Three-dimensional zinc phosphates with open architectures

Abstract

Two new zinc phosphates, [C₃N₂H₁₂]₂ [Zn₄(PO₄)₄], I, [C₃N₂H₁₂]₂[Zn₅(H₂O) (PO₄)₄(HPO₄)], II, have been synthesized hydrothermally in the presence of 1,3-diaminopropane (DAP). Both I and II consist of the vertex linking ZnO₄ and PO₄ tetrahedral units forming channels bound by eight T atoms (T = Zn, P). The structure of II possesses similar building units as that of the naturally occurring aluminosilicate mineral, thomsonite, but interruptions in the connectivity between the building units creates marginal differences. To our knowledge, II is the first analogue of thomsonite. The amine molecules, in I and II, are situated within the channels and the loss of the amine molecule causes the collapse of the framework forming condensed zinc phosphates. Crystal data: [NH₃(CH₂)₃NH₃]₂ [Zn₄P₄O₁₆] (I), M = 793.6, monoclinic, space group = P2₁ (no. 4), a = 10.200(1), b = 9.998(1), c = 10.447(1) Å, β = 92.24(1)°, V = 1064.62(3) ų, Z = 2, ρ_calc = 2.476 g cm^-3, μ(Mo Kα) = 4.840 mm^-1, R₁ = 0.038, wR₂ = 0.099 [2231 observed reflections with I > 2σ(I)]; [C₃N₂H₁₂]₂[Zn₅(H₂O) (PO₄)₄(HPO₄)] (II), M = 973.02, monoclinic, space group = P2₁ (no. 4), a = 9.299(4), b = 9.751(1), c = 14.335(1) Å, β = 90.97(4)°, V = 1299.67(9) ų, Z = 2, ρ_calc = 2.486 g cm^-3, μ(MoKα) = 4.955 mm^-1, R₁ = 0.028, wR₂ = 0.063 [3389 observed reflections with I > 2σ(I)].