Crystal structure of an unknown solvate of dodecakis­(μ2-alaninato-1:2κ2O:N,O)cerium(III)hexa­nickel(II) aqua­tris­(hydroxido-κO)tris­(nitrato-κ2O,O′)cerate(III)

Bezzubov, S.I.; Doljenko, V.D.; Churakov, A.V.; Zharinova, I.S.; Kiselev, Y.M.

doi:10.1107/S2056989015017132

metal-organic compounds

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ISSN: 2056-9890

Volume 71| Part 10| October 2015| Pages m183-m184

doi:10.1107/S2056989015017132

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Crystal structure of an unknown solvate of dodecakis(μ₂-alaninato-1:2κ²O:N,O)cerium(III)hexanickel(II) aquatris(hydroxido-κO)tris(nitrato-κ²O,O′)cerate(III)

Stanislav I. Bezzubov,^a ^* Vladimir D. Doljenko,^b Andrei V. Churakov,^a Irina S. Zharinova ^b and Yuri M. Kiselev ^b

^aInstitute of General and Inorganic Chemistry, Russian Academy of Sciences, Leninskii prosp. 31, Moscow 119991, Russian Federation, and ^bDepartment of Chemistry, M.V. Lomonosov Moscow State University, Leninskie Gory 1/3, Moscow 119991, Russian Federation
^*Correspondence e-mail: stas.bezzubov@gmail.com

Edited by M. Weil, Vienna University of Technology, Austria (Received 5 September 2015; accepted 12 September 2015; online 17 September 2015)

The chiral title compound, [CeNi₆(C₃H₆NO₂)₁₂][Ce(NO₃)₃(OH)₃(H₂O)], comprises a complex heterometallic Ni/Ce cation and a homonuclear Ce anion. Both the cation and anion exhibit point group symmetry 3. with the Ce^III atom situated on the threefold rotation axis. The cation metal core consists of six Ni^II atoms coordinated in a slightly distorted octahedral N₂O₄ configuration by N and O atoms of 12 deprotonated L-alaninate ligands exhibiting both bridging and chelating modes. This metal–organic coordination motif encapsulates one Ce^III atom that shows an icosahedral coordination by the O-donor atoms of the L-alaninate ligands, with Ce—O distances varying in the range 2.455 (5)–2.675 (3) Å. In the anion, the central Ce^III ion is bound to three bidentate nitrate ligands, to three hydroxide ligands and to one water molecule, with Ce—O distances in the range 2.6808 (19)–2.741 (2) Å. The H atoms of the coordinating water molecule are disordered over three positions due to its location on a threefold rotation axis. Disorder is also observed in fragments of two L-alaninate ligands, with occupancy ratios of 0.608 (14):0.392 (14) and 0.669 (8):0.331 (8), respectively, for the two sets of sites. In the crystal, the complex cations and anions assemble through O—H⋯O and N—H⋯O hydrogen bonds into a three-dimensional network with large voids of approximately 1020 Å³. The contributions of highly disordered ethanol and water solvent molecules to the diffraction data were removed with the SQUEEZE procedure [Spek (2015 ). Acta Cryst. C71, 9–18]. The given chemical formula and other crystal data do not take into account the unknown amount of these solvent molecules.

Keywords: crystal structure; cerium complex; L-alaninate ligand; SQUEEZE procedure.

CCDC reference: 1421600

1. Related literature

Molecular magnets based on 3d–4f heterometallic constituents can be prepared easily by self-assembling of simple building blocks such as d-metal amino acid salts and lanthanide nitrates (Peristeraki et al., 2011 ; Yukawa et al., 2005 ; Igarashi et al., 2000 ). For an icosahedral coordination environment observed in similar compounds, see: Peristeraki et al. (2011); Zhang et al. (2004 ). For background to and application of the SQUEEZE procedure, see: Spek (2015).

2. Experimental

2.1. Crystal data

[CeNi₆(C₃H₆NO₂)₁₂][Ce(NO₃)₃(OH)₃(H₂O)]
M_r = 1944.63
Trigonal, R 3
a = 14.6418 (4) Å
c = 31.7767 (19) Å
V = 5899.7 (6) Å³
Z = 3
Mo Kα radiation
μ = 2.62 mm⁻¹
T = 150 K
0.40 × 0.40 × 0.40 mm

2.2. Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2008 ) T_min = 0.420, T_max = 0.420
21829 measured reflections
6978 independent reflections
6734 reflections with I > 2σ(I)
R_int = 0.021

2.3. Refinement

R[F² > 2σ(F²)] = 0.025
wR(F²) = 0.066
S = 1.02
6978 reflections
327 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.57 e Å⁻³
Δρ_min = −0.69 e Å⁻³
Absolute structure: Flack (1983 ), 3493 Friedel pairs
Absolute structure parameter: −0.012 (11)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯O17ⁱ	0.85	1.93	2.758 (3)	165
N11—H11B⋯O6ⁱⁱ	0.92	2.38	3.158 (5)	143
N12—H12D⋯O5ⁱⁱⁱ	0.92	2.17	3.086 (4)	174
N13—H13B⋯O2^iv	0.92	2.66	3.284 (4)	126
Symmetry codes: (i) x-1, y, z; (ii) -y+4, x-y+4, z; (iii) -x+y, -x+3, z; (iv) $[-x+y-{\script{1\over 3}}, -x+10/3, z+{\script{1\over 3}}]$ .

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information

CCDC reference: 1421600

Crystal structure: contains datablock I. DOI: 10.1107/S2056989015017132/wm5213sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S2056989015017132/wm5213Isup2.hkl

Supporting information file. DOI: 10.1107/S2056989015017132/wm5213Isup3.mol

checkCIF report

Related literature top

Molecular magnets based on 3d–4f heterometallic constituents can be prepared easily by self-assembling of simple building blocks such as d-metal amino acid salts and lanthanide nitrates (Peristeraki et al., 2011; Yukawa et al., 2005; Igarashi et al., 2000). For an icosahedral coordination environment observed in similar compounds, see: Peristeraki et al. (2011); Zhang et al. (2004). For background to and application of the SQUEEZE procedure, see: Spek (2015).

Experimental top

Crystals of the title complex were obtained in the course of several days after addition of a Ce(NO₃)₃ solution in a water-ethanol-methanol mixture to an aquous solution of Ni^II L-alaninate.

Computing details top

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the {Ni(ala)₂}₆ unit of the cation (ala = deprotonated L-alanine). Displacement ellipsoids are shown at the 50% probability level. Hydrogen atoms are omitted for clarity.
	Fig. 2. The coordination polyhedron of Ce2 in the complex cation of the title compound. Displacement ellipsoids are shown at the 50% probability level. A and B indicate symmetry operators -y + 3, x - y + 4, z and -x + y, -x + 3, z, respectively.
	Fig. 3. The structure of the complex anion [Ce(NO₃)₃(OH)₃(H₂O)]^3- in the title compound. Displacement ellipsoids are shown at the 50% probability level. Only one of the orientations of the water molecule is shown.
	Fig. 4. Hydrogen-bonding interactions (dotted lines) between the anion and cations.

Dodecakis(µ₂-alaninato-1:2κ²O:N,O)cerium(III)hexanickel(II) aquatris(hydroxido-κO)tris(nitrato-κ²O,O')cerate(III) top

Crystal data top

[CeNi₆(C₃H₆NO₂)₁₂][Ce(NO₃)₃(OH)₃(H₂O)]	D_x = 1.642 Mg m⁻³
M_r = 1944.63	Mo Kα radiation, λ = 0.71073 Å
Trigonal, R3	Cell parameters from 9898 reflections
Hall symbol: R 3	θ = 2.3–30.5°
a = 14.6418 (4) Å	µ = 2.62 mm⁻¹
c = 31.7767 (19) Å	T = 150 K
V = 5899.7 (6) Å³	Prism, violet
Z = 3	0.40 × 0.40 × 0.40 mm
F(000) = 2934

Data collection top

Bruker APEXII CCD diffractometer	6978 independent reflections
Radiation source: fine-focus sealed tube	6734 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.021
ω scans	θ_max = 29.0°, θ_min = 1.7°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −19→19
T_min = 0.420, T_max = 0.420	k = −19→19
21829 measured reflections	l = −43→43

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)] = 0.025	H-atom parameters constrained
wR(F²) = 0.066	w = 1/[σ²(F_o²) + (0.0434P)² + 4.4547P] where P = (F_o² + 2F_c²)/3
S = 1.02	(Δ/σ)_max = 0.003
6978 reflections	Δρ_max = 0.57 e Å⁻³
327 parameters	Δρ_min = −0.69 e Å⁻³
1 restraint	Absolute structure: Flack (1983), 3493 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.012 (11)

Crystal data top

[CeNi₆(C₃H₆NO₂)₁₂][Ce(NO₃)₃(OH)₃(H₂O)]	Z = 3
M_r = 1944.63	Mo Kα radiation
Trigonal, R3	µ = 2.62 mm⁻¹
a = 14.6418 (4) Å	T = 150 K
c = 31.7767 (19) Å	0.40 × 0.40 × 0.40 mm
V = 5899.7 (6) Å³

Data collection top

Bruker APEXII CCD diffractometer	6978 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2008)	6734 reflections with I > 2σ(I)
T_min = 0.420, T_max = 0.420	R_int = 0.021
21829 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.025	H-atom parameters constrained
wR(F²) = 0.066	Δρ_max = 0.57 e Å⁻³
S = 1.02	Δρ_min = −0.69 e Å⁻³
6978 reflections	Absolute structure: Flack (1983), 3493 Friedel pairs
327 parameters	Absolute structure parameter: −0.012 (11)
1 restraint

Special details top

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

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
Ce1	0.6667	2.3333	−1.143417 (9)	0.03086 (6)
Ce2	1.0000	2.0000	−1.058354 (6)	0.02110 (5)
Ni1	1.22355 (3)	2.18294 (3)	−1.125638 (10)	0.02623 (8)
Ni2	1.04234 (3)	2.22458 (3)	−0.991516 (11)	0.03043 (9)
O1	0.53783 (17)	2.31437 (18)	−1.08711 (7)	0.0354 (5)
H1	0.4768	2.2597	−1.0881	0.053*
O2	0.9922 (2)	2.4685 (3)	−1.17180 (10)	0.0583 (8)
O3	0.6667	2.3333	−1.22069 (16)	0.0798 (17)
H3	0.7213	2.3777	−1.2341	0.096*	0.3333
H2	0.6121	2.2889	−1.2341	0.096*	0.3333
O5	0.83829 (19)	2.33357 (19)	−1.15778 (8)	0.0441 (5)
O6	0.8541 (2)	2.4859 (2)	−1.17100 (9)	0.0484 (6)
O11	0.95267 (16)	2.15480 (15)	−1.04388 (6)	0.0252 (4)
O12	1.12234 (16)	2.02412 (17)	−1.12577 (6)	0.0268 (4)
O13	1.15557 (16)	2.20363 (16)	−1.07328 (6)	0.0274 (4)
O14	1.09798 (16)	2.12172 (17)	−0.99153 (6)	0.0299 (4)
O15	1.1670 (2)	2.3264 (2)	−1.02855 (8)	0.0402 (6)
O16	0.9167 (2)	2.1220 (2)	−0.95514 (7)	0.0446 (6)
O17	1.32725 (16)	2.16186 (16)	−1.08770 (6)	0.0286 (4)
O18	1.12072 (18)	2.20121 (19)	−1.16376 (7)	0.0362 (5)
N1	0.8977 (2)	2.4307 (2)	−1.16730 (9)	0.0407 (6)
N11	1.3169 (3)	2.3429 (2)	−1.12060 (12)	0.0541 (9)
H11B	1.3868	2.3617	−1.1229	0.065*
H11C	1.3012	2.3757	−1.1418	0.065*
N12	1.2828 (2)	2.1486 (2)	−1.17775 (8)	0.0328 (5)
H12E	1.2995	2.1995	−1.1980	0.039*
H12D	1.3432	2.1473	−1.1708	0.039*
N13	1.1359 (3)	2.2836 (3)	−0.93873 (9)	0.0460 (7)
H13A	1.1661	2.3558	−0.9378	0.055*
H13B	1.0962	2.2556	−0.9148	0.055*
N14	0.9681 (2)	2.3129 (2)	−0.99455 (9)	0.0375 (6)
H14A	0.9169	2.2909	−0.9741	0.045*
H14B	1.0163	2.3829	−0.9899	0.045*
C1	1.1303 (2)	1.9766 (2)	−1.15825 (9)	0.0290 (5)
C2	1.2482 (4)	1.9884 (4)	−1.21822 (13)	0.0582 (12)
H2A	1.2934	2.0342	−1.2409	0.087*
H2B	1.1908	1.9234	−1.2303	0.087*
H2C	1.2900	1.9710	−1.1992	0.087*
C3	1.2025 (3)	2.0449 (3)	−1.19394 (9)	0.0370 (7)
H3A	1.1575	2.0578	−1.2140	0.044*
C4	1.3104 (6)	2.4840 (5)	−1.0800 (4)	0.069 (3)	0.608 (14)
H4A	1.3773	2.5341	−1.0934	0.104*	0.608 (14)
H4B	1.3104	2.5057	−1.0508	0.104*	0.608 (14)
H4C	1.2519	2.4830	−1.0953	0.104*	0.608 (14)
C6	1.2977 (9)	2.3741 (8)	−1.0806 (4)	0.0300 (17)	0.608 (14)
H6A	1.3546	2.3787	−1.0617	0.036*	0.608 (14)
C41	1.2506 (9)	2.4577 (8)	−1.1104 (4)	0.053 (3)	0.392 (14)
H41A	1.3097	2.5160	−1.1252	0.080*	0.392 (14)
H41B	1.2183	2.4858	−1.0912	0.080*	0.392 (14)
H41C	1.1980	2.4109	−1.1309	0.080*	0.392 (14)
C61	1.2894 (14)	2.3979 (13)	−1.0862 (6)	0.034 (3)	0.392 (14)
H61A	1.3514	2.4445	−1.0682	0.041*	0.392 (14)
C5	0.9200 (3)	2.3002 (2)	−1.03646 (10)	0.0339 (6)
H5A	0.8506	2.2970	−1.0332	0.041*
C7	0.9018 (2)	2.1977 (2)	−1.05742 (9)	0.0256 (5)
C8	1.1977 (2)	2.2971 (2)	−1.06015 (10)	0.0327 (6)
C9	0.9906 (3)	2.3928 (3)	−1.06485 (13)	0.0509 (9)
H9A	1.0024	2.4586	−1.0518	0.076*
H9B	0.9564	2.3839	−1.0922	0.076*
H9C	1.0583	2.3956	−1.0687	0.076*
C10	0.8608 (4)	2.0257 (3)	−0.96288 (11)	0.0478 (9)
C11	1.2173 (4)	2.2543 (4)	−0.94147 (14)	0.0377 (12)	0.669 (8)
H11A	1.2765	2.3064	−0.9595	0.045*	0.669 (8)
C12	1.2588 (6)	2.2508 (6)	−0.89832 (19)	0.0550 (18)	0.669 (8)
H12A	1.3132	2.2308	−0.9010	0.082*	0.669 (8)
H12B	1.2009	2.1989	−0.8809	0.082*	0.669 (8)
H12C	1.2892	2.3205	−0.8852	0.082*	0.669 (8)
C21	1.1527 (10)	2.1841 (9)	−0.9212 (3)	0.041 (3)	0.331 (8)
H21A	1.2253	2.2204	−0.9089	0.049*	0.331 (8)
C22	1.0844 (12)	2.1161 (9)	−0.8863 (3)	0.056 (3)	0.331 (8)
H22A	1.1039	2.0628	−0.8794	0.084*	0.331 (8)
H22B	1.0103	2.0810	−0.8951	0.084*	0.331 (8)
H22C	1.0940	2.1597	−0.8615	0.084*	0.331 (8)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ce1	0.03464 (9)	0.03464 (9)	0.02330 (11)	0.01732 (4)	0.000	0.000
Ce2	0.02472 (7)	0.02472 (7)	0.01385 (9)	0.01236 (3)	0.000	0.000
Ni1	0.02819 (18)	0.03022 (17)	0.02059 (16)	0.01484 (14)	0.00288 (13)	0.00459 (13)
Ni2	0.0361 (2)	0.0351 (2)	0.02166 (16)	0.01905 (16)	−0.00561 (13)	−0.01041 (14)
O1	0.0299 (10)	0.0360 (11)	0.0344 (11)	0.0120 (9)	0.0075 (8)	−0.0004 (9)
O2	0.0441 (15)	0.0612 (17)	0.0574 (17)	0.0173 (13)	0.0195 (13)	0.0173 (14)
O3	0.106 (3)	0.106 (3)	0.027 (2)	0.0530 (14)	0.000	0.000
O5	0.0432 (12)	0.0381 (11)	0.0496 (13)	0.0192 (10)	0.0168 (10)	0.0074 (10)
O6	0.0564 (15)	0.0383 (12)	0.0498 (14)	0.0231 (12)	0.0179 (12)	0.0144 (11)
O11	0.0291 (9)	0.0269 (9)	0.0205 (9)	0.0147 (8)	−0.0004 (7)	−0.0026 (7)
O12	0.0302 (10)	0.0337 (10)	0.0165 (8)	0.0160 (9)	0.0014 (7)	0.0002 (7)
O13	0.0325 (10)	0.0319 (10)	0.0203 (9)	0.0179 (8)	−0.0003 (7)	0.0001 (7)
O14	0.0341 (10)	0.0383 (11)	0.0199 (9)	0.0201 (9)	−0.0066 (8)	−0.0077 (8)
O15	0.0399 (13)	0.0391 (13)	0.0344 (12)	0.0144 (10)	−0.0044 (10)	−0.0138 (10)
O16	0.0693 (17)	0.0407 (13)	0.0265 (10)	0.0297 (13)	0.0145 (11)	0.0006 (9)
O17	0.0254 (9)	0.0325 (10)	0.0255 (9)	0.0127 (8)	0.0000 (8)	0.0033 (8)
O18	0.0357 (11)	0.0485 (13)	0.0271 (10)	0.0231 (10)	0.0071 (9)	0.0162 (9)
N1	0.0426 (14)	0.0381 (14)	0.0331 (13)	0.0139 (12)	0.0149 (11)	0.0092 (10)
N11	0.067 (2)	0.0319 (15)	0.059 (2)	0.0219 (15)	0.0316 (17)	0.0141 (14)
N12	0.0294 (12)	0.0392 (13)	0.0273 (12)	0.0154 (11)	0.0064 (9)	0.0074 (10)
N13	0.0585 (18)	0.0634 (19)	0.0288 (13)	0.0398 (16)	−0.0168 (12)	−0.0241 (13)
N14	0.0449 (15)	0.0342 (13)	0.0348 (13)	0.0209 (12)	−0.0044 (11)	−0.0103 (11)
C1	0.0288 (13)	0.0352 (14)	0.0177 (11)	0.0121 (11)	0.0011 (9)	−0.0003 (10)
C2	0.055 (2)	0.060 (2)	0.037 (2)	0.0111 (19)	0.0209 (17)	−0.0129 (17)
C3	0.0332 (14)	0.0494 (18)	0.0184 (12)	0.0131 (13)	0.0031 (10)	−0.0014 (12)
C4	0.044 (4)	0.029 (3)	0.126 (8)	0.010 (3)	0.020 (4)	−0.002 (4)
C6	0.034 (3)	0.015 (4)	0.040 (4)	0.011 (3)	−0.003 (3)	−0.006 (3)
C41	0.051 (6)	0.040 (5)	0.071 (8)	0.024 (5)	0.016 (5)	0.018 (5)
C61	0.032 (5)	0.017 (7)	0.047 (6)	0.007 (4)	0.001 (4)	0.005 (5)
C5	0.0357 (15)	0.0308 (14)	0.0352 (15)	0.0167 (12)	−0.0037 (12)	−0.0101 (12)
C7	0.0240 (12)	0.0240 (12)	0.0252 (12)	0.0094 (10)	0.0020 (9)	−0.0014 (10)
C8	0.0288 (14)	0.0334 (14)	0.0324 (14)	0.0129 (12)	−0.0075 (11)	−0.0071 (12)
C9	0.060 (2)	0.0285 (15)	0.053 (2)	0.0138 (15)	−0.0117 (17)	0.0019 (14)
C10	0.077 (3)	0.0445 (18)	0.0289 (15)	0.0355 (19)	0.0287 (16)	0.0066 (13)
C11	0.034 (2)	0.051 (3)	0.028 (2)	0.021 (2)	−0.0061 (17)	−0.019 (2)
C12	0.069 (4)	0.080 (4)	0.040 (3)	0.055 (4)	−0.032 (3)	−0.032 (3)
C21	0.061 (7)	0.045 (6)	0.034 (5)	0.040 (6)	−0.016 (5)	−0.013 (4)
C22	0.088 (9)	0.046 (6)	0.025 (5)	0.027 (6)	−0.013 (5)	−0.004 (4)

Geometric parameters (Å, º) top

Ce1—O3	2.455 (5)	N12—C3	1.472 (4)
Ce1—O1ⁱ	2.513 (2)	N12—H12E	0.9200
Ce1—O1ⁱⁱ	2.513 (2)	N12—H12D	0.9200
Ce1—O1	2.513 (2)	N13—C11	1.457 (6)
Ce1—O5ⁱⁱ	2.552 (2)	N13—C21	1.689 (11)
Ce1—O5	2.552 (2)	N13—H13A	0.9200
Ce1—O5ⁱ	2.552 (2)	N13—H13B	0.9200
Ce1—O6ⁱⁱ	2.675 (3)	N14—C5	1.474 (4)
Ce1—O6ⁱ	2.675 (3)	N14—H14A	0.9200
Ce1—O6	2.675 (3)	N14—H14B	0.9200
Ce2—O14ⁱⁱⁱ	2.6808 (19)	C1—O18ⁱⁱⁱ	1.246 (4)
Ce2—O14^iv	2.6808 (19)	C1—C3	1.532 (4)
Ce2—O14	2.6809 (19)	C2—C3	1.510 (5)
Ce2—O12	2.700 (2)	C2—H2A	0.9800
Ce2—O12ⁱⁱⁱ	2.700 (2)	C2—H2B	0.9800
Ce2—O12^iv	2.700 (2)	C2—H2C	0.9800
Ce2—O11ⁱⁱⁱ	2.7202 (19)	C3—H3A	1.0000
Ce2—O11	2.720 (2)	C4—C6	1.525 (11)
Ce2—O11^iv	2.720 (2)	C4—H4A	0.9800
Ce2—O13ⁱⁱⁱ	2.741 (2)	C4—H4B	0.9800
Ce2—O13	2.741 (2)	C4—H4C	0.9800
Ce2—O13^iv	2.741 (2)	C6—C8	1.478 (12)
Ni1—O13	2.038 (2)	C6—H6A	1.0000
Ni1—O12	2.039 (2)	C41—C61	1.476 (17)
Ni1—N11	2.044 (3)	C41—H41A	0.9800
Ni1—N12	2.045 (3)	C41—H41B	0.9800
Ni1—O18	2.051 (2)	C41—H41C	0.9800
Ni1—O17	2.079 (2)	C61—C8	1.638 (17)
Ni2—O14	2.039 (2)	C61—H61A	1.0000
Ni2—O11	2.048 (2)	C5—C9	1.523 (5)
Ni2—O16	2.053 (3)	C5—C7	1.537 (4)
Ni2—O15	2.054 (3)	C5—H5A	1.0000
Ni2—N13	2.062 (3)	C7—O17^iv	1.256 (4)
Ni2—N14	2.066 (3)	C9—H9A	0.9800
O1—H1	0.8512	C9—H9B	0.9800
O2—N1	1.214 (4)	C9—H9C	0.9800
O3—H3	0.8501	C10—O14^iv	1.267 (4)
O3—H2	0.8501	C10—C21^iv	1.528 (11)
O5—N1	1.278 (4)	C10—C11^iv	1.612 (6)
O6—N1	1.262 (4)	C11—C12	1.511 (7)
O11—C7	1.267 (3)	C11—C10ⁱⁱⁱ	1.612 (6)
O12—C1	1.282 (3)	C11—H11A	1.0000
O13—C8	1.259 (4)	C12—H12A	0.9800
O14—C10ⁱⁱⁱ	1.266 (4)	C12—H12B	0.9800
O15—C8	1.259 (4)	C12—H12C	0.9800
O16—C10	1.251 (5)	C21—C22	1.493 (18)
O17—C7ⁱⁱⁱ	1.256 (4)	C21—C10ⁱⁱⁱ	1.528 (10)
O18—C1^iv	1.247 (4)	C21—H21A	1.0000
N11—C6	1.427 (12)	C22—H22A	0.9800
N11—C61	1.53 (2)	C22—H22B	0.9800
N11—H11B	0.9200	C22—H22C	0.9800
N11—H11C	0.9200

O3—Ce1—O1ⁱ	135.41 (5)	H3—O3—H2	120.0
O3—Ce1—O1ⁱⁱ	135.41 (6)	N1—O5—Ce1	99.56 (19)
O1ⁱ—Ce1—O1ⁱⁱ	74.89 (8)	N1—O6—Ce1	94.10 (17)
O3—Ce1—O1	135.41 (5)	C7—O11—Ni2	114.71 (17)
O1ⁱ—Ce1—O1	74.89 (8)	C7—O11—Ce2	144.52 (17)
O1ⁱⁱ—Ce1—O1	74.89 (8)	Ni2—O11—Ce2	100.73 (8)
O3—Ce1—O5ⁱⁱ	79.70 (6)	C1—O12—Ni1	114.16 (18)
O1ⁱ—Ce1—O5ⁱⁱ	82.30 (8)	C1—O12—Ce2	143.31 (18)
O1ⁱⁱ—Ce1—O5ⁱⁱ	144.27 (8)	Ni1—O12—Ce2	101.76 (8)
O1—Ce1—O5ⁱⁱ	72.80 (8)	C8—O13—Ni1	114.99 (19)
O3—Ce1—O5	79.70 (6)	C8—O13—Ce2	144.54 (19)
O1ⁱ—Ce1—O5	72.80 (8)	Ni1—O13—Ce2	100.46 (8)
O1ⁱⁱ—Ce1—O5	82.30 (8)	C10ⁱⁱⁱ—O14—Ni2	113.9 (2)
O1—Ce1—O5	144.27 (8)	C10ⁱⁱⁱ—O14—Ce2	143.8 (2)
O5ⁱⁱ—Ce1—O5	116.87 (4)	Ni2—O14—Ce2	102.27 (8)
O3—Ce1—O5ⁱ	79.70 (6)	C8—O15—Ni2	123.2 (2)
O1ⁱ—Ce1—O5ⁱ	144.27 (8)	C10—O16—Ni2	123.8 (2)
O1ⁱⁱ—Ce1—O5ⁱ	72.80 (8)	C7ⁱⁱⁱ—O17—Ni1	122.13 (18)
O1—Ce1—O5ⁱ	82.30 (8)	C1^iv—O18—Ni1	123.56 (18)
O5ⁱⁱ—Ce1—O5ⁱ	116.87 (4)	O2—N1—O6	121.5 (3)
O5—Ce1—O5ⁱ	116.88 (4)	O2—N1—O5	121.5 (3)
O3—Ce1—O6ⁱⁱ	70.88 (6)	O6—N1—O5	117.0 (3)
O1ⁱ—Ce1—O6ⁱⁱ	66.55 (8)	C6—N11—C61	17.5 (5)
O1ⁱⁱ—Ce1—O6ⁱⁱ	136.51 (8)	C6—N11—Ni1	108.1 (5)
O1—Ce1—O6ⁱⁱ	111.86 (8)	C61—N11—Ni1	117.3 (7)
O5ⁱⁱ—Ce1—O6ⁱⁱ	48.87 (8)	C6—N11—H11B	110.1
O5—Ce1—O6ⁱⁱ	68.01 (8)	C61—N11—H11B	116.5
O5ⁱ—Ce1—O6ⁱⁱ	148.93 (9)	Ni1—N11—H11B	110.1
O3—Ce1—O6ⁱ	70.88 (6)	C6—N11—H11C	110.1
O1ⁱ—Ce1—O6ⁱ	136.51 (8)	C61—N11—H11C	92.7
O1ⁱⁱ—Ce1—O6ⁱ	111.86 (8)	Ni1—N11—H11C	110.1
O1—Ce1—O6ⁱ	66.55 (8)	H11B—N11—H11C	108.4
O5ⁱⁱ—Ce1—O6ⁱ	68.01 (8)	C3—N12—Ni1	108.54 (18)
O5—Ce1—O6ⁱ	148.93 (9)	C3—N12—H12E	110.0
O5ⁱ—Ce1—O6ⁱ	48.87 (8)	Ni1—N12—H12E	110.0
O6ⁱⁱ—Ce1—O6ⁱ	109.82 (6)	C3—N12—H12D	110.0
O3—Ce1—O6	70.88 (6)	Ni1—N12—H12D	110.0
O1ⁱ—Ce1—O6	111.86 (8)	H12E—N12—H12D	108.4
O1ⁱⁱ—Ce1—O6	66.55 (8)	C11—N13—C21	43.3 (5)
O1—Ce1—O6	136.51 (8)	C11—N13—Ni2	107.3 (2)
O5ⁱⁱ—Ce1—O6	148.93 (9)	C21—N13—Ni2	105.0 (4)
O5—Ce1—O6	48.87 (8)	C11—N13—H13A	110.3
O5ⁱ—Ce1—O6	68.01 (8)	C21—N13—H13A	141.9
O6ⁱⁱ—Ce1—O6	109.82 (6)	Ni2—N13—H13A	110.3
O6ⁱ—Ce1—O6	109.82 (6)	C11—N13—H13B	110.3
O14ⁱⁱⁱ—Ce2—O14^iv	63.82 (8)	C21—N13—H13B	71.1
O14ⁱⁱⁱ—Ce2—O14	63.82 (8)	Ni2—N13—H13B	110.3
O14^iv—Ce2—O14	63.82 (8)	H13A—N13—H13B	108.5
O14ⁱⁱⁱ—Ce2—O12	116.32 (6)	C5—N14—Ni2	109.29 (19)
O14^iv—Ce2—O12	179.85 (7)	C5—N14—H14A	109.8
O14—Ce2—O12	116.23 (6)	Ni2—N14—H14A	109.8
O14ⁱⁱⁱ—Ce2—O12ⁱⁱⁱ	116.23 (6)	C5—N14—H14B	109.8
O14^iv—Ce2—O12ⁱⁱⁱ	116.32 (6)	Ni2—N14—H14B	109.8
O14—Ce2—O12ⁱⁱⁱ	179.85 (9)	H14A—N14—H14B	108.3
O12—Ce2—O12ⁱⁱⁱ	63.62 (7)	O18ⁱⁱⁱ—C1—O12	125.0 (3)
O14ⁱⁱⁱ—Ce2—O12^iv	179.85 (7)	O18ⁱⁱⁱ—C1—C3	117.4 (3)
O14^iv—Ce2—O12^iv	116.23 (6)	O12—C1—C3	117.5 (3)
O14—Ce2—O12^iv	116.33 (6)	C3—C2—H2A	109.5
O12—Ce2—O12^iv	63.62 (7)	C3—C2—H2B	109.5
O12ⁱⁱⁱ—Ce2—O12^iv	63.62 (7)	H2A—C2—H2B	109.5
O14ⁱⁱⁱ—Ce2—O11ⁱⁱⁱ	65.59 (6)	C3—C2—H2C	109.5
O14^iv—Ce2—O11ⁱⁱⁱ	117.85 (6)	H2A—C2—H2C	109.5
O14—Ce2—O11ⁱⁱⁱ	62.89 (6)	H2B—C2—H2C	109.5
O12—Ce2—O11ⁱⁱⁱ	62.27 (6)	N12—C3—C2	113.6 (3)
O12ⁱⁱⁱ—Ce2—O11ⁱⁱⁱ	116.99 (6)	N12—C3—C1	110.5 (2)
O12^iv—Ce2—O11ⁱⁱⁱ	114.45 (6)	C2—C3—C1	111.8 (3)
O14ⁱⁱⁱ—Ce2—O11	117.85 (6)	N12—C3—H3A	106.9
O14^iv—Ce2—O11	62.89 (6)	C2—C3—H3A	106.9
O14—Ce2—O11	65.59 (6)	C1—C3—H3A	106.9
O12—Ce2—O11	116.99 (6)	C6—C4—H4A	109.5
O12ⁱⁱⁱ—Ce2—O11	114.44 (6)	C6—C4—H4B	109.5
O12^iv—Ce2—O11	62.27 (6)	H4A—C4—H4B	109.5
O11ⁱⁱⁱ—Ce2—O11	117.20 (2)	C6—C4—H4C	109.5
O14ⁱⁱⁱ—Ce2—O11^iv	62.89 (6)	H4A—C4—H4C	109.5
O14^iv—Ce2—O11^iv	65.59 (6)	H4B—C4—H4C	109.5
O14—Ce2—O11^iv	117.85 (6)	N11—C6—C8	115.2 (7)
O12—Ce2—O11^iv	114.45 (6)	N11—C6—C4	114.2 (8)
O12ⁱⁱⁱ—Ce2—O11^iv	62.27 (6)	C8—C6—C4	110.6 (7)
O12^iv—Ce2—O11^iv	116.99 (6)	N11—C6—H6A	105.3
O11ⁱⁱⁱ—Ce2—O11^iv	117.20 (2)	C8—C6—H6A	105.3
O11—Ce2—O11^iv	117.20 (2)	C4—C6—H6A	105.3
O14ⁱⁱⁱ—Ce2—O13ⁱⁱⁱ	62.38 (6)	C61—C41—H41A	109.5
O14^iv—Ce2—O13ⁱⁱⁱ	117.36 (6)	C61—C41—H41B	109.5
O14—Ce2—O13ⁱⁱⁱ	114.53 (6)	H41A—C41—H41B	109.5
O12—Ce2—O13ⁱⁱⁱ	62.76 (6)	C61—C41—H41C	109.5
O12ⁱⁱⁱ—Ce2—O13ⁱⁱⁱ	65.43 (6)	H41A—C41—H41C	109.5
O12^iv—Ce2—O13ⁱⁱⁱ	117.50 (6)	H41B—C41—H41C	109.5
O11ⁱⁱⁱ—Ce2—O13ⁱⁱⁱ	62.76 (6)	C41—C61—N11	102.8 (12)
O11—Ce2—O13ⁱⁱⁱ	179.74 (7)	C41—C61—C8	114.4 (12)
O11^iv—Ce2—O13ⁱⁱⁱ	62.97 (6)	N11—C61—C8	101.6 (9)
O14ⁱⁱⁱ—Ce2—O13	117.36 (6)	C41—C61—H61A	112.4
O14^iv—Ce2—O13	114.53 (6)	N11—C61—H61A	112.4
O14—Ce2—O13	62.38 (6)	C8—C61—H61A	112.4
O12—Ce2—O13	65.43 (6)	N14—C5—C9	110.7 (3)
O12ⁱⁱⁱ—Ce2—O13	117.50 (6)	N14—C5—C7	110.7 (3)
O12^iv—Ce2—O13	62.76 (6)	C9—C5—C7	108.8 (3)
O11ⁱⁱⁱ—Ce2—O13	62.97 (6)	N14—C5—H5A	108.9
O11—Ce2—O13	62.76 (6)	C9—C5—H5A	108.9
O11^iv—Ce2—O13	179.74 (7)	C7—C5—H5A	108.9
O13ⁱⁱⁱ—Ce2—O13	117.07 (2)	O17^iv—C7—O11	125.7 (3)
O14ⁱⁱⁱ—Ce2—O13^iv	114.53 (6)	O17^iv—C7—C5	115.7 (2)
O14^iv—Ce2—O13^iv	62.38 (6)	O11—C7—C5	118.6 (2)
O14—Ce2—O13^iv	117.36 (6)	O13—C8—O15	124.8 (3)
O12—Ce2—O13^iv	117.50 (6)	O13—C8—C6	116.3 (5)
O12ⁱⁱⁱ—Ce2—O13^iv	62.76 (6)	O15—C8—C6	118.4 (5)
O12^iv—Ce2—O13^iv	65.43 (6)	O13—C8—C61	123.2 (7)
O11ⁱⁱⁱ—Ce2—O13^iv	179.74 (7)	O15—C8—C61	111.6 (7)
O11—Ce2—O13^iv	62.97 (6)	C6—C8—C61	15.9 (6)
O11^iv—Ce2—O13^iv	62.76 (6)	C5—C9—H9A	109.5
O13ⁱⁱⁱ—Ce2—O13^iv	117.07 (2)	C5—C9—H9B	109.5
O13—Ce2—O13^iv	117.07 (2)	H9A—C9—H9B	109.5
O13—Ni1—O12	92.34 (8)	C5—C9—H9C	109.5
O13—Ni1—N11	82.07 (11)	H9A—C9—H9C	109.5
O12—Ni1—N11	174.40 (11)	H9B—C9—H9C	109.5
O13—Ni1—N12	175.09 (10)	O16—C10—O14^iv	125.5 (3)
O12—Ni1—N12	82.76 (10)	O16—C10—C21^iv	107.9 (4)
N11—Ni1—N12	102.83 (12)	O14^iv—C10—C21^iv	117.7 (5)
O13—Ni1—O18	91.03 (9)	O16—C10—C11^iv	117.9 (3)
O12—Ni1—O18	89.15 (9)	O14^iv—C10—C11^iv	115.5 (4)
N11—Ni1—O18	90.61 (15)	C21^iv—C10—C11^iv	44.1 (5)
N12—Ni1—O18	89.03 (10)	N13—C11—C12	111.0 (4)
O13—Ni1—O17	89.77 (8)	N13—C11—C10ⁱⁱⁱ	107.6 (3)
O12—Ni1—O17	90.01 (8)	C12—C11—C10ⁱⁱⁱ	109.7 (5)
N11—Ni1—O17	90.31 (14)	N13—C11—H11A	109.5
N12—Ni1—O17	90.11 (10)	C12—C11—H11A	109.5
O18—Ni1—O17	178.87 (10)	C10ⁱⁱⁱ—C11—H11A	109.5
O14—Ni2—O11	91.41 (8)	C11—C12—H12A	109.5
O14—Ni2—O16	90.15 (10)	C11—C12—H12B	109.5
O11—Ni2—O16	88.63 (10)	H12A—C12—H12B	109.5
O14—Ni2—O15	89.88 (10)	C11—C12—H12C	109.5
O11—Ni2—O15	90.69 (9)	H12A—C12—H12C	109.5
O16—Ni2—O15	179.32 (11)	H12B—C12—H12C	109.5
O14—Ni2—N13	83.28 (10)	C22—C21—C10ⁱⁱⁱ	122.7 (9)
O11—Ni2—N13	174.65 (11)	C22—C21—N13	118.9 (9)
O16—Ni2—N13	90.76 (13)	C10ⁱⁱⁱ—C21—N13	100.7 (6)
O15—Ni2—N13	89.92 (12)	C22—C21—H21A	104.2
O14—Ni2—N14	172.61 (10)	C10ⁱⁱⁱ—C21—H21A	104.2
O11—Ni2—N14	82.40 (10)	N13—C21—H21A	104.2
O16—Ni2—N14	85.68 (12)	C21—C22—H22A	109.5
O15—Ni2—N14	94.21 (12)	C21—C22—H22B	109.5
N13—Ni2—N14	102.85 (12)	H22A—C22—H22B	109.5
Ce1—O1—H1	117.0	C21—C22—H22C	109.5
Ce1—O3—H3	120.0	H22A—C22—H22C	109.5
Ce1—O3—H2	120.0	H22B—C22—H22C	109.5

Symmetry codes: (i) −y+3, x−y+4, z; (ii) −x+y−1, −x+3, z; (iii) −x+y, −x+3, z; (iv) −y+3, x−y+3, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O17^v	0.85	1.93	2.758 (3)	165
N11—H11B···O6^vi	0.92	2.38	3.158 (5)	143
N12—H12D···O5ⁱⁱⁱ	0.92	2.17	3.086 (4)	174
N13—H13B···O2^vii	0.92	2.66	3.284 (4)	126

Symmetry codes: (iii) −x+y, −x+3, z; (v) x−1, y, z; (vi) −y+4, x−y+4, z; (vii) −x+y−1/3, −x+10/3, z+1/3.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O17ⁱ	0.85	1.93	2.758 (3)	165.3
N11—H11B···O6ⁱⁱ	0.92	2.38	3.158 (5)	142.8
N12—H12D···O5ⁱⁱⁱ	0.92	2.17	3.086 (4)	173.5
N13—H13B···O2^iv	0.92	2.66	3.284 (4)	126.0

Symmetry codes: (i) x−1, y, z; (ii) −y+4, x−y+4, z; (iii) −x+y, −x+3, z; (iv) −x+y−1/3, −x+10/3, z+1/3.

Acknowledgements

This work was partially supported by the RFBR (project 13-03-00972 A).

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