Li3NbV2O6 is Caswellsilverite-derived structured and crystallizes in the triclinic P-1 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(3), one O(4), two equivalent O(5), and two equivalent O(6) atoms to form LiO6 octahedra that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one V(2)O6 octahedra, corners with four equivalent Nb(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Nb(1)O6 octahedra, edges with two equivalent V(1)O6 octahedra, and edges with two equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 1-8°. In the second Li site, Li(2) is bonded to one O(1), one O(3), one O(4), one O(5), and two equivalent O(2) atoms to form LiO6 octahedra that share  a cornercorner with one Nb(1)O6 octahedra,  a cornercorner with one V(1)O6 octahedra, corners with four equivalent V(2)O6 octahedra,  an edgeedge with one Li(2)O6 octahedra,  an edgeedge with one V(2)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Nb(1)O6 octahedra, edges with three equivalent Li(3)O6 octahedra, and edges with three equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-8°. In the third Li site, Li(3) is bonded to one O(2), one O(3), one O(4), one O(6), and two equivalent O(1) atoms to form LiO6 octahedra that share  a cornercorner with one Nb(1)O6 octahedra,  a cornercorner with one V(2)O6 octahedra, corners with four equivalent V(1)O6 octahedra,  an edgeedge with one Li(3)O6 octahedra,  an edgeedge with one V(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Nb(1)O6 octahedra, edges with three equivalent Li(2)O6 octahedra, and edges with three equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 1-7°. Nb(1) is bonded to one O(1), one O(2), two equivalent O(5), and two equivalent O(6) atoms to form NbO6 octahedra that share  a cornercorner with one Li(2)O6 octahedra,  a cornercorner with one Li(3)O6 octahedra, corners with four equivalent Li(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Nb(1)O6 octahedra, edges with two equivalent V(1)O6 octahedra, and edges with two equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 6-8°. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(2), one O(4), one O(5), and two equivalent O(3) atoms to form VO6 octahedra that share  a cornercorner with one Li(1)O6 octahedra,  a cornercorner with one Li(2)O6 octahedra, corners with four equivalent Li(3)O6 octahedra,  an edgeedge with one Li(3)O6 octahedra,  an edgeedge with one V(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Nb(1)O6 octahedra, edges with three equivalent Li(2)O6 octahedra, and edges with three equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 1-7°. In the second V site, V(2) is bonded to one O(1), one O(2), one O(3), one O(6), and two equivalent O(4) atoms to form VO6 octahedra that share  a cornercorner with one Li(1)O6 octahedra,  a cornercorner with one Li(3)O6 octahedra, corners with four equivalent Li(2)O6 octahedra,  an edgeedge with one Li(2)O6 octahedra,  an edgeedge with one V(2)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Nb(1)O6 octahedra, edges with three equivalent Li(3)O6 octahedra, and edges with three equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-7°. There are six inequivalent O sites. In the first O site, O(1) is bonded to one Li(2), two equivalent Li(3), one Nb(1), one V(1), and one V(2) atom to form OLi3NbV2 octahedra that share  a cornercorner with one O(6)Li3Nb2V octahedra,  a cornercorner with one O(2)Li3NbV2 octahedra, corners with four equivalent O(3)Li3V3 octahedra,  an edgeedge with one O(1)Li3NbV2 octahedra,  an edgeedge with one O(3)Li3V3 octahedra, edges with two equivalent O(5)Li3Nb2V octahedra, edges with two equivalent O(6)Li3Nb2V octahedra, edges with three equivalent O(2)Li3NbV2 octahedra, and edges with three equivalent O(4)Li3V3 octahedra. The corner-sharing octahedral tilt angles range from 2-11°. In the second O site, O(2) is bonded to one Li(3), two equivalent Li(2), one Nb(1), one V(1), and one V(2) atom to form OLi3NbV2 octahedra that share  a cornercorner with one O(5)Li3Nb2V octahedra,  a cornercorner with one O(1)Li3NbV2 octahedra, corners with four equivalent O(4)Li3V3 octahedra,  an edgeedge with one O(2)Li3NbV2 octahedra,  an edgeedge with one O(4)Li3V3 octahedra, edges with two equivalent O(5)Li3Nb2V octahedra, edges with two equivalent O(6)Li3Nb2V octahedra, edges with three equivalent O(1)Li3NbV2 octahedra, and edges with three equivalent O(3)Li3V3 octahedra. The corner-sharing octahedral tilt angles range from 1-11°. In the third O site, O(3) is bonded to one Li(1), one Li(2), one Li(3), one V(2), and two equivalent V(1) atoms to form OLi3V3 octahedra that share  a cornercorner with one O(5)Li3Nb2V octahedra,  a cornercorner with one O(4)Li3V3 octahedra, corners with four equivalent O(1)Li3NbV2 octahedra,  an edgeedge with one O(1)Li3NbV2 octahedra,  an edgeedge with one O(3)Li3V3 octahedra, edges with two equivalent O(5)Li3Nb2V octahedra, edges with two equivalent O(6)Li3Nb2V octahedra, edges with three equivalent O(2)Li3NbV2 octahedra, and edges with three equivalent O(4)Li3V3 octahedra. The corner-sharing octahedral tilt angles range from 1-6°. In the fourth O site, O(4) is bonded to one Li(1), one Li(2), one Li(3), one V(1), and two equivalent V(2) atoms to form OLi3V3 octahedra that share  a cornercorner with one O(6)Li3Nb2V octahedra,  a cornercorner with one O(3)Li3V3 octahedra, corners with four equivalent O(2)Li3NbV2 octahedra,  an edgeedge with one O(2)Li3NbV2 octahedra,  an edgeedge with one O(4)Li3V3 octahedra, edges with two equivalent O(5)Li3Nb2V octahedra, edges with two equivalent O(6)Li3Nb2V octahedra, edges with three equivalent O(1)Li3NbV2 octahedra, and edges with three equivalent O(3)Li3V3 octahedra. The corner-sharing octahedral tilt angles range from 1-5°. In the fifth O site, O(5) is bonded to one Li(2), two equivalent Li(1), two equivalent Nb(1), and one V(1) atom to form OLi3Nb2V octahedra that share  a cornercorner with one O(2)Li3NbV2 octahedra,  a cornercorner with one O(3)Li3V3 octahedra, corners with four equivalent O(6)Li3Nb2V octahedra, edges with two equivalent O(5)Li3Nb2V octahedra, edges with two equivalent O(6)Li3Nb2V octahedra, edges with two equivalent O(1)Li3NbV2 octahedra, edges with two equivalent O(2)Li3NbV2 octahedra, edges with two equivalent O(3)Li3V3 octahedra, and edges with two equivalent O(4)Li3V3 octahedra. The corner-sharing octahedral tilt angles range from 3-11°. In the sixth O site, O(6) is bonded to one Li(3), two equivalent Li(1), two equivalent Nb(1), and one V(2) atom to form OLi3Nb2V octahedra that share  a cornercorner with one O(1)Li3NbV2 octahedra,  a cornercorner with one O(4)Li3V3 octahedra, corners with four equivalent O(5)Li3Nb2V octahedra, edges with two equivalent O(5)Li3Nb2V octahedra, edges with two equivalent O(6)Li3Nb2V octahedra, edges with two equivalent O(1)Li3NbV2 octahedra, edges with two equivalent O(2)Li3NbV2 octahedra, edges with two equivalent O(3)Li3V3 octahedra, and edges with two equivalent O(4)Li3V3 octahedra. The corner-sharing octahedral tilt angles range from 3-11°.
Li3NbV2O6 is Caswellsilverite-derived structured and crystallizes in the triclinic P-1 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(3), one O(4), two equivalent O(5), and two equivalent O(6) atoms to form LiO6 octahedra that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one V(2)O6 octahedra, corners with four equivalent Nb(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Nb(1)O6 octahedra, edges with two equivalent V(1)O6 octahedra, and edges with two equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 1-8°. The Li(1)-O(3) bond length is 2.21 Å. The Li(1)-O(4) bond length is 2.19 Å. There is one shorter (2.18 Å) and one longer (2.23 Å) Li(1)-O(5) bond length. Both Li(1)-O(6) bond lengths are 2.08 Å. In the second Li site, Li(2) is bonded to one O(1), one O(3), one O(4), one O(5), and two equivalent O(2) atoms to form LiO6 octahedra that share  a cornercorner with one Nb(1)O6 octahedra,  a cornercorner with one V(1)O6 octahedra, corners with four equivalent V(2)O6 octahedra,  an edgeedge with one Li(2)O6 octahedra,  an edgeedge with one V(2)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Nb(1)O6 octahedra, edges with three equivalent Li(3)O6 octahedra, and edges with three equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-8°. The Li(2)-O(1) bond length is 2.20 Å. The Li(2)-O(3) bond length is 2.13 Å. The Li(2)-O(4) bond length is 2.14 Å. The Li(2)-O(5) bond length is 2.25 Å. There is one shorter (2.19 Å) and one longer (2.23 Å) Li(2)-O(2) bond length. In the third Li site, Li(3) is bonded to one O(2), one O(3), one O(4), one O(6), and two equivalent O(1) atoms to form LiO6 octahedra that share  a cornercorner with one Nb(1)O6 octahedra,  a cornercorner with one V(2)O6 octahedra, corners with four equivalent V(1)O6 octahedra,  an edgeedge with one Li(3)O6 octahedra,  an edgeedge with one V(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Nb(1)O6 octahedra, edges with three equivalent Li(2)O6 octahedra, and edges with three equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 1-7°. The Li(3)-O(2) bond length is 2.36 Å. The Li(3)-O(3) bond length is 2.12 Å. The Li(3)-O(4) bond length is 2.13 Å. The Li(3)-O(6) bond length is 2.14 Å. There is one shorter (2.13 Å) and one longer (2.29 Å) Li(3)-O(1) bond length. Nb(1) is bonded to one O(1), one O(2), two equivalent O(5), and two equivalent O(6) atoms to form NbO6 octahedra that share  a cornercorner with one Li(2)O6 octahedra,  a cornercorner with one Li(3)O6 octahedra, corners with four equivalent Li(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Nb(1)O6 octahedra, edges with two equivalent V(1)O6 octahedra, and edges with two equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 6-8°. The Nb(1)-O(1) bond length is 2.05 Å. The Nb(1)-O(2) bond length is 2.05 Å. Both Nb(1)-O(5) bond lengths are 2.21 Å. There is one shorter (2.12 Å) and one longer (2.13 Å) Nb(1)-O(6) bond length. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(2), one O(4), one O(5), and two equivalent O(3) atoms to form VO6 octahedra that share  a cornercorner with one Li(1)O6 octahedra,  a cornercorner with one Li(2)O6 octahedra, corners with four equivalent Li(3)O6 octahedra,  an edgeedge with one Li(3)O6 octahedra,  an edgeedge with one V(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Nb(1)O6 octahedra, edges with three equivalent Li(2)O6 octahedra, and edges with three equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 1-7°. The V(1)-O(1) bond length is 2.14 Å. The V(1)-O(2) bond length is 2.09 Å. The V(1)-O(4) bond length is 2.01 Å. The V(1)-O(5) bond length is 2.05 Å. There is one shorter (2.01 Å) and one longer (2.09 Å) V(1)-O(3) bond length. In the second V site, V(2) is bonded to one O(1), one O(2), one O(3), one O(6), and two equivalent O(4) atoms to form VO6 octahedra that share  a cornercorner with one Li(1)O6 octahedra,  a cornercorner with one Li(3)O6 octahedra, corners with four equivalent Li(2)O6 octahedra,  an edgeedge with one Li(2)O6 octahedra,  an edgeedge with one V(2)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Nb(1)O6 octahedra, edges with three equivalent Li(3)O6 octahedra, and edges with three equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-7°. The V(2)-O(1) bond length is 2.14 Å. The V(2)-O(2) bond length is 2.14 Å. The V(2)-O(3) bond length is 2.12 Å. The V(2)-O(6) bond length is 2.14 Å. There is one shorter (2.09 Å) and one longer (2.12 Å) V(2)-O(4) bond length. There are six inequivalent O sites. In the first O site, O(1) is bonded to one Li(2), two equivalent Li(3), one Nb(1), one V(1), and one V(2) atom to form OLi3NbV2 octahedra that share  a cornercorner with one O(6)Li3Nb2V octahedra,  a cornercorner with one O(2)Li3NbV2 octahedra, corners with four equivalent O(3)Li3V3 octahedra,  an edgeedge with one O(1)Li3NbV2 octahedra,  an edgeedge with one O(3)Li3V3 octahedra, edges with two equivalent O(5)Li3Nb2V octahedra, edges with two equivalent O(6)Li3Nb2V octahedra, edges with three equivalent O(2)Li3NbV2 octahedra, and edges with three equivalent O(4)Li3V3 octahedra. The corner-sharing octahedral tilt angles range from 2-11°. In the second O site, O(2) is bonded to one Li(3), two equivalent Li(2), one Nb(1), one V(1), and one V(2) atom to form OLi3NbV2 octahedra that share  a cornercorner with one O(5)Li3Nb2V octahedra,  a cornercorner with one O(1)Li3NbV2 octahedra, corners with four equivalent O(4)Li3V3 octahedra,  an edgeedge with one O(2)Li3NbV2 octahedra,  an edgeedge with one O(4)Li3V3 octahedra, edges with two equivalent O(5)Li3Nb2V octahedra, edges with two equivalent O(6)Li3Nb2V octahedra, edges with three equivalent O(1)Li3NbV2 octahedra, and edges with three equivalent O(3)Li3V3 octahedra. The corner-sharing octahedral tilt angles range from 1-11°. In the third O site, O(3) is bonded to one Li(1), one Li(2), one Li(3), one V(2), and two equivalent V(1) atoms to form OLi3V3 octahedra that share  a cornercorner with one O(5)Li3Nb2V octahedra,  a cornercorner with one O(4)Li3V3 octahedra, corners with four equivalent O(1)Li3NbV2 octahedra,  an edgeedge with one O(1)Li3NbV2 octahedra,  an edgeedge with one O(3)Li3V3 octahedra, edges with two equivalent O(5)Li3Nb2V octahedra, edges with two equivalent O(6)Li3Nb2V octahedra, edges with three equivalent O(2)Li3NbV2 octahedra, and edges with three equivalent O(4)Li3V3 octahedra. The corner-sharing octahedral tilt angles range from 1-6°. In the fourth O site, O(4) is bonded to one Li(1), one Li(2), one Li(3), one V(1), and two equivalent V(2) atoms to form OLi3V3 octahedra that share  a cornercorner with one O(6)Li3Nb2V octahedra,  a cornercorner with one O(3)Li3V3 octahedra, corners with four equivalent O(2)Li3NbV2 octahedra,  an edgeedge with one O(2)Li3NbV2 octahedra,  an edgeedge with one O(4)Li3V3 octahedra, edges with two equivalent O(5)Li3Nb2V octahedra, edges with two equivalent O(6)Li3Nb2V octahedra, edges with three equivalent O(1)Li3NbV2 octahedra, and edges with three equivalent O(3)Li3V3 octahedra. The corner-sharing octahedral tilt angles range from 1-5°. In the fifth O site, O(5) is bonded to one Li(2), two equivalent Li(1), two equivalent Nb(1), and one V(1) atom to form OLi3Nb2V octahedra that share  a cornercorner with one O(2)Li3NbV2 octahedra,  a cornercorner with one O(3)Li3V3 octahedra, corners with four equivalent O(6)Li3Nb2V octahedra, edges with two equivalent O(5)Li3Nb2V octahedra, edges with two equivalent O(6)Li3Nb2V octahedra, edges with two equivalent O(1)Li3NbV2 octahedra, edges with two equivalent O(2)Li3NbV2 octahedra, edges with two equivalent O(3)Li3V3 octahedra, and edges with two equivalent O(4)Li3V3 octahedra. The corner-sharing octahedral tilt angles range from 3-11°. In the sixth O site, O(6) is bonded to one Li(3), two equivalent Li(1), two equivalent Nb(1), and one V(2) atom to form OLi3Nb2V octahedra that share  a cornercorner with one O(1)Li3NbV2 octahedra,  a cornercorner with one O(4)Li3V3 octahedra, corners with four equivalent O(5)Li3Nb2V octahedra, edges with two equivalent O(5)Li3Nb2V octahedra, edges with two equivalent O(6)Li3Nb2V octahedra, edges with two equivalent O(1)Li3NbV2 octahedra, edges with two equivalent O(2)Li3NbV2 octahedra, edges with two equivalent O(3)Li3V3 octahedra, and edges with two equivalent O(4)Li3V3 octahedra. The corner-sharing octahedral tilt angles range from 3-11°.