THE CRYSTAL-CHEMICAL LAWS WITHIN THE ISODIMORPHOUS SUBSTITUTION SERIES Na<sub>4</sub>[Zn<sub><i>x</i></sub>Ni<sub>(1–<i>x</i>)</sub>{N(CH<sub>2</sub>PO<sub>3</sub>)<sub>3</sub>}] ⋅ <i>n</i>H<sub>2</sub>O (<i>x</i> = 0–1)

Abstract

Heterometallic complexes of zinc and nickel with nitrilo-tris(methylenephosphonic acid) Na4[ZnxNi {N(CH2PO3)3}] ⋅ nH2O (x = 0–1) form an isodimorphous substitution series during crystallization. The extreme zinc and nickel terms have, respectively, triclinic and monoclinic structures. The intermediate terms are crystallized in one of the following phases: either in the triclinic phase with dominance of zinc, Na4[(Zn,Ni){N(CH2PO3)3}] ⋅ 13H2O (sp. gr. P , Z = 2, a = 11.171(4)–11.2396(2) Å, b = 11.2612(5)–11.28800(10) Å, c = 12.3241(5)–12.35530(10) Å, α =108.422(4)°–108.4510(10)°, β = 97.1603(16)°–97.1790(10)°, γ = 117.0870(10)°–117.133(2)°) and trigonal-bipyramidal coordination of metal atom, or in the monoclinic phase with dominance of nickel, Na4[(Ni,Zn)(H2O){N(CH2PO3)3}] ⋅ 11H2O (sp. gr. C2/c, Z = 4, a = 11.9987(2)–12.05615(18) Å, b = 18.6231(3)–18.7073(3) Å, c = 21.0758(3)–21.1264(4) Å, β =104.3044(17)°–104.3688(16)°) and octahedral coordination of metal atom. The dependence of the bond angle, type of chemical bonding, and spectroscopic and magnetic properties on the fraction of zinc among complexing metals in the crystal, x = [Zn]/([Zn] + [Ni]), has been studied.