Materials Data on Li9V3(WO4)7 by Materials Project

Li9V3(WO4)7 crystallizes in the trigonal R3m space group. The structure is three-dimensional. there are two inequivalent Li1+ sites. In the first Li1+ site, Li1+ is bonded in a 6-coordinate geometry to six O2- atoms. There are a spread of Li–O bond distances ranging from 2.01–2.56 Å. In the second Li1+ site, Li1+ is bonded in a 6-coordinate geometry to six O2- atoms. There are a spread of Li–O bond distances ranging from 1.99–2.65 Å. V+4.33+ is bonded to six O2- atoms to form VO6 octahedra that share corners with two equivalent WO4 tetrahedra and edges with two equivalent WO6 octahedra. There are a spread of V–O bond distances ranging from 2.09–2.29 Å. There are three inequivalent W+4.86+ sites. In the first W+4.86+ site, W+4.86+ is bonded in a 6-coordinate geometry to six O2- atoms. There are three shorter (1.88 Å) and three longer (2.38 Å) W–O bond lengths. In the second W+4.86+ site, W+4.86+ is bonded to six O2- atoms to form distorted WO6 octahedra that share edges with two equivalent VO6 octahedra and edges with two equivalent WO6 octahedra. There are a spread of W–O bond distances ranging from 1.81–2.18 Å. In the third W+4.86+ site, W+4.86+ is bonded to four O2- atoms to form WO4 tetrahedra that share corners with two equivalent VO6 octahedra. The corner-sharing octahedral tilt angles are 55°. There are a spread of W–O bond distances ranging from 1.80–1.83 Å. There are eight inequivalent O2- sites. In the first O2- site, O2- is bonded to two equivalent Li1+, one V+4.33+, and three W+4.86+ atoms to form distorted edge-sharing OLi2VW3 octahedra. In the second O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to two Li1+, one V+4.33+, and one W+4.86+ atom. In the third O2- site, O2- is bonded in a distorted trigonal planar geometry to one Li1+, one V+4.33+, and one W+4.86+ atom. In the fourth O2- site, O2- is bonded in a 6-coordinate geometry to three equivalent Li1+ and three equivalent W+4.86+ atoms. In the fifth O2- site, O2- is bonded in a trigonal planar geometry to two equivalent Li1+ and one W+4.86+ atom. In the sixth O2- site, O2- is bonded in a distorted see-saw-like geometry to three Li1+ and one W+4.86+ atom. In the seventh O2- site, O2- is bonded in a distorted see-saw-like geometry to two equivalent Li1+, one V+4.33+, and one W+4.86+ atom. In the eighth O2- site, O2- is bonded in a trigonal planar geometry to two equivalent Li1+ and one W+4.86+ atom.

Li₉V₃(WO₄)₇晶体属于三方晶系（trigonal）R3m空间群，其结构为三维骨架结构。体系中存在两类不等价的Li⁺配位位点：在第一类Li⁺位点中，Li⁺采取六配位几何（coordinate geometry）构型，与六个O²⁻原子成键，Li-O键长分布范围为2.01~2.56 Å；在第二类Li⁺位点中，Li⁺同样采用六配位几何构型，与六个O²⁻原子成键，Li-O键长分布范围为1.99~2.65 Å。V⁴·³³⁺与六个O²⁻原子配位形成VO₆八面体（octahedra），该八面体与两个等价的WO₄四面体（tetrahedra）共享顶点，同时与两个等价的WO₆八面体共享边，V-O键长分布范围为2.09~2.29 Å。体系中存在三类不等价的W⁴·⁸⁶⁺配位位点：在第一类W⁴·⁸⁶⁺位点中，W⁴·⁸⁶⁺采取六配位几何构型，与六个O²⁻原子成键，存在3条较短的W-O键（键长1.88 Å）与3条较长的W-O键（键长2.38 Å）；在第二类W⁴·⁸⁶⁺位点中，W⁴·⁸⁶⁺与六个O²⁻原子配位形成畸变的WO₆八面体，该八面体与两个等价的VO₆八面体共享边，同时与两个等价的WO₆八面体共享边，W-O键长分布范围为1.81~2.18 Å；在第三类W⁴·⁸⁶⁺位点中，W⁴·⁸⁶⁺与四个O²⁻原子配位形成WO₄四面体，该四面体与两个等价的VO₆八面体共享顶点，共顶点八面体的倾斜角为55°，W-O键长分布范围为1.80~1.83 Å。体系中存在八类不等价的O²⁻配位位点：在第一类O²⁻位点中，O²⁻与两个等价的Li⁺、一个V⁴·³³⁺以及三个W⁴·⁸⁶⁺原子成键，形成畸变的边共享OLi₂VW₃多面体；在第二类O²⁻位点中，O²⁻采取畸变矩形跷跷板状配位构型，与两个Li⁺、一个V⁴·³³⁺以及一个W⁴·⁸⁶⁺原子成键；在第三类O²⁻位点中，O²⁻采取畸变三角平面配位构型，与一个Li⁺、一个V⁴·³³⁺以及一个W⁴·⁸⁶⁺原子成键；在第四类O²⁻位点中，O²⁻采取六配位几何构型，与三个等价的Li⁺以及三个等价的W⁴·⁸⁶⁺原子成键；在第五类O²⁻位点中，O²⁻采取三角平面配位构型，与两个等价的Li⁺以及一个W⁴·⁸⁶⁺原子成键；在第六类O²⁻位点中，O²⁻采取畸变跷跷板状配位构型，与三个Li⁺以及一个W⁴·⁸⁶⁺原子成键；在第七类O²⁻位点中，O²⁻采取畸变跷跷板状配位构型，与两个等价的Li⁺、一个V⁴·³³⁺以及一个W⁴·⁸⁶⁺原子成键；在第八类O²⁻位点中，O²⁻采取三角平面配位构型，与两个等价的Li⁺以及一个W⁴·⁸⁶⁺原子成键。