Materials Data on Mn3O4 by Materials Project

Mn3O4 crystallizes in the triclinic P1 space group. The structure is three-dimensional. there are twelve inequivalent Mn+2.67+ sites. In the first Mn+2.67+ site, Mn+2.67+ is bonded to six O2- atoms to form a mixture of distorted edge and corner-sharing MnO6 octahedra. The corner-sharing octahedra tilt angles range from 2–3°. There are a spread of Mn–O bond distances ranging from 2.09–2.52 Å. In the second Mn+2.67+ site, Mn+2.67+ is bonded in a see-saw-like geometry to four O2- atoms. There are a spread of Mn–O bond distances ranging from 1.88–1.90 Å. In the third Mn+2.67+ site, Mn+2.67+ is bonded to six O2- atoms to form a mixture of distorted edge and corner-sharing MnO6 octahedra. The corner-sharing octahedral tilt angles are 2°. There are a spread of Mn–O bond distances ranging from 2.09–2.47 Å. In the fourth Mn+2.67+ site, Mn+2.67+ is bonded in a 6-coordinate geometry to six O2- atoms. There are a spread of Mn–O bond distances ranging from 2.09–2.60 Å. In the fifth Mn+2.67+ site, Mn+2.67+ is bonded to six O2- atoms to form distorted MnO6 octahedra that share a cornercorner with one MnO6 octahedra, corners with two equivalent MnO5 square pyramids, edges with four MnO6 octahedra, and an edgeedge with one MnO5 square pyramid. The corner-sharing octahedral tilt angles are 3°. There are a spread of Mn–O bond distances ranging from 2.09–2.40 Å. In the sixth Mn+2.67+ site, Mn+2.67+ is bonded to six O2- atoms to form a mixture of distorted edge and corner-sharing MnO6 octahedra. The corner-sharing octahedral tilt angles are 0°. There are a spread of Mn–O bond distances ranging from 2.10–2.41 Å. In the seventh Mn+2.67+ site, Mn+2.67+ is bonded to six O2- atoms to form a mixture of distorted edge and corner-sharing MnO6 octahedra. The corner-sharing octahedral tilt angles are 0°. There are a spread of Mn–O bond distances ranging from 2.08–2.52 Å. In the eighth Mn+2.67+ site, Mn+2.67+ is bonded in a 6-coordinate geometry to six O2- atoms. There are a spread of Mn–O bond distances ranging from 2.09–2.61 Å. In the ninth Mn+2.67+ site, Mn+2.67+ is bonded in a see-saw-like geometry to four O2- atoms. There is two shorter (1.88 Å) and two longer (1.89 Å) Mn–O bond length. In the tenth Mn+2.67+ site, Mn+2.67+ is bonded to five O2- atoms to form distorted MnO5 square pyramids that share corners with two equivalent MnO6 octahedra, an edgeedge with one MnO6 octahedra, and edges with two equivalent MnO5 square pyramids. The corner-sharing octahedral tilt angles are 3°. There are a spread of Mn–O bond distances ranging from 2.08–2.15 Å. In the eleventh Mn+2.67+ site, Mn+2.67+ is bonded in a distorted see-saw-like geometry to four O2- atoms. There are a spread of Mn–O bond distances ranging from 1.86–1.91 Å. In the twelfth Mn+2.67+ site, Mn+2.67+ is bonded in a see-saw-like geometry to four O2- atoms. There are a spread of Mn–O bond distances ranging from 1.86–1.91 Å. There are sixteen inequivalent O2- sites. In the first O2- site, O2- is bonded to four Mn+2.67+ atoms to form a mixture of distorted edge and corner-sharing OMn4 trigonal pyramids. In the second O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to four Mn+2.67+ atoms. In the third O2- site, O2- is bonded in a square co-planar geometry to four Mn+2.67+ atoms. In the fourth O2- site, O2- is bonded in a square co-planar geometry to four Mn+2.67+ atoms. In the fifth O2- site, O2- is bonded to four Mn+2.67+ atoms to form a mixture of distorted edge and corner-sharing OMn4 trigonal pyramids. In the sixth O2- site, O2- is bonded in a distorted bent 120 degrees geometry to four Mn+2.67+ atoms. In the seventh O2- site, O2- is bonded in a distorted see-saw-like geometry to four Mn+2.67+ atoms. In the eighth O2- site, O2- is bonded to four Mn+2.67+ atoms to form a mixture of distorted edge and corner-sharing OMn4 trigonal pyramids. In the ninth O2- site, O2- is bonded to four Mn+2.67+ atoms to form distorted corner-sharing OMn4 trigonal pyramids. In the tenth O2- site, O2- is bonded to four Mn+2.67+ atoms to form a mixture of distorted edge and corner-sharing OMn4 trigonal pyramids. In the eleventh O2- site, O2- is bonded to four Mn+2.67+ atoms to form a mixture of distorted edge and corner-sharing OMn4 trigonal pyramids. In the twelfth O2- site, O2- is bonded in a 2-coordinate geometry to three Mn+2.67+ atoms. In the thirteenth O2- site, O2- is bonded to four Mn+2.67+ atoms to form a mixture of distorted edge and corner-sharing OMn4 trigonal pyramids. In the fourteenth O2- site, O2- is bonded in a distorted see-saw-like geometry to four Mn+2.67+ atoms. In the fifteenth O2- site, O2- is bonded in a square co-planar geometry to four Mn+2.67+ atoms. In the sixteenth O2- site, O2- is bonded in a square co-planar geometry to four Mn+2.67+ atoms.

四氧化三锰（Mn₃O₄）结晶于三斜晶系P1空间群（triclinic P1 space group），其晶体结构为三维网状结构。体系中存在12个不等价的Mn⁺².⁶⁺位点。在第一个Mn⁺².⁶⁺位点中，Mn⁺².⁶⁺与6个O²⁻配位，形成兼具畸变棱共享与角共享的MnO₆八面体（MnO₆ octahedra），角共享八面体的倾斜角范围为2°~3°，Mn-O键长分布区间为2.09~2.52 Å。在第二个Mn⁺².⁶⁺位点中，Mn⁺².⁶⁺以类跷跷板配位构型（see-saw-like geometry）与4个O²⁻配位，Mn-O键长分布区间为1.88~1.90 Å。在第三个Mn⁺².⁶⁺位点中，Mn⁺².⁶⁺与6个O²⁻配位，形成兼具畸变棱共享与角共享的MnO₆八面体，角共享八面体的倾斜角为2°，Mn-O键长分布区间为2.09~2.47 Å。在第四个Mn⁺².⁶⁺位点中，Mn⁺².⁶⁺以六配位构型与6个O²⁻配位，Mn-O键长分布区间为2.09~2.60 Å。在第五个Mn⁺².⁶⁺位点中，Mn⁺².⁶⁺与6个O²⁻配位，形成畸变MnO₆八面体，该八面体与1个MnO₆八面体共享1组角-角相互作用、与2个等价MnO₅四方锥（square pyramids）共享多个角、与4个MnO₆八面体共享多条棱，还与1个MnO₅四方锥共享1组棱-棱相互作用；角共享八面体的倾斜角为3°，Mn-O键长分布区间为2.09~2.40 Å。在第六个Mn⁺².⁶⁺位点中，Mn⁺².⁶⁺与6个O²⁻配位，形成兼具畸变棱共享与角共享的MnO₆八面体，角共享八面体的倾斜角为0°，Mn-O键长分布区间为2.10~2.41 Å。在第七个Mn⁺².⁶⁺位点中，Mn⁺².⁶⁺与6个O²⁻配位，形成兼具畸变棱共享与角共享的MnO₆八面体，角共享八面体的倾斜角为0°，Mn-O键长分布区间为2.08~2.52 Å。在第八个Mn⁺².⁶⁺位点中，Mn⁺².⁶⁺以六配位构型与6个O²⁻配位，Mn-O键长分布区间为2.09~2.61 Å。在第九个Mn⁺².⁶⁺位点中，Mn⁺².⁶⁺以类跷跷板配位构型与4个O²⁻配位，存在2条较短（1.88 Å）与2条较长（1.89 Å）的Mn-O键长。在第十个Mn⁺².⁶⁺位点中，Mn⁺².⁶⁺与5个O²⁻配位，形成畸变MnO₅四方锥，该四方锥与2个等价MnO₆八面体共享角、与1个MnO₆八面体共享1组棱-棱相互作用，还与2个等价MnO₅四方锥共享多条棱；角共享八面体的倾斜角为3°，Mn-O键长分布区间为2.08~2.15 Å。在第十一个Mn⁺².⁶⁺位点中，Mn⁺².⁶⁺以畸变类跷跷板配位构型与4个O²⁻配位，Mn-O键长分布区间为1.86~1.91 Å。在第十二个Mn⁺².⁶⁺位点中，Mn⁺².⁶⁺以类跷跷板配位构型与4个O²⁻配位，Mn-O键长分布区间为1.86~1.91 Å。

体系中同时存在16个不等价的O²⁻位点。在第一个O²⁻位点中，O²⁻与4个Mn⁺².⁶⁺配位，形成兼具畸变棱共享与角共享的OMn₄三角锥（trigonal pyramids）。在第二个O²⁻位点中，O²⁻以畸变矩形类跷跷板配位构型与4个Mn⁺².⁶⁺配位。在第三个O²⁻位点中，O²⁻以平面正方形配位构型与4个Mn⁺².⁶⁺配位。在第四个O²⁻位点中，O²⁻以平面正方形配位构型与4个Mn⁺².⁶⁺配位。在第五个O²⁻位点中，O²⁻与4个Mn⁺².⁶⁺配位，形成兼具畸变棱共享与角共享的OMn₄三角锥。在第六个O²⁻位点中，O²⁻以畸变120°弯折配位构型与4个Mn⁺².⁶⁺配位。在第七个O²⁻位点中，O²⁻以畸变类跷跷板配位构型与4个Mn⁺².⁶⁺配位。在第八个O²⁻位点中，O²⁻与4个Mn⁺².⁶⁺配位，形成兼具畸变棱共享与角共享的OMn₄三角锥。在第九个O²⁻位点中，O²⁻与4个Mn⁺².⁶⁺配位，形成畸变角共享OMn₄三角锥。在第十个O²⁻位点中，O²⁻与4个Mn⁺².⁶⁺配位，形成兼具畸变棱共享与角共享的OMn₄三角锥。在第十一个O²⁻位点中，O²⁻与4个Mn⁺².⁶⁺配位，形成兼具畸变棱共享与角共享的OMn₄三角锥。在第十二个O²⁻位点中，O²⁻以二配位构型与3个Mn⁺².⁶⁺配位。在第十三个O²⁻位点中，O²⁻与4个Mn⁺².⁶⁺配位，形成兼具畸变棱共享与角共享的OMn₄三角锥。在第十四个O²⁻位点中，O²⁻以畸变类跷跷板配位构型与4个Mn⁺².⁶⁺配位。在第十五个O²⁻位点中，O²⁻以平面正方形配位构型与4个Mn⁺².⁶⁺配位。在第十六个O²⁻位点中，O²⁻以平面正方形配位构型与4个Mn⁺².⁶⁺配位。