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Ba 5 Tr 2 (Ge,Sn) 2 P 8 and Ba 5 Tr 5 (Ga,Tt) 2 P 12 (Tr = Al, Ga; Tt = Ge, Sn): Phosphides with Triel and Tetrel Mixing
Author(s) -
Pan MingYan,
Xia ShengQing,
Liu XiaoCun,
Tao XuTang
Publication year - 2015
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201500251
Subject(s) - orthorhombic crystal system , crystallography , chemistry , monoclinic crystal system , crystal structure , space group , x ray crystallography , diffraction , physics , optics
A series of new multinary phosphide Zintl compounds, Ba 5 Ga 2 GeSnP 8 , Ba 5 Al 2 GeSnP 8 , Ba 5 Ga 6 GeP 12 , and Ba 5 Ga 6 SnP 12 , have been synthesized through high‐temperature Pb or Sn flux reactions. The structures of the compounds, which have been determined by single‐crystal X‐ray diffraction, feature two different new structural types bearing various polyanion chain fragments. Ba 5 Tr 2 GeSnP 8 ( Tr = Al, Ga) crystallize in the monoclinic C 2/ m (No. 12) space group with cell parameters: a = 16.8211(10)/16.7586(21) Å, b = 6.0115(4)/6.0867(8) Å, c = 9.5873(6)/9.5983(12) Å, β = 111.9270(10)/112.1880(10)° for the Al‐ and Ga‐containing compounds, respectively. For Ba 5 Ga 6 Tt P 12 ( Tt = Ge, Sn), the compounds belong to a different orthorhombic system [space group: Cmcm (No. 63)] with the cell dimensions: a = 10.5222(6)/10.5802(9) Å, b = 16.2717(10)/16.3529(14) Å, c = 13.9093(8)/13.9643(12) Å for Ba 5 Ga 6 GeP 12 and Ba 5 Ga 6 SnP 12 . Despite the clear differences in the crystallographic parameters, these two types of structures are closely related through the [ Tr 2 P 4 ] and [ Tr 5 P 12 ] polyanion chains ( Tr = triels) as well as the significant mixing between the triel and tetrel atoms. The close relationships between these phases and some previously reported analogues are also discussed in detail. Theoretical calculations based on DFT methods confirm the precise electron nature of these compounds, which are also consistent with results from crystallographic data and the optical absorption measurements.