Hydrothermal Synthesis and Structures of Three-Dimensional Zinc Phosphates Built-Up from Two-Dimensional Layers and One-Dimensional Chains and Ladders

Three new zinc phosphates, I, [(NH4)(CH3CH2CH2NH3)][Zn3(HPO4)(PO4)2]; II, [NH3(CH2)3NH(CH2)3NH3][Zn3(H2PO4)(HPO4)2(PO4)]·H2O; and III, [NH3(CH2)3NH2(CH2)3NH3][Zn3(HPO4)3(PO4)], have been synthesized
in the presence of 1,3,5-triethylhexahydrotriazine (TEHT) and dipropylenetriamine (DPTA), and their structures
have been determined by single-crystal X-ray diffraction. The structures consist of vertex-linking ZnO4 and PO4
tetrahedral units forming channels bound by 8-, 10-, and 16-T atoms (T = Zn, P). While the structures of I and II
are built up from two-dimensional layers cross-linked by one-dimensional ladders or chains, that of III is built up
by cross-linking of ladders. The framework structure of II and III is built up from strictly alternating ZnO4 and PO4
units, and in I, infinite Zn−O−Zn chains are observed, formed by two Zn atoms sharing two three-coordinated
oxygen atoms. The amine molecule in I, propylamine, has been obtained by the decomposition of TEHT under
hydrothermal conditions. The amine molecules in I−III occupy the channels. Crystal data:  I, triclinic, space group
= P(−1) (no. 2), M = 559.18, a = 5.0986(6) Å, b = 10.4943(1) Å, c = 12.4457(1) Å, α = 87.614(2)°, β = 87.258(1)°, γ
= 89.994(2)°, V = 664.6(1) Å3, R1 = 0.0342, wR2 = 0.091 [1913 observed reflections with I > 2σ(I)]; II, triclinic,
space group = P(−1) (no. 2), M = 731.28, a = 8.4821(7) Å, b = 9.1326(8) Å, c = 14.7961(1) Å, α = 90.382(2)°, β =
100.123(2)°, γ = 107.04(1)°, V = 1076.7(1) Å3, R1 = 0.0332, wR2 = 0.0747 [2954 observed reflections with I > 2σ(I)]
III, monoclinic, space group = Cc (no. 7), M = 713.26, a = 15.1085(4) Å, b = 8.8403(4) Å, c = 17.2628(6) Å, β =
114.537(2)°, V = 2097.5(1) Å3, R1 = 0.0315, wR2 = 0.0804 [2323 observed reflections with I > 2σ(I)].

三种新型的锌磷酸盐I、II和III，分别为[(NH4)(CH3CH2CH2NH3)][Zn3(HPO4)(PO4)2]、[NH3(CH2)3NH(CH2)3NH3][Zn3(H2PO4)(HPO4)2(PO4)]·H2O和[NH3(CH2)3NH2(CH2)3NH3][Zn3(HPO4)3(PO4)]，在1,3,5-三乙基六氢三嗪(TEHT)和二丙二烯三胺(DPTA)的存在下成功合成。通过单晶X射线衍射技术确定了其结构，该结构由顶点连接的ZnO4和PO4四面体单元形成，并由8-T、10-T和16-T原子（T = Zn, P）构成的通道所限定。其中，I和II的结构由二维层通过一维梯状或链状结构相互交联而成，而III的结构则通过梯状结构的交联构建。II和III的框架结构由严格交替的ZnO4和PO4单元构成，而在I中，观察到由两个锌原子共享两个三配位氧原子形成的无限Zn−O−Zn链。I中的胺分子——丙胺，是通过在氢热条件下TEHT分解获得的。I至III中的胺分子占据通道位置。晶体数据：I，三斜晶系，空间群P(−1)（编号2），摩尔质量M = 559.18，a = 5.0986(6) Å，b = 10.4943(1) Å，c = 12.4457(1) Å，α = 87.614(2)°，β = 87.258(1)°，γ = 89.994(2)°，V = 664.6(1) Å3，R1 = 0.0342，wR2 = 0.091 [观察到1913个反射，I > 2σ(I)]；II，三斜晶系，空间群P(−1)（编号2），M = 731.28，a = 8.4821(7) Å，b = 9.1326(8) Å，c = 14.7961(1) Å，α = 90.382(2)°，β = 100.123(2)°，γ = 107.04(1)°，V = 1076.7(1) Å3，R1 = 0.0332，wR2 = 0.0747 [观察到2954个反射，I > 2σ(I)]；III，单斜晶系，空间群Cc（编号7），M = 713.26，a = 15.1085(4) Å，b = 8.8403(4) Å，c = 17.2628(6) Å，β = 114.537(2)°，V = 2097.5(1) Å3，R1 = 0.0315，wR2 = 0.0804 [观察到2323个反射，I > 2σ(I)]。