Abstract
In the penta-nuclear title complex, [SmZn2(C22H18N2O4)2(NCS)2(C3H7NO)2][Zn2(C22H18N2O4)(NCS)3]·C3H7NO·0.32H2O, namely bis-{μ2-6,6'-dimeth-oxy-2,2'-[phenyl-ene-1,2-diylbis(nitrilo-methanylyl-idene)]diphenolato}-1κ4 O,N,N',O':2κ3 O,O',O 6;2κ3 O,O',O 6:3κ4 O,N,N',O'-bis-(di-methyl-formamide-2κO)di-thiocyanato-1κN,3κN-2-samarium(III)-1,3-dizinc(II) {μ2-6,6'-dimeth-oxy-2,2'-[phenyl-ene-1,2-diylbis(nitrilo-methanylyl-idene)]diphenolato-1κ4 O,N,N',O':2κ2 O,O'}trithio-cyan-ato-1κN;2κ2 N,N-dizinc(II) di-methyl-formamide monosolvate 1.32-hydrate, a dinuclear unit and a trinuclear unit co-exist. One of the ZnII centers in the dinuclear unit as well as the two ZnII centers in the trinuclear unit are located in the inner N2O2 cavity of the ligand and are coordinated to the nitro-gen atom of one thio-cyanate moiety, giving rise to a square-pyramidal geometry. The second ZnII center in the dinuclear unit is coordinated to the two phenolate oxygen atoms of the ligand and to two thio-cyanate groups via the nitro-gen atom in a tetra-hedral geometry. The SmIII ion is eight-coordinated by four phenolate O atoms from the two ligand mol-ecules, two meth-oxy O atoms from the two ligand mol-ecules and two O atoms from the DFM solvent mol-ecule. In the dinuclear unit, the two meth-oxy oxygen atoms remain uncoordinated while in the trinuclear unit, for each ligand one meth-oxy oxygen is coordinated and the other one remains uncoordinated. In the crystal, the trinuclear cationic units and dinuclear anionic units are assembled into infinite layers. These layers are held together via electrostatic inter-actions, forming a three-dimensional structure. In the dinuclear unit, the C and S atoms of one of the thio-cyanate groups are disordered over two sets of sites in a 0.680 (4)(4):0.320 (4) ratio.
Highlights
Mamour Sarr,a Mayoro Diop,a Elhadj Ibrahima Thiam,a Mohamed Gaye,a* Aliou Hamady Barry,b James B
One of the ZnII centers in the dinuclear unit as well as the two ZnII centers in the trinuclear unit are located in the inner N2O2 cavity of the ligand and are coordinated to the nitrogen atom of one thiocyanate moiety, giving rise to a square-pyramidal geometry
The second ZnII center in the dinuclear unit is coordinated to the two phenolate oxygen atoms of the ligand and to two thiocyanate groups via the nitrogen atom in a tetrahedral geometry
Summary
Polyheteronuclear complexes of 3d and 4f metals have been studied with increasing interest by chemists (Cristovao et al, 2017; Cristovao & Miroslaw, 2013; Ding et al, 2015; Tian et al, 2012; Wu & Hou, 2010). The equatorial planes around each of these two zinc ions in the trinuclear unit are formed, respectively, by two imino nitrogen atoms and two phenolate oxygen atoms. The Zn— Ophenoxo bond lengths in both the dinuclear and trinuclear units are in the range 1.9985 (13)–2.0395 (12) A These values are comparable with the distances for the dinuclear complex [Zn(H2O)(valdmpn)Sm(O2NO)3] [where valdmpn is N,N0bis(3-methoxysalicylidene)(2,2-dimethylpropylidene)-1,3-diamine); Pasatoiu et al, 2012]. The deformation of the basal plane around the Zn62 atom is indicated by the values of the transoid [138.41 (6) and 144.96 (7)] and cisoid angles [88.34 (6) and 88.94 (6)], which are different from the ideal values of 180 and 90 for a square-planar geometry (Table 1). The N—C— S angles vary between 177.7 (2) and 179.4 (2), showing that these three atoms adopt an almost linear alignment
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