Cs4Na2MgV2O8 crystallizes in the triclinic P1 space group. There are four inequivalent Cs sites. In the first Cs site, Cs(1) is bonded in a 5-coordinate geometry to one Mg(1), one O(2), one O(3), one O(6), and one O(8) atom. In the second Cs site, Cs(2) is bonded in a 5-coordinate geometry to one O(1), one O(4), one O(5), one O(6), and one O(8) atom. In the third Cs site, Cs(3) is bonded in a 8-coordinate geometry to one O(2), one O(3), one O(5), one O(6), two equivalent O(4), and two equivalent O(7) atoms. In the fourth Cs site, Cs(4) is bonded in a 7-coordinate geometry to one O(1), one O(2), one O(3), one O(7), one O(8), and two equivalent O(5) atoms. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded in a 4-coordinate geometry to one O(2), one O(3), one O(4), and one O(5) atom. In the second Na site, Na(2) is bonded to one O(1), one O(2), one O(3), and one O(7) atom to form NaO4 tetrahedra that share corners with two equivalent V(1)O4 tetrahedra and corners with two equivalent V(2)O4 tetrahedra. Mg(1) is bonded in a 3-coordinate geometry to one Cs(1), one O(6), one O(7), and one O(8) atom. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(4), one O(7), and one O(8) atom to form VO4 tetrahedra that share corners with two equivalent Na(2)O4 tetrahedra. In the second V site, V(2) is bonded to one O(2), one O(3), one O(5), and one O(6) atom to form VO4 tetrahedra that share corners with two equivalent Na(2)O4 tetrahedra. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a distorted bent 120 degrees geometry to one Cs(2), one Cs(4), one Na(2), and one V(1) atom. In the second O site, O(2) is bonded in a 4-coordinate geometry to one Cs(1), one Cs(3), one Cs(4), one Na(1), one Na(2), and one V(2) atom. In the third O site, O(3) is bonded in a 6-coordinate geometry to one Cs(1), one Cs(3), one Cs(4), one Na(1), one Na(2), and one V(2) atom. In the fourth O site, O(4) is bonded in a 2-coordinate geometry to one Cs(2), two equivalent Cs(3), one Na(1), and one V(1) atom. In the fifth O site, O(5) is bonded in a 2-coordinate geometry to one Cs(2), one Cs(3), two equivalent Cs(4), one Na(1), and one V(2) atom. In the sixth O site, O(6) is bonded in a distorted bent 120 degrees geometry to one Cs(1), one Cs(2), one Cs(3), one Mg(1), and one V(2) atom. In the seventh O site, O(7) is bonded in a 3-coordinate geometry to one Cs(4), two equivalent Cs(3), one Na(2), one Mg(1), and one V(1) atom. In the eighth O site, O(8) is bonded in a 2-coordinate geometry to one Cs(1), one Cs(2), one Cs(4), one Mg(1), and one V(1) atom.
Cs4Na2MgV2O8 crystallizes in the triclinic P1 space group. There are four inequivalent Cs sites. In the first Cs site, Cs(1) is bonded in a 5-coordinate geometry to one Mg(1), one O(2), one O(3), one O(6), and one O(8) atom. The Cs(1)-Mg(1) bond length is 3.22 Å. The Cs(1)-O(2) bond length is 2.85 Å. The Cs(1)-O(3) bond length is 2.98 Å. The Cs(1)-O(6) bond length is 3.19 Å. The Cs(1)-O(8) bond length is 2.96 Å. In the second Cs site, Cs(2) is bonded in a 5-coordinate geometry to one O(1), one O(4), one O(5), one O(6), and one O(8) atom. The Cs(2)-O(1) bond length is 3.32 Å. The Cs(2)-O(4) bond length is 3.03 Å. The Cs(2)-O(5) bond length is 3.22 Å. The Cs(2)-O(6) bond length is 3.03 Å. The Cs(2)-O(8) bond length is 3.11 Å. In the third Cs site, Cs(3) is bonded in a 8-coordinate geometry to one O(2), one O(3), one O(5), one O(6), two equivalent O(4), and two equivalent O(7) atoms. The Cs(3)-O(2) bond length is 3.23 Å. The Cs(3)-O(3) bond length is 3.46 Å. The Cs(3)-O(5) bond length is 3.22 Å. The Cs(3)-O(6) bond length is 3.46 Å. There is one shorter (3.10 Å) and one longer (3.72 Å) Cs(3)-O(4) bond length. There is one shorter (3.21 Å) and one longer (3.44 Å) Cs(3)-O(7) bond length. In the fourth Cs site, Cs(4) is bonded in a 7-coordinate geometry to one O(1), one O(2), one O(3), one O(7), one O(8), and two equivalent O(5) atoms. The Cs(4)-O(1) bond length is 3.15 Å. The Cs(4)-O(2) bond length is 3.54 Å. The Cs(4)-O(3) bond length is 3.15 Å. The Cs(4)-O(7) bond length is 3.41 Å. The Cs(4)-O(8) bond length is 3.25 Å. There is one shorter (3.29 Å) and one longer (3.33 Å) Cs(4)-O(5) bond length. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded in a 4-coordinate geometry to one O(2), one O(3), one O(4), and one O(5) atom. The Na(1)-O(2) bond length is 2.60 Å. The Na(1)-O(3) bond length is 2.45 Å. The Na(1)-O(4) bond length is 2.31 Å. The Na(1)-O(5) bond length is 2.41 Å. In the second Na site, Na(2) is bonded to one O(1), one O(2), one O(3), and one O(7) atom to form NaO4 tetrahedra that share corners with two equivalent V(1)O4 tetrahedra and corners with two equivalent V(2)O4 tetrahedra. The Na(2)-O(1) bond length is 2.29 Å. The Na(2)-O(2) bond length is 2.41 Å. The Na(2)-O(3) bond length is 2.40 Å. The Na(2)-O(7) bond length is 2.39 Å. Mg(1) is bonded in a 3-coordinate geometry to one Cs(1), one O(6), one O(7), and one O(8) atom. The Mg(1)-O(6) bond length is 1.89 Å. The Mg(1)-O(7) bond length is 1.93 Å. The Mg(1)-O(8) bond length is 1.93 Å. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(4), one O(7), and one O(8) atom to form VO4 tetrahedra that share corners with two equivalent Na(2)O4 tetrahedra. The V(1)-O(1) bond length is 1.76 Å. The V(1)-O(4) bond length is 1.75 Å. The V(1)-O(7) bond length is 1.95 Å. The V(1)-O(8) bond length is 1.93 Å. In the second V site, V(2) is bonded to one O(2), one O(3), one O(5), and one O(6) atom to form VO4 tetrahedra that share corners with two equivalent Na(2)O4 tetrahedra. The V(2)-O(2) bond length is 1.83 Å. The V(2)-O(3) bond length is 1.83 Å. The V(2)-O(5) bond length is 1.79 Å. The V(2)-O(6) bond length is 1.92 Å. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a distorted bent 120 degrees geometry to one Cs(2), one Cs(4), one Na(2), and one V(1) atom. In the second O site, O(2) is bonded in a 4-coordinate geometry to one Cs(1), one Cs(3), one Cs(4), one Na(1), one Na(2), and one V(2) atom. In the third O site, O(3) is bonded in a 6-coordinate geometry to one Cs(1), one Cs(3), one Cs(4), one Na(1), one Na(2), and one V(2) atom. In the fourth O site, O(4) is bonded in a 2-coordinate geometry to one Cs(2), two equivalent Cs(3), one Na(1), and one V(1) atom. In the fifth O site, O(5) is bonded in a 2-coordinate geometry to one Cs(2), one Cs(3), two equivalent Cs(4), one Na(1), and one V(2) atom. In the sixth O site, O(6) is bonded in a distorted bent 120 degrees geometry to one Cs(1), one Cs(2), one Cs(3), one Mg(1), and one V(2) atom. In the seventh O site, O(7) is bonded in a 3-coordinate geometry to one Cs(4), two equivalent Cs(3), one Na(2), one Mg(1), and one V(1) atom. In the eighth O site, O(8) is bonded in a 2-coordinate geometry to one Cs(1), one Cs(2), one Cs(4), one Mg(1), and one V(1) atom.