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

Liu, C.-S.; Yan, L.-F.; Chang, Z.; Wang, J.-J.

doi:10.1107/S1600536807062241

metal-organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 64| Part 1| January 2008| Pages m15-m16

https://doi.org/10.1107/S1600536807062241

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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 and Jun-Jie Wang ^b

^aZhengzhou University of Light Industry, Henan Provincial Key Laboratory of Surface and Interface Science, Henan, Zhengzhou 450002, People's Republic of China, and ^bDepartment of Chemistry, Nankai University, Tianjin 300071, People's Republic of China
^*Correspondence e-mail: chunsenliu@mail.nankai.edu.cn

(Received 16 November 2007; accepted 22 November 2007; online 6 December 2007)

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, $[P \overline 1]$
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[F² > 2σ(F²)] = 0.029
wR(F²) = 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

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)

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)
Symmetry code: (i) -x+1, -y+1, -z+1.

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 ).

Supporting information

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

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536807062241/su2026Isup2.hkl

checkCIF report

Comment top

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).

Related literature top

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 top

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%.

Structure description top

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).

Computing details top

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).

Figures top

	Fig. 1. The molecular structure of complex (I). Displacement ellipsoids are drawn at the 30% probability level. Atoms labelled with the suffix A are generated by the symmetry operation (1 - x, 1 - y, 1 - z). For the sake of clarity, all H atoms have been omitted.
	Fig. 2. Part of the crystal packing in complex (I), showing a π···π stacking (dashed solid lines) chain. All H atoms have been omitted for clarity.

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

Crystal data top

[La₂(C₁₅H₉O₂)₆(C₁₀H₈N₂)₂]	Z = 1
M_r = 1917.52	F(000) = 968
Triclinic, P1	D_x = 1.504 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 12.1038 (7) Å	Cell parameters from 6220 reflections
b = 13.4887 (8) Å	θ = 2.4–28.2°
c = 15.4568 (14) Å	µ = 1.07 mm⁻¹
α = 113.036 (4)°	T = 273 K
β = 103.257 (4)°	Block, yellow
γ = 102.913 (3)°	0.20 × 0.14 × 0.12 mm
V = 2117.7 (3) Å³

Data collection top

CCD area-detector diffractometer	7432 independent reflections
Radiation source: fine-focus sealed tube	6474 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.045
φ and ω scans	θ_max = 25.0°, θ_min = 1.7°
Absorption correction: multi-scan (SADABS; Bruker, 1998)	h = −14→14
T_min = 0.815, T_max = 0.883	k = −16→13
32552 measured reflections	l = −18→18

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.029	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.076	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.0402P)² + 0.7206P] where P = (F_o² + 2F_c²)/3
7432 reflections	(Δ/σ)_max = 0.008
577 parameters	Δρ_max = 0.79 e Å⁻³
0 restraints	Δρ_min = −0.86 e Å⁻³

Crystal data top

[La₂(C₁₅H₉O₂)₆(C₁₀H₈N₂)₂]	γ = 102.913 (3)°
M_r = 1917.52	V = 2117.7 (3) Å³
Triclinic, P1	Z = 1
a = 12.1038 (7) Å	Mo Kα radiation
b = 13.4887 (8) Å	µ = 1.07 mm⁻¹
c = 15.4568 (14) Å	T = 273 K
α = 113.036 (4)°	0.20 × 0.14 × 0.12 mm
β = 103.257 (4)°

Data collection top

CCD area-detector diffractometer	7432 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 1998)	6474 reflections with I > 2σ(I)
T_min = 0.815, T_max = 0.883	R_int = 0.045
32552 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.029	0 restraints
wR(F²) = 0.076	H-atom parameters constrained
S = 1.05	Δρ_max = 0.79 e Å⁻³
7432 reflections	Δρ_min = −0.86 e Å⁻³
577 parameters

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
La1	0.676202 (12)	0.570648 (12)	0.595266 (10)	0.03410 (7)
C1	0.4637 (3)	0.2753 (2)	0.4356 (2)	0.0417 (6)
C2	0.5386 (2)	0.2008 (2)	0.4404 (2)	0.0413 (6)
C3	0.5804 (3)	0.1540 (2)	0.3612 (2)	0.0470 (7)
C4	0.5564 (3)	0.1751 (3)	0.2769 (3)	0.0621 (9)
H4A	0.5098	0.2204	0.2724	0.074*
C5	0.6003 (4)	0.1301 (4)	0.2026 (3)	0.0801 (12)
H5A	0.5845	0.1455	0.1483	0.096*
C6	0.6698 (4)	0.0602 (4)	0.2080 (3)	0.0879 (14)
H6A	0.6992	0.0295	0.1567	0.105*
C7	0.6943 (4)	0.0371 (3)	0.2856 (3)	0.0772 (11)
H7A	0.7398	−0.0098	0.2869	0.093*
C8	0.6519 (3)	0.0833 (3)	0.3665 (3)	0.0553 (8)
C9	0.6768 (3)	0.0623 (3)	0.4482 (3)	0.0614 (9)
H9A	0.7222	0.0155	0.4504	0.074*
C10	0.6364 (3)	0.1086 (3)	0.5273 (3)	0.0524 (8)
C11	0.6596 (3)	0.0849 (3)	0.6105 (3)	0.0678 (10)
H11A	0.7037	0.0372	0.6129	0.081*
C12	0.6187 (4)	0.1304 (4)	0.6856 (3)	0.0742 (11)
H12A	0.6346	0.1137	0.7392	0.089*
C13	0.5520 (4)	0.2029 (3)	0.6833 (3)	0.0685 (10)
H13A	0.5254	0.2350	0.7361	0.082*
C14	0.5261 (3)	0.2266 (3)	0.6052 (2)	0.0549 (8)
H14A	0.4811	0.2742	0.6051	0.066*
C15	0.5660 (2)	0.1803 (2)	0.5236 (2)	0.0438 (7)
C16	0.8859 (2)	0.7626 (2)	0.7512 (2)	0.0419 (7)
C17	0.9949 (3)	0.8618 (2)	0.8350 (2)	0.0442 (7)
C18	1.0854 (3)	0.8381 (3)	0.8901 (2)	0.0494 (7)
C19	1.0865 (3)	0.7256 (3)	0.8641 (3)	0.0663 (10)
H19A	1.0251	0.6636	0.8079	0.080*
C20	1.1754 (4)	0.7066 (4)	0.9198 (4)	0.0891 (13)
H20A	1.1752	0.6320	0.9005	0.107*
C21	1.2676 (4)	0.7984 (4)	1.0063 (4)	0.0918 (14)
H21A	1.3272	0.7840	1.0445	0.110*
C22	1.2707 (3)	0.9062 (4)	1.0342 (3)	0.0714 (11)
H22A	1.3328	0.9658	1.0916	0.086*
C23	1.1809 (3)	0.9318 (3)	0.9780 (2)	0.0505 (8)
C24	1.1819 (3)	1.0422 (3)	1.0058 (2)	0.0502 (8)
H24A	1.2421	1.1020	1.0644	0.060*
C25	1.0950 (3)	1.0675 (2)	0.9486 (2)	0.0449 (7)
C26	1.0969 (3)	1.1815 (3)	0.9768 (2)	0.0562 (8)
H26A	1.1579	1.2422	1.0344	0.067*
C27	1.0122 (4)	1.2028 (3)	0.9217 (3)	0.0664 (10)
H27A	1.0144	1.2781	0.9418	0.080*
C28	0.9189 (3)	1.1124 (3)	0.8327 (3)	0.0662 (9)
H28A	0.8623	1.1293	0.7942	0.079*
C29	0.9114 (3)	1.0020 (3)	0.8034 (2)	0.0518 (8)
H29A	0.8488	0.9434	0.7458	0.062*
C30	0.9994 (3)	0.9749 (2)	0.8606 (2)	0.0441 (7)
C31	0.4199 (3)	0.4836 (2)	0.6572 (2)	0.0398 (6)
C32	0.3754 (2)	0.4597 (2)	0.7333 (2)	0.0405 (6)
C33	0.4244 (3)	0.5438 (3)	0.8357 (2)	0.0432 (7)
C34	0.5145 (3)	0.6538 (3)	0.8742 (2)	0.0510 (7)
H34A	0.5438	0.6736	0.8304	0.061*
C35	0.5585 (3)	0.7305 (3)	0.9737 (2)	0.0606 (9)
H35A	0.6169	0.8017	0.9963	0.073*
C36	0.5174 (3)	0.7041 (3)	1.0432 (3)	0.0646 (9)
H36A	0.5497	0.7566	1.1112	0.078*
C37	0.4315 (3)	0.6030 (3)	1.0101 (3)	0.0620 (9)
H37A	0.4040	0.5864	1.0560	0.074*
C38	0.3804 (3)	0.5196 (3)	0.9068 (2)	0.0506 (7)
C39	0.2918 (3)	0.4143 (3)	0.8735 (3)	0.0610 (9)
H39A	0.2636	0.3992	0.9198	0.073*
C40	0.2441 (3)	0.3311 (3)	0.7739 (3)	0.0548 (8)
C41	0.1542 (4)	0.2229 (4)	0.7433 (4)	0.0769 (11)
H41A	0.1273	0.2088	0.7905	0.092*
C42	0.1084 (4)	0.1412 (4)	0.6463 (4)	0.0841 (13)
H42A	0.0496	0.0714	0.6269	0.101*
C43	0.1487 (3)	0.1611 (3)	0.5753 (3)	0.0732 (11)
H43A	0.1166	0.1035	0.5090	0.088*
C44	0.2334 (3)	0.2621 (3)	0.6001 (3)	0.0572 (8)
H44A	0.2581	0.2723	0.5505	0.069*
C45	0.2853 (3)	0.3533 (3)	0.7012 (2)	0.0466 (7)
C46	0.8254 (3)	0.4121 (3)	0.4462 (2)	0.0567 (8)
H46A	0.7874	0.4405	0.4067	0.068*
C47	0.8931 (3)	0.3470 (3)	0.4104 (3)	0.0637 (9)
H47A	0.8997	0.3313	0.3480	0.076*
C48	0.9498 (4)	0.3063 (3)	0.4680 (3)	0.0731 (11)
H48A	0.9977	0.2637	0.4464	0.088*
C49	0.9358 (3)	0.3287 (3)	0.5586 (3)	0.0682 (10)
H49A	0.9728	0.2999	0.5982	0.082*
C50	0.8664 (3)	0.3944 (2)	0.5909 (2)	0.0478 (7)
C51	0.8494 (3)	0.4215 (2)	0.6884 (2)	0.0482 (7)
C52	0.9075 (4)	0.3890 (4)	0.7559 (3)	0.0806 (12)
H52A	0.9579	0.3472	0.7400	0.097*
C53	0.8904 (4)	0.4186 (4)	0.8458 (3)	0.0865 (13)
H53A	0.9299	0.3979	0.8915	0.104*
C54	0.8158 (4)	0.4782 (3)	0.8680 (3)	0.0648 (9)
H54A	0.8026	0.4985	0.9286	0.078*
C55	0.7601 (3)	0.5081 (3)	0.7987 (2)	0.0530 (8)
H55A	0.7089	0.5492	0.8140	0.064*
N1	0.7758 (2)	0.4809 (2)	0.71062 (18)	0.0458 (6)
N2	0.8112 (2)	0.4367 (2)	0.53454 (18)	0.0477 (6)
O1	0.53299 (17)	0.53114 (18)	0.68098 (14)	0.0478 (5)
O2	0.51838 (17)	0.38292 (15)	0.47574 (14)	0.0429 (5)
O3	0.3521 (2)	0.23338 (18)	0.3940 (2)	0.0691 (7)
O4	0.79298 (19)	0.73251 (18)	0.77239 (15)	0.0539 (5)
O5	0.65790 (17)	0.54654 (17)	0.42597 (14)	0.0463 (5)
O6	0.88922 (19)	0.7120 (2)	0.66595 (16)	0.0647 (7)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
La1	0.02422 (9)	0.03431 (10)	0.03495 (10)	0.00919 (7)	0.00716 (7)	0.01018 (7)
C1	0.0407 (16)	0.0328 (14)	0.0416 (15)	0.0117 (13)	0.0086 (13)	0.0118 (12)
C2	0.0337 (15)	0.0296 (13)	0.0490 (16)	0.0089 (11)	0.0086 (13)	0.0120 (12)
C3	0.0426 (16)	0.0338 (14)	0.0514 (17)	0.0087 (13)	0.0115 (14)	0.0127 (13)
C4	0.064 (2)	0.056 (2)	0.057 (2)	0.0152 (17)	0.0173 (17)	0.0218 (17)
C5	0.090 (3)	0.077 (3)	0.062 (2)	0.018 (2)	0.032 (2)	0.025 (2)
C6	0.097 (3)	0.075 (3)	0.080 (3)	0.025 (3)	0.052 (3)	0.016 (2)
C7	0.075 (3)	0.065 (2)	0.093 (3)	0.035 (2)	0.046 (2)	0.023 (2)
C8	0.0467 (18)	0.0410 (16)	0.070 (2)	0.0174 (14)	0.0216 (16)	0.0167 (15)
C9	0.0497 (19)	0.0471 (18)	0.086 (3)	0.0260 (16)	0.0185 (18)	0.0275 (18)
C10	0.0399 (17)	0.0426 (16)	0.066 (2)	0.0122 (14)	0.0061 (15)	0.0253 (15)
C11	0.053 (2)	0.062 (2)	0.081 (3)	0.0163 (18)	0.0016 (19)	0.040 (2)
C12	0.069 (3)	0.078 (3)	0.065 (2)	0.009 (2)	0.005 (2)	0.042 (2)
C13	0.070 (2)	0.068 (2)	0.055 (2)	0.012 (2)	0.0168 (18)	0.0258 (18)
C14	0.0515 (19)	0.0472 (17)	0.0571 (19)	0.0133 (15)	0.0149 (16)	0.0205 (15)
C15	0.0345 (15)	0.0336 (14)	0.0507 (17)	0.0076 (12)	0.0062 (13)	0.0148 (13)
C16	0.0257 (14)	0.0412 (15)	0.0504 (17)	0.0108 (12)	0.0085 (12)	0.0166 (13)
C17	0.0319 (15)	0.0437 (16)	0.0445 (16)	0.0089 (12)	0.0115 (13)	0.0123 (13)
C18	0.0317 (15)	0.0540 (18)	0.0555 (18)	0.0139 (14)	0.0116 (14)	0.0216 (15)
C19	0.0448 (19)	0.056 (2)	0.079 (2)	0.0209 (16)	0.0081 (17)	0.0194 (18)
C20	0.074 (3)	0.080 (3)	0.110 (3)	0.048 (2)	0.018 (3)	0.038 (3)
C21	0.061 (3)	0.097 (3)	0.101 (3)	0.046 (2)	0.005 (2)	0.034 (3)
C22	0.0365 (18)	0.086 (3)	0.069 (2)	0.0188 (18)	−0.0009 (17)	0.027 (2)
C23	0.0316 (15)	0.059 (2)	0.0506 (17)	0.0093 (14)	0.0103 (13)	0.0217 (15)
C24	0.0334 (15)	0.0551 (19)	0.0411 (16)	0.0009 (14)	0.0056 (13)	0.0144 (14)
C25	0.0396 (16)	0.0440 (16)	0.0381 (15)	0.0003 (13)	0.0121 (13)	0.0155 (13)
C26	0.057 (2)	0.0443 (17)	0.0518 (18)	0.0040 (15)	0.0138 (16)	0.0183 (15)
C27	0.080 (3)	0.0425 (18)	0.070 (2)	0.0149 (18)	0.019 (2)	0.0273 (17)
C28	0.062 (2)	0.066 (2)	0.071 (2)	0.0210 (18)	0.0108 (19)	0.0391 (19)
C29	0.0437 (17)	0.0533 (18)	0.0469 (17)	0.0085 (14)	0.0063 (14)	0.0225 (15)
C30	0.0372 (15)	0.0477 (16)	0.0400 (15)	0.0062 (13)	0.0111 (13)	0.0195 (13)
C31	0.0392 (16)	0.0403 (15)	0.0402 (15)	0.0177 (13)	0.0162 (13)	0.0157 (12)
C32	0.0314 (14)	0.0476 (16)	0.0484 (16)	0.0188 (13)	0.0147 (13)	0.0250 (13)
C33	0.0378 (15)	0.0534 (17)	0.0501 (16)	0.0233 (14)	0.0197 (13)	0.0288 (14)
C34	0.0517 (18)	0.0562 (18)	0.0481 (17)	0.0194 (15)	0.0232 (15)	0.0239 (15)
C35	0.055 (2)	0.064 (2)	0.0520 (19)	0.0182 (17)	0.0194 (16)	0.0186 (16)
C36	0.063 (2)	0.080 (3)	0.0449 (18)	0.031 (2)	0.0173 (17)	0.0215 (18)
C37	0.067 (2)	0.086 (3)	0.0514 (19)	0.036 (2)	0.0290 (18)	0.0400 (19)
C38	0.0497 (18)	0.064 (2)	0.0537 (18)	0.0286 (16)	0.0238 (15)	0.0348 (16)
C39	0.062 (2)	0.076 (2)	0.070 (2)	0.0271 (19)	0.0358 (18)	0.050 (2)
C40	0.0447 (17)	0.0577 (19)	0.076 (2)	0.0205 (15)	0.0251 (17)	0.0416 (18)
C41	0.063 (2)	0.073 (3)	0.108 (3)	0.015 (2)	0.036 (2)	0.057 (3)
C42	0.064 (3)	0.058 (2)	0.117 (4)	0.003 (2)	0.022 (3)	0.042 (3)
C43	0.056 (2)	0.054 (2)	0.082 (3)	0.0096 (18)	0.008 (2)	0.0211 (19)
C44	0.0427 (18)	0.0528 (19)	0.068 (2)	0.0162 (15)	0.0133 (16)	0.0241 (16)
C45	0.0339 (15)	0.0495 (17)	0.0608 (18)	0.0194 (13)	0.0159 (14)	0.0276 (15)
C46	0.0452 (18)	0.067 (2)	0.0551 (19)	0.0247 (16)	0.0202 (15)	0.0216 (16)
C47	0.053 (2)	0.069 (2)	0.065 (2)	0.0260 (18)	0.0319 (18)	0.0183 (18)
C48	0.065 (2)	0.075 (2)	0.099 (3)	0.046 (2)	0.048 (2)	0.037 (2)
C49	0.066 (2)	0.073 (2)	0.090 (3)	0.047 (2)	0.042 (2)	0.041 (2)
C50	0.0342 (15)	0.0405 (16)	0.0613 (19)	0.0153 (13)	0.0123 (14)	0.0181 (14)
C51	0.0399 (16)	0.0421 (16)	0.0556 (18)	0.0166 (13)	0.0095 (14)	0.0193 (14)
C52	0.097 (3)	0.090 (3)	0.077 (3)	0.066 (3)	0.029 (2)	0.043 (2)
C53	0.113 (4)	0.097 (3)	0.072 (3)	0.064 (3)	0.025 (3)	0.051 (2)
C54	0.072 (2)	0.068 (2)	0.0527 (19)	0.0237 (19)	0.0171 (18)	0.0290 (17)
C55	0.0466 (18)	0.0565 (19)	0.0508 (18)	0.0193 (15)	0.0131 (15)	0.0218 (15)
N1	0.0374 (13)	0.0460 (14)	0.0504 (14)	0.0164 (11)	0.0131 (11)	0.0195 (11)
N2	0.0338 (13)	0.0489 (14)	0.0506 (14)	0.0163 (11)	0.0147 (11)	0.0129 (12)
O1	0.0324 (11)	0.0619 (13)	0.0439 (11)	0.0120 (9)	0.0152 (9)	0.0212 (10)
O2	0.0362 (10)	0.0302 (10)	0.0521 (11)	0.0110 (8)	0.0116 (9)	0.0120 (9)
O3	0.0373 (13)	0.0405 (12)	0.0923 (18)	0.0074 (10)	−0.0081 (12)	0.0162 (12)
O4	0.0465 (12)	0.0508 (12)	0.0424 (11)	0.0008 (10)	0.0138 (10)	0.0106 (9)
O5	0.0364 (11)	0.0573 (12)	0.0421 (11)	0.0165 (9)	0.0117 (9)	0.0214 (10)
O6	0.0363 (12)	0.0677 (14)	0.0507 (13)	0.0010 (10)	0.0174 (10)	−0.0016 (11)

Geometric parameters (Å, º) top

La1—O2	2.4561 (18)	C26—C27	1.335 (5)
La1—O5	2.4574 (19)	C26—H26A	0.9300
La1—O1	2.4974 (18)	C27—C28	1.419 (5)
La1—O6	2.522 (2)	C27—H27A	0.9300
La1—O4	2.535 (2)	C28—C29	1.350 (5)
La1—O2ⁱ	2.6750 (19)	C28—H28A	0.9300
La1—O3ⁱ	2.687 (2)	C29—C30	1.429 (4)
La1—N1	2.730 (2)	C29—H29A	0.9300
La1—N2	2.741 (2)	C31—O5ⁱ	1.254 (3)
La1—C16	2.886 (3)	C31—O1	1.270 (3)
La1—C1ⁱ	3.064 (3)	C31—C32	1.512 (4)
La1—La1ⁱ	4.0880 (4)	C32—C45	1.411 (4)
C1—O3	1.238 (3)	C32—C33	1.416 (4)
C1—O2	1.268 (3)	C33—C34	1.426 (4)
C1—C2	1.508 (4)	C33—C38	1.439 (4)
C1—La1ⁱ	3.064 (3)	C34—C35	1.360 (4)
C2—C15	1.400 (4)	C34—H34A	0.9300
C2—C3	1.406 (4)	C35—C36	1.413 (5)
C3—C4	1.421 (5)	C35—H35A	0.9300
C3—C8	1.435 (4)	C36—C37	1.334 (5)
C4—C5	1.358 (5)	C36—H36A	0.9300
C4—H4A	0.9300	C37—C38	1.423 (5)
C5—C6	1.411 (7)	C37—H37A	0.9300
C5—H5A	0.9300	C38—C39	1.388 (5)
C6—C7	1.339 (6)	C39—C40	1.383 (5)
C6—H6A	0.9300	C39—H39A	0.9300
C7—C8	1.430 (5)	C40—C41	1.432 (5)
C7—H7A	0.9300	C40—C45	1.433 (4)
C8—C9	1.382 (5)	C41—C42	1.350 (6)
C9—C10	1.392 (5)	C41—H41A	0.9300
C9—H9A	0.9300	C42—C43	1.389 (6)
C10—C11	1.423 (5)	C42—H42A	0.9300
C10—C15	1.434 (4)	C43—C44	1.358 (5)
C11—C12	1.345 (6)	C43—H43A	0.9300
C11—H11A	0.9300	C44—C45	1.432 (4)
C12—C13	1.406 (6)	C44—H44A	0.9300
C12—H12A	0.9300	C46—N2	1.334 (4)
C13—C14	1.352 (5)	C46—C47	1.378 (5)
C13—H13A	0.9300	C46—H46A	0.9300
C14—C15	1.419 (4)	C47—C48	1.355 (5)
C14—H14A	0.9300	C47—H47A	0.9300
C16—O6	1.240 (3)	C48—C49	1.371 (5)
C16—O4	1.267 (3)	C48—H48A	0.9300
C16—C17	1.510 (4)	C49—C50	1.386 (4)
C17—C18	1.403 (4)	C49—H49A	0.9300
C17—C30	1.403 (4)	C50—N2	1.350 (4)
C18—C19	1.414 (5)	C50—C51	1.481 (4)
C18—C23	1.436 (4)	C51—N1	1.341 (4)
C19—C20	1.355 (5)	C51—C52	1.391 (5)
C19—H19A	0.9300	C52—C53	1.366 (6)
C20—C21	1.403 (6)	C52—H52A	0.9300
C20—H20A	0.9300	C53—C54	1.353 (6)
C21—C22	1.333 (6)	C53—H53A	0.9300
C21—H21A	0.9300	C54—C55	1.376 (5)
C22—C23	1.424 (5)	C54—H54A	0.9300
C22—H22A	0.9300	C55—N1	1.336 (4)
C23—C24	1.375 (5)	C55—H55A	0.9300
C24—C25	1.405 (4)	O2—La1ⁱ	2.6750 (19)
C24—H24A	0.9300	O3—La1ⁱ	2.687 (2)
C25—C26	1.418 (4)	O5—C31ⁱ	1.254 (3)
C25—C30	1.433 (4)

O2—La1—O5	73.16 (7)	C20—C19—C18	121.2 (3)
O2—La1—O1	73.15 (6)	C20—C19—H19A	119.4
O5—La1—O1	135.97 (6)	C18—C19—H19A	119.4
O2—La1—O6	151.98 (7)	C19—C20—C21	120.6 (4)
O5—La1—O6	90.68 (7)	C19—C20—H20A	119.7
O1—La1—O6	130.65 (7)	C21—C20—H20A	119.7
O2—La1—O4	151.37 (7)	C22—C21—C20	120.7 (4)
O5—La1—O4	135.00 (7)	C22—C21—H21A	119.7
O1—La1—O4	79.76 (6)	C20—C21—H21A	119.7
O6—La1—O4	51.39 (7)	C21—C22—C23	121.4 (4)
O2—La1—O2ⁱ	74.44 (6)	C21—C22—H22A	119.3
O5—La1—O2ⁱ	71.53 (6)	C23—C22—H22A	119.3
O1—La1—O2ⁱ	72.74 (6)	C24—C23—C22	122.3 (3)
O6—La1—O2ⁱ	122.70 (7)	C24—C23—C18	119.4 (3)
O4—La1—O2ⁱ	106.39 (7)	C22—C23—C18	118.2 (3)
O2—La1—O3ⁱ	121.09 (6)	C23—C24—C25	122.2 (3)
O5—La1—O3ⁱ	77.60 (8)	C23—C24—H24A	118.9
O1—La1—O3ⁱ	96.65 (8)	C25—C24—H24A	118.9
O6—La1—O3ⁱ	75.51 (8)	C24—C25—C26	122.1 (3)
O4—La1—O3ⁱ	70.62 (7)	C24—C25—C30	119.0 (3)
O2ⁱ—La1—O3ⁱ	47.91 (6)	C26—C25—C30	118.9 (3)
O2—La1—N1	91.57 (7)	C27—C26—C25	120.8 (3)
O5—La1—N1	134.60 (7)	C27—C26—H26A	119.6
O1—La1—N1	73.52 (7)	C25—C26—H26A	119.6
O6—La1—N1	83.64 (8)	C26—C27—C28	121.0 (3)
O4—La1—N1	71.68 (7)	C26—C27—H27A	119.5
O2ⁱ—La1—N1	145.95 (7)	C28—C27—H27A	119.5
O3ⁱ—La1—N1	142.16 (7)	C29—C28—C27	120.7 (3)
O2—La1—N2	78.12 (7)	C29—C28—H28A	119.7
O5—La1—N2	75.60 (7)	C27—C28—H28A	119.7
O1—La1—N2	123.19 (7)	C28—C29—C30	120.3 (3)
O6—La1—N2	75.71 (7)	C28—C29—H29A	119.8
O4—La1—N2	110.34 (7)	C30—C29—H29A	119.8
O2ⁱ—La1—N2	141.93 (7)	C17—C30—C29	122.9 (3)
O3ⁱ—La1—N2	140.02 (8)	C17—C30—C25	118.8 (3)
N1—La1—N2	59.30 (7)	C29—C30—C25	118.3 (3)
O2—La1—C16	167.67 (7)	O5ⁱ—C31—O1	124.4 (3)
O5—La1—C16	113.22 (8)	O5ⁱ—C31—C32	117.3 (2)
O1—La1—C16	105.56 (7)	O1—C31—C32	118.3 (2)
O6—La1—C16	25.37 (7)	C45—C32—C33	120.7 (3)
O4—La1—C16	26.01 (7)	C45—C32—C31	119.4 (3)
O2ⁱ—La1—C16	117.24 (7)	C33—C32—C31	119.9 (2)
O3ⁱ—La1—C16	71.17 (7)	C32—C33—C34	124.3 (3)
N1—La1—C16	76.45 (8)	C32—C33—C38	119.1 (3)
N2—La1—C16	93.00 (8)	C34—C33—C38	116.6 (3)
O2—La1—C1ⁱ	98.51 (7)	C35—C34—C33	121.4 (3)
O5—La1—C1ⁱ	74.95 (7)	C35—C34—H34A	119.3
O1—La1—C1ⁱ	82.90 (7)	C33—C34—H34A	119.3
O6—La1—C1ⁱ	99.13 (8)	C34—C35—C36	121.4 (3)
O4—La1—C1ⁱ	87.00 (8)	C34—C35—H35A	119.3
O2ⁱ—La1—C1ⁱ	24.33 (6)	C36—C35—H35A	119.3
O3ⁱ—La1—C1ⁱ	23.71 (7)	C37—C36—C35	119.1 (3)
N1—La1—C1ⁱ	150.44 (7)	C37—C36—H36A	120.4
N2—La1—C1ⁱ	150.03 (8)	C35—C36—H36A	120.4
C16—La1—C1ⁱ	93.44 (8)	C36—C37—C38	122.3 (3)
O2—La1—La1ⁱ	39.08 (4)	C36—C37—H37A	118.8
O5—La1—La1ⁱ	67.58 (5)	C38—C37—H37A	118.8
O1—La1—La1ⁱ	68.39 (4)	C39—C38—C37	121.7 (3)
O6—La1—La1ⁱ	152.12 (6)	C39—C38—C33	119.2 (3)
O4—La1—La1ⁱ	135.40 (5)	C37—C38—C33	119.1 (3)
O2ⁱ—La1—La1ⁱ	35.37 (4)	C40—C39—C38	122.3 (3)
O3ⁱ—La1—La1ⁱ	82.63 (4)	C40—C39—H39A	118.9
N1—La1—La1ⁱ	123.96 (5)	C38—C39—H39A	118.9
N2—La1—La1ⁱ	113.04 (5)	C39—C40—C41	120.3 (3)
C16—La1—La1ⁱ	152.43 (6)	C39—C40—C45	119.7 (3)
C1ⁱ—La1—La1ⁱ	59.52 (5)	C41—C40—C45	119.9 (3)
O3—C1—O2	120.6 (3)	C42—C41—C40	120.4 (4)
O3—C1—C2	121.4 (2)	C42—C41—H41A	119.8
O2—C1—C2	118.0 (2)	C40—C41—H41A	119.8
O3—C1—La1ⁱ	60.80 (16)	C41—C42—C43	120.2 (4)
O2—C1—La1ⁱ	60.37 (14)	C41—C42—H42A	119.9
C2—C1—La1ⁱ	172.5 (2)	C43—C42—H42A	119.9
C15—C2—C3	121.4 (3)	C44—C43—C42	121.9 (4)
C15—C2—C1	119.7 (3)	C44—C43—H43A	119.1
C3—C2—C1	119.0 (3)	C42—C43—H43A	119.1
C2—C3—C4	122.8 (3)	C43—C44—C45	121.1 (3)
C2—C3—C8	118.6 (3)	C43—C44—H44A	119.5
C4—C3—C8	118.6 (3)	C45—C44—H44A	119.5
C5—C4—C3	121.1 (4)	C32—C45—C44	124.5 (3)
C5—C4—H4A	119.4	C32—C45—C40	119.0 (3)
C3—C4—H4A	119.4	C44—C45—C40	116.5 (3)
C4—C5—C6	120.0 (4)	N2—C46—C47	123.7 (3)
C4—C5—H5A	120.0	N2—C46—H46A	118.2
C6—C5—H5A	120.0	C47—C46—H46A	118.2
C7—C6—C5	121.2 (4)	C48—C47—C46	118.6 (3)
C7—C6—H6A	119.4	C48—C47—H47A	120.7
C5—C6—H6A	119.4	C46—C47—H47A	120.7
C6—C7—C8	121.2 (4)	C47—C48—C49	119.2 (3)
C6—C7—H7A	119.4	C47—C48—H48A	120.4
C8—C7—H7A	119.4	C49—C48—H48A	120.4
C9—C8—C7	122.7 (3)	C48—C49—C50	119.8 (4)
C9—C8—C3	119.5 (3)	C48—C49—H49A	120.1
C7—C8—C3	117.9 (3)	C50—C49—H49A	120.1
C8—C9—C10	122.5 (3)	N2—C50—C49	121.2 (3)
C8—C9—H9A	118.8	N2—C50—C51	117.1 (3)
C10—C9—H9A	118.8	C49—C50—C51	121.7 (3)
C9—C10—C11	122.6 (3)	N1—C51—C52	120.4 (3)
C9—C10—C15	118.6 (3)	N1—C51—C50	117.1 (3)
C11—C10—C15	118.8 (3)	C52—C51—C50	122.5 (3)
C12—C11—C10	121.2 (4)	C53—C52—C51	119.9 (4)
C12—C11—H11A	119.4	C53—C52—H52A	120.1
C10—C11—H11A	119.4	C51—C52—H52A	120.1
C11—C12—C13	120.2 (4)	C54—C53—C52	119.7 (4)
C11—C12—H12A	119.9	C54—C53—H53A	120.2
C13—C12—H12A	119.9	C52—C53—H53A	120.2
C14—C13—C12	120.9 (4)	C53—C54—C55	118.3 (4)
C14—C13—H13A	119.6	C53—C54—H54A	120.8
C12—C13—H13A	119.6	C55—C54—H54A	120.8
C13—C14—C15	121.4 (3)	N1—C55—C54	123.2 (3)
C13—C14—H14A	119.3	N1—C55—H55A	118.4
C15—C14—H14A	119.3	C54—C55—H55A	118.4
C2—C15—C14	123.0 (3)	C55—N1—C51	118.5 (3)
C2—C15—C10	119.4 (3)	C55—N1—La1	117.7 (2)
C14—C15—C10	117.6 (3)	C51—N1—La1	123.5 (2)
O6—C16—O4	122.0 (2)	C46—N2—C50	117.5 (3)
O6—C16—C17	120.7 (3)	C46—N2—La1	119.7 (2)
O4—C16—C17	117.3 (3)	C50—N2—La1	122.81 (19)
O6—C16—La1	60.64 (14)	C31—O1—La1	137.62 (17)
O4—C16—La1	61.34 (14)	C1—O2—La1	157.44 (19)
C17—C16—La1	178.3 (2)	C1—O2—La1ⁱ	95.30 (17)
C18—C17—C30	121.5 (3)	La1—O2—La1ⁱ	105.56 (6)
C18—C17—C16	118.8 (3)	C1—O3—La1ⁱ	95.49 (17)
C30—C17—C16	119.5 (3)	C16—O4—La1	92.64 (16)
C17—C18—C19	123.1 (3)	C31ⁱ—O5—La1	141.40 (18)
C17—C18—C23	118.9 (3)	C16—O6—La1	93.99 (16)
C19—C18—C23	118.0 (3)

O3—C1—C2—C15	−92.3 (4)	C49—C50—C51—N1	−176.9 (3)
O2—C1—C2—C15	87.7 (3)	N2—C50—C51—C52	−175.9 (3)
O3—C1—C2—C3	88.3 (4)	C49—C50—C51—C52	4.0 (5)
O2—C1—C2—C3	−91.8 (3)	N1—C51—C52—C53	−0.5 (6)
C15—C2—C3—C4	−178.7 (3)	C50—C51—C52—C53	178.5 (4)
C1—C2—C3—C4	0.8 (4)	C51—C52—C53—C54	0.7 (7)
C15—C2—C3—C8	0.4 (4)	C52—C53—C54—C55	−0.6 (7)
C1—C2—C3—C8	179.9 (3)	C53—C54—C55—N1	0.1 (6)
C2—C3—C4—C5	178.7 (3)	C54—C55—N1—C51	0.1 (5)
C8—C3—C4—C5	−0.4 (5)	C54—C55—N1—La1	−173.1 (3)
C3—C4—C5—C6	0.8 (6)	C52—C51—N1—C55	0.1 (5)
C4—C5—C6—C7	−0.3 (7)	C50—C51—N1—C55	−179.0 (3)
C5—C6—C7—C8	−0.6 (7)	C52—C51—N1—La1	172.9 (3)
C6—C7—C8—C9	−179.2 (4)	C50—C51—N1—La1	−6.2 (4)
C6—C7—C8—C3	0.9 (6)	O2—La1—N1—C55	−107.2 (2)
C2—C3—C8—C9	0.5 (4)	O5—La1—N1—C55	−174.87 (19)
C4—C3—C8—C9	179.7 (3)	O1—La1—N1—C55	−35.3 (2)
C2—C3—C8—C7	−179.6 (3)	O6—La1—N1—C55	100.5 (2)
C4—C3—C8—C7	−0.5 (4)	O4—La1—N1—C55	49.1 (2)
C7—C8—C9—C10	179.3 (3)	O2ⁱ—La1—N1—C55	−43.2 (3)
C3—C8—C9—C10	−0.9 (5)	O3ⁱ—La1—N1—C55	44.1 (3)
C8—C9—C10—C11	178.5 (3)	N2—La1—N1—C55	177.6 (2)
C8—C9—C10—C15	0.2 (5)	C16—La1—N1—C55	75.7 (2)
C9—C10—C11—C12	−179.6 (3)	C1ⁱ—La1—N1—C55	3.2 (3)
C15—C10—C11—C12	−1.3 (5)	La1ⁱ—La1—N1—C55	−83.8 (2)
C10—C11—C12—C13	−0.2 (6)	O2—La1—N1—C51	79.9 (2)
C11—C12—C13—C14	1.2 (6)	O5—La1—N1—C51	12.2 (3)
C12—C13—C14—C15	−0.6 (5)	O1—La1—N1—C51	151.8 (2)
C3—C2—C15—C14	179.6 (3)	O6—La1—N1—C51	−72.4 (2)
C1—C2—C15—C14	0.1 (4)	O4—La1—N1—C51	−123.8 (2)
C3—C2—C15—C10	−1.1 (4)	O2ⁱ—La1—N1—C51	143.9 (2)
C1—C2—C15—C10	179.5 (2)	O3ⁱ—La1—N1—C51	−128.8 (2)
C13—C14—C15—C2	178.5 (3)	N2—La1—N1—C51	4.7 (2)
C13—C14—C15—C10	−0.8 (4)	C16—La1—N1—C51	−97.2 (2)
C9—C10—C15—C2	0.8 (4)	C1ⁱ—La1—N1—C51	−169.7 (2)
C11—C10—C15—C2	−177.6 (3)	La1ⁱ—La1—N1—C51	103.3 (2)
C9—C10—C15—C14	−179.9 (3)	C47—C46—N2—C50	−0.3 (5)
C11—C10—C15—C14	1.8 (4)	C47—C46—N2—La1	179.0 (3)
O2—La1—C16—O6	90.1 (4)	C49—C50—N2—C46	0.5 (4)
O5—La1—C16—O6	−29.0 (2)	C51—C50—N2—C46	−179.6 (3)
O1—La1—C16—O6	172.30 (19)	C49—C50—N2—La1	−178.8 (2)
O4—La1—C16—O6	179.9 (3)	C51—C50—N2—La1	1.1 (3)
O2ⁱ—La1—C16—O6	−109.4 (2)	O2—La1—N2—C46	78.9 (2)
O3ⁱ—La1—C16—O6	−95.9 (2)	O5—La1—N2—C46	3.4 (2)
N1—La1—C16—O6	104.0 (2)	O1—La1—N2—C46	139.4 (2)
N2—La1—C16—O6	46.6 (2)	O6—La1—N2—C46	−91.0 (2)
C1ⁱ—La1—C16—O6	−104.1 (2)	O4—La1—N2—C46	−129.7 (2)
La1ⁱ—La1—C16—O6	−114.7 (2)	O2ⁱ—La1—N2—C46	34.3 (3)
O2—La1—C16—O4	−89.8 (4)	O3ⁱ—La1—N2—C46	−45.9 (3)
O5—La1—C16—O4	151.05 (17)	N1—La1—N2—C46	177.9 (2)
O1—La1—C16—O4	−7.62 (19)	C16—La1—N2—C46	−109.8 (2)
O6—La1—C16—O4	−179.9 (3)	C1ⁱ—La1—N2—C46	−7.6 (3)
O2ⁱ—La1—C16—O4	70.66 (19)	La1ⁱ—La1—N2—C46	61.0 (2)
O3ⁱ—La1—C16—O4	84.21 (18)	O2—La1—N2—C50	−101.9 (2)
N1—La1—C16—O4	−75.91 (18)	O5—La1—N2—C50	−177.3 (2)
N2—La1—C16—O4	−133.33 (18)	O1—La1—N2—C50	−41.3 (2)
C1ⁱ—La1—C16—O4	75.96 (18)	O6—La1—N2—C50	88.2 (2)
La1ⁱ—La1—C16—O4	65.3 (2)	O4—La1—N2—C50	49.6 (2)
O6—C16—C17—C18	−84.6 (4)	O2ⁱ—La1—N2—C50	−146.37 (19)
O4—C16—C17—C18	94.2 (3)	O3ⁱ—La1—N2—C50	133.4 (2)
O6—C16—C17—C30	99.8 (4)	N1—La1—N2—C50	−2.8 (2)
O4—C16—C17—C30	−81.4 (4)	C16—La1—N2—C50	69.5 (2)
C30—C17—C18—C19	−177.4 (3)	C1ⁱ—La1—N2—C50	171.70 (19)
C16—C17—C18—C19	7.1 (5)	La1ⁱ—La1—N2—C50	−119.8 (2)
C30—C17—C18—C23	3.7 (4)	O5ⁱ—C31—O1—La1	−10.6 (5)
C16—C17—C18—C23	−171.8 (3)	C32—C31—O1—La1	168.53 (18)
C17—C18—C19—C20	−179.6 (4)	O2—La1—O1—C31	−35.7 (3)
C23—C18—C19—C20	−0.7 (6)	O5—La1—O1—C31	5.8 (3)
C18—C19—C20—C21	1.4 (7)	O6—La1—O1—C31	161.4 (3)
C19—C20—C21—C22	−1.2 (8)	O4—La1—O1—C31	153.7 (3)
C20—C21—C22—C23	0.2 (7)	O2ⁱ—La1—O1—C31	42.8 (3)
C21—C22—C23—C24	179.6 (4)	O3ⁱ—La1—O1—C31	84.8 (3)
C21—C22—C23—C18	0.5 (6)	N1—La1—O1—C31	−132.6 (3)
C17—C18—C23—C24	−0.4 (5)	N2—La1—O1—C31	−98.6 (3)
C19—C18—C23—C24	−179.4 (3)	C16—La1—O1—C31	157.1 (3)
C17—C18—C23—C22	178.7 (3)	C1ⁱ—La1—O1—C31	65.4 (3)
C19—C18—C23—C22	−0.3 (5)	La1ⁱ—La1—O1—C31	5.5 (3)
C22—C23—C24—C25	178.2 (3)	O3—C1—O2—La1	149.3 (4)
C18—C23—C24—C25	−2.7 (5)	C2—C1—O2—La1	−30.6 (6)
C23—C24—C25—C26	−179.3 (3)	La1ⁱ—C1—O2—La1	157.7 (5)
C23—C24—C25—C30	2.6 (4)	O3—C1—O2—La1ⁱ	−8.4 (3)
C24—C25—C26—C27	−179.1 (3)	C2—C1—O2—La1ⁱ	171.7 (2)
C30—C25—C26—C27	−1.0 (5)	O5—La1—O2—C1	128.1 (5)
C25—C26—C27—C28	−0.8 (6)	O1—La1—O2—C1	−80.7 (5)
C26—C27—C28—C29	2.1 (6)	O6—La1—O2—C1	71.0 (5)
C27—C28—C29—C30	−1.4 (5)	O4—La1—O2—C1	−61.1 (5)
C18—C17—C30—C29	177.2 (3)	O2ⁱ—La1—O2—C1	−156.9 (5)
C16—C17—C30—C29	−7.4 (4)	O3ⁱ—La1—O2—C1	−168.3 (5)
C18—C17—C30—C25	−3.8 (4)	N1—La1—O2—C1	−8.4 (5)
C16—C17—C30—C25	171.7 (3)	N2—La1—O2—C1	49.7 (5)
C28—C29—C30—C17	178.7 (3)	C16—La1—O2—C1	5.1 (7)
C28—C29—C30—C25	−0.4 (5)	C1ⁱ—La1—O2—C1	−160.5 (4)
C24—C25—C30—C17	0.6 (4)	La1ⁱ—La1—O2—C1	−156.9 (5)
C26—C25—C30—C17	−177.5 (3)	O5—La1—O2—La1ⁱ	−74.97 (7)
C24—C25—C30—C29	179.7 (3)	O1—La1—O2—La1ⁱ	76.26 (7)
C26—C25—C30—C29	1.6 (4)	O6—La1—O2—La1ⁱ	−132.12 (15)
O5ⁱ—C31—C32—C45	42.2 (4)	O4—La1—O2—La1ⁱ	95.82 (15)
O1—C31—C32—C45	−137.0 (3)	O2ⁱ—La1—O2—La1ⁱ	0.0
O5ⁱ—C31—C32—C33	−138.0 (3)	O3ⁱ—La1—O2—La1ⁱ	−11.37 (11)
O1—C31—C32—C33	42.8 (4)	N1—La1—O2—La1ⁱ	148.51 (8)
C45—C32—C33—C34	−179.2 (3)	N2—La1—O2—La1ⁱ	−153.33 (9)
C31—C32—C33—C34	0.9 (4)	C16—La1—O2—La1ⁱ	162.1 (3)
C45—C32—C33—C38	−0.4 (4)	C1ⁱ—La1—O2—La1ⁱ	−3.61 (8)
C31—C32—C33—C38	179.8 (3)	O2—C1—O3—La1ⁱ	8.3 (3)
C32—C33—C34—C35	−179.5 (3)	C2—C1—O3—La1ⁱ	−171.7 (2)
C38—C33—C34—C35	1.6 (5)	O6—C16—O4—La1	−0.1 (3)
C33—C34—C35—C36	0.4 (5)	C17—C16—O4—La1	−178.8 (2)
C34—C35—C36—C37	−1.6 (5)	O2—La1—O4—C16	153.53 (17)
C35—C36—C37—C38	0.8 (6)	O5—La1—O4—C16	−39.0 (2)
C36—C37—C38—C39	179.4 (3)	O1—La1—O4—C16	172.54 (19)
C36—C37—C38—C33	1.3 (5)	O6—La1—O4—C16	0.04 (17)
C32—C33—C38—C39	0.5 (4)	O2ⁱ—La1—O4—C16	−119.02 (18)
C34—C33—C38—C39	179.4 (3)	O3ⁱ—La1—O4—C16	−86.61 (18)
C32—C33—C38—C37	178.6 (3)	N1—La1—O4—C16	96.65 (18)
C34—C33—C38—C37	−2.4 (4)	N2—La1—O4—C16	50.78 (19)
C37—C38—C39—C40	−178.0 (3)	C1ⁱ—La1—O4—C16	−104.14 (18)
C33—C38—C39—C40	0.1 (5)	La1ⁱ—La1—O4—C16	−143.20 (15)
C38—C39—C40—C41	178.9 (3)	O2—La1—O5—C31ⁱ	46.3 (3)
C38—C39—C40—C45	−0.8 (5)	O1—La1—O5—C31ⁱ	4.8 (3)
C39—C40—C41—C42	−179.4 (4)	O6—La1—O5—C31ⁱ	−156.9 (3)
C45—C40—C41—C42	0.3 (6)	O4—La1—O5—C31ⁱ	−127.5 (3)
C40—C41—C42—C43	0.5 (7)	O2ⁱ—La1—O5—C31ⁱ	−32.5 (3)
C41—C42—C43—C44	−0.6 (7)	O3ⁱ—La1—O5—C31ⁱ	−81.9 (3)
C42—C43—C44—C45	0.0 (6)	N1—La1—O5—C31ⁱ	121.3 (3)
C33—C32—C45—C44	−178.0 (3)	N2—La1—O5—C31ⁱ	128.0 (3)
C31—C32—C45—C44	1.8 (4)	C16—La1—O5—C31ⁱ	−144.9 (3)
C33—C32—C45—C40	−0.2 (4)	C1ⁱ—La1—O5—C31ⁱ	−57.7 (3)
C31—C32—C45—C40	179.6 (3)	La1ⁱ—La1—O5—C31ⁱ	5.1 (3)
C43—C44—C45—C32	178.6 (3)	O4—C16—O6—La1	0.1 (3)
C43—C44—C45—C40	0.8 (5)	C17—C16—O6—La1	178.8 (2)
C39—C40—C45—C32	0.8 (5)	O2—La1—O6—C16	−152.95 (17)
C41—C40—C45—C32	−178.9 (3)	O5—La1—O6—C16	153.5 (2)
C39—C40—C45—C44	178.8 (3)	O1—La1—O6—C16	−9.8 (2)
C41—C40—C45—C44	−0.9 (5)	O4—La1—O6—C16	−0.04 (17)
N2—C46—C47—C48	−0.7 (5)	O2ⁱ—La1—O6—C16	85.2 (2)
C46—C47—C48—C49	1.5 (6)	O3ⁱ—La1—O6—C16	76.5 (2)
C47—C48—C49—C50	−1.4 (6)	N1—La1—O6—C16	−71.6 (2)
C48—C49—C50—N2	0.3 (5)	N2—La1—O6—C16	−131.5 (2)
C48—C49—C50—C51	−179.6 (3)	C1ⁱ—La1—O6—C16	78.7 (2)
N2—C50—C51—N1	3.2 (4)	La1ⁱ—La1—O6—C16	115.99 (18)

Symmetry code: (i) −x+1, −y+1, −z+1.

Experimental details

Crystal data
Chemical formula	[La₂(C₁₅H₉O₂)₆(C₁₀H₈N₂)₂]
M_r	1917.52
Crystal system, space group	Triclinic, P1
Temperature (K)	273
a, b, c (Å)	12.1038 (7), 13.4887 (8), 15.4568 (14)
α, β, γ (°)	113.036 (4), 103.257 (4), 102.913 (3)
V (Å³)	2117.7 (3)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	1.07
Crystal size (mm)	0.20 × 0.14 × 0.12

Data collection
Diffractometer	CCD area-detector
Absorption correction	Multi-scan (SADABS; Bruker, 1998)
T_min, T_max	0.815, 0.883
No. of measured, independent and observed [I > 2σ(I)] reflections	32552, 7432, 6474
R_int	0.045
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.029, 0.076, 1.05
No. of reflections	7432
No. of parameters	577
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.79, −0.86

Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1998), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1998), SHELXTL and PLATON (Spek, 2003).

Selected geometric parameters (Å, º) top

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

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

Symmetry code: (i) −x+1, −y+1, −z+1.

Acknowledgements

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.

References

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ISSN: 2056-9890

Volume 64| Part 1| January 2008| Pages m15-m16

https://doi.org/10.1107/S1600536807062241

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metal-organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

metal-organic compounds

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