Materials Data on Na5Co2As(CO4)4 by Materials Project

Na5Co2As(CO4)4 crystallizes in the orthorhombic F222 space group. The structure is three-dimensional. there are five inequivalent Na1+ sites. In the first Na1+ site, Na1+ is bonded to six O2- atoms to form distorted NaO6 octahedra that share corners with eight NaO6 octahedra, edges with two equivalent CoO6 octahedra, and an edgeedge with one AsO4 tetrahedra. The corner-sharing octahedra tilt angles range from 59–88°. There are a spread of Na–O bond distances ranging from 2.45–2.54 Å. In the second Na1+ site, Na1+ is bonded to six O2- atoms to form distorted NaO6 octahedra that share corners with six NaO6 octahedra, edges with two equivalent CoO6 octahedra, and an edgeedge with one AsO4 tetrahedra. The corner-sharing octahedra tilt angles range from 59–88°. There are four shorter (2.47 Å) and two longer (2.57 Å) Na–O bond lengths. In the third Na1+ site, Na1+ is bonded to six O2- atoms to form distorted NaO6 octahedra that share corners with six NaO6 octahedra, edges with two equivalent CoO6 octahedra, and an edgeedge with one AsO4 tetrahedra. The corner-sharing octahedra tilt angles range from 60–88°. There are a spread of Na–O bond distances ranging from 2.47–2.55 Å. In the fourth Na1+ site, Na1+ is bonded to six O2- atoms to form distorted NaO6 octahedra that share corners with six NaO6 octahedra, edges with two equivalent CoO6 octahedra, and an edgeedge with one AsO4 tetrahedra. The corner-sharing octahedra tilt angles range from 55–88°. There are a spread of Na–O bond distances ranging from 2.42–2.55 Å. In the fifth Na1+ site, Na1+ is bonded to six O2- atoms to form distorted NaO6 octahedra that share corners with six NaO6 octahedra, edges with two equivalent CoO6 octahedra, and an edgeedge with one AsO4 tetrahedra. The corner-sharing octahedra tilt angles range from 55–88°. There are a spread of Na–O bond distances ranging from 2.42–2.54 Å. Co3+ is bonded to six O2- atoms to form CoO6 octahedra that share edges with five NaO6 octahedra. There are a spread of Co–O bond distances ranging from 2.02–2.10 Å. There are two inequivalent C4+ sites. In the first C4+ site, C4+ is bonded in a trigonal planar geometry to three O2- atoms. There is one shorter (1.29 Å) and two longer (1.30 Å) C–O bond length. In the second C4+ site, C4+ is bonded in a trigonal planar geometry to three O2- atoms. There are a spread of C–O bond distances ranging from 1.28–1.31 Å. There are two inequivalent As5+ sites. In the first As5+ site, As5+ is bonded to four equivalent O2- atoms to form AsO4 tetrahedra that share edges with four NaO6 octahedra. All As–O bond lengths are 1.72 Å. In the second As5+ site, As5+ is bonded to four equivalent O2- atoms to form AsO4 tetrahedra that share edges with six NaO6 octahedra. All As–O bond lengths are 1.72 Å. There are eight inequivalent O2- sites. In the first O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to two Na1+, one Co3+, and one C4+ atom. In the second O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to two Na1+, one Co3+, and one C4+ atom. In the third O2- site, O2- is bonded in a 3-coordinate geometry to one Na1+, one Co3+, and one C4+ atom. In the fourth O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to two Na1+, one Co3+, and one C4+ atom. In the fifth O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to two Na1+, one Co3+, and one C4+ atom. In the sixth O2- site, O2- is bonded in a 3-coordinate geometry to two Na1+ and one As5+ atom. In the seventh O2- site, O2- is bonded in a 3-coordinate geometry to one Na1+, one Co3+, and one C4+ atom. In the eighth O2- site, O2- is bonded to three Na1+ and one As5+ atom to form distorted edge-sharing ONa3As trigonal pyramids.

Na₅Co₂As(CO₄)₄结晶于正交晶系F222空间群。该结构为三维骨架结构。存在5个不等价的Na¹⁺位点。在第一个Na¹⁺位点中，Na¹⁺与6个O²⁻配位形成畸变的NaO₆八面体，该八面体与8个NaO₆八面体共角、与2个等价的CoO₆八面体共边，且与1个AsO₄四面体共边。共角八面体的倾斜角范围为59°~88°。Na–O键的键长分布区间为2.45~2.54 Å。
在第二个Na¹⁺位点中，Na¹⁺与6个O²⁻配位形成畸变的NaO₆八面体，该八面体与6个NaO₆八面体共角、与2个等价的CoO₆八面体共边，且与1个AsO₄四面体共边。共角八面体的倾斜角范围为59°~88°。该位点的Na–O键存在4条较短键长（2.47 Å）与2条较长键长（2.57 Å）。
在第三个Na¹⁺位点中，Na¹⁺与6个O²⁻配位形成畸变的NaO₆八面体，该八面体与6个NaO₆八面体共角、与2个等价的CoO₆八面体共边，且与1个AsO₄四面体共边。共角八面体的倾斜角范围为60°~88°。Na–O键的键长分布区间为2.47~2.55 Å。
在第四个Na¹⁺位点中，Na¹⁺与6个O²⁻配位形成畸变的NaO₆八面体，该八面体与6个NaO₆八面体共角、与2个等价的CoO₆八面体共边，且与1个AsO₄四面体共边。共角八面体的倾斜角范围为55°~88°。Na–O键的键长分布区间为2.42~2.55 Å。
在第五个Na¹⁺位点中，Na¹⁺与6个O²⁻配位形成畸变的NaO₆八面体，该八面体与6个NaO₆八面体共角、与2个等价的CoO₆八面体共边，且与1个AsO₄四面体共边。共角八面体的倾斜角范围为55°~88°。Na–O键的键长分布区间为2.42~2.54 Å。
Co³+与6个O²⁻配位形成CoO₆八面体，该八面体与5个NaO₆八面体共边。Co–O键的键长分布区间为2.02~2.10 Å。
存在2个不等价的C⁴+位点。在第一个C⁴+位点中，C⁴+采取平面三角形配位构型与3个O²⁻配位。该位点的C–O键存在1条较短键长（1.29 Å）与2条较长键长（1.30 Å）。在第二个C⁴+位点中，C⁴+采取平面三角形配位构型与3个O²⁻配位。C–O键的键长分布区间为1.28~1.31 Å。
存在2个不等价的As⁵+位点。在第一个As⁵+位点中，As⁵+与4个等价的O²⁻配位形成AsO₄四面体，该四面体与4个NaO₆八面体共边。所有As–O键的键长均为1.72 Å。在第二个As⁵+位点中，As⁵+与4个等价的O²⁻配位形成AsO₄四面体，该四面体与6个NaO₆八面体共边。所有As–O键的键长均为1.72 Å。
存在8个不等价的O²⁻位点。在第一个O²⁻位点中，O²⁻采取畸变的矩形跷跷板状配位构型，与2个Na¹⁺、1个Co³+以及1个C⁴+配位。在第二个O²⁻位点中，O²⁻采取畸变的矩形跷跷板状配位构型，与2个Na¹⁺、1个Co³+以及1个C⁴+配位。在第三个O²⁻位点中，O²⁻采取三配位构型，与1个Na¹⁺、1个Co³+以及1个C⁴+配位。在第四个O²⁻位点中，O²⁻采取畸变的矩形跷跷板状配位构型，与2个Na¹⁺、1个Co³+以及1个C⁴+配位。在第五个O²⁻位点中，O²⁻采取畸变的矩形跷跷板状配位构型，与2个Na¹⁺、1个Co³+以及1个C⁴+配位。在第六个O²⁻位点中，O²⁻采取三配位构型，与2个Na¹⁺以及1个As⁵+配位。在第七个O²⁻位点中，O²⁻采取三配位构型，与1个Na¹⁺、1个Co³+以及1个C⁴+配位。在第八个O²⁻位点中，O²⁻与3个Na¹⁺以及1个As⁵+配位，形成畸变的边共享ONa₃As三角锥结构。