Materials Data on Li6V3W3O16 by Materials Project

Li6V3W3O16 is Hausmannite-derived structured and crystallizes in the triclinic P1 space group. The structure is three-dimensional. there are six 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 2.13–2.59 Å. In the second Li1+ site, Li1+ is bonded to four O2- atoms to form LiO4 tetrahedra that share corners with four WO6 octahedra and corners with five VO6 octahedra. The corner-sharing octahedra tilt angles range from 54–63°. There are a spread of Li–O bond distances ranging from 2.03–2.13 Å. In the third Li1+ site, Li1+ is bonded in a rectangular see-saw-like geometry to four O2- atoms. There are a spread of Li–O bond distances ranging from 1.82–1.97 Å. In the fourth Li1+ site, Li1+ is bonded in a rectangular see-saw-like geometry to four O2- atoms. There are a spread of Li–O bond distances ranging from 1.82–1.97 Å. In the fifth 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 2.10–2.59 Å. In the sixth Li1+ site, Li1+ is bonded to four O2- atoms to form LiO4 tetrahedra that share corners with four VO6 octahedra and corners with five WO6 octahedra. The corner-sharing octahedra tilt angles range from 51–62°. There are a spread of Li–O bond distances ranging from 2.01–2.10 Å. There are three inequivalent V5+ sites. In the first V5+ site, V5+ is bonded to six O2- atoms to form VO6 octahedra that share corners with three LiO4 tetrahedra and edges with four WO6 octahedra. There are a spread of V–O bond distances ranging from 2.03–2.13 Å. In the second V5+ site, V5+ is bonded to six O2- atoms to form VO6 octahedra that share corners with three LiO4 tetrahedra, edges with two equivalent VO6 octahedra, and edges with two equivalent WO6 octahedra. There are a spread of V–O bond distances ranging from 1.84–2.09 Å. In the third V5+ site, V5+ is bonded to six O2- atoms to form VO6 octahedra that share corners with three LiO4 tetrahedra, edges with two equivalent VO6 octahedra, and edges with two equivalent WO6 octahedra. There are a spread of V–O bond distances ranging from 2.03–2.15 Å. There are three inequivalent W+3.67+ sites. In the first W+3.67+ site, W+3.67+ is bonded to six O2- atoms to form WO6 octahedra that share corners with three LiO4 tetrahedra, edges with two equivalent VO6 octahedra, and edges with two equivalent WO6 octahedra. There are a spread of W–O bond distances ranging from 1.93–2.07 Å. In the second W+3.67+ site, W+3.67+ is bonded to six O2- atoms to form WO6 octahedra that share corners with three LiO4 tetrahedra, edges with two equivalent VO6 octahedra, and edges with two equivalent WO6 octahedra. There are a spread of W–O bond distances ranging from 1.92–2.08 Å. In the third W+3.67+ site, W+3.67+ is bonded to six O2- atoms to form WO6 octahedra that share corners with three LiO4 tetrahedra and edges with four VO6 octahedra. There are a spread of W–O bond distances ranging from 1.92–2.00 Å. There are sixteen inequivalent O2- sites. In the first O2- site, O2- is bonded in a rectangular see-saw-like geometry to two Li1+, one V5+, and one W+3.67+ atom. In the second O2- site, O2- is bonded to two Li1+ and two W+3.67+ atoms to form distorted OLi2W2 tetrahedra that share corners with two OLi2VW tetrahedra, a cornercorner with one OLi2V2 trigonal pyramid, and edges with two OLi2VW tetrahedra. In the third O2- site, O2- is bonded in a rectangular see-saw-like geometry to one Li1+, one V5+, and two W+3.67+ atoms. In the fourth O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to one Li1+, one V5+, and two W+3.67+ atoms. In the fifth O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to one Li1+, two V5+, and one W+3.67+ atom. In the sixth O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to two Li1+, one V5+, and one W+3.67+ atom. In the seventh O2- site, O2- is bonded to two Li1+, one V5+, and one W+3.67+ atom to form distorted OLi2VW tetrahedra that share corners with two OLi2W2 tetrahedra, a cornercorner with one OLi2V2 trigonal pyramid, and edges with two OLi2VW tetrahedra. In the eighth O2- site, O2- is bonded to two Li1+, one V5+, and one W+3.67+ atom to form distorted OLi2VW tetrahedra that share corners with two OLi2W2 tetrahedra, a cornercorner with one OLi2V2 trigonal pyramid, and edges with two OLi2VW tetrahedra. In the ninth O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to two Li1+ and two W+3.67+ atoms. In the tenth O2- site, O2- is bonded to two Li1+ and two V5+ atoms to form distorted corner-sharing OLi2V2 trigonal pyramids. In the eleventh O2- site, O2- is bonded to two Li1+, one V5+, and one W+3.67+ atom to form distorted OLi2VW tetrahedra that share a cornercorner with one OLi2VW tetrahedra, a cornercorner with one OLi2V2 trigonal pyramid, and an edgeedge with one OLi2VW tetrahedra. In the twelfth O2- site, O2- is bonded to two Li1+, one V5+, and one W+3.67+ atom to form distorted OLi2VW tetrahedra that share a cornercorner with one OLi2VW tetrahedra, a cornercorner with one OLi2V2 trigonal pyramid, and an edgeedge with one OLi2VW tetrahedra. In the thirteenth O2- site, O2- is bonded in a rectangular see-saw-like geometry to one Li1+, two V5+, and one W+3.67+ atom. In the fourteenth O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to two Li1+, one V5+, and one W+3.67+ atom. In the fifteenth O2- site, O2- is bonded in a 4-coordinate geometry to two Li1+ and two V5+ atoms. In the sixteenth O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to two Li1+, one V5+, and one W+3.67+ atom.

Li₆V₃W₃O₁₆为黑锰矿（Hausmannite）衍生结构，结晶于三斜晶系P1空间群，整体为三维框架结构。该结构包含6个不等价Li⁺配位位点：
1. 第一个Li⁺位点中，Li⁺采用六配位几何构型与6个O²⁻原子成键，Li-O键长分布范围为2.13~2.59 Å；
2. 第二个Li⁺位点中，Li⁺与4个O²⁻原子成键形成LiO₄四面体，该四面体与4个WO₆八面体、5个VO₆八面体共顶相连，共顶八面体的倾斜角范围为54°~63°，Li-O键长分布范围为2.03~2.13 Å；
3. 第三个Li⁺位点中，Li⁺采用类矩形跷板式几何构型与4个O²⁻原子成键，Li-O键长分布范围为1.82~1.97 Å；
4. 第四个Li⁺位点与第三个Li⁺位点配位环境一致，Li-O键长分布范围为1.82~1.97 Å；
5. 第五个Li⁺位点中，Li⁺采用六配位几何构型与6个O²⁻原子成键，Li-O键长分布范围为2.10~2.59 Å；
6. 第六个Li⁺位点中，Li⁺与4个O²⁻原子成键形成LiO₄四面体，该四面体与4个VO₆八面体、5个WO₆八面体共顶相连，共顶八面体的倾斜角范围为51°~62°，Li-O键长分布范围为2.01~2.10 Å。

该结构包含3个不等价V⁵⁺配位位点：
1. 第一个V⁵⁺位点中，V⁵⁺与6个O²⁻原子成键形成VO₆八面体，该八面体与3个LiO₄四面体共顶相连，与4个WO₆八面体共棱相连，V-O键长分布范围为2.03~2.13 Å；
2. 第二个V⁵⁺位点中，V⁵⁺与6个O²⁻原子成键形成VO₆八面体，该八面体与3个LiO₄四面体共顶相连，与2个等价VO₆八面体、2个等价WO₆八面体共棱相连，V-O键长分布范围为1.84~2.09 Å；
3. 第三个V⁵⁺位点中，V⁵⁺与6个O²⁻原子成键形成VO₆八面体，该八面体与3个LiO₄四面体共顶相连，与2个等价VO₆八面体、2个等价WO₆八面体共棱相连，V-O键长分布范围为2.03~2.15 Å。

该结构包含3个不等价W⁺3.67配位位点：
1. 第一个W⁺3.67位点中，W⁺3.67与6个O²⁻原子成键形成WO₆八面体，该八面体与3个LiO₄四面体共顶相连，与2个等价VO₆八面体、2个等价WO₆八面体共棱相连，W-O键长分布范围为1.93~2.07 Å；
2. 第二个W⁺3.67位点中，W⁺3.67与6个O²⁻原子成键形成WO₆八面体，该八面体与3个LiO₄四面体共顶相连，与2个等价VO₆八面体、2个等价WO₆八面体共棱相连，W-O键长分布范围为1.92~2.08 Å；
3. 第三个W⁺3.67位点中，W⁺3.67与6个O²⁻原子成键形成WO₆八面体，该八面体与3个LiO₄四面体共顶相连，与4个VO₆八面体共棱相连，W-O键长分布范围为1.92~2.00 Å。

该结构包含16个不等价O²⁻配位位点：
1. 第一个O²⁻位点中，O²⁻采用类矩形跷板式几何构型，与2个Li⁺、1个V⁵⁺及1个W⁺3.67原子成键；
2. 第二个O²⁻位点中，O²⁻与2个Li⁺及2个W⁺3.67原子成键，形成畸变OLi₂W₂四面体，该四面体与2个OLi₂VW四面体共顶相连，与1个OLi₂V₂三角锥共享一个顶角，并与2个OLi₂VW四面体共棱相连；
3. 第三个O²⁻位点中，O²⁻采用类矩形跷板式几何构型，与1个Li⁺、1个V⁵⁺及2个W⁺3.67原子成键；
4. 第四个O²⁻位点中，O²⁻采用畸变类矩形跷板式几何构型，与1个Li⁺、1个V⁵⁺及2个W⁺3.67原子成键；
5. 第五个O²⁻位点中，O²⁻采用畸变类矩形跷板式几何构型，与1个Li⁺、2个V⁵⁺及1个W⁺3.67原子成键；
6. 第六个O²⁻位点中，O²⁻采用畸变类矩形跷板式几何构型，与2个Li⁺、1个V⁵⁺及1个W⁺3.67原子成键；
7. 第七个O²⁻位点中，O²⁻与2个Li⁺、1个V⁵⁺及1个W⁺3.67原子成键，形成畸变OLi₂VW四面体，该四面体与2个OLi₂W₂四面体共顶相连，与1个OLi₂V₂三角锥共享一个顶角，并与2个OLi₂VW四面体共棱相连；
8. 第八个O²⁻位点中，O²⁻与2个Li⁺、1个V⁵⁺及1个W⁺3.67原子成键，形成畸变OLi₂VW四面体，该四面体与2个OLi₂W₂四面体共顶相连，与1个OLi₂V₂三角锥共享一个顶角，并与2个OLi₂VW四面体共棱相连；
9. 第九个O²⁻位点中，O²⁻采用畸变类矩形跷板式几何构型，与2个Li⁺及2个W⁺3.67原子成键；
10. 第十个O²⁻位点中，O²⁻与2个Li⁺及2个V⁵⁺原子成键，形成畸变OLi₂V₂三角锥，且各三角锥之间通过顶角相连；
11. 第十一个O²⁻位点中，O²⁻与2个Li⁺、1个V⁵⁺及1个W⁺3.67原子成键，形成畸变OLi₂VW四面体，该四面体与1个OLi₂VW四面体共顶相连，与1个OLi₂V₂三角锥共享一个顶角，并与1个OLi₂VW四面体共棱相连；
12. 第十二个O²⁻位点中，O²⁻与2个Li⁺、1个V⁵⁺及1个W⁺3.67原子成键，形成畸变OLi₂VW四面体，该四面体与1个OLi₂VW四面体共顶相连，与1个OLi₂V₂三角锥共享一个顶角，并与1个OLi₂VW四面体共棱相连；
13. 第十三个O²⁻位点中，O²⁻采用类矩形跷板式几何构型，与1个Li⁺、2个V⁵⁺及1个W⁺3.67原子成键；
14. 第十四个O²⁻位点中，O²⁻采用畸变类矩形跷板式几何构型，与2个Li⁺、1个V⁵⁺及1个W⁺3.67原子成键；
15. 第十五个O²⁻位点中，O²⁻采用四配位几何构型，与2个Li⁺及2个V⁵⁺原子成键；
16. 第十六个O²⁻位点中，O²⁻采用畸变类矩形跷板式几何构型，与2个Li⁺、1个V⁵⁺及1个W⁺3.67原子成键。