Li3Zr4(PO4)6 crystallizes in the triclinic P1 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded in a distorted rectangular see-saw-like geometry to one O(11), one O(12), one O(18), and one O(6) atom. In the second Li site, Li(2) is bonded in a distorted rectangular see-saw-like geometry to one O(13), one O(14), one O(19), and one O(8) atom. In the third Li site, Li(3) is bonded in a 4-coordinate geometry to one O(1), one O(20), one O(22), and one O(7) atom. There are four inequivalent Zr sites. In the first Zr site, Zr(1) is bonded to one O(10), one O(13), one O(18), one O(20), one O(6), and one O(9) atom to form ZrO6 octahedra that share  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra,  a cornercorner with one P(5)O4 tetrahedra, and  a cornercorner with one P(6)O4 tetrahedra. In the second Zr site, Zr(2) is bonded to one O(1), one O(11), one O(17), one O(22), one O(23), and one O(4) atom to form ZrO6 octahedra that share  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra,  a cornercorner with one P(5)O4 tetrahedra, and  a cornercorner with one P(6)O4 tetrahedra. In the third Zr site, Zr(3) is bonded to one O(12), one O(15), one O(16), one O(19), one O(5), and one O(8) atom to form ZrO6 octahedra that share  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra,  a cornercorner with one P(5)O4 tetrahedra, and  a cornercorner with one P(6)O4 tetrahedra. In the fourth Zr site, Zr(4) is bonded to one O(14), one O(2), one O(21), one O(24), one O(3), and one O(7) atom to form ZrO6 octahedra that share  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra,  a cornercorner with one P(5)O4 tetrahedra, and  a cornercorner with one P(6)O4 tetrahedra. There are six inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(15), one O(2), and one O(6) atom to form PO4 tetrahedra that share  a cornercorner with one Zr(1)O6 octahedra,  a cornercorner with one Zr(2)O6 octahedra,  a cornercorner with one Zr(3)O6 octahedra, and  a cornercorner with one Zr(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 21-42°. In the second P site, P(2) is bonded to one O(20), one O(4), one O(7), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one Zr(1)O6 octahedra,  a cornercorner with one Zr(2)O6 octahedra,  a cornercorner with one Zr(3)O6 octahedra, and  a cornercorner with one Zr(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 18-45°. In the third P site, P(3) is bonded to one O(11), one O(12), one O(3), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one Zr(1)O6 octahedra,  a cornercorner with one Zr(2)O6 octahedra,  a cornercorner with one Zr(3)O6 octahedra, and  a cornercorner with one Zr(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 19-41°. In the fourth P site, P(4) is bonded to one O(13), one O(14), one O(16), and one O(22) atom to form PO4 tetrahedra that share  a cornercorner with one Zr(1)O6 octahedra,  a cornercorner with one Zr(2)O6 octahedra,  a cornercorner with one Zr(3)O6 octahedra, and  a cornercorner with one Zr(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 19-44°. In the fifth P site, P(5) is bonded to one O(17), one O(18), one O(21), and one O(5) atom to form PO4 tetrahedra that share  a cornercorner with one Zr(1)O6 octahedra,  a cornercorner with one Zr(2)O6 octahedra,  a cornercorner with one Zr(3)O6 octahedra, and  a cornercorner with one Zr(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 17-45°. In the sixth P site, P(6) is bonded to one O(10), one O(19), one O(23), and one O(24) atom to form PO4 tetrahedra that share  a cornercorner with one Zr(1)O6 octahedra,  a cornercorner with one Zr(2)O6 octahedra,  a cornercorner with one Zr(3)O6 octahedra, and  a cornercorner with one Zr(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 22-42°. There are twenty-four inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one Li(3), one Zr(2), and one P(1) atom. In the second O site, O(2) is bonded in a bent 150 degrees geometry to one Zr(4) and one P(1) atom. In the third O site, O(3) is bonded in a bent 150 degrees geometry to one Zr(4) and one P(3) atom. In the fourth O site, O(4) is bonded in a bent 150 degrees geometry to one Zr(2) and one P(2) atom. In the fifth O site, O(5) is bonded in a bent 150 degrees geometry to one Zr(3) and one P(5) atom. In the sixth O site, O(6) is bonded in a distorted trigonal planar geometry to one Li(1), one Zr(1), and one P(1) atom. In the seventh O site, O(7) is bonded in a distorted trigonal planar geometry to one Li(3), one Zr(4), and one P(2) atom. In the eighth O site, O(8) is bonded in a distorted trigonal planar geometry to one Li(2), one Zr(3), and one P(2) atom. In the ninth O site, O(9) is bonded in a bent 150 degrees geometry to one Zr(1) and one P(3) atom. In the tenth O site, O(10) is bonded in a bent 150 degrees geometry to one Zr(1) and one P(6) atom. In the eleventh O site, O(11) is bonded in a 3-coordinate geometry to one Li(1), one Zr(2), and one P(3) atom. In the twelfth O site, O(12) is bonded in a 3-coordinate geometry to one Li(1), one Zr(3), and one P(3) atom. In the thirteenth O site, O(13) is bonded in a 3-coordinate geometry to one Li(2), one Zr(1), and one P(4) atom. In the fourteenth O site, O(14) is bonded in a 3-coordinate geometry to one Li(2), one Zr(4), and one P(4) atom. In the fifteenth O site, O(15) is bonded in a bent 150 degrees geometry to one Zr(3) and one P(1) atom. In the sixteenth O site, O(16) is bonded in a bent 150 degrees geometry to one Zr(3) and one P(4) atom. In the seventeenth O site, O(17) is bonded in a bent 150 degrees geometry to one Zr(2) and one P(5) atom. In the eighteenth O site, O(18) is bonded in a distorted trigonal planar geometry to one Li(1), one Zr(1), and one P(5) atom. In the nineteenth O site, O(19) is bonded in a distorted trigonal planar geometry to one Li(2), one Zr(3), and one P(6) atom. In the twentieth O site, O(20) is bonded in a 3-coordinate geometry to one Li(3), one Zr(1), and one P(2) atom. In the twenty-first O site, O(21) is bonded in a linear geometry to one Zr(4) and one P(5) atom. In the twenty-second O site, O(22) is bonded in a distorted trigonal planar geometry to one Li(3), one Zr(2), and one P(4) atom. In the twenty-third O site, O(23) is bonded in a bent 150 degrees geometry to one Zr(2) and one P(6) atom. In the twenty-fourth O site, O(24) is bonded in a bent 150 degrees geometry to one Zr(4) and one P(6) atom.
Li3Zr4(PO4)6 crystallizes in the triclinic P1 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded in a distorted rectangular see-saw-like geometry to one O(11), one O(12), one O(18), and one O(6) atom. The Li(1)-O(11) bond length is 2.18 Å. The Li(1)-O(12) bond length is 2.15 Å. The Li(1)-O(18) bond length is 1.99 Å. The Li(1)-O(6) bond length is 2.15 Å. In the second Li site, Li(2) is bonded in a distorted rectangular see-saw-like geometry to one O(13), one O(14), one O(19), and one O(8) atom. The Li(2)-O(13) bond length is 2.14 Å. The Li(2)-O(14) bond length is 2.25 Å. The Li(2)-O(19) bond length is 2.06 Å. The Li(2)-O(8) bond length is 2.02 Å. In the third Li site, Li(3) is bonded in a 4-coordinate geometry to one O(1), one O(20), one O(22), and one O(7) atom. The Li(3)-O(1) bond length is 2.10 Å. The Li(3)-O(20) bond length is 2.53 Å. The Li(3)-O(22) bond length is 2.00 Å. The Li(3)-O(7) bond length is 2.06 Å. There are four inequivalent Zr sites. In the first Zr site, Zr(1) is bonded to one O(10), one O(13), one O(18), one O(20), one O(6), and one O(9) atom to form ZrO6 octahedra that share  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra,  a cornercorner with one P(5)O4 tetrahedra, and  a cornercorner with one P(6)O4 tetrahedra. The Zr(1)-O(10) bond length is 2.09 Å. The Zr(1)-O(13) bond length is 2.18 Å. The Zr(1)-O(18) bond length is 2.18 Å. The Zr(1)-O(20) bond length is 2.14 Å. The Zr(1)-O(6) bond length is 2.18 Å. The Zr(1)-O(9) bond length is 2.09 Å. In the second Zr site, Zr(2) is bonded to one O(1), one O(11), one O(17), one O(22), one O(23), and one O(4) atom to form ZrO6 octahedra that share  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra,  a cornercorner with one P(5)O4 tetrahedra, and  a cornercorner with one P(6)O4 tetrahedra. The Zr(2)-O(1) bond length is 2.18 Å. The Zr(2)-O(11) bond length is 2.14 Å. The Zr(2)-O(17) bond length is 2.10 Å. The Zr(2)-O(22) bond length is 2.20 Å. The Zr(2)-O(23) bond length is 2.09 Å. The Zr(2)-O(4) bond length is 2.09 Å. In the third Zr site, Zr(3) is bonded to one O(12), one O(15), one O(16), one O(19), one O(5), and one O(8) atom to form ZrO6 octahedra that share  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra,  a cornercorner with one P(5)O4 tetrahedra, and  a cornercorner with one P(6)O4 tetrahedra. The Zr(3)-O(12) bond length is 2.14 Å. The Zr(3)-O(15) bond length is 2.08 Å. The Zr(3)-O(16) bond length is 2.08 Å. The Zr(3)-O(19) bond length is 2.17 Å. The Zr(3)-O(5) bond length is 2.07 Å. The Zr(3)-O(8) bond length is 2.16 Å. In the fourth Zr site, Zr(4) is bonded to one O(14), one O(2), one O(21), one O(24), one O(3), and one O(7) atom to form ZrO6 octahedra that share  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra,  a cornercorner with one P(5)O4 tetrahedra, and  a cornercorner with one P(6)O4 tetrahedra. The Zr(4)-O(14) bond length is 2.20 Å. The Zr(4)-O(2) bond length is 2.07 Å. The Zr(4)-O(21) bond length is 2.07 Å. The Zr(4)-O(24) bond length is 2.07 Å. The Zr(4)-O(3) bond length is 2.09 Å. The Zr(4)-O(7) bond length is 2.16 Å. There are six inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(15), one O(2), and one O(6) atom to form PO4 tetrahedra that share  a cornercorner with one Zr(1)O6 octahedra,  a cornercorner with one Zr(2)O6 octahedra,  a cornercorner with one Zr(3)O6 octahedra, and  a cornercorner with one Zr(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 21-42°. The P(1)-O(1) bond length is 1.55 Å. The P(1)-O(15) bond length is 1.54 Å. The P(1)-O(2) bond length is 1.55 Å. The P(1)-O(6) bond length is 1.55 Å. In the second P site, P(2) is bonded to one O(20), one O(4), one O(7), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one Zr(1)O6 octahedra,  a cornercorner with one Zr(2)O6 octahedra,  a cornercorner with one Zr(3)O6 octahedra, and  a cornercorner with one Zr(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 18-45°. The P(2)-O(20) bond length is 1.55 Å. The P(2)-O(4) bond length is 1.53 Å. The P(2)-O(7) bond length is 1.56 Å. The P(2)-O(8) bond length is 1.55 Å. In the third P site, P(3) is bonded to one O(11), one O(12), one O(3), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one Zr(1)O6 octahedra,  a cornercorner with one Zr(2)O6 octahedra,  a cornercorner with one Zr(3)O6 octahedra, and  a cornercorner with one Zr(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 19-41°. The P(3)-O(11) bond length is 1.56 Å. The P(3)-O(12) bond length is 1.56 Å. The P(3)-O(3) bond length is 1.54 Å. The P(3)-O(9) bond length is 1.53 Å. In the fourth P site, P(4) is bonded to one O(13), one O(14), one O(16), and one O(22) atom to form PO4 tetrahedra that share  a cornercorner with one Zr(1)O6 octahedra,  a cornercorner with one Zr(2)O6 octahedra,  a cornercorner with one Zr(3)O6 octahedra, and  a cornercorner with one Zr(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 19-44°. The P(4)-O(13) bond length is 1.56 Å. The P(4)-O(14) bond length is 1.55 Å. The P(4)-O(16) bond length is 1.54 Å. The P(4)-O(22) bond length is 1.56 Å. In the fifth P site, P(5) is bonded to one O(17), one O(18), one O(21), and one O(5) atom to form PO4 tetrahedra that share  a cornercorner with one Zr(1)O6 octahedra,  a cornercorner with one Zr(2)O6 octahedra,  a cornercorner with one Zr(3)O6 octahedra, and  a cornercorner with one Zr(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 17-45°. The P(5)-O(17) bond length is 1.54 Å. The P(5)-O(18) bond length is 1.56 Å. The P(5)-O(21) bond length is 1.54 Å. The P(5)-O(5) bond length is 1.54 Å. In the sixth P site, P(6) is bonded to one O(10), one O(19), one O(23), and one O(24) atom to form PO4 tetrahedra that share  a cornercorner with one Zr(1)O6 octahedra,  a cornercorner with one Zr(2)O6 octahedra,  a cornercorner with one Zr(3)O6 octahedra, and  a cornercorner with one Zr(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 22-42°. The P(6)-O(10) bond length is 1.54 Å. The P(6)-O(19) bond length is 1.56 Å. The P(6)-O(23) bond length is 1.54 Å. The P(6)-O(24) bond length is 1.54 Å. There are twenty-four inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one Li(3), one Zr(2), and one P(1) atom. In the second O site, O(2) is bonded in a bent 150 degrees geometry to one Zr(4) and one P(1) atom. In the third O site, O(3) is bonded in a bent 150 degrees geometry to one Zr(4) and one P(3) atom. In the fourth O site, O(4) is bonded in a bent 150 degrees geometry to one Zr(2) and one P(2) atom. In the fifth O site, O(5) is bonded in a bent 150 degrees geometry to one Zr(3) and one P(5) atom. In the sixth O site, O(6) is bonded in a distorted trigonal planar geometry to one Li(1), one Zr(1), and one P(1) atom. In the seventh O site, O(7) is bonded in a distorted trigonal planar geometry to one Li(3), one Zr(4), and one P(2) atom. In the eighth O site, O(8) is bonded in a distorted trigonal planar geometry to one Li(2), one Zr(3), and one P(2) atom. In the ninth O site, O(9) is bonded in a bent 150 degrees geometry to one Zr(1) and one P(3) atom. In the tenth O site, O(10) is bonded in a bent 150 degrees geometry to one Zr(1) and one P(6) atom. In the eleventh O site, O(11) is bonded in a 3-coordinate geometry to one Li(1), one Zr(2), and one P(3) atom. In the twelfth O site, O(12) is bonded in a 3-coordinate geometry to one Li(1), one Zr(3), and one P(3) atom. In the thirteenth O site, O(13) is bonded in a 3-coordinate geometry to one Li(2), one Zr(1), and one P(4) atom. In the fourteenth O site, O(14) is bonded in a 3-coordinate geometry to one Li(2), one Zr(4), and one P(4) atom. In the fifteenth O site, O(15) is bonded in a bent 150 degrees geometry to one Zr(3) and one P(1) atom. In the sixteenth O site, O(16) is bonded in a bent 150 degrees geometry to one Zr(3) and one P(4) atom. In the seventeenth O site, O(17) is bonded in a bent 150 degrees geometry to one Zr(2) and one P(5) atom. In the eighteenth O site, O(18) is bonded in a distorted trigonal planar geometry to one Li(1), one Zr(1), and one P(5) atom. In the nineteenth O site, O(19) is bonded in a distorted trigonal planar geometry to one Li(2), one Zr(3), and one P(6) atom. In the twentieth O site, O(20) is bonded in a 3-coordinate geometry to one Li(3), one Zr(1), and one P(2) atom. In the twenty-first O site, O(21) is bonded in a linear geometry to one Zr(4) and one P(5) atom. In the twenty-second O site, O(22) is bonded in a distorted trigonal planar geometry to one Li(3), one Zr(2), and one P(4) atom. In the twenty-third O site, O(23) is bonded in a bent 150 degrees geometry to one Zr(2) and one P(6) atom. In the twenty-fourth O site, O(24) is bonded in a bent 150 degrees geometry to one Zr(4) and one P(6) atom.