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三种新的含多个质子化砷/磷基团的酸性砷酸盐和磷酸盐。

Three new acid M arsenates and phosphates with multiply protonated As/PO groups.

作者信息

Schwendtner Karolina, Kolitsch Uwe

机构信息

Institute for Chemical Technology and Analytics, Division of Structural Chemistry, TU Wien, Getreidemarkt 9, Wien 1060, Austria.

Mineralogisch-Petrographische Abteilung, Naturhistorisches Museum, Burgring 7, Wien 1010, Austria.

出版信息

Acta Crystallogr C Struct Chem. 2019 Aug 1;75(Pt 8):1134-1141. doi: 10.1107/S2053229619008489. Epub 2019 Jul 25.

DOI:10.1107/S2053229619008489
PMID:31380796
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC6681722/
Abstract

The crystal structures of caesium dihydrogen arsenate(V) bis[trihydrogen arsenate(V)], Cs(HAsO)(HAsO), ammonium dihydrogen arsenate(V) trihydrogen arsenate(V), NH(HAsO)(HAsO), and dilithium bis(dihydrogen phosphate), Li(HPO), were solved from single-crystal X-ray diffraction data. NH(HAsO)(HAsO), which was hydrothermally synthesized (T = 493 K), is homeotypic with Rb(HAsO)(HAsO), while Cs(HAsO)(HAsO) crystallizes in a novel structure type and Li(HPO) represents a new polymorph of this composition. The Cs and Li compounds grew at room temperature from highly acidic aqueous solutions. Li(HPO) forms a three-dimensional (3D) framework of PO tetrahedra sharing corners with LiO dimers built of edge-sharing LiO groups, which is reinforced by hydrogen bonds. The two arsenate compounds are characterized by a 3D network of AsO groups that are connected solely via multiple strong hydrogen bonds. A statistical evaluation of the As-O bond lengths in singly, doubly and triply protonated AsO groups gave average values of 1.70 (2) Å for 199 As-OH bonds, 1.728 (19) Å for As-OH bonds in HAsO groups, 1.714 (12) Å for As-OH bonds in HAsO groups and 1.694 (16) Å for As-OH bonds in HAsO groups, and a grand mean value of 1.667 (18) Å for As-O bonds to nonprotonated O atoms.

摘要

通过单晶X射线衍射数据解析了砷酸二氢铯（V）双[砷酸三氢（V）]，Cs（HAsO₄）（H₂AsO₄）、砷酸二氢铵（V）砷酸三氢（V），NH₄（HAsO₄）（H₂AsO₄）以及磷酸二氢锂，Li₂（H₂PO₄）₂的晶体结构。水热合成（T = 493 K）的NH₄（HAsO₄）（H₂AsO₄）与Rb（HAsO₄）（H₂AsO₄）是同型的，而Cs（HAsO₄）（H₂AsO₄）以一种新型结构类型结晶，Li₂（H₂PO₄）₂代表了该组成的一种新的多晶型物。Cs和Li化合物在室温下从高酸性水溶液中生长。Li₂（H₂PO₄）₂形成了一个由PO₄四面体构成的三维（3D）框架，这些四面体与由边共享的LiO基团构成的Li₂O二聚体共用角，通过氢键得到加强。这两种砷酸盐化合物的特征是由AsO₄基团构成的3D网络，它们仅通过多个强氢键相连。对单质子化、双质子化和三质子化AsO₄基团中As - O键长的统计评估得出，199个As - OH键的平均值为1.70（2）Å，HAsO₄基团中As - OH键的平均值为1.728（19）Å，H₂AsO₄基团中As - OH键的平均值为1.714（12）Å，H₃AsO₄基团中As - OH键的平均值为1.694（16）Å，与非质子化O原子形成的As - O键的总平均值为1.667（18）Å。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/0cfc/6681722/172c704938fb/c-75-01134-fig8.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/0cfc/6681722/66a0c120c983/c-75-01134-fig1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/0cfc/6681722/75167bb441a5/c-75-01134-fig2.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/0cfc/6681722/243896f8db1c/c-75-01134-fig3.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/0cfc/6681722/446daa54c0b8/c-75-01134-fig4.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/0cfc/6681722/80288ca38526/c-75-01134-fig5.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/0cfc/6681722/1f594b10189b/c-75-01134-fig6.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/0cfc/6681722/963141d60611/c-75-01134-fig7.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/0cfc/6681722/172c704938fb/c-75-01134-fig8.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/0cfc/6681722/66a0c120c983/c-75-01134-fig1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/0cfc/6681722/75167bb441a5/c-75-01134-fig2.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/0cfc/6681722/243896f8db1c/c-75-01134-fig3.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/0cfc/6681722/446daa54c0b8/c-75-01134-fig4.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/0cfc/6681722/80288ca38526/c-75-01134-fig5.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/0cfc/6681722/1f594b10189b/c-75-01134-fig6.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/0cfc/6681722/963141d60611/c-75-01134-fig7.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/0cfc/6681722/172c704938fb/c-75-01134-fig8.jpg

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