Abstract
The crystal structures of two zincophosphate networks prepared in the presence of 1,5-diaminopentane (dap) are described. In Zn3(PO4)2(C5H14N2)2·3H2O (1) the dap forms Zn–N coordinate bonds to generate an unusual three-dimensional “hybrid” framework constructed from ZnO3N, ZnO2N2 and PO4 tetrahedra with three different types of elongated channels occupied by water molecules. In C5H16N2·Zn3(PO4)2(HPO4)·H2O; (2) the doubly-protonated H2dap acts in a more typical way to template double layers of vertex-sharing ZnO4, PO4 and HPO4 tetrahedra incorporating 10-rings and interacts with the inorganic component via N–H O hydrogen bonds. Crystal data: 1 (C10H34N4O11P2Zn3), Mr = 644.46, monoclinic, C2 (No. 4), Z = 4, a = 25.302 (7) Å, b = 4.9327 (13) Å, c = 19.808 (6) Å, b = 107.377 (8)°, V = 2359.4 (12) Å3, R(F) = 0.054, wR(F2) = 0.139. 2 (C5H19N2O13P3Zn3), Mr = 604.24, monoclinic, P21/c (No. 14), Z = 4, a = 11.3275 (15) Å, b = 8.3235 (11) Å, c = 18.588 (2) Å, b = 96.979 (3)°, V = 1739.6 (4) Å3, R(F) = 0.056, wR(F2) = 0.119.
Highlights
Linear-chain alkyl diamines of formula H2N(CH2)nNH2 are versatile and effective templates for a wide variety of porous inorganic networks incorporating many different metal ions [1,2,3,4]
As might be Crystals 2012, 2 expected, the chain length n of the methylene groups of the diamine plays an important role in defining the resulting crystal structure: this is demonstrated with diamine-templated zinc phosphates (ZnPOs) and varied structures with n = 2 [5], n = 3 [6], n = 4 [7] and n = 6 [8] have been described
As an extension of these studies we describe the structures of two zincophosphate networks incorporating the n = 5 member of this series, 1,5-diaminopentane [H2N(CH2)5NH2; C5H14N2; dap], as the structure-directing agent
Summary
Linear-chain alkyl diamines of formula H2N(CH2)nNH2 are versatile and effective templates for a wide variety of porous inorganic networks incorporating many different metal ions [1,2,3,4]. As might be Crystals 2012, 2 expected, the chain length n of the methylene groups of the diamine plays an important role in defining the resulting crystal structure: this is demonstrated with diamine-templated zinc phosphates (ZnPOs) and varied structures with n = 2 (i.e., ethylenediamine) [5], n = 3 [6], n = 4 [7] and n = 6 [8] have been described. In Zn3(PO4)2(C5H14N2)2·3H2O (1) the neutral dap molecule bonds directly to the zinc ions as a bridging ligand to generate an unusual structure containing elongated “hybrid”. H2dap dications help to template a layered ZnPO network via N-H O hydrogen bonds. As we are aware, there are no other known dap-ZnPO structures, H2dap dications have been shown to template zinc phosphite (containing HPO32− groups) [9] and zinc diphosphonate [10] materials
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