High-resolution crystal structure of the double nitrate hydrate [La(NO3)6]2[Ni(H2O)6]3·6H2O

Bi, D.W.; Liu, Y.; Magrez, A.

doi:10.1107/S205698902400327X

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ISSN: 2056-9890

Volume 80| Part 6| June 2024| Pages 586-589

https://doi.org/10.1107/S205698902400327X

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High-resolution crystal structure of the double nitrate hydrate [La(NO₃)₆]₂[Ni(H₂O)₆]₃·6H₂O

David Wenhua Bi,^a ^* Yong Liu ^a and Arnaud Magrez ^a

^aCrystal Growth Facility, Institute of Physics, École Polytechnique Fédérale de Lausanne (EPFL), Switzerland
^*Correspondence e-mail: wen.bi@epfl.ch

Edited by B. Therrien, University of Neuchâtel, Switzerland (Received 13 March 2024; accepted 15 April 2024; online 10 May 2024)

This study introduces bis[hexakis(nitrato-κ²O,O′)lanthanum(III)] tris[hexaaquanickel(II)] hexahydrate, [La(NO₃)₆]₂[Ni(H₂O)₆]₃·6H₂O, with a structure refined in the hexagonal space group R $[\overline{3}]$ . The salt comprises [La(NO₃)₆]³⁻ icosahedra and [Ni(H₂O)₆]²⁺ octahedra, thus forming an intricate network of interpenetrating honeycomb lattices arranged in layers. This arrangement is stabilized through strong hydrogen bonds. Two successive layers are connected via the second [Ni(H₂O)₆]²⁺ octahedra, forming sheets which are stacked perpendicular to the c axis and held in the crystal by van der Waals forces. The synthesis of [La(NO₃)₆]₂[Ni(H₂O)₆]₃·6H₂O involves dissolving lanthanum(III) and nickel(II) oxides in nitric acid, followed by slow evaporation, yielding green hexagonal plate-like crystals.

Keywords: crystal structure; double nitrate; X-ray diffraction; hydrogen bonding.

CCDC reference: 2348374

1. Chemical context

Double nitrates, which contain two different metal cations and nitrate anions, have applications in various fields. They exhibit unique solubility properties, crystalline structures and special magnetic properties, and act as excellent precursors for the synthesis of mixed oxides. For example, double nitrates of Zn and Cu have been used to produce a mixed Cu and Zn oxide that exhibits high catalytic activity in reactions such as the water gas shift reaction to produce CO₂ and H₂ from CO and H₂O (Smith et al., 2010 ), as well as selective CO₂ hydrogenation into methanol (Zhong et al., 2020 ). Rare earth (RE) transition-metal (TM) double nitrates with the general formula RE₂TM₃(NO₃)₁₂·24H₂O attracted much attention in the 1960s, in which the RE is a trivalent cation with an atomic number lower than that of Ho and the TM is a divalent cation, including Mg²⁺, Mn²⁺, Fe²⁺, Co²⁺, Ni²⁺, Cu²⁺ and Zn²⁺ (Hellwege & Hellwege, 1953 ; Brochard & Hellwege, 1953 ; Buckmaster et al., 1968 ). It should be noted that when RE has a +4 oxidation state, double nitrates are isomorphic with the triclinic MgTh(NO₃)₆(H₂O)₈ salt (Šćavničar & Prodić, 1965 ). Cerium(III) magnesium and cerium(III) zinc double nitrates have been used extensively in nuclear orientation experiments because very low temperatures can be obtained by adiabatic demagnetization of the salt (Culvahouse, 1961 ). Their properties make them suitable magnetic thermometers (Thornley, 1963 ). Like ruby single crystals (Cr³⁺:Al₂O₃), a Ce-doped lanthanum magnesium double nitrate is an ideal medium to study phonon avalanche, a delayed and sudden relaxation of paramagnetic ions by the emission of phonons (Mims & Taylor, 1969 ). Heat capacity and susceptibility measurements suggested that Mn, Ni, Co and Cu lanthanum double nitrates show antiferromagnetic transitions below 0.5 K (Mess et al., 1967 , 1968 ). The lack of high-quality crystalline structures of these salts limits the profound understanding of the magnetic properties, as well as their theoretical investigation. We report herein on the growth of centimeter-large crystals of [La(NO₃)₆]₂[Ni(H₂O)₆]₃·6H₂O (Fig. 1) and the crystal structure determined by single-crystal X-ray diffraction.

Figure 1
Left: large green crystals of [La(NO₃)₆]₂[Ni(H₂O)₆]₃·6H₂O with a pseudo-hexagonal shape placed on a scale paper. The distance between two thick lines is 1 cm. Right: powder X-ray diffraction patterns of [La(NO₃)₆]₂[Ni(H₂O)₆]₃·6H₂O. The PDF5 (ID = 00-049-1235) pattern available in the database is shown in green. The PXRD pattern calculated from the structure refined from single-crystal data and the experimental pattern measured on a Panalytical Empyrean diffractometer with Cu Kα₁ radiation (λ = 1.540596 Å) are shown in blue and red, respectively. In the inset, the high-intensity diffraction peaks absent in the PDF5 pattern are highlighted with purple rectangles.

2. Structural commentary

Similar to those found in the corresponding magnesium double salt, the title compound is made up of two types of ions, [Ni(H₂O)₆]²⁺ and [La(NO₃)₆]³⁻, which are linked together by hydrogen bonds with water molecules in the structure. The La atom on the threefold axis is coordinated by 12 O atoms from six nitrate groups to form a slightly distorted icosahedron. The La—O distances range from 2.6339 (8) to 2.7012 (8) Å, which are comparable to those found in La₂Mg₃(NO₃)₁₂·24H₂O determined by neutron diffraction (Anderson et al., 1977 ). As depicted in Fig. 2, the structure includes two crystallographically independent positions for Ni²⁺. Three water H7a—O7–H7b molecules and three water H8a—O8—H8b molecules surround Ni1, resulting in a distorted [Ni(H₂O)₆]²⁺ octahedron with C3 symmetry. In contrast, the Ni2-containing [Ni(H₂O)₆]²⁺ octahedron is highly symmetric, as Ni2 is situated in a site with $[\overline{3}]$ symmetry. The Ni—O bond lengths in both octahedra vary from 2.0471 (8) to 2.0531 (8) Å, similar to those found in [Ni(H₂O)₆](NO₃)₂ (Breternitz et al., 2015 ).

Figure 2
The molecular structure of [La(NO₃)₆]₂[Ni(H₂O)₆]₃·6H₂O, with displacement ellipsoids for all non-H atoms drawn at the 50% probability level. H atoms are represented by small spheres of arbitrary radius. H-atom labels have been omitted for clarity. The colour scheme for the different elements can be found in the legend. The viewing direction is slightly tilted from the c axis, in order to prevent overlap between atoms. Hydrogen bonds are indicated with thin dotted lines.

As illustrated in Fig. 3, each [La(NO₃)₆]³⁻ icosahedron is surrounded by three Ni1-containing [Ni(H₂O)₆]²⁺ clusters, and each Ni1-containing octahedron is surrounded by three icosahedra. These two interpenetrating honeycomb networks are arranged in a layer parallel to the ab plane. In this layer, the icosahedra are linked to the [Ni(H₂O)₆]²⁺ clusters through strong O7—H7A⋯O4, O9—H9A⋯O1 and O10—H10A⋯O9 hydrogen bonds. The six water H9A—O9—H9B molecules per unit cell do not participate in the coordination of either La or Ni. Two successive layers are separated by Ni2-containing [Ni(H₂O)₆]²⁺ clusters, which bridge the layers between them via O10—H10A⋯O9 hydrogen bonds. The complex hydrogen-bonding network between the clusters is shown in Fig. 2 and the actual data for the hydrogen bonds are given in Table 1. The network of bonded clusters form sheets that are stacked perpendicular to the c axis (Fig. 4). The sheets are held together by van der Waals forces in the [La(NO₃)₆]₂[Ni(H₂O)₆]₃·6H₂O structure.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O8—H8A⋯O9	0.85	2.00	2.8386 (15)	169
O10—H10A⋯O9ⁱ	0.85	2.03	2.8149 (13)	153
O10—H10B⋯O5ⁱⁱ	0.86	2.14	2.9626 (13)	161
O7—H7A⋯O4ⁱⁱⁱ	0.86	1.92	2.7656 (11)	168
O7—H7B⋯O6^iv	0.86	2.13	2.9393 (11)	158
Symmetry codes: (i) ; (ii) ; (iii) ; (iv) .

Figure 3
The [La(NO₃)₆]₂[Ni(H₂O)₆]₃·6H₂O structure represented along the c axis. The colour scheme for the different elements of the structure can be found in the figure inset. [Ni(H₂O)₆]²⁺ octahedra and [La(NO₃)₆]³⁻ icosahedra are plotted as pink and green front-opening polyhedron, respectively. The unit-cell edges are plotted with blue lines.

Figure 4
The [La(NO₃)₆]₂[Ni(H₂O)₆]₃·6H₂O structure represented along the a axis. The colour scheme for the different elements of the structure can be found in the inset. [Ni(H₂O)₆]²⁺ octahedra and [La(NO₃)₆]³⁻ icosahedra are plotted as pink and green polyhedra, respectively. The unit-cell edges are plotted with blue lines.

3. Database survey

No record of the same compound was found in the Crystallography Open Database (COD) or the Inorganic Crystal Structure Database (ICSD). It is listed only once in the Powder Diffraction File (PDF) 2024 version, entry 00-049-1235, without any atomic positions provided. The powder X-ray diffraction (PXRD) pattern available in this database deviates significantly from both the theoretical pattern simulated from the structure refined via single-crystal XRD data and the experimental pattern recorded with powder obtained by crushing a few [La(NO₃)₆]₂[Ni(H₂O)₆]₃·6H₂O single crystals. Notably, peaks below 10°, as well as those in the 22–23° region, are missing in the pattern found in PDF-00-49-1235 (Fig. 1).

4. Synthesis and crystallization

Lanthanum(III) oxide was dissolved in dilute HNO₃ with a concentration of 1 mol l⁻¹ (1 M) and nickel(II) oxide in dilute HNO₃ with a concentration of 0.5 mol l⁻¹ (0.5 M). In order to dissolve the nickel(II) oxide in the dilute HNO₃, the solution was heated at 423 K over a period of 12 h until the nickel(II) oxide completely dissolved and a green transparent solution was obtained. Lanthanum(III) oxide solution (0.2 l) was first mixed with nickel(II) oxide solution (1.2 l) and then 1 mol of citric acid was added to the mixture under vigorous stirring until complete dissolution. The solution was transferred to a fume hood for slow evaporation. After 30 d, green hexagonal plate-shaped crystals formed with different sizes, the maximum dimension being 2 cm.

5. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. H atoms on O atoms were first located in a difference Fourier map and then refined isotropically in riding mode, with U_iso(H) values of 1.5U_eq of the parent O atoms. The O—H distance was refined against the residual peaks, without further constraint.

Table 2
Experimental details

Crystal data
Chemical formula	[La(NO₃)₆]₂[Ni(H₂O)₆]₃·6H₂O
M_r	1630.45
Crystal system, space group	Hexagonal, R $[\overline{3}]$
Temperature (K)	297
a, c (Å)	11.0230 (1), 34.4826 (4)
V (Å³)	3628.53 (8)
Z	3
Radiation type	Mo Kα
μ (mm⁻¹)	3.04
Crystal size (mm)	0.21 × 0.19 × 0.11

Data collection
Diffractometer	XtaLAB Synergy-i HyPix3000
Absorption correction	Gaussian (CrysAlis PRO; Rigaku OD, 2023 $[Rigaku OD (2023). CrysAlis PRO. Rigaku Oxford Diffraction Ltd, Yarnton, Oxfordshire, England.]$ )
T_min, T_max	0.573, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	27264, 2833, 2663
R_int	0.023
(sin θ/λ)_max (Å⁻¹)	0.746

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.013, 0.034, 1.06
No. of reflections	2833
No. of parameters	126
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.30, −0.38
Computer programs: CrysAlis PRO (Rigaku OD, 2023 $[Rigaku OD (2023). CrysAlis PRO. Rigaku Oxford Diffraction Ltd, Yarnton, Oxfordshire, England.]$ ), SHELXT2018 (Sheldrick, 2015a ), SHELXL2018 (Sheldrick, 2015b ), DIAMOND (Brandenburg, 2006 ) and publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 2348374

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S205698902400327X/tx2083sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S205698902400327X/tx2083Isup2.hkl

checkCIF report

Computing details top

Bis[hexakis(nitrato-κ²O,O')lanthanum(III)] tris[hexaaquanickel(II)] hexahydrate top

Crystal data top

[La(NO₃)₆]₂[Ni(H₂O)₆]₃·6H₂O	D_x = 2.238 Mg m⁻³
M_r = 1630.45	Mo Kα radiation, λ = 0.71073 Å
Hexagonal, R3	Cell parameters from 22661 reflections
a = 11.0230 (1) Å	θ = 2.2–36.2°
c = 34.4826 (4) Å	µ = 3.04 mm⁻¹
V = 3628.53 (8) Å³	T = 297 K
Z = 3	Plate, blue
F(000) = 2430	0.21 × 0.19 × 0.11 mm

Data collection top

XtaLAB Synergy-i HyPix3000 diffractometer	2663 reflections with I > 2σ(I)
Radiation source: micro-focus sealed X-ray tube	R_int = 0.023
ω scans	θ_max = 32.0°, θ_min = 2.2°
Absorption correction: gaussian (CrysAlis PRO; Rigaku OD, 2023)	h = −16→16
T_min = 0.573, T_max = 1.000	k = −16→16
27264 measured reflections	l = −51→51
2833 independent reflections

Refinement top

Refinement on F²	Hydrogen site location: difference Fourier map
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.013	w = 1/[σ²(F_o²) + (0.0161P)² + 2.1621P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.034	(Δ/σ)_max = 0.001
S = 1.06	Δρ_max = 0.30 e Å⁻³
2833 reflections	Δρ_min = −0.38 e Å⁻³
126 parameters	Extinction correction: SHELXL2018 (Sheldrick, 2015b), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.00015 (2)

Special details top

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.

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

	x	y	z	U_iso*/U_eq
La1	0.666667	0.333333	0.58402 (2)	0.01660 (3)
Ni1	0.333333	0.666667	0.59443 (2)	0.02146 (5)
O1	0.82133 (9)	0.59977 (8)	0.60265 (2)	0.03067 (17)
N1	0.88316 (10)	0.58535 (9)	0.63163 (3)	0.02614 (17)
Ni2	0.000000	0.000000	0.500000	0.02201 (6)
O2	0.97264 (11)	0.68693 (10)	0.64928 (3)	0.0487 (2)
N2	0.45188 (9)	0.08678 (9)	0.53286 (2)	0.02312 (16)
O3	0.84704 (10)	0.46142 (9)	0.64135 (2)	0.03567 (19)
O10	0.14730 (9)	0.15389 (9)	0.53499 (2)	0.03423 (18)
H10A	0.107682	0.185298	0.549969	0.051*
H10B	0.202599	0.224634	0.521158	0.051*
O9	0.76944 (11)	0.83079 (11)	0.60307 (3)	0.0422 (2)
H9A	0.807994	0.887099	0.621866	0.063*
H9B	0.807786	0.780452	0.602857	0.063*
O4	0.51001 (9)	0.06874 (8)	0.56231 (2)	0.02866 (16)
O5	0.36341 (10)	−0.01345 (9)	0.51426 (3)	0.03803 (19)
O6	0.49052 (9)	0.21141 (8)	0.52368 (2)	0.02951 (16)
O7	0.18944 (8)	0.68410 (8)	0.56094 (2)	0.02971 (16)
H7A	0.114671	0.604003	0.559052	0.045*
H7B	0.219721	0.704444	0.537602	0.045*
O8	0.48738 (10)	0.66808 (11)	0.62819 (3)	0.0386 (2)
H8A	0.572758	0.707366	0.621395	0.058*
H8B	0.478129	0.605850	0.644424	0.058*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
La1	0.01709 (4)	0.01709 (4)	0.01561 (5)	0.00855 (2)	0.000	0.000
Ni1	0.02300 (7)	0.02300 (7)	0.01838 (10)	0.01150 (3)	0.000	0.000
O1	0.0387 (4)	0.0262 (4)	0.0281 (4)	0.0169 (3)	−0.0104 (3)	−0.0022 (3)
N1	0.0273 (4)	0.0246 (4)	0.0244 (4)	0.0113 (3)	−0.0047 (3)	−0.0029 (3)
Ni2	0.02193 (9)	0.02193 (9)	0.02215 (14)	0.01097 (4)	0.000	0.000
O2	0.0486 (6)	0.0326 (5)	0.0447 (5)	0.0052 (4)	−0.0219 (4)	−0.0080 (4)
N2	0.0238 (4)	0.0218 (4)	0.0237 (4)	0.0114 (3)	−0.0024 (3)	−0.0033 (3)
O3	0.0502 (5)	0.0268 (4)	0.0307 (4)	0.0198 (4)	−0.0134 (4)	−0.0016 (3)
O10	0.0303 (4)	0.0312 (4)	0.0322 (4)	0.0086 (3)	−0.0002 (3)	−0.0060 (3)
O9	0.0550 (6)	0.0493 (6)	0.0348 (5)	0.0353 (5)	0.0018 (4)	0.0013 (4)
O4	0.0368 (4)	0.0233 (3)	0.0258 (4)	0.0149 (3)	−0.0086 (3)	−0.0018 (3)
O5	0.0370 (4)	0.0285 (4)	0.0420 (5)	0.0115 (4)	−0.0174 (4)	−0.0113 (3)
O6	0.0382 (4)	0.0229 (3)	0.0281 (4)	0.0158 (3)	−0.0059 (3)	0.0002 (3)
O7	0.0262 (4)	0.0313 (4)	0.0279 (4)	0.0116 (3)	−0.0052 (3)	−0.0006 (3)
O8	0.0364 (4)	0.0502 (5)	0.0326 (4)	0.0244 (4)	−0.0028 (3)	0.0101 (4)

Geometric parameters (Å, º) top

La1—O1	2.6339 (8)	N1—O2	1.2217 (12)
La1—O1ⁱ	2.6340 (8)	N1—O3	1.2621 (12)
La1—O1ⁱⁱ	2.6340 (8)	Ni2—O10	2.0531 (8)
La1—O4	2.6481 (8)	Ni2—O10^v	2.0531 (8)
La1—O4ⁱⁱ	2.6481 (8)	Ni2—O10^vi	2.0531 (8)
La1—O4ⁱ	2.6481 (8)	Ni2—O10^vii	2.0531 (8)
La1—O3	2.6546 (8)	Ni2—O10^viii	2.0531 (8)
La1—O3ⁱ	2.6547 (8)	Ni2—O10^ix	2.0531 (8)
La1—O3ⁱⁱ	2.6547 (8)	N2—O5	1.2271 (11)
La1—O6ⁱⁱ	2.7011 (8)	N2—O6	1.2585 (11)
La1—O6ⁱ	2.7011 (8)	N2—O4	1.2684 (11)
La1—O6	2.7012 (8)	O10—H10A	0.8536
Ni1—O7ⁱⁱⁱ	2.0471 (8)	O10—H10B	0.8554
Ni1—O7^iv	2.0471 (8)	O9—H9A	0.8499
Ni1—O7	2.0472 (8)	O9—H9B	0.8492
Ni1—O8	2.0526	O7—H7A	0.8576
Ni1—O8ⁱⁱⁱ	2.0526	O7—H7B	0.8571
Ni1—O8^iv	2.0526	O8—H8A	0.8489
O1—N1	1.2638 (11)	O8—H8B	0.8510

O1—La1—O1ⁱ	114.254 (14)	O4—La1—O6	47.44 (2)
O1—La1—O1ⁱⁱ	114.253 (14)	O4ⁱⁱ—La1—O6	111.22 (2)
O1ⁱ—La1—O1ⁱⁱ	114.252 (14)	O4ⁱ—La1—O6	70.19 (3)
O1—La1—O4	177.58 (2)	O3—La1—O6	177.63 (2)
O1ⁱ—La1—O4	67.33 (2)	O3ⁱ—La1—O6	111.60 (3)
O1ⁱⁱ—La1—O4	66.00 (2)	O3ⁱⁱ—La1—O6	110.71 (3)
O1—La1—O4ⁱⁱ	67.33 (2)	O6ⁱⁱ—La1—O6	67.04 (3)
O1ⁱ—La1—O4ⁱⁱ	66.00 (2)	O6ⁱ—La1—O6	67.04 (3)
O1ⁱⁱ—La1—O4ⁱⁱ	177.58 (2)	O7ⁱⁱⁱ—Ni1—O7^iv	91.31 (3)
O4—La1—O4ⁱⁱ	112.340 (15)	O7ⁱⁱⁱ—Ni1—O7	91.31 (3)
O1—La1—O4ⁱ	66.00 (2)	O7^iv—Ni1—O7	91.31 (3)
O1ⁱ—La1—O4ⁱ	177.58 (2)	O7ⁱⁱⁱ—Ni1—O8	92.55 (4)
O1ⁱⁱ—La1—O4ⁱ	67.33 (2)	O7^iv—Ni1—O8	85.37 (4)
O4—La1—O4ⁱ	112.341 (15)	O7—Ni1—O8	174.96 (4)
O4ⁱⁱ—La1—O4ⁱ	112.340 (15)	O7ⁱⁱⁱ—Ni1—O8ⁱⁱⁱ	174.96 (4)
O1—La1—O3	47.95 (2)	O7^iv—Ni1—O8ⁱⁱⁱ	92.55 (4)
O1ⁱ—La1—O3	72.20 (3)	O7—Ni1—O8ⁱⁱⁱ	85.37 (3)
O1ⁱⁱ—La1—O3	115.50 (3)	O8—Ni1—O8ⁱⁱⁱ	91.0
O4—La1—O3	134.33 (2)	O7ⁱⁱⁱ—Ni1—O8^iv	85.37 (4)
O4ⁱⁱ—La1—O3	66.91 (3)	O7^iv—Ni1—O8^iv	174.96 (4)
O4ⁱ—La1—O3	108.96 (3)	O7—Ni1—O8^iv	92.55 (4)
O1—La1—O3ⁱ	115.51 (3)	O8—Ni1—O8^iv	91.0
O1ⁱ—La1—O3ⁱ	47.95 (2)	O8ⁱⁱⁱ—Ni1—O8^iv	91.0
O1ⁱⁱ—La1—O3ⁱ	72.20 (3)	N1—O1—La1	98.15 (6)
O4—La1—O3ⁱ	66.91 (3)	O2—N1—O3	122.21 (10)
O4ⁱⁱ—La1—O3ⁱ	108.96 (3)	O2—N1—O1	121.18 (10)
O4ⁱ—La1—O3ⁱ	134.33 (2)	O3—N1—O1	116.61 (9)
O3—La1—O3ⁱ	70.62 (3)	O10—Ni2—O10^v	180.0
O1—La1—O3ⁱⁱ	72.20 (3)	O10—Ni2—O10^vi	91.03 (3)
O1ⁱ—La1—O3ⁱⁱ	115.50 (3)	O10^v—Ni2—O10^vi	88.97 (3)
O1ⁱⁱ—La1—O3ⁱⁱ	47.95 (2)	O10—Ni2—O10^vii	88.97 (3)
O4—La1—O3ⁱⁱ	108.96 (3)	O10^v—Ni2—O10^vii	91.03 (3)
O4ⁱⁱ—La1—O3ⁱⁱ	134.33 (2)	O10^vi—Ni2—O10^vii	91.03 (3)
O4ⁱ—La1—O3ⁱⁱ	66.91 (3)	O10—Ni2—O10^viii	91.03 (3)
O3—La1—O3ⁱⁱ	70.62 (3)	O10^v—Ni2—O10^viii	88.97 (3)
O3ⁱ—La1—O3ⁱⁱ	70.62 (3)	O10^vi—Ni2—O10^viii	88.97 (3)
O1—La1—O6ⁱⁱ	108.56 (3)	O10^vii—Ni2—O10^viii	180.00 (4)
O1ⁱ—La1—O6ⁱⁱ	66.37 (3)	O10—Ni2—O10^ix	88.97 (3)
O1ⁱⁱ—La1—O6ⁱⁱ	130.25 (2)	O10^v—Ni2—O10^ix	91.03 (3)
O4—La1—O6ⁱⁱ	70.19 (3)	O10^vi—Ni2—O10^ix	180.00 (4)
O4ⁱⁱ—La1—O6ⁱⁱ	47.43 (2)	O10^vii—Ni2—O10^ix	88.97 (3)
O4ⁱ—La1—O6ⁱⁱ	111.22 (2)	O10^viii—Ni2—O10^ix	91.03 (3)
O3—La1—O6ⁱⁱ	111.60 (3)	O5—N2—O6	122.29 (9)
O3ⁱ—La1—O6ⁱⁱ	110.71 (3)	O5—N2—O4	120.90 (9)
O3ⁱⁱ—La1—O6ⁱⁱ	177.63 (2)	O6—N2—O4	116.80 (8)
O1—La1—O6ⁱ	66.37 (3)	N1—O3—La1	97.19 (6)
O1ⁱ—La1—O6ⁱ	130.25 (2)	Ni2—O10—H10A	109.7
O1ⁱⁱ—La1—O6ⁱ	108.56 (3)	Ni2—O10—H10B	109.5
O4—La1—O6ⁱ	111.22 (2)	H10A—O10—H10B	104.1
O4ⁱⁱ—La1—O6ⁱ	70.19 (3)	H9A—O9—H9B	104.7
O4ⁱ—La1—O6ⁱ	47.43 (2)	N2—O4—La1	98.97 (6)
O3—La1—O6ⁱ	110.71 (3)	N2—O6—La1	96.66 (6)
O3ⁱ—La1—O6ⁱ	177.63 (2)	Ni1—O7—H7A	109.7
O3ⁱⁱ—La1—O6ⁱ	111.60 (3)	Ni1—O7—H7B	109.6
O6ⁱⁱ—La1—O6ⁱ	67.04 (3)	H7A—O7—H7B	104.2
O1—La1—O6	130.25 (2)	Ni1—O8—H8A	123.3
O1ⁱ—La1—O6	108.57 (3)	Ni1—O8—H8B	127.0
O1ⁱⁱ—La1—O6	66.37 (3)	H8A—O8—H8B	104.4

La1—O1—N1—O2	177.19 (10)	O5—N2—O4—La1	−177.06 (9)
La1—O1—N1—O3	−3.22 (10)	O6—N2—O4—La1	3.67 (9)
O2—N1—O3—La1	−177.23 (10)	O5—N2—O6—La1	177.16 (9)
O1—N1—O3—La1	3.19 (10)	O4—N2—O6—La1	−3.58 (9)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O8—H8A···O9	0.85	2.00	2.8386 (15)	169
O10—H10A···O9^iv	0.85	2.03	2.8149 (13)	153
O10—H10B···O5^vi	0.86	2.14	2.9626 (13)	161
O7—H7A···O4^vii	0.86	1.92	2.7656 (11)	168
O7—H7B···O6^x	0.86	2.13	2.9393 (11)	158

Symmetry codes: (iv) −x+y, −x+1, z; (vi) x−y, x, −z+1; (vii) −y, x−y, z; (x) y, −x+y+1, −z+1.

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