DOE OSTI2020
Ba6Mn4Si12O34Cl3 crystallizes in the monoclinic Pm space group. The structure is three-dimensional. there are six inequivalent Ba2+ sites. In the first Ba2+ site, Ba2+ is bonded in a 9-coordinate geometry to seven O2- and two Cl1- atoms. There are a spread of Ba–O bond distances ranging from 2.86–3.40 Å. There are one shorter (2.98 Å) and one longer (3.31 Å) Ba–Cl bond lengths. In the second Ba2+ site, Ba2+ is bonded in a 2-coordinate geometry to seven O2- and two Cl1- atoms. There are a spread of Ba–O bond distances ranging from 2.71–3.29 Å. There are one shorter (3.07 Å) and one longer (3.69 Å) Ba–Cl bond lengths. In the third Ba2+ site, Ba2+ is bonded in a 12-coordinate geometry to ten O2- and two equivalent Cl1- atoms. There are a spread of Ba–O bond distances ranging from 2.65–3.39 Å. Both Ba–Cl bond lengths are 3.60 Å. In the fourth Ba2+ site, Ba2+ is bonded in a 12-coordinate geometry to ten O2- and two equivalent Cl1- atoms. There are a spread of Ba–O bond distances ranging from 2.64–3.46 Å. Both Ba–Cl bond lengths are 3.50 Å. In the fifth Ba2+ site, Ba2+ is bonded in a 8-coordinate geometry to seven O2- and one Cl1- atom. There are a spread of Ba–O bond distances ranging from 2.68–3.23 Å. The Ba–Cl bond length is 3.02 Å. In the sixth Ba2+ site, Ba2+ is bonded in a 8-coordinate geometry to six O2- and two Cl1- atoms. There are a spread of Ba–O bond distances ranging from 2.80–3.20 Å. There are one shorter (2.98 Å) and one longer (3.22 Å) Ba–Cl bond lengths. There are four inequivalent Mn+2.75+ sites. In the first Mn+2.75+ site, Mn+2.75+ is bonded to five O2- atoms to form MnO5 square pyramids that share corners with five SiO4 tetrahedra. There are a spread of Mn–O bond distances ranging from 2.00–2.13 Å. In the second Mn+2.75+ site, Mn+2.75+ is bonded to five O2- atoms to form MnO5 square pyramids that share corners with five SiO4 tetrahedra. There are a spread of Mn–O bond distances ranging from 1.98–2.13 Å. In the third Mn+2.75+ site, Mn+2.75+ is bonded to six O2- atoms to form distorted MnO6 octahedra that share corners with seven SiO4 tetrahedra. There are a spread of Mn–O bond distances ranging from 1.96–2.62 Å. In the fourth Mn+2.75+ site, Mn+2.75+ is bonded to six O2- atoms to form distorted MnO6 octahedra that share corners with seven SiO4 tetrahedra. There are a spread of Mn–O bond distances ranging from 1.95–2.64 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 MnO6 octahedra, a cornercorner with one MnO5 square pyramid, and corners with two SiO4 tetrahedra. The corner-sharing octahedral tilt angles are 49°. There are a spread of Si–O bond distances ranging from 1.62–1.65 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, a cornercorner with one MnO5 square pyramid, and corners with two SiO4 tetrahedra. The corner-sharing octahedral tilt angles are 48°. There are a spread of Si–O bond distances ranging from 1.62–1.66 Å. In the third 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 MnO5 square pyramid, and corners with two SiO4 tetrahedra. The corner-sharing octahedral tilt angles are 39°. There are a spread of Si–O bond distances ranging from 1.62–1.66 Å. In the fourth 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 MnO5 square pyramid, and corners with two SiO4 tetrahedra. The corner-sharing octahedral tilt angles are 40°. There are a spread of Si–O bond distances ranging from 1.62–1.68 Å. In the fifth 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 MnO5 square pyramid, and corners with three SiO4 tetrahedra. The corner-sharing octahedral tilt angles are 65°. There are a spread of Si–O bond distances ranging from 1.60–1.67 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 MnO5 square pyramid, and corners with three SiO4 tetrahedra. The corner-sharing octahedral tilt angles are 66°. There are a spread of Si–O bond distances ranging from 1.59–1.67 Å. In the seventh Si4+ site, Si4+ is bonded to four O2- atoms to form SiO4 tetrahedra that share corners with two MnO6 octahedra and corners with three SiO4 tetrahedra. The corner-sharing octahedra tilt angles range from 60–74°. There are a spread of Si–O bond distances ranging from 1.59–1.66 Å. In the eighth Si4+ site, Si4+ is bonded to four O2- atoms to form SiO4 tetrahedra that share corners with two MnO6 octahedra and corners with three SiO4 tetrahedra. The corner-sharing octahedra tilt angles range from 60–73°. There are a spread of Si–O bond distances ranging from 1.58–1.66 Å. There are twenty-two inequivalent O2- sites. In the first O2- site, O2- is bonded in a distorted bent 120 degrees geometry to two Ba2+ and two Si4+ atoms. In the second O2- site, O2- is bonded in a distorted bent 120 degrees geometry to two Ba2+ and two Si4+ atoms. In the third O2- site, O2- is bonded in a distorted bent 150 degrees geometry to one Ba2+ and two Si4+ atoms. In the fourth O2- site, O2- is bonded in a distorted bent 150 degrees geometry to one Ba2+ and two Si4+ atoms. In the fifth O2- site, O2- is bonded in a distorted bent 120 degrees geometry to two Ba2+, one Mn+2.75+, and one Si4+ atom. In the sixth O2- site, O2- is bonded in a 2-coordinate geometry to two Ba2+, one Mn+2.75+, and one Si4+ atom. In the seventh O2- site, O2- is bonded in a 2-coordinate geometry to one Ba2+, one Mn+2.75+, and one Si4+ atom. In the eighth O2- site, O2- is bonded in a 2-coordinate geometry to one Ba2+, one Mn+2.75+, and one Si4+ atom. In the ninth O2- site, O2- is bonded in a 2-coordinate geometry to one Ba2+, one Mn+2.75+, and one Si4+ atom. In the tenth O2- site, O2- is bonded in a 2-coordinate geometry to one Ba2+, one Mn+2.75+, and one Si4+ atom. In the eleventh O2- site, O2- is bonded in a 2-coordinate geometry to one Mn+2.75+ and two Si4+ atoms. In the twelfth O2- site, O2- is bonded in a 2-coordinate geometry to one Mn+2.75+ and two Si4+ atoms. In the thirteenth O2- site, O2- is bonded in a 3-coordinate geometry to one Ba2+, one Mn+2.75+, and one Si4+ atom. In the fourteenth O2- site, O2- is bonded in a 3-coordinate geometry to one Ba2+, one Mn+2.75+, and one Si4+ atom. In the fifteenth O2- site, O2- is bonded in a 2-coordinate geometry to two Ba2+, one Mn+2.75+, and one Si4+ atom. In the sixteenth O2- site, O2- is bonded in a 2-coordinate geometry to two Ba2+, one Mn+2.75+, and one Si4+ atom. In the seventeenth O2- site, O2- is bonded in a linear geometry to one Ba2+ and two equivalent Si4+ atoms. In the eighteenth O2- site, O2- is bonded in a linear geometry to two equivalent Si4+ atoms. In the nineteenth O2- site, O2- is bonded in a linear geometry to one Ba2+ and two equivalent Si4+ atoms. In the twentieth O2- site, O2- is bonded in a distorted bent 150 degrees geometry to one Ba2+ and two equivalent Si4+ atoms. In the twenty-first O2- site, O2- is bonded in a distorted bent 120 degrees geometry to two Ba2+, one Mn+2.75+, and one Si4+ atom. In the twenty-second O2- site, O2- is bonded in a 2-coordinate geometry to two Ba2+, one Mn+2.75+, and one Si4+ atom. There are three inequivalent Cl1- sites. In the first Cl1- site, Cl1- is bonded in a 2-coordinate geometry to four Ba2+ atoms. In the second Cl1- site, Cl1- is bonded in a bent 120 degrees geometry to two Ba2+ atoms. In the third Cl1- site, Cl1- is bonded in a 4-coordinate geometry to five Ba2+ atoms.