LiNb(BO3)2 crystallizes in the monoclinic P2_1/c space group. Li(1) is bonded to one O(2), one O(4), and two equivalent O(3) atoms to form distorted LiO4 tetrahedra that share corners with two equivalent Nb(1)O6 octahedra,  an edgeedge with one Nb(1)O6 octahedra, and  an edgeedge with one Li(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 63-67°. Nb(1) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form distorted NbO6 octahedra that share corners with two equivalent Li(1)O4 tetrahedra and  an edgeedge with one Li(1)O4 tetrahedra. There are two inequivalent B sites. In the first B site, B(1) is bonded in a trigonal planar geometry to one O(2), one O(3), and one O(6) atom. In the second B site, B(2) is bonded in a trigonal planar geometry to one O(1), one O(4), and one O(5) atom. There are six inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to one Nb(1) and one B(2) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Li(1), one Nb(1), and one B(1) atom. In the third O site, O(3) is bonded in a 4-coordinate geometry to two equivalent Li(1), one Nb(1), and one B(1) atom. In the fourth O site, O(4) is bonded in a distorted trigonal planar geometry to one Li(1), one Nb(1), and one B(2) atom. In the fifth O site, O(5) is bonded in a distorted bent 150 degrees geometry to one Nb(1) and one B(2) atom. In the sixth O site, O(6) is bonded in an L-shaped geometry to one Nb(1) and one B(1) atom.
LiNb(BO3)2 crystallizes in the monoclinic P2_1/c space group. Li(1) is bonded to one O(2), one O(4), and two equivalent O(3) atoms to form distorted LiO4 tetrahedra that share corners with two equivalent Nb(1)O6 octahedra,  an edgeedge with one Nb(1)O6 octahedra, and  an edgeedge with one Li(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 63-67°. The Li(1)-O(2) bond length is 2.01 Å. The Li(1)-O(4) bond length is 2.06 Å. There is one shorter (1.98 Å) and one longer (2.09 Å) Li(1)-O(3) bond length. Nb(1) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form distorted NbO6 octahedra that share corners with two equivalent Li(1)O4 tetrahedra and  an edgeedge with one Li(1)O4 tetrahedra. The Nb(1)-O(1) bond length is 1.95 Å. The Nb(1)-O(2) bond length is 2.05 Å. The Nb(1)-O(3) bond length is 2.25 Å. The Nb(1)-O(4) bond length is 2.06 Å. The Nb(1)-O(5) bond length is 1.94 Å. The Nb(1)-O(6) bond length is 1.97 Å. There are two inequivalent B sites. In the first B site, B(1) is bonded in a trigonal planar geometry to one O(2), one O(3), and one O(6) atom. The B(1)-O(2) bond length is 1.38 Å. The B(1)-O(3) bond length is 1.37 Å. The B(1)-O(6) bond length is 1.42 Å. In the second B site, B(2) is bonded in a trigonal planar geometry to one O(1), one O(4), and one O(5) atom. The B(2)-O(1) bond length is 1.38 Å. The B(2)-O(4) bond length is 1.37 Å. The B(2)-O(5) bond length is 1.39 Å. There are six inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to one Nb(1) and one B(2) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Li(1), one Nb(1), and one B(1) atom. In the third O site, O(3) is bonded in a 4-coordinate geometry to two equivalent Li(1), one Nb(1), and one B(1) atom. In the fourth O site, O(4) is bonded in a distorted trigonal planar geometry to one Li(1), one Nb(1), and one B(2) atom. In the fifth O site, O(5) is bonded in a distorted bent 150 degrees geometry to one Nb(1) and one B(2) atom. In the sixth O site, O(6) is bonded in an L-shaped geometry to one Nb(1) and one B(1) atom.