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Li9V12Cr7O48 crystallizes in the triclinic P1 space group. The structure is three-dimensional. there are nine inequivalent Li1+ sites. In the first Li1+ site, Li1+ is bonded to six O2- atoms to form distorted LiO6 octahedra that share a cornercorner with one CrO6 octahedra, a cornercorner with one LiO6 pentagonal pyramid, corners with six VO4 tetrahedra, and edges with two equivalent CrO6 octahedra. The corner-sharing octahedral tilt angles are 59°. There are a spread of Li–O bond distances ranging from 1.99–2.29 Å. In the second Li1+ site, Li1+ is bonded to six O2- atoms to form distorted LiO6 pentagonal pyramids that share a cornercorner with one LiO6 octahedra, a cornercorner with one CrO6 octahedra, corners with six VO4 tetrahedra, and edges with two equivalent LiO6 pentagonal pyramids. The corner-sharing octahedra tilt angles range from 61–70°. There are a spread of Li–O bond distances ranging from 2.05–2.26 Å. In the third Li1+ site, Li1+ is bonded to six O2- atoms to form distorted LiO6 pentagonal pyramids that share a cornercorner with one LiO6 octahedra, a cornercorner with one CrO6 octahedra, corners with six VO4 tetrahedra, and edges with two equivalent LiO6 pentagonal pyramids. The corner-sharing octahedra tilt angles range from 58–69°. There are a spread of Li–O bond distances ranging from 2.08–2.22 Å. In the fourth Li1+ site, Li1+ is bonded to six O2- atoms to form distorted LiO6 octahedra that share a cornercorner with one CrO6 octahedra, a cornercorner with one LiO6 pentagonal pyramid, corners with six VO4 tetrahedra, and edges with two equivalent CrO6 octahedra. The corner-sharing octahedral tilt angles are 57°. There are a spread of Li–O bond distances ranging from 2.00–2.31 Å. In the fifth Li1+ site, Li1+ is bonded to six O2- atoms to form LiO6 octahedra that share corners with six VO4 tetrahedra and faces with two equivalent CrO6 octahedra. There are a spread of Li–O bond distances ranging from 2.00–2.15 Å. In the sixth Li1+ site, Li1+ is bonded to six O2- atoms to form LiO6 octahedra that share corners with six VO4 tetrahedra and faces with two equivalent CrO6 octahedra. There are a spread of Li–O bond distances ranging from 2.02–2.15 Å. In the seventh Li1+ site, Li1+ is bonded to six O2- atoms to form distorted LiO6 octahedra that share a cornercorner with one CrO6 octahedra, a cornercorner with one LiO6 pentagonal pyramid, corners with six VO4 tetrahedra, and edges with two equivalent CrO6 octahedra. The corner-sharing octahedral tilt angles are 58°. There are a spread of Li–O bond distances ranging from 2.01–2.31 Å. In the eighth Li1+ site, Li1+ is bonded to six O2- atoms to form distorted LiO6 pentagonal pyramids that share corners with two CrO6 octahedra, corners with six VO4 tetrahedra, and edges with two equivalent LiO6 pentagonal pyramids. The corner-sharing octahedra tilt angles range from 58–61°. There are a spread of Li–O bond distances ranging from 2.12–2.23 Å. In the ninth Li1+ site, Li1+ is bonded to six O2- atoms to form distorted LiO6 pentagonal pyramids that share a cornercorner with one LiO6 octahedra, a cornercorner with one CrO6 octahedra, corners with six VO4 tetrahedra, and edges with two equivalent LiO6 pentagonal pyramids. The corner-sharing octahedra tilt angles range from 60–71°. There are a spread of Li–O bond distances ranging from 2.07–2.26 Å. There are twelve inequivalent V5+ sites. In the first V5+ site, V5+ is bonded to four O2- atoms to form VO4 tetrahedra that share corners with two LiO6 octahedra and corners with six CrO6 octahedra. The corner-sharing octahedra tilt angles range from 21–66°. There are a spread of V–O bond distances ranging from 1.71–1.83 Å. In the second V5+ site, V5+ is bonded to four O2- atoms to form VO4 tetrahedra that share corners with two CrO6 octahedra, corners with three LiO6 octahedra, and corners with three LiO6 pentagonal pyramids. The corner-sharing octahedra tilt angles range from 24–58°. There are a spread of V–O bond distances ranging from 1.68–1.83 Å. In the third V5+ site, V5+ is bonded to four O2- atoms to form VO4 tetrahedra that share corners with two LiO6 octahedra, corners with three CrO6 octahedra, and corners with three LiO6 pentagonal pyramids. The corner-sharing octahedra tilt angles range from 24–62°. There are a spread of V–O bond distances ranging from 1.66–1.82 Å. In the fourth V5+ site, V5+ is bonded to four O2- atoms to form VO4 tetrahedra that share corners with two LiO6 octahedra, corners with three CrO6 octahedra, and corners with three LiO6 pentagonal pyramids. The corner-sharing octahedra tilt angles range from 35–61°. There are a spread of V–O bond distances ranging from 1.64–1.86 Å. In the fifth V5+ site, V5+ is bonded to four O2- atoms to form VO4 tetrahedra that share a cornercorner with one LiO6 octahedra, corners with four CrO6 octahedra, and corners with three LiO6 pentagonal pyramids. The corner-sharing octahedra tilt angles range from 34–60°. There are a spread of V–O bond distances ranging from 1.64–1.83 Å. In the sixth V5+ site, V5+ is bonded to four O2- atoms to form VO4 tetrahedra that share corners with four LiO6 octahedra and corners with four CrO6 octahedra. The corner-sharing octahedra tilt angles range from 30–66°. There are a spread of V–O bond distances ranging from 1.72–1.78 Å. In the seventh V5+ site, V5+ is bonded to four O2- atoms to form VO4 tetrahedra that share corners with four LiO6 octahedra and corners with four CrO6 octahedra. The corner-sharing octahedra tilt angles range from 31–66°. There are a spread of V–O bond distances ranging from 1.72–1.78 Å. In the eighth V5+ site, V5+ is bonded to four O2- atoms to form VO4 tetrahedra that share a cornercorner with one LiO6 octahedra, corners with four CrO6 octahedra, and corners with three LiO6 pentagonal pyramids. The corner-sharing octahedra tilt angles range from 34–60°. There are a spread of V–O bond distances ranging from 1.65–1.83 Å. In the ninth V5+ site, V5+ is bonded to four O2- atoms to form VO4 tetrahedra that share corners with two CrO6 octahedra, corners with three LiO6 octahedra, and corners with three LiO6 pentagonal pyramids. The corner-sharing octahedra tilt angles range from 35–57°. There are a spread of V–O bond distances ranging from 1.68–1.81 Å. In the tenth V5+ site, V5+ is bonded to four O2- atoms to form VO4 tetrahedra that share corners with two CrO6 octahedra, corners with three LiO6 octahedra, and corners with three LiO6 pentagonal pyramids. The corner-sharing octahedra tilt angles range from 24–57°. There are a spread of V–O bond distances ranging from 1.68–1.82 Å. In the eleventh V5+ site, V5+ is bonded to four O2- atoms to form VO4 tetrahedra that share corners with two LiO6 octahedra, corners with three CrO6 octahedra, and corners with three LiO6 pentagonal pyramids. The corner-sharing octahedra tilt angles range from 22–62°. There are a spread of V–O bond distances ranging from 1.66–1.82 Å. In the twelfth V5+ site, V5+ is bonded to four O2- atoms to form VO4 tetrahedra that share corners with three LiO6 octahedra and corners with five CrO6 octahedra. The corner-sharing octahedra tilt angles range from 20–65°. There are a spread of V–O bond distances ranging from 1.71–1.81 Å. There are seven inequivalent Cr+3.86+ sites. In the first Cr+3.86+ site, Cr+3.86+ is bonded to six O2- atoms to form CrO6 octahedra that share corners with six VO4 tetrahedra and faces with two equivalent LiO6 octahedra. There are a spread of Cr–O bond distances ranging from 1.85–2.04 Å. In the second Cr+3.86+ site, Cr+3.86+ is bonded to six O2- atoms to form CrO6 octahedra that share a cornercorner with one LiO6 octahedra, a cornercorner with one LiO6 pentagonal pyramid, corners with six VO4 tetrahedra, and edges with two equivalent CrO6 octahedra. The corner-sharing octahedral tilt angles are 59°. There are a spread of Cr–O bond distances ranging from 1.89–2.03 Å. In the third Cr+3.86+ site, Cr+3.86+ is bonded to six O2- atoms to form CrO6 octahedra that share a cornercorner with one LiO6 octahedra, a cornercorner with one LiO6 pentagonal pyramid, corners with six VO4 tetrahedra, and edges with two equivalent LiO6 octahedra. The corner-sharing octahedral tilt angles are 57°. There are a spread of Cr–O bond distances ranging from 1.90–1.98 Å. In the fourth Cr+3.86+ site, Cr+3.86+ is bonded to six O2- atoms to form CrO6 octahedra that share a cornercorner with one LiO6 octahedra, a cornercorner with one LiO6 pentagonal pyramid, corners with six VO4 tetrahedra, and edges with two equivalent LiO6 octahedra. The corner-sharing octahedral tilt angles are 58°. There are a spread of Cr–O bond distances ranging from 1.89–1.99 Å. In the fifth Cr+3.86+ site, Cr+3.86+ is bonded to six O2- atoms to form CrO6 octahedra that share a cornercorner with one CrO6 octahedra, a cornercorner with one LiO6 pentagonal pyramid, corners with six VO4 tetrahedra, and edges with two equivalent LiO6 octahedra. The corner-sharing octahedral tilt angles are 54°. There are a spread of Cr–O bond distances ranging from 1.86–2.08 Å. In the sixth Cr+3.86+ site, Cr+3.86+ is bonded to six O2- atoms to form CrO6 octahedra that share a cornercorner with one CrO6 octahedra, a cornercorner with one LiO6 pentagonal pyramid, corners with six VO4 tetrahedra, and edges with two equivalent CrO6 octahedra. The corner-sharing octahedral tilt angles are 54°. There are a spread of Cr–O bond distances ranging from 1.96–2.06 Å. In the seventh Cr+3.86+ site, Cr+3.86+ is bonded to six O2- atoms to form CrO6 octahedra that share corners with six VO4 tetrahedra and faces with two equivalent LiO6 octahedra. There are a spread of Cr–O bond distances ranging from 1.85–2.08 Å. There are forty-eight inequivalent O2- sites. In the first O2- site, O2- is bonded in a trigonal planar geometry to one Li1+, one V5+, and one Cr+3.86+ atom. In the second O2- site, O2- is bonded in a trigonal planar geometry to two Li1+ and one V5+ atom. In the third O2- site, O2- is bonded in a trigonal planar geometry to one Li1+, one V5+, and one Cr+3.86+ atom. In the fourth O2- site, O2- is bonded in a 3-coordinate geometry to two Li1+ and one V5+ atom. In the fifth O2- site, O2- is bonded in a 3-coordinate geometry to two Li1+ and one V5+ atom. In the sixth O2- site, O2- is bonded in a distorted trigonal planar geometry to one Li1+, one V5+, and one Cr+3.86+ atom. In the seventh O2- site, O2- is bonded in a 3-coordinate geometry to one Li1+, one V5+, and one Cr+3.86+ atom. In the eighth O2- site, O2- is bonded in a distorted trigonal planar geometry to one V5+ and two Cr+3.86+ atoms. In the ninth O2- site, O2- is bonded in a distorted trigonal planar geometry to one Li1+, one V5+, and one Cr+3.86+ atom. In the tenth O2- site, O2- is bonded in a 3-coordinate geometry to one Li1+, one V5+, and one Cr+3.86+ atom. In the eleventh O2- site, O2- is bonded in a 3-coordinate geometry to one Li1+, one V5+, and one Cr+3.86+ atom. In the twelfth O2- site, O2- is bonded in a distorted trigonal planar geometry to one Li1+, one V5+, and one Cr+3.86+ atom. In the thirteenth O2- site, O2- is bonded in a 3-coordinate geometry to one Li1+, one V5+, and one Cr+3.86+ atom. In the fourteenth O2- site, O2- is bonded in a 3-coordinate geometry to one Li1+, one V5+, and one Cr+3.86+ atom. In the fifteenth O2- site, O2- is bonded in a 3-coordinate geometry to one Li1+, one V5+, and one Cr+3.86+ atom. In the sixteenth O2- site, O2- is bonded in a distorted trigonal planar geometry to one Li1+, one V5+, and one Cr+3.86+ atom. In the seventeenth O2- site, O2- is bonded in a distorted trigonal planar geometry to one Li1+, one V5+, and one Cr+3.86+ atom. In the eighteenth O2- site, O2- is bonded in a distorted trigonal planar geometry to one V5+ and two Cr+3.86+ atoms. In the nineteenth O2- site, O2- is bonded in a 3-coordinate geometry to one Li1+, one V5+, and one Cr+3.86+ atom. In the twentieth O2- site, O2- is bonded in a 3-coordinate geometry to two Li1+ and one V5

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