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 BiO6 octahedra, corners with two LiO4 tetrahedra, and corners with four PO4 tetrahedra. The corner-sharing octahedral tilt angles are 67°. There are a spread of Li–O bond distances ranging from 1.94–2.06 Å. In the second Li1+ site, Li1+ is bonded to four O2- atoms to form LiO4 tetrahedra that share a cornercorner with one BiO6 octahedra, corners with two LiO4 tetrahedra, and corners with four PO4 tetrahedra. The corner-sharing octahedral tilt angles are 65°. There are a spread of Li–O bond distances ranging from 1.93–2.05 Å. In the third Li1+ site, Li1+ is bonded in a 3-coordinate geometry to six O2- atoms. There are a spread of Li–O bond distances ranging from 2.00–2.58 Å. In the fourth Li1+ site, Li1+ is bonded to four O2- atoms to form LiO4 tetrahedra that share 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 1.95–2.07 Å. In the fifth Li1+ site, Li1+ is bonded in a 6-coordinate geometry to six O2- atoms. There are a spread of Li–O bond distances ranging from 2.21–2.57 Å. In the sixth Li1+ site, Li1+ is bonded in a 6-coordinate geometry to six O2- atoms. There are a spread of Li–O bond distances ranging from 2.01–2.56 Å. In the seventh Li1+ site, Li1+ is bonded to four O2- atoms to form LiO4 tetrahedra that share 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 1.92–2.05 Å. In the eighth Li1+ site, Li1+ is bonded to four O2- atoms to form LiO4 tetrahedra that share 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 1.93–2.06 Å. In the ninth Li1+ site, Li1+ is bonded to four O2- atoms to form LiO4 tetrahedra that share a cornercorner with one BiO6 octahedra, corners with two LiO4 tetrahedra, and corners with four PO4 tetrahedra. The corner-sharing octahedral tilt angles are 67°. There are a spread of Li–O bond distances ranging from 1.93–2.06 Å. There are three inequivalent Bi3+ sites. In the first Bi3+ site, Bi3+ is bonded to six O2- atoms to form distorted BiO6 octahedra that share corners with three LiO4 tetrahedra and corners with six PO4 tetrahedra. There are a spread of Bi–O bond distances ranging from 2.32–2.43 Å. In the second Bi3+ site, Bi3+ is bonded to six O2- atoms to form distorted BiO6 octahedra that share corners with three LiO4 tetrahedra and corners with six PO4 tetrahedra. There are a spread of Bi–O bond distances ranging from 2.34–2.49 Å. In the third Bi3+ site, Bi3+ is bonded in a 9-coordinate geometry to nine O2- atoms. There are a spread of Bi–O bond distances ranging from 2.46–2.80 Å. 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 and corners with four LiO4 tetrahedra. The corner-sharing octahedra tilt angles range from 56–58°. There are a spread of P–O bond distances ranging from 1.54–1.57 Å. In the second P5+ site, P5+ is bonded to four O2- atoms to form PO4 tetrahedra that share corners with two BiO6 octahedra and corners with four LiO4 tetrahedra. The corner-sharing octahedra tilt angles range from 46–60°. 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 and corners with four LiO4 tetrahedra. The corner-sharing octahedra tilt angles range from 52–60°. There are a spread of P–O bond distances ranging from 1.54–1.57 Å. In the fourth P5+ site, P5+ is bonded to four O2- atoms to form PO4 tetrahedra that share corners with two BiO6 octahedra and corners with four LiO4 tetrahedra. The corner-sharing octahedra tilt angles range from 47–61°. There are a spread of P–O bond distances ranging from 1.55–1.57 Å. In the fifth P5+ site, P5+ is bonded to four O2- atoms to form PO4 tetrahedra that share corners with two BiO6 octahedra and corners with four LiO4 tetrahedra. The corner-sharing octahedra tilt angles range from 53–58°. There are a spread of P–O bond distances ranging from 1.54–1.58 Å. In the sixth P5+ site, P5+ is bonded to four O2- atoms to form PO4 tetrahedra that share corners with two BiO6 octahedra and corners with four LiO4 tetrahedra. The corner-sharing octahedra tilt angles range from 48–59°. 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 to three Li1+ and one P5+ atom to form distorted corner-sharing OLi3P tetrahedra. In the second O2- site, O2- is bonded in a distorted single-bond geometry to two Bi3+ and one P5+ atom. 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 distorted single-bond geometry to one Bi3+ and one P5+ atom. In the sixth O2- site, O2- is bonded to three Li1+ and one P5+ atom to form distorted corner-sharing OLi3P tetrahedra. In the seventh O2- site, O2- is bonded in a 2-coordinate geometry to two Li1+, one Bi3+, and one P5+ atom. In the eighth O2- site, O2- is bonded in a 2-coordinate geometry to two Li1+, one Bi3+, and one P5+ atom. In the ninth O2- site, O2- is bonded in a 3-coordinate geometry to two Li1+, one Bi3+, and one P5+ atom. In the tenth O2- site, O2- is bonded to three Li1+ and one P5+ atom to form distorted corner-sharing OLi3P tetrahedra. 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 in a 1-coordinate geometry to one Bi3+ and one P5+ atom. In the fourteenth O2- site, O2- is bonded in a 2-coordinate geometry to two Li1+, one Bi3+, and one P5+ atom. In the fifteenth O2- site, O2- is bonded in a distorted single-bond geometry to two Bi3+ and one P5+ atom. In the sixteenth O2- site, O2- is bonded in a 1-coordinate geometry to 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 to three Li1+ and one P5+ atom to form distorted corner-sharing OLi3P tetrahedra. 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 distorted corner-sharing OLi3P tetrahedra. In the twenty-second O2- site, O2- is bonded in a distorted bent 120 degrees geometry to two Li1+, one Bi3+, and one P5+ atom. In the twenty-third O2- site, O2- is bonded in a 2-coordinate geometry to two Li1+, one Bi3+, and one P5+ atom. In the twenty-fourth O2- site, O2- is bonded to three Li1+ and one P5+ atom to form distorted corner-sharing OLi3P tetrahedra.