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首页> 外文期刊>Zeitschrift fur Naturforschung, B. A Journal of Chemical Sciences >The crystal structures and thermal behaviour of the mercury arsenates Hg-2(H2AsO4)(2), Hg2As2O6 and HgAs2O6
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The crystal structures and thermal behaviour of the mercury arsenates Hg-2(H2AsO4)(2), Hg2As2O6 and HgAs2O6

机译：汞砷酸盐Hg-2（H2AsO4）（2），Hg2As2O6和HgAs2O6的晶体结构和热行为

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摘要

Crystals of Hg-2(H2AsO4)(2), which are isotypic with the corresponding dihydrogenphosphate Hg-2(H2PO4)(2), were obtained from a concentrated arsenic acid solution. The crystal structure (P2(1), a = 6.1838(4), b = 15.0987(9), c = 4.7989(3) Angstrom, beta = 91.977(1)degrees, Z = 2, R = 0.045 for 1318 structure factors, 56 variables) contains a Hg-2(2+) dumbbell with a distance d(Hg-Hg) = 2.5030(10) Angstrom and a symmetrical coordination of four oxygen atoms for each mercury atom. The oxygen atoms also belong to tetrahedral dihydrogenarsenate groups H2AsO4-, which stabilize the structure by hydrogen bonding. On heating Hg-2(H(2)ASO(4))(2) condenses to give the mercury(I) metaarsenate Hg2As2O6. Crystals of that compound were obtained under hydrothermal conditions at 165 degrees C starting from elemental mercury in 60 wt% aqueous H3AsO4. The crystal structure (P (3) over bar 1m, a = 4.8411(2), c = 7.5961(9) Angstrom, Z = 1, R = 0.037 for 376 structure factors, 13 variables) may be represented by sheets of edge sharing [AsO6] octahedra and layers of Hg-2(2+) dumbbells. which alternate along the c axis. The dumbbells show a distance d(Hg-Hg)= 2.5190(10) Angstrom and are coordinated symmetrically by six oxygen atoms at a distance d(Hg-O) = 2.374(4) Angstrom. They are positioned above and below the vacant sites of adjacent [As2O6](2-) layers. On further heating Hg2As2O6 disproportionates into elemental mercury and mercury(II) metaarsenate, HgAs2O6. Single crystals of HgAs2O6 were grown via chemical vapor transport from microcrystalline HgAs2O6 with HgCl2 as transport agent, using a temperature gradient of 650 --> 550 degrees C. HgAs2O6 (P (3) over bar 1m, a = 4.8482(2), c = 4.9789(10) Angstrom, Z = 1, R = 0.031 for 367 structure factors, 12 variables) crystallizes in the PbSb2O6 structure type, where anionic [Sb2O6](2-) layers have the same arrangement. The divalent mercury atoms have a pseudooctahedral environment of oxygen atoms with a distance d(Hg-O) = 2.353(3) Angstrom. [References: 29]
机译：Hg-2（H2AsO4）（2）晶体与相应的磷酸二氢盐Hg-2（H2PO4）（2）同型，是从浓砷酸溶液中获得的。晶体结构（P2（1）/ n，a = 6.1838（4），b = 15.0987（9），c = 4.7989（3）埃，beta = 91.977（1）度，Z = 2，R = 0.045对于1318结构因子，共56个变量）包含一个Hg-2（2+）哑铃，其距离d（Hg-Hg）= 2.5030（10）埃，每个汞原子对称分布四个氧原子。氧原子还属于四面体二氢砷酸盐基团H2AsO4-，它们通过氢键稳定结构。加热时，Hg-2（H（2）ASO（4））（2）冷凝，得到汞（I）偏砷酸盐Hg2As2O6。该化合物的晶体是在165摄氏度的水热条件下从60％重量的H3AsO4水溶液中的元素汞开始获得的。晶体结构（1 m处的P（3），a = 4.8411（2），c = 7.5961（9）埃，Z = 1，R = 0.037（376个结构因数，13个变量））可以由边共享片表示[AsO6]八面体和Hg-2（2+）哑铃层。沿c轴交替排列。哑铃的距离为d（Hg-Hg）= 2.5190（10）埃，并由六个氧原子在距离d（Hg-O）= 2.374（4）埃上对称地协调。它们位于相邻的[As2O6]（2-）层的空位上方和下方。在进一步加热时，Hg2As2O6歧化成元素汞和偏砷酸汞（II）HgAs2O6。 HgAs2O6的单晶是通过以650-> 550摄氏度的温度梯度通过以HgCl2为传输剂的微晶HgAs2O6的化学气相传输而生长的.HgAs2O6（P（3）在bar 1m上，a = 4.8482（2），c对于367个结构因子（12个变量），= 4.9789（10）埃，Z = 1，R = 0.031）在PbSb2O6结构类型中结晶，其中阴离子[Sb2O6]（2-）层的排列相同。二价汞原子具有氧原子的伪八面体环境，距离为d（Hg-O）= 2.353（3）埃。 [参考：29]

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