NaBi3V2O10 crystallizes in the triclinic P1 space group. Na(1) is bonded in a 6-coordinate geometry to one O(1), one O(2), one O(3), one O(6), one O(8), and one O(9) atom. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(10), one O(3), one O(6), and one O(7) atom to form VO4 tetrahedra that share  a cornercorner with one Bi(2)O5 square pyramid. In the second V site, V(2) is bonded to one O(4), one O(5), one O(8), and one O(9) atom to form VO4 tetrahedra that share corners with two equivalent Bi(2)O5 square pyramids. There are three inequivalent Bi sites. In the first Bi site, Bi(1) is bonded in a 5-coordinate geometry to one O(1), one O(2), one O(3), one O(5), and one O(7) atom. In the second Bi site, Bi(2) is bonded to one O(1), one O(2), one O(4), one O(6), and one O(8) atom to form distorted BiO5 square pyramids that share  a cornercorner with one V(1)O4 tetrahedra and corners with two equivalent V(2)O4 tetrahedra. In the third Bi site, Bi(3) is bonded in a 6-coordinate geometry to one O(1), one O(10), one O(2), one O(4), one O(5), and one O(7) atom. There are ten inequivalent O sites. In the first O site, O(1) is bonded to one Na(1), one Bi(1), one Bi(2), and one Bi(3) atom to form edge-sharing ONaBi3 tetrahedra. In the second O site, O(2) is bonded to one Na(1), one Bi(1), one Bi(2), and one Bi(3) atom to form edge-sharing ONaBi3 tetrahedra. In the third O site, O(3) is bonded in a distorted trigonal non-coplanar geometry to one Na(1), one V(1), and one Bi(1) atom. In the fourth O site, O(4) is bonded in a 1-coordinate geometry to one V(2), one Bi(2), and one Bi(3) atom. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to one V(2), one Bi(1), and one Bi(3) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one Na(1), one V(1), and one Bi(2) atom. In the seventh O site, O(7) is bonded in a 3-coordinate geometry to one V(1), one Bi(1), and one Bi(3) atom. In the eighth O site, O(8) is bonded in a 3-coordinate geometry to one Na(1), one V(2), and one Bi(2) atom. In the ninth O site, O(9) is bonded in a distorted bent 120 degrees geometry to one Na(1) and one V(2) atom. In the tenth O site, O(10) is bonded in a single-bond geometry to one V(1) and one Bi(3) atom.
NaBi3V2O10 crystallizes in the triclinic P1 space group. Na(1) is bonded in a 6-coordinate geometry to one O(1), one O(2), one O(3), one O(6), one O(8), and one O(9) atom. The Na(1)-O(1) bond length is 2.57 Å. The Na(1)-O(2) bond length is 2.43 Å. The Na(1)-O(3) bond length is 2.49 Å. The Na(1)-O(6) bond length is 2.50 Å. The Na(1)-O(8) bond length is 2.50 Å. The Na(1)-O(9) bond length is 2.70 Å. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(10), one O(3), one O(6), and one O(7) atom to form VO4 tetrahedra that share  a cornercorner with one Bi(2)O5 square pyramid. The V(1)-O(10) bond length is 1.71 Å. The V(1)-O(3) bond length is 1.76 Å. The V(1)-O(6) bond length is 1.75 Å. The V(1)-O(7) bond length is 1.78 Å. In the second V site, V(2) is bonded to one O(4), one O(5), one O(8), and one O(9) atom to form VO4 tetrahedra that share corners with two equivalent Bi(2)O5 square pyramids. The V(2)-O(4) bond length is 1.78 Å. The V(2)-O(5) bond length is 1.79 Å. The V(2)-O(8) bond length is 1.73 Å. The V(2)-O(9) bond length is 1.69 Å. There are three inequivalent Bi sites. In the first Bi site, Bi(1) is bonded in a 5-coordinate geometry to one O(1), one O(2), one O(3), one O(5), and one O(7) atom. The Bi(1)-O(1) bond length is 2.17 Å. The Bi(1)-O(2) bond length is 2.31 Å. The Bi(1)-O(3) bond length is 2.31 Å. The Bi(1)-O(5) bond length is 2.44 Å. The Bi(1)-O(7) bond length is 2.40 Å. In the second Bi site, Bi(2) is bonded to one O(1), one O(2), one O(4), one O(6), and one O(8) atom to form distorted BiO5 square pyramids that share  a cornercorner with one V(1)O4 tetrahedra and corners with two equivalent V(2)O4 tetrahedra. The Bi(2)-O(1) bond length is 2.32 Å. The Bi(2)-O(2) bond length is 2.20 Å. The Bi(2)-O(4) bond length is 2.40 Å. The Bi(2)-O(6) bond length is 2.36 Å. The Bi(2)-O(8) bond length is 2.27 Å. In the third Bi site, Bi(3) is bonded in a 6-coordinate geometry to one O(1), one O(10), one O(2), one O(4), one O(5), and one O(7) atom. The Bi(3)-O(1) bond length is 2.28 Å. The Bi(3)-O(10) bond length is 2.80 Å. The Bi(3)-O(2) bond length is 2.29 Å. The Bi(3)-O(4) bond length is 2.40 Å. The Bi(3)-O(5) bond length is 2.38 Å. The Bi(3)-O(7) bond length is 2.42 Å. There are ten inequivalent O sites. In the first O site, O(1) is bonded to one Na(1), one Bi(1), one Bi(2), and one Bi(3) atom to form edge-sharing ONaBi3 tetrahedra. In the second O site, O(2) is bonded to one Na(1), one Bi(1), one Bi(2), and one Bi(3) atom to form edge-sharing ONaBi3 tetrahedra. In the third O site, O(3) is bonded in a distorted trigonal non-coplanar geometry to one Na(1), one V(1), and one Bi(1) atom. In the fourth O site, O(4) is bonded in a 1-coordinate geometry to one V(2), one Bi(2), and one Bi(3) atom. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to one V(2), one Bi(1), and one Bi(3) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one Na(1), one V(1), and one Bi(2) atom. In the seventh O site, O(7) is bonded in a 3-coordinate geometry to one V(1), one Bi(1), and one Bi(3) atom. In the eighth O site, O(8) is bonded in a 3-coordinate geometry to one Na(1), one V(2), and one Bi(2) atom. In the ninth O site, O(9) is bonded in a distorted bent 120 degrees geometry to one Na(1) and one V(2) atom. In the tenth O site, O(10) is bonded in a single-bond geometry to one V(1) and one Bi(3) atom.