DOE OSTI2020
Li3Bi(PO4)2 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 four O2- atoms to form LiO4 tetrahedra that share a cornercorner with one BiO12 cuboctahedra, a cornercorner with one BiO6 octahedra, corners with two LiO4 tetrahedra, and corners with four PO4 tetrahedra. The corner-sharing octahedral tilt angles are 66°. There are a spread of Li–O bond distances ranging from 1.91–2.09 Å. In the second Li1+ site, Li1+ is bonded to four O2- atoms to form LiO4 tetrahedra that share a cornercorner with one BiO12 cuboctahedra, a cornercorner with one BiO6 octahedra, corners with two LiO4 tetrahedra, and corners with four PO4 tetrahedra. The corner-sharing octahedral tilt angles are 66°. There are a spread of Li–O bond distances ranging from 1.91–2.09 Å. In the third Li1+ site, Li1+ is bonded in a distorted trigonal non-coplanar geometry to six O2- atoms. There are a spread of Li–O bond distances ranging from 1.95–2.57 Å. In the fourth Li1+ site, Li1+ is bonded to four O2- atoms to form LiO4 tetrahedra that share a cornercorner with one BiO12 cuboctahedra, a cornercorner with one BiO6 octahedra, corners with two LiO4 tetrahedra, and corners with four PO4 tetrahedra. The corner-sharing octahedral tilt angles are 66°. There are a spread of Li–O bond distances ranging from 1.91–2.09 Å. In the fifth Li1+ site, Li1+ is bonded to four O2- atoms to form LiO4 tetrahedra that share a cornercorner with one BiO12 cuboctahedra, a cornercorner with one BiO6 octahedra, corners with two LiO4 tetrahedra, and corners with four PO4 tetrahedra. The corner-sharing octahedral tilt angles are 66°. There are a spread of Li–O bond distances ranging from 1.91–2.08 Å. In the sixth Li1+ site, Li1+ is bonded to four O2- atoms to form LiO4 tetrahedra that share a cornercorner with one BiO12 cuboctahedra, a cornercorner with one BiO6 octahedra, corners with two LiO4 tetrahedra, and corners with four PO4 tetrahedra. The corner-sharing octahedral tilt angles are 66°. There are a spread of Li–O bond distances ranging from 1.91–2.08 Å. In the seventh Li1+ site, Li1+ is bonded in a distorted trigonal non-coplanar geometry to six O2- atoms. There are three shorter (1.96 Å) and three longer (2.57 Å) Li–O bond lengths. In the eighth Li1+ site, Li1+ is bonded to four O2- atoms to form LiO4 tetrahedra that share a cornercorner with one BiO12 cuboctahedra, a cornercorner with one BiO6 octahedra, corners with two LiO4 tetrahedra, and corners with four PO4 tetrahedra. The corner-sharing octahedral tilt angles are 66°. There are a spread of Li–O bond distances ranging from 1.91–2.09 Å. In the ninth Li1+ site, Li1+ is bonded in a 6-coordinate geometry to six O2- atoms. There are four shorter (2.31 Å) and two longer (2.32 Å) Li–O bond lengths. There are three inequivalent Bi3+ sites. In the first Bi3+ site, Bi3+ is bonded to twelve O2- atoms to form BiO12 cuboctahedra that share corners with six BiO6 octahedra, corners with six LiO4 tetrahedra, and edges with six PO4 tetrahedra. The corner-sharing octahedral tilt angles are 41°. There are a spread of Bi–O bond distances ranging from 2.62–2.84 Å. In the second Bi3+ site, Bi3+ is bonded to six O2- atoms to form distorted BiO6 octahedra that share corners with three equivalent BiO12 cuboctahedra, corners with three LiO4 tetrahedra, and corners with six PO4 tetrahedra. There are three shorter (2.34 Å) and three longer (2.44 Å) Bi–O bond lengths. In the third Bi3+ site, Bi3+ is bonded to six O2- atoms to form distorted BiO6 octahedra that share corners with three equivalent BiO12 cuboctahedra, corners with three LiO4 tetrahedra, and corners with six PO4 tetrahedra. There are three shorter (2.34 Å) and three longer (2.44 Å) Bi–O bond lengths. There are six inequivalent P5+ sites. In the first P5+ site, P5+ is bonded to four O2- atoms to form PO4 tetrahedra that share corners with two BiO6 octahedra, corners with four LiO4 tetrahedra, and an edgeedge with one BiO12 cuboctahedra. The corner-sharing octahedra tilt angles range from 55–61°. There is three shorter (1.55 Å) and one longer (1.58 Å) P–O bond length. In the second P5+ site, P5+ is bonded to four O2- atoms to form PO4 tetrahedra that share corners with two BiO6 octahedra, corners with four LiO4 tetrahedra, and an edgeedge with one BiO12 cuboctahedra. The corner-sharing octahedra tilt angles range from 56–61°. There is three shorter (1.55 Å) and one longer (1.58 Å) P–O bond length. In the third P5+ site, P5+ is bonded to four O2- atoms to form PO4 tetrahedra that share corners with two BiO6 octahedra, corners with four LiO4 tetrahedra, and an edgeedge with one BiO12 cuboctahedra. The corner-sharing octahedra tilt angles range from 55–61°. There is three shorter (1.55 Å) and one longer (1.58 Å) P–O bond length. In the fourth P5+ site, P5+ is bonded to four O2- atoms to form PO4 tetrahedra that share corners with two BiO6 octahedra, corners with four LiO4 tetrahedra, and an edgeedge with one BiO12 cuboctahedra. The corner-sharing octahedra tilt angles range from 56–61°. There is three shorter (1.55 Å) and one longer (1.58 Å) P–O bond length. In the fifth P5+ site, P5+ is bonded to four O2- atoms to form PO4 tetrahedra that share corners with two BiO6 octahedra, corners with four LiO4 tetrahedra, and an edgeedge with one BiO12 cuboctahedra. The corner-sharing octahedra tilt angles range from 56–61°. There is three shorter (1.55 Å) and one longer (1.58 Å) P–O bond length. In the sixth P5+ site, P5+ is bonded to four O2- atoms to form PO4 tetrahedra that share corners with two BiO6 octahedra, corners with four LiO4 tetrahedra, and an edgeedge with one BiO12 cuboctahedra. The corner-sharing octahedra tilt angles range from 56–61°. There is three shorter (1.55 Å) and one longer (1.58 Å) P–O bond length. There are twenty-four inequivalent O2- sites. In the first O2- site, O2- is bonded in a 2-coordinate geometry to two Li1+, one Bi3+, and one P5+ atom. In the second O2- site, O2- is bonded to three Li1+ and one P5+ atom to form corner-sharing OLi3P tetrahedra. In the third O2- site, O2- is bonded in a 2-coordinate geometry to two Li1+, one Bi3+, and one P5+ atom. In the fourth O2- site, O2- is bonded in a 2-coordinate geometry to two Li1+, one Bi3+, and one P5+ atom. In the fifth O2- site, O2- is bonded in a 2-coordinate geometry to two Li1+, one Bi3+, and one P5+ atom. In the sixth O2- site, O2- is bonded to three Li1+ and one P5+ atom to form corner-sharing OLi3P tetrahedra. In the seventh O2- site, O2- is bonded in a distorted single-bond geometry to two Bi3+ and one P5+ atom. In the eighth O2- site, O2- is bonded in a distorted single-bond geometry to two Bi3+ and one P5+ atom. In the ninth O2- site, O2- is bonded in a 2-coordinate geometry to two Li1+, one Bi3+, and one P5+ atom. In the tenth O2- site, O2- is bonded in a distorted single-bond geometry to two Bi3+ and one P5+ atom. In the eleventh O2- site, O2- is bonded in a 2-coordinate geometry to two Li1+, one Bi3+, and one P5+ atom. In the twelfth O2- site, O2- is bonded in a 2-coordinate geometry to two Li1+, one Bi3+, and one P5+ atom. In the thirteenth O2- site, O2- is bonded to three Li1+ and one P5+ atom to form corner-sharing OLi3P tetrahedra. In the fourteenth O2- site, O2- is bonded in a distorted single-bond geometry to two Bi3+ and one P5+ atom. In the fifteenth O2- site, O2- is bonded to three Li1+ and one P5+ atom to form corner-sharing OLi3P tetrahedra. In the sixteenth O2- site, O2- is bonded in a 2-coordinate geometry to two Li1+, one Bi3+, and one P5+ atom. In the seventeenth O2- site, O2- is bonded in a 2-coordinate geometry to two Li1+, one Bi3+, and one P5+ atom. In the eighteenth O2- site, O2- is bonded in a 2-coordinate geometry to two Li1+, one Bi3+, and one P5+ atom. In the nineteenth O2- site, O2- is bonded in a 2-coordinate geometry to two Li1+, one Bi3+, and one P5+ atom. In the twentieth O2- site, O2- is bonded in a distorted single-bond geometry to two Bi3+ and one P5+ atom. In the twenty-first O2- site, O2- is bonded to three Li1+ and one P5+ atom to form corner-sharing OLi3P tetrahedra. In the twenty-second O2- site, O2- is bonded in a 2-coordinate geometry to two Li1+, one Bi3+, and one P5+ atom. In the twenty-third O2- site, O2- is bonded to three Li1+ and one P5+ atom to form corner-sharing OLi3P tetrahedra. In the twenty-fourth O2- site, O2- is bonded in a distorted single-bond geometry to two Bi3+ and one P5+ atom.