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Acta Cryst. (2007). E63, m2069-m2070    [ doi:10.1107/S1600536807032059 ]

Poly[[tetraaquabis(5-carboxypyridine-2-carboxylato-[kappa]2N,O)bis([mu]4-pyridine-2,5-dicarboxylato-[kappa]5N,O:O:O':O'')dilanthanum(III)] dihydrate]

F. Zhang, B. Yu, X.-Q. Wang, G.-Q. Shen and D.-Z. Shen

Abstract top

The title compound, {[La2(C7H4NO4)2(C7H3NO4)2(H2O)4]·2H2O}n, was prepared by a hydrothermal reaction at 433 K. The asymmetric unit contains two LaIII ions. Each LaIII ion is nine-coordinated in a slightly distorted tricapped trigonal-prismatic coordination geometry, formed by two N atoms from 5-carboxypyridine-2-carboxylate (Hpydc) and pyridine-2,5-dicarboxylate (pydc) ligands, five O atoms from carboxylate groups of one Hpydc and four pydc ligands, and two water molecules. Adjacent LaIII ions are linked together through single bridging carboxylate O atoms and carboxylate groups in a syn-anti mode, forming a two-dimensional layered polymeric structure. Extensive O-H...O hydrogen bonding connects adjacent layers into an infinite three-dimensional supramolecular network structure. The crystal studied was an inversion twin.

Comment top

In recent years, studies on the syntheses, structures and properties of coordination complexes containing lanthanum and aromatic carboxylate have intensely attracted much attention, because they possess potential application on catalysis, separation, gas deposition and luminescence (Chae et al., 2004; Seo et al., 2000; Bradshaw et al., 2004; Lu et al., 2006). As a multi-functional ligand, pyridine-2,5-dicarboxylic acid has been widely used in the preparation of 3 d-4f heterometallic coordination polymers (Liang et al., 2000; Liang et al., 2001) and transition metallic supra-molecular compounds (Min et al., 2001; Xu et al., 2001; Gao et al., 2005). However the investigation on the lanthanum complexes is relative limited (Song et al., 2005). We report here the crystal structure of the title LaIII polymeric compound.

A segment of the polymeric structure of the title compound is illustrated in Fig. 1. Each LaIII ion is nine-coordinated by two nitrogen atoms from Hpydc and pydc ligands, five oxygen atoms from carboxylate groups of one Hpydc and four pydc ligands and two water molecules. The pydc2- anion acts as chelating-bridging pentadentate ligand towards four LaIII ions. The pyridine nitrogen atom and the ortho-carboxylic oxygen atom chelate one La ion, and this oxygen atom and other two carboxylic oxygen atoms of the pydc ligand bridge another three different La ions. The Hpydc- anion acts as chelating bidentate ligand towards the La ion with a pyridine nitrogen atom and the ortho carboxylic oxygen atom, which is similar to the coordination mode of Hpydc in [Dy(Hpydc)(pydc)(phen)(H2O).H2O]n [phen=1,10-phenanthroline] (Song et al., 2005) and [Ln(Hpydc)(pydc)] [Ln = Sm, Eu, Gd] (Qin et al., 2005). The La···La separations in the same unit and between adjacent units are 4.339 (9) and 5.619 (9) Å, respectively. The La center is in a slightly distorted tricapped trigonal prism coordination geometry. Adjacent La ions are linked together through single-atom carboxylate oxygen atom and carboxylate group in the syn-anti mode, forming a two-dimensional polymeric layer structure as represented in Fig. 2. Selected geometric parameters are listed in Table 1. The La—O bond lengths fall in range from 2.498 (10) to 2.658 (9) Å.

Extensive N—H···O and O—H···O hydrogen bonding occur in the crystal structure of the title compound, and connect adjacent layers into the infinite three-dimensional supramolecular network structure (Table 2 and Fig. 3).

Related literature top

For general background, see: Chae et al. (2004); Seo et al. (2000); Bradshaw et al. (2004); Lu et al. (2006); Liang et al. (2000, 2001); Min et al. (2001); Xu et al. (2001); Gao et al. (2005). For related structures, see: Song et al. (2005); Qin et al. (2005).

Experimental top

A mixture of La(NO3)3.6H2O (0.060 g, 0.25 mmol), pyridine-2,5-dicarboxylic acid (0.084 g, 0.50 mmol) and H2O (15 ml) was sealed in a 25 ml stainless steel reactor with a Teflon liner and heated at 433 K for 72 h. The mixture was cooled slowly to room temperature at a rate of 10 K.h-1. Straw yellow prism crystals of the title complex were collected by filtration and were obtained in 21% yield. Analysis calculated for C14H13LaN2O11 (%): C 32.08, H 2.50, N 5.34; found: C 32.11, H 2.53, N 5.36

Refinement top

Aromatic H atoms were placed in geometrically idealized positions with C—H = 0.93 Å and refined in the riding-model approximation with Uiso(H) = 1.2Ueq(C). Carboxyl H atoms were placed in calculated position with O—H = 0.82 Å and refined in riding mode with Uiso(H) = 1.5Ueq(O). Water H atoms were placed in calculated positions with O—H = 0.85 Å and refined in riding mode with Uiso(H) = 1.2Ueq(O). The highest peak and deepest hole appear at 1.22 Å from H14 and 0.83 Å from H21A, respectively.

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); 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, 1997); software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. The structure of the title compound with displacement ellipsoids drawn at the 50% probability level. H atoms have been omitted for clarity.
[Figure 2] Fig. 2. View of the two-dimensional network in the crystal structure of the title compound. H atoms and uncoordinated water molecules have been omitted.
[Figure 3] Fig. 3. View of the packing of the three-dimensional network of the title compound along the b axis (H atoms and uncoordinated water molecules have been omitted for clarity).
Poly[[tetraaquabis(5-carboxypyridine-2-carboxylato-κ2N,O)bis(µ4– pyridine-2,5-dicarboxylato-κ5N,O:O:O':O'')dilanthanum(III)] dihydrate] top
Crystal data top
[La2(C7H4NO4)2(C7H3NO4)2(H2O)4]·2H2OF(000) = 1024
Mr = 1048.35Dx = 2.088 Mg m−3
Monoclinic, P21Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ybCell parameters from 3211 reflections
a = 9.2203 (18) Åθ = 2.2–20.5°
b = 19.744 (4) ŵ = 2.63 mm−1
c = 9.3552 (19) ÅT = 293 K
β = 101.72 (3)°Prism, yellow
V = 1667.5 (6) Å30.35 × 0.34 × 0.27 mm
Z = 2
Data collection top
Bruker SMART CCD area-detector
diffractometer		5778 independent reflections
Radiation source: fine-focus sealed tube5491 reflections with I > 2σ(I)
graphiteRint = 0.093
φ and ω scansθmax = 25.0°, θmin = 3.0°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −10→10
Tmin = 0.428, Tmax = 0.490k = −23→23
12319 measured reflectionsl = −11→11
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.064H-atom parameters constrained
wR(F2) = 0.174 w = 1/[σ2(Fo2) + (0.0958P)2 + 9.9455P]
where P = (Fo2 + 2Fc2)/3
S = 1.06(Δ/σ)max = 0.001
5778 reflectionsΔρmax = 1.82 e Å−3
505 parametersΔρmin = −3.93 e Å−3
1 restraintAbsolute structure: Flack (1983), 2752 Friedel pairs
Primary atom site location: structure-invariant direct methodsFlack parameter: 0.50 (4)
Crystal data top
[La2(C7H4NO4)2(C7H3NO4)2(H2O)4]·2H2OV = 1667.5 (6) Å3
Mr = 1048.35Z = 2
Monoclinic, P21Mo Kα radiation
a = 9.2203 (18) ŵ = 2.63 mm−1
b = 19.744 (4) ÅT = 293 K
c = 9.3552 (19) Å0.35 × 0.34 × 0.27 mm
β = 101.72 (3)°
Data collection top
Bruker SMART CCD area-detector
diffractometer		5778 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		5491 reflections with I > 2σ(I)
Tmin = 0.428, Tmax = 0.490Rint = 0.093
12319 measured reflectionsθmax = 25.0°
Refinement top
R[F2 > 2σ(F2)] = 0.064H-atom parameters constrained
wR(F2) = 0.174Δρmax = 1.82 e Å−3
S = 1.06Δρmin = −3.93 e Å−3
5778 reflectionsAbsolute structure: Flack (1983), 2752 Friedel pairs
505 parametersFlack parameter: 0.50 (4)
1 restraint
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
xyzUiso*/Ueq
La10.46937 (8)0.05700 (3)0.39796 (8)0.0112 (2)
La20.28724 (8)0.07667 (3)0.93428 (8)0.0107 (2)
N10.5695 (13)−0.0629 (6)0.5397 (14)0.016 (3)
N2−0.2524 (13)0.0334 (6)0.3592 (13)0.014 (3)
N30.0116 (13)0.1009 (6)0.9728 (13)0.015 (3)
N40.1862 (13)0.1969 (6)0.7924 (13)0.014 (3)
O10.3674 (11)−0.0545 (5)0.2910 (11)0.015 (2)
O20.2676 (12)−0.1539 (5)0.3372 (12)0.024 (2)
O30.9397 (13)−0.0864 (6)0.8710 (13)0.024 (3)
O40.8767 (12)−0.1922 (5)0.9100 (13)0.026 (3)
H4B0.9385−0.18840.98600.038*
O50.2708 (11)0.0173 (5)0.5298 (11)0.014 (2)
O60.1288 (10)0.0513 (5)0.6871 (10)0.0148 (19)
O7−0.3646 (11)−0.0298 (6)0.0010 (12)0.021 (2)
O8−0.4868 (10)0.0364 (5)0.1292 (10)0.011 (2)
O90.4727 (13)0.2909 (5)1.0127 (13)0.029 (3)
O100.3905 (11)0.1868 (5)1.0408 (11)0.016 (2)
O11−0.1719 (12)0.2227 (5)0.4463 (12)0.020 (2)
O12−0.0761 (13)0.3223 (5)0.3902 (13)0.026 (3)
H12A−0.14760.32210.32180.040*
O130.2497 (11)0.0993 (5)1.2010 (11)0.015 (2)
O140.1265 (12)0.1662 (6)1.3299 (12)0.023 (2)
O15−0.3697 (10)0.0818 (5)0.6455 (10)0.0145 (19)
O16−0.5110 (11)0.1124 (5)0.7993 (11)0.017 (2)
O170.3846 (11)−0.0285 (5)0.8125 (11)0.016 (2)
H17A0.4683−0.03110.87050.019*
H17C0.3985−0.00530.74000.019*
O180.1967 (11)−0.0318 (5)1.0239 (11)0.016 (2)
H18A0.2358−0.04571.10900.019*
H18C0.1178−0.05420.99290.019*
O190.3764 (12)0.1608 (5)0.5188 (12)0.018 (2)
H19A0.28620.15730.47560.022*
H19B0.38690.14310.60310.022*
O200.5648 (11)0.1658 (5)0.3042 (12)0.019 (2)
H20A0.55040.15490.21450.022*
H20B0.65620.16060.34140.022*
O210.7230 (12)0.3388 (5)0.1594 (13)0.027 (3)
H21B0.64640.31900.11180.033*
H21C0.70030.37960.17340.033*
O220.1319 (14)0.7993 (6)0.0723 (16)0.040 (3)
H22A0.17750.81470.15400.048*
H22B0.17790.81190.00680.048*
C10.3653 (16)−0.1095 (7)0.3636 (16)0.016 (3)
C20.4906 (16)−0.1192 (7)0.4931 (16)0.015 (3)
C30.5209 (16)−0.1821 (8)0.5549 (17)0.017 (3)
H3A0.4613−0.21910.52050.021*
C40.6448 (16)−0.1899 (7)0.6723 (17)0.018 (3)
H4A0.6699−0.23180.71560.021*
C50.7253 (16)−0.1331 (7)0.7187 (17)0.016 (3)
C60.8590 (16)−0.1344 (7)0.8433 (17)0.017 (3)
C70.6853 (16)−0.0696 (8)0.6544 (16)0.016 (3)
H7A0.7393−0.03150.69130.019*
C80.1461 (15)0.0313 (7)0.5627 (16)0.014 (3)
C90.0120 (16)0.0184 (7)0.4480 (16)0.013 (3)
C100.0192 (16)−0.0138 (7)0.3160 (16)0.015 (3)
H10A0.1094−0.03020.30070.018*
C11−0.1064 (15)−0.0214 (7)0.2089 (17)0.014 (3)
H11A−0.1001−0.04310.12210.017*
C12−0.2384 (16)0.0021 (7)0.2280 (16)0.014 (3)
C13−0.3733 (15)0.0021 (7)0.1096 (16)0.014 (3)
C14−0.1313 (15)0.0397 (7)0.4643 (16)0.014 (3)
H14−0.14100.05900.55260.017*
C150.1360 (16)0.1339 (7)1.2190 (16)0.014 (3)
C16−0.0017 (16)0.1304 (7)1.0937 (16)0.013 (3)
C17−0.1335 (16)0.1583 (7)1.1211 (17)0.016 (3)
H17B−0.13600.18131.20730.019*
C18−0.2594 (16)0.1499 (7)1.0130 (16)0.014 (3)
H18B−0.35030.16651.02590.017*
C19−0.2479 (16)0.1164 (7)0.8852 (16)0.014 (3)
C20−0.3863 (15)0.1042 (7)0.7739 (16)0.013 (3)
C21−0.1135 (15)0.0917 (7)0.8690 (15)0.014 (3)
H21A−0.10750.06790.78460.017*
C220.3880 (16)0.2428 (7)0.9726 (16)0.017 (3)
C230.2723 (16)0.2512 (7)0.8339 (16)0.016 (3)
C240.2569 (17)0.3121 (7)0.7608 (17)0.018 (3)
H24A0.32190.34780.79110.022*
C250.1432 (17)0.3188 (7)0.6423 (17)0.017 (3)
H25A0.12940.35960.59170.021*
C260.0477 (16)0.2643 (7)0.5970 (16)0.015 (3)
C27−0.0788 (16)0.2672 (7)0.4702 (16)0.015 (3)
C280.0747 (16)0.2054 (7)0.6777 (16)0.015 (3)
H28A0.01090.16910.65030.018*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
La10.0075 (4)0.0194 (4)0.0072 (4)0.0004 (3)0.0030 (3)−0.0004 (3)
La20.0075 (4)0.0192 (4)0.0057 (4)0.0007 (3)0.0022 (3)−0.0004 (3)
N10.013 (6)0.022 (6)0.012 (7)0.001 (5)0.002 (5)0.000 (5)
N20.010 (6)0.024 (6)0.008 (6)0.002 (5)0.003 (5)−0.003 (5)
N30.012 (6)0.024 (6)0.008 (6)0.000 (5)0.002 (5)−0.001 (5)
N40.012 (6)0.023 (6)0.008 (6)0.000 (5)0.003 (5)0.001 (5)
O10.013 (5)0.024 (5)0.008 (5)0.001 (4)0.003 (4)0.001 (4)
O20.018 (6)0.032 (6)0.019 (6)−0.008 (5)−0.005 (5)0.002 (5)
O30.023 (6)0.026 (6)0.020 (6)−0.004 (5)−0.004 (5)−0.001 (5)
O40.022 (6)0.032 (6)0.018 (6)−0.003 (5)−0.005 (5)0.003 (4)
O50.011 (5)0.025 (5)0.009 (5)0.002 (4)0.005 (4)−0.001 (4)
O60.011 (4)0.024 (5)0.010 (5)0.001 (4)0.004 (4)−0.001 (4)
O70.012 (5)0.037 (6)0.011 (6)0.004 (5)−0.003 (4)−0.009 (5)
O80.003 (4)0.023 (5)0.007 (5)0.002 (3)−0.001 (4)−0.004 (4)
O90.023 (6)0.031 (6)0.028 (7)−0.007 (5)−0.006 (5)0.002 (5)
O100.014 (5)0.023 (5)0.010 (5)0.001 (4)0.001 (4)0.001 (4)
O110.013 (5)0.029 (6)0.015 (6)−0.001 (5)−0.002 (4)−0.002 (4)
O120.021 (6)0.035 (6)0.017 (6)−0.003 (5)−0.011 (5)0.009 (4)
O130.016 (5)0.023 (5)0.010 (5)−0.002 (4)0.008 (4)0.000 (4)
O140.017 (6)0.035 (6)0.016 (6)0.005 (5)0.001 (5)−0.012 (5)
O150.011 (5)0.024 (5)0.008 (5)0.002 (4)0.001 (4)−0.002 (4)
O160.011 (5)0.027 (5)0.012 (5)0.000 (4)0.002 (4)0.001 (4)
O170.014 (5)0.025 (5)0.009 (5)0.004 (4)0.004 (4)0.003 (4)
O180.012 (5)0.028 (5)0.010 (5)−0.005 (4)0.006 (4)0.003 (4)
O190.014 (5)0.028 (6)0.012 (6)0.003 (4)0.000 (4)0.002 (5)
O200.013 (5)0.030 (6)0.013 (6)−0.002 (4)0.001 (4)0.001 (4)
O210.022 (6)0.024 (5)0.030 (7)−0.005 (4)−0.009 (5)0.006 (5)
O220.034 (8)0.045 (7)0.036 (8)0.000 (6)−0.003 (6)−0.002 (6)
C10.012 (7)0.023 (7)0.011 (8)0.001 (6)0.003 (6)−0.001 (6)
C20.011 (7)0.023 (7)0.011 (8)0.000 (6)0.003 (6)0.001 (6)
C30.014 (8)0.024 (7)0.014 (8)0.000 (6)0.002 (6)0.001 (6)
C40.013 (8)0.026 (7)0.014 (8)0.001 (6)0.001 (6)0.001 (6)
C50.012 (7)0.024 (7)0.011 (7)0.001 (6)0.003 (6)0.001 (6)
C60.014 (8)0.025 (7)0.012 (8)0.003 (6)0.003 (6)0.001 (6)
C70.012 (7)0.024 (7)0.012 (8)0.001 (6)0.003 (6)0.000 (6)
C80.011 (7)0.023 (7)0.009 (7)0.001 (6)0.003 (6)0.000 (6)
C90.008 (7)0.024 (7)0.008 (7)0.000 (6)0.002 (6)0.000 (6)
C100.011 (7)0.024 (7)0.010 (7)0.000 (6)0.004 (6)−0.001 (6)
C110.010 (7)0.024 (7)0.008 (8)0.001 (5)0.003 (6)−0.002 (6)
C120.012 (7)0.023 (7)0.008 (7)−0.001 (6)0.000 (6)−0.005 (6)
C130.008 (7)0.023 (7)0.009 (8)−0.001 (5)0.002 (6)−0.001 (6)
C140.010 (7)0.024 (8)0.008 (7)−0.001 (5)0.003 (5)−0.002 (5)
C150.011 (7)0.022 (7)0.010 (8)−0.001 (5)0.002 (6)0.000 (6)
C160.010 (7)0.023 (7)0.007 (7)0.001 (6)0.005 (6)0.001 (5)
C170.013 (7)0.025 (7)0.011 (7)0.001 (6)0.003 (6)−0.001 (6)
C180.011 (7)0.024 (7)0.008 (7)−0.001 (6)0.004 (6)−0.001 (6)
C190.012 (7)0.023 (7)0.008 (7)−0.001 (6)0.004 (6)0.000 (6)
C200.010 (7)0.022 (6)0.008 (7)−0.001 (6)0.002 (6)0.003 (6)
C210.011 (7)0.024 (8)0.009 (7)0.001 (5)0.004 (5)−0.001 (5)
C220.013 (7)0.024 (7)0.013 (8)0.001 (6)0.002 (6)−0.002 (6)
C230.012 (7)0.024 (7)0.012 (8)0.001 (6)0.003 (6)−0.001 (6)
C240.015 (8)0.025 (7)0.013 (8)−0.002 (6)−0.001 (6)0.000 (6)
C250.015 (7)0.023 (7)0.012 (8)−0.001 (6)0.000 (6)0.002 (6)
C260.011 (7)0.024 (7)0.010 (7)0.000 (5)0.003 (6)−0.001 (6)
C270.012 (7)0.024 (7)0.010 (7)0.000 (6)0.003 (6)0.000 (5)
C280.012 (7)0.024 (7)0.010 (8)0.000 (6)0.003 (6)−0.001 (6)
Geometric parameters (Å, °) top
La1—O12.520 (10)O16—La2iv2.551 (10)
La1—O52.531 (10)O17—H17A0.8500
La1—O8i2.658 (9)O17—H17C0.8500
La1—O13ii2.584 (10)O18—H18A0.8500
La1—O15i2.531 (9)O18—H18C0.8500
La1—O192.570 (11)O19—H19A0.8500
La1—O202.543 (10)O19—H19B0.8501
La1—N12.778 (13)O20—H20A0.8500
La1—N2i2.703 (12)O20—H20B0.8500
La2—O62.522 (9)O21—H21B0.8500
La2—O8iii2.599 (9)O21—H21C0.8500
La2—O102.498 (10)O22—H22A0.8500
La2—O132.626 (10)O22—H22B0.8500
La2—O16i2.551 (10)C1—C21.51 (2)
La2—O172.613 (10)C2—C31.38 (2)
La2—O182.505 (10)C3—C41.42 (2)
La2—N32.681 (12)C3—H3A0.9300
La2—N42.786 (12)C4—C51.37 (2)
N1—C21.351 (19)C4—H4A0.9300
N1—C71.357 (19)C5—C71.41 (2)
N2—C141.335 (18)C5—C61.51 (2)
N2—C121.403 (19)C7—H7A0.9300
N2—La1iv2.703 (12)C8—C91.49 (2)
N3—C161.300 (19)C9—C101.40 (2)
N3—C211.361 (18)C9—C141.42 (2)
N4—C281.337 (19)C10—C111.38 (2)
N4—C231.344 (19)C10—H10A0.9300
O1—C11.282 (17)C11—C121.35 (2)
O2—C11.246 (18)C11—H11A0.9300
O3—C61.201 (18)C12—C131.488 (19)
O4—C61.296 (18)C14—H140.9300
O4—H4B0.8200C15—C161.545 (19)
O5—C81.279 (17)C16—C171.40 (2)
O6—C81.270 (17)C17—C181.39 (2)
O7—C131.211 (18)C17—H17B0.9300
O8—C131.290 (17)C18—C191.39 (2)
O8—La2v2.599 (9)C18—H18B0.9300
O8—La1iv2.658 (9)C19—C211.37 (2)
O9—C221.237 (18)C19—C201.494 (19)
O10—C221.276 (18)C21—H21A0.9300
O11—C271.216 (18)C22—C231.512 (19)
O12—C271.323 (18)C23—C241.38 (2)
O12—H12A0.8200C24—C251.37 (2)
O13—C151.291 (17)C24—H24A0.9300
O13—La1vi2.584 (10)C25—C261.40 (2)
O14—C151.237 (18)C25—H25A0.9300
O15—C201.317 (18)C26—C281.38 (2)
O15—La1iv2.531 (9)C26—C271.486 (19)
O16—C201.232 (18)C28—H28A0.9300
O1—La1—O571.0 (3)C15—O13—La2118.8 (9)
O1—La1—O15i129.4 (3)La1vi—O13—La2112.8 (4)
O5—La1—O15i87.8 (3)C20—O15—La1iv138.1 (8)
O1—La1—O20136.7 (3)C20—O16—La2iv149.6 (10)
O5—La1—O20139.9 (3)La2—O17—H17A96.8
O15i—La1—O2088.4 (3)La2—O17—H17C92.3
O1—La1—O19137.8 (3)H17A—O17—H17C106.2
O5—La1—O1972.1 (3)La2—O18—H18A118.8
O15i—La1—O1968.2 (3)La2—O18—H18C130.6
O20—La1—O1969.4 (4)H18A—O18—H18C108.8
O1—La1—O13ii79.9 (3)La1—O19—H19A96.2
O5—La1—O13ii84.7 (3)La1—O19—H19B95.5
O15i—La1—O13ii145.0 (3)H19A—O19—H19B108.9
O20—La1—O13ii76.0 (3)La1—O20—H20A97.6
O19—La1—O13ii76.9 (3)La1—O20—H20B98.1
O1—La1—O8i66.8 (3)H20A—O20—H20B108.5
O5—La1—O8i132.7 (3)H21B—O21—H21C108.2
O15i—La1—O8i136.2 (3)H22A—O22—H22B108.5
O20—La1—O8i70.9 (3)O2—C1—O1125.4 (13)
O19—La1—O8i131.8 (3)O2—C1—C2118.4 (13)
O13ii—La1—O8i67.8 (3)O1—C1—C2116.2 (12)
O1—La1—N2i94.8 (3)N1—C2—C3123.9 (13)
O5—La1—N2i144.3 (3)N1—C2—C1115.4 (12)
O15i—La1—N2i76.1 (3)C3—C2—C1120.7 (13)
O20—La1—N2i72.3 (3)C2—C3—C4118.9 (13)
O19—La1—N2i127.4 (3)C2—C3—H3A120.5
O13ii—La1—N2i126.0 (3)C4—C3—H3A120.5
O8i—La1—N2i61.0 (3)C5—C4—C3117.2 (14)
O1—La1—N160.4 (4)C5—C4—H4A121.4
O5—La1—N173.0 (3)C3—C4—H4A121.4
O15i—La1—N169.6 (3)C4—C5—C7121.1 (14)
O20—La1—N1141.2 (3)C4—C5—C6122.4 (13)
O19—La1—N1125.3 (4)C7—C5—C6116.5 (13)
O13ii—La1—N1138.8 (3)O3—C6—O4125.5 (14)
O8i—La1—N1102.8 (3)O3—C6—C5121.6 (13)
N2i—La1—N171.6 (4)O4—C6—C5112.8 (12)
O10—La2—O18137.5 (3)N1—C7—C5121.4 (14)
O10—La2—O6129.9 (3)N1—C7—H7A119.3
O18—La2—O688.1 (3)C5—C7—H7A119.3
O10—La2—O16i72.5 (3)O6—C8—O5125.1 (13)
O18—La2—O16i136.8 (3)O6—C8—C9118.3 (12)
O6—La2—O16i86.9 (3)O5—C8—C9116.5 (13)
O10—La2—O16i72.5 (3)C10—C9—C14116.1 (13)
O18—La2—O16i136.8 (3)C10—C9—C8122.1 (13)
O6—La2—O16i86.9 (3)C14—C9—C8121.8 (13)
O16i—La2—O16i0.0 (4)C11—C10—C9120.4 (14)
O10—La2—O8iii78.5 (3)C11—C10—H10A119.8
O18—La2—O8iii77.1 (3)C9—C10—H10A119.8
O6—La2—O8iii144.6 (3)C12—C11—C10121.0 (14)
O16i—La2—O8iii82.6 (3)C12—C11—H11A119.5
O16i—La2—O8iii82.6 (3)C10—C11—H11A119.5
O10—La2—O17136.8 (3)C11—C12—N2120.9 (13)
O18—La2—O1768.5 (4)C11—C12—C13122.8 (14)
O6—La2—O1768.2 (3)N2—C12—C13116.1 (12)
O16i—La2—O1769.8 (3)O7—C13—O8125.8 (13)
O16i—La2—O1769.8 (3)O7—C13—C12115.9 (13)
O8iii—La2—O1776.4 (3)O8—C13—C12118.2 (12)
O10—La2—O1365.6 (3)N2—C14—C9123.3 (13)
O18—La2—O1373.1 (3)N2—C14—H14118.4
O6—La2—O13137.9 (3)C9—C14—H14118.4
O16i—La2—O13132.3 (3)O14—C15—O13125.5 (13)
O16i—La2—O13132.3 (3)O14—C15—C16118.2 (13)
O8iii—La2—O1368.1 (3)O13—C15—C16116.2 (12)
O17—La2—O13132.3 (3)N3—C16—C17125.0 (14)
O10—La2—N394.9 (3)N3—C16—C15118.1 (13)
O18—La2—N373.6 (3)C17—C16—C15116.9 (13)
O6—La2—N376.7 (3)C18—C17—C16116.6 (14)
O16i—La2—N3145.4 (3)C18—C17—H17B121.7
O16i—La2—N3145.4 (3)C16—C17—H17B121.7
O8iii—La2—N3127.4 (3)C17—C18—C19119.0 (14)
O17—La2—N3128.3 (3)C17—C18—H18B120.5
O13—La2—N362.0 (3)C19—C18—H18B120.5
O10—La2—N460.8 (4)C21—C19—C18119.6 (14)
O18—La2—N4141.8 (3)C21—C19—C20122.0 (13)
O6—La2—N469.9 (3)C18—C19—C20118.2 (13)
O16i—La2—N474.7 (3)O16—C20—O15120.4 (13)
O16i—La2—N474.7 (3)O16—C20—C19122.9 (13)
O8iii—La2—N4137.6 (3)O15—C20—C19116.7 (12)
O17—La2—N4125.5 (4)N3—C21—C19121.9 (13)
O13—La2—N4102.2 (3)N3—C21—H21A119.0
N3—La2—N471.2 (4)C19—C21—H21A119.0
C2—N1—C7117.4 (13)O9—C22—O10124.5 (14)
C2—N1—La1116.2 (9)O9—C22—C23117.9 (13)
C7—N1—La1126.4 (10)O10—C22—C23117.5 (12)
C14—N2—C12118.3 (12)N4—C23—C24124.0 (14)
C14—N2—La1iv124.0 (9)N4—C23—C22115.7 (13)
C12—N2—La1iv116.8 (8)C24—C23—C22120.4 (13)
C16—N3—C21117.7 (12)C25—C24—C23118.1 (14)
C16—N3—La2117.2 (9)C25—C24—H24A120.9
C21—N3—La2124.7 (9)C23—C24—H24A120.9
C28—N4—C23116.4 (13)C24—C25—C26120.2 (14)
C28—N4—La2128.1 (10)C24—C25—H25A119.9
C23—N4—La2114.9 (9)C26—C25—H25A119.9
C1—O1—La1125.0 (9)C28—C26—C25116.7 (13)
C6—O4—H4B109.5C28—C26—C27119.5 (13)
C8—O5—La1145.6 (9)C25—C26—C27123.7 (13)
C8—O6—La2138.2 (8)O11—C27—O12125.6 (13)
C13—O8—La2v128.2 (8)O11—C27—C26122.0 (13)
C13—O8—La1iv119.9 (8)O12—C27—C26112.4 (12)
La2v—O8—La1iv111.2 (3)N4—C28—C26124.6 (14)
C22—O10—La2126.1 (9)N4—C28—H28A117.7
C27—O12—H12A109.5C26—C28—H28A117.7
C15—O13—La1vi128.2 (9)
O1—La1—N1—C2−12.5 (9)La1—O1—C1—O2146.7 (12)
O5—La1—N1—C264.9 (10)La1—O1—C1—C2−31.7 (17)
O15i—La1—N1—C2159.0 (11)C7—N1—C2—C30(2)
O20—La1—N1—C2−141.6 (10)La1—N1—C2—C3−177.3 (12)
O19—La1—N1—C2117.4 (10)C7—N1—C2—C1−178.7 (13)
O13ii—La1—N1—C24.7 (13)La1—N1—C2—C14.0 (16)
O8i—La1—N1—C2−66.2 (11)O2—C1—C2—N1−162.9 (14)
N2i—La1—N1—C2−119.4 (11)O1—C1—C2—N115.6 (19)
O1—La1—N1—C7170.5 (13)O2—C1—C2—C318 (2)
O5—La1—N1—C7−112.0 (12)O1—C1—C2—C3−163.1 (14)
O15i—La1—N1—C7−18.0 (11)N1—C2—C3—C4−2(2)
O20—La1—N1—C741.5 (14)C1—C2—C3—C4176.8 (13)
O19—La1—N1—C7−59.6 (13)C2—C3—C4—C51(2)
O13ii—La1—N1—C7−172.3 (10)C3—C4—C5—C71(2)
O8i—La1—N1—C7116.9 (12)C3—C4—C5—C6179.6 (13)
N2i—La1—N1—C763.6 (11)C4—C5—C6—O3170.4 (15)
O10—La2—N3—C16−39.9 (11)C7—C5—C6—O3−11 (2)
O18—La2—N3—C1698.3 (11)C4—C5—C6—O4−8(2)
O6—La2—N3—C16−169.8 (11)C7—C5—C6—O4170.9 (14)
O16i—La2—N3—C16−105.9 (11)C2—N1—C7—C52(2)
O16i—La2—N3—C16−105.9 (11)La1—N1—C7—C5179.4 (11)
O8iii—La2—N3—C1639.4 (12)C4—C5—C7—N1−3(2)
O17—La2—N3—C16142.4 (10)C6—C5—C7—N1178.4 (13)
O13—La2—N3—C1619.0 (10)La2—O6—C8—O50(2)
N4—La2—N3—C16−96.7 (11)La2—O6—C8—C9175.4 (9)
O10—La2—N3—C21132.3 (10)La1—O5—C8—O6−104.4 (18)
O18—La2—N3—C21−89.5 (10)La1—O5—C8—C979.9 (19)
O6—La2—N3—C212.4 (10)O6—C8—C9—C10−169.6 (13)
O16i—La2—N3—C2166.3 (12)O5—C8—C9—C106(2)
O16i—La2—N3—C2166.3 (12)O6—C8—C9—C1412 (2)
O8iii—La2—N3—C21−148.4 (9)O5—C8—C9—C14−172.0 (13)
O17—La2—N3—C21−45.4 (12)C14—C9—C10—C112(2)
O13—La2—N3—C21−168.8 (11)C8—C9—C10—C11−176.3 (13)
N4—La2—N3—C2175.5 (10)C9—C10—C11—C120(2)
O10—La2—N4—C28−172.5 (13)C10—C11—C12—N2−2(2)
O18—La2—N4—C28−41.6 (15)C10—C11—C12—C13172.9 (14)
O6—La2—N4—C2816.9 (11)C14—N2—C12—C111(2)
O16i—La2—N4—C28109.2 (12)La1iv—N2—C12—C11−169.3 (11)
O16i—La2—N4—C28109.2 (12)C14—N2—C12—C13−174.5 (12)
O8iii—La2—N4—C28169.3 (10)La1iv—N2—C12—C1315.7 (15)
O17—La2—N4—C2858.7 (13)La2v—O8—C13—O7−16 (2)
O13—La2—N4—C28−119.8 (12)La1iv—O8—C13—O7153.7 (12)
N3—La2—N4—C28−65.4 (12)La2v—O8—C13—C12162.2 (9)
O10—La2—N4—C2316.5 (10)La1iv—O8—C13—C12−27.8 (16)
O18—La2—N4—C23147.4 (9)C11—C12—C13—O711 (2)
O6—La2—N4—C23−154.0 (11)N2—C12—C13—O7−174.1 (13)
O16i—La2—N4—C23−61.7 (10)C11—C12—C13—O8−167.7 (14)
O16i—La2—N4—C23−61.7 (10)N2—C12—C13—O87.3 (19)
O8iii—La2—N4—C23−1.6 (13)C12—N2—C14—C92(2)
O17—La2—N4—C23−112.3 (10)La1iv—N2—C14—C9171.2 (10)
O13—La2—N4—C2369.2 (11)C10—C9—C14—N2−4(2)
N3—La2—N4—C23123.7 (11)C8—C9—C14—N2175.0 (13)
O5—La1—O1—C1−56.9 (11)La1vi—O13—C15—O1417 (2)
O15i—La1—O1—C113.5 (12)La2—O13—C15—O14−155.8 (12)
O20—La1—O1—C1158.6 (10)La1vi—O13—C15—C16−158.9 (9)
O19—La1—O1—C1−87.4 (11)La2—O13—C15—C1628.0 (15)
O13ii—La1—O1—C1−144.7 (11)C21—N3—C16—C17−5(2)
O8i—La1—O1—C1145.2 (11)La2—N3—C16—C17167.4 (12)
N2i—La1—O1—C189.5 (11)C21—N3—C16—C15173.2 (12)
N1—La1—O1—C123.8 (10)La2—N3—C16—C15−14.0 (16)
O1—La1—O5—C8−120.5 (16)O14—C15—C16—N3174.7 (14)
O15i—La1—O5—C8106.3 (16)O13—C15—C16—N3−8.8 (19)
O20—La1—O5—C821.3 (18)O14—C15—C16—C17−7(2)
O19—La1—O5—C838.4 (16)O13—C15—C16—C17169.9 (13)
O13ii—La1—O5—C8−39.5 (16)N3—C16—C17—C184(2)
O8i—La1—O5—C8−92.5 (16)C15—C16—C17—C18−174.7 (13)
N2i—La1—O5—C8168.6 (15)C16—C17—C18—C19−1(2)
N1—La1—O5—C8175.6 (17)C17—C18—C19—C211(2)
O10—La2—O6—C895.6 (14)C17—C18—C19—C20176.4 (13)
O18—La2—O6—C8−105.5 (13)La2iv—O16—C20—O15110.5 (19)
O16i—La2—O6—C831.6 (13)La2iv—O16—C20—C19−67 (2)
O16i—La2—O6—C831.6 (13)La1iv—O15—C20—O168(2)
O8iii—La2—O6—C8−41.0 (16)La1iv—O15—C20—C19−174.1 (9)
O17—La2—O6—C8−37.9 (13)C21—C19—C20—O16163.5 (14)
O13—La2—O6—C8−167.5 (12)C18—C19—C20—O16−12 (2)
N3—La2—O6—C8−179.1 (14)C21—C19—C20—O15−15 (2)
N4—La2—O6—C8106.4 (14)C18—C19—C20—O15170.0 (13)
O18—La2—O10—C22−156.8 (11)C16—N3—C21—C194(2)
O6—La2—O10—C22−9.0 (13)La2—N3—C21—C19−167.7 (10)
O16i—La2—O10—C2261.3 (11)C18—C19—C21—N3−2(2)
O16i—La2—O10—C2261.3 (11)C20—C19—C21—N3−177.7 (12)
O8iii—La2—O10—C22147.1 (12)La2—O10—C22—O9−158.6 (12)
O17—La2—O10—C2291.6 (12)La2—O10—C22—C2322.0 (18)
O13—La2—O10—C22−141.9 (12)C28—N4—C23—C24−4(2)
N3—La2—O10—C22−85.8 (12)La2—N4—C23—C24168.3 (12)
N4—La2—O10—C22−20.6 (11)C28—N4—C23—C22174.1 (12)
O10—La2—O13—C1585.7 (10)La2—N4—C23—C22−13.8 (16)
O18—La2—O13—C15−104.7 (9)O9—C22—C23—N4178.0 (14)
O6—La2—O13—C15−37.5 (11)O10—C22—C23—N4−3(2)
O16i—La2—O13—C15116.3 (9)O9—C22—C23—C24−4(2)
O16i—La2—O13—C15116.3 (9)O10—C22—C23—C24175.3 (14)
O8iii—La2—O13—C15172.6 (10)N4—C23—C24—C253(2)
O17—La2—O13—C15−142.4 (9)C22—C23—C24—C25−175.0 (14)
N3—La2—O13—C15−24.7 (9)C23—C24—C25—C26−1(2)
N4—La2—O13—C1536.0 (10)C24—C25—C26—C280(2)
O10—La2—O13—La1vi−88.4 (4)C24—C25—C26—C27179.6 (14)
O18—La2—O13—La1vi81.1 (4)C28—C26—C27—O1110 (2)
O6—La2—O13—La1vi148.4 (4)C25—C26—C27—O11−169.3 (15)
O16i—La2—O13—La1vi−57.8 (5)C28—C26—C27—O12−169.6 (13)
O16i—La2—O13—La1vi−57.8 (5)C25—C26—C27—O1211 (2)
O8iii—La2—O13—La1vi−1.5 (4)C23—N4—C28—C263(2)
O17—La2—O13—La1vi43.5 (6)La2—N4—C28—C26−167.7 (11)
N3—La2—O13—La1vi161.2 (5)C25—C26—C28—N4−1(2)
N4—La2—O13—La1vi−138.1 (4)C27—C26—C28—N4179.2 (13)
Symmetry codes: (i) x+1, y, z; (ii) x, y, z−1; (iii) x+1, y, z+1; (iv) x−1, y, z; (v) x−1, y, z−1; (vi) x, y, z+1.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O22—H22B···O21vii0.852.032.88 (2)176
O22—H22A···O2viii0.851.852.702 (17)177
O21—H21C···O17ix0.851.992.833 (15)171
O21—H21B···O9ii0.851.772.612 (15)171
O20—H20B···O11i0.852.092.759 (14)136
O20—H20A···O8i0.852.473.020 (14)123
O20—H20A···O10ii0.852.062.687 (14)130
O19—H19B···O16i0.851.982.787 (15)158
O19—H19A···O14ii0.851.802.605 (15)157
O18—H18C···O3iv0.851.912.728 (15)162
O18—H18A···O1vi0.851.892.706 (14)161
O17—H17C···O16i0.852.492.955 (14)115
O17—H17C···O50.852.122.791 (14)135
O17—H17A···O7iii0.851.762.608 (14)174
O12—H12A···O21iv0.821.762.564 (15)166
O4—H4B···O22x0.821.822.534 (14)145
Symmetry codes: (vii) −x+1, y+1/2, −z; (viii) x, y+1, z; (ix) −x+1, y+1/2, −z+1; (ii) x, y, z−1; (i) x+1, y, z; (iv) x−1, y, z; (vi) x, y, z+1; (iii) x+1, y, z+1; (x) x+1, y−1, z+1.
Table 1
Selected geometric parameters (Å) top
La1—O12.520 (10)La2—O62.522 (9)
La1—O52.531 (10)La2—O8iii2.599 (9)
La1—O8i2.658 (9)La2—O102.498 (10)
La1—O13ii2.584 (10)La2—O132.626 (10)
La1—O15i2.531 (9)La2—O16i2.551 (10)
La1—O192.570 (11)La2—O172.613 (10)
La1—O202.543 (10)La2—O182.505 (10)
La1—N12.778 (13)La2—N32.681 (12)
La1—N2i2.703 (12)La2—N42.786 (12)
Symmetry codes: (i) x+1, y, z; (ii) x, y, z−1; (iii) x+1, y, z+1.
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O22—H22B···O21iv0.852.032.88 (2)176
O22—H22A···O2v0.851.852.702 (17)177
O21—H21C···O17vi0.851.992.833 (15)171
O21—H21B···O9ii0.851.772.612 (15)171
O20—H20B···O11i0.852.092.759 (14)136
O20—H20A···O8i0.852.473.020 (14)123
O20—H20A···O10ii0.852.062.687 (14)130
O19—H19B···O16i0.851.982.787 (15)158
O19—H19A···O14ii0.851.802.605 (15)157
O18—H18C···O3vii0.851.912.728 (15)162
O18—H18A···O1viii0.851.892.706 (14)161
O17—H17C···O16i0.852.492.955 (14)115
O17—H17C···O50.852.122.791 (14)135
O17—H17A···O7iii0.851.762.608 (14)174
O12—H12A···O21vii0.821.762.564 (15)166
O4—H4B···O22ix0.821.822.534 (14)145
Symmetry codes: (iv) −x+1, y+1/2, −z; (v) x, y+1, z; (vi) −x+1, y+1/2, −z+1; (ii) x, y, z−1; (i) x+1, y, z; (vii) x−1, y, z; (viii) x, y, z+1; (iii) x+1, y, z+1; (ix) x+1, y−1, z+1.
Acknowledgements top

We acknowledge financial support by the National Natural Science Foundation of China (No. 50590402).

references
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