DOE OSTI2020
Na2Ca2Zr2MnFeSi4O17F is Esseneite-derived structured and crystallizes in the triclinic P1 space group. The structure is three-dimensional. there are four inequivalent Na1+ sites. In the first Na1+ site, Na1+ is bonded in a 6-coordinate geometry to five O2- and one F1- atom. There are a spread of Na–O bond distances ranging from 2.35–2.63 Å. The Na–F bond length is 2.40 Å. In the second Na1+ site, Na1+ is bonded in a 8-coordinate geometry to seven O2- and one F1- atom. There are a spread of Na–O bond distances ranging from 2.43–3.07 Å. The Na–F bond length is 2.28 Å. In the third Na1+ site, Na1+ is bonded in a 8-coordinate geometry to seven O2- and one F1- atom. There are a spread of Na–O bond distances ranging from 2.46–3.02 Å. The Na–F bond length is 2.27 Å. In the fourth Na1+ site, Na1+ is bonded in a 6-coordinate geometry to five O2- and one F1- atom. There are a spread of Na–O bond distances ranging from 2.34–2.61 Å. The Na–F bond length is 2.40 Å. There are four inequivalent Ca2+ sites. In the first Ca2+ site, Ca2+ is bonded in a 8-coordinate geometry to eight O2- atoms. There are a spread of Ca–O bond distances ranging from 2.21–2.99 Å. In the second Ca2+ site, Ca2+ is bonded in a 8-coordinate geometry to seven O2- and one F1- atom. There are a spread of Ca–O bond distances ranging from 2.33–2.91 Å. The Ca–F bond length is 2.23 Å. In the third Ca2+ site, Ca2+ is bonded in a 8-coordinate geometry to seven O2- and one F1- atom. There are a spread of Ca–O bond distances ranging from 2.35–2.88 Å. The Ca–F bond length is 2.24 Å. In the fourth Ca2+ site, Ca2+ is bonded in a 8-coordinate geometry to eight O2- atoms. There are a spread of Ca–O bond distances ranging from 2.22–2.94 Å. There are four inequivalent Zr4+ sites. In the first Zr4+ site, Zr4+ is bonded to six O2- atoms to form ZrO6 octahedra that share a cornercorner with one MnO5F octahedra, a cornercorner with one FeO6 octahedra, corners with five SiO4 tetrahedra, and an edgeedge with one FeO5F octahedra. The corner-sharing octahedra tilt angles range from 54–59°. There are a spread of Zr–O bond distances ranging from 2.01–2.32 Å. In the second Zr4+ site, Zr4+ is bonded to six O2- atoms to form ZrO6 octahedra that share a cornercorner with one MnO6 octahedra, a cornercorner with one FeO5F octahedra, corners with five SiO4 tetrahedra, and an edgeedge with one FeO6 octahedra. The corner-sharing octahedra tilt angles range from 53–54°. There are a spread of Zr–O bond distances ranging from 1.97–2.32 Å. In the third Zr4+ site, Zr4+ is bonded to six O2- atoms to form ZrO6 octahedra that share a cornercorner with one MnO5F octahedra, a cornercorner with one FeO6 octahedra, corners with five SiO4 tetrahedra, and an edgeedge with one MnO6 octahedra. The corner-sharing octahedra tilt angles range from 47–57°. There are a spread of Zr–O bond distances ranging from 1.99–2.37 Å. In the fourth Zr4+ site, Zr4+ is bonded to six O2- atoms to form ZrO6 octahedra that share a cornercorner with one MnO6 octahedra, a cornercorner with one FeO5F octahedra, corners with five SiO4 tetrahedra, and an edgeedge with one MnO5F octahedra. The corner-sharing octahedra tilt angles range from 54–59°. There are a spread of Zr–O bond distances ranging from 2.00–2.32 Å. There are two inequivalent Mn2+ sites. In the first Mn2+ site, Mn2+ is bonded to six O2- atoms to form distorted MnO6 octahedra that share corners with two ZrO6 octahedra, corners with three SiO4 tetrahedra, an edgeedge with one ZrO6 octahedra, and an edgeedge with one FeO5F octahedra. The corner-sharing octahedral tilt angles are 54°. There are a spread of Mn–O bond distances ranging from 1.84–2.45 Å. In the second Mn2+ site, Mn2+ is bonded to five O2- and one F1- atom to form MnO5F octahedra that share corners with two ZrO6 octahedra, corners with three SiO4 tetrahedra, an edgeedge with one ZrO6 octahedra, and an edgeedge with one FeO6 octahedra. The corner-sharing octahedra tilt angles range from 57–59°. There are a spread of Mn–O bond distances ranging from 2.18–2.45 Å. The Mn–F bond length is 2.24 Å. There are two inequivalent Fe3+ sites. In the first Fe3+ site, Fe3+ is bonded to five O2- and one F1- atom to form FeO5F octahedra that share corners with two ZrO6 octahedra, corners with three SiO4 tetrahedra, an edgeedge with one ZrO6 octahedra, and an edgeedge with one MnO6 octahedra. The corner-sharing octahedra tilt angles range from 53–59°. There are a spread of Fe–O bond distances ranging from 2.14–2.43 Å. The Fe–F bond length is 2.25 Å. In the second Fe3+ site, Fe3+ is bonded to six O2- atoms to form distorted FeO6 octahedra that share corners with two ZrO6 octahedra, corners with three SiO4 tetrahedra, an edgeedge with one ZrO6 octahedra, and an edgeedge with one MnO5F octahedra. The corner-sharing octahedra tilt angles range from 47–54°. There are a spread of Fe–O bond distances ranging from 1.85–2.42 Å. There are eight inequivalent Si4+ sites. In the first Si4+ site, Si4+ is bonded to four O2- atoms to form SiO4 tetrahedra that share a cornercorner with one MnO5F octahedra, corners with three ZrO6 octahedra, and a cornercorner with one SiO4 tetrahedra. The corner-sharing octahedra tilt angles range from 38–56°. There are a spread of Si–O bond distances ranging from 1.63–1.65 Å. In the second Si4+ site, Si4+ is bonded to four O2- atoms to form SiO4 tetrahedra that share a cornercorner with one MnO6 octahedra, corners with three ZrO6 octahedra, and a cornercorner with one SiO4 tetrahedra. The corner-sharing octahedra tilt angles range from 38–59°. There are a spread of Si–O bond distances ranging from 1.63–1.65 Å. In the third Si4+ site, Si4+ is bonded to four O2- atoms to form SiO4 tetrahedra that share a cornercorner with one FeO6 octahedra, corners with three ZrO6 octahedra, and a cornercorner with one SiO4 tetrahedra. The corner-sharing octahedra tilt angles range from 38–57°. There are a spread of Si–O bond distances ranging from 1.63–1.65 Å. In the fourth Si4+ site, Si4+ is bonded to four O2- atoms to form SiO4 tetrahedra that share a cornercorner with one FeO5F octahedra, corners with three ZrO6 octahedra, and a cornercorner with one SiO4 tetrahedra. The corner-sharing octahedra tilt angles range from 37–56°. There are a spread of Si–O bond distances ranging from 1.62–1.65 Å. In the fifth Si4+ site, Si4+ is bonded to four O2- atoms to form SiO4 tetrahedra that share a cornercorner with one MnO5F octahedra, a cornercorner with one FeO5F octahedra, corners with two ZrO6 octahedra, and a cornercorner with one SiO4 tetrahedra. The corner-sharing octahedra tilt angles range from 43–66°. There are a spread of Si–O bond distances ranging from 1.61–1.65 Å. In the sixth Si4+ site, Si4+ is bonded to four O2- atoms to form SiO4 tetrahedra that share a cornercorner with one MnO6 octahedra, a cornercorner with one FeO6 octahedra, corners with two ZrO6 octahedra, and a cornercorner with one SiO4 tetrahedra. The corner-sharing octahedra tilt angles range from 46–68°. There are a spread of Si–O bond distances ranging from 1.62–1.65 Å. In the seventh Si4+ site, Si4+ is bonded to four O2- atoms to form SiO4 tetrahedra that share a cornercorner with one MnO6 octahedra, a cornercorner with one FeO6 octahedra, corners with two ZrO6 octahedra, and a cornercorner with one SiO4 tetrahedra. The corner-sharing octahedra tilt angles range from 45–68°. There are a spread of Si–O bond distances ranging from 1.61–1.65 Å. In the eighth Si4+ site, Si4+ is bonded to four O2- atoms to form SiO4 tetrahedra that share a cornercorner with one MnO5F octahedra, a cornercorner with one FeO5F octahedra, corners with two ZrO6 octahedra, and a cornercorner with one SiO4 tetrahedra. The corner-sharing octahedra tilt angles range from 42–67°. There are a spread of Si–O bond distances ranging from 1.61–1.65 Å. There are thirty-four inequivalent O2- sites. In the first O2- site, O2- is bonded in a 4-coordinate geometry to one Na1+, one Ca2+, one Zr4+, and one Si4+ atom. In the second O2- site, O2- is bonded in a 4-coordinate geometry to one Na1+, one Ca2+, one Zr4+, and one Si4+ atom. In the third O2- site, O2- is bonded in a 4-coordinate geometry to one Na1+, one Ca2+, one Zr4+, and one Si4+ atom. In the fourth O2- site, O2- is bonded in a 4-coordinate geometry to one Na1+, one Ca2+, one Zr4+, and one Si4+ atom. In the fifth O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to one Na1+, one Zr4+, one Mn2+, and one Fe3+ atom. In the sixth O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to one Na1+, one Zr4+, one Mn2+, and one Fe3+ atom. In the seventh O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to one Na1+, one Zr4+, one Mn2+, and one Fe3+ atom. In the eighth O2- site, O2- is bonded to one Na1+, one Zr4+, one Mn2+, and one Fe3+ atom to form distorted ONaZrMnFe tetrahedra that share an edgeedge with one FNa2CaFe tetrahedra. In the ninth O2- site, O2- is bonded in a 3-coordinate geometry to one Ca2+, one Zr4+, and one Si4+ atom. In the tenth O2- site, O2- is bonded in a 3-coordinate geometry to one Na1+, one Ca2+, one Zr4+, and one Si4+ atom. In the eleventh O2- site, O2- is bonded in a 3-coordinate geometry to one Na1+, one Ca2+, one Zr4+, and one Si4+ atom. In the twelfth O2- site, O2- is bonded in a 3-coordinate geometry to one Ca2+, one Zr4+, and one Si4+ atom. In the thirteenth O2- site, O2- is bonded in a distorted linear geometry to two Ca2+ and two Si4+ atoms. In the fourteenth O2- site, O2- is bonded in a linear geometry to one Na1+, two Ca2+, and two Si4+ atoms. In the fifteenth O2- site, O2- is bonded in a linear geometry to one Na1+, two Ca2+, and two Si4+ atoms. In the sixteenth O2- site, O2- is bonded in a distorted linear geometry to two Ca2+ and two Si4+ atoms. In the seventeenth O2- site, O2- is bonded in a 1-coordinate geometry to one Na1+, one Ca2+, one Fe3+, and one Si4+ atom. In the eighteenth O2- site, O2- is bonded in a 4-coordinate geometry to one Na1+, one Ca2+, one Fe3+, and one Si4+ atom. In the nineteenth O2- site, O2- is bonded in a 4-coordinate geometry to one Na1+, one Ca2+, one Mn2+, and one Si4+ atom. In the twentieth O2- site, O2- is bonded in a 4-coordinate geometry to one Na1+, one Ca2+, one Mn2+, and one Si4+ atom. In the twenty-first O2- site, O2- is bonded in a 3-coordinate geometry to one Ca2+, one Zr4+, and one Si4+ atom. In the twenty-second O2- site, O2- is bonded in a 3-coordinate geometry to one Ca2+, one Zr4+, and one Si4+ atom. In the twenty-third O2- site, O2- is bonded in a 3-coordinate geometry to one Ca2+, one Zr4+, and one Si4+ atom. In the twenty-fourth O2- site, O2- is bonded in a 3-coordinate geometry to one Ca2+, one Zr4+, and one Si4+ atom. In the twenty-fifth O2- site, O2- is bonded in a 4-coordinate geometry to one Ca2+, one Zr4+, one Fe3+, and one Si4+ atom. In the twenty-sixth O2- site, O2- is bonded in a 4-coordinate geometry to one Ca2+, one Zr4+, one Fe3+, and one Si4+ atom. In the twenty-seventh O2- site, O2- is bonded in a 4-coordinate geometry to one Ca2+, one Zr4+, one Mn2+, and one Si4+ atom. In the twenty-eighth O2- site, O2- is bonded in a 4-coordinate geometry to one Ca2+, one Zr4+, one Mn2+, and one Si4+ atom. In the twenty-ninth O2- site, O2- is bonded in a 4-coordinate geometry to one Na1+, one Zr4+, one Fe3+, and one Si4+ atom. In the thirtieth O2- site, O2- is bonded in a 4-coordinate geometry to one Na1+, one Zr4+, one Fe3+, and one Si4+ atom. In the thirty-first O2- site, O2- is bonded in a 4-coordinate geometry to one Na1+, one Zr4+, one Mn2+, and one Si4+ atom. In the thirty-second O2- site, O2- is bonded in a 4-coordinate geometry to one Na1+, one Zr4+, one Mn2+, and one Si4+ atom. In the thirty-third O2- site, O2- is bonded in a distorted trigonal pyramidal geometry to two Na1+, one Ca2+, and one Fe3+ atom. In the thirty-fourth O2- site, O2- is bonded in a 4-coordinate geometry to two Na1+, one Ca2+, and one Mn2+