Crystal Structures of a Series of Novel Alkylammonium Phosphates and Their Formation in Aluminophosphate Synthesis Mixtures.
Crystal Structures of a Series of Novel Alkylammonium Phosphates and Their Formation in Aluminophosphate Synthesis Mixtures.
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DOI：
10.1021/ic980069w
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发表时间：
1998-09
影响因子：
4.6
通讯作者：
S. Oliver;A. Lough;G. Ozin
中科院分区：
文献类型：
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作者：
S. Oliver;A. Lough;G. Ozin
通过单晶X射线方法测定了几种新型烷基磷酸铵盐的晶体结构：环戊基磷酸一氢铵（CMP）（[C(5)H(9)NH(3)(+)](2)[HPO(4)(2)(-)]，单斜晶系，空间群P2(1)/n，Z = 4，a = 14.197(3) Å，b = 5.992(1) 埃，c = 16.580(3) 埃，β = 98.57(2) 度)；磷酸二氢辛铵 (ODP) ([CH(3)(CH(2))(7)NH(3)(+)][H(2)PO(4)(-)]，单斜晶系，空间群 P2(1)/c，Z = 4，a = 4.554(1) Å，b = 34.652(3) Å，c = 7.328(1) Å，beta = 90.66（1）度）；和磷酸二氢癸铵 (DDP) ([CH(3)(CH(2))(9)NH(3)(+)][H(2)PO(4)(-)]，单斜晶系，空间群 P2(1)/n，Z = 4，a = 7.358(2) Å，b = 39.749(12) Å，c = 9.131(4) Å，beta = 90.45(2) 度）。每个结构均由氢键磷酸盐分子的阴离子层组成，并由电荷平衡烷基铵阳离子分隔开。 ODP 和 DDP 中的长链烷基铵是叉指状的，而 CMP 中的环戊基铵则形成双层排列。通过重结晶生长大晶体，但也观察到该材料在相应的溶剂热铝磷酸盐合成混合物中形成。我们在含有各种不同烷基胺的磷酸铝合成混合物中分离出了磷酸盐化合物，并表明只要烷基胺是伯胺或仲胺，它们就最初存在于此类实验中。
The crystal structures of several novel alkylammonium phosphate salts were determined by single-crystal X-ray methods: cyclopentylammonium monohydrogen phosphate (CMP) ([C(5)H(9)NH(3)(+)](2)[HPO(4)(2)(-)], monoclinic, space group P2(1)/n, Z = 4, a = 14.197(3) Å, b = 5.992(1) Å, c = 16.580(3) Å, beta = 98.57(2) degrees ); octylammonium dihydrogen phosphate (ODP) ([CH(3)(CH(2))(7)NH(3)(+)][H(2)PO(4)(-)], monoclinic, space group P2(1)/c, Z = 4, a = 4.554(1) Å, b = 34.652(3) Å, c = 7.328(1) Å, beta = 90.66(1) degrees ); and decylammonium dihydrogen phosphate (DDP) ([CH(3)(CH(2))(9)NH(3)(+)][H(2)PO(4)(-)], monoclinic, space group P2(1)/n, Z = 4, a = 7.358(2) Å, b = 39.749(12) Å, c = 9.131(4) Å, beta = 90.45(2) degrees ). Each are composed of anionic layers of hydrogen-bonded phosphate molecules, separated by charge-balancing alkylammonium cations. The long-chain alkylammoniums in ODP and DDP are interdigitated, while the cyclopentylammoniums in CMP define a bilayer-like arrangement. Large crystals were grown by recrystallization, but the materials were also observed to form in the corresponding solvothermal aluminophosphate synthesis mixtures. We have isolated phosphate salt compounds in aluminophosphate synthesis mixtures containing a variety of different alkylamines and suggest they are initially present in such experiments whenever the alkylamine is primary or secondary.