Crystal structure of poly[[di-μ3-acetato-tetra-aqua-bis-(μ2-cyclo-hexane-1,4-di-carboxyl-ato)dilanth-an-um(III)] dihydrate].

The title compound, {[La2(CH3COO)2(C8H10O4)2(H2O)4]·2H2O} n or [La2(ac)2(e,a-cis-1,4-chdc)2(H2O)4]·2H2O, where ac is acetate and 1,4-chdc is cyclo-hexane-1,4-di-carboxyl-ate anion, is a binuclear lanthanum(III) complex. Each metal atom is deca-coordinated by four O atoms from two distinct 1,4-chdc2- ligands, four O atoms from three acetate groups and two O atoms from coordinated water mol-ecules to form a distorted bicapped square-anti-prismatic geometry. Two non-coordinated water mol-ecules are also present in the formula unit. The most remarkable feature of this compound is that it possesses a only cis conformation for cyclo-hexane-1,4-di-carb-oxy-lic acid, although the raw material consists of a mixture of cis and trans isomers. The μ3-η2:η2 coordination mode of the bridging acetate group and the flexible di-carboxyl-ate fragments of 1,4-chdc2- results in the formation of infinite two-dimensional lanthanide-carboxyl-ate layers within the crystal structure. The directionality of strong inter-molecular O-H⋯O and weak C-H⋯O inter-actions provides robustness to the layers, which leads to the construction of a three-dimensional supra-molecular network. The crystal studied was refined as a two-component twin.

Chemical context

1,4-Cyclo­hexa­nedi­carboxyic acid (1,4-chdcH2) is a flexible alicyclic, ditopic ligand having a chair-type backbone structure, which has been used for the construction of many coord­ination polymers (CPs) with remarkable architectures (Liu et al., 2010 ▸). It can exist in three different conformations – two trans isomers, (a,a) and (e,e), and one cis (e,a) form. From a thermodynamical point of view, the trans (e,e) form is the most stable of the three different conformations as a result of the equatorial–equatorial –COOH groups and the trans (a,a) isomer is the least stable because of 1,3-diaxial hindrance (Yu et al., 2007 ▸; Gong et al., 2005 ▸; Bi et al., 2003 ▸; Du et al., 2005 ▸; Chen et al., 2014 ▸)·Theoretical calculations suggest that the isomers tend to cause conformational inversion within the ligand structure due to the flexibility of the C—C bond rotation and also because of the extremely low free energy change between them (Qiblawi et al., 2013 ▸; Lin & Tong, 2011 ▸; Liu et al., 2010 ▸). Furthermore, the isomeric separation of the organic ligand can be controlled by several factors such as the pH of the solution, the nature of the metal ion, the co-ligand, the reaction solvent and the temperature (Lin & Tong, 2011 ▸; Liu et al., 2010 ▸).

Structural commentary

The asymmetric unit of the title compound consists of one crystallographically unique La metal ion, a fully deprotonated 1,4-chdc2− anion, an acetate moiety and three water mol­ecules (two coordinated and one non-coordinated). From the mol­ecular structure (Fig. 1 ▸), it is evident that each LaIII atom has a distorted bicapped square-anti­prismatic coordination sphere defined by four oxygen atoms from two distinct 1,4-chdc2− ligands (O1, O2, O7, O8), four oxygen atoms from three acetate groups (O5, O6, O5′, O6′) and two oxygen atoms from coordinated water mol­ecules (O3, O4) to form a [LaO10] coordination polyhedron (Fig. 2 ▸). Of the three prevalent conformations of 1,4-chdcH2, low temperature usually favours the cis (e,a) and high temperature favours the trans (e,e) conformational compounds (Lin & Tong, 2011 ▸; Lu et al., 2008 ▸; Bi et al., 2004 ▸). Here, the bent structure of the organic linker possesses an L-shaped cis (e,a) conformation within the crystal structure. The corresponding La—O bond lengths are in the range 2.506 (8)—2.792 (7) Å and the O—La—O bond angles vary from 46.51 (19) to 170.7 (2)°. The La—O bond distances are comparable with those in several reported structures in which 1,4-cyclo­hexa­nedi­carb­oxy­lic acid exists in various coordination modes and conformations (Rao et al., 2007 ▸; Qi et al., 2008 ▸).

Figure 1

ORTEP view of the mol­ecular structure of the title complex with the atom-numbering scheme and ellipsoids drawn at the 50% probability level..

Figure 2

Bicapped square-anti­prismatic geometry of an [LaO10] polyhedron. Displacement ellipsoids are drawn at the 80% probability level.

The bridging μ3-η2 :η2 coordination mode (each oxygen atom connects two metal atoms) of the acetate group joins two [LaO10] polyhedra by edge sharing to form a dimeric structure. The dimers are then inter­linked by La—O—La bonding and as a consequence of this, infinite zigzag 1D [La2O2] chains are formed. Within these chains, La⋯La non-bonding distances are found to be 4.5835 (9) and 4.4125 (9) Å. Additionally, the bis-bidentate chelating μ2-η1 :η1 :η1 :η1 coordination mode of the di­carboxyl­ate group of 1,4-chdc2− connects two metal atoms and hence converts it into a 2D coordination polymeric structure parallel to the ab plane. A perspective view of the packing along the c axis in a wireframe model (Fig. 3 ▸) shows the formation of infinite 2D lanthanide–carboxyl­ate layers. The [La2O2] chains are then further inter­connected by a di­carboxyl­ate anion from two 1,4-chdc2− units to form a 24-membered macrocyclic ring as shown in Fig. 4 ▸. A series of organotin complexes of the cis and trans isomers of 1,4-chdcH2 show similar 2D networks containing 26- and 36-membered tetra­tin macrocyclic rings (Ma et al., 2009 ▸).

Figure 3

Perspective view of the packing along the c axis.

Figure 4

The 24-membered macrocyclic ring formation by 1,4-chdc2− between two [La2O2] chains.

Supra­molecular features

From the polyhedral view along the a axis (Fig. 5 ▸), it is clear that the two lattice water mol­ecules residing in the voids of the 1,4-chdc2− units are responsible for the development of hydro­philic channels within the crystal structure. The hydrogen-bonding inter­actions (Table 1 ▸) shown in Fig. 6 ▸ play a vital role in increasing the stability and higher dimensionality of the crystal packing. Here, the oxygen atom O9 of the lattice water mol­ecule acts as a donor for hydrogen bonds with oxygen atoms O1 and O2 of the carboxyl­ate group of the 1,4-chdc2− ligand [O9—H9A⋯O2 = 2.786 (12) Å and O9—H9B⋯O1iii = 2.846 (11) Å]. It also acts as the hydrogen-bond acceptor for oxygen atoms O3 and O4 of the coordinated water mol­ecules [O3—H3C⋯O9 = 2.858 (12) Å and O4—H4D⋯O9ii 2.812 (11) Å]. Similarly, oxygen atom O7 of the carboxyl­ate group of 1,4-chdc acts as an acceptor to atoms O3 and O4 of the coordinated water mol­ecules [O3—H3D⋯O7ii = 2.750 (11) Å and O4—H4C⋯O7i = 2.771 (10) Å]. Apart from this strong inter­molecular hydrogen bonding, there are also weak C—H⋯O inter­actions between the carbon atom C10 of the coordinated acetate group and the O1 oxygen atom of a carboxyl­ate group of the organic linker [C10—H10C⋯O1 = 3.295 (14) Å].

Figure 5

Polyhedral view along the a axis showing the free water mol­ecules.

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C10—H10C⋯O1	0.96	2.49	3.295 (14)	141
O4—H4C⋯O7i	0.90 (2)	1.92 (5)	2.771 (10)	158 (12)
O4—H4D⋯O9ii	0.89 (2)	1.96 (6)	2.812 (11)	158 (12)
O3—H3C⋯O9	0.90 (2)	1.97 (3)	2.858 (12)	172 (13)
O3—H3D⋯O7ii	0.90 (2)	1.86 (3)	2.750 (11)	170 (14)
O9—H9A⋯O2	0.90 (2)	2.20 (11)	2.786 (12)	122 (11)
O9—H9B⋯O1iii	0.90 (2)	1.97 (5)	2.846 (11)	164 (13)

Symmetry codes: (i) ; (ii) ; (iii) .

Figure 6

Hydrogen-bonding inter­actions (dashed lines) in the structure of the title compound. For symmetry operations, see Table 1 ▸.

Database survey

In the three-dimensional structures of [La2(1,4-chdc)3(H2O)4], [La3(1,4-Hchdc)2(1,4-chdc)5(H2O)2]·H2O and [La2(1,4-chdc)3(H2O)]·2.5H2O, the di­carboxyl­ate anion exists in different conformations obtained under hydro­thermal conditions (Rao et al., 2007 ▸). Similarly a two-dimensional lanthanum coordin­ation polymer [La2(1,10-phen)2(1,4-chdc)3]·2.5H2O with π–π stacking was observed by the incorporation of 1,10-phenanthroline as a co-ligand along with 1,4-cyclo­hexa­nedi­carb­oxy­lic acid (Qi et al., 2008 ▸). Additionally, dimethyl formamide (DMF) and dimethyl sulfoxide (DMSO) solvent-coordinated lanthanum complexes, one-dimensional [La(cis-chdc)(DMF)2(NO3)] and three-dimensional [La2(trans-chdc)3(DMSO)4] have also been reported. The presence of solvent mol­ecules can completely segregate the cis and trans conformations of 1,4-chdc (Tian et al., 2009 ▸).

Synthesis and crystallization

Single crystals of the title compound were prepared by the gel-diffusion technique at ambient temperature using sodium metasilicate nona­hydrate (Na2S2O3·9H2O) as the gel medium. The optimum condition for crystal growth was obtained by dissolving 0.75 g of 1,4-H2chdc in 25 ml of 1.04 g cm−3 dense gel medium. 5 ml of the above solution was poured into glass tubes and the pH of the solution was set to 7.0 by adding glacial acetic acid drop by drop. On completion of the gel-setting process, 3 ml of 0.5 M concentration of aqueous lanthanum nitrate solution was added as the upper reagent. The whole arrangement was kept undisturbed at room temperature and was covered to protect it from the foreign matter present in the atmosphere. Within seven days, transparent, colourless block-shaped crystals were observed at the gel inter­face. The diffusion of La3+ ions and 1,4-chdcH2 through the fine pores of the gel media lead to the expected chemical reaction as shown below:

2La(NO → [La

Elemental analysis calculated (%) for C20H38La2O18 (844.32): C, 28.42; H, 4.50. Found (%): C, 28.36; H, 4.33. IR (KBr, cm−1): 3380, 2940, 1573, 1460, 743, 673, 597.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2 ▸. Carbon-bound hydrogen atoms were placed in calculated positions and included in the refinement in the riding-model approximation with C—H distances of 0.96–0.98 Å and with U iso(H) = 1.2U eq(C) for methyl hydrogen atoms and U iso(H) = 1.2U eq(C) for all others. Water hydrogen atoms were located from difference-Fourier maps and refined with an O—H distance restraint of 0.90 (2) Å and an H⋯H separation of 1.39 (2) Å. The isotropic displacement parameters of the hydrogen atoms attached to atoms O3, O4 and O9 were made equal by using an EDAP instruction. The crystal studied was refined as a two-component twin (BASF = 0.4203).

Table 2

Experimental details

Crystal data
Chemical formula	[La2(C2H3O2)2(C8H10O4)2(H2O)4]·2H2O
M r	844.32
Crystal system, space group	Triclinic, P
Temperature (K)	293
a, b, c (Å)	6.9341 (8), 8.9597 (13), 12.3030 (16)
α, β, γ (°)	110.217 (5), 91.060 (5), 93.280 (5)
V (Å3)	715.49 (16)
Z	1
Radiation type	Mo Kα
μ (mm−1)	3.02
Crystal size (mm)	0.20 × 0.15 × 0.15
Data collection
Diffractometer	Bruker Kappa APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2004 ▸)
T min, T max	0.60, 0.74
No. of measured, independent and observed [I > 2σ(I)] reflections	2818, 2815, 2447
(sin θ/λ)max (Å−1)	0.617
Refinement
R[F 2 > 2σ(F 2)], wR(F 2), S	0.041, 0.146, 1.07
No. of reflections	2818
No. of parameters	204
No. of restraints	9
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å−3)	2.17, −2.46

Computer programs: APEX2, SAINT and XPREP (Bruker, 2004 ▸), SIR92 (Sheldrick, 2015 ▸), DIAMOND (Brandenburg, 2010 ▸), SHELXL2014 (Sheldrick, 2015 ▸) and publCIF (Westrip, 2010 ▸).

Crystal structure: contains datablock(s) I. DOI: 10.1107/S2056989017016103/vn2132sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989017016103/vn2132Isup2.hkl

CCDC reference: 1546730

Additional supporting information: crystallographic information; 3D view; checkCIF report

[La2(C2H3O2)2(C8H10O4)2(H2O)4]·2H2O	Z = 1
Mr = 844.32	F(000) = 416
Triclinic, P1	Dx = 1.960 Mg m−3
a = 6.9341 (8) Å	Mo Kα radiation, λ = 0.71073 Å
b = 8.9597 (13) Å	Cell parameters from 7100 reflections
c = 12.3030 (16) Å	θ = 2.8–30.9°
α = 110.217 (5)°	µ = 3.02 mm−1
β = 91.060 (5)°	T = 293 K
γ = 93.280 (5)°	Block, colourless
V = 715.49 (16) Å3	0.20 × 0.15 × 0.15 mm

Bruker Kappa APEXII CCD diffractometer	2815 independent reflections
Radiation source: Sealed tube	2447 reflections with I > 2σ(I)
ω and φ scan	θmax = 26.0°, θmin = 2.4°
Absorption correction: multi-scan (SADABS; Bruker, 2004)	h = −8→8
Tmin = 0.60, Tmax = 0.74	k = −11→10
2818 measured reflections	l = 0→15

Refinement on F2	9 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F2 > 2σ(F2)] = 0.041	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.146	w = 1/[σ2(Fo2) + (0.0821P)2 + 6.1459P] where P = (Fo2 + 2Fc2)/3
S = 1.07	(Δ/σ)max = 0.005
2818 reflections	Δρmax = 2.17 e Å−3
204 parameters	Δρmin = −2.46 e Å−3

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

Refinement. Refined as a two-component twin.

	x	y	z	Uiso*/Ueq
C1	0.2377 (17)	0.7936 (10)	0.7752 (7)	0.0203 (18)
C2	0.2486 (18)	0.7706 (11)	0.8920 (8)	0.030 (2)
H2	0.2447	0.8760	0.9522	0.036*
C3	0.0724 (17)	0.6681 (16)	0.9058 (11)	0.033 (3)
H3A	0.0698	0.6715	0.9855	0.040*
H3B	−0.0448	0.7116	0.8889	0.040*
C4	0.0778 (17)	0.4962 (14)	0.8253 (10)	0.030 (3)
H4A	0.0694	0.4919	0.7455	0.036*
H4B	−0.0331	0.4339	0.8379	0.036*
C5	0.2631 (16)	0.4239 (11)	0.8460 (7)	0.024 (2)
H5	0.2633	0.4196	0.9245	0.028*
C6	0.4375 (16)	0.5264 (15)	0.8372 (11)	0.030 (3)
H6A	0.4468	0.5213	0.7574	0.036*
H6B	0.5526	0.4836	0.8576	0.036*
C7	0.4325 (17)	0.6994 (14)	0.9147 (10)	0.028 (2)
H7A	0.5438	0.7602	0.9010	0.034*
H7B	0.4403	0.7067	0.9952	0.034*
C8	0.2736 (16)	0.2574 (10)	0.7614 (8)	0.0229 (19)
C9	0.7522 (14)	1.0347 (9)	0.6555 (7)	0.0141 (16)
C10	0.7542 (18)	1.0729 (13)	0.7831 (8)	0.030 (2)
H10A	0.7030	1.1749	0.8194	0.046*
H10B	0.8846	1.0758	0.8118	0.046*
H10C	0.6763	0.9926	0.8006	0.046*
O1	0.3916 (11)	0.7991 (10)	0.7225 (7)	0.0280 (18)
O2	0.0804 (11)	0.8116 (10)	0.7334 (7)	0.0272 (18)
O3	−0.0144 (11)	0.6946 (10)	0.4871 (7)	0.0310 (18)
O4	0.3865 (13)	0.6914 (10)	0.4470 (8)	0.039 (2)
O5	0.5999 (10)	0.9978 (10)	0.5957 (6)	0.0219 (16)
O6	0.9100 (10)	1.0455 (9)	0.6066 (6)	0.0220 (16)
O7	0.2827 (11)	0.2366 (7)	0.6530 (5)	0.0223 (14)
O8	0.2635 (12)	0.1397 (7)	0.7932 (5)	0.0283 (15)
O9	−0.2682 (13)	0.6345 (9)	0.6499 (7)	0.0384 (18)
La1	0.23952 (8)	0.92768 (5)	0.58722 (4)	0.01486 (18)
H4C	0.474 (15)	0.704 (14)	0.398 (8)	0.05 (3)*
H4D	0.326 (16)	0.597 (8)	0.406 (8)	0.05 (3)*
H3C	−0.088 (14)	0.668 (17)	0.538 (9)	0.06 (3)*
H3D	−0.105 (12)	0.705 (17)	0.437 (9)	0.06 (3)*
H9A	−0.207 (15)	0.687 (15)	0.719 (6)	0.06 (3)*
H9B	−0.388 (9)	0.669 (17)	0.663 (10)	0.06 (3)*

	U11	U22	U33	U12	U13	U23
C1	0.026 (5)	0.012 (4)	0.025 (4)	−0.004 (4)	0.006 (5)	0.008 (3)
C2	0.047 (7)	0.023 (5)	0.019 (4)	0.003 (5)	−0.002 (5)	0.008 (4)
C3	0.029 (7)	0.041 (7)	0.034 (7)	0.011 (5)	0.007 (5)	0.017 (6)
C4	0.031 (7)	0.027 (6)	0.030 (6)	0.004 (5)	0.003 (4)	0.005 (5)
C5	0.030 (6)	0.026 (5)	0.016 (4)	−0.005 (4)	−0.002 (4)	0.011 (4)
C6	0.022 (6)	0.037 (7)	0.033 (6)	0.004 (5)	−0.005 (4)	0.014 (5)
C7	0.041 (8)	0.025 (6)	0.017 (5)	0.001 (5)	−0.004 (4)	0.007 (4)
C8	0.017 (5)	0.024 (5)	0.029 (5)	0.002 (4)	−0.001 (4)	0.012 (4)
C9	0.010 (4)	0.012 (3)	0.018 (4)	0.003 (4)	−0.002 (4)	0.001 (3)
C10	0.026 (6)	0.042 (6)	0.020 (4)	−0.006 (5)	0.003 (5)	0.007 (4)
O1	0.016 (4)	0.039 (5)	0.039 (5)	0.005 (3)	0.005 (3)	0.025 (4)
O2	0.026 (5)	0.031 (5)	0.028 (4)	0.004 (3)	−0.005 (3)	0.015 (4)
O3	0.026 (5)	0.035 (5)	0.034 (5)	−0.005 (3)	−0.002 (3)	0.017 (4)
O4	0.033 (5)	0.022 (4)	0.051 (5)	−0.009 (3)	0.023 (4)	−0.001 (4)
O5	0.012 (4)	0.037 (4)	0.020 (4)	−0.001 (3)	0.002 (3)	0.014 (3)
O6	0.011 (4)	0.032 (4)	0.025 (4)	−0.001 (3)	0.002 (3)	0.011 (3)
O7	0.025 (4)	0.024 (3)	0.018 (3)	0.001 (3)	0.006 (3)	0.007 (2)
O8	0.042 (4)	0.021 (3)	0.024 (3)	−0.001 (4)	−0.004 (3)	0.011 (3)
O9	0.023 (5)	0.033 (4)	0.057 (5)	0.004 (4)	0.004 (4)	0.013 (4)
La1	0.0121 (3)	0.0169 (3)	0.0169 (3)	0.0017 (2)	0.0015 (2)	0.00745 (18)

C1—O2	1.240 (13)	C9—La1ii	3.119 (8)
C1—O1	1.266 (13)	C10—H10A	0.9600
C1—C2	1.522 (12)	C10—H10B	0.9600
C1—La1	2.952 (8)	C10—H10C	0.9600
C2—C7	1.521 (17)	O1—La1	2.570 (7)
C2—C3	1.533 (17)	O2—La1	2.601 (8)
C2—H2	0.9800	O3—La1	2.588 (8)
C3—C4	1.519 (18)	O3—H3C	0.90 (2)
C3—H3A	0.9700	O3—H3D	0.90 (2)
C3—H3B	0.9700	O4—La1	2.506 (8)
C4—C5	1.527 (16)	O4—H4C	0.90 (2)
C4—H4A	0.9700	O4—H4D	0.89 (2)
C4—H4B	0.9700	O5—La1	2.533 (7)
C5—C8	1.502 (12)	O5—La1ii	2.792 (7)
C5—C6	1.505 (15)	O6—La1iii	2.552 (7)
C5—H5	0.9800	O6—La1ii	2.674 (7)
C6—C7	1.516 (17)	O7—La1i	2.598 (6)
C6—H6A	0.9700	O8—La1i	2.585 (6)
C6—H6B	0.9700	O9—H9A	0.90 (2)
C7—H7A	0.9700	O9—H9B	0.90 (2)
C7—H7B	0.9700	La1—O6iv	2.552 (7)
C8—O8	1.244 (11)	La1—O8v	2.585 (6)
C8—O7	1.284 (11)	La1—O7v	2.598 (6)
C8—La1i	2.983 (9)	La1—O6ii	2.674 (7)
C9—O5	1.237 (11)	La1—O5ii	2.792 (7)
C9—O6	1.273 (11)	La1—C8v	2.983 (9)
C9—C10	1.487 (11)
O2—C1—O1	120.1 (8)	C9—O6—La1ii	98.1 (5)
O2—C1—C2	120.4 (9)	La1iii—O6—La1ii	115.2 (3)
O1—C1—C2	119.5 (10)	C8—O7—La1i	94.3 (5)
O2—C1—La1	61.6 (5)	C8—O8—La1i	96.0 (5)
O1—C1—La1	60.2 (5)	H9A—O9—H9B	101 (3)
C2—C1—La1	164.8 (6)	O4—La1—O5	73.2 (3)
C1—C2—C7	114.2 (9)	O4—La1—O6iv	135.8 (3)
C1—C2—C3	110.9 (9)	O5—La1—O6iv	143.4 (2)
C7—C2—C3	109.4 (8)	O4—La1—O1	77.7 (3)
C1—C2—H2	107.4	O5—La1—O1	73.8 (2)
C7—C2—H2	107.4	O6iv—La1—O1	126.4 (2)
C3—C2—H2	107.4	O4—La1—O8v	146.0 (3)
C4—C3—C2	111.4 (9)	O5—La1—O8v	82.5 (3)
C4—C3—H3A	109.4	O6iv—La1—O8v	76.9 (2)
C2—C3—H3A	109.4	O1—La1—O8v	72.8 (2)
C4—C3—H3B	109.4	O4—La1—O3	67.5 (3)
C2—C3—H3B	109.4	O5—La1—O3	140.7 (3)
H3A—C3—H3B	108.0	O6iv—La1—O3	73.0 (3)
C3—C4—C5	111.4 (10)	O1—La1—O3	96.1 (3)
C3—C4—H4A	109.4	O8v—La1—O3	131.7 (3)
C5—C4—H4A	109.4	O4—La1—O7v	138.0 (2)
C3—C4—H4B	109.4	O5—La1—O7v	73.7 (2)
C5—C4—H4B	109.4	O6iv—La1—O7v	69.9 (2)
H4A—C4—H4B	108.0	O1—La1—O7v	116.4 (2)
C8—C5—C6	110.0 (9)	O8v—La1—O7v	49.88 (18)
C8—C5—C4	111.2 (9)	O3—La1—O7v	140.6 (2)
C6—C5—C4	110.4 (8)	O4—La1—O2	103.1 (3)
C8—C5—H5	108.4	O5—La1—O2	121.8 (2)
C6—C5—H5	108.4	O6iv—La1—O2	78.8 (2)
C4—C5—H5	108.4	O1—La1—O2	49.7 (2)
C5—C6—C7	113.4 (9)	O8v—La1—O2	69.9 (2)
C5—C6—H6A	108.9	O3—La1—O2	67.7 (3)
C7—C6—H6A	108.9	O7v—La1—O2	116.2 (2)
C5—C6—H6B	108.9	O4—La1—O6ii	83.0 (3)
C7—C6—H6B	108.9	O5—La1—O6ii	107.7 (2)
H6A—C6—H6B	107.7	O6iv—La1—O6ii	64.8 (3)
C6—C7—C2	111.4 (9)	O1—La1—O6ii	159.3 (3)
C6—C7—H7A	109.3	O8v—La1—O6ii	127.8 (2)
C2—C7—H7A	109.3	O3—La1—O6ii	69.3 (2)
C6—C7—H7B	109.3	O7v—La1—O6ii	83.2 (2)
C2—C7—H7B	109.3	O2—La1—O6ii	129.9 (2)
H7A—C7—H7B	108.0	O4—La1—O5ii	68.8 (3)
O8—C8—O7	119.6 (8)	O5—La1—O5ii	61.3 (3)
O8—C8—C5	121.6 (8)	O6iv—La1—O5ii	103.7 (2)
O7—C8—C5	118.7 (7)	O1—La1—O5ii	129.6 (2)
O8—C8—La1i	59.5 (5)	O8v—La1—O5ii	119.3 (2)
O7—C8—La1i	60.3 (4)	O3—La1—O5ii	104.2 (2)
C5—C8—La1i	172.5 (8)	O7v—La1—O5ii	72.9 (2)
O5—C9—O6	118.9 (7)	O2—La1—O5ii	170.7 (2)
O5—C9—C10	121.7 (9)	O6ii—La1—O5ii	46.51 (19)
O6—C9—C10	119.4 (9)	O4—La1—C1	93.6 (3)
O5—C9—La1ii	63.3 (4)	O5—La1—C1	97.2 (3)
O6—C9—La1ii	58.1 (4)	O6iv—La1—C1	101.4 (3)
C10—C9—La1ii	161.8 (6)	O1—La1—C1	25.3 (3)
C9—C10—H10A	109.5	O8v—La1—C1	65.9 (2)
C9—C10—H10B	109.5	O3—La1—C1	84.1 (3)
H10A—C10—H10B	109.5	O7v—La1—C1	115.7 (2)
C9—C10—H10C	109.5	O2—La1—C1	24.8 (3)
H10A—C10—H10C	109.5	O6ii—La1—C1	152.5 (3)
H10B—C10—H10C	109.5	O5ii—La1—C1	154.8 (3)
C1—O1—La1	94.4 (6)	O4—La1—C8v	151.3 (3)
C1—O2—La1	93.6 (6)	O5—La1—C8v	78.0 (3)
La1—O3—H3C	113 (9)	O6iv—La1—C8v	70.6 (3)
La1—O3—H3D	120 (9)	O1—La1—C8v	94.8 (3)
H3C—O3—H3D	101 (3)	O8v—La1—C8v	24.5 (2)
La1—O4—H4C	121 (8)	O3—La1—C8v	141.2 (3)
La1—O4—H4D	127 (8)	O7v—La1—C8v	25.4 (2)
H4C—O4—H4D	102 (3)	O2—La1—C8v	92.3 (3)
C9—O5—La1	147.1 (6)	O6ii—La1—C8v	105.7 (2)
C9—O5—La1ii	93.4 (5)	O5ii—La1—C8v	97.0 (2)
La1—O5—La1ii	118.7 (3)	C1—La1—C8v	90.4 (2)
C9—O6—La1iii	138.0 (6)
O2—C1—C2—C7	161.8 (9)	C4—C5—C8—O7	63.7 (13)
O1—C1—C2—C7	−20.4 (13)	O2—C1—O1—La1	15.4 (9)
La1—C1—C2—C7	−105 (3)	C2—C1—O1—La1	−162.5 (7)
O2—C1—C2—C3	37.7 (12)	O1—C1—O2—La1	−15.2 (9)
O1—C1—C2—C3	−144.5 (9)	C2—C1—O2—La1	162.6 (7)
La1—C1—C2—C3	131 (3)	O6—C9—O5—La1	174.3 (8)
C1—C2—C3—C4	69.6 (12)	C10—C9—O5—La1	−8.2 (16)
C7—C2—C3—C4	−57.2 (11)	La1ii—C9—O5—La1	−168.1 (12)
C2—C3—C4—C5	57.2 (12)	O6—C9—O5—La1ii	−17.7 (8)
C3—C4—C5—C8	−176.5 (9)	C10—C9—O5—La1ii	159.9 (7)
C3—C4—C5—C6	−54.1 (12)	O5—C9—O6—La1iii	−124.4 (8)
C8—C5—C6—C7	176.5 (9)	C10—C9—O6—La1iii	58.0 (12)
C4—C5—C6—C7	53.4 (11)	La1ii—C9—O6—La1iii	−143.1 (9)
C5—C6—C7—C2	−55.0 (12)	O5—C9—O6—La1ii	18.6 (9)
C1—C2—C7—C6	−69.6 (12)	C10—C9—O6—La1ii	−158.9 (7)
C3—C2—C7—C6	55.3 (11)	O8—C8—O7—La1i	4.7 (11)
C6—C5—C8—O8	124.8 (11)	C5—C8—O7—La1i	−171.5 (9)
C4—C5—C8—O8	−112.5 (12)	O7—C8—O8—La1i	−4.8 (11)
C6—C5—C8—O7	−59.0 (13)	C5—C8—O8—La1i	171.4 (9)

D—H···A	D—H	H···A	D···A	D—H···A
C10—H10C···O1	0.96	2.49	3.295 (14)	141
O4—H4C···O7vi	0.90 (2)	1.92 (5)	2.771 (10)	158 (12)
O4—H4D···O9vii	0.89 (2)	1.96 (6)	2.812 (11)	158 (12)
O3—H3C···O9	0.90 (2)	1.97 (3)	2.858 (12)	172 (13)
O3—H3D···O7vii	0.90 (2)	1.86 (3)	2.750 (11)	170 (14)
O9—H9A···O2	0.90 (2)	2.20 (11)	2.786 (12)	122 (11)
O9—H9B···O1iv	0.90 (2)	1.97 (5)	2.846 (11)	164 (13)