Li3Nb2CrO6 is Caswellsilverite-derived structured and crystallizes in the monoclinic C2/m space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent O(2) and four equivalent O(3) atoms to form LiO6 octahedra that share corners with two equivalent Nb(1)O6 octahedra, corners with four equivalent Cr(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Cr(1)O6 octahedra, edges with four equivalent Li(2)O6 octahedra, and edges with four equivalent Nb(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 9-10°. In the second Li site, Li(2) is bonded to one O(3), two equivalent O(2), and three equivalent O(1) atoms to form distorted LiO6 octahedra that share  a cornercorner with one Cr(1)O6 octahedra, corners with five equivalent Nb(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Cr(1)O6 octahedra, edges with four equivalent Li(2)O6 octahedra, and edges with four equivalent Nb(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-8°. Nb(1) is bonded to one O(3), two equivalent O(1), and three equivalent O(2) atoms to form NbO6 octahedra that share  a cornercorner with one Li(1)O6 octahedra, corners with five equivalent Li(2)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Cr(1)O6 octahedra, edges with four equivalent Li(2)O6 octahedra, and edges with four equivalent Nb(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 6-10°. Cr(1) is bonded to two equivalent O(1) and four equivalent O(3) atoms to form CrO6 octahedra that share corners with two equivalent Li(2)O6 octahedra, corners with four equivalent Li(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Cr(1)O6 octahedra, edges with four equivalent Li(2)O6 octahedra, and edges with four equivalent Nb(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-9°. There are three inequivalent O sites. In the first O site, O(1) is bonded to three equivalent Li(2), two equivalent Nb(1), and one Cr(1) atom to form OLi3Nb2Cr octahedra that share  a cornercorner with one O(1)Li3Nb2Cr octahedra,  a cornercorner with one O(3)Li3NbCr2 octahedra, corners with four equivalent O(2)Li3Nb3 octahedra, edges with four equivalent O(1)Li3Nb2Cr octahedra, edges with four equivalent O(2)Li3Nb3 octahedra, and edges with four equivalent O(3)Li3NbCr2 octahedra. The corner-sharing octahedral tilt angles range from 0-15°. In the second O site, O(2) is bonded to one Li(1), two equivalent Li(2), and three equivalent Nb(1) atoms to form OLi3Nb3 octahedra that share  a cornercorner with one O(2)Li3Nb3 octahedra,  a cornercorner with one O(3)Li3NbCr2 octahedra, corners with four equivalent O(1)Li3Nb2Cr octahedra, edges with four equivalent O(1)Li3Nb2Cr octahedra, edges with four equivalent O(2)Li3Nb3 octahedra, and edges with four equivalent O(3)Li3NbCr2 octahedra. The corner-sharing octahedral tilt angles range from 0-15°. In the third O site, O(3) is bonded to one Li(2), two equivalent Li(1), one Nb(1), and two equivalent Cr(1) atoms to form OLi3NbCr2 octahedra that share  a cornercorner with one O(1)Li3Nb2Cr octahedra,  a cornercorner with one O(2)Li3Nb3 octahedra, corners with four equivalent O(3)Li3NbCr2 octahedra, edges with four equivalent O(1)Li3Nb2Cr octahedra, edges with four equivalent O(2)Li3Nb3 octahedra, and edges with four equivalent O(3)Li3NbCr2 octahedra. The corner-sharing octahedral tilt angles range from 0-12°.
Li3Nb2CrO6 is Caswellsilverite-derived structured and crystallizes in the monoclinic C2/m space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent O(2) and four equivalent O(3) atoms to form LiO6 octahedra that share corners with two equivalent Nb(1)O6 octahedra, corners with four equivalent Cr(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Cr(1)O6 octahedra, edges with four equivalent Li(2)O6 octahedra, and edges with four equivalent Nb(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 9-10°. Both Li(1)-O(2) bond lengths are 2.06 Å. All Li(1)-O(3) bond lengths are 2.23 Å. In the second Li site, Li(2) is bonded to one O(3), two equivalent O(2), and three equivalent O(1) atoms to form distorted LiO6 octahedra that share  a cornercorner with one Cr(1)O6 octahedra, corners with five equivalent Nb(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Cr(1)O6 octahedra, edges with four equivalent Li(2)O6 octahedra, and edges with four equivalent Nb(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-8°. The Li(2)-O(3) bond length is 2.16 Å. Both Li(2)-O(2) bond lengths are 2.07 Å. There are two shorter (2.12 Å) and one longer (2.54 Å) Li(2)-O(1) bond length. Nb(1) is bonded to one O(3), two equivalent O(1), and three equivalent O(2) atoms to form NbO6 octahedra that share  a cornercorner with one Li(1)O6 octahedra, corners with five equivalent Li(2)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Cr(1)O6 octahedra, edges with four equivalent Li(2)O6 octahedra, and edges with four equivalent Nb(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 6-10°. The Nb(1)-O(3) bond length is 2.19 Å. Both Nb(1)-O(1) bond lengths are 2.16 Å. There are two shorter (2.18 Å) and one longer (2.23 Å) Nb(1)-O(2) bond length. Cr(1) is bonded to two equivalent O(1) and four equivalent O(3) atoms to form CrO6 octahedra that share corners with two equivalent Li(2)O6 octahedra, corners with four equivalent Li(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Cr(1)O6 octahedra, edges with four equivalent Li(2)O6 octahedra, and edges with four equivalent Nb(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-9°. Both Cr(1)-O(1) bond lengths are 2.05 Å. All Cr(1)-O(3) bond lengths are 2.03 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded to three equivalent Li(2), two equivalent Nb(1), and one Cr(1) atom to form OLi3Nb2Cr octahedra that share  a cornercorner with one O(1)Li3Nb2Cr octahedra,  a cornercorner with one O(3)Li3NbCr2 octahedra, corners with four equivalent O(2)Li3Nb3 octahedra, edges with four equivalent O(1)Li3Nb2Cr octahedra, edges with four equivalent O(2)Li3Nb3 octahedra, and edges with four equivalent O(3)Li3NbCr2 octahedra. The corner-sharing octahedral tilt angles range from 0-15°. In the second O site, O(2) is bonded to one Li(1), two equivalent Li(2), and three equivalent Nb(1) atoms to form OLi3Nb3 octahedra that share  a cornercorner with one O(2)Li3Nb3 octahedra,  a cornercorner with one O(3)Li3NbCr2 octahedra, corners with four equivalent O(1)Li3Nb2Cr octahedra, edges with four equivalent O(1)Li3Nb2Cr octahedra, edges with four equivalent O(2)Li3Nb3 octahedra, and edges with four equivalent O(3)Li3NbCr2 octahedra. The corner-sharing octahedral tilt angles range from 0-15°. In the third O site, O(3) is bonded to one Li(2), two equivalent Li(1), one Nb(1), and two equivalent Cr(1) atoms to form OLi3NbCr2 octahedra that share  a cornercorner with one O(1)Li3Nb2Cr octahedra,  a cornercorner with one O(2)Li3Nb3 octahedra, corners with four equivalent O(3)Li3NbCr2 octahedra, edges with four equivalent O(1)Li3Nb2Cr octahedra, edges with four equivalent O(2)Li3Nb3 octahedra, and edges with four equivalent O(3)Li3NbCr2 octahedra. The corner-sharing octahedral tilt angles range from 0-12°.