Tetra­kis(μ-anthracene-9-carboxyl­ato)bis­[(anthracene-9-carboxyl­ato)(2,2′-bipyrid­yl)lanthanum(III)]

Chun-Sen Liu; Li-Fen Yan; Ze Chang; Jun-Jie Wang

doi:10.1107/S1600536807062241

. 2007 Dec 6;64(Pt 1):m15–m16. doi: 10.1107/S1600536807062241

Tetrakis(μ-anthracene-9-carboxylato)bis[(anthracene-9-carboxylato)(2,2′-bipyridyl)lanthanum(III)]

Chun-Sen Liu ^a,^b,^*, Li-Fen Yan ^b, Ze Chang ^b, Jun-Jie Wang ^b

PMCID: PMC2914908 PMID: 21200503

Abstract

The title complex, [La₂(C₁₅H₉O₂)₆(C₁₀H₈N₂)₂], has a centrosymmetric binuclear cage structure in which two La^IIIatoms are both nine-coordinated and bridged by four anthracene-9-carboxylate ligands, with an La⋯La separation of 4.0880 (4) Å. The remaining coordination sites are occupied by two N atoms of a 2,2′-bipyridine (bipy) and two O atoms of an anthracene-9-carboxylate ligand. The six anthracene-9-carboxylate groups coordinate each La^IIIatom in three different ways. Adjacent discrete dinuclear units are arranged into a one-dimensional chain along the [111] direction by intermolecular π–π stacking interactions, with a centroid–centroid separation of 3.704 (7) Å.

Related literature

For related literature, see: Bünzli (2006 ▶); Fu et al. (2005 ▶); Janiak (2000 ▶); Roh et al. (2005 ▶); Shi et al. (2001 ▶); Suárez et al. (2004 ▶); Wan et al. (2003 ▶); Wang et al. (1999 ▶, 2006 ▶); Ye et al. (2005 ▶).

Experimental

Crystal data

[La₂(C₁₅H₉O₂)₆(C₁₀H₈N₂)₂]
M _r = 1917.52
Triclinic,
a = 12.1038 (7) Å
b = 13.4887 (8) Å
c = 15.4568 (14) Å
α = 113.036 (4)°
β = 103.257 (4)°
γ = 102.913 (3)°
V = 2117.7 (3) Å³
Z = 1
Mo Kα radiation
μ = 1.07 mm⁻¹
T = 273 (2) K
0.20 × 0.14 × 0.12 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 1998 ▶) T _min = 0.815, T _max = 0.883
32552 measured reflections
7432 independent reflections
6474 reflections with I > 2σ(I)
R _int = 0.045

Refinement

R[F ² > 2σ(F ²)] = 0.029
wR(F ²) = 0.076
S = 1.05
7432 reflections
577 parameters
H-atom parameters constrained
Δρ_max = 0.79 e Å⁻³
Δρ_min = −0.86 e Å⁻³

Data collection: SMART (Bruker, 1998 ▶); cell refinement: SAINT (Bruker, 1998 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997 ▶); molecular graphics: SHELXTL (Bruker, 1998 ▶); software used to prepare material for publication: SHELXTL and PLATON (Spek, 2003 ▶).

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536807062241/su2026sup1.cif

e-64-00m15-sup1.cif^{(41.3KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536807062241/su2026Isup2.hkl

e-64-00m15-Isup2.hkl^{(363.6KB, hkl)}

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

Table 1. Selected geometric parameters (Å, °).

La1—O2	2.4561 (18)
La1—O5	2.4574 (19)
La1—O1	2.4974 (18)
La1—O6	2.522 (2)
La1—O4	2.535 (2)
La1—O2ⁱ	2.6750 (19)
La1—O3ⁱ	2.687 (2)
La1—N1	2.730 (2)
La1—N2	2.741 (2)

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O2—La1—O5	73.16 (7)
O2—La1—O1	73.15 (6)
O5—La1—O1	135.97 (6)
O2—La1—O6	151.98 (7)
O5—La1—O6	90.68 (7)
O1—La1—O6	130.65 (7)
O2—La1—O4	151.37 (7)
O5—La1—O4	135.00 (7)
O1—La1—O4	79.76 (6)
O6—La1—O4	51.39 (7)
O2—La1—O2ⁱ	74.44 (6)
O5—La1—O2ⁱ	71.53 (6)
O1—La1—O2ⁱ	72.74 (6)
O6—La1—O2ⁱ	122.70 (7)
O4—La1—O2ⁱ	106.39 (7)
O2—La1—O3ⁱ	121.09 (6)
O5—La1—O3ⁱ	77.60 (8)
O1—La1—O3ⁱ	96.65 (8)
O6—La1—O3ⁱ	75.51 (8)
O4—La1—O3ⁱ	70.62 (7)
O2ⁱ—La1—O3ⁱ	47.91 (6)
O2—La1—N1	91.57 (7)
O5—La1—N1	134.60 (7)
O1—La1—N1	73.52 (7)
O6—La1—N1	83.64 (8)
O4—La1—N1	71.68 (7)
O2ⁱ—La1—N1	145.95 (7)
O3ⁱ—La1—N1	142.16 (7)
O2—La1—N2	78.12 (7)
O5—La1—N2	75.60 (7)
O1—La1—N2	123.19 (7)
O6—La1—N2	75.71 (7)
O4—La1—N2	110.34 (7)
O2ⁱ—La1—N2	141.93 (7)
O3ⁱ—La1—N2	140.02 (8)
N1—La1—N2	59.30 (7)

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Symmetry code: (i) Inline graphic .

Acknowledgments

This work was supported by the Startup Fund for PhDs in Natural Scientific Research of Zhengzhou University of Light Industry (grant No. 2008 to CSL). The authors also gratefully thank Nankai University and Henan Provincial Key Laboratory of Surface and Interface Science for supporting this research.

supplementary crystallographic information

Comment

In recent years, the rational design and synthesis of functional rare-earth (RE) coordination complexes with various N– and/or O-donor ligands has attracted great interest not only because of their fascinating structural diversities but also becasue of their potential applications as functional materials, for example, optical materials, electronic materials, catalytic materials, and molecular-based magnets (Bünzli, 2006; Fu et al., 2005; Suárez et al., 2004). The effective and facile approach for the synthesis of such complexes is still the appropriate choice of well designed organic ligands as bridges or terminal groups (building blocks), with metal ions or metal clusters as nodes (Ye et al., 2005). Among such ligands, versatile carboxylic acids exhibiting diverse coordination modes have been well used in the preparations of various functional rare-earth (RE) complexes (Roh et al., 2005; Shi et al., 2001; Wan et al., 2003; Wang et al., 1999; Wang et al., 2006). Besides, the introduction of 2,2'-bipyridyl-like bidentate chelating molecules (2,2'-bipyridine or 1,10-phenanthroline) into the reaction systems, the use of various carboxylic acid ligands, as auxiliary ligands, can generate some interesting coordination architectures (Ye et al., 2005). We report here the crystal structure of the title complex (I), a La^III complex with anthracene-9-carboxylate (L) and chelating 2,2'-bipyridine (bipy) as ligands.

The structure of complex (I) consists of a centrosymmetric dinuclear unit [La₂(L)₆(bipy)₂] with central La^III ions nine-coordinated by two N-atom donors from one chelating bipy ligand and seven O atoms from five distinct L ligands (Fig. 1). The La–O distances are in the range of 2.4561 (18) - 2.687 (2) Å, which are normal and in agreement with those found in other carboxylato-containing La^IIIcomplexes (Shi et al., 2001). The ligand bipy acts as a typical chelating ligand coordinating to the La^III ion with La–N bond distances of 2.730 (2) and 2.741 (2) Å, and an N–La–N angle of 59.30 (7)°. For L, there exists three different kinds of carboxylic coordination modes with the La^III center, namely syn-syn bridging (µ₂-η¹:η¹-bridging), symmetric bidentate chelate ((µ₁-η¹:η¹-chelating), and tridentate chelating/bridging (η-O,O'-µ-O,O). In this manner two La^III ions are connected to form an eight-membered ring [La(1)–O(1)–C(31)–O(5 A)–La(1 A)–O(1 A)–C(31 A)–O(5)], as well as a four-membered ring [La(1)–O(2)–La(1 A)–O(2 A)]. The non-bonding La(1)···La(1 A) separation is 4.0880 (4) Å (symmetry operation (A) = 1 - x, 1 - y, 1 - z).

In the crystal adjacent dinuclear [La₂(L)₆(bipy)₂] units are arranged into one-dimensional chains, along the [111] direction, by the intermolecular π···π stacking interactions (symmetry operation: 2 - x, 2 - y, 2 - z; dashed solid lines in Fig. 2) between the completely parallel anthracene rings of different L ligands, with a centroid-centroid separation of 3.704 (7) Å (Janiak et al., 2000).

Experimental

A mixed solution of anthracene-9-carboxylic acid (0.05 mmol) and 2,2'-bipyridine (0.05 mmol) in CH₃OH (10 ml) in the presence of excess 2,6-dimethylpyridine (ca 0.05 ml for adjusting the pH value to basic condition) was carefully layered on top of a H₂O solution (15 ml) of La(NO₃)₃ (0.1 mmol) in a test tube. Yellow single crystals suitable for X-ray analysis of the title complex (I) appeared at the tube wall after ca two weeks at room temperature. Yield: ~40% based on anthracene-9-carboxylic acid. Elemental analysis calculated for C₁₁₀H₇₀La₂O₁₂N₄: C 68.90, H 3.68, N 2.92%; found: C 68.69, H 3.77, N 3.03%.