Na3V(BO3)2 crystallizes in the monoclinic P2_1/c space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded in a 4-coordinate geometry to one O(1), one O(3), one O(5), and one O(6) atom. In the second Na site, Na(2) is bonded to one O(1), one O(2), one O(3), one O(4), and one O(6) atom to form distorted NaO5 trigonal bipyramids that share corners with two equivalent Na(3)O5 trigonal bipyramids,  an edgeedge with one Na(3)O5 trigonal bipyramid, and edges with two equivalent V(1)O5 trigonal bipyramids. In the third Na site, Na(3) is bonded to one O(2), one O(4), one O(5), and two equivalent O(3) atoms to form NaO5 trigonal bipyramids that share  a cornercorner with one V(1)O5 trigonal bipyramid, corners with two equivalent Na(2)O5 trigonal bipyramids,  an edgeedge with one Na(2)O5 trigonal bipyramid,  an edgeedge with one Na(3)O5 trigonal bipyramid, and  an edgeedge with one V(1)O5 trigonal bipyramid. V(1) is bonded to one O(1), one O(2), one O(4), one O(5), and one O(6) atom to form VO5 trigonal bipyramids that share  a cornercorner with one Na(3)O5 trigonal bipyramid,  an edgeedge with one Na(3)O5 trigonal bipyramid, and edges with two equivalent Na(2)O5 trigonal bipyramids. 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 4-coordinate geometry to one Na(1), one Na(2), one V(1), and one B(2) atom. In the second O site, O(2) is bonded in a distorted rectangular see-saw-like geometry to one Na(2), one Na(3), one V(1), and one B(1) atom. In the third O site, O(3) is bonded in a 5-coordinate geometry to one Na(1), one Na(2), two equivalent Na(3), and one B(1) atom. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to one Na(2), one Na(3), one V(1), and one B(2) atom. In the fifth O site, O(5) is bonded in a 4-coordinate geometry to one Na(1), one Na(3), one V(1), and one B(2) atom. In the sixth O site, O(6) is bonded in a 4-coordinate geometry to one Na(1), one Na(2), one V(1), and one B(1) atom.
Na3V(BO3)2 crystallizes in the monoclinic P2_1/c space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded in a 4-coordinate geometry to one O(1), one O(3), one O(5), and one O(6) atom. The Na(1)-O(1) bond length is 2.33 Å. The Na(1)-O(3) bond length is 2.48 Å. The Na(1)-O(5) bond length is 2.31 Å. The Na(1)-O(6) bond length is 2.28 Å. In the second Na site, Na(2) is bonded to one O(1), one O(2), one O(3), one O(4), and one O(6) atom to form distorted NaO5 trigonal bipyramids that share corners with two equivalent Na(3)O5 trigonal bipyramids,  an edgeedge with one Na(3)O5 trigonal bipyramid, and edges with two equivalent V(1)O5 trigonal bipyramids. The Na(2)-O(1) bond length is 2.30 Å. The Na(2)-O(2) bond length is 2.35 Å. The Na(2)-O(3) bond length is 2.29 Å. The Na(2)-O(4) bond length is 2.31 Å. The Na(2)-O(6) bond length is 2.37 Å. In the third Na site, Na(3) is bonded to one O(2), one O(4), one O(5), and two equivalent O(3) atoms to form NaO5 trigonal bipyramids that share  a cornercorner with one V(1)O5 trigonal bipyramid, corners with two equivalent Na(2)O5 trigonal bipyramids,  an edgeedge with one Na(2)O5 trigonal bipyramid,  an edgeedge with one Na(3)O5 trigonal bipyramid, and  an edgeedge with one V(1)O5 trigonal bipyramid. The Na(3)-O(2) bond length is 2.43 Å. The Na(3)-O(4) bond length is 2.34 Å. The Na(3)-O(5) bond length is 2.45 Å. There is one shorter (2.34 Å) and one longer (2.44 Å) Na(3)-O(3) bond length. V(1) is bonded to one O(1), one O(2), one O(4), one O(5), and one O(6) atom to form VO5 trigonal bipyramids that share  a cornercorner with one Na(3)O5 trigonal bipyramid,  an edgeedge with one Na(3)O5 trigonal bipyramid, and edges with two equivalent Na(2)O5 trigonal bipyramids. The V(1)-O(1) bond length is 2.06 Å. The V(1)-O(2) bond length is 1.98 Å. The V(1)-O(4) bond length is 2.17 Å. The V(1)-O(5) bond length is 1.96 Å. The V(1)-O(6) bond length is 1.98 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 1.40 Å. The B(1)-O(3) bond length is 1.37 Å. The B(1)-O(6) bond length is 1.40 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 1.39 Å. The B(2)-O(4) bond length is 1.38 Å. The B(2)-O(5) bond length is 1.42 Å. There are six inequivalent O sites. In the first O site, O(1) is bonded in a 4-coordinate geometry to one Na(1), one Na(2), one V(1), and one B(2) atom. In the second O site, O(2) is bonded in a distorted rectangular see-saw-like geometry to one Na(2), one Na(3), one V(1), and one B(1) atom. In the third O site, O(3) is bonded in a 5-coordinate geometry to one Na(1), one Na(2), two equivalent Na(3), and one B(1) atom. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to one Na(2), one Na(3), one V(1), and one B(2) atom. In the fifth O site, O(5) is bonded in a 4-coordinate geometry to one Na(1), one Na(3), one V(1), and one B(2) atom. In the sixth O site, O(6) is bonded in a 4-coordinate geometry to one Na(1), one Na(2), one V(1), and one B(1) atom.