Li3Ni3(PO4)4 crystallizes in the monoclinic P2_1 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(11), one O(12), one O(13), one O(4), and one O(8) atom to form distorted LiO5 trigonal bipyramids that share  a cornercorner with one Ni(3)O6 octahedra,  a cornercorner with one P(2)O4 tetrahedra, corners with two equivalent P(3)O4 tetrahedra,  an edgeedge with one Ni(2)O6 octahedra,  an edgeedge with one P(4)O4 tetrahedra, and  an edgeedge with one Li(3)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles are 56°. In the second Li site, Li(2) is bonded to one O(10), one O(15), one O(2), one O(5), and one O(6) atom to form distorted LiO5 trigonal bipyramids that share  a cornercorner with one Ni(3)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra,  an edgeedge with one Ni(3)O6 octahedra,  an edgeedge with one P(1)O4 tetrahedra, and  an edgeedge with one Ni(1)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles are 55°. In the third Li site, Li(3) is bonded to one O(1), one O(12), one O(16), one O(3), and one O(4) atom to form distorted LiO5 trigonal bipyramids that share  a cornercorner with one Ni(2)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra,  an edgeedge with one Ni(2)O6 octahedra,  an edgeedge with one P(2)O4 tetrahedra, and  an edgeedge with one Li(1)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles are 57°. There are three inequivalent Ni sites. In the first Ni site, Ni(1) is bonded to one O(10), one O(14), one O(6), one O(7), and one O(9) atom to form distorted NiO5 trigonal bipyramids that share  a cornercorner with one Ni(2)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra, corners with two equivalent P(4)O4 tetrahedra,  an edgeedge with one Ni(3)O6 octahedra,  an edgeedge with one P(3)O4 tetrahedra, and  an edgeedge with one Li(2)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles are 53°. In the second Ni site, Ni(2) is bonded to one O(1), one O(11), one O(14), one O(16), one O(3), and one O(8) atom to form distorted NiO6 octahedra that share  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, corners with two equivalent P(3)O4 tetrahedra,  a cornercorner with one Li(3)O5 trigonal bipyramid,  a cornercorner with one Ni(1)O5 trigonal bipyramid,  an edgeedge with one Li(1)O5 trigonal bipyramid, and  an edgeedge with one Li(3)O5 trigonal bipyramid. In the third Ni site, Ni(3) is bonded to one O(13), one O(15), one O(2), one O(5), one O(7), and one O(9) atom to form NiO6 octahedra that share  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(4)O4 tetrahedra,  a cornercorner with one Li(1)O5 trigonal bipyramid,  a cornercorner with one Li(2)O5 trigonal bipyramid,  an edgeedge with one Li(2)O5 trigonal bipyramid, and  an edgeedge with one Ni(1)O5 trigonal bipyramid. There are four inequivalent P sites. In the first P site, P(1) is bonded to one O(15), one O(2), one O(3), and one O(6) atom to form PO4 tetrahedra that share  a cornercorner with one Ni(2)O6 octahedra, corners with two equivalent Ni(3)O6 octahedra,  a cornercorner with one Li(2)O5 trigonal bipyramid,  a cornercorner with one Li(3)O5 trigonal bipyramid,  a cornercorner with one Ni(1)O5 trigonal bipyramid, and  an edgeedge with one Li(2)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 39-51°. In the second P site, P(2) is bonded to one O(1), one O(16), one O(4), and one O(5) atom to form PO4 tetrahedra that share  a cornercorner with one Ni(3)O6 octahedra, corners with two equivalent Ni(2)O6 octahedra,  a cornercorner with one Li(1)O5 trigonal bipyramid,  a cornercorner with one Li(2)O5 trigonal bipyramid,  a cornercorner with one Li(3)O5 trigonal bipyramid, and  an edgeedge with one Li(3)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 44-54°. In the third P site, P(3) is bonded to one O(11), one O(12), one O(14), and one O(7) atom to form PO4 tetrahedra that share  a cornercorner with one Ni(3)O6 octahedra, corners with two equivalent Ni(2)O6 octahedra,  a cornercorner with one Li(3)O5 trigonal bipyramid, corners with two equivalent Li(1)O5 trigonal bipyramids, and  an edgeedge with one Ni(1)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 41-54°. In the fourth P site, P(4) is bonded to one O(10), one O(13), one O(8), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one Ni(2)O6 octahedra, corners with two equivalent Ni(3)O6 octahedra,  a cornercorner with one Li(2)O5 trigonal bipyramid, corners with two equivalent Ni(1)O5 trigonal bipyramids, and  an edgeedge with one Li(1)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 39-52°. There are sixteen inequivalent O sites. In the first O site, O(1) is bonded in a distorted T-shaped geometry to one Li(3), one Ni(2), and one P(2) atom. In the second O site, O(2) is bonded in a T-shaped geometry to one Li(2), one Ni(3), and one P(1) atom. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to one Li(3), one Ni(2), and one P(1) atom. In the fourth O site, O(4) is bonded in a distorted trigonal planar geometry to one Li(1), one Li(3), and one P(2) atom. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to one Li(2), one Ni(3), and one P(2) atom. In the sixth O site, O(6) is bonded in a distorted trigonal planar geometry to one Li(2), one Ni(1), and one P(1) atom. In the seventh O site, O(7) is bonded in a distorted T-shaped geometry to one Ni(1), one Ni(3), and one P(3) atom. In the eighth O site, O(8) is bonded in a distorted T-shaped geometry to one Li(1), one Ni(2), and one P(4) atom. In the ninth O site, O(9) is bonded in a 3-coordinate geometry to one Ni(1), one Ni(3), and one P(4) atom. In the tenth O site, O(10) is bonded in a distorted trigonal planar geometry to one Li(2), one Ni(1), and one P(4) atom. In the eleventh O site, O(11) is bonded in a distorted trigonal planar geometry to one Li(1), one Ni(2), and one P(3) atom. In the twelfth O site, O(12) is bonded in a distorted trigonal planar geometry to one Li(1), one Li(3), and one P(3) atom. In the thirteenth O site, O(13) is bonded in a 3-coordinate geometry to one Li(1), one Ni(3), and one P(4) atom. In the fourteenth O site, O(14) is bonded in a 3-coordinate geometry to one Ni(1), one Ni(2), and one P(3) atom. In the fifteenth O site, O(15) is bonded in a 3-coordinate geometry to one Li(2), one Ni(3), and one P(1) atom. In the sixteenth O site, O(16) is bonded in a distorted trigonal planar geometry to one Li(3), one Ni(2), and one P(2) atom.
Li3Ni3(PO4)4 crystallizes in the monoclinic P2_1 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(11), one O(12), one O(13), one O(4), and one O(8) atom to form distorted LiO5 trigonal bipyramids that share  a cornercorner with one Ni(3)O6 octahedra,  a cornercorner with one P(2)O4 tetrahedra, corners with two equivalent P(3)O4 tetrahedra,  an edgeedge with one Ni(2)O6 octahedra,  an edgeedge with one P(4)O4 tetrahedra, and  an edgeedge with one Li(3)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles are 56°. The Li(1)-O(11) bond length is 2.03 Å. The Li(1)-O(12) bond length is 1.88 Å. The Li(1)-O(13) bond length is 2.06 Å. The Li(1)-O(4) bond length is 1.90 Å. The Li(1)-O(8) bond length is 2.19 Å. In the second Li site, Li(2) is bonded to one O(10), one O(15), one O(2), one O(5), and one O(6) atom to form distorted LiO5 trigonal bipyramids that share  a cornercorner with one Ni(3)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra,  an edgeedge with one Ni(3)O6 octahedra,  an edgeedge with one P(1)O4 tetrahedra, and  an edgeedge with one Ni(1)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles are 55°. The Li(2)-O(10) bond length is 2.01 Å. The Li(2)-O(15) bond length is 2.10 Å. The Li(2)-O(2) bond length is 2.10 Å. The Li(2)-O(5) bond length is 2.00 Å. The Li(2)-O(6) bond length is 1.89 Å. In the third Li site, Li(3) is bonded to one O(1), one O(12), one O(16), one O(3), and one O(4) atom to form distorted LiO5 trigonal bipyramids that share  a cornercorner with one Ni(2)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra,  an edgeedge with one Ni(2)O6 octahedra,  an edgeedge with one P(2)O4 tetrahedra, and  an edgeedge with one Li(1)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles are 57°. The Li(3)-O(1) bond length is 2.21 Å. The Li(3)-O(12) bond length is 1.98 Å. The Li(3)-O(16) bond length is 2.04 Å. The Li(3)-O(3) bond length is 2.01 Å. The Li(3)-O(4) bond length is 1.86 Å. There are three inequivalent Ni sites. In the first Ni site, Ni(1) is bonded to one O(10), one O(14), one O(6), one O(7), and one O(9) atom to form distorted NiO5 trigonal bipyramids that share  a cornercorner with one Ni(2)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra, corners with two equivalent P(4)O4 tetrahedra,  an edgeedge with one Ni(3)O6 octahedra,  an edgeedge with one P(3)O4 tetrahedra, and  an edgeedge with one Li(2)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles are 53°. The Ni(1)-O(10) bond length is 1.86 Å. The Ni(1)-O(14) bond length is 1.85 Å. The Ni(1)-O(6) bond length is 1.92 Å. The Ni(1)-O(7) bond length is 1.90 Å. The Ni(1)-O(9) bond length is 2.10 Å. In the second Ni site, Ni(2) is bonded to one O(1), one O(11), one O(14), one O(16), one O(3), and one O(8) atom to form distorted NiO6 octahedra that share  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, corners with two equivalent P(3)O4 tetrahedra,  a cornercorner with one Li(3)O5 trigonal bipyramid,  a cornercorner with one Ni(1)O5 trigonal bipyramid,  an edgeedge with one Li(1)O5 trigonal bipyramid, and  an edgeedge with one Li(3)O5 trigonal bipyramid. The Ni(2)-O(1) bond length is 1.90 Å. The Ni(2)-O(11) bond length is 1.95 Å. The Ni(2)-O(14) bond length is 2.50 Å. The Ni(2)-O(16) bond length is 2.08 Å. The Ni(2)-O(3) bond length is 1.92 Å. The Ni(2)-O(8) bond length is 1.90 Å. In the third Ni site, Ni(3) is bonded to one O(13), one O(15), one O(2), one O(5), one O(7), and one O(9) atom to form NiO6 octahedra that share  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(4)O4 tetrahedra,  a cornercorner with one Li(1)O5 trigonal bipyramid,  a cornercorner with one Li(2)O5 trigonal bipyramid,  an edgeedge with one Li(2)O5 trigonal bipyramid, and  an edgeedge with one Ni(1)O5 trigonal bipyramid. The Ni(3)-O(13) bond length is 2.28 Å. The Ni(3)-O(15) bond length is 2.14 Å. The Ni(3)-O(2) bond length is 1.92 Å. The Ni(3)-O(5) bond length is 1.89 Å. The Ni(3)-O(7) bond length is 1.99 Å. The Ni(3)-O(9) bond length is 1.93 Å. There are four inequivalent P sites. In the first P site, P(1) is bonded to one O(15), one O(2), one O(3), and one O(6) atom to form PO4 tetrahedra that share  a cornercorner with one Ni(2)O6 octahedra, corners with two equivalent Ni(3)O6 octahedra,  a cornercorner with one Li(2)O5 trigonal bipyramid,  a cornercorner with one Li(3)O5 trigonal bipyramid,  a cornercorner with one Ni(1)O5 trigonal bipyramid, and  an edgeedge with one Li(2)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 39-51°. The P(1)-O(15) bond length is 1.54 Å. The P(1)-O(2) bond length is 1.56 Å. The P(1)-O(3) bond length is 1.57 Å. The P(1)-O(6) bond length is 1.55 Å. In the second P site, P(2) is bonded to one O(1), one O(16), one O(4), and one O(5) atom to form PO4 tetrahedra that share  a cornercorner with one Ni(3)O6 octahedra, corners with two equivalent Ni(2)O6 octahedra,  a cornercorner with one Li(1)O5 trigonal bipyramid,  a cornercorner with one Li(2)O5 trigonal bipyramid,  a cornercorner with one Li(3)O5 trigonal bipyramid, and  an edgeedge with one Li(3)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 44-54°. The P(2)-O(1) bond length is 1.58 Å. The P(2)-O(16) bond length is 1.56 Å. The P(2)-O(4) bond length is 1.50 Å. The P(2)-O(5) bond length is 1.58 Å. In the third P site, P(3) is bonded to one O(11), one O(12), one O(14), and one O(7) atom to form PO4 tetrahedra that share  a cornercorner with one Ni(3)O6 octahedra, corners with two equivalent Ni(2)O6 octahedra,  a cornercorner with one Li(3)O5 trigonal bipyramid, corners with two equivalent Li(1)O5 trigonal bipyramids, and  an edgeedge with one Ni(1)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 41-54°. The P(3)-O(11) bond length is 1.54 Å. The P(3)-O(12) bond length is 1.49 Å. The P(3)-O(14) bond length is 1.61 Å. The P(3)-O(7) bond length is 1.62 Å. In the fourth P site, P(4) is bonded to one O(10), one O(13), one O(8), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one Ni(2)O6 octahedra, corners with two equivalent Ni(3)O6 octahedra,  a cornercorner with one Li(2)O5 trigonal bipyramid, corners with two equivalent Ni(1)O5 trigonal bipyramids, and  an edgeedge with one Li(1)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 39-52°. The P(4)-O(10) bond length is 1.55 Å. The P(4)-O(13) bond length is 1.53 Å. The P(4)-O(8) bond length is 1.55 Å. The P(4)-O(9) bond length is 1.59 Å. There are sixteen inequivalent O sites. In the first O site, O(1) is bonded in a distorted T-shaped geometry to one Li(3), one Ni(2), and one P(2) atom. In the second O site, O(2) is bonded in a T-shaped geometry to one Li(2), one Ni(3), and one P(1) atom. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to one Li(3), one Ni(2), and one P(1) atom. In the fourth O site, O(4) is bonded in a distorted trigonal planar geometry to one Li(1), one Li(3), and one P(2) atom. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to one Li(2), one Ni(3), and one P(2) atom. In the sixth O site, O(6) is bonded in a distorted trigonal planar geometry to one Li(2), one Ni(1), and one P(1) atom. In the seventh O site, O(7) is bonded in a distorted T-shaped geometry to one Ni(1), one Ni(3), and one P(3) atom. In the eighth O site, O(8) is bonded in a distorted T-shaped geometry to one Li(1), one Ni(2), and one P(4) atom. In the ninth O site, O(9) is bonded in a 3-coordinate geometry to one Ni(1), one Ni(3), and one P(4) atom. In the tenth O site, O(10) is bonded in a distorted trigonal planar geometry to one Li(2), one Ni(1), and one P(4) atom. In the eleventh O site, O(11) is bonded in a distorted trigonal planar geometry to one Li(1), one Ni(2), and one P(3) atom. In the twelfth O site, O(12) is bonded in a distorted trigonal planar geometry to one Li(1), one Li(3), and one P(3) atom. In the thirteenth O site, O(13) is bonded in a 3-coordinate geometry to one Li(1), one Ni(3), and one P(4) atom. In the fourteenth O site, O(14) is bonded in a 3-coordinate geometry to one Ni(1), one Ni(2), and one P(3) atom. In the fifteenth O site, O(15) is bonded in a 3-coordinate geometry to one Li(2), one Ni(3), and one P(1) atom. In the sixteenth O site, O(16) is bonded in a distorted trigonal planar geometry to one Li(3), one Ni(2), and one P(2) atom.