Hydrothermal synthesis and structural characterization of organically templated zincophosphites: [Zn(C 4N 3H 13)][Zn 4(HPO 3) 6]⋅(C 4N 3H 15) and [Zn 5(H 2O) 4(HPO 3) 6]⋅(C 7NH 10) 2(H 2O)

Abstract

Two organically templated zincophosphites, [Zn(C 4N 3H 13)][Zn 4(HPO 3) 6]⋅(C 4N 3H 15) and [Zn 5(H 2O) 4(HPO 3) 6]⋅(C 7NH 10) 2(H 2O) were synthesized using diethylenetriamine and benzylamine as templates and characterized by single-crystal X-ray diffraction. [Zn(C 4N 3H 13)][Zn 4(HPO 3) 6]⋅(C 4N 3H 15) crystallizes in orthorhombic Cmca with cell parameters a = 18.9617 ( 7 ) Å , b = 10.0192 ( 3 ) Å , c = 16.1415 ( 4 ) Å . [Zn 5(H 2O) 4(HPO 3) 6]⋅(C 7NH 10) 2(H 2O) crystallizes in triclinic P - 1 with cell parameters a = 10.0039 ( 9 ) Å , b = 10.2172 ( 9 ) Å , c = 11.6488 ( 9 ) Å , and α = 69.646 ( 5 ) ° , β = 88.003 ( 5 ) ° , γ = 62.994 ( 5 ) ° . [Zn(C 4N 3H 13)][Zn 4(HPO 3) 6]⋅(C 4N 3H 15) consist of alternatively linked ZnO 4, ZnO 2N 3 and [ HPO 3 2 − ] units. In this structure, the structure-directing amines as ligands to zinc are present in two distinct forms, the free state and bonded state, and the two species occurring in channels. [Zn 5(H 2O) 4(HPO 3) 6]⋅(C 7NH 10) 2(H 2O) is made up of ZnO 4, ZnO 6 and [ HPO 3 2 − ] moieties forming distinct channels, the protonated aromatic amine molecules are located in the intersection of the channels. In the compounds, the connections ZnO 2N 3 and ZnO 6 of Zn atoms are the first reported in the synthesis of zincophosphite materials. Two zincophosphites, having two-dimensional structures with 4, 6, 8-membered rings channels, were also characterized by IR spectroscopy, thermogravimetric and differential thermal analyses.