Crystallization of the $${\text{Mn}}^{{\text{II}}}[12{\text{-MC}}_{{\text{Mn}}^{{\text{III}}}{\text{(N)shi}}}{\text{-}}4]^{2+}$$ Mn II [ 12 -MC Mn III (N)shi - 4 ] 2 + Structure with 1,2,4-Triazolate from Methanol

Abstract

The metallacrown (MC) dimer complex {MnII(OAc)(1,2,4-trz) $$[12{\text{-MC}}_{{\text{Mn}}^{{\text{III}}}{\text{(N)shi}}}{\text{-}}4]$$ (CH3OH)4.46(H2O)0.54}2·1.53CH3OH·6.47H2O, 1, where −OAc is acetate, 1,2,4-trz is triazolate, and shi3− is salicylhydroximate, has been synthesized and characterized by single-crystal X-ray diffraction. The compound crystallizes in the monoclinic space group P21/c with a = 10.9139(17) A, b = 28.319(4) A, c = 15.675(2) A, α = 90.00°, β 93.362(3)°, γ = 90.00°, V = 4836.4(13) A3, and Z = 2. The compound is an example of a $$12{\text{-MC}}_{{\text{Mn}}^{{\text{III}}}{\text{(N)shi}}}{\text{-}}4$$ complex crystallized from methanol in the presence of a basic nitrogen-containing aromatic heterocycle. The dimer formation is a result of the two 1,2,4-triazolate anions being able to form N1, N2, N4-bridges between ring and central cavity manganese ions thus linking two neighboring MCs. An individual MC unit of 1 is nearly planar as evident from the average angle between the axial oxygen or nitrogen atoms, the ring MnIII ion, and the calculated centroid of the oxime oxygen atoms being 90.12° about the MC ring. This manuscript provides a structural description of a manganese-based MC dimer with the composition {MnII(OAc)(1,2,4-trz) $$[12{\text{-MC}}_{{\text{Mn}}^{{\text{III}}}{\text{(N)shi}}}{\text{-}}4]$$ (CH3OH)4.46(H2O)0.54}2 ·1.53CH3OH·6.47H2O, where two 1,2,4-triazolate (trz) anions bind in a N1,N2,N4 fashion and form bridges between two neighboring MCs