Polymeric tetra­aqua­tris­(malonato)­dilanthanum(III) monohydrate

The title compound, [La₂(C₃H₂O₄)₃(H₂O)₄]·H₂O, forms a layer-type polymeric structure. The layers, which contain infinite puckered four-membered La-O-La-O rings in a pseudo-ternary symmetry, are formed by the lanthanum and one independent malonate group. They are interconnected by the second independent malonate group, giving a three-dimensional framework in which wide channels accommodate one disordered water mol­ecule of crystallization. The La atom lies on a twofold axis and is ten-coordinated by eight O atoms from carboxyl­ate groups and two water mol­ecules. One malonate group is monodentate and triply bridging chelating, whilst the other is doubly monodentate. The extensive network of hydrogen bonds and bridge bonds observed in this structure enhances the structural stability. Despite some identical subfeatures, this structure is quite different from that observed in [La₂(C₃H₂O₄)₃(H₂O)₃]·2H₂O.

S1. Comment

In the binary complexes of lanthanides with malonic acid, there are three different isostructural series characterized by the number of water molecules and the lanthanoid cation (Hansson, 1973a). For the complexes of lanthanum two structural studies have been published, one containing malonate ions (Marrot & Trombe, 1993) and the other both malonate and hydrogen malonate ions as ligands (Marrot & Trombe, 1994). The complex [La₂(C₃H₂O₄)₃·5H₂O] was presented as showing two different phases in the monoclinic system and the structure of one of these phases, (I), is the subject of the present publication, only its space group and unit-cell dimensions having been reported previously. Our overall goal is to improve the conditions of the synthesis leading to a pure single phase, and to investigate the factors enhancing the stability of solid dicarboxylate lanthanides as a function of the chain length of the carboxylic acid molecule. \sch

The general features of the structure, without the hydrogen bonding, are shown in Fig. 1. There are two crystallographically independent malonate ligands, L1, of point symmetry 1, and L2, of point symmetry 2. The three-dimensional packing of the ligand complexes is essentially built from a two-dimensional substructure. Indeed, the structure can be described in terms of a layer-type polymeric structure built up from lanthanum-malonate L1 layers parallel to (100), including puckered four-membered rings La—O—La—O running in a zigzag manner along the b axis. Each lanthanum atom is surrounded by three such rings in a pseudo-ternary symmetry. These layers are connected together through L2 malonates to form the three-dimensional network. The resulting packing shows wide channels parallel to the b axis surrounded by the carbon backbone chain of the L2 malonates and by the oxygen atoms of the coordinating water molecules. Of the two and a half nominal water molecules in each asymmetric unit, two are coordinated to the lanthanum atom as intra-layer water and the rest are located in a disordered fashion in the channels and are not coordinated to lanthanum.

A view of the ten-coordination around the lanthanum atom is shown in Fig. 2. The ten coordinating O atoms are made up of seven from four L1 malonates, one from one L2 malonate and two from two water molecules. One of the L1 malonates is unidentate through the O2a oxygen atom and the other three are chelating including a six-membered ring (called the `malonate' mode). Moreover, each oxygen atom in L1 coordinates to two lanthanum atoms leading to bridging interactions, except for O4a which only coordinates to one lanthanum atom. As a result, there are two kinds of four-membered rings: one is the La—O—C—O chelate ring formed by the bidentate coordination and the other involves the La—O—La—O rings formed by the bridging structure. Across this latter, the closest distance between two La³⁺ ions is equal to 4.5479 (4) Å. Each L1 malonate is surrounded by four lanthanum atoms, while the L2 malonate which is doubly unidentate, bridges two lanthanum atoms. The two metal-bonded O atoms in this ligand are trans, as a consequence of its twofold symmetry. Despite this feature, and the fact that the malonate ligand is less sterically demanding than other dicarboxylates, the coordination polyhedron is a very distorted bicapped dodecahedron. This is probably due to the large distortions imposed by the bite angles which are considerably smaller [46.90 (5) and 48.41 (6)°] than those found in other malonate compounds (Tapparo et al., 1996; Barbaro et al., 1997), as a consequence of the two coordinating water molecules which are far from a trans-coordination, the angle between them being 134.07 (7)°. Within the layers described above, each polyhedron shares three common edges [O1a—O2a, O1aⁱ—O2aⁱ, O3a—O3aⁱⁱ; symmetry codes: see Table 1)] with three adjacent polyhedra.

The distances and angles in the two independent ligands and the La—O bond lengths of lanthanum to oxygen agree with those found in analogous compounds (Marrot & Trombe, 1993, 1994), with one La—O bond being considerably longer. This kind of distance seems to be rather typical of the chelating carboxylate group (Hansson, 1973a, 1973b).

All water molecules are involved in an extensive network of hydrogen bonds amongst themselves and with the non-bridging oxygen atoms of the ligands (O2b, O4a). It appears that, in addition to the oxygen bridge bonds involving by the L1 malonate, the hydrogen bonds are responsible for the stability of the structure. This explains why all known well defined crystalline dicarboxylate lanthanides are hydrated, except for one complex of neodymium (Hansson, 1973c) and one of gadolinium (Trollet et al., 1997).

A comparison with other recently reported dicarboxylate lanthanides (Wen Mei et al., 1992; Serpaggi & Férey, 1998; Serpaggi et al., 1999) reveals that all these structures contain the same structural subfeature, including four-membered rings. However, the phase La₂(C₃H₂O₄)₃(H₂O)₃·2H₂O reported earlier (Marrot & Trombe, 1993) is quite different as two crystallographically independent lanthanum atoms are present. One is coordinated to nine malonate oxygen atoms and one water molecule whilst the other is bonded to eight malonate oxygen atoms and two water molecules. Moreover the three independent malonate ligands exhibit different coordination modes including a triply unidentate mode.

S2. Experimental

The preparation process is comparable to that used by Marrot (1993), with carefully controlled pH (4) and temperature (353 K). The single crystals were grown at 313 K after having been stored for one month in mother liquor at the same temperature.

S3. Refinement

The uncoordinated water molecule (O3w) is disordered and its population parameter has been refined to 0.501 (11). The H atoms of L1 and L2 were observed and refined with isotropic displacement parameters and the H atoms of the coordinated water molecules were refined with restraints on bond lengths and bond angles. The H atoms of the uncoordinated disordered water molecule could not be located. C2b is located in special position 4 e.

Computing details

Data collection: CAD-4 Software (Enraf-Nonius, 1989); cell refinement: Xtal latcon; data reduction: DIFFRAC (Flack et al., 1992) and Xtal (Hall et al., 1992); program(s) used to solve structure: MULTAN87 (Main et al., 1987); program(s) used to refine structure: XTAL_crylsq; molecular graphics: XTAL_gx3 (Hall & Boulay, 1997); software used to prepare material for publication: XTAL_bondla_cifio.

Figures

	Fig. 1. A projection of the crystal structure along the b axis. H atoms have been omitted for clarity.
	Fig. 2. Perspective drawing showing the local coordination environment, the labelling scheme, and 50% probability displacement parameters. [symmetry codes: (i) 3/2 - x, 1/2 + y, 1/2 - z; (ii) 3/2 - x, 3/2 - y, 1 - z; (iii) 3/2 - x, y - 1/2, 1/2 - z; (iv) 1 - x, y, 1/2 - z; (v) x, y + 1, z].

(I)

Crystal data

[La2(C3H2O4)3(H2O)4](H2O)	Dx = 2.454 Mg m^−3
Mr = 674.0	Mo Kα radiation, λ = 0.71073 Å
Monoclinic, C2/c	Cell parameters from 23 reflections
a = 19.289 (1) Å	θ = 14–25°
b = 7.0740 (6) Å	µ = 4.71 mm^−1
c = 14.575 (2) Å	T = 293 K
β = 113.448 (9)°	Plate, colourless
V = 1824.5 (4) Å^3	0.37 × 0.26 × 0.07 mm
Z = 4

Data collection

Enraf-Nonius CAD4 diffractometer	Rint = 0.018
ω–2θ scans	θmax = 35°
Absorption correction: analytical (xtal_lsabs; Flack et al., 1992)	h = −30→28
Tmin = 0.244, Tmax = 0.719	k = 0→11
4447 measured reflections	l = 0→23
3995 independent reflections	2 standard reflections every 30 min
3640 reflections with refl observed if Fo > 4.0 σ(Fo)	intensity decay: 2.3%

Refinement

Refinement on F	\<i>w = 1/[σ^2(Fo) + 0.00025(Fo^2)]
R[F^2 > 2σ(F^2)] = 0.022	(Δ/σ)max = 0.006
wR(F^2) = 0.028	Δρmax = 0.82 e Å^−3
S = 1.16	Δρmin = −0.74 e Å^−3
3640 reflections	Extinction correction: Iso type I (Zachariasen, 1967)
162 parameters	Extinction coefficient: 30 (2) x 10 2
H atoms treated by a mixture of independent and constrained refinement

Special details

Refinement. The structure was refined using anisotropic displacement parameters for all non-H atoms.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
La	0.736341 (6)	0.697043 (15)	0.339472 (8)	0.01124 (6)
O1a	0.79709 (10)	0.5389 (3)	0.22245 (12)	0.0184 (6)
O2a	0.70260 (11)	0.3470 (3)	0.29165 (13)	0.0211 (7)
O3a	0.73956 (10)	0.9386 (3)	0.47810 (11)	0.0191 (6)
O4a	0.83653 (11)	0.4493 (3)	0.45635 (12)	0.0232 (7)
C1a	0.81386 (12)	0.6865 (3)	0.18623 (15)	0.0138 (7)
C2a	0.85430 (15)	0.6687 (4)	0.11694 (18)	0.0210 (9)
C3a	0.68528 (12)	1.0448 (3)	0.47374 (14)	0.0147 (7)
O1b	0.61430 (11)	0.6843 (3)	0.34857 (16)	0.0308 (9)
O2b	0.51775 (12)	0.7108 (4)	0.39250 (17)	0.0410 (11)
C1b	0.54734 (13)	0.6482 (4)	0.33680 (16)	0.0205 (8)
C2b	0.50000	0.5210 (6)	0.25000	0.0250 (13)
O1w	0.63229 (10)	0.6875 (3)	0.15540 (13)	0.0203 (7)
O2w	0.86967 (12)	0.8240 (3)	0.41797 (15)	0.0274 (8)
O3w	0.5229 (5)	1.1101 (12)	0.1380 (7)	0.089 (6)	.501 (11)
H2a1	0.867 (3)	0.792 (5)	0.093 (3)	0.038 (11)*
H2a2	0.906 (3)	0.615 (7)	0.150 (3)	0.042 (11)*
H2b1	0.535 (3)	0.436 (6)	0.229 (3)	0.047 (11)*
H1w1	0.5773 (16)	0.694 (5)	0.143 (3)	0.055 (14)*
H1w2	0.642 (2)	0.780 (5)	0.108 (3)	0.043 (11)*
H2w1	0.881 (3)	0.965 (5)	0.405 (4)	0.066 (14)*
H2w2	0.916 (3)	0.772 (7)	0.476 (4)	0.11 (3)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
La	0.01388 (6)	0.01033 (6)	0.01061 (6)	0.00076 (4)	0.00603 (4)	0.00009 (4)
O1a	0.0267 (8)	0.0140 (7)	0.0192 (7)	−0.0028 (6)	0.0142 (6)	−0.0020 (6)
O2a	0.0316 (9)	0.0124 (7)	0.0209 (7)	−0.0032 (7)	0.0120 (7)	0.0011 (6)
O3a	0.0230 (8)	0.0187 (7)	0.0156 (6)	0.0086 (6)	0.0078 (6)	0.0019 (5)
O4a	0.0327 (9)	0.0252 (8)	0.0167 (7)	0.0082 (7)	0.0152 (7)	0.0037 (6)
C1a	0.0172 (9)	0.0125 (8)	0.0125 (8)	−0.0009 (7)	0.0066 (7)	−0.0022 (6)
C2a	0.0264 (11)	0.0232 (10)	0.0196 (9)	−0.0120 (9)	0.0158 (9)	−0.0093 (8)
C3a	0.0217 (9)	0.0108 (8)	0.0114 (7)	0.0014 (7)	0.0063 (7)	0.0004 (6)
O1b	0.0162 (8)	0.0484 (13)	0.0294 (10)	−0.0034 (8)	0.0107 (7)	−0.0018 (8)
O2b	0.0223 (10)	0.0743 (18)	0.0285 (10)	−0.0043 (10)	0.0124 (8)	−0.0168 (10)
C1b	0.0146 (9)	0.0300 (11)	0.0162 (9)	0.0007 (8)	0.0053 (7)	0.0012 (8)
C2b	0.0254 (15)	0.0221 (15)	0.0233 (14)	0.00000	0.0053 (12)	0.00000
O1w	0.0183 (8)	0.0226 (8)	0.0194 (7)	−0.0009 (6)	0.0066 (6)	0.0040 (6)
O2w	0.0225 (9)	0.0305 (10)	0.0218 (8)	−0.0062 (7)	0.0010 (7)	0.0032 (7)
O3w	0.069 (5)	0.076 (6)	0.138 (8)	−0.018 (5)	0.059 (5)	−0.035 (5)

Geometric parameters (Å, º)

La—O1a	2.669 (2)	C1a—C2a	1.507 (5)
La—O2a	2.5844 (17)	C2a—H2a1	1.00 (4)
La—O3a	2.6281 (17)	C2a—H2a2	0.99 (4)
La—O4a	2.6625 (17)	C2a—C3a^iii	1.515 (3)
La—O1b	2.412 (3)	O1b—C1b	1.259 (4)
La—O1w	2.6354 (16)	O2b—C1b	1.245 (4)
La—O2w	2.527 (2)	C1b—C2b	1.525 (4)
La—O1a^i	2.5723 (16)	C2b—H2b1	1.04 (5)
La—O2a^i	2.821 (3)	C2b—H2b1^iv	1.04 (5)
La—O3a^ii	2.6877 (17)	O1w—H1w1	1.00 (4)
O1a—C1a	1.268 (3)	O1w—H1w2	1.02 (4)
O2a—C1a^iii	1.255 (3)	O2w—H2w1	1.05 (4)
O3a—C3a	1.270 (3)	O2w—H2w2	1.02 (4)
O4a—C3a^ii	1.248 (4)
O1a—La—O2a	63.49 (7)	O1a^i—La—O2a^i	61.49 (6)
O1a—La—O3a	151.85 (6)	O1a^i—La—O3a^ii	127.11 (6)
O1a—La—O4a	75.02 (6)	O2a^i—La—O3a^ii	148.23 (5)
O1a—La—O1b	134.90 (6)	La—O1a—C1a	99.83 (14)
O1a—La—O1w	71.87 (6)	La—O1a—La^iii	120.37 (8)
O1a—La—O2w	79.15 (7)	C1a—O1a—La^iii	134.24 (15)
O1a—La—O1a^i	106.40 (6)	La—O2a—La^iii	114.51 (8)
O1a—La—O2a^i	46.90 (5)	La—O2a—C1a^iii	149.28 (17)
O1a—La—O3a^ii	122.38 (5)	La^iii—O2a—C1a^iii	92.89 (15)
O2a—La—O3a	139.18 (7)	La—O3a—C3a	125.42 (12)
O2a—La—O4a	65.33 (5)	La—O3a—La^ii	118.05 (6)
O2a—La—O1b	80.35 (8)	C3a—O3a—La^ii	94.32 (14)
O2a—La—O1w	72.11 (5)	La—O4a—C3a^ii	96.07 (14)
O2a—La—O2w	124.34 (7)	O1a—C1a—C2a	119.7 (2)
O2a—La—O1a^i	143.62 (5)	O1a—C1a—O2a^i	120.3 (3)
O2a—La—O2a^i	107.81 (6)	C2a—C1a—O2a^i	119.9 (3)
O2a—La—O3a^ii	81.40 (6)	C1a—C2a—H2a1	115 (3)
O3a—La—O4a	98.46 (5)	C1a—C2a—H2a2	113 (3)
O3a—La—O1b	72.97 (7)	C1a—C2a—C3a^iii	114.7 (3)
O3a—La—O1w	125.08 (6)	H2a1—C2a—H2a2	100 (4)
O3a—La—O2w	73.29 (7)	H2a1—C2a—C3a^iii	107 (3)
O3a—La—O1a^i	65.43 (6)	H2a2—C2a—C3a^iii	105 (3)
O3a—La—O2a^i	112.82 (6)	O3a—C3a—C2a^i	120.4 (3)
O3a—La—O3a^ii	61.95 (5)	O3a—C3a—O4a^ii	121.20 (18)
O4a—La—O1b	114.58 (7)	C2a^i—C3a—O4a^ii	118.4 (3)
O4a—La—O1w	134.38 (5)	La—O1b—C1b	166.09 (19)
O4a—La—O2w	66.14 (6)	O1b—C1b—O2b	123.4 (3)
O4a—La—O1a^i	149.34 (5)	O1b—C1b—C2b	118.4 (3)
O4a—La—O2a^i	106.78 (6)	O2b—C1b—C2b	118.2 (2)
O4a—La—O3a^ii	48.41 (6)	C1b—C2b—H2b1	109.7 (19)
O1b—La—O1w	71.96 (7)	C1b—C2b—C1b^iv	107.6 (3)
O1b—La—O2w	145.91 (8)	C1b—C2b—H2b1^iv	110 (3)
O1b—La—O1a^i	86.59 (7)	H2b1—C2b—C1b^iv	110 (3)
O1b—La—O2a^i	136.99 (6)	H2b1—C2b—H2b1^iv	110 (4)
O1b—La—O3a^ii	73.77 (7)	C1b^iv—C2b—H2b1^iv	109.7 (19)
O1w—La—O2w	134.07 (7)	La—O1w—H1w1	120 (3)
O1w—La—O1a^i	71.57 (5)	La—O1w—H1w2	114.0 (17)
O1w—La—O2a^i	70.98 (6)	H1w1—O1w—H1w2	108 (3)
O1w—La—O3a^ii	139.45 (6)	La—O2w—H2w1	120 (3)
O2w—La—O1a^i	83.84 (6)	La—O2w—H2w2	130 (3)
O2w—La—O2a^i	63.20 (6)	H2w1—O2w—H2w2	108 (4)
O2w—La—O3a^ii	86.26 (6)
O2a—La—O1a—C1a	160.46 (13)	O3a^ii—La—O1w—H1w2	170 (3)
O2a—La—O1a—La^iii	3.21 (6)	O1a—La—O2w—H2w1	104 (4)
O3a—La—O1a—C1a	−50.20 (16)	O1a—La—O2w—H2w2	−93 (4)
O3a—La—O1a—La^iii	152.55 (8)	O2a—La—O2w—H2w1	151 (4)
O4a—La—O1a—C1a	−129.99 (12)	O2a—La—O2w—H2w2	−46 (4)
O4a—La—O1a—La^iii	72.76 (7)	O3a—La—O2w—H2w1	−70 (4)
O1b—La—O1a—C1a	120.04 (13)	O3a—La—O2w—H2w2	93 (4)
O1b—La—O1a—La^iii	−37.20 (11)	O4a—La—O2w—H2w1	−177 (4)
O1w—La—O1a—C1a	81.87 (12)	O4a—La—O2w—H2w2	−15 (4)
O1w—La—O1a—La^iii	−75.38 (7)	O1b—La—O2w—H2w1	−78 (4)
O2w—La—O1a—C1a	−62.02 (12)	O1b—La—O2w—H2w2	84 (4)
O2w—La—O1a—La^iii	140.73 (8)	O1w—La—O2w—H2w1	53 (4)
O1a^i—La—O1a—C1a	18.17 (12)	O1w—La—O2w—H2w2	−144 (4)
O1a^i—La—O1a—La^iii	−139.08 (6)	O1a^i—La—O2w—H2w1	−4 (4)
O2a^i—La—O1a—C1a	1.27 (11)	O1a^i—La—O2w—H2w2	159 (4)
O2a^i—La—O1a—La^iii	−155.98 (10)	O2a^i—La—O2w—H2w1	57 (4)
O3a^ii—La—O1a—C1a	−140.48 (11)	O2a^i—La—O2w—H2w2	−140 (4)
O3a^ii—La—O1a—La^iii	62.28 (8)	O3a^ii—La—O2w—H2w1	−132 (4)
O1a—La—O2a—La^iii	−2.78 (5)	O3a^ii—La—O2w—H2w2	31 (4)
O1a—La—O2a—C1a^iii	148.3 (4)	O1a—La—O2a^i—C1a	−1.27 (10)
O3a—La—O2a—La^iii	−161.18 (6)	O2a—La—O2a^i—C1a	−20.78 (13)
O3a—La—O2a—C1a^iii	−10.1 (4)	O3a—La—O2a^i—C1a	155.13 (11)
O4a—La—O2a—La^iii	−87.69 (8)	O4a—La—O2a^i—C1a	48.06 (12)
O4a—La—O2a—C1a^iii	63.4 (3)	O1b—La—O2a^i—C1a	−115.72 (13)
O1b—La—O2a—La^iii	149.46 (8)	O1w—La—O2a^i—C1a	−83.91 (12)
O1b—La—O2a—C1a^iii	−59.4 (4)	O2w—La—O2a^i—C1a	99.33 (13)
O1w—La—O2a—La^iii	75.43 (7)	O1a^i—La—O2a^i—C1a	−162.76 (13)
O1w—La—O2a—C1a^iii	−133.4 (4)	O3a^ii—La—O2a^i—C1a	81.96 (14)
O2w—La—O2a—La^iii	−56.22 (9)	O1a—La—O3a^ii—La^ii	147.68 (7)
O2w—La—O2a—C1a^iii	94.9 (4)	O1a—La—O3a^ii—C3a^ii	13.34 (14)
O1a^i—La—O2a—La^iii	78.88 (13)	O2a—La—O3a^ii—La^ii	−161.40 (9)
O1a^i—La—O2a—C1a^iii	−130.0 (3)	O2a—La—O3a^ii—C3a^ii	64.27 (12)
O2a^i—La—O2a—La^iii	13.04 (8)	O3a—La—O3a^ii—La^ii	−0.00 (6)
O2a^i—La—O2a—C1a^iii	164.2 (3)	O3a—La—O3a^ii—C3a^ii	−134.34 (13)
O3a^ii—La—O2a—La^iii	−135.67 (7)	O4a—La—O3a^ii—La^ii	134.09 (10)
O3a^ii—La—O2a—C1a^iii	15.5 (3)	O4a—La—O3a^ii—C3a^ii	−0.25 (11)
O1a—La—O3a—C3a	134.19 (17)	O1b—La—O3a^ii—La^ii	−79.01 (9)
O1a—La—O3a—La^ii	−106.88 (11)	O1b—La—O3a^ii—C3a^ii	146.65 (13)
O2a—La—O3a—C3a	−90.08 (19)	O1w—La—O3a^ii—La^ii	−112.27 (8)
O2a—La—O3a—La^ii	28.85 (11)	O1w—La—O3a^ii—C3a^ii	113.39 (13)
O4a—La—O3a—C3a	−151.83 (18)	O2w—La—O3a^ii—La^ii	73.04 (8)
O4a—La—O3a—La^ii	−32.90 (8)	O2w—La—O3a^ii—C3a^ii	−61.30 (12)
O1b—La—O3a—C3a	−38.60 (18)	O1a^i—La—O3a^ii—La^ii	−6.34 (11)
O1b—La—O3a—La^ii	80.33 (8)	O1a^i—La—O3a^ii—C3a^ii	−140.68 (12)
O1w—La—O3a—C3a	13.7 (3)	O2a^i—La—O3a^ii—La^ii	88.52 (12)
O1w—La—O3a—La^ii	132.67 (7)	O2a^i—La—O3a^ii—C3a^ii	−45.82 (16)
O2w—La—O3a—C3a	146.32 (19)	La—O1a—C1a—C2a	177.10 (15)
O2w—La—O3a—La^ii	−94.75 (8)	La—O1a—C1a—O2a^i	−2.41 (19)
O1a^i—La—O3a—C3a	55.51 (18)	La^iii—O1a—C1a—C2a	−30.7 (3)
O1a^i—La—O3a—La^ii	174.44 (9)	La^iii—O1a—C1a—O2a^i	149.83 (16)
O2a^i—La—O3a—C3a	95.89 (18)	La—O1a—La^iii—O2a	−2.99 (6)
O2a^i—La—O3a—La^ii	−145.18 (7)	C1a—O1a—La^iii—O2a	−150.9 (3)
O3a^ii—La—O3a—C3a	−118.93 (19)	La—O2a—La^iii—O1a	2.93 (5)
O3a^ii—La—O3a—La^ii	0.00 (6)	C1a^iii—O2a—La^iii—O1a	−162.76 (13)
O1a—La—O4a—C3a^ii	−167.89 (14)	La—O3a—C3a—C2a^i	−51.6 (3)
O2a—La—O4a—C3a^ii	−100.56 (14)	La—O3a—C3a—O4a^ii	128.76 (17)
O3a—La—O4a—C3a^ii	40.12 (13)	La^ii—O3a—C3a—C2a^i	179.19 (17)
O1b—La—O4a—C3a^ii	−34.96 (14)	La^ii—O3a—C3a—O4a^ii	−0.5 (2)
O1w—La—O4a—C3a^ii	−123.31 (13)	La—O3a—La^ii—O3a^ii	0.00 (6)
O2w—La—O4a—C3a^ii	107.55 (14)	La—O3a—La^ii—O4a^ii	−134.09 (10)
O1a^i—La—O4a—C3a^ii	95.12 (18)	C3a—O3a—La^ii—O3a^ii	134.34 (13)
O2a^i—La—O4a—C3a^ii	157.13 (12)	C3a—O3a—La^ii—O4a^ii	0.25 (11)
O3a^ii—La—O4a—C3a^ii	0.26 (11)	La—O4a—C3a^ii—O3a^ii	−0.5 (3)
O1a—La—O1b—C1b	4.7 (8)	O1a—C1a—C2a—H2a1	−179 (3)
O2a—La—O1b—C1b	−31.3 (8)	O1a—C1a—C2a—H2a2	−65 (3)
O3a—La—O1b—C1b	179.9 (8)	O1a—C1a—C2a—C3a^iii	55.8 (3)
O4a—La—O1b—C1b	−88.4 (8)	O2a^i—C1a—C2a—H2a1	0 (3)
O1w—La—O1b—C1b	42.9 (8)	O2a^i—C1a—C2a—H2a2	115 (3)
O2w—La—O1b—C1b	−171.7 (7)	O2a^i—C1a—C2a—C3a^iii	−124.7 (2)
O1a^i—La—O1b—C1b	114.6 (8)	O1a—C1a—O2a^i—La	2.25 (18)
O2a^i—La—O1b—C1b	74.5 (8)	C2a—C1a—O2a^i—La	−177.26 (15)
O3a^ii—La—O1b—C1b	−115.1 (8)	O3a—C3a—O4a^ii—La^ii	0.5 (3)
O1a—La—O1w—H1w1	158 (3)	C2a^i—C3a—O4a^ii—La^ii	−179.19 (16)
O1a—La—O1w—H1w2	−71 (3)	La—O1b—C1b—O2b	172.4 (6)
O2a—La—O1w—H1w1	91 (3)	La—O1b—C1b—C2b	−7.5 (9)
O2a—La—O1w—H1w2	−138 (3)	O1b—C1b—C2b—H2b1	23 (3)
O3a—La—O1w—H1w1	−47 (3)	O1b—C1b—C2b—C1b^iv	−96.3 (3)
O3a—La—O1w—H1w2	83 (3)	O1b—C1b—C2b—H2b1^iv	144 (3)
O4a—La—O1w—H1w1	113 (3)	O2b—C1b—C2b—H2b1	−156 (3)
O4a—La—O1w—H1w2	−117 (3)	O2b—C1b—C2b—C1b^iv	83.8 (3)
O1b—La—O1w—H1w1	6 (3)	O2b—C1b—C2b—H2b1^iv	−36 (3)
O1b—La—O1w—H1w2	136 (3)	O3a—La^ii—O3a^ii—La	0.00 (6)
O2w—La—O1w—H1w1	−148 (3)	O3a—La^ii—O3a^ii—C3a^ii	118.93 (19)
O2w—La—O1w—H1w2	−18 (3)	O4a^ii—La^ii—O3a^ii—La	32.90 (9)
O1a^i—La—O1w—H1w1	−87 (3)	O4a^ii—La^ii—O3a^ii—C3a^ii	151.83 (18)
O1a^i—La—O1w—H1w2	44 (3)	O3a—La^ii—O4a^ii—C3a	−0.26 (11)
O2a^i—La—O1w—H1w1	−152 (3)	O3a^ii—La^ii—O4a^ii—C3a	−40.12 (13)
O2a^i—La—O1w—H1w2	−22 (3)	La—O3a^ii—C3a^ii—O4a	0.5 (2)
O3a^ii—La—O1w—H1w1	39 (3)	La^ii—O3a^ii—C3a^ii—O4a	−128.76 (17)

Symmetry codes: (i) −x+3/2, y+1/2, −z+1/2; (ii) −x+3/2, −y+3/2, −z+1; (iii) −x+3/2, y−1/2, −z+1/2; (iv) −x+1, y, −z+1/2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O2w—H2w1···O1w^i	1.06 (3)	1.77 (3)	2.779 (3)	158 (3)
O1w—H1w2···O4a^i	1.02 (4)	1.67 (4)	2.688 (3)	172 (3)
O1w—H1w1···O2b^iv	1.00 (3)	1.70 (3)	2.699 (3)	173 (3)
O2w—H2w2···O2b^ii	1.02 (3)	1.84 (4)	2.763 (3)	149 (4)

Symmetry codes: (i) −x+3/2, y+1/2, −z+1/2; (ii) −x+3/2, −y+3/2, −z+1; (iv) −x+1, y, −z+1/2.