DOE OSTI2020
Li17Fe4(CO3)16 crystallizes in the triclinic P1 space group. The structure is three-dimensional. there are seventeen inequivalent Li sites. In the first Li site, Li is bonded to five O atoms to form distorted LiO5 trigonal bipyramids that share a cornercorner with one FeO6 octahedra, a cornercorner with one LiO5 square pyramid, an edgeedge with one LiO4 tetrahedra, and an edgeedge with one LiO5 trigonal bipyramid. The corner-sharing octahedral tilt angles are 62°. There are a spread of Li–O bond distances ranging from 2.06–2.29 Å. In the second Li site, Li is bonded to five O atoms to form LiO5 square pyramids that share corners with two FeO6 octahedra, a cornercorner with one LiO5 trigonal bipyramid, and an edgeedge with one LiO4 trigonal pyramid. The corner-sharing octahedra tilt angles range from 73–79°. There are a spread of Li–O bond distances ranging from 2.00–2.19 Å. In the third Li site, Li is bonded to five O atoms to form LiO5 square pyramids that share corners with two FeO6 octahedra and a cornercorner with one LiO4 tetrahedra. The corner-sharing octahedra tilt angles range from 74–81°. There are a spread of Li–O bond distances ranging from 2.02–2.18 Å. In the fourth Li site, Li is bonded to four O atoms to form distorted LiO4 trigonal pyramids that share corners with two LiO4 tetrahedra and an edgeedge with one LiO5 square pyramid. There are a spread of Li–O bond distances ranging from 1.93–2.07 Å. In the fifth Li site, Li is bonded in a distorted rectangular see-saw-like geometry to four O atoms. There are a spread of Li–O bond distances ranging from 2.01–2.09 Å. In the sixth Li site, Li is bonded to four O atoms to form distorted LiO4 tetrahedra that share a cornercorner with one LiO4 trigonal pyramid, an edgeedge with one FeO6 octahedra, and an edgeedge with one LiO5 trigonal bipyramid. There are a spread of Li–O bond distances ranging from 1.96–2.07 Å. In the seventh Li site, Li is bonded to four O atoms to form distorted LiO4 tetrahedra that share a cornercorner with one LiO4 trigonal pyramid and an edgeedge with one FeO6 octahedra. There are a spread of Li–O bond distances ranging from 1.96–2.05 Å. In the eighth Li site, Li is bonded to four O atoms to form distorted LiO4 tetrahedra that share corners with three FeO6 octahedra and a cornercorner with one LiO5 square pyramid. The corner-sharing octahedra tilt angles range from 17–66°. There are a spread of Li–O bond distances ranging from 1.99–2.16 Å. In the ninth Li site, Li is bonded in a 4-coordinate geometry to five O atoms. There are a spread of Li–O bond distances ranging from 1.98–2.55 Å. In the tenth Li site, Li is bonded to four O atoms to form distorted LiO4 tetrahedra that share a cornercorner with one LiO5 trigonal bipyramid and an edgeedge with one FeO6 octahedra. There are a spread of Li–O bond distances ranging from 1.96–2.05 Å. In the eleventh Li site, Li is bonded to four O atoms to form LiO4 trigonal pyramids that share a cornercorner with one LiO5 trigonal bipyramid, an edgeedge with one FeO6 octahedra, and an edgeedge with one LiO5 trigonal bipyramid. There are a spread of Li–O bond distances ranging from 1.97–2.08 Å. In the twelfth Li site, Li is bonded in a distorted see-saw-like geometry to four O atoms. There are a spread of Li–O bond distances ranging from 1.94–2.13 Å. In the thirteenth Li site, Li is bonded to five O atoms to form distorted LiO5 trigonal bipyramids that share a cornercorner with one LiO4 tetrahedra, a cornercorner with one LiO4 trigonal pyramid, and an edgeedge with one LiO5 square pyramid. There are a spread of Li–O bond distances ranging from 1.98–2.30 Å. In the fourteenth Li site, Li is bonded to five O atoms to form LiO5 square pyramids that share corners with two FeO6 octahedra. The corner-sharing octahedra tilt angles range from 75–80°. There are a spread of Li–O bond distances ranging from 2.01–2.19 Å. In the fifteenth Li site, Li is bonded to five O atoms to form LiO5 square pyramids that share corners with two FeO6 octahedra, a cornercorner with one LiO5 trigonal bipyramid, and an edgeedge with one LiO5 trigonal bipyramid. The corner-sharing octahedra tilt angles range from 73–76°. There are a spread of Li–O bond distances ranging from 2.03–2.26 Å. In the sixteenth Li site, Li is bonded in a 5-coordinate geometry to five O atoms. There are a spread of Li–O bond distances ranging from 2.05–2.43 Å. In the seventeenth Li site, Li is bonded to five O atoms to form LiO5 trigonal bipyramids that share a cornercorner with one FeO6 octahedra, a cornercorner with one LiO5 square pyramid, an edgeedge with one LiO5 trigonal bipyramid, and an edgeedge with one LiO4 trigonal pyramid. The corner-sharing octahedral tilt angles are 63°. There are a spread of Li–O bond distances ranging from 2.06–2.28 Å. There are four inequivalent Fe sites. In the first Fe site, Fe is bonded to six O atoms to form distorted FeO6 octahedra that share corners with two LiO5 square pyramids, a cornercorner with one LiO4 tetrahedra, a cornercorner with one LiO5 trigonal bipyramid, and an edgeedge with one LiO4 tetrahedra. There are a spread of Fe–O bond distances ranging from 2.05–2.10 Å. In the second Fe site, Fe is bonded to six O atoms to form distorted FeO6 octahedra that share corners with two LiO5 square pyramids, a cornercorner with one LiO4 tetrahedra, and an edgeedge with one LiO4 tetrahedra. There are a spread of Fe–O bond distances ranging from 2.00–2.16 Å. In the third Fe site, Fe is bonded to six O atoms to form distorted FeO6 octahedra that share corners with two LiO5 square pyramids and an edgeedge with one LiO4 tetrahedra. There are a spread of Fe–O bond distances ranging from 2.05–2.09 Å. In the fourth Fe site, Fe is bonded to six O atoms to form distorted FeO6 octahedra that share corners with two LiO5 square pyramids, a cornercorner with one LiO4 tetrahedra, a cornercorner with one LiO5 trigonal bipyramid, and an edgeedge with one LiO4 trigonal pyramid. There are a spread of Fe–O bond distances ranging from 2.02–2.15 Å. There are sixteen inequivalent C sites. In the first C site, C is bonded in a trigonal planar geometry to three O atoms. There is two shorter (1.28 Å) and one longer (1.32 Å) C–O bond length. In the second C site, C is bonded in a trigonal planar geometry to three O atoms. There are a spread of C–O bond distances ranging from 1.27–1.32 Å. In the third C site, C is bonded in a trigonal planar geometry to three O atoms. There is two shorter (1.27 Å) and one longer (1.34 Å) C–O bond length. In the fourth C site, C is bonded in a trigonal planar geometry to three O atoms. There are a spread of C–O bond distances ranging from 1.28–1.31 Å. In the fifth C site, C is bonded in a trigonal planar geometry to three O atoms. There are a spread of C–O bond distances ranging from 1.26–1.32 Å. In the sixth C site, C is bonded in a trigonal planar geometry to three O atoms. There are a spread of C–O bond distances ranging from 1.28–1.31 Å. In the seventh C site, C is bonded in a trigonal planar geometry to three O atoms. There are a spread of C–O bond distances ranging from 1.27–1.32 Å. In the eighth C site, C is bonded in a trigonal planar geometry to three O atoms. There are a spread of C–O bond distances ranging from 1.26–1.32 Å. In the ninth C site, C is bonded in a trigonal planar geometry to three O atoms. There are a spread of C–O bond distances ranging from 1.27–1.32 Å. In the tenth C site, C is bonded in a trigonal planar geometry to three O atoms. There are a spread of C–O bond distances ranging from 1.26–1.32 Å. In the eleventh C site, C is bonded in a trigonal planar geometry to three O atoms. There is one shorter (1.26 Å) and two longer (1.31 Å) C–O bond length. In the twelfth C site, C is bonded in a trigonal planar geometry to three O atoms. There are a spread of C–O bond distances ranging from 1.28–1.31 Å. In the thirteenth C site, C is bonded in a trigonal planar geometry to three O atoms. There are a spread of C–O bond distances ranging from 1.27–1.33 Å. In the fourteenth C site, C is bonded in a trigonal planar geometry to three O atoms. There are a spread of C–O bond distances ranging from 1.27–1.34 Å. In the fifteenth C site, C is bonded in a trigonal planar geometry to three O atoms. There are a spread of C–O bond distances ranging from 1.26–1.32 Å. In the sixteenth C site, C is bonded in a trigonal planar geometry to three O atoms. There are a spread of C–O bond distances ranging from 1.27–1.32 Å. There are forty-eight inequivalent O sites. In the first O site, O is bonded in a 3-coordinate geometry to two Li and one C atom. In the second O site, O is bonded in a distorted bent 120 degrees geometry to one Li and one C atom. In the third O site, O is bonded in a bent 120 degrees geometry to one Li and one C atom. In the fourth O site, O is bonded in a 1-coordinate geometry to two Li and one C atom. In the fifth O site, O is bonded in a distorted trigonal planar geometry to one Li, one Fe, and one C atom. In the sixth O site, O is bonded in a 3-coordinate geometry to one Li, one Fe, and one C atom. In the seventh O site, O is bonded in a trigonal planar geometry to two Li and one C atom. In the eighth O site, O is bonded to three Li and one C atom to form distorted edge-sharing OLi3C tetrahedra. In the ninth O site, O is bonded in a distorted T-shaped geometry to two Li and one C atom. In the tenth O site, O is bonded in a distorted T-shaped geometry to two Li and one C atom. In the eleventh O site, O is bonded to two Li, one Fe, and one C atom to form distorted edge-sharing OLi2FeC tetrahedra. In the twelfth O site, O is bonded in a distorted trigonal planar geometry to one Li, one Fe, and one C atom. In the thirteenth O site, O is bonded in a distorted trigonal planar geometry to two Li and one C atom. In the fourteenth O site, O is bonded in a 3-coordinate geometry to one Li, one Fe, and one C atom. In the fifteenth O site, O is bonded in a distorted rectangular see-saw-like geometry to three Li and one C atom. In the sixteenth O site, O is bonded in a distorted trigonal non-coplanar geometry to one Li, one Fe, and one C atom. In the seventeenth O site, O is bonded in a distorted trigonal planar geometry to one Li, one Fe, and one C atom. In the eighteenth O site, O is bonded in a distorted trigonal planar geometry to one Li, one Fe, and one C atom. In the nineteenth O site, O is bonded in a distorted trigonal planar geometry to two Li and one C atom. In the twentieth O site, O is bonded in a 3-coordinate geometry to two Li and one C atom. In the twenty-first O site, O is bonded in a distorted trigonal non-coplanar geometry to one Li, one Fe, and one C atom. In the twenty-second O site, O is bonded in a distorted T-shaped geometry to one Li, one Fe, and one C atom. In the twenty-third O site, O is bonded in an L-shaped geometry to one Fe and one C atom. In the twenty-fourth O site, O is bonded in a 3-coordinate geometry to one Li, one Fe, and one C atom. In the twenty-fifth O site, O is bonded in an L-shaped geometry to one Fe and one C atom. In the twenty-sixth O site, O is bonded in a 3-coordinate geometry to one Li, one Fe, and one C atom. In the twenty-seventh O site, O is bonded in a distorted trigonal non-coplanar geometry to one Li, one Fe, and one C atom. In the twenty-eighth O site, O is bonded in a distorted T-shaped geometry to one Li, one Fe, and one C atom. In the twenty-ninth O site, O is bonded in a distorted T-shaped geometry to two Li and one C atom. In the thirtieth O site, O is bonded in a distorted trigonal planar geometry to two Li and one C atom. In the thirty-first O site, O is bonded in a distorted trigonal planar geometry to one Li, one Fe, and one C atom. In the thirty-second O site, O is bonded in a distorted trigonal planar geometry to one Li, one Fe, and one C atom. In the thirty-third O site, O is bonded in a 3-coordinate geometry to two Li, one Fe, and one C atom. In the thirty-fo