Guo Min, Yu Jihong, Li Jiyang, Li Yi, Xu Ruren
State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, College of Chemistry, Jilin University, Changchun 130012, PR China.
Inorg Chem. 2006 Apr 17;45(8):3281-6. doi: 10.1021/ic051906e.
The first two low-dimensional beryllium phosphates, [C5H14N2]2[Be3(HPO4)5].H2O (BePO-CJ29) and [C6H18N2]0.5[Be2(PO4)(HPO4)OH].0.5 H2O (BePO-CJ30), have been successfully synthesized under mild hydrothermal/solvothermal conditions. BePO-CJ29 is built up from strict alternation of BeO4 and HPO4 tetrahedra forming a unique one-dimensional double chains with 12-ring apertures. There are pseudo-10-ring apertures enclosed by two double chains through H-bonds. BePO-CJ29 can also be viewed as a pseudo 2-D layered structure stabilized by strong H-bonds. The diprotonated 2-methylpiperazium cations are located at three positions (i.e., inside the 12-ring aperture, inside the pseudo-10-ring aperture, and in the interlayer of the inorganic pseudo-layers. BePO-CJ30 is constructed by the alternation of Be-centered tetrahedra (including BeO4 and HBeO4) and P-centered tetrahedra (including PO4 and HPO4) resulting in a two-dimensional layered structure parallel to the (0 1 1) direction. The complex layer is composed of coupled 4.8 net sheets. The diprotonated 1,6-hexandiamine cations and water molecules reside in the interlayer regions and interact with the inorganic layers through H-bonds. Crystal data are as follows: [C5H14N2]2[Be3(HPO4)5].H2O (BePO-CJ29), triclinic, P1 (No. 2), a = 8.1000(9) A, b = 8.4841(14) A, c = 19.665(2) A, alpha = 89.683(10) degrees, beta = 78.182(8) degrees, gamma = 87.932(9) degrees, V = 1321.9(3) A3, Z = 2, R1 = 0.0523 (I > 2sigma(I)), and wR2 = 0.1643 (all data); [C6H18N2]0.5[Be2(PO4)(HPO4)OH].0.5 H2O (BePO-CJ30), orthorhombic, Pccn (No. 56), a = 26.01(4) A, b = 8.431(12) A, c = 9.598(13) A, V = 2105(5) A3, Z = 8, R1 = 0.0833 (I > 2sigma(I)), and wR2 = 0.2278 (all data).
前两种低维磷酸铍，[C5H14N2]2[Be3(HPO4)5].H2O（BePO-CJ29）和[C6H18N2]0.5[Be2(PO4)(HPO4)OH].0.5 H2O（BePO-CJ30），已在温和的水热/溶剂热条件下成功合成。BePO-CJ29由BeO4和HPO4四面体严格交替构成，形成具有12元环孔道的独特一维双链结构。通过氢键，两条双链包围形成了伪10元环孔道。BePO-CJ29也可视为由强氢键稳定的伪二维层状结构。双质子化的2-甲基哌嗪阳离子位于三个位置（即12元环孔道内、伪10元环孔道内以及无机伪层的层间）。BePO-CJ30由以Be为中心的四面体（包括BeO4和HBeO4）和以P为中心的四面体（包括PO4和HPO4）交替构成，形成平行于(0 1 1)方向的二维层状结构。复合层由耦合的4.8网层组成。双质子化的1,6-己二胺阳离子和水分子位于层间区域，并通过氢键与无机层相互作用。晶体数据如下：[C5H14N2]2[Be3(HPO4)5].H2O（BePO-CJ29），三斜晶系，P1（编号2），a = 8.1000(9) Å，b = 8.4841(14) Å，c = 19.665(2) Å，α = 89.683(10)°，β = 78.182(8)°，γ = 87.932(9)°，V = 1321.9(3) Å3，Z = 2，R1 = 0.0523（I > 2σ(I)），wR2 = 0.1643（所有数据）；[C6H18N2]0.5[Be2(PO4)(HPO4)OH].0.5 H2O（BePO-CJ30），正交晶系，Pccn（编号56），a = 26.01(4) Å，b = 8.431(12) Å，c = 9.598(13) Å，V = 2105(5) Å3，Z = 8，R1 = 0.0833（I > 2σ(I)），wR2 = 0.2278（所有数据）。
