Sodalite networks formed by metal squarates

Abstract

Sodalite structures have not hitherto been obtained by rational design based on linking of square building units. We have, for the first time, succeeded in synthesizing sodalite networks by making use of squaric acid as the 4-membered square unit. Cobalt, manganese and zinc squarates with this architecture have been obtained (Crystal data for 1, Co(H₂O)₂(C₄O₄): cubic, space group Pn-3n (No. 222), a=16.280(5) Å, α=β=γ=90°, V=4315(2) ų, Z=48, ρ_calc=1.912 mg m⁻³, R₁=0.041 for Mo Kα, λ=0.71073 Å. Crystal data for 2, Mn(H₂O)₂(C₄O₄): trigonal, space group R−3 (No. 148), a=b=11.607(5), c=14.66(3) Å, α=β=90°, γ=120°, V=1711(4) ų, Z=18, ρ_calc=1.773 mg m⁻³, R₁=0.029. Crystal data for 3, Zn(H₂O)₂(C₄O₄): cubic, space group Pn-3n (No. 222), a=16.256(3) Å, α=β=γ=90°, V=4295.6(15) ų, Z=48, ρ_calc=1.980 mg m⁻³, final R₁=0.033. In the sodalite structures obtained by us, twelve metal(H₂O)₂O₄ units link the squares, instead of oxygen atoms as in the normal aluminosilicate sodalite.