Tetra­kis(μ-3,4-dimeth­oxy­phenyl­acetato)­bis­[(3,4-dimeth­oxy­phenyl­acetato)(1,10-phenanthroline)holmium(III)]

Guo-Liang Zhao; Jia-Lu Liu; Jian-Feng Liu

doi:10.1107/S1600536810036408

. 2010 Sep 18;66(Pt 10):m1272–m1273. doi: 10.1107/S1600536810036408

Tetrakis(μ-3,4-dimethoxyphenylacetato)bis[(3,4-dimethoxyphenylacetato)(1,10-phenanthroline)holmium(III)]

Guo-Liang Zhao ^a,^*, Jia-Lu Liu ^a, Jian-Feng Liu ^a

PMCID: PMC2983278 PMID: 21587417

Abstract

In the centrosymmetric title compound, [Ho₂(C₁₀H₁₁O₄)₆(C₁₂H₈N₂)₂], the Ho^III atom is nine-coordinated by seven O atoms from the 3,4-dimethoxyphenylacetate (L) anions and two N atoms from a 1,10-phenanthroline (phen) molecule. The L ligands are coordinated to the Ho^III ions in three modes: chelating, bridging and bridging–tridentate. Intramolecular C—H⋯O interactions occur. The crystal packing is stabilized by intermolecular C—H⋯O interactions and weak aromatic π–π interactions between phen molecules and the aromatic rings of the L ligands [centroid–centroid distance = 3.821 (2) Å].

Related literature

For related structures, see: Li et al. (2005 ▶); Li & Zou (2005 ▶); Wang et al. (2010 ▶); Liu et al. (2010 ▶).

Experimental

Crystal data

[Ho₂(C₁₀H₁₁O₄)₆(C₁₂H₈N₂)₂]
M _r = 1861.40
Triclinic,
a = 12.3069 (2) Å
b = 12.3789 (2) Å
c = 14.6591 (2) Å
α = 91.020 (1)°
β = 103.547 (1)°
γ = 115.477 (1)°
V = 1942.03 (5) Å³
Z = 1
Mo Kα radiation
μ = 2.11 mm⁻¹
T = 296 K
0.30 × 0.16 × 0.05 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.676, T _max = 0.909
31540 measured reflections
8930 independent reflections
7217 reflections with I > 2σ(I)
R _int = 0.048

Refinement

R[F ² > 2σ(F ²)] = 0.033
wR(F ²) = 0.068
S = 1.04
8930 reflections
514 parameters
H-atom parameters constrained
Δρ_max = 0.92 e Å⁻³
Δρ_min = −0.57 e Å⁻³

Data collection: APEX2 (Bruker, 2006 ▶); cell refinement: SAINT (Bruker, 2006 ▶); 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: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810036408/pv2299sup1.cif

e-66-m1272-sup1.cif^{(40.3KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810036408/pv2299Isup2.hkl

e-66-m1272-Isup2.hkl^{(436.8KB, 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
C40—H40A⋯O3	0.93	2.52	2.972 (4)	110
C8—H8A⋯O6ⁱ	0.96	2.55	3.319 (5)	138
C16—H16A⋯O4ⁱⁱ	0.93	2.51	3.410 (4)	162
C18—H18C⋯O4ⁱⁱ	0.96	2.36	3.266 (4)	156
C21—H21C⋯O1	0.96	2.83	3.291 (6)	111
C21—H21C⋯O2	0.96	2.82	3.749 (6)	162
C31—H31A⋯O11ⁱⁱⁱ	0.93	2.37	3.008 (4)	126
C38—H38A⋯O7^iv	0.93	2.36	3.215 (4)	153

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

supplementary crystallographic information

Comment

The rare earth complexes with aromatic carboxylates have a variety of structures due to the various coordination modes of carboxylate groups, which have received considerable attention for many years (Li & Zou, 2005; Li et al., 2005). We have reported some similar mixed-ligands lanthanide carboxylate complexes with dimeric structures (Wang et al., 2010; Liu et al., 2010). We have now prepared a new holmium complex [Ho(L)₃phen]₂, wherein L = 3,4-dimethoxyphenylacetate and phen = 1,10-phenanthroline]. In this paper, the crystal structure of the title complex is reported.

The structure of the title complex is shown in Fig. 1. It is a centrosymmetric dimer which consists of six 3,4-dimethoxyphenylacetate anions, two 1,10-phenanthroline molecules and two Ho^III ions. The Ho^III ion is nine-coordinated by two N atoms from one 1,10-phenanthroline and seven O atoms from carboxylate groups with a mean Ho—O bond length of 2.400 (2) Å. The ligands (L) are coordinated to the Ho^III ions in three different modes: chelating, bridging and bridging tridentate. Around each Ho^III, there is one L ligand in chelating mode through two O atoms from the carboxyl group. Two symmetric L ligands bridge the two Ho centers though carboxyl O atoms. Two L ligands in bidentate mode form bonds with Ho^III ion with two carboxyl O atoms and simultaneously bond to another Ho^III ion with one of the carboxyl O atom. The Ho—Ho separation is 3.8741 (3) Å. The packing plot of the title complex is shown in Fig. 2. The most significant forces contribulting to the formation and stabilization of the crystal packing are intermolecular interactions of the type C—H···O hydrogen bonds and weak π–π aromatic interactions from phen molecules and aromatic rings of the L ligands. The ring [N(2)/C(40)—C(41)] stacks with its symmetry related ring of an adjacent molecule. The distance of Cg and Cg* [* = -x, 1-y, -z] being 3.821 (2) Å, where Cg is the center of the ring.

Experimental

A mixture of 3,4-dimethoxyphenylacetic acid (0.5886 g, 3 mmol), Ho₂O₃ (0.1889 g, 0.5 mmol), 1,10-phenanthroline (0.1982 g, 1 mmol) and purified water (20 ml) was sealed in a 25 ml stainless steel reactor and kept at 433 K for 3 d. The reactor was cooled to room temperature at a speed of 5 ° per hour. A few colourless single crystals were obtained from the solution.