Two new three-dimensional zinc phosphates I, [NH(CH2)2NH2(CH2)2NH3]2+[Zn5(PO4)4]2-, and II, [CN5H6]+[Zn2(PO4)(HPO4)]-, where the structure-directing organic amine acts as a ligand, have been synthesized hydrothermally. Crystal data for I: a=27.071(2), b=5.215(1), c=17.920(1) Å, β=130.3(1)°; U=1930.9(3) Å3; space group=Cc (no. 9); Z=4; M=811.01; Dcalc=2.789 g cm-3; MoKα and for II: a=8.089(1), b=12.771(1), c=10.067(1) Å, β=105.3(1)°; U=1000.3(2) Å3; space group=P21/n (no. 14); Z=4; M=409.8; Dcalc=2.713 g cm-3; MoKα. Compound I is novel in the sense that it is dominated by the presence of a large number of three-coordinated oxygen atoms (25%), leading to the formation of infinite Zn–O–Zn chains. The presence of a distorted bipyramidal ZnO3N2 unit as well as a 2-membered ring in II is noteworthy. These structures are formed by the networking of ZnO4, ZnO3N, PO4 and ZnO3N2 moieties, leading to the formation of three-dimensional structures possessing channels with I forming a 10-membered one-dimensional channel system and II forming two 8-membered channels.
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