The Atomic Order of the Pnictogen and Chalcogen Atoms in Equiatomic Ternary Compounds TPnCh (T=Ni, Pd; Pn=P, As, Sb; Ch=S, Se, Te)
The Atomic Order of the Pnictogen and Chalcogen Atoms in Equiatomic Ternary Compounds TPnCh (T=Ni, Pd; Pn=P, As, Sb; Ch=S, Se, Te)
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DOI：
10.1006/jssc.2001.9342
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发表时间：
2001-11
影响因子：
5.4
通讯作者：
Aloys J. Foecker;W. Jeitschko
中科院分区：
文献类型：
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作者：
Aloys J. Foecker;W. Jeitschko
根据单晶X射线衍射仪的数据，对化合物NiAs、NiSbS、PdAsS、PdAsSe、PdSbSe和PdSbTe的晶体结构进行了精炼。在这些立方化合物中，镍和硫原子呈有序分布，对应于锰矿(NiSbS)型结构(空间群P2 1 3，Z=4)。以此类推，NIPS和Niasse可以假设这一点，尽管对于这些化合物来说，结构的改进不可能区分铅和硫化物原子的无序分布(对应于黄铁矿结构)或有序分布(对应于锰铁矿或钴铁矿)。所有原子位置在±2%的误差范围内被完全占据。通过对X射线粉末数据的改进，确定了NiSbSe的锰矿结构。从单晶数据中提炼出PdPSe的PPDS型结构。在Ni-P-Se、Ni-P-Te、Ni-As-Te、Ni-Sb-Te、Pd-P-Te、Pd-As-Te等三元系中没有观察到等原子的三元化合物。对单晶数据的修正表明，Ni_(0.766)(5)Sb_(0.50)(3)Te_(0.50)(3)晶化为缺陷-NiAs型结构。通过X射线粉末数据的结构修正，观察到准二元系NiP2-NiS2的扩展固溶体，其中缓慢冷却的等原子样品含有NiP 1.86(4)Se 0.14(4)和NiP 0.24(4)Se 1.76(4)作为极限组分。简要讨论了这些化合物中的化学键。
Abstract The crystal structures of the compounds NiAsS, NiSbS, PdAsS, PdAsSe, PdSbSe, and PdSbTe were refined from single-crystal X-ray diffractometer data. In these cubic compounds the pnictogen and chalcogen atoms show an ordered distribution corresponding to the ullmannite (NiSbS) type structure (space group P 2 1 3, Z =4). By analogy this can be assumed for NiPS and NiAsSe, although for these compounds the structure refinements did not make it possible to distinguish between a disordered distribution of the pnictogen and chalcogen atoms (corresponding to the pyrite structure) or an ordered distribution (corresponding to ullmannite or cobaltite). All atomic positions are fully occupied within the error limits of ±2%. A refinement from X-ray powder data established the ullmannite structure also for NiSbSe. The PdPS type structure of PdPSe was refined from single-crystal data. No equiatomic ternary compounds were observed in the ternary systems Ni–P–Se, Ni–P–Te, Ni–As–Te, Ni–Sb–Te, Pd–P–Te, and Pd–As–Te. A refinement from single-crystal data showed Ni 0.766(5) Sb 0.50(3) Te 0.50(3) to crystallize with a defect-NiAs type structure. Extended solid solutions were observed for the pseudobinary system NiP 2 –NiSe 2 , where a slowly cooled equiatomic sample contained NiP 1.86(4) Se 0.14(4) and NiP 0.24(4) Se 1.76(4) as limiting compositions, as shown by structure refinements from X-ray powder data. Chemical bonding in these compounds is briefly discussed.