Crystal structure of an unknown solvate of dodecakis-(μ2-alaninato-1:2κ(2) O:N,O)cerium(III)hexa-nickel(II) aqua-tris-(hydroxido-κO)tris-(nitrato-κ(2) O,O')cerate(III).

Stanislav I Bezzubov,Yuri M Kiselev,Irina S Zharinova,Vladimir D Doljenko,Andrei V Churakov

doi:10.1107/s2056989015017132

Abstract

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 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.

Highlights

Molecular magnets based on 3d–4f heterometallic constituents can be prepared 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
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 CeIII atom situated on the threefold rotation axis

Summary

Introduction

Molecular magnets based on 3d–4f heterometallic constituents can be prepared 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). Crystal structure of an unknown solvate of dodecakis(l2-alaninato1:2j2O:N,O)cerium(III)hexanickel(II) 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. The H atoms of the coordinating water molecule are disordered over three positions due to its location on a threefold rotation axis.

Results

Conclusion