Poly[[tetra­aqua­bis­(μ3-pyridine-2,6-dicarboxyl­ato)(μ2-pyridine-2,6-dicarboxyl­ato)dilanthanum(III)] dihydrate]

Lush, S.F.; Shen, F.M.

doi:10.1107/S1600536811030807

metal-organic compounds

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ISSN: 2056-9890

Volume 67| Part 9| September 2011| Pages m1195-m1196

doi:10.1107/S1600536811030807

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Poly[[tetraaquabis(μ₃-pyridine-2,6-dicarboxylato)(μ₂-pyridine-2,6-dicarboxylato)dilanthanum(III)] dihydrate]

Shie Fu Lush ^a and Fwu Ming Shen ^b ^*

^aDepartment of General Education Center, Yuanpei University, HsinChu 30015, Taiwan, and ^bDepartment of Biotechnology, Yuanpei University, No. 306 Yuanpei St, HsinChu 30015 Taiwan
^*Correspondence e-mail: fmshen@mail.ypu.edu.tw

(Received 11 July 2011; accepted 1 August 2011; online 6 August 2011)

There are two independent La^III cations in the polymeric title compound, {[La₂(C₇H₃NO₄)₃(H₂O)₄]·2H₂O}_n. One is nine-coordinated in an LaN₂O₇ tricapped trigonal–prismatic geometry formed by three pyridine-2,6-dicarboxylate anions and two water molecules, while the other is ten-coordinated in an LaNO₉ bicapped square-antiprismatic geometry formed by four pyridine-2,6-dicarboxylate anions and two water molecules. The two La^III cations are separated by a non-bonding distance of 5.026 (3) Å. The pyridine-2,6-dicarboxylate anions bridge the La^III cations, forming a three-dimensional polymeric complex. The crystal structure contains extensive classical O—H⋯O hydrogen bonds and weak intermolecular C—H⋯O hydrogen bonds. The crystal structure is further consolidated by π–π stacking between pyridine rings, the shortest centroid–centroid distance between parallel pyridine rings being 3.700 (5) Å.

Related literature

For applications of lanthanide metal carboxylate systems in supramolecular chemistry and functional materials, see: Yang et al. (2011 ); Chantal et al. (2008 ). For similar structures, see: Brouca et al. (2002 ); Ghosh & Bharadwaj (2004 ).

Experimental

Crystal data

[La₂(C₇H₃NO₄)₃(H₂O)₄]·2H₂O
M_r = 881.23
Triclinic, $[P \overline 1]$
a = 10.4910 (2) Å
b = 10.9197 (2) Å
c = 13.0850 (3) Å
α = 77.915 (1)°
β = 76.702 (1)°
γ = 86.049 (1)°
V = 1426.14 (5) Å³
Z = 2
Mo Kα radiation
μ = 3.04 mm⁻¹
T = 293 K
0.17 × 0.13 × 0.11 mm

Data collection

Nonius KappaCCD diffractometer
Absorption correction: multi-scan (SCALEPACK; Otwinowski & Minor, 1997 ) T_min = 0.592, T_max = 0.699
10097 measured reflections
4496 independent reflections
4014 reflections with I > 2σ(I)
R_int = 0.059

Refinement

R[F² > 2σ(F²)] = 0.045
wR(F²) = 0.126
S = 1.03
4496 reflections
398 parameters
H-atom parameters constrained
Δρ_max = 3.36 e Å⁻³
Δρ_min = −1.06 e Å⁻³

Table 1
Selected bond lengths (Å)

La1—N1	2.644 (5)
La1—N2ⁱ	2.728 (6)
La1—O1	2.502 (5)
La1—O3	2.614 (5)
La1—O8ⁱ	2.575 (5)
La1—O11ⁱ	2.578 (5)
La1—O11ⁱⁱ	2.600 (5)
La1—O13	2.593 (5)
La1—O14	2.525 (5)
La2—N3ⁱⁱⁱ	2.688 (6)
La2—O3	2.674 (5)
La2—O4	2.605 (5)
La2—O5	2.865 (6)
La2—O6	2.591 (5)
La2—O6ⁱⁱⁱ	2.615 (5)
La2—O7	2.524 (5)
La2—O10ⁱⁱⁱ	2.539 (5)
La2—O15	2.574 (5)
La2—O16	2.575 (6)
Symmetry codes: (i) -x+1, -y, -z; (ii) x, y, z+1; (iii) -x+1, -y+1, -z.

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O13—H13A⋯O5	0.85	2.04	2.766 (8)	143
O13—H13B⋯O1^iv	0.85	1.91	2.721 (7)	160
O14—H14A⋯O5	0.97	2.23	3.062 (8)	143
O14—H14B⋯O9^v	0.83	2.44	3.225 (10)	160
O14—H14B⋯O10^v	0.83	2.22	2.712 (8)	119
O15—H15A⋯O7ⁱⁱⁱ	0.85	2.14	2.948 (8)	160
O15—H15B⋯O12ⁱⁱ	0.85	2.16	2.849 (7)	138
O16—H16A⋯O8	0.85	2.12	2.760 (8)	132
O16—H16B⋯O17ⁱⁱⁱ	0.85	2.05	2.843 (15)	155
O17—H17A⋯O9^vi	0.82	2.13	2.816 (17)	141
O17—H17B⋯O9^vii	0.82	2.39	2.758 (15)	108
O18—H18A⋯O2^viii	0.82	2.31	2.75 (2)	114
O18—H18B⋯O18^ix	0.88	2.46	2.89 (3)	110
C11—H11⋯O2^x	0.93	2.45	3.320 (11)	155
C12—H12⋯O18^xi	0.93	2.51	3.36 (2)	152
Symmetry codes: (ii) x, y, z+1; (iii) -x+1, -y+1, -z; (iv) -x+1, -y, -z+1; (v) x, y-1, z; (vi) -x+1, -y+2, -z; (vii) x-1, y, z; (viii) -x, -y, -z+1; (ix) -x, -y+1, -z+1; (x) x, y+1, z-1; (xi) x, y, z-1.

Data collection: COLLECT (Nonius, 2000 ); cell refinement: SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO (Otwinowski & Minor, 1997) and SCALEPACK; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009 ); software used to prepare material for publication: PLATON.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811030807/xu5269sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811030807/xu5269Isup2.hkl

checkCIF report

Comment top

Pyridine-2,6-dicarboxylic acid (pydH₂) and its deprotonated anion behave as multifunctional ligands to act as bridging ligands in metal complexes with five coordination sites involving the oxygen atoms of the carboxylate groups and the nitrogen atom of the pyridine ring. In recent years, the chemistry of lanthanide metal carboxylate systems is of great interest because of their extensive usage in supramolecular chemistry and functional materials (Brouca et al. 2002; Ghosh et al. 2004; Yang et al. 2011; Chantal et al. 2008). Here, we report a new La^III complex with pyridine-2,6-dicarboxylic acid, [[La₂(pyd)₃(H₂O)₄].2H₂O]_n, from hydrothermal reaction.

The structure of the title compound is shown as Fig 1. There are two independent La^III ions where La(1) is nine coordinated with N₂O₇ donors sets to form tricapped trigonal prism geometries, where La(2) is ten coordinated with NO₉ donor sets to from bicapped square antiprisms geometries. The selected bond lengths (Å) of title compound are listed in Table 2. The La^III—O and La^III—N distances are similar to those found in other La^III complex (Brouca, et al.2002; Ghosh, et al. 2004). The bond distances and bond angles in the ligand moiety are within normal ranges.

The structure consists of two types of ligand-binding modes contributing to link the LaO₅N₂(H₂O)₂ and LaO₇N(H₂O)₂ polyhedral chains to three-dimensional network. This network can be described in terms of a 20-membered ring related to each other by the intermediate C8 carboxylate group. It results in a La1—La1 distance equal to 4.440 (1) Å. A projection of one 20-membered ring along x axis is shown in Fig. 2. Rings built from eight lanthanum atoms can be seen. In these rings, long La—La distances are found:La1—La2 = 6.190 (3) Å through C8 carboxylate group of pda1, La1—La2 =5.026 (3) Å through C7 carboxylate group of pda2. The La2—La2 distance through theµ-O6 atom is apart from the others with the shortest value of 4.514 (2) Å.

In the title crystal structure stabilized via O—H···O and weak C—H···O hydrogen bonds (Fig.3) (full details and symmetry codes are given in Table 3). The π–π stacking interaction is also observed, the centroid···centroid distance between the parallel aryl ring being 3.969 (4)Å and 3.700 (5) Å [Cg2^vi···Cg2(N2/C9—C13), Cg3^vii···Cg3(N3/C16—C20)] (symmetry code: (vi)1-X, 1-Y, 1-Z,(vii) 2-X, 1-Y, –Z). C1—O2···Cg1^viii((N1/C2—C6) is 3.892 (6) Å((viii) –X, –Y, 1-Z).

Related literature top

For applications of lanthanide metal carboxylate systems in supramolecular chemistry and functional materials, see: Yang et al. (2011); Chantal et al. (2008). For similar structures, see: Brouca et al. (2002); Ghosh & Bharadwaj (2004).

Experimental top

LaCl₃.6H₂O (0.0899 g, 0.25 mmol), pydridine-2,6-dicarboxylic acid (0.0418 g, 0.25 mmol) and 1,2-bis(4-pyridyl)ethane were mixed in 10 ml of deionized water. After stirring for 30 min, the mixture was placed in a 23 ml Teflon-lined reactor, heated at 453 K for 72 h, then cooled slowly to room temperature. The colorless transparent single crystals of the title compound were obtained in 35.10% yield (based on La).

Computing details top

Data collection: COLLECT (Nonius, 2000); cell refinement: SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO and SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: PLATON (Spek, 2009).

Figures top

	Fig. 1. View of the title compound with the atom numbering scheme. Displacement ellipsoids for non-H atoms are drawn at the 50% probability level. H atoms have been omitted for clarity [symmetry code:(i) x, y, z + 1; (ii) -x + 1, -y, -z; (iii) -x + 1, -y + 1, -z].
	Fig. 2. Perspective view of carboxylate-bridged-metal rings of La₈C₂O₁₀.
	Fig. 3. The molecular packing for the title compound, viewed along the a axis. Hydrogen bonds are shown as dashed lines.

Poly[[tetraaquabis(µ₃-pyridine-2,6-dicarboxylato)(µ₂-pyridine- 2,6-dicarboxylato)dilanthanum(III)] dihydrate] top

Crystal data top

[La₂(C₇H₃NO₄)₃(H₂O)₄]·2H₂O	Z = 2
M_r = 881.23	F(000) = 852
Triclinic, P1	D_x = 2.052 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 10.4910 (2) Å	Cell parameters from 11712 reflections
b = 10.9197 (2) Å	θ = 2.0–25.4°
c = 13.0850 (3) Å	µ = 3.04 mm⁻¹
α = 77.915 (1)°	T = 293 K
β = 76.702 (1)°	Prism, colorless
γ = 86.049 (1)°	0.17 × 0.13 × 0.11 mm
V = 1426.14 (5) Å³

Data collection top

Nonius KappaCCD diffractometer	4496 independent reflections
Radiation source: fine-focus sealed tube	4014 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.059
Detector resolution: 9 pixels mm^-1	θ_max = 24.2°, θ_min = 2.8°
ω/2θ scans	h = −12→11
Absorption correction: multi-scan (SCALEPACK; Otwinowski & Minor, 1997)	k = −12→12
T_min = 0.592, T_max = 0.699	l = −14→15
10097 measured reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.045	H-atom parameters constrained
wR(F²) = 0.126	w = 1/[σ²(F_o²) + (0.0734P)² + 6.7391P] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max = 0.001
4496 reflections	Δρ_max = 3.36 e Å⁻³
398 parameters	Δρ_min = −1.06 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=KFc[1+0.001Fc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0024 (7)

Crystal data top

[La₂(C₇H₃NO₄)₃(H₂O)₄]·2H₂O	γ = 86.049 (1)°
M_r = 881.23	V = 1426.14 (5) Å³
Triclinic, P1	Z = 2
a = 10.4910 (2) Å	Mo Kα radiation
b = 10.9197 (2) Å	µ = 3.04 mm⁻¹
c = 13.0850 (3) Å	T = 293 K
α = 77.915 (1)°	0.17 × 0.13 × 0.11 mm
β = 76.702 (1)°

Data collection top

Nonius KappaCCD diffractometer	4496 independent reflections
Absorption correction: multi-scan (SCALEPACK; Otwinowski & Minor, 1997)	4014 reflections with I > 2σ(I)
T_min = 0.592, T_max = 0.699	R_int = 0.059
10097 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.045	0 restraints
wR(F²) = 0.126	H-atom parameters constrained
S = 1.03	Δρ_max = 3.36 e Å⁻³
4496 reflections	Δρ_min = −1.06 e Å⁻³
398 parameters

Special details top

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

Refinement. Refinement on F² for ALL reflections except those flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The observed criterion of F² > σ(F²) is used only for calculating -R-factor-obs 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	0.44785 (3)	−0.02327 (3)	0.35019 (3)	0.0209 (2)
La2	0.41829 (4)	0.30745 (3)	0.02503 (3)	0.0252 (2)
O1	0.3054 (5)	−0.1677 (5)	0.5004 (4)	0.0337 (17)
O2	0.1185 (5)	−0.2630 (5)	0.5862 (5)	0.0492 (19)
O3	0.3593 (4)	0.1173 (4)	0.1926 (4)	0.0272 (16)
O4	0.1922 (5)	0.2287 (5)	0.1428 (4)	0.0399 (17)
O5	0.6510 (6)	0.2726 (5)	0.1081 (5)	0.0463 (19)
O6	0.6152 (5)	0.4494 (4)	0.0013 (4)	0.0328 (17)
O7	0.5246 (5)	0.3575 (5)	−0.1722 (4)	0.0356 (17)
O8	0.5833 (5)	0.1871 (4)	−0.2427 (4)	0.0319 (17)
O9	0.9032 (7)	0.8529 (6)	0.0852 (8)	0.081 (3)
O10	0.7051 (5)	0.8128 (5)	0.0666 (4)	0.0393 (17)
O11	0.3996 (4)	0.0804 (4)	−0.4828 (4)	0.0262 (14)
O12	0.3094 (5)	0.2114 (5)	−0.6006 (4)	0.0374 (17)
O13	0.5983 (5)	0.1647 (5)	0.3240 (4)	0.0423 (17)
O14	0.6366 (5)	−0.0113 (5)	0.1893 (4)	0.0446 (17)
O15	0.3833 (7)	0.3857 (5)	0.2021 (4)	0.051 (2)
O16	0.5634 (7)	0.1192 (5)	−0.0243 (5)	0.053 (2)
N1	0.1958 (5)	−0.0293 (5)	0.3519 (4)	0.0275 (17)
N2	0.4329 (5)	0.2539 (5)	−0.3812 (4)	0.0236 (17)
N3	0.7679 (6)	0.5744 (5)	0.0726 (5)	0.0294 (17)
C1	0.1846 (7)	−0.1889 (7)	0.5121 (6)	0.032 (2)
C2	0.1188 (7)	−0.1139 (6)	0.4260 (6)	0.031 (2)
C3	−0.0104 (8)	−0.1294 (8)	0.4229 (7)	0.049 (3)
C4	−0.0596 (8)	−0.0556 (10)	0.3409 (8)	0.061 (3)
C5	0.0167 (8)	0.0337 (9)	0.2682 (7)	0.048 (3)
C6	0.1450 (7)	0.0440 (7)	0.2754 (6)	0.029 (2)
C7	0.2362 (7)	0.1378 (6)	0.1992 (5)	0.028 (2)
C8	0.5249 (7)	0.2914 (7)	−0.2401 (6)	0.031 (2)
C9	0.4483 (7)	0.3385 (7)	−0.3250 (6)	0.029 (2)
C10	0.3945 (8)	0.4592 (7)	−0.3418 (6)	0.041 (3)
C11	0.3248 (10)	0.4928 (8)	−0.4212 (8)	0.057 (3)
C12	0.3085 (9)	0.4063 (7)	−0.4800 (7)	0.045 (3)
C13	0.3647 (7)	0.2886 (7)	−0.4586 (6)	0.029 (2)
C14	0.3545 (6)	0.1889 (6)	−0.5189 (5)	0.0235 (19)
C15	0.6790 (7)	0.3836 (6)	0.0665 (5)	0.031 (2)
C16	0.7822 (7)	0.4492 (7)	0.0935 (6)	0.034 (2)
C17	0.8816 (8)	0.3878 (8)	0.1402 (7)	0.047 (3)
C18	0.9714 (9)	0.4597 (9)	0.1617 (9)	0.057 (3)
C19	0.9565 (8)	0.5869 (8)	0.1416 (8)	0.049 (3)
C20	0.8519 (8)	0.6423 (7)	0.0988 (6)	0.037 (2)
C21	0.8212 (8)	0.7801 (8)	0.0811 (7)	0.043 (3)
O17	0.1654 (11)	0.9097 (12)	0.0235 (15)	0.203 (8)
O18	0.0497 (18)	0.4499 (17)	0.4043 (14)	0.262 (11)
H3	−0.06240	−0.18810	0.47480	0.0590*
H4	−0.14450	−0.06660	0.33500	0.0730*
H5	−0.01690	0.08680	0.21480	0.0570*
H10	0.40520	0.51580	−0.30040	0.0490*
H11	0.28900	0.57330	−0.43500	0.0680*
H12	0.26060	0.42700	−0.53310	0.0530*
H13A	0.60750	0.22650	0.27140	0.0510*
H13B	0.63440	0.18290	0.37070	0.0510*
H14A	0.67250	0.07070	0.18120	0.0670*
H14B	0.70090	−0.05880	0.17820	0.0670*
H15A	0.38940	0.46430	0.19540	0.0620*
H15B	0.32620	0.35990	0.25900	0.0620*
H16A	0.55550	0.09510	−0.08010	0.0640*
H16B	0.64370	0.13440	−0.03160	0.0640*
H17	0.88720	0.30080	0.15640	0.0560*
H18	1.04150	0.42180	0.18960	0.0690*
H19	1.01600	0.63630	0.15650	0.0590*
H17A	0.15910	0.98620	0.01620	0.3010*
H17B	0.12280	0.88870	−0.01490	0.3010*
H18A	0.00000	0.44490	0.36500	0.3970*
H18B	0.01520	0.40770	0.46880	0.3970*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
La1	0.0260 (3)	0.0196 (2)	0.0178 (3)	0.0006 (2)	−0.0064 (2)	−0.0041 (2)
La2	0.0369 (3)	0.0184 (3)	0.0199 (3)	−0.0007 (2)	−0.0063 (2)	−0.0032 (2)
O1	0.033 (3)	0.031 (3)	0.037 (3)	−0.008 (2)	−0.018 (2)	0.007 (2)
O2	0.040 (3)	0.046 (3)	0.047 (4)	−0.008 (3)	−0.002 (3)	0.017 (3)
O3	0.027 (2)	0.028 (3)	0.026 (3)	0.001 (2)	−0.0075 (19)	−0.003 (2)
O4	0.037 (3)	0.037 (3)	0.037 (3)	0.010 (2)	−0.008 (2)	0.008 (2)
O5	0.074 (4)	0.021 (3)	0.044 (3)	−0.005 (3)	−0.021 (3)	0.003 (2)
O6	0.046 (3)	0.024 (3)	0.031 (3)	−0.001 (2)	−0.017 (2)	−0.002 (2)
O7	0.051 (3)	0.033 (3)	0.028 (3)	−0.004 (2)	−0.012 (2)	−0.013 (2)
O8	0.046 (3)	0.028 (3)	0.028 (3)	0.006 (2)	−0.018 (2)	−0.011 (2)
O9	0.060 (4)	0.046 (4)	0.148 (8)	−0.008 (3)	−0.043 (5)	−0.022 (4)
O10	0.044 (3)	0.030 (3)	0.049 (3)	−0.001 (2)	−0.012 (3)	−0.017 (2)
O11	0.029 (2)	0.029 (3)	0.022 (2)	−0.001 (2)	−0.005 (2)	−0.009 (2)
O12	0.046 (3)	0.040 (3)	0.030 (3)	0.003 (2)	−0.020 (2)	−0.004 (2)
O13	0.058 (3)	0.047 (3)	0.024 (3)	−0.025 (3)	−0.012 (2)	−0.001 (2)
O14	0.049 (3)	0.041 (3)	0.037 (3)	−0.001 (3)	0.008 (3)	−0.012 (3)
O15	0.097 (5)	0.028 (3)	0.026 (3)	−0.013 (3)	−0.002 (3)	−0.007 (2)
O16	0.087 (5)	0.043 (3)	0.040 (3)	0.023 (3)	−0.030 (3)	−0.021 (3)
N1	0.029 (3)	0.026 (3)	0.026 (3)	−0.001 (2)	−0.004 (2)	−0.004 (2)
N2	0.030 (3)	0.021 (3)	0.021 (3)	0.001 (2)	−0.007 (2)	−0.006 (2)
N3	0.038 (3)	0.024 (3)	0.027 (3)	0.005 (3)	−0.009 (3)	−0.007 (3)
C1	0.044 (4)	0.023 (4)	0.024 (4)	0.004 (3)	−0.004 (3)	−0.001 (3)
C2	0.026 (3)	0.027 (4)	0.035 (4)	−0.001 (3)	−0.003 (3)	0.000 (3)
C3	0.035 (4)	0.046 (5)	0.057 (6)	−0.005 (4)	−0.012 (4)	0.013 (4)
C4	0.022 (4)	0.073 (6)	0.078 (7)	−0.013 (4)	−0.020 (4)	0.022 (5)
C5	0.035 (4)	0.054 (5)	0.048 (5)	0.006 (4)	−0.015 (4)	0.010 (4)
C6	0.029 (4)	0.025 (4)	0.032 (4)	0.006 (3)	−0.009 (3)	−0.001 (3)
C7	0.035 (4)	0.025 (4)	0.024 (4)	0.004 (3)	−0.011 (3)	−0.002 (3)
C8	0.041 (4)	0.028 (4)	0.025 (4)	−0.010 (3)	−0.003 (3)	−0.011 (3)
C9	0.032 (4)	0.028 (4)	0.027 (4)	0.001 (3)	−0.001 (3)	−0.010 (3)
C10	0.061 (5)	0.025 (4)	0.037 (4)	0.007 (4)	−0.012 (4)	−0.010 (3)
C11	0.092 (7)	0.025 (4)	0.060 (6)	0.025 (4)	−0.033 (5)	−0.016 (4)
C12	0.060 (5)	0.034 (4)	0.043 (5)	0.016 (4)	−0.024 (4)	−0.005 (4)
C13	0.032 (4)	0.030 (4)	0.025 (4)	0.004 (3)	−0.007 (3)	−0.008 (3)
C14	0.023 (3)	0.026 (4)	0.021 (3)	0.002 (3)	−0.006 (3)	−0.003 (3)
C15	0.045 (4)	0.024 (4)	0.021 (4)	−0.001 (3)	−0.003 (3)	−0.006 (3)
C16	0.036 (4)	0.034 (4)	0.032 (4)	0.005 (3)	−0.006 (3)	−0.008 (3)
C17	0.057 (5)	0.030 (4)	0.055 (5)	0.011 (4)	−0.024 (4)	−0.004 (4)
C18	0.051 (5)	0.047 (5)	0.083 (7)	0.014 (4)	−0.038 (5)	−0.014 (5)
C19	0.044 (5)	0.047 (5)	0.064 (6)	0.001 (4)	−0.022 (4)	−0.016 (4)
C20	0.041 (4)	0.039 (4)	0.035 (4)	0.003 (3)	−0.011 (3)	−0.012 (4)
C21	0.041 (4)	0.039 (4)	0.053 (5)	−0.009 (4)	−0.010 (4)	−0.014 (4)
O17	0.079 (7)	0.110 (9)	0.37 (2)	0.004 (6)	0.030 (10)	−0.030 (12)
O18	0.26 (2)	0.29 (2)	0.244 (18)	−0.205 (18)	−0.175 (17)	0.126 (17)

Geometric parameters (Å, º) top

La1—N1	2.644 (5)	O16—H16B	0.8500
La1—N2ⁱ	2.728 (6)	O17—H17A	0.8200
La1—O1	2.502 (5)	O17—H17B	0.8200
La1—O3	2.614 (5)	O18—H18A	0.8200
La1—O8ⁱ	2.575 (5)	O18—H18B	0.8800
La1—O11ⁱ	2.578 (5)	N1—C2	1.347 (9)
La1—O11ⁱⁱ	2.600 (5)	N1—C6	1.333 (9)
La1—O13	2.593 (5)	N2—C13	1.348 (9)
La1—O14	2.525 (5)	N2—C9	1.334 (9)
La2—N3ⁱⁱⁱ	2.688 (6)	N3—C16	1.342 (10)
La2—O3	2.674 (5)	N3—C20	1.334 (10)
La2—O4	2.605 (5)	C1—C2	1.520 (11)
La2—O5	2.865 (6)	C2—C3	1.388 (12)
La2—O6	2.591 (5)	C3—C4	1.379 (13)
La2—O6ⁱⁱⁱ	2.615 (5)	C4—C5	1.366 (14)
La2—O7	2.524 (5)	C5—C6	1.385 (12)
La2—O10ⁱⁱⁱ	2.539 (5)	C6—C7	1.492 (10)
La2—O15	2.574 (5)	C8—C9	1.503 (11)
La2—O16	2.575 (6)	C9—C10	1.392 (11)
O1—C1	1.273 (9)	C10—C11	1.379 (13)
O2—C1	1.231 (10)	C11—C12	1.379 (13)
O3—C7	1.282 (9)	C12—C13	1.378 (11)
O4—C7	1.237 (9)	C13—C14	1.495 (10)
O5—C15	1.245 (9)	C15—C16	1.483 (11)
O6—C15	1.277 (9)	C16—C17	1.391 (12)
O7—C8	1.256 (9)	C17—C18	1.378 (13)
O8—C8	1.259 (9)	C18—C19	1.363 (14)
O9—C21	1.228 (11)	C19—C20	1.390 (12)
O10—C21	1.290 (10)	C20—C21	1.498 (12)
O11—C14	1.281 (8)	C3—H3	0.9300
O12—C14	1.239 (8)	C4—H4	0.9300
O13—H13B	0.8500	C5—H5	0.9300
O13—H13A	0.8500	C10—H10	0.9300
O14—H14A	0.9700	C11—H11	0.9300
O14—H14B	0.8300	C12—H12	0.9300
O15—H15B	0.8500	C17—H17	0.9300
O15—H15A	0.8500	C18—H18	0.9300
O16—H16A	0.8500	C19—H19	0.9300

O1—La1—O3	122.79 (16)	La1ⁱ—O8—C8	127.8 (5)
O1—La1—O13	138.55 (16)	La2ⁱⁱⁱ—O10—C21	122.7 (5)
O1—La1—O14	144.85 (18)	La1^iv—O11—C14	102.4 (4)
O1—La1—N1	61.51 (17)	La1ⁱ—O11—C14	128.0 (4)
O1—La1—O11ⁱⁱ	72.38 (16)	La1^iv—O11—La1ⁱ	118.03 (17)
O1—La1—O8ⁱ	82.61 (17)	H13A—O13—H13B	108.00
O1—La1—O11ⁱ	79.37 (16)	La1—O13—H13A	125.00
O1—La1—N2ⁱ	70.50 (17)	La1—O13—H13B	126.00
O3—La1—O13	83.61 (15)	H14A—O14—H14B	105.00
O3—La1—O14	75.24 (16)	La1—O14—H14A	104.00
O3—La1—N1	61.30 (15)	La1—O14—H14B	130.00
O3—La1—O11ⁱⁱ	111.02 (14)	H15A—O15—H15B	108.00
O3—La1—O8ⁱ	78.74 (15)	La2—O15—H15A	115.00
O3—La1—O11ⁱ	155.18 (14)	La2—O15—H15B	126.00
O3—La1—N2ⁱ	134.90 (15)	H16A—O16—H16B	108.00
O13—La1—O14	66.84 (17)	La2—O16—H16A	117.00
O13—La1—N1	130.64 (17)	La2—O16—H16B	110.00
O11ⁱⁱ—La1—O13	68.07 (15)	H17A—O17—H17B	108.00
O8ⁱ—La1—O13	137.30 (16)	H18A—O18—H18B	108.00
O11ⁱ—La1—O13	71.66 (15)	La1—N1—C6	121.0 (4)
O13—La1—N2ⁱ	115.33 (17)	C2—N1—C6	118.9 (6)
O14—La1—N1	126.86 (16)	La1—N1—C2	120.0 (4)
O11ⁱⁱ—La1—O14	133.32 (16)	La1ⁱ—N2—C13	121.0 (4)
O8ⁱ—La1—O14	71.15 (17)	La1ⁱ—N2—C9	120.7 (4)
O11ⁱ—La1—O14	92.63 (16)	C9—N2—C13	118.1 (6)
O14—La1—N2ⁱ	76.04 (16)	La2ⁱⁱⁱ—N3—C20	119.1 (5)
O11ⁱⁱ—La1—N1	92.06 (15)	C16—N3—C20	118.4 (7)
O8ⁱ—La1—N1	71.66 (17)	La2ⁱⁱⁱ—N3—C16	122.5 (5)
O11ⁱ—La1—N1	138.66 (15)	O2—C1—C2	118.6 (7)
N1—La1—N2ⁱ	114.03 (17)	O1—C1—O2	125.8 (7)
O8ⁱ—La1—O11ⁱⁱ	154.60 (15)	O1—C1—C2	115.7 (6)
O11ⁱⁱ—La1—O11ⁱ	61.97 (14)	N1—C2—C1	114.6 (6)
O11ⁱⁱ—La1—N2ⁱ	114.01 (15)	N1—C2—C3	121.8 (7)
O8ⁱ—La1—O11ⁱ	118.28 (15)	C1—C2—C3	123.5 (7)
O8ⁱ—La1—N2ⁱ	59.34 (16)	C2—C3—C4	118.3 (8)
O11ⁱ—La1—N2ⁱ	58.97 (15)	C3—C4—C5	119.9 (8)
O3—La2—O4	49.45 (15)	C4—C5—C6	118.9 (8)
O3—La2—O5	76.72 (15)	C5—C6—C7	122.8 (7)
O3—La2—O6	121.38 (15)	N1—C6—C5	122.1 (7)
O3—La2—O7	142.63 (16)	N1—C6—C7	115.1 (6)
O3—La2—O15	69.42 (16)	O3—C7—O4	122.5 (6)
O3—La2—O16	73.31 (17)	O4—C7—C6	120.0 (7)
O3—La2—O6ⁱⁱⁱ	134.20 (15)	O3—C7—C6	117.5 (6)
O3—La2—O10ⁱⁱⁱ	85.13 (15)	O8—C8—C9	116.5 (7)
O3—La2—N3ⁱⁱⁱ	121.02 (16)	O7—C8—O8	125.4 (7)
O4—La2—O5	121.66 (17)	O7—C8—C9	118.1 (7)
O4—La2—O6	146.54 (16)	N2—C9—C10	122.6 (7)
O4—La2—O7	136.93 (17)	N2—C9—C8	114.5 (6)
O4—La2—O15	72.17 (19)	C8—C9—C10	122.9 (7)
O4—La2—O16	109.57 (19)	C9—C10—C11	118.4 (7)
O4—La2—O6ⁱⁱⁱ	101.96 (17)	C10—C11—C12	119.6 (8)
O4—La2—O10ⁱⁱⁱ	66.56 (16)	C11—C12—C13	118.7 (8)
O4—La2—N3ⁱⁱⁱ	72.45 (18)	C12—C13—C14	122.8 (7)
O5—La2—O6	47.20 (16)	N2—C13—C14	114.6 (6)
O5—La2—O7	98.49 (18)	N2—C13—C12	122.7 (7)
O5—La2—O15	68.8 (2)	O11—C14—C13	115.7 (6)
O5—La2—O16	65.89 (19)	O11—C14—O12	122.5 (6)
O5—La2—O6ⁱⁱⁱ	101.06 (16)	O12—C14—C13	121.8 (6)
O5—La2—O10ⁱⁱⁱ	137.38 (17)	O5—C15—O6	121.2 (7)
O5—La2—N3ⁱⁱⁱ	159.07 (17)	O5—C15—C16	122.6 (7)
O6—La2—O7	72.46 (17)	O6—C15—C16	116.1 (6)
O6—La2—O15	74.76 (19)	C15—C16—C17	123.7 (7)
O6—La2—O16	93.97 (19)	N3—C16—C17	122.7 (7)
O6—La2—O6ⁱⁱⁱ	59.73 (16)	N3—C16—C15	113.5 (6)
O6—La2—O10ⁱⁱⁱ	145.86 (16)	C16—C17—C18	118.1 (8)
O6—La2—N3ⁱⁱⁱ	112.19 (17)	C17—C18—C19	119.4 (9)
O7—La2—O15	143.95 (18)	C18—C19—C20	119.7 (8)
O7—La2—O16	71.09 (19)	C19—C20—C21	123.9 (8)
O6ⁱⁱⁱ—La2—O7	83.17 (17)	N3—C20—C21	114.5 (7)
O7—La2—O10ⁱⁱⁱ	73.54 (17)	N3—C20—C19	121.7 (7)
O7—La2—N3ⁱⁱⁱ	74.28 (18)	O9—C21—C20	119.5 (8)
O15—La2—O16	126.2 (2)	O9—C21—O10	124.6 (8)
O6ⁱⁱⁱ—La2—O15	67.46 (16)	O10—C21—C20	115.8 (7)
O10ⁱⁱⁱ—La2—O15	138.7 (2)	C2—C3—H3	121.00
O15—La2—N3ⁱⁱⁱ	105.3 (2)	C4—C3—H3	121.00
O6ⁱⁱⁱ—La2—O16	148.18 (19)	C3—C4—H4	120.00
O10ⁱⁱⁱ—La2—O16	72.1 (2)	C5—C4—H4	120.00
O16—La2—N3ⁱⁱⁱ	127.1 (2)	C4—C5—H5	121.00
O6ⁱⁱⁱ—La2—O10ⁱⁱⁱ	118.78 (17)	C6—C5—H5	120.00
O6ⁱⁱⁱ—La2—N3ⁱⁱⁱ	59.01 (17)	C11—C10—H10	121.00
O10ⁱⁱⁱ—La2—N3ⁱⁱⁱ	60.36 (17)	C9—C10—H10	121.00
La1—O1—C1	127.8 (5)	C10—C11—H11	120.00
La1—O3—La2	143.82 (18)	C12—C11—H11	120.00
La1—O3—C7	121.3 (4)	C11—C12—H12	121.00
La2—O3—C7	91.7 (4)	C13—C12—H12	121.00
La2—O4—C7	96.0 (4)	C18—C17—H17	121.00
La2—O5—C15	89.2 (5)	C16—C17—H17	121.00
La2—O6—C15	101.4 (4)	C17—C18—H18	120.00
La2—O6—La2ⁱⁱⁱ	120.3 (2)	C19—C18—H18	120.00
La2ⁱⁱⁱ—O6—C15	124.5 (4)	C20—C19—H19	120.00
La2—O7—C8	126.9 (5)	C18—C19—H19	120.00

O3—La1—O1—C1	2.6 (7)	N3ⁱⁱⁱ—La2—O7—C8	−87.9 (6)
O13—La1—O1—C1	124.6 (6)	O3—La2—O6ⁱⁱⁱ—La2ⁱⁱⁱ	105.9 (2)
O14—La1—O1—C1	−110.3 (6)	O3—La2—O6ⁱⁱⁱ—C15ⁱⁱⁱ	−121.3 (5)
N1—La1—O1—C1	4.2 (6)	O4—La2—O6ⁱⁱⁱ—La2ⁱⁱⁱ	149.7 (2)
O11ⁱⁱ—La1—O1—C1	106.7 (6)	O4—La2—O6ⁱⁱⁱ—C15ⁱⁱⁱ	−77.5 (5)
O8ⁱ—La1—O1—C1	−68.9 (6)	O5—La2—O6ⁱⁱⁱ—La2ⁱⁱⁱ	23.7 (2)
O11ⁱ—La1—O1—C1	170.4 (6)	O5—La2—O6ⁱⁱⁱ—C15ⁱⁱⁱ	156.5 (5)
N2ⁱ—La1—O1—C1	−128.9 (6)	O6—La2—O6ⁱⁱⁱ—La2ⁱⁱⁱ	0.02 (17)
O1—La1—O3—La2	168.6 (3)	O6—La2—O6ⁱⁱⁱ—C15ⁱⁱⁱ	132.8 (6)
O1—La1—O3—C7	15.8 (5)	O7—La2—O6ⁱⁱⁱ—La2ⁱⁱⁱ	−73.7 (2)
O13—La1—O3—La2	23.0 (3)	O7—La2—O6ⁱⁱⁱ—C15ⁱⁱⁱ	59.1 (5)
O13—La1—O3—C7	−129.8 (5)	O15—La2—O6ⁱⁱⁱ—La2ⁱⁱⁱ	85.0 (3)
O14—La1—O3—La2	−44.7 (3)	O15—La2—O6ⁱⁱⁱ—C15ⁱⁱⁱ	−142.2 (6)
O14—La1—O3—C7	162.6 (5)	O16—La2—O6ⁱⁱⁱ—La2ⁱⁱⁱ	−38.0 (5)
N1—La1—O3—La2	167.0 (4)	O16—La2—O6ⁱⁱⁱ—C15ⁱⁱⁱ	94.8 (6)
N1—La1—O3—C7	14.2 (4)	O3—La2—O10ⁱⁱⁱ—C21ⁱⁱⁱ	104.9 (6)
O11ⁱⁱ—La1—O3—La2	86.5 (3)	O4—La2—O10ⁱⁱⁱ—C21ⁱⁱⁱ	57.3 (6)
O11ⁱⁱ—La1—O3—C7	−66.2 (5)	O5—La2—O10ⁱⁱⁱ—C21ⁱⁱⁱ	169.2 (5)
O8ⁱ—La1—O3—La2	−117.9 (3)	O6—La2—O10ⁱⁱⁱ—C21ⁱⁱⁱ	−111.4 (6)
O8ⁱ—La1—O3—C7	89.3 (5)	O7—La2—O10ⁱⁱⁱ—C21ⁱⁱⁱ	−106.1 (6)
O11ⁱ—La1—O3—La2	18.2 (6)	O15—La2—O10ⁱⁱⁱ—C21ⁱⁱⁱ	54.0 (7)
O11ⁱ—La1—O3—C7	−134.6 (5)	O16—La2—O10ⁱⁱⁱ—C21ⁱⁱⁱ	178.9 (6)
N2ⁱ—La1—O3—La2	−96.7 (3)	O3—La2—N3ⁱⁱⁱ—C16ⁱⁱⁱ	130.4 (5)
N2ⁱ—La1—O3—C7	110.5 (5)	O3—La2—N3ⁱⁱⁱ—C20ⁱⁱⁱ	−47.7 (6)
O1—La1—N1—C2	−6.0 (5)	O4—La2—N3ⁱⁱⁱ—C16ⁱⁱⁱ	120.7 (6)
O1—La1—N1—C6	179.1 (6)	O4—La2—N3ⁱⁱⁱ—C20ⁱⁱⁱ	−57.4 (5)
O3—La1—N1—C2	172.4 (5)	O5—La2—N3ⁱⁱⁱ—C16ⁱⁱⁱ	−14.9 (9)
O3—La1—N1—C6	−2.5 (5)	O5—La2—N3ⁱⁱⁱ—C20ⁱⁱⁱ	167.0 (5)
O13—La1—N1—C2	−137.2 (5)	O6—La2—N3ⁱⁱⁱ—C16ⁱⁱⁱ	−24.0 (6)
O13—La1—N1—C6	48.0 (6)	O6—La2—N3ⁱⁱⁱ—C20ⁱⁱⁱ	157.9 (5)
O14—La1—N1—C2	133.1 (5)	O7—La2—N3ⁱⁱⁱ—C16ⁱⁱⁱ	−87.1 (6)
O14—La1—N1—C6	−41.8 (6)	O7—La2—N3ⁱⁱⁱ—C20ⁱⁱⁱ	94.9 (6)
O11ⁱⁱ—La1—N1—C2	−74.7 (5)	O15—La2—N3ⁱⁱⁱ—C16ⁱⁱⁱ	55.5 (6)
O11ⁱⁱ—La1—N1—C6	110.5 (5)	O15—La2—N3ⁱⁱⁱ—C20ⁱⁱⁱ	−122.6 (5)
O8ⁱ—La1—N1—C2	85.5 (5)	O16—La2—N3ⁱⁱⁱ—C16ⁱⁱⁱ	−137.7 (5)
O8ⁱ—La1—N1—C6	−89.4 (5)	O16—La2—N3ⁱⁱⁱ—C20ⁱⁱⁱ	44.3 (6)
O11ⁱ—La1—N1—C2	−26.8 (6)	La1—O1—C1—O2	178.3 (6)
O11ⁱ—La1—N1—C6	158.3 (5)	La1—O1—C1—C2	−2.2 (9)
N2ⁱ—La1—N1—C2	42.9 (5)	La1—O3—C7—O4	158.7 (5)
N2ⁱ—La1—N1—C6	−132.0 (5)	La1—O3—C7—C6	−23.8 (8)
O1—La1—O11ⁱⁱ—C14ⁱⁱ	−126.6 (4)	La2—O3—C7—O4	−5.6 (7)
O3—La1—O11ⁱⁱ—C14ⁱⁱ	−7.4 (4)	La2—O3—C7—C6	171.9 (5)
O13—La1—O11ⁱⁱ—C14ⁱⁱ	66.1 (4)	La2—O4—C7—O3	5.8 (7)
O14—La1—O11ⁱⁱ—C14ⁱⁱ	81.8 (4)	La2—O4—C7—C6	−171.6 (5)
N1—La1—O11ⁱⁱ—C14ⁱⁱ	−67.4 (4)	La2—O5—C15—O6	−9.7 (7)
O1—La1—O8ⁱ—C8ⁱ	−79.6 (6)	La2—O5—C15—C16	166.9 (6)
O3—La1—O8ⁱ—C8ⁱ	154.8 (6)	La2—O6—C15—O5	11.0 (7)
O13—La1—O8ⁱ—C8ⁱ	87.3 (6)	La2—O6—C15—C16	−165.8 (5)
O14—La1—O8ⁱ—C8ⁱ	76.7 (6)	La2ⁱⁱⁱ—O6—C15—O5	150.7 (5)
N1—La1—O8ⁱ—C8ⁱ	−141.9 (6)	La2ⁱⁱⁱ—O6—C15—C16	−26.1 (8)
O1—La1—O11ⁱ—C14ⁱ	61.0 (5)	La2—O7—C8—O8	−67.8 (10)
O3—La1—O11ⁱ—C14ⁱ	−144.0 (5)	La2—O7—C8—C9	111.4 (7)
O13—La1—O11ⁱ—C14ⁱ	−149.1 (5)	La1ⁱ—O8—C8—O7	165.7 (5)
O14—La1—O11ⁱ—C14ⁱ	−84.5 (5)	La1ⁱ—O8—C8—C9	−13.5 (9)
N1—La1—O11ⁱ—C14ⁱ	79.5 (6)	La2ⁱⁱⁱ—O10—C21—O9	150.6 (8)
O1—La1—N2ⁱ—C9ⁱ	93.4 (5)	La2ⁱⁱⁱ—O10—C21—C20	−32.3 (9)
O1—La1—N2ⁱ—C13ⁱ	−81.9 (5)	La1^iv—O11—C14—O12	20.2 (7)
O3—La1—N2ⁱ—C9ⁱ	−23.9 (6)	La1^iv—O11—C14—C13	−157.4 (5)
O3—La1—N2ⁱ—C13ⁱ	160.9 (5)	La1ⁱ—O11—C14—O12	161.8 (5)
O13—La1—N2ⁱ—C9ⁱ	−131.2 (5)	La1ⁱ—O11—C14—C13	−15.8 (8)
O13—La1—N2ⁱ—C13ⁱ	53.5 (5)	La1—N1—C2—C1	7.4 (8)
O14—La1—N2ⁱ—C9ⁱ	−75.7 (5)	La1—N1—C2—C3	−173.0 (6)
O14—La1—N2ⁱ—C13ⁱ	109.1 (5)	C6—N1—C2—C1	−177.6 (6)
N1—La1—N2ⁱ—C9ⁱ	48.8 (5)	C6—N1—C2—C3	2.0 (10)
N1—La1—N2ⁱ—C13ⁱ	−126.5 (5)	La1—N1—C6—C5	173.3 (6)
O4—La2—O3—La1	−154.0 (4)	La1—N1—C6—C7	−7.1 (8)
O4—La2—O3—C7	3.0 (4)	C2—N1—C6—C5	−1.7 (11)
O5—La2—O3—La1	1.7 (3)	C2—N1—C6—C7	178.0 (6)
O5—La2—O3—C7	158.7 (4)	C13—N2—C9—C8	179.7 (6)
O6—La2—O3—La1	−14.2 (4)	C13—N2—C9—C10	1.4 (11)
O6—La2—O3—C7	142.8 (4)	La1ⁱ—N2—C9—C8	−4.9 (8)
O7—La2—O3—La1	88.4 (4)	La1ⁱ—N2—C9—C10	176.8 (6)
O7—La2—O3—C7	−114.7 (4)	C9—N2—C13—C12	−1.4 (11)
O15—La2—O3—La1	−70.3 (3)	C9—N2—C13—C14	178.9 (6)
O15—La2—O3—C7	86.7 (4)	La1ⁱ—N2—C13—C12	−176.8 (6)
O16—La2—O3—La1	70.2 (3)	La1ⁱ—N2—C13—C14	3.5 (8)
O16—La2—O3—C7	−132.8 (4)	C20—N3—C16—C15	176.8 (6)
O6ⁱⁱⁱ—La2—O3—La1	−90.9 (4)	C20—N3—C16—C17	−0.7 (11)
O6ⁱⁱⁱ—La2—O3—C7	66.1 (4)	La2ⁱⁱⁱ—N3—C16—C15	−5.1 (8)
O10ⁱⁱⁱ—La2—O3—La1	142.9 (3)	La2ⁱⁱⁱ—N3—C16—C17	177.4 (6)
O10ⁱⁱⁱ—La2—O3—C7	−60.1 (4)	C16—N3—C20—C19	3.4 (11)
N3ⁱⁱⁱ—La2—O3—La1	−166.2 (3)	C16—N3—C20—C21	−175.0 (7)
N3ⁱⁱⁱ—La2—O3—C7	−9.2 (4)	La2ⁱⁱⁱ—N3—C20—C19	−174.8 (6)
O3—La2—O4—C7	−3.1 (4)	La2ⁱⁱⁱ—N3—C20—C21	6.9 (9)
O5—La2—O4—C7	−31.1 (5)	O1—C1—C2—N1	−3.7 (9)
O6—La2—O4—C7	−90.1 (5)	O1—C1—C2—C3	176.6 (7)
O7—La2—O4—C7	125.0 (4)	O2—C1—C2—N1	175.9 (7)
O15—La2—O4—C7	−80.9 (4)	O2—C1—C2—C3	−3.8 (11)
O16—La2—O4—C7	42.1 (4)	N1—C2—C3—C4	0.2 (12)
O6ⁱⁱⁱ—La2—O4—C7	−142.2 (4)	C1—C2—C3—C4	179.8 (8)
O10ⁱⁱⁱ—La2—O4—C7	101.4 (4)	C2—C3—C4—C5	−2.8 (14)
N3ⁱⁱⁱ—La2—O4—C7	166.0 (4)	C3—C4—C5—C6	3.2 (15)
O3—La2—O5—C15	−155.8 (4)	C4—C5—C6—N1	−1.0 (13)
O4—La2—O5—C15	−134.3 (4)	C4—C5—C6—C7	179.5 (8)
O6—La2—O5—C15	5.6 (4)	N1—C6—C7—O3	20.1 (9)
O7—La2—O5—C15	62.0 (4)	N1—C6—C7—O4	−162.4 (6)
O15—La2—O5—C15	−83.0 (4)	C5—C6—C7—O3	−160.3 (7)
O16—La2—O5—C15	126.8 (5)	C5—C6—C7—O4	17.3 (11)
O6ⁱⁱⁱ—La2—O5—C15	−22.7 (4)	O7—C8—C9—N2	−168.0 (7)
O10ⁱⁱⁱ—La2—O5—C15	136.9 (4)	O7—C8—C9—C10	10.2 (11)
N3ⁱⁱⁱ—La2—O5—C15	−5.9 (8)	O8—C8—C9—N2	11.2 (10)
O3—La2—O6—C15	15.8 (4)	O8—C8—C9—C10	−170.6 (7)
O3—La2—O6—La2ⁱⁱⁱ	−126.1 (2)	N2—C9—C10—C11	−1.3 (12)
O4—La2—O6—C15	78.5 (5)	C8—C9—C10—C11	−179.4 (8)
O4—La2—O6—La2ⁱⁱⁱ	−63.4 (4)	C9—C10—C11—C12	1.1 (14)
O5—La2—O6—C15	−5.5 (4)	C10—C11—C12—C13	−1.1 (14)
O5—La2—O6—La2ⁱⁱⁱ	−147.5 (3)	C11—C12—C13—N2	1.3 (13)
O7—La2—O6—C15	−125.8 (4)	C11—C12—C13—C14	−179.0 (8)
O7—La2—O6—La2ⁱⁱⁱ	92.3 (2)	N2—C13—C14—O11	6.8 (9)
O15—La2—O6—C15	69.4 (4)	N2—C13—C14—O12	−170.8 (6)
O15—La2—O6—La2ⁱⁱⁱ	−72.5 (2)	C12—C13—C14—O11	−172.9 (7)
O16—La2—O6—C15	−57.1 (4)	C12—C13—C14—O12	9.5 (11)
O16—La2—O6—La2ⁱⁱⁱ	161.0 (2)	O5—C15—C16—N3	−157.5 (7)
O6ⁱⁱⁱ—La2—O6—C15	141.9 (4)	O5—C15—C16—C17	19.9 (12)
O6ⁱⁱⁱ—La2—O6—La2ⁱⁱⁱ	−0.02 (18)	O6—C15—C16—N3	19.3 (9)
O10ⁱⁱⁱ—La2—O6—C15	−120.5 (4)	O6—C15—C16—C17	−163.3 (7)
O10ⁱⁱⁱ—La2—O6—La2ⁱⁱⁱ	97.6 (3)	N3—C16—C17—C18	−2.6 (13)
N3ⁱⁱⁱ—La2—O6—C15	170.0 (4)	C15—C16—C17—C18	−179.8 (8)
N3ⁱⁱⁱ—La2—O6—La2ⁱⁱⁱ	28.1 (3)	C16—C17—C18—C19	3.1 (14)
O3—La2—O7—C8	33.0 (7)	C17—C18—C19—C20	−0.6 (15)
O4—La2—O7—C8	−47.3 (7)	C18—C19—C20—N3	−2.7 (14)
O5—La2—O7—C8	112.3 (6)	C18—C19—C20—C21	175.5 (9)
O6—La2—O7—C8	152.1 (6)	N3—C20—C21—O9	−167.8 (9)
O15—La2—O7—C8	177.6 (6)	N3—C20—C21—O10	15.0 (10)
O16—La2—O7—C8	51.5 (6)	C19—C20—C21—O9	13.9 (14)
O6ⁱⁱⁱ—La2—O7—C8	−147.5 (6)	C19—C20—C21—O10	−163.3 (8)
O10ⁱⁱⁱ—La2—O7—C8	−24.8 (6)

Symmetry codes: (i) −x+1, −y, −z; (ii) x, y, z+1; (iii) −x+1, −y+1, −z; (iv) x, y, z−1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O13—H13A···O5	0.85	2.04	2.766 (8)	143
O13—H13B···O1^v	0.85	1.91	2.721 (7)	160
O14—H14A···O5	0.97	2.23	3.062 (8)	143
O14—H14B···O9^vi	0.83	2.44	3.225 (10)	160
O14—H14B···O10^vi	0.83	2.22	2.712 (8)	119
O15—H15A···O7ⁱⁱⁱ	0.85	2.14	2.948 (8)	160
O15—H15B···O12ⁱⁱ	0.85	2.16	2.849 (7)	138
O16—H16A···O8	0.85	2.12	2.760 (8)	132
O16—H16B···O17ⁱⁱⁱ	0.85	2.05	2.843 (15)	155
O17—H17A···O9^vii	0.82	2.13	2.816 (17)	141
O17—H17B···O9^viii	0.82	2.39	2.758 (15)	108
O18—H18A···O2^ix	0.82	2.31	2.75 (2)	114
O18—H18B···O18^x	0.88	2.46	2.89 (3)	110
C11—H11···O2^xi	0.93	2.45	3.320 (11)	155
C12—H12···O18^iv	0.93	2.51	3.36 (2)	152

Symmetry codes: (ii) x, y, z+1; (iii) −x+1, −y+1, −z; (iv) x, y, z−1; (v) −x+1, −y, −z+1; (vi) x, y−1, z; (vii) −x+1, −y+2, −z; (viii) x−1, y, z; (ix) −x, −y, −z+1; (x) −x, −y+1, −z+1; (xi) x, y+1, z−1.

Experimental details

Crystal data
Chemical formula	[La₂(C₇H₃NO₄)₃(H₂O)₄]·2H₂O
M_r	881.23
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	10.4910 (2), 10.9197 (2), 13.0850 (3)
α, β, γ (°)	77.915 (1), 76.702 (1), 86.049 (1)
V (Å³)	1426.14 (5)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	3.04
Crystal size (mm)	0.17 × 0.13 × 0.11

Data collection
Diffractometer	Nonius KappaCCD diffractometer
Absorption correction	Multi-scan (SCALEPACK; Otwinowski & Minor, 1997)
T_min, T_max	0.592, 0.699
No. of measured, independent and observed [I > 2σ(I)] reflections	10097, 4496, 4014
R_int	0.059
(sin θ/λ)_max (Å⁻¹)	0.576

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.045, 0.126, 1.03
No. of reflections	4496
No. of parameters	398
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	3.36, −1.06

Computer programs: COLLECT (Nonius, 2000), DENZO and SCALEPACK (Otwinowski & Minor, 1997), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009).

Selected bond lengths (Å) top

La1—N1	2.644 (5)	La2—O3	2.674 (5)
La1—N2ⁱ	2.728 (6)	La2—O4	2.605 (5)
La1—O1	2.502 (5)	La2—O5	2.865 (6)
La1—O3	2.614 (5)	La2—O6	2.591 (5)
La1—O8ⁱ	2.575 (5)	La2—O6ⁱⁱⁱ	2.615 (5)
La1—O11ⁱ	2.578 (5)	La2—O7	2.524 (5)
La1—O11ⁱⁱ	2.600 (5)	La2—O10ⁱⁱⁱ	2.539 (5)
La1—O13	2.593 (5)	La2—O15	2.574 (5)
La1—O14	2.525 (5)	La2—O16	2.575 (6)
La2—N3ⁱⁱⁱ	2.688 (6)

Symmetry codes: (i) −x+1, −y, −z; (ii) x, y, z+1; (iii) −x+1, −y+1, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O13—H13A···O5	0.85	2.04	2.766 (8)	143
O13—H13B···O1^iv	0.85	1.91	2.721 (7)	160
O14—H14A···O5	0.97	2.23	3.062 (8)	143
O14—H14B···O9^v	0.83	2.44	3.225 (10)	160
O14—H14B···O10^v	0.83	2.22	2.712 (8)	119
O15—H15A···O7ⁱⁱⁱ	0.85	2.14	2.948 (8)	160
O15—H15B···O12ⁱⁱ	0.85	2.16	2.849 (7)	138
O16—H16A···O8	0.85	2.12	2.760 (8)	132
O16—H16B···O17ⁱⁱⁱ	0.85	2.05	2.843 (15)	155
O17—H17A···O9^vi	0.82	2.13	2.816 (17)	141
O17—H17B···O9^vii	0.82	2.39	2.758 (15)	108
O18—H18A···O2^viii	0.82	2.31	2.75 (2)	114
O18—H18B···O18^ix	0.88	2.46	2.89 (3)	110
C11—H11···O2^x	0.93	2.45	3.320 (11)	155
C12—H12···O18^xi	0.93	2.51	3.36 (2)	152

Symmetry codes: (ii) x, y, z+1; (iii) −x+1, −y+1, −z; (iv) −x+1, −y, −z+1; (v) x, y−1, z; (vi) −x+1, −y+2, −z; (vii) x−1, y, z; (viii) −x, −y, −z+1; (ix) −x, −y+1, −z+1; (x) x, y+1, z−1; (xi) x, y, z−1.

Acknowledgements

This work was supported financially by Yuanpei University, Taiwan.

References

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