Three new amine-templated zinc phosphates, [C4N2H14][Zn(HPO4)(2)]-H2O, AU-I, [C4N2H14][Zn-2(H0.5PO4)(2)(H2PO4)], AU-II, and [C4N2H14[Zn-5(H2O)(PO4)(4)], AU-III, are prepared by hydrothermal synthesis using an organic amine, N,N'-dimethylethylendiamine CH3NHCH2CH2NHCH3, as structure-directing agent. The three materials are prepared from the same reaction mixture, 1Zn(CH3CO2)(2):3.05H(3)PO(4):2.25CH(3)NHCH(2)CH(2)NHCH(3):138H(2)O (pH = 5.1), AU-I at RT AU-II at 60 degreesC, and AU-III at 170 degreesC. The materials are built from corner-sharing ZnO4 and PO4 tetrahedra forming chains, layers, or framework structures for AU-I to III, respectively, and are linked together by hydrogen bonds via the diprotonated amine ions. The complete hydrogen-bond scheme is resolved for these new compounds and reveals some interesting phenomena, for example, a hydrogen shared between two phosphate groups in AU-II, thereby forming H0.5PO4 groups. Furthermore, the water molecules are different; that is, in AU-I they act as hydrogen-bond donor and acceptor, whereas they act as ligand in AU-III with coordination to Zn. The structures of the compounds are determined by single-crystal X-ray diffraction analysis, AU-I, [C4N2H14][Zn(HPO4)(2)]-H2O, crystallizes in the triclinic space group P-1, a = 8.215(2), b = 8.810(3), c = 8.861(3) Angstrom, alpha = 88.001(4)degrees, beta = 89.818(5)degrees, and gamma = 89.773(5)degrees, Z = 2. AU-II, [C4N2H14][Zn-2(H0.5PO4)(2)(H2PO4)], is monoclinic, P2/n, a = 11.7877(4), b = 5.2093(2), c = 12.2031(4) Angstrom, beta = 98.198(1)degrees, Z = 2. AU-III, [C4N2H14][Zn-5(H2O)(PO4)(4)], crystallizes in the orthorhombic space group Pna2(1) with lattice parameters, a = 20.723(2), b = 5.2095(6), c = 17.874(2) Angstrom, Z = 4. The phase stability investigated by systematic hydrothermal synthesis is presented, and the materials are further characterized by P-31 solid-state MAS NMR, for example, by determination of P-31 chemical shift anisotropies for AU-III, while the thermal behavior is investigated by thermogravimetry (TG).