Li4Ni(BO3)2 crystallizes in the monoclinic P2_1 space group. There are eight inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(2); one O(5); one O(6); and two O(3,3) atoms to form distorted LiO5 trigonal bipyramids that share corners with two Li(4,4)O4 tetrahedra; corners with two equivalent Li(1)O5 trigonal bipyramids; edges with two Ni(1,1)O6 octahedra; and  an edgeedge with one Li(2)O5 trigonal bipyramid. In the second Li site, Li(1) is bonded to one O(2); one O(5); one O(6); and two O(3,3) atoms to form distorted LiO5 trigonal bipyramids that share corners with two Li(4,4)O4 tetrahedra; corners with two equivalent Li(1)O5 trigonal bipyramids; edges with two Ni(1,1)O6 octahedra; and  an edgeedge with one Li(2)O5 trigonal bipyramid. In the third Li site, Li(2) is bonded to one O(1); one O(5); one O(6); and two O(4,4) atoms to form distorted LiO5 trigonal bipyramids that share  a cornercorner with one Li(4)O4 tetrahedra; corners with two equivalent Li(2)O5 trigonal bipyramids; edges with two Ni(1,1)O6 octahedra; edges with two Li(4,4)O4 tetrahedra; and  an edgeedge with one Li(1)O5 trigonal bipyramid. In the fourth Li site, Li(2) is bonded to one O(1); one O(5); one O(6); and two O(4,4) atoms to form distorted LiO5 trigonal bipyramids that share  a cornercorner with one Li(4)O4 tetrahedra; corners with two equivalent Li(2)O5 trigonal bipyramids; edges with two Ni(1,1)O6 octahedra; edges with two Li(4,4)O4 tetrahedra; and  an edgeedge with one Li(1)O5 trigonal bipyramid. In the fifth Li site, Li(3) is bonded in a 4-coordinate geometry to one O(2); one O(3); and two O(5,5) atoms. In the sixth Li site, Li(3) is bonded in a 4-coordinate geometry to one O(2); one O(3); and two O(5,5) atoms. In the seventh Li site, Li(4) is bonded to one O(1); one O(4); and two O(6,6) atoms to form distorted LiO4 tetrahedra that share corners with three Ni(1,1)O6 octahedra; corners with two equivalent Li(4)O4 tetrahedra;  a cornercorner with one Li(2)O5 trigonal bipyramid; corners with two Li(1,1)O5 trigonal bipyramids; and edges with two Li(2,2)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 22-77°. In the eighth Li site, Li(4) is bonded to one O(1); one O(4); and two O(6,6) atoms to form distorted LiO4 tetrahedra that share corners with three Ni(1,1)O6 octahedra; corners with two equivalent Li(4)O4 tetrahedra;  a cornercorner with one Li(2)O5 trigonal bipyramid; corners with two Li(1,1)O5 trigonal bipyramids; and edges with two Li(2,2)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 22-77°. There are two inequivalent Ni sites. In the first Ni site, Ni(1) is bonded to one O(3); one O(4); two O(1,1); and two O(2,2) atoms to form NiO6 octahedra that share corners with three Li(4,4)O4 tetrahedra; edges with two equivalent Ni(1)O6 octahedra; edges with two Li(1,1)O5 trigonal bipyramids; and edges with two Li(2,2)O5 trigonal bipyramids. In the second Ni site, Ni(1) is bonded to one O(3); one O(4); two O(1,1); and two O(2,2) atoms to form NiO6 octahedra that share corners with three Li(4,4)O4 tetrahedra; edges with two equivalent Ni(1)O6 octahedra; edges with two Li(1,1)O5 trigonal bipyramids; and edges with two Li(2,2)O5 trigonal bipyramids. There are four inequivalent B sites. In the first B site, B(1) is bonded in a trigonal planar geometry to one O(1), one O(4), and one O(5) atom. In the second B site, B(1) is bonded in a trigonal planar geometry to one O(1), one O(4), and one O(5) atom. In the third B site, B(2) is bonded in a trigonal planar geometry to one O(2), one O(3), and one O(6) atom. In the fourth B site, B(2) is bonded in a trigonal planar geometry to one O(2), one O(3), and one O(6) atom. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a 5-coordinate geometry to one Li(2); one Li(4); two Ni(1,1); and one B(1) atom. In the second O site, O(1) is bonded in a 5-coordinate geometry to one Li(2); one Li(4); two Ni(1,1); and one B(1) atom. In the third O site, O(2) is bonded in a 5-coordinate geometry to one Li(1); one Li(3); two Ni(1,1); and one B(2) atom. In the fourth O site, O(2) is bonded in a 5-coordinate geometry to one Li(1); one Li(3); two Ni(1,1); and one B(2) atom. In the fifth O site, O(3) is bonded in a 5-coordinate geometry to one Li(3); two Li(1,1); one Ni(1); and one B(2) atom. In the sixth O site, O(3) is bonded in a 5-coordinate geometry to one Li(3); two Li(1,1); one Ni(1); and one B(2) atom. In the seventh O site, O(4) is bonded in a 5-coordinate geometry to one Li(4); two Li(2,2); one Ni(1); and one B(1) atom. In the eighth O site, O(4) is bonded in a 5-coordinate geometry to one Li(4); two Li(2,2); one Ni(1); and one B(1) atom. In the ninth O site, O(5) is bonded to one Li(1); one Li(2); two Li(3,3); and one B(1) atom to form a mixture of distorted edge and corner-sharing OLi4B trigonal bipyramids. In the tenth O site, O(5) is bonded to one Li(1); one Li(2); two Li(3,3); and one B(1) atom to form a mixture of distorted edge and corner-sharing OLi4B trigonal bipyramids. In the eleventh O site, O(6) is bonded to one Li(1); one Li(2); two Li(4,4); and one B(2) atom to form a mixture of distorted edge and corner-sharing OLi4B trigonal bipyramids. In the twelfth O site, O(6) is bonded to one Li(1); one Li(2); two Li(4,4); and one B(2) atom to form a mixture of distorted edge and corner-sharing OLi4B trigonal bipyramids.
Li4Ni(BO3)2 crystallizes in the monoclinic P2_1 space group. There are eight inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(2); one O(5); one O(6); and two O(3,3) atoms to form distorted LiO5 trigonal bipyramids that share corners with two Li(4,4)O4 tetrahedra; corners with two equivalent Li(1)O5 trigonal bipyramids; edges with two Ni(1,1)O6 octahedra; and  an edgeedge with one Li(2)O5 trigonal bipyramid. The Li(1)-O(2) bond length is 2.32 Å. The Li(1)-O(5) bond length is 2.08 Å. The Li(1)-O(6) bond length is 1.91 Å. Both Li(1)-O(3,3) bond lengths are 1.97 Å. In the second Li site, Li(1) is bonded to one O(2); one O(5); one O(6); and two O(3,3) atoms to form distorted LiO5 trigonal bipyramids that share corners with two Li(4,4)O4 tetrahedra; corners with two equivalent Li(1)O5 trigonal bipyramids; edges with two Ni(1,1)O6 octahedra; and  an edgeedge with one Li(2)O5 trigonal bipyramid. The Li(1)-O(2) bond length is 2.32 Å. The Li(1)-O(5) bond length is 2.08 Å. The Li(1)-O(6) bond length is 1.91 Å. Both Li(1)-O(3,3) bond lengths are 1.97 Å. In the third Li site, Li(2) is bonded to one O(1); one O(5); one O(6); and two O(4,4) atoms to form distorted LiO5 trigonal bipyramids that share  a cornercorner with one Li(4)O4 tetrahedra; corners with two equivalent Li(2)O5 trigonal bipyramids; edges with two Ni(1,1)O6 octahedra; edges with two Li(4,4)O4 tetrahedra; and  an edgeedge with one Li(1)O5 trigonal bipyramid. The Li(2)-O(1) bond length is 2.32 Å. The Li(2)-O(5) bond length is 1.92 Å. The Li(2)-O(6) bond length is 2.08 Å. Both Li(2)-O(4,4) bond lengths are 1.97 Å. In the fourth Li site, Li(2) is bonded to one O(1); one O(5); one O(6); and two O(4,4) atoms to form distorted LiO5 trigonal bipyramids that share  a cornercorner with one Li(4)O4 tetrahedra; corners with two equivalent Li(2)O5 trigonal bipyramids; edges with two Ni(1,1)O6 octahedra; edges with two Li(4,4)O4 tetrahedra; and  an edgeedge with one Li(1)O5 trigonal bipyramid. The Li(2)-O(1) bond length is 2.32 Å. The Li(2)-O(5) bond length is 1.91 Å. The Li(2)-O(6) bond length is 2.08 Å. Both Li(2)-O(4,4) bond lengths are 1.97 Å. In the fifth Li site, Li(3) is bonded in a 4-coordinate geometry to one O(2); one O(3); and two O(5,5) atoms. The Li(3)-O(2) bond length is 1.92 Å. The Li(3)-O(3) bond length is 2.02 Å. Both Li(3)-O(5,5) bond lengths are 1.90 Å. In the sixth Li site, Li(3) is bonded in a 4-coordinate geometry to one O(2); one O(3); and two O(5,5) atoms. The Li(3)-O(2) bond length is 1.92 Å. The Li(3)-O(3) bond length is 2.02 Å. There is one shorter (1.89 Å) and one longer (1.90 Å) Li(3)-O(5,5) bond length. In the seventh Li site, Li(4) is bonded to one O(1); one O(4); and two O(6,6) atoms to form distorted LiO4 tetrahedra that share corners with three Ni(1,1)O6 octahedra; corners with two equivalent Li(4)O4 tetrahedra;  a cornercorner with one Li(2)O5 trigonal bipyramid; corners with two Li(1,1)O5 trigonal bipyramids; and edges with two Li(2,2)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 22-77°. The Li(4)-O(1) bond length is 1.92 Å. The Li(4)-O(4) bond length is 2.02 Å. Both Li(4)-O(6,6) bond lengths are 1.89 Å. In the eighth Li site, Li(4) is bonded to one O(1); one O(4); and two O(6,6) atoms to form distorted LiO4 tetrahedra that share corners with three Ni(1,1)O6 octahedra; corners with two equivalent Li(4)O4 tetrahedra;  a cornercorner with one Li(2)O5 trigonal bipyramid; corners with two Li(1,1)O5 trigonal bipyramids; and edges with two Li(2,2)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 22-77°. The Li(4)-O(1) bond length is 1.92 Å. The Li(4)-O(4) bond length is 2.01 Å. Both Li(4)-O(6,6) bond lengths are 1.89 Å. There are two inequivalent Ni sites. In the first Ni site, Ni(1) is bonded to one O(3); one O(4); two O(1,1); and two O(2,2) atoms to form NiO6 octahedra that share corners with three Li(4,4)O4 tetrahedra; edges with two equivalent Ni(1)O6 octahedra; edges with two Li(1,1)O5 trigonal bipyramids; and edges with two Li(2,2)O5 trigonal bipyramids. The Ni(1)-O(3) bond length is 2.46 Å. The Ni(1)-O(4) bond length is 2.47 Å. Both Ni(1)-O(1,1) bond lengths are 2.12 Å. Both Ni(1)-O(2,2) bond lengths are 2.12 Å. In the second Ni site, Ni(1) is bonded to one O(3); one O(4); two O(1,1); and two O(2,2) atoms to form NiO6 octahedra that share corners with three Li(4,4)O4 tetrahedra; edges with two equivalent Ni(1)O6 octahedra; edges with two Li(1,1)O5 trigonal bipyramids; and edges with two Li(2,2)O5 trigonal bipyramids. The Ni(1)-O(3) bond length is 2.46 Å. The Ni(1)-O(4) bond length is 2.46 Å. Both Ni(1)-O(1,1) bond lengths are 2.12 Å. Both Ni(1)-O(2,2) bond lengths are 2.12 Å. There are four inequivalent B sites. In the first B site, B(1) is bonded in a trigonal planar geometry to one O(1), one O(4), and one O(5) atom. The B(1)-O(1) bond length is 1.43 Å. The B(1)-O(4) bond length is 1.39 Å. The B(1)-O(5) bond length is 1.36 Å. In the second B site, B(1) is bonded in a trigonal planar geometry to one O(1), one O(4), and one O(5) atom. The B(1)-O(1) bond length is 1.43 Å. The B(1)-O(4) bond length is 1.39 Å. The B(1)-O(5) bond length is 1.36 Å. In the third B site, B(2) is bonded in a trigonal planar geometry to one O(2), one O(3), and one O(6) atom. The B(2)-O(2) bond length is 1.43 Å. The B(2)-O(3) bond length is 1.39 Å. The B(2)-O(6) bond length is 1.36 Å. In the fourth B site, B(2) is bonded in a trigonal planar geometry to one O(2), one O(3), and one O(6) atom. The B(2)-O(2) bond length is 1.43 Å. The B(2)-O(3) bond length is 1.39 Å. The B(2)-O(6) bond length is 1.36 Å. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a 5-coordinate geometry to one Li(2); one Li(4); two Ni(1,1); and one B(1) atom. In the second O site, O(1) is bonded in a 5-coordinate geometry to one Li(2); one Li(4); two Ni(1,1); and one B(1) atom. In the third O site, O(2) is bonded in a 5-coordinate geometry to one Li(1); one Li(3); two Ni(1,1); and one B(2) atom. In the fourth O site, O(2) is bonded in a 5-coordinate geometry to one Li(1); one Li(3); two Ni(1,1); and one B(2) atom. In the fifth O site, O(3) is bonded in a 5-coordinate geometry to one Li(3); two Li(1,1); one Ni(1); and one B(2) atom. In the sixth O site, O(3) is bonded in a 5-coordinate geometry to one Li(3); two Li(1,1); one Ni(1); and one B(2) atom. In the seventh O site, O(4) is bonded in a 5-coordinate geometry to one Li(4); two Li(2,2); one Ni(1); and one B(1) atom. In the eighth O site, O(4) is bonded in a 5-coordinate geometry to one Li(4); two Li(2,2); one Ni(1); and one B(1) atom. In the ninth O site, O(5) is bonded to one Li(1); one Li(2); two Li(3,3); and one B(1) atom to form a mixture of distorted edge and corner-sharing OLi4B trigonal bipyramids. In the tenth O site, O(5) is bonded to one Li(1); one Li(2); two Li(3,3); and one B(1) atom to form a mixture of distorted edge and corner-sharing OLi4B trigonal bipyramids. In the eleventh O site, O(6) is bonded to one Li(1); one Li(2); two Li(4,4); and one B(2) atom to form a mixture of distorted edge and corner-sharing OLi4B trigonal bipyramids. In the twelfth O site, O(6) is bonded to one Li(1); one Li(2); two Li(4,4); and one B(2) atom to form a mixture of distorted edge and corner-sharing OLi4B trigonal bipyramids.