NaV(SO4)2 crystallizes in the triclinic P-1 space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded to two equivalent O(10), two equivalent O(14), and two equivalent O(4) atoms to form distorted NaO6 octahedra that share corners with two equivalent S(1)O4 tetrahedra, corners with four equivalent S(2)O4 tetrahedra, and edges with two equivalent V(1)O6 octahedra. In the second Na site, Na(2) is bonded to one O(12), one O(13), one O(16), one O(2), one O(3), and one O(9) atom to form distorted NaO6 octahedra that share  a cornercorner with one S(2)O4 tetrahedra,  a cornercorner with one S(3)O4 tetrahedra, corners with two equivalent S(1)O4 tetrahedra, corners with two equivalent S(4)O4 tetrahedra,  an edgeedge with one V(2)O6 octahedra, and  an edgeedge with one V(3)O6 octahedra. In the third Na site, Na(3) is bonded to two equivalent O(1), two equivalent O(11), and two equivalent O(15) atoms to form distorted NaO6 octahedra that share corners with two equivalent S(4)O4 tetrahedra, corners with four equivalent S(3)O4 tetrahedra, and edges with two equivalent V(1)O6 octahedra. There are three inequivalent V sites. In the first V site, V(1) is bonded to one O(10), one O(11), one O(14), one O(15), one O(5), and one O(8) atom to form VO6 octahedra that share  a cornercorner with one S(1)O4 tetrahedra,  a cornercorner with one S(4)O4 tetrahedra, corners with two equivalent S(2)O4 tetrahedra, corners with two equivalent S(3)O4 tetrahedra,  an edgeedge with one Na(1)O6 octahedra, and  an edgeedge with one Na(3)O6 octahedra. In the second V site, V(2) is bonded to two equivalent O(13), two equivalent O(6), and two equivalent O(9) atoms to form VO6 octahedra that share corners with two equivalent S(2)O4 tetrahedra, corners with four equivalent S(4)O4 tetrahedra, and edges with two equivalent Na(2)O6 octahedra. In the third V site, V(3) is bonded to two equivalent O(12), two equivalent O(16), and two equivalent O(7) atoms to form VO6 octahedra that share corners with two equivalent S(3)O4 tetrahedra, corners with four equivalent S(1)O4 tetrahedra, and edges with two equivalent Na(2)O6 octahedra. There are four inequivalent S sites. In the first S site, S(1) is bonded to one O(12), one O(16), one O(4), and one O(5) atom to form SO4 tetrahedra that share  a cornercorner with one Na(1)O6 octahedra,  a cornercorner with one V(1)O6 octahedra, corners with two equivalent Na(2)O6 octahedra, and corners with two equivalent V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 36-65°. In the second S site, S(2) is bonded to one O(10), one O(14), one O(2), and one O(6) atom to form SO4 tetrahedra that share  a cornercorner with one Na(2)O6 octahedra,  a cornercorner with one V(2)O6 octahedra, corners with two equivalent Na(1)O6 octahedra, and corners with two equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 37-65°. In the third S site, S(3) is bonded to one O(11), one O(15), one O(3), and one O(7) atom to form SO4 tetrahedra that share  a cornercorner with one Na(2)O6 octahedra,  a cornercorner with one V(3)O6 octahedra, corners with two equivalent Na(3)O6 octahedra, and corners with two equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 36-65°. In the fourth S site, S(4) is bonded to one O(1), one O(13), one O(8), and one O(9) atom to form SO4 tetrahedra that share  a cornercorner with one Na(3)O6 octahedra,  a cornercorner with one V(1)O6 octahedra, corners with two equivalent Na(2)O6 octahedra, and corners with two equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 36-65°. There are sixteen inequivalent O sites. In the first O site, O(1) is bonded in a distorted bent 120 degrees geometry to one Na(3) and one S(4) atom. In the second O site, O(2) is bonded in a distorted bent 120 degrees geometry to one Na(2) and one S(2) atom. In the third O site, O(3) is bonded in a distorted bent 120 degrees geometry to one Na(2) and one S(3) atom. In the fourth O site, O(4) is bonded in a distorted bent 120 degrees geometry to one Na(1) and one S(1) atom. In the fifth O site, O(5) is bonded in a bent 150 degrees geometry to one V(1) and one S(1) atom. In the sixth O site, O(6) is bonded in a bent 150 degrees geometry to one V(2) and one S(2) atom. In the seventh O site, O(7) is bonded in a bent 150 degrees geometry to one V(3) and one S(3) atom. In the eighth O site, O(8) is bonded in a bent 150 degrees geometry to one V(1) and one S(4) atom. In the ninth O site, O(9) is bonded in a 3-coordinate geometry to one Na(2), one V(2), and one S(4) atom. In the tenth O site, O(10) is bonded in a 3-coordinate geometry to one Na(1), one V(1), and one S(2) atom. In the eleventh O site, O(11) is bonded in a 3-coordinate geometry to one Na(3), one V(1), and one S(3) atom. In the twelfth O site, O(12) is bonded in a 3-coordinate geometry to one Na(2), one V(3), and one S(1) atom. In the thirteenth O site, O(13) is bonded in a 3-coordinate geometry to one Na(2), one V(2), and one S(4) atom. In the fourteenth O site, O(14) is bonded in a 3-coordinate geometry to one Na(1), one V(1), and one S(2) atom. In the fifteenth O site, O(15) is bonded in a 3-coordinate geometry to one Na(3), one V(1), and one S(3) atom. In the sixteenth O site, O(16) is bonded in a 3-coordinate geometry to one Na(2), one V(3), and one S(1) atom.
NaV(SO4)2 crystallizes in the triclinic P-1 space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded to two equivalent O(10), two equivalent O(14), and two equivalent O(4) atoms to form distorted NaO6 octahedra that share corners with two equivalent S(1)O4 tetrahedra, corners with four equivalent S(2)O4 tetrahedra, and edges with two equivalent V(1)O6 octahedra. Both Na(1)-O(10) bond lengths are 2.60 Å. Both Na(1)-O(14) bond lengths are 2.61 Å. Both Na(1)-O(4) bond lengths are 2.43 Å. In the second Na site, Na(2) is bonded to one O(12), one O(13), one O(16), one O(2), one O(3), and one O(9) atom to form distorted NaO6 octahedra that share  a cornercorner with one S(2)O4 tetrahedra,  a cornercorner with one S(3)O4 tetrahedra, corners with two equivalent S(1)O4 tetrahedra, corners with two equivalent S(4)O4 tetrahedra,  an edgeedge with one V(2)O6 octahedra, and  an edgeedge with one V(3)O6 octahedra. The Na(2)-O(12) bond length is 2.60 Å. The Na(2)-O(13) bond length is 2.60 Å. The Na(2)-O(16) bond length is 2.61 Å. The Na(2)-O(2) bond length is 2.43 Å. The Na(2)-O(3) bond length is 2.43 Å. The Na(2)-O(9) bond length is 2.60 Å. In the third Na site, Na(3) is bonded to two equivalent O(1), two equivalent O(11), and two equivalent O(15) atoms to form distorted NaO6 octahedra that share corners with two equivalent S(4)O4 tetrahedra, corners with four equivalent S(3)O4 tetrahedra, and edges with two equivalent V(1)O6 octahedra. Both Na(3)-O(1) bond lengths are 2.43 Å. Both Na(3)-O(11) bond lengths are 2.60 Å. Both Na(3)-O(15) bond lengths are 2.60 Å. There are three inequivalent V sites. In the first V site, V(1) is bonded to one O(10), one O(11), one O(14), one O(15), one O(5), and one O(8) atom to form VO6 octahedra that share  a cornercorner with one S(1)O4 tetrahedra,  a cornercorner with one S(4)O4 tetrahedra, corners with two equivalent S(2)O4 tetrahedra, corners with two equivalent S(3)O4 tetrahedra,  an edgeedge with one Na(1)O6 octahedra, and  an edgeedge with one Na(3)O6 octahedra. The V(1)-O(10) bond length is 2.06 Å. The V(1)-O(11) bond length is 2.05 Å. The V(1)-O(14) bond length is 2.04 Å. The V(1)-O(15) bond length is 2.05 Å. The V(1)-O(5) bond length is 2.03 Å. The V(1)-O(8) bond length is 2.03 Å. In the second V site, V(2) is bonded to two equivalent O(13), two equivalent O(6), and two equivalent O(9) atoms to form VO6 octahedra that share corners with two equivalent S(2)O4 tetrahedra, corners with four equivalent S(4)O4 tetrahedra, and edges with two equivalent Na(2)O6 octahedra. Both V(2)-O(13) bond lengths are 2.03 Å. Both V(2)-O(6) bond lengths are 2.03 Å. Both V(2)-O(9) bond lengths are 2.07 Å. In the third V site, V(3) is bonded to two equivalent O(12), two equivalent O(16), and two equivalent O(7) atoms to form VO6 octahedra that share corners with two equivalent S(3)O4 tetrahedra, corners with four equivalent S(1)O4 tetrahedra, and edges with two equivalent Na(2)O6 octahedra. Both V(3)-O(12) bond lengths are 2.05 Å. Both V(3)-O(16) bond lengths are 2.05 Å. Both V(3)-O(7) bond lengths are 2.03 Å. There are four inequivalent S sites. In the first S site, S(1) is bonded to one O(12), one O(16), one O(4), and one O(5) atom to form SO4 tetrahedra that share  a cornercorner with one Na(1)O6 octahedra,  a cornercorner with one V(1)O6 octahedra, corners with two equivalent Na(2)O6 octahedra, and corners with two equivalent V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 36-65°. The S(1)-O(12) bond length is 1.51 Å. The S(1)-O(16) bond length is 1.52 Å. The S(1)-O(4) bond length is 1.45 Å. The S(1)-O(5) bond length is 1.48 Å. In the second S site, S(2) is bonded to one O(10), one O(14), one O(2), and one O(6) atom to form SO4 tetrahedra that share  a cornercorner with one Na(2)O6 octahedra,  a cornercorner with one V(2)O6 octahedra, corners with two equivalent Na(1)O6 octahedra, and corners with two equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 37-65°. The S(2)-O(10) bond length is 1.51 Å. The S(2)-O(14) bond length is 1.52 Å. The S(2)-O(2) bond length is 1.45 Å. The S(2)-O(6) bond length is 1.48 Å. In the third S site, S(3) is bonded to one O(11), one O(15), one O(3), and one O(7) atom to form SO4 tetrahedra that share  a cornercorner with one Na(2)O6 octahedra,  a cornercorner with one V(3)O6 octahedra, corners with two equivalent Na(3)O6 octahedra, and corners with two equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 36-65°. The S(3)-O(11) bond length is 1.52 Å. The S(3)-O(15) bond length is 1.51 Å. The S(3)-O(3) bond length is 1.45 Å. The S(3)-O(7) bond length is 1.48 Å. In the fourth S site, S(4) is bonded to one O(1), one O(13), one O(8), and one O(9) atom to form SO4 tetrahedra that share  a cornercorner with one Na(3)O6 octahedra,  a cornercorner with one V(1)O6 octahedra, corners with two equivalent Na(2)O6 octahedra, and corners with two equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 36-65°. The S(4)-O(1) bond length is 1.45 Å. The S(4)-O(13) bond length is 1.52 Å. The S(4)-O(8) bond length is 1.48 Å. The S(4)-O(9) bond length is 1.51 Å. There are sixteen inequivalent O sites. In the first O site, O(1) is bonded in a distorted bent 120 degrees geometry to one Na(3) and one S(4) atom. In the second O site, O(2) is bonded in a distorted bent 120 degrees geometry to one Na(2) and one S(2) atom. In the third O site, O(3) is bonded in a distorted bent 120 degrees geometry to one Na(2) and one S(3) atom. In the fourth O site, O(4) is bonded in a distorted bent 120 degrees geometry to one Na(1) and one S(1) atom. In the fifth O site, O(5) is bonded in a bent 150 degrees geometry to one V(1) and one S(1) atom. In the sixth O site, O(6) is bonded in a bent 150 degrees geometry to one V(2) and one S(2) atom. In the seventh O site, O(7) is bonded in a bent 150 degrees geometry to one V(3) and one S(3) atom. In the eighth O site, O(8) is bonded in a bent 150 degrees geometry to one V(1) and one S(4) atom. In the ninth O site, O(9) is bonded in a 3-coordinate geometry to one Na(2), one V(2), and one S(4) atom. In the tenth O site, O(10) is bonded in a 3-coordinate geometry to one Na(1), one V(1), and one S(2) atom. In the eleventh O site, O(11) is bonded in a 3-coordinate geometry to one Na(3), one V(1), and one S(3) atom. In the twelfth O site, O(12) is bonded in a 3-coordinate geometry to one Na(2), one V(3), and one S(1) atom. In the thirteenth O site, O(13) is bonded in a 3-coordinate geometry to one Na(2), one V(2), and one S(4) atom. In the fourteenth O site, O(14) is bonded in a 3-coordinate geometry to one Na(1), one V(1), and one S(2) atom. In the fifteenth O site, O(15) is bonded in a 3-coordinate geometry to one Na(3), one V(1), and one S(3) atom. In the sixteenth O site, O(16) is bonded in a 3-coordinate geometry to one Na(2), one V(3), and one S(1) atom.