Materials Data on Li4V3Co2Sb3O16 by Materials Project

Li4V3Co2Sb3O16 is Hausmannite-derived structured and crystallizes in the monoclinic Cm space group. The structure is three-dimensional. there are four inequivalent Li1+ sites. In the first Li1+ site, Li1+ is bonded to four O2- atoms to form LiO4 tetrahedra that share corners with three equivalent CoO6 octahedra, corners with four SbO6 octahedra, and corners with five VO6 octahedra. The corner-sharing octahedra tilt angles range from 52–63°. There are a spread of Li–O bond distances ranging from 1.99–2.21 Å. In the second 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 1.76–2.06 Å. In the third Li1+ site, Li1+ is bonded in a distorted rectangular see-saw-like geometry to four O2- atoms. There are a spread of Li–O bond distances ranging from 1.82–1.96 Å. In the fourth Li1+ site, Li1+ is bonded to four O2- atoms to form LiO4 tetrahedra that share corners with four VO6 octahedra and corners with five SbO6 octahedra. The corner-sharing octahedra tilt angles range from 56–58°. There are a spread of Li–O bond distances ranging from 1.99–2.10 Å. There are two inequivalent V5+ sites. In the first V5+ site, V5+ is bonded to six O2- atoms to form VO6 octahedra that share corners with two equivalent CoO6 octahedra, corners with three LiO4 tetrahedra, and edges with four equivalent SbO6 octahedra. The corner-sharing octahedral tilt angles are 51°. There are a spread of V–O bond distances ranging from 2.02–2.13 Å. In the second V5+ site, V5+ is bonded to six O2- atoms to form VO6 octahedra that share corners with three LiO4 tetrahedra, an edgeedge with one CoO6 octahedra, edges with two equivalent VO6 octahedra, and edges with two equivalent SbO6 octahedra. There are a spread of V–O bond distances ranging from 2.02–2.10 Å. There are two inequivalent Co2+ sites. In the first Co2+ site, Co2+ is bonded in a 6-coordinate geometry to six O2- atoms. There are a spread of Co–O bond distances ranging from 2.00–2.50 Å. In the second Co2+ site, Co2+ is bonded to six O2- atoms to form CoO6 octahedra that share corners with two equivalent VO6 octahedra, corners with four equivalent SbO6 octahedra, corners with three equivalent LiO4 tetrahedra, an edgeedge with one SbO6 octahedra, and edges with two equivalent VO6 octahedra. The corner-sharing octahedra tilt angles range from 51–54°. There are a spread of Co–O bond distances ranging from 2.07–2.38 Å. There are two inequivalent Sb3+ sites. In the first Sb3+ site, Sb3+ is bonded to six O2- atoms to form SbO6 octahedra that share corners with two equivalent CoO6 octahedra, corners with three LiO4 tetrahedra, edges with two equivalent VO6 octahedra, and edges with two equivalent SbO6 octahedra. The corner-sharing octahedra tilt angles range from 53–54°. There are a spread of Sb–O bond distances ranging from 1.98–2.06 Å. In the second Sb3+ site, Sb3+ is bonded to six O2- atoms to form SbO6 octahedra that share corners with three LiO4 tetrahedra, an edgeedge with one CoO6 octahedra, and edges with four equivalent VO6 octahedra. There are a spread of Sb–O bond distances ranging from 2.00–2.05 Å. There are twelve inequivalent O2- sites. In the first O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to one Li1+, one V5+, one Co2+, and one Sb3+ atom. In the second O2- site, O2- is bonded in a 4-coordinate geometry to one Li1+, one Co2+, and two equivalent Sb3+ atoms. In the third O2- site, O2- is bonded in a rectangular see-saw-like geometry to one Li1+, one V5+, and two equivalent Sb3+ atoms. In the fourth O2- site, O2- is bonded to one Li1+, one V5+, and two equivalent Sb3+ atoms to form a mixture of distorted edge and corner-sharing OLiVSb2 tetrahedra. In the fifth O2- site, O2- is bonded to one Li1+, two equivalent V5+, and one Sb3+ atom to form distorted OLiV2Sb tetrahedra that share corners with two equivalent OLiV2Co tetrahedra and corners with two equivalent OLiVCoSb trigonal pyramids. In the sixth O2- site, O2- is bonded to one Li1+, one V5+, one Co2+, and one Sb3+ atom to form distorted OLiVCoSb tetrahedra that share corners with three OLiVSb2 tetrahedra, corners with three equivalent OLiVCoSb trigonal pyramids, and an edgeedge with one OLiVCoSb tetrahedra. In the seventh O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to one Li1+, one Co2+, and two equivalent Sb3+ atoms. In the eighth O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to one Li1+, two equivalent V5+, and one Co2+ atom. In the ninth O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to one Li1+, one V5+, one Co2+, and one Sb3+ atom. In the tenth O2- site, O2- is bonded in a rectangular see-saw-like geometry to one Li1+, two equivalent V5+, and one Sb3+ atom. In the eleventh O2- site, O2- is bonded to one Li1+, one V5+, one Co2+, and one Sb3+ atom to form distorted OLiVCoSb trigonal pyramids that share corners with five OLiV2Co tetrahedra, a cornercorner with one OLiVCoSb trigonal pyramid, an edgeedge with one OLiVSb2 tetrahedra, and an edgeedge with one OLiVCoSb trigonal pyramid. In the twelfth O2- site, O2- is bonded to one Li1+, two equivalent V5+, and one Co2+ atom to form distorted OLiV2Co tetrahedra that share corners with two equivalent OLiV2Sb tetrahedra and corners with two equivalent OLiVCoSb trigonal pyramids.

Li₄V₃Co₂Sb₃O₁₆为源自硬锰矿（Hausmannite）的晶体材料，其结构属于单斜晶系Cm空间群，整体呈三维框架结构。存在4种不等价的Li⁺位点：在第一种Li⁺位点中，Li⁺与4个O²⁻原子配位形成LiO₄四面体，该四面体与3个等价的CoO₆八面体、4个等价的SbO₆八面体以及5个等价的VO₆八面体通过共顶点相连，共顶点八面体的倾斜角范围为52°~63°，Li-O键长分布在1.99~2.21 Å之间；在第二种Li⁺位点中，Li⁺以类矩形跷板式配位几何与4个O²⁻原子结合，Li-O键长分布在1.76~2.06 Å之间；在第三种Li⁺位点中，Li⁺以畸变类矩形跷板式配位几何与4个O²⁻原子结合，Li-O键长分布在1.82~1.96 Å之间；在第四种Li⁺位点中，Li⁺与4个O²⁻原子配位形成LiO₄四面体，该四面体与4个VO₆八面体、5个SbO₆八面体通过共顶点相连，共顶点八面体的倾斜角范围为56°~58°，Li-O键长分布在1.99~2.10 Å之间。
存在2种不等价的V⁵⁺位点：在第一种V⁵⁺位点中，V⁵⁺与6个O²⁻原子配位形成VO₆八面体，该八面体与2个等价的CoO₆八面体共顶点、与3个LiO₄四面体共顶点、与4个等价的SbO₆八面体共边，共顶点八面体的倾斜角为51°，V-O键长分布在2.02~2.13 Å之间；在第二种V⁵⁺位点中，V⁵⁺与6个O²⁻原子配位形成VO₆八面体，该八面体与3个LiO₄四面体共顶点、与1个CoO₆八面体共边、与2个等价的VO₆八面体共边、与2个等价的SbO₆八面体共边，V-O键长分布在2.02~2.10 Å之间。
存在2种不等价的Co²⁺位点：在第一种Co²⁺位点中，Co²⁺以六配位几何构型与6个O²⁻原子结合，Co-O键长分布在2.00~2.50 Å之间；在第二种Co²⁺位点中，Co²⁺与6个O²⁻原子配位形成CoO₆八面体，该八面体与2个等价的VO₆八面体共顶点、与4个等价的SbO₆八面体共顶点、与3个等价的LiO₄四面体共顶点、与1个SbO₆八面体共边、与2个等价的VO₆八面体共边，共顶点八面体的倾斜角范围为51°~54°，Co-O键长分布在2.07~2.38 Å之间。
存在2种不等价的Sb³⁺位点：在第一种Sb³⁺位点中，Sb³⁺与6个O²⁻原子配位形成SbO₆八面体，该八面体与2个等价的CoO₆八面体共顶点、与3个LiO₄四面体共顶点、与2个等价的VO₆八面体共边、与2个等价的SbO₆八面体共边，共顶点八面体的倾斜角范围为53°~54°，Sb-O键长分布在1.98~2.06 Å之间；在第二种Sb³⁺位点中，Sb³⁺与6个O²⁻原子配位形成SbO₆八面体，该八面体与3个LiO₄四面体共顶点、与1个CoO₆八面体共边、与4个等价的VO₆八面体共边，Sb-O键长分布在2.00~2.05 Å之间。
存在12种不等价的O²⁻位点：第一种O²⁻位点中，O²⁻以畸变类矩形跷板式配位几何分别与1个Li⁺、1个V⁵⁺、1个Co²⁺以及1个Sb³⁺原子结合；第二种O²⁻位点中，O²⁻以四配位几何分别与1个Li⁺、1个Co²⁺以及2个等价的Sb³⁺原子结合；第三种O²⁻位点中，O²⁻以类矩形跷板式配位几何分别与1个Li⁺、1个V⁵⁺以及2个等价的Sb³⁺原子结合；第四种O²⁻位点中，O²⁻与1个Li⁺、1个V⁵⁺以及2个等价的Sb³⁺原子结合，形成兼具畸变共边与共顶点结构的OLiVSb₂四面体；第五种O²⁻位点中，O²⁻与1个Li⁺、2个等价的V⁵⁺以及1个Sb³⁺原子结合，形成畸变OLiV₂Sb四面体，该四面体与2个等价的OLiV₂Co四面体共顶点、与2个等价的OLiVCoSb三角锥共顶点；第六种O²⁻位点中，O²⁻与1个Li⁺、1个V⁵⁺、1个Co²⁺以及1个Sb³⁺原子结合，形成畸变OLiVCoSb四面体，该四面体与3个OLiVSb₂四面体共顶点、与3个等价的OLiVCoSb三角锥共顶点、与1个OLiVCoSb四面体共边；第七种O²⁻位点中，O²⁻以畸变类矩形跷板式配位几何分别与1个Li⁺、1个Co²⁺以及2个等价的Sb³⁺原子结合；第八种O²⁻位点中，O²⁻以畸变类矩形跷板式配位几何分别与1个Li⁺、2个等价的V⁵⁺以及1个Co²⁺原子结合；第九种O²⁻位点中，O²⁻以畸变类矩形跷板式配位几何分别与1个Li⁺、1个V⁵⁺、1个Co²⁺以及1个Sb³⁺原子结合；第十种O²⁻位点中，O²⁻以类矩形跷板式配位几何分别与1个Li⁺、2个等价的V⁵⁺以及1个Sb³⁺原子结合；第十一种O²⁻位点中，O²⁻与1个Li⁺、1个V⁵⁺、1个Co²⁺以及1个Sb³⁺原子结合，形成畸变OLiVCoSb三角锥，该三角锥与5个OLiV₂Co四面体共顶点、与1个OLiVCoSb三角锥共顶点、与1个OLiVSb₂四面体共边、与1个OLiVCoSb三角锥共边；第十二种O²⁻位点中，O²⁻与1个Li⁺、2个等价的V⁵⁺以及1个Co²⁺原子结合，形成畸变OLiV₂Co四面体，该四面体与2个等价的OLiV₂Sb四面体共顶点、与2个等价的OLiVCoSb三角锥共顶点。