metal-organic compounds
μ2-alaninato-1:2κ2O:N,O)cerium(III)hexanickel(II) aquatris(hydroxido-κO)tris(nitrato-κ2O,O′)cerate(III)
of an unknown solvate of dodecakis(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
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 symmetry 3. with the CeIII atom situated on the threefold rotation axis. The cation metal core consists of six NiII 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 CeIII 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 CeIII 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
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Data collection: APEX2 (Bruker, 2008); cell 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
10.1107/S2056989015017132/wm5213sup1.cif
contains datablock I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S2056989015017132/wm5213Isup2.hkl
Supporting information file. DOI: 10.1107/S2056989015017132/wm5213Isup3.mol
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 NiII L-alaninate.
The title complex crystallizes in a
due to the presence of optically pure L-alanine in the cation.A region of electron density was treated with the SQUEEZE procedure in PLATON (Spek, 2015). The total potential solvent-accessible void volume is 1020.6 Å3, with an estimated electron count of 437. This accounts to approximately 12–15 disordered solvent ethanol and 6–9 water molecules. Their contributions to the total intensity data were removed. The given chemical formula and other crystal data do not take into account the amount of the unknown solvent molecules.
A part of the L-alaninato ligands were found to be disordered over two sets of sites with refined component ratios of 0.608 (14):0.392 (14) for the (C4—C6)/(C41—C61) fragment and 0.669 (8):0.331 (8) for the (C11—C12)/(C21—C22) fragment. Disorder was also observed for the coordinating water molecule (O3) situated on a threefold rotation axis. Owing to symmetry restraints the attached hydrogen atoms are disordered over three sites with an occupancy of one-thirds each.
Hydrogen atoms involved in hydrogen bonds (H1, H11B, H12D, and H13B) were located from difference maps and refined using a riding model, with O—H = 0.85 Å and Uiso(H) = 1.5Ueq(O), N—H = 0.92 Å and Uiso(H) = 1.2Ueq(N). All other hydrogen atoms were placed in calculated positions and refined using a riding model with C—H = 0.98 –1.00 Å and Uiso(H) = 1.5Ueq(CH3), 1.2Ueq(CH).
Data collection: APEX2 (Bruker, 2008); cell
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).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. |
[CeNi6(C3H6NO2)12][Ce(NO3)3(OH)3(H2O)] | Dx = 1.642 Mg m−3 |
Mr = 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 |
Bruker APEXII CCD diffractometer | 6978 independent reflections |
Radiation source: fine-focus sealed tube | 6734 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.021 |
ω scans | θmax = 29.0°, θmin = 1.7° |
Absorption correction: multi-scan (SADABS; Bruker, 2008) | h = −19→19 |
Tmin = 0.420, Tmax = 0.420 | k = −19→19 |
21829 measured reflections | l = −43→43 |
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(Fo2) + (0.0434P)2 + 4.4547P] where P = (Fo2 + 2Fc2)/3 |
S = 1.02 | (Δ/σ)max = 0.003 |
6978 reflections | Δρmax = 0.57 e Å−3 |
327 parameters | Δρmin = −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) |
[CeNi6(C3H6NO2)12][Ce(NO3)3(OH)3(H2O)] | Z = 3 |
Mr = 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 |
Bruker APEXII CCD diffractometer | 6978 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2008) | 6734 reflections with I > 2σ(I) |
Tmin = 0.420, Tmax = 0.420 | Rint = 0.021 |
21829 measured reflections |
R[F2 > 2σ(F2)] = 0.025 | H-atom parameters constrained |
wR(F2) = 0.066 | Δρmax = 0.57 e Å−3 |
S = 1.02 | Δρmin = −0.69 e Å−3 |
6978 reflections | Absolute structure: Flack (1983), 3493 Friedel pairs |
327 parameters | Absolute structure parameter: −0.012 (11) |
1 restraint |
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. |
x | y | z | Uiso*/Ueq | 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) |
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) |
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—O14iv | 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—O12iv | 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—O11iv | 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—O13iv | 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—O17iv | 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—O14iv | 1.267 (4) |
O3—H2 | 0.8501 | C10—C21iv | 1.528 (11) |
O5—N1 | 1.278 (4) | C10—C11iv | 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—C1iv | 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) | C1iv—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—O14iv | 63.82 (8) | C21—N13—H13B | 71.1 |
O14iii—Ce2—O14 | 63.82 (8) | Ni2—N13—H13B | 110.3 |
O14iv—Ce2—O14 | 63.82 (8) | H13A—N13—H13B | 108.5 |
O14iii—Ce2—O12 | 116.32 (6) | C5—N14—Ni2 | 109.29 (19) |
O14iv—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 |
O14iv—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—O12iv | 179.85 (7) | O18iii—C1—C3 | 117.4 (3) |
O14iv—Ce2—O12iv | 116.23 (6) | O12—C1—C3 | 117.5 (3) |
O14—Ce2—O12iv | 116.33 (6) | C3—C2—H2A | 109.5 |
O12—Ce2—O12iv | 63.62 (7) | C3—C2—H2B | 109.5 |
O12iii—Ce2—O12iv | 63.62 (7) | H2A—C2—H2B | 109.5 |
O14iii—Ce2—O11iii | 65.59 (6) | C3—C2—H2C | 109.5 |
O14iv—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) |
O12iv—Ce2—O11iii | 114.45 (6) | C2—C3—C1 | 111.8 (3) |
O14iii—Ce2—O11 | 117.85 (6) | N12—C3—H3A | 106.9 |
O14iv—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 |
O12iv—Ce2—O11 | 62.27 (6) | H4A—C4—H4B | 109.5 |
O11iii—Ce2—O11 | 117.20 (2) | C6—C4—H4C | 109.5 |
O14iii—Ce2—O11iv | 62.89 (6) | H4A—C4—H4C | 109.5 |
O14iv—Ce2—O11iv | 65.59 (6) | H4B—C4—H4C | 109.5 |
O14—Ce2—O11iv | 117.85 (6) | N11—C6—C8 | 115.2 (7) |
O12—Ce2—O11iv | 114.45 (6) | N11—C6—C4 | 114.2 (8) |
O12iii—Ce2—O11iv | 62.27 (6) | C8—C6—C4 | 110.6 (7) |
O12iv—Ce2—O11iv | 116.99 (6) | N11—C6—H6A | 105.3 |
O11iii—Ce2—O11iv | 117.20 (2) | C8—C6—H6A | 105.3 |
O11—Ce2—O11iv | 117.20 (2) | C4—C6—H6A | 105.3 |
O14iii—Ce2—O13iii | 62.38 (6) | C61—C41—H41A | 109.5 |
O14iv—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 |
O12iv—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) |
O11iv—Ce2—O13iii | 62.97 (6) | N11—C61—C8 | 101.6 (9) |
O14iii—Ce2—O13 | 117.36 (6) | C41—C61—H61A | 112.4 |
O14iv—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) |
O12iv—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 |
O11iv—Ce2—O13 | 179.74 (7) | C7—C5—H5A | 108.9 |
O13iii—Ce2—O13 | 117.07 (2) | O17iv—C7—O11 | 125.7 (3) |
O14iii—Ce2—O13iv | 114.53 (6) | O17iv—C7—C5 | 115.7 (2) |
O14iv—Ce2—O13iv | 62.38 (6) | O11—C7—C5 | 118.6 (2) |
O14—Ce2—O13iv | 117.36 (6) | O13—C8—O15 | 124.8 (3) |
O12—Ce2—O13iv | 117.50 (6) | O13—C8—C6 | 116.3 (5) |
O12iii—Ce2—O13iv | 62.76 (6) | O15—C8—C6 | 118.4 (5) |
O12iv—Ce2—O13iv | 65.43 (6) | O13—C8—C61 | 123.2 (7) |
O11iii—Ce2—O13iv | 179.74 (7) | O15—C8—C61 | 111.6 (7) |
O11—Ce2—O13iv | 62.97 (6) | C6—C8—C61 | 15.9 (6) |
O11iv—Ce2—O13iv | 62.76 (6) | C5—C9—H9A | 109.5 |
O13iii—Ce2—O13iv | 117.07 (2) | C5—C9—H9B | 109.5 |
O13—Ce2—O13iv | 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—O14iv | 125.5 (3) |
O12—Ni1—N12 | 82.76 (10) | O16—C10—C21iv | 107.9 (4) |
N11—Ni1—N12 | 102.83 (12) | O14iv—C10—C21iv | 117.7 (5) |
O13—Ni1—O18 | 91.03 (9) | O16—C10—C11iv | 117.9 (3) |
O12—Ni1—O18 | 89.15 (9) | O14iv—C10—C11iv | 115.5 (4) |
N11—Ni1—O18 | 90.61 (15) | C21iv—C10—C11iv | 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. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···O17v | 0.85 | 1.93 | 2.758 (3) | 165 |
N11—H11B···O6vi | 0.92 | 2.38 | 3.158 (5) | 143 |
N12—H12D···O5iii | 0.92 | 2.17 | 3.086 (4) | 174 |
N13—H13B···O2vii | 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. |
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···O2iv | 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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