Materials Data on Li4V2Fe3Cu3O16 by Materials Project

Li4V2Fe3Cu3O16 is Hausmannite-derived structured and crystallizes in the triclinic P1 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 VO6 octahedra, corners with four CuO6 octahedra, and corners with five FeO6 octahedra. The corner-sharing octahedra tilt angles range from 58–62°. There are a spread of Li–O bond distances ranging from 1.94–2.01 Å. In the second Li1+ site, Li1+ is bonded to four O2- atoms to form LiO4 tetrahedra that share a cornercorner with one CuO6 octahedra, corners with two FeO6 octahedra, corners with three equivalent VO6 octahedra, an edgeedge with one FeO6 octahedra, and edges with two CuO6 octahedra. The corner-sharing octahedra tilt angles range from 53–67°. There are a spread of Li–O bond distances ranging from 1.83–2.01 Å. In the third Li1+ site, Li1+ is bonded to four O2- atoms to form distorted LiO4 tetrahedra that share a cornercorner with one FeO6 octahedra, corners with two CuO6 octahedra, corners with three equivalent VO6 octahedra, an edgeedge with one CuO6 octahedra, and edges with two FeO6 octahedra. The corner-sharing octahedra tilt angles range from 54–69°. There are a spread of Li–O bond distances ranging from 1.84–2.06 Å. In the fourth Li1+ site, Li1+ is bonded to four O2- atoms to form LiO4 tetrahedra that share corners with three equivalent VO6 octahedra, corners with four FeO6 octahedra, and corners with five CuO6 octahedra. The corner-sharing octahedra tilt angles range from 56–63°. There are a spread of Li–O bond distances ranging from 1.94–2.06 Å. There are two inequivalent V5+ sites. In the first V5+ site, V5+ is bonded to six O2- atoms to form distorted VO6 octahedra that share corners with two equivalent CuO6 octahedra, corners with four FeO6 octahedra, corners with six LiO4 tetrahedra, an edgeedge with one FeO6 octahedra, and edges with two CuO6 octahedra. The corner-sharing octahedra tilt angles range from 49–52°. There are a spread of V–O bond distances ranging from 1.82–2.07 Å. In the second V5+ site, V5+ is bonded to six O2- atoms to form distorted VO6 octahedra that share corners with two equivalent FeO6 octahedra, corners with four CuO6 octahedra, corners with six LiO4 tetrahedra, an edgeedge with one CuO6 octahedra, and edges with two FeO6 octahedra. The corner-sharing octahedra tilt angles range from 48–53°. There are a spread of V–O bond distances ranging from 1.82–2.08 Å. There are three inequivalent Fe3+ sites. In the first Fe3+ site, Fe3+ is bonded to six O2- atoms to form FeO6 octahedra that share corners with two equivalent VO6 octahedra, corners with four LiO4 tetrahedra, an edgeedge with one VO6 octahedra, edges with four CuO6 octahedra, and an edgeedge with one LiO4 tetrahedra. The corner-sharing octahedra tilt angles range from 48–49°. There are a spread of Fe–O bond distances ranging from 1.96–2.16 Å. In the second Fe3+ site, Fe3+ is bonded to six O2- atoms to form FeO6 octahedra that share corners with two equivalent VO6 octahedra, corners with four LiO4 tetrahedra, an edgeedge with one VO6 octahedra, edges with two equivalent FeO6 octahedra, edges with two equivalent CuO6 octahedra, and an edgeedge with one LiO4 tetrahedra. The corner-sharing octahedra tilt angles range from 49–51°. There are a spread of Fe–O bond distances ranging from 1.94–2.18 Å. In the third Fe3+ site, Fe3+ is bonded to six O2- atoms to form FeO6 octahedra that share corners with two equivalent VO6 octahedra, corners with four LiO4 tetrahedra, an edgeedge with one VO6 octahedra, edges with two equivalent FeO6 octahedra, edges with two equivalent CuO6 octahedra, and an edgeedge with one LiO4 tetrahedra. The corner-sharing octahedra tilt angles range from 49–51°. There are a spread of Fe–O bond distances ranging from 1.94–2.17 Å. There are three inequivalent Cu3+ sites. In the first Cu3+ site, Cu3+ is bonded to six O2- atoms to form CuO6 octahedra that share corners with two equivalent VO6 octahedra, corners with four LiO4 tetrahedra, an edgeedge with one VO6 octahedra, edges with two equivalent FeO6 octahedra, edges with two equivalent CuO6 octahedra, and an edgeedge with one LiO4 tetrahedra. The corner-sharing octahedra tilt angles range from 52–53°. There are a spread of Cu–O bond distances ranging from 1.88–2.17 Å. In the second Cu3+ site, Cu3+ is bonded to six O2- atoms to form CuO6 octahedra that share corners with two equivalent VO6 octahedra, corners with four LiO4 tetrahedra, an edgeedge with one VO6 octahedra, edges with two equivalent FeO6 octahedra, edges with two equivalent CuO6 octahedra, and an edgeedge with one LiO4 tetrahedra. The corner-sharing octahedra tilt angles range from 50–52°. There are a spread of Cu–O bond distances ranging from 1.92–2.21 Å. In the third Cu3+ site, Cu3+ is bonded to six O2- atoms to form CuO6 octahedra that share corners with two equivalent VO6 octahedra, corners with four LiO4 tetrahedra, an edgeedge with one VO6 octahedra, edges with four FeO6 octahedra, and an edgeedge with one LiO4 tetrahedra. The corner-sharing octahedral tilt angles are 52°. There are a spread of Cu–O bond distances ranging from 1.93–2.19 Å. There are sixteen 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 Fe3+, and one Cu3+ atom. In the second O2- site, O2- is bonded to one Li1+, one V5+, and two Cu3+ atoms to form distorted OLiVCu2 tetrahedra that share corners with three OLiFeCu2 tetrahedra, an edgeedge with one OLiVFeCu tetrahedra, and an edgeedge with one OLiFeCu2 trigonal pyramid. In the third O2- site, O2- is bonded to one Li1+, one Fe3+, and two Cu3+ atoms to form distorted OLiFeCu2 trigonal pyramids that share corners with four OLiFeCu2 tetrahedra and edges with two OLiVFeCu tetrahedra. In the fourth O2- site, O2- is bonded to one Li1+, one Fe3+, and two Cu3+ atoms to form OLiFeCu2 tetrahedra that share corners with four OLiVCu2 tetrahedra and corners with three equivalent OLiFeCu2 trigonal pyramids. In the fifth O2- site, O2- is bonded to one Li1+, two Fe3+, and one Cu3+ atom to form corner-sharing OLiFe2Cu tetrahedra. In the sixth O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to one Li1+, one V5+, one Fe3+, and one Cu3+ atom. In the seventh O2- site, O2- is bonded to one Li1+, one V5+, one Fe3+, and one Cu3+ atom to form distorted OLiVFeCu tetrahedra that share corners with three OLiVCu2 tetrahedra, an edgeedge with one OLiVCu2 tetrahedra, and an edgeedge with one OLiFeCu2 trigonal pyramid. In the eighth O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to one Li1+, one V5+, one Fe3+, and one Cu3+ atom. In the ninth O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to one Li1+, one V5+, and two Cu3+ atoms. In the tenth O2- site, O2- is bonded in a rectangular see-saw-like geometry to one Li1+, one V5+, and two Fe3+ atoms. In the eleventh O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to one Li1+, one V5+, one Fe3+, and one Cu3+ atom. In the twelfth O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to one Li1+, one V5+, one Fe3+, and one Cu3+ atom. In the thirteenth O2- site, O2- is bonded in a rectangular see-saw-like geometry to one Li1+, two Fe3+, and one Cu3+ atom. In the fourteenth O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to one Li1+, one V5+, one Fe3+, and one Cu3+ atom. In the fifteenth O2- site, O2- is bonded to one Li1+, one V5+, and two Fe3+ atoms to form distorted OLiVFe2 tetrahedra that share corners with two equivalent OLiFe2Cu tetrahedra and a cornercorner with one OLiFeCu2 trigonal pyramid. In the sixteenth O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to one Li1+, one V5+, one Fe3+, and one Cu3+ atom.

Li₄V₂Fe₃Cu₃O₁₆为黑锰矿衍生结构，结晶于三斜晶系P1空间群，其结构为三维框架。
该体系存在4种不等价Li⁺位点：
在第一种Li⁺位点中，Li⁺与4个O²⁻成键，形成LiO₄四面体，该四面体与3个等价的VO₆八面体、4个CuO₆八面体以及5个FeO₆八面体共顶点。共顶点八面体的倾斜角范围为58°~62°，Li-O键长分布在1.94~2.01 Å之间。
在第二种Li⁺位点中，Li⁺与4个O²⁻成键，形成LiO₄四面体，该四面体与1个CuO₆八面体共顶点、与2个FeO₆八面体共顶点、与3个等价的VO₆八面体共顶点，同时与1个FeO₆八面体共边，以及与2个CuO₆八面体共边。共顶点八面体的倾斜角范围为53°~67°，Li-O键长分布在1.83~2.01 Å之间。
在第三种Li⁺位点中，Li⁺与4个O²⁻成键，形成畸变LiO₄四面体，该四面体与1个FeO₆八面体共顶点、与2个CuO₆八面体共顶点、与3个等价的VO₆八面体共顶点，同时与1个CuO₆八面体共边，以及与2个FeO₆八面体共边。共顶点八面体的倾斜角范围为54°~69°，Li-O键长分布在1.84~2.06 Å之间。
在第四种Li⁺位点中，Li⁺与4个O²⁻成键，形成LiO₄四面体，该四面体与3个等价的VO₆八面体、4个FeO₆八面体以及5个CuO₆八面体共顶点。共顶点八面体的倾斜角范围为56°~63°，Li-O键长分布在1.94~2.06 Å之间。
存在2种不等价V⁵+位点：
在第一种V⁵+位点中，V⁵+与6个O²⁻成键，形成畸变VO₆八面体，该八面体与2个等价的CuO₆八面体共顶点、与4个FeO₆八面体共顶点、与6个LiO₄四面体共顶点，同时与1个FeO₆八面体共边，以及与2个CuO₆八面体共边。共顶点八面体的倾斜角范围为49°~52°，V-O键长分布在1.82~2.07 Å之间。
在第二种V⁵+位点中，V⁵+与6个O²⁻成键，形成畸变VO₆八面体，该八面体与2个等价的FeO₆八面体共顶点、与4个CuO₆八面体共顶点、与6个LiO₄四面体共顶点，同时与1个CuO₆八面体共边，以及与2个FeO₆八面体共边。共顶点八面体的倾斜角范围为48°~53°，V-O键长分布在1.82~2.08 Å之间。
存在3种不等价Fe³+位点：
在第一种Fe³+位点中，Fe³+与6个O²⁻成键，形成FeO₆八面体，该八面体与2个等价的VO₆八面体共顶点、与4个LiO₄四面体共顶点，同时与1个VO₆八面体共边、与4个CuO₆八面体共边，以及与1个LiO₄四面体共边。共顶点八面体的倾斜角范围为48°~49°，Fe-O键长分布在1.96~2.16 Å之间。
在第二种Fe³+位点中，Fe³+与6个O²⁻成键，形成FeO₆八面体，该八面体与2个等价的VO₆八面体共顶点、与4个LiO₄四面体共顶点，同时与1个VO₆八面体共边、与2个等价的FeO₆八面体共边、与2个等价的CuO₆八面体共边，以及与1个LiO₄四面体共边。共顶点八面体的倾斜角范围为49°~51°，Fe-O键长分布在1.94~2.18 Å之间。
在第三种Fe³+位点中，Fe³+与6个O²⁻成键，形成FeO₆八面体，该八面体与2个等价的VO₆八面体共顶点、与4个LiO₄四面体共顶点，同时与1个VO₆八面体共边、与2个等价的FeO₆八面体共边、与2个等价的CuO₆八面体共边，以及与1个LiO₄四面体共边。共顶点八面体的倾斜角范围为49°~51°，Fe-O键长分布在1.94~2.17 Å之间。
存在3种不等价Cu³+位点：
在第一种Cu³+位点中，Cu³+与6个O²⁻成键，形成CuO₆八面体，该八面体与2个等价的VO₆八面体共顶点、与4个LiO₄四面体共顶点，同时与1个VO₆八面体共边、与2个等价的FeO₆八面体共边、与2个等价的CuO₆八面体共边，以及与1个LiO₄四面体共边。共顶点八面体的倾斜角范围为52°~53°，Cu-O键长分布在1.88~2.17 Å之间。
在第二种Cu³+位点中，Cu³+与6个O²⁻成键，形成CuO₆八面体，该八面体与2个等价的VO₆八面体共顶点、与4个LiO₄四面体共顶点，同时与1个VO₆八面体共边、与2个等价的FeO₆八面体共边、与2个等价的CuO₆八面体共边，以及与1个LiO₄四面体共边。共顶点八面体的倾斜角范围为50°~52°，Cu-O键长分布在1.92~2.21 Å之间。
在第三种Cu³+位点中，Cu³+与6个O²⁻成键，形成CuO₆八面体，该八面体与2个等价的VO₆八面体共顶点、与4个LiO₄四面体共顶点，同时与1个VO₆八面体共边、与4个FeO₆八面体共边，以及与1个LiO₄四面体共边。共顶点八面体的倾斜角为52°，Cu-O键长分布在1.93~2.19 Å之间。
存在16种不等价O²⁻位点：
在第一种O²⁻位点中，O²⁻以畸变矩形跷跷板状配位构型，与1个Li⁺、1个V⁵+、1个Fe³+以及1个Cu³+成键。
在第二种O²⁻位点中，O²⁻与1个Li⁺、1个V⁵+以及2个Cu³+成键，形成畸变OLiVCu₂四面体，该四面体与3个OLiFeCu₂四面体共顶点、与1个OLiVFeCu四面体共边，以及与1个OLiFeCu₂三角锥共边。
在第三种O²⁻位点中，O²⁻与1个Li⁺、1个Fe³+以及2个Cu³+成键，形成畸变OLiFeCu₂三角锥，该三角锥与4个OLiFeCu₂四面体共顶点，且与2个OLiVFeCu四面体共边。
在第四种O²⁻位点中，O²⁻与1个Li⁺、1个Fe³+以及2个Cu³+成键，形成OLiFeCu₂四面体，该四面体与4个OLiVCu₂四面体共顶点，且与3个等价的OLiFeCu₂三角锥共顶点。
在第五种O²⁻位点中，O²⁻与1个Li⁺、2个Fe³+以及1个Cu³+成键，形成共顶点OLiFe₂Cu四面体。
在第六种O²⁻位点中，O²⁻以畸变矩形跷跷板状配位构型，与1个Li⁺、1个V⁵+、1个Fe³+以及1个Cu³+成键。
在第七种O²⁻位点中，O²⁻与1个Li⁺、1个V⁵+、1个Fe³+以及1个Cu³+成键，形成畸变OLiVFeCu四面体，该四面体与3个OLiVCu₂四面体共顶点、与1个OLiVCu₂四面体共边，以及与1个OLiFeCu₂三角锥共边。
在第八种O²⁻位点中，O²⁻以畸变矩形跷跷板状配位构型，与1个Li⁺、1个V⁵+、1个Fe³+以及1个Cu³+成键。
在第九种O²⁻位点中，O²⁻以畸变矩形跷跷板状配位构型，与1个Li⁺、1个V⁵+以及2个Cu³+成键。
在第十种O²⁻位点中，O²⁻以矩形跷跷板状配位构型，与1个Li⁺、1个V⁵+以及2个Fe³+成键。
在第十一种O²⁻位点中，O²⁻以畸变矩形跷跷板状配位构型，与1个Li⁺、1个V⁵+、1个Fe³+以及1个Cu³+成键。
在第十二种O²⁻位点中，O²⁻以畸变矩形跷跷板状配位构型，与1个Li⁺、1个V⁵+、1个Fe³+以及1个Cu³+成键。
在第十三种O²⁻位点中，O²⁻以矩形跷跷板状配位构型，与1个Li⁺、2个Fe³+以及1个Cu³+成键。
在第十四种O²⁻位点中，O²⁻以畸变矩形跷跷板状配位构型，与1个Li⁺、1个V⁵+、1个Fe³+以及1个Cu³+成键。
在第十五种O²⁻位点中，O²⁻与1个Li⁺、1个V⁵+以及2个Fe³+成键，形成畸变OLiVFe₂四面体，该四面体与2个等价的OLiFe₂Cu四面体共顶点，且与1个OLiFeCu₂三角锥共顶点。
在第十六种O²⁻位点中，O²⁻以畸变矩形跷跷板状配位构型，与1个Li⁺、1个V⁵+、1个Fe³+以及1个Cu³+成键。