Tetrahedral-Network Organo-zincophosphates: Syntheses and Structures of (N2C6H14)· Zn(HPO4)2·H2O, H3N(CH2)3NH3·Zn2(HPO4)3, and (N2C6H14)·Zn3(HPO4)4

The solution-mediated syntheses and single crystal structures of (N2C6H14)·Zn(HPO4)2·H2O (I), H3N(CH2)3NH3·Zn2(HPO4)3 (II), and (N2C6H14)·Zn3(HPO4)4 (III) are described. These phases contain vertex-sharing ZnO4 and HPO4 tetrahedra, accompanied by doubly protonated organic cations. Despite their formal chemical relationship, as members of the series of t·Znn(HPO4)n+1 (t=template, n=1–3), these phases adopt fundamentally different crystal structures, as onedimensional, two-dimensional, and three-dimensional ZnO4/HPO4 networks, for I, II, and III, respectively. Similarities and differences to some other zinc phosphates are briefly discussed. Crystal data: (N2C6H14)·Zn(HPO4)2·H2O, Mr=389.54, monoclinic, space group P21/n (No. 14), a=9.864(4) ?, b=8.679(4) ?, c=15.780(3) ?, =106.86(2)°, V=1294.2(8) ?3, Z=4, R(F)= 4.58%, Rw(F)=5.28% [1055 reflections with I>3(I)]. H3N(CH2)3NH3·Zn2(HPO4)3, Mr=494.84, monoclinic, space group P21/c (No. 14), a=8.593(2) ?, b=9.602(2) ?, c=17.001 (3) ?, = 93.571(8)°, V=1400.0(5) ?3, Z=4, R(F)=4.09%, Rw(F)=4.81% [2794 reflections with I>3(I)]. (N2C6H14)·Zn3(HPO4)4, Mr=694.25, monoclinic, space group P21/n (No. 14), a=9.535(2) ?, b=23.246(4) ?, c=9.587(2) ?, =117.74(2)°, V=1880.8(8) ?3, Z=4, R(F)=3.23%, Rw(F)= 3.89% [4255 reflections with I>3(I)].