Variants of the Bi6TiP2O16 structure: The preparation and crystal structure of the isomorph Bi6(Mn0.6Bi0.4)P2O15 |
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| Affiliation: | 1. Department of Chemical Engineering, Texas Materials Institute, University of Texas at Austin, 1 University Station C0400, Austin, TX 78712, United States;2. Department of Chemistry, University of Texas at Austin, Austin, TX 78712, United States;3. R. L. Harlow & Co. Inc. Silver Springs, MD 20906, United States;1. College of Materials and Chemical Engineering, Three Gorges University, Yichang, 443002, China;2. State Key Laboratory Breeding Base of Nonferrous Metals and Specific Materials Processing, Guangxi Universities Key Laboratory of Non-Ferrous Metal Oxide Electronic Functional Materials and Devices, College of Material Science and Engineering, Guilin University of Technology, Guilin, 541004, China;3. Guangxi New Future Information Industry Co. Ltd, Beihai, 536005, China;1. Key Laboratory for Robot and Intelligent Technology of Shandong Province, College of Electrical Engineering and Automation, Shandong University of Science and Technology, Qingdao 266590, PR China;2. School of Optical and Electronic Information, Huazhong University of Science and Technology, Wuhan 430074, PR China |
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| Abstract: | Compounds with the composition Bi6(Bi1−yMy)X2O16−z, M = transition metal or Pb, X = P, V, As, display pseudo-tetragonal crystal systems. They are, however, monoclinic with space group I2 and the heavy atom positions mimic the δ-Bi2O3 structure. The title compound is monoclinic, a = 11.284(2) Å, b = 5.4259(11) Å, c = 11.112(2) Å, β = 96.25(3)°, I2, Z = 2. Least-squares refinement of single-crystal X-ray diffraction data on F2 converged to R1 = 0.050, wR2 = 0.130. The crystal is twinned by two-fold rotation about [0 1 0] and each twin consists of its inverted component forming a racemate. The structure consists of chains of edge sharing (OBi4) tetrahedra parallel to [1 0 −1]. The chains are bridged parallel to [1 0 1] by linked PO4 tetrahedra and (Mn/Bi)O6 octahedra parallel to [1 0 −1], into a three-dimensional structure. The lone-pair electrons of adjacent Bi atoms along the chain point in opposite directions along the b-axis. The Bi atoms are in distorted trigonal prismatic coordination that has one or two faces capped. The Bi O bond lengths vary from 2.08(5) to 3.05(2) Å. The Mn/Bi atoms are disordered around the two-fold axis. Three oxygen atom sites contain vacancies. |
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