atoms are bridged by two carboxylate groups from two isonicotinate ligands, forming an extended chain along [001]. These chains are linked through O—H⋯N hydrogen bonds into a three-dimensional network with channels in which the chloride anions form O—H⋯Cl hydrogen bonds. Intrachain O—H⋯O hydrogen bonds and π–π interactions [centroid–centroid distance = 3.908 (2) Å] are also observed.

Related literature

For lanthanide complexes with nicotinic acid, isonicotinic acid and isonicotinic acid N-oxide ligands, see: Cai et al. (2003 ▶); Chen & Fukuzumi (2009 ▶); Cui et al. (1999 ▶); Kay et al. (1972 ▶); Ma et al. (1996 ▶, 1999 ▶); Mao et al. (1998 ▶); Starynowicz (1991 ▶, 1993 ▶); Wu et al. (2008 ▶); Zeng et al. (2000 ▶); Zhang et al. (1999 ▶).

Experimental

Crystal data

[La(C₆H₄NO₂)₂(H₂O)₄]Cl
M _r = 490.63
Orthorhombic,
a = 8.987 (3) Å
b = 19.769 (3) Å
c = 10.305 (3) Å
V = 1830.8 (9) Å³
Z = 4
Mo Kα radiation
μ = 2.52 mm⁻¹
T = 296 K
0.36 × 0.34 × 0.32 mm

Data collection

Bruker SMART 1000 CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.464, T _max = 0.500
9336 measured reflections
1652 independent reflections
1442 reflections with I > 2σ(I)
R _int = 0.029

Refinement

R[F ² > 2σ(F ²)] = 0.025
wR(F ²) = 0.058
S = 1.07
1652 reflections
110 parameters
H-atom parameters constrained
Δρ_max = 0.46 e Å⁻³
Δρ_min = −0.83 e Å⁻³

Data collection: SMART (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Brandenburg, 1999 ▶); software used to prepare material for publication: SHELXTL (Sheldrick, 2008 ▶).

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812027778/hy2530sup1.cif

e-68-0m972-sup1.cif^{(14.4KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812027778/hy2530Isup2.hkl

e-68-0m972-Isup2.hkl^{(81.5KB, 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
O3—H3A⋯N1ⁱ	0.85	1.85	2.699 (4)	175
O3—H3B⋯Cl1ⁱⁱ	0.85	2.36	3.212 (2)	175
O4—H4C⋯O3ⁱⁱⁱ	0.85	2.01	2.860 (3)	180
O4—H4D⋯Cl1	0.85	2.17	3.024 (3)	180

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

supplementary crystallographic information

Comment

Much attention has been devoted to the research on lanthanide metal polynuclear compounds because of their magnetic and luminescent properties. Most of these types of compounds were synthesized by the reaction of rare-earth metal ions with bi- or multi-dentate ligands such as nicotinic acid (Kay et al., 1972; Ma, Hu et al., 1996; Starynowicz, 1991, 1993), isonicotinic acid (Chen & Fukuzumi, 2009; Ma, Evans et al., 1999; Wu et al., 2008; Zeng et al., 2000) and isonicotinic acid N-oxide (Mao et al., 1998). In the course of research in this area, our extended group has reported several such compounds with different bridging ligands (Cai et al., 2003; Cui et al., 1999; Zhang et al., 1999). Herein, we report the synthesis and crystal structure of a new lanthanum complex with isonicotinic ligand.

The title compound contains extended [La(C₆H₄NO₂)₂(H₂O)₄]_n cationic chains and Cl^- anions. The La^III ion, lying on a twofold rotation axis, is eight-coordinated by four O atoms belonging to four different isonicotinic ligands [average La—O = 2.451 (3) Å] and four water molecules [average La—O = 2.563 (3) Å] (Fig. 1). The coordination geometry of the La^III ion is best described as slightly distorted square-antiprismatic. The La atoms are bridged each other by two syn-syn µ-O:O'-carboxylate groups of the isonicotinic ligands, forming an extended chain along [0 0 1]. This geometry is similar to that found in [Eu(L)₂(H₂O)₄]_n.nH₂O (L = isonicotinic acid N-oxide) (Mao et al., 1998) and [La(C₆H₄NO₂)₂(H₂O)₄](NO₃) (Cai et al., 2003), but differs from those found in Ln(isonicotinate)₃(H₂O)₂ (Ln = Ce, Pr, Nd, Sm, Eu, Tb) (Ma, Evans et al., 1999), in which the Ln^III atoms are bridged by four syn-syn µ-O:O'-carboxylate groups of the isonicotinic ligands (Ln = Ce, Pr, Nd) or coordinated by both two syn-syn µ-O:O'-carboxylate groups and chelating carboxylate groups of the isonicotinic ligands (Ln = Sm, Eu, Tb). To the best of our knowledge, the arrangement in the present complex is rare in the lanthanide analogs.

There are three kinds of hydrogen bonds, O—H···Cl, O—H···O and O—H···N (Table 1). Interchain O—H···N hydrogen bonds between the coordinated water molecules and uncoordinated N atoms of the isonicotinate ligands link the cationic chains into a three-dimensional network with channels along [0 0 1], in which the chloride anions are located, as shown in Fig. 2, forming O—H···Cl hydrogen bonds. Intrachain O—H···O hydrogen bonds are also present. π–π stacking interactions exist between two adjacent isonicotinate ligands located in a same chain [centroid–centroid distance = 3.908 (2) Å].

Experimental

LaCl₃.7H₂O (0.3174 g, 1 mmol), isonicotinic acid (0.2442 g, 2 mmol), NaOH (0.08 g, 2 mmol) were added to a mixture of water (15 ml) and ethanol (10 ml). The resulting mixture was stirred at 423 K for 4 h and filtered off. The filtrate was allowed to stand at room temperature and slow evaporation afforded colorless block crystals of the title complex (yield: 65%). Analysis, calculated for C₁₂H₁₆ClLaN₂O₈: C 29.38, N 5.71, H 3.29%; found: C 29.36, N 5.74, H 3.28%.