DOE OSTI2020
Li9Mg12Fe(PO4)12 crystallizes in the triclinic P1 space group. The structure is three-dimensional. there are nine inequivalent Li sites. In the first Li site, Li is bonded in a distorted trigonal planar geometry to three O atoms. There are a spread of Li–O bond distances ranging from 1.94–2.06 Å. In the second Li site, Li is bonded to four O atoms to form distorted LiO4 trigonal pyramids that share corners with two PO4 tetrahedra. There are a spread of Li–O bond distances ranging from 1.99–2.33 Å. In the third Li site, Li is bonded in a 3-coordinate geometry to three O atoms. There are a spread of Li–O bond distances ranging from 1.83–2.15 Å. In the fourth Li site, Li is bonded to four O atoms to form distorted LiO4 tetrahedra that share a cornercorner with one PO4 tetrahedra. There are a spread of Li–O bond distances ranging from 1.95–2.57 Å. In the fifth Li site, Li is bonded in a 4-coordinate geometry to four O atoms. There are a spread of Li–O bond distances ranging from 1.96–2.11 Å. In the sixth Li site, Li is bonded in a distorted pentagonal planar geometry to five O atoms. There are a spread of Li–O bond distances ranging from 2.10–2.27 Å. In the seventh Li site, Li is bonded in a 2-coordinate geometry to four O atoms. There are a spread of Li–O bond distances ranging from 1.92–2.57 Å. In the eighth Li site, Li is bonded to five O atoms to form LiO5 trigonal bipyramids that share a cornercorner with one MgO4 tetrahedra, a cornercorner with one PO4 tetrahedra, and an edgeedge with one MgO5 square pyramid. There are a spread of Li–O bond distances ranging from 1.90–2.21 Å. In the ninth 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 2.00–2.40 Å. There are twelve inequivalent Mg sites. In the first Mg site, Mg is bonded in a 6-coordinate geometry to six O atoms. There are a spread of Mg–O bond distances ranging from 1.93–2.57 Å. In the second Mg site, Mg is bonded in a 4-coordinate geometry to four O atoms. There are a spread of Mg–O bond distances ranging from 1.89–2.25 Å. In the third Mg site, Mg is bonded in a 4-coordinate geometry to four O atoms. There are a spread of Mg–O bond distances ranging from 2.01–2.14 Å. In the fourth Mg site, Mg is bonded in a 5-coordinate geometry to five O atoms. There are a spread of Mg–O bond distances ranging from 1.93–2.15 Å. In the fifth Mg site, Mg is bonded to four O atoms to form distorted MgO4 trigonal pyramids that share corners with two PO4 tetrahedra. There are a spread of Mg–O bond distances ranging from 1.96–2.01 Å. In the sixth Mg site, Mg is bonded to four O atoms to form MgO4 tetrahedra that share a cornercorner with one PO4 tetrahedra. There are a spread of Mg–O bond distances ranging from 1.95–2.00 Å. In the seventh Mg site, Mg is bonded in a 3-coordinate geometry to three O atoms. There are a spread of Mg–O bond distances ranging from 1.85–2.03 Å. In the eighth Mg site, Mg is bonded in a 5-coordinate geometry to one P and four O atoms. The Mg–P bond length is 2.71 Å. There are a spread of Mg–O bond distances ranging from 1.96–2.25 Å. In the ninth Mg site, Mg is bonded to four O atoms to form MgO4 tetrahedra that share corners with two PO4 tetrahedra and a cornercorner with one LiO5 trigonal bipyramid. There are a spread of Mg–O bond distances ranging from 1.89–2.04 Å. In the tenth Mg site, Mg is bonded to four O atoms to form distorted MgO4 tetrahedra that share a cornercorner with one MgO5 square pyramid and corners with two PO4 tetrahedra. There are a spread of Mg–O bond distances ranging from 1.96–2.12 Å. In the eleventh Mg site, Mg is bonded in a 5-coordinate geometry to five O atoms. There are a spread of Mg–O bond distances ranging from 2.00–2.20 Å. In the twelfth Mg site, Mg is bonded to five O atoms to form distorted MgO5 square pyramids that share a cornercorner with one MgO4 tetrahedra, a cornercorner with one PO4 tetrahedra, and an edgeedge with one LiO5 trigonal bipyramid. There are a spread of Mg–O bond distances ranging from 2.02–2.09 Å. Fe is bonded in a 4-coordinate geometry to four O atoms. There are a spread of Fe–O bond distances ranging from 2.02–2.43 Å. There are twelve inequivalent P sites. In the first P site, P is bonded in a distorted trigonal non-coplanar geometry to three O atoms. There are a spread of P–O bond distances ranging from 1.55–1.74 Å. In the second P site, P is bonded in a 3-coordinate geometry to one Mg and three O atoms. There are a spread of P–O bond distances ranging from 1.54–1.74 Å. In the third P site, P is bonded to four O atoms to form PO4 tetrahedra that share a cornercorner with one MgO5 square pyramid, a cornercorner with one MgO4 tetrahedra, and a cornercorner with one LiO5 trigonal bipyramid. There are a spread of P–O bond distances ranging from 1.52–1.62 Å. In the fourth P site, P is bonded in a distorted trigonal non-coplanar geometry to three O atoms. There are a spread of P–O bond distances ranging from 1.58–1.64 Å. In the fifth P site, P is bonded in a distorted trigonal non-coplanar geometry to three O atoms. There are a spread of P–O bond distances ranging from 1.58–1.72 Å. In the sixth P site, P is bonded to four O atoms to form PO4 tetrahedra that share a cornercorner with one MgO4 tetrahedra and a cornercorner with one LiO4 trigonal pyramid. There is two shorter (1.55 Å) and two longer (1.56 Å) P–O bond length. In the seventh P site, P is bonded to four O atoms to form PO4 tetrahedra that share a cornercorner with one MgO4 tetrahedra, a cornercorner with one LiO4 trigonal pyramid, and a cornercorner with one MgO4 trigonal pyramid. There is one shorter (1.53 Å) and three longer (1.57 Å) P–O bond length. In the eighth P site, P is bonded in a trigonal non-coplanar geometry to three O atoms. There are a spread of P–O bond distances ranging from 1.52–1.65 Å. In the ninth P site, P is bonded in a trigonal non-coplanar geometry to three O atoms. There is one shorter (1.58 Å) and two longer (1.71 Å) P–O bond length. In the tenth P site, P is bonded in a trigonal planar geometry to three O atoms. There are a spread of P–O bond distances ranging from 1.48–1.51 Å. In the eleventh P site, P is bonded to four O atoms to form PO4 tetrahedra that share a cornercorner with one LiO4 tetrahedra, corners with two MgO4 tetrahedra, and a cornercorner with one MgO4 trigonal pyramid. There are a spread of P–O bond distances ranging from 1.50–1.62 Å. In the twelfth P site, P is bonded in a trigonal non-coplanar geometry to three O atoms. There is one shorter (1.55 Å) and two longer (1.58 Å) P–O bond length. There are forty-eight inequivalent O sites. In the first O site, O is bonded in a distorted T-shaped geometry to one Li and two Mg atoms. In the second O site, O is bonded in a trigonal planar geometry to one Li, one Mg, and one P atom. In the third O site, O is bonded in a 3-coordinate geometry to one Li, one Mg, and one P atom. In the fourth O site, O is bonded in a distorted bent 150 degrees geometry to one Mg and one P atom. In the fifth O site, O is bonded in a rectangular see-saw-like geometry to two Li, one Mg, and one P atom. In the sixth O site, O is bonded in a distorted trigonal planar geometry to one Li, one Mg, and one P atom. In the seventh O site, O is bonded in a trigonal planar geometry to one Li and two Mg atoms. In the eighth O site, O is bonded in a 3-coordinate geometry to one Li, one P, and one O atom. The O–O bond length is 1.49 Å. In the ninth O site, O is bonded in a distorted single-bond geometry to one P atom. In the tenth O site, O is bonded to one Li and three Mg atoms to form corner-sharing OLiMg3 tetrahedra. In the eleventh O site, O is bonded in a distorted trigonal planar geometry to one Li, one Mg, and one P atom. In the twelfth O site, O is bonded in a distorted T-shaped geometry to one Li, one Mg, and one P atom. In the thirteenth O site, O is bonded in a trigonal planar geometry to one Li, one Mg, and one P atom. In the fourteenth O site, O is bonded in a distorted T-shaped geometry to one Li, one Mg, and one P atom. In the fifteenth O site, O is bonded in a 4-coordinate geometry to one Li, two Mg, and one O atom. The O–O bond length is 1.55 Å. In the sixteenth O site, O is bonded in a 3-coordinate geometry to one Li, one Mg, and one P atom. In the seventeenth O site, O is bonded in a 2-coordinate geometry to one Mg, one P, and one O atom. In the eighteenth O site, O is bonded in a distorted T-shaped geometry to one Li, one Mg, and one P atom. In the nineteenth O site, O is bonded in a 3-coordinate geometry to one Li, one Mg, and one P atom. In the twentieth O site, O is bonded in a distorted bent 150 degrees geometry to one Li and one P atom. In the twenty-first O site, O is bonded in a distorted T-shaped geometry to one Li, one Mg, and one P atom. In the twenty-second O site, O is bonded in a 2-coordinate geometry to one Li and one Mg atom. In the twenty-third O site, O is bonded in a trigonal planar geometry to two Mg and one P atom. In the twenty-fourth O site, O is bonded in a distorted T-shaped geometry to two Mg and one P atom. In the twenty-fifth O site, O is bonded in a distorted bent 120 degrees geometry to one Mg, one P, and one O atom. The O–O bond length is 1.47 Å. In the twenty-sixth O site, O is bonded in a distorted trigonal planar geometry to two Li and one O atom. The O–O bond length is 1.48 Å. In the twenty-seventh O site, O is bonded in a linear geometry to one Mg and one P atom. In the twenty-eighth O site, O is bonded in a 3-coordinate geometry to one Li, one Mg, and one P atom. In the twenty-ninth O site, O is bonded in a distorted trigonal planar geometry to two Li and one P atom. In the thirtieth O site, O is bonded in a distorted bent 150 degrees geometry to one Li, one Mg, and one P atom. In the thirty-first O site, O is bonded in a distorted trigonal planar geometry to one Mg, one Fe, and one P atom. In the thirty-second O site, O is bonded in a 4-coordinate geometry to one Li, one Mg, one Fe, and one P atom. In the thirty-third O site, O is bonded in a distorted T-shaped geometry to two Mg and one P atom. In the thirty-fourth O site, O is bonded in a distorted trigonal non-coplanar geometry to one Mg, one Fe, and one P atom. In the thirty-fifth O site, O is bonded in a bent 150 degrees geometry to two P atoms. In the thirty-sixth O site, O is bonded in a distorted single-bond geometry to one P and one O atom. The O–O bond length is 1.51 Å. In the thirty-seventh O site, O is bonded in a distorted trigonal non-coplanar geometry to one Li, one Mg, and one P atom. In the thirty-eighth O site, O is bonded in a 3-coordinate geometry to two Mg and one P atom. In the thirty-ninth O site, O is bonded in a distorted trigonal non-coplanar geometry to two Li and one O atom. In the fortieth O site, O is bonded in a distorted single-bond geometry to one P and one O atom. In the forty-first O site, O is bonded to one Li, two Mg, and one P atom to form distorted corner-sharing OLiMg2P trigonal pyramids. In the forty-second O site, O is bonded in a distorted bent 150 degrees geometry to two Mg and one O atom. In the forty-third O site, O is bonded in a distorted rectangular see-saw-like geometry to two Li, one Mg, and one O atom. In the forty-fourth O site, O is bonded in a distorted rectangular see-saw-like geometry to one Li, one Mg, one Fe, and one P atom. In the forty-fifth O site, O is bonded in a 4-coordinate geometry to one Li, two Mg, and one P atom. In the forty-sixth O site, O is bonded in a bent 120 degrees geometry to one Mg and one P atom. In the forty-seventh O site, O is bonded to one Li, two Mg, and one P atom to form distorted OLiMg2P tetrahedra that share a cornercorner with one OLiMg3 tetrahedra and a cornercorner with one OLiMg2P trigonal pyramid. In the forty-eighth O site, O is bonded in a distorted trigonal planar geometry to one Li, one Mg, and one P atom.