Na3(VSe2)5 crystallizes in the triclinic P1 space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded in a 6-coordinate geometry to one Se(1), one Se(10), one Se(4), one Se(5), one Se(6), and one Se(7) atom. In the second Na site, Na(2) is bonded in a 6-coordinate geometry to one Se(2), one Se(3), one Se(6), one Se(7), one Se(8), and one Se(9) atom. In the third Na site, Na(3) is bonded in a 6-coordinate geometry to one Se(1), one Se(10), one Se(4), one Se(5), one Se(8), and one Se(9) atom. There are five inequivalent V sites. In the first V site, V(1) is bonded to one Se(1), one Se(10), one Se(2), one Se(5), one Se(6), and one Se(9) atom to form edge-sharing VSe6 octahedra. In the second V site, V(2) is bonded to one Se(10), one Se(2), one Se(3), one Se(4), one Se(7), and one Se(8) atom to form edge-sharing VSe6 octahedra. In the third V site, V(3) is bonded to one Se(1), one Se(3), one Se(4), one Se(5), one Se(6), and one Se(9) atom to form edge-sharing VSe6 octahedra. In the fourth V site, V(4) is bonded to one Se(10), one Se(2), one Se(5), one Se(6), one Se(7), and one Se(8) atom to form edge-sharing VSe6 octahedra. In the fifth V site, V(5) is bonded to one Se(1), one Se(3), one Se(4), one Se(7), one Se(8), and one Se(9) atom to form edge-sharing VSe6 octahedra. There are ten inequivalent Se sites. In the first Se site, Se(1) is bonded to one Na(1), one Na(3), one V(1), one V(3), and one V(5) atom to form distorted SeNa2V3 trigonal bipyramids that share  a cornercorner with one Se(10)Na2V3 square pyramid, corners with two equivalent Se(5)Na2V3 square pyramids, corners with two equivalent Se(7)Na2V3 square pyramids, corners with two equivalent Se(9)Na2V3 square pyramids,  a cornercorner with one Se(6)Na2V3 trigonal bipyramid,  a cornercorner with one Se(2)NaV3 trigonal pyramid,  an edgeedge with one Se(10)Na2V3 square pyramid,  an edgeedge with one Se(5)Na2V3 square pyramid,  an edgeedge with one Se(9)Na2V3 square pyramid,  an edgeedge with one Se(6)Na2V3 trigonal bipyramid,  an edgeedge with one Se(8)Na2V3 trigonal bipyramid, and edges with two equivalent Se(4)Na2V3 trigonal bipyramids. In the second Se site, Se(2) is bonded to one Na(2), one V(1), one V(2), and one V(4) atom to form a mixture of distorted corner and edge-sharing SeNaV3 trigonal pyramids. In the third Se site, Se(3) is bonded in a distorted rectangular see-saw-like geometry to one Na(2), one V(2), one V(3), and one V(5) atom. In the fourth Se site, Se(4) is bonded to one Na(1), one Na(3), one V(2), one V(3), and one V(5) atom to form distorted SeNa2V3 trigonal bipyramids that share  a cornercorner with one Se(5)Na2V3 square pyramid,  a cornercorner with one Se(7)Na2V3 square pyramid,  a cornercorner with one Se(9)Na2V3 square pyramid, corners with three equivalent Se(10)Na2V3 square pyramids,  a cornercorner with one Se(8)Na2V3 trigonal bipyramid,  a cornercorner with one Se(2)NaV3 trigonal pyramid,  an edgeedge with one Se(5)Na2V3 square pyramid,  an edgeedge with one Se(7)Na2V3 square pyramid,  an edgeedge with one Se(9)Na2V3 square pyramid,  an edgeedge with one Se(6)Na2V3 trigonal bipyramid,  an edgeedge with one Se(8)Na2V3 trigonal bipyramid, and edges with two equivalent Se(1)Na2V3 trigonal bipyramids. In the fifth Se site, Se(5) is bonded to one Na(1), one Na(3), one V(1), one V(3), and one V(4) atom to form SeNa2V3 square pyramids that share  a cornercorner with one Se(9)Na2V3 square pyramid,  a cornercorner with one Se(4)Na2V3 trigonal bipyramid, corners with two equivalent Se(1)Na2V3 trigonal bipyramids, corners with two equivalent Se(6)Na2V3 trigonal bipyramids, corners with two equivalent Se(8)Na2V3 trigonal bipyramids,  an edgeedge with one Se(7)Na2V3 square pyramid,  an edgeedge with one Se(9)Na2V3 square pyramid, edges with two equivalent Se(10)Na2V3 square pyramids,  an edgeedge with one Se(1)Na2V3 trigonal bipyramid,  an edgeedge with one Se(4)Na2V3 trigonal bipyramid,  an edgeedge with one Se(6)Na2V3 trigonal bipyramid, and  an edgeedge with one Se(2)NaV3 trigonal pyramid. In the sixth Se site, Se(6) is bonded to one Na(1), one Na(2), one V(1), one V(3), and one V(4) atom to form distorted SeNa2V3 trigonal bipyramids that share  a cornercorner with one Se(10)Na2V3 square pyramid,  a cornercorner with one Se(7)Na2V3 square pyramid,  a cornercorner with one Se(9)Na2V3 square pyramid, corners with two equivalent Se(5)Na2V3 square pyramids,  a cornercorner with one Se(1)Na2V3 trigonal bipyramid,  a cornercorner with one Se(2)NaV3 trigonal pyramid,  an edgeedge with one Se(10)Na2V3 square pyramid,  an edgeedge with one Se(5)Na2V3 square pyramid,  an edgeedge with one Se(7)Na2V3 square pyramid,  an edgeedge with one Se(9)Na2V3 square pyramid,  an edgeedge with one Se(1)Na2V3 trigonal bipyramid,  an edgeedge with one Se(4)Na2V3 trigonal bipyramid,  an edgeedge with one Se(8)Na2V3 trigonal bipyramid, and  an edgeedge with one Se(2)NaV3 trigonal pyramid. In the seventh Se site, Se(7) is bonded to one Na(1), one Na(2), one V(2), one V(4), and one V(5) atom to form distorted SeNa2V3 square pyramids that share  a cornercorner with one Se(10)Na2V3 square pyramid,  a cornercorner with one Se(4)Na2V3 trigonal bipyramid,  a cornercorner with one Se(6)Na2V3 trigonal bipyramid, corners with two equivalent Se(1)Na2V3 trigonal bipyramids, corners with two equivalent Se(8)Na2V3 trigonal bipyramids,  a cornercorner with one Se(2)NaV3 trigonal pyramid,  an edgeedge with one Se(10)Na2V3 square pyramid,  an edgeedge with one Se(5)Na2V3 square pyramid,  an edgeedge with one Se(9)Na2V3 square pyramid,  an edgeedge with one Se(4)Na2V3 trigonal bipyramid,  an edgeedge with one Se(6)Na2V3 trigonal bipyramid,  an edgeedge with one Se(8)Na2V3 trigonal bipyramid, and  an edgeedge with one Se(2)NaV3 trigonal pyramid. In the eighth Se site, Se(8) is bonded to one Na(2), one Na(3), one V(2), one V(4), and one V(5) atom to form distorted SeNa2V3 trigonal bipyramids that share  a cornercorner with one Se(10)Na2V3 square pyramid,  a cornercorner with one Se(9)Na2V3 square pyramid, corners with two equivalent Se(5)Na2V3 square pyramids, corners with two equivalent Se(7)Na2V3 square pyramids,  a cornercorner with one Se(4)Na2V3 trigonal bipyramid,  a cornercorner with one Se(2)NaV3 trigonal pyramid,  an edgeedge with one Se(10)Na2V3 square pyramid,  an edgeedge with one Se(7)Na2V3 square pyramid,  an edgeedge with one Se(9)Na2V3 square pyramid,  an edgeedge with one Se(1)Na2V3 trigonal bipyramid,  an edgeedge with one Se(4)Na2V3 trigonal bipyramid,  an edgeedge with one Se(6)Na2V3 trigonal bipyramid, and  an edgeedge with one Se(2)NaV3 trigonal pyramid. In the ninth Se site, Se(9) is bonded to one Na(2), one Na(3), one V(1), one V(3), and one V(5) atom to form SeNa2V3 square pyramids that share  a cornercorner with one Se(5)Na2V3 square pyramid,  a cornercorner with one Se(4)Na2V3 trigonal bipyramid,  a cornercorner with one Se(6)Na2V3 trigonal bipyramid,  a cornercorner with one Se(8)Na2V3 trigonal bipyramid, corners with two equivalent Se(1)Na2V3 trigonal bipyramids, corners with two equivalent Se(2)NaV3 trigonal pyramids,  an edgeedge with one Se(10)Na2V3 square pyramid,  an edgeedge with one Se(5)Na2V3 square pyramid,  an edgeedge with one Se(7)Na2V3 square pyramid,  an edgeedge with one Se(1)Na2V3 trigonal bipyramid,  an edgeedge with one Se(4)Na2V3 trigonal bipyramid,  an edgeedge with one Se(6)Na2V3 trigonal bipyramid, and  an edgeedge with one Se(8)Na2V3 trigonal bipyramid. In the tenth Se site, Se(10) is bonded to one Na(1), one Na(3), one V(1), one V(2), and one V(4) atom to form distorted SeNa2V3 square pyramids that share  a cornercorner with one Se(7)Na2V3 square pyramid,  a cornercorner with one Se(1)Na2V3 trigonal bipyramid,  a cornercorner with one Se(6)Na2V3 trigonal bipyramid,  a cornercorner with one Se(8)Na2V3 trigonal bipyramid, corners with three equivalent Se(4)Na2V3 trigonal bipyramids,  a cornercorner with one Se(2)NaV3 trigonal pyramid,  an edgeedge with one Se(7)Na2V3 square pyramid,  an edgeedge with one Se(9)Na2V3 square pyramid, edges with two equivalent Se(5)Na2V3 square pyramids,  an edgeedge with one Se(1)Na2V3 trigonal bipyramid,  an edgeedge with one Se(6)Na2V3 trigonal bipyramid,  an edgeedge with one Se(8)Na2V3 trigonal bipyramid, and  an edgeedge with one Se(2)NaV3 trigonal pyramid.
Na3(VSe2)5 crystallizes in the triclinic P1 space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded in a 6-coordinate geometry to one Se(1), one Se(10), one Se(4), one Se(5), one Se(6), and one Se(7) atom. The Na(1)-Se(1) bond length is 3.00 Å. The Na(1)-Se(10) bond length is 3.21 Å. The Na(1)-Se(4) bond length is 3.04 Å. The Na(1)-Se(5) bond length is 3.03 Å. The Na(1)-Se(6) bond length is 3.09 Å. The Na(1)-Se(7) bond length is 2.97 Å. In the second Na site, Na(2) is bonded in a 6-coordinate geometry to one Se(2), one Se(3), one Se(6), one Se(7), one Se(8), and one Se(9) atom. The Na(2)-Se(2) bond length is 3.10 Å. The Na(2)-Se(3) bond length is 3.13 Å. The Na(2)-Se(6) bond length is 3.00 Å. The Na(2)-Se(7) bond length is 2.91 Å. The Na(2)-Se(8) bond length is 2.93 Å. The Na(2)-Se(9) bond length is 3.02 Å. In the third Na site, Na(3) is bonded in a 6-coordinate geometry to one Se(1), one Se(10), one Se(4), one Se(5), one Se(8), and one Se(9) atom. The Na(3)-Se(1) bond length is 3.06 Å. The Na(3)-Se(10) bond length is 2.97 Å. The Na(3)-Se(4) bond length is 3.12 Å. The Na(3)-Se(5) bond length is 2.99 Å. The Na(3)-Se(8) bond length is 2.96 Å. The Na(3)-Se(9) bond length is 3.09 Å. There are five inequivalent V sites. In the first V site, V(1) is bonded to one Se(1), one Se(10), one Se(2), one Se(5), one Se(6), and one Se(9) atom to form edge-sharing VSe6 octahedra. The V(1)-Se(1) bond length is 2.59 Å. The V(1)-Se(10) bond length is 2.53 Å. The V(1)-Se(2) bond length is 2.51 Å. The V(1)-Se(5) bond length is 2.47 Å. The V(1)-Se(6) bond length is 2.62 Å. The V(1)-Se(9) bond length is 2.60 Å. In the second V site, V(2) is bonded to one Se(10), one Se(2), one Se(3), one Se(4), one Se(7), and one Se(8) atom to form edge-sharing VSe6 octahedra. The V(2)-Se(10) bond length is 2.51 Å. The V(2)-Se(2) bond length is 2.49 Å. The V(2)-Se(3) bond length is 2.66 Å. The V(2)-Se(4) bond length is 2.55 Å. The V(2)-Se(7) bond length is 2.56 Å. The V(2)-Se(8) bond length is 2.54 Å. In the third V site, V(3) is bonded to one Se(1), one Se(3), one Se(4), one Se(5), one Se(6), and one Se(9) atom to form edge-sharing VSe6 octahedra. The V(3)-Se(1) bond length is 2.48 Å. The V(3)-Se(3) bond length is 2.53 Å. The V(3)-Se(4) bond length is 2.58 Å. The V(3)-Se(5) bond length is 2.55 Å. The V(3)-Se(6) bond length is 2.58 Å. The V(3)-Se(9) bond length is 2.63 Å. In the fourth V site, V(4) is bonded to one Se(10), one Se(2), one Se(5), one Se(6), one Se(7), and one Se(8) atom to form edge-sharing VSe6 octahedra. The V(4)-Se(10) bond length is 2.64 Å. The V(4)-Se(2) bond length is 2.50 Å. The V(4)-Se(5) bond length is 2.58 Å. The V(4)-Se(6) bond length is 2.60 Å. The V(4)-Se(7) bond length is 2.45 Å. The V(4)-Se(8) bond length is 2.60 Å. In the fifth V site, V(5) is bonded to one Se(1), one Se(3), one Se(4), one Se(7), one Se(8), and one Se(9) atom to form edge-sharing VSe6 octahedra. The V(5)-Se(1) bond length is 2.57 Å. The V(5)-Se(3) bond length is 2.45 Å. The V(5)-Se(4) bond length is 2.65 Å. The V(5)-Se(7) bond length is 2.59 Å. The V(5)-Se(8) bond length is 2.47 Å. The V(5)-Se(9) bond length is 2.60 Å. There are ten inequivalent Se sites. In the first Se site, Se(1) is bonded to one Na(1), one Na(3), one V(1), one V(3), and one V(5) atom to form distorted SeNa2V3 trigonal bipyramids that share  a cornercorner with one Se(10)Na2V3 square pyramid, corners with two equivalent Se(5)Na2V3 square pyramids, corners with two equivalent Se(7)Na2V3 square pyramids, corners with two equivalent Se(9)Na2V3 square pyramids,  a cornercorner with one Se(6)Na2V3 trigonal bipyramid,  a cornercorner with one Se(2)NaV3 trigonal pyramid,  an edgeedge with one Se(10)Na2V3 square pyramid,  an edgeedge with one Se(5)Na2V3 square pyramid,  an edgeedge with one Se(9)Na2V3 square pyramid,  an edgeedge with one Se(6)Na2V3 trigonal bipyramid,  an edgeedge with one Se(8)Na2V3 trigonal bipyramid, and edges with two equivalent Se(4)Na2V3 trigonal bipyramids. In the second Se site, Se(2) is bonded to one Na(2), one V(1), one V(2), and one V(4) atom to form a mixture of distorted corner and edge-sharing SeNaV3 trigonal pyramids. In the third Se site, Se(3) is bonded in a distorted rectangular see-saw-like geometry to one Na(2), one V(2), one V(3), and one V(5) atom. In the fourth Se site, Se(4) is bonded to one Na(1), one Na(3), one V(2), one V(3), and one V(5) atom to form distorted SeNa2V3 trigonal bipyramids that share  a cornercorner with one Se(5)Na2V3 square pyramid,  a cornercorner with one Se(7)Na2V3 square pyramid,  a cornercorner with one Se(9)Na2V3 square pyramid, corners with three equivalent Se(10)Na2V3 square pyramids,  a cornercorner with one Se(8)Na2V3 trigonal bipyramid,  a cornercorner with one Se(2)NaV3 trigonal pyramid,  an edgeedge with one Se(5)Na2V3 square pyramid,  an edgeedge with one Se(7)Na2V3 square pyramid,  an edgeedge with one Se(9)Na2V3 square pyramid,  an edgeedge with one Se(6)Na2V3 trigonal bipyramid,  an edgeedge with one Se(8)Na2V3 trigonal bipyramid, and edges with two equivalent Se(1)Na2V3 trigonal bipyramids. In the fifth Se site, Se(5) is bonded to one Na(1), one Na(3), one V(1), one V(3), and one V(4) atom to form SeNa2V3 square pyramids that share  a cornercorner with one Se(9)Na2V3 square pyramid,  a cornercorner with one Se(4)Na2V3 trigonal bipyramid, corners with two equivalent Se(1)Na2V3 trigonal bipyramids, corners with two equivalent Se(6)Na2V3 trigonal bipyramids, corners with two equivalent Se(8)Na2V3 trigonal bipyramids,  an edgeedge with one Se(7)Na2V3 square pyramid,  an edgeedge with one Se(9)Na2V3 square pyramid, edges with two equivalent Se(10)Na2V3 square pyramids,  an edgeedge with one Se(1)Na2V3 trigonal bipyramid,  an edgeedge with one Se(4)Na2V3 trigonal bipyramid,  an edgeedge with one Se(6)Na2V3 trigonal bipyramid, and  an edgeedge with one Se(2)NaV3 trigonal pyramid. In the sixth Se site, Se(6) is bonded to one Na(1), one Na(2), one V(1), one V(3), and one V(4) atom to form distorted SeNa2V3 trigonal bipyramids that share  a cornercorner with one Se(10)Na2V3 square pyramid,  a cornercorner with one Se(7)Na2V3 square pyramid,  a cornercorner with one Se(9)Na2V3 square pyramid, corners with two equivalent Se(5)Na2V3 square pyramids,  a cornercorner with one Se(1)Na2V3 trigonal bipyramid,  a cornercorner with one Se(2)NaV3 trigonal pyramid,  an edgeedge with one Se(10)Na2V3 square pyramid,  an edgeedge with one Se(5)Na2V3 square pyramid,  an edgeedge with one Se(7)Na2V3 square pyramid,  an edgeedge with one Se(9)Na2V3 square pyramid,  an edgeedge with one Se(1)Na2V3 trigonal bipyramid,  an edgeedge with one Se(4)Na2V3 trigonal bipyramid,  an edgeedge with one Se(8)Na2V3 trigonal bipyramid, and  an edgeedge with one Se(2)NaV3 trigonal pyramid. In the seventh Se site, Se(7) is bonded to one Na(1), one Na(2), one V(2), one V(4), and one V(5) atom to form distorted SeNa2V3 square pyramids that share  a cornercorner with one Se(10)Na2V3 square pyramid,  a cornercorner with one Se(4)Na2V3 trigonal bipyramid,  a cornercorner with one Se(6)Na2V3 trigonal bipyramid, corners with two equivalent Se(1)Na2V3 trigonal bipyramids, corners with two equivalent Se(8)Na2V3 trigonal bipyramids,  a cornercorner with one Se(2)NaV3 trigonal pyramid,  an edgeedge with one Se(10)Na2V3 square pyramid,  an edgeedge with one Se(5)Na2V3 square pyramid,  an edgeedge with one Se(9)Na2V3 square pyramid,  an edgeedge with one Se(4)Na2V3 trigonal bipyramid,  an edgeedge with one Se(6)Na2V3 trigonal bipyramid,  an edgeedge with one Se(8)Na2V3 trigonal bipyramid, and  an edgeedge with one Se(2)NaV3 trigonal pyramid. In the eighth Se site, Se(8) is bonded to one Na(2), one Na(3), one V(2), one V(4), and one V(5) atom to form distorted SeNa2V3 trigonal bipyramids that share  a cornercorner with one Se(10)Na2V3 square pyramid,  a cornercorner with one Se(9)Na2V3 square pyramid, corners with two equivalent Se(5)Na2V3 square pyramids, corners with two equivalent Se(7)Na2V3 square pyramids,  a cornercorner with one Se(4)Na2V3 trigonal bipyramid,  a cornercorner with one Se(2)NaV3 trigonal pyramid,  an edgeedge with one Se(10)Na2V3 square pyramid,  an edgeedge with one Se(7)Na2V3 square pyramid,  an edgeedge with one Se(9)Na2V3 square pyramid,  an edgeedge with one Se(1)Na2V3 trigonal bipyramid,  an edgeedge with one Se(4)Na2V3 trigonal bipyramid,  an edgeedge with one Se(6)Na2V3 trigonal bipyramid, and  an edgeedge with one Se(2)NaV3 trigonal pyramid. In the ninth Se site, Se(9) is bonded to one Na(2), one Na(3), one V(1), one V(3), and one V(5) atom to form SeNa2V3 square pyramids that share  a cornercorner with one Se(5)Na2V3 square pyramid,  a cornercorner with one Se(4)Na2V3 trigonal bipyramid,  a cornercorner with one Se(6)Na2V3 trigonal bipyramid,  a cornercorner with one Se(8)Na2V3 trigonal bipyramid, corners with two equivalent Se(1)Na2V3 trigonal bipyramids, corners with two equivalent Se(2)NaV3 trigonal pyramids,  an edgeedge with one Se(10)Na2V3 square pyramid,  an edgeedge with one Se(5)Na2V3 square pyramid,  an edgeedge with one Se(7)Na2V3 square pyramid,  an edgeedge with one Se(1)Na2V3 trigonal bipyramid,  an edgeedge with one Se(4)Na2V3 trigonal bipyramid,  an edgeedge with one Se(6)Na2V3 trigonal bipyramid, and  an edgeedge with one Se(8)Na2V3 trigonal bipyramid. In the tenth Se site, Se(10) is bonded to one Na(1), one Na(3), one V(1), one V(2), and one V(4) atom to form distorted SeNa2V3 square pyramids that share  a cornercorner with one Se(7)Na2V3 square pyramid,  a cornercorner with one Se(1)Na2V3 trigonal bipyramid,  a cornercorner with one Se(6)Na2V3 trigonal bipyramid,  a cornercorner with one Se(8)Na2V3 trigonal bipyramid, corners with three equivalent Se(4)Na2V3 trigonal bipyramids,  a cornercorner with one Se(2)NaV3 trigonal pyramid,  an edgeedge with one Se(7)Na2V3 square pyramid,  an edgeedge with one Se(9)Na2V3 square pyramid, edges with two equivalent Se(5)Na2V3 square pyramids,  an edgeedge with one Se(1)Na2V3 trigonal bipyramid,  an edgeedge with one Se(6)Na2V3 trigonal bipyramid,  an edgeedge with one Se(8)Na2V3 trigonal bipyramid, and  an edgeedge with one Se(2)NaV3 trigonal pyramid.