KCd4(VO4)3 crystallizes in the monoclinic Cc space group. K(1) is bonded in a 6-coordinate geometry to one O(12), one O(5), two equivalent O(1), and two equivalent O(4) atoms. There are three inequivalent V sites. In the first V site, V(1) is bonded to one O(11), one O(3), one O(4), and one O(6) atom to form VO4 tetrahedra that share  a cornercorner with one Cd(3)O6 octahedra, corners with three equivalent Cd(4)O6 octahedra, and corners with two equivalent Cd(1)O6 pentagonal pyramids. The corner-sharing octahedral tilt angles range from 39-63°. In the second V site, V(2) is bonded to one O(1), one O(2), one O(8), and one O(9) atom to form VO4 tetrahedra that share  a cornercorner with one Cd(4)O6 octahedra, corners with three equivalent Cd(3)O6 octahedra, and corners with two equivalent Cd(1)O6 pentagonal pyramids. The corner-sharing octahedral tilt angles range from 41-66°. In the third V site, V(3) is bonded to one O(10), one O(12), one O(5), and one O(7) atom to form VO4 tetrahedra that share corners with two equivalent Cd(3)O6 octahedra, corners with two equivalent Cd(4)O6 octahedra, and corners with two equivalent Cd(1)O6 pentagonal pyramids. The corner-sharing octahedral tilt angles range from 53-62°. There are four inequivalent Cd sites. In the first Cd site, Cd(1) is bonded to one O(12), one O(2), one O(3), one O(5), one O(6), and one O(9) atom to form distorted CdO6 pentagonal pyramids that share corners with two equivalent V(1)O4 tetrahedra, corners with two equivalent V(2)O4 tetrahedra, corners with two equivalent V(3)O4 tetrahedra,  an edgeedge with one Cd(3)O6 octahedra, and  an edgeedge with one Cd(4)O6 octahedra. In the second Cd site, Cd(2) is bonded in a 5-coordinate geometry to one O(10), one O(2), one O(7), and two equivalent O(3) atoms. In the third Cd site, Cd(3) is bonded to one O(1), one O(10), one O(11), one O(5), one O(8), and one O(9) atom to form CdO6 octahedra that share  a cornercorner with one V(1)O4 tetrahedra, corners with two equivalent V(3)O4 tetrahedra, corners with three equivalent V(2)O4 tetrahedra,  an edgeedge with one Cd(4)O6 octahedra, and  an edgeedge with one Cd(1)O6 pentagonal pyramid. In the fourth Cd site, Cd(4) is bonded to one O(11), one O(12), one O(4), one O(6), one O(7), and one O(8) atom to form CdO6 octahedra that share  a cornercorner with one V(2)O4 tetrahedra, corners with two equivalent V(3)O4 tetrahedra, corners with three equivalent V(1)O4 tetrahedra,  an edgeedge with one Cd(3)O6 octahedra, and  an edgeedge with one Cd(1)O6 pentagonal pyramid. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a 4-coordinate geometry to two equivalent K(1), one V(2), and one Cd(3) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one V(2), one Cd(1), and one Cd(2) atom. In the third O site, O(3) is bonded to one V(1), one Cd(1), and two equivalent Cd(2) atoms to form distorted corner-sharing OVCd3 tetrahedra. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to two equivalent K(1), one V(1), and one Cd(4) atom. In the fifth O site, O(5) is bonded in a 4-coordinate geometry to one K(1), one V(3), one Cd(1), and one Cd(3) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one V(1), one Cd(1), and one Cd(4) atom. In the seventh O site, O(7) is bonded in a distorted trigonal planar geometry to one V(3), one Cd(2), and one Cd(4) atom. In the eighth O site, O(8) is bonded in a 3-coordinate geometry to one V(2), one Cd(3), and one Cd(4) atom. In the ninth O site, O(9) is bonded in a 3-coordinate geometry to one V(2), one Cd(1), and one Cd(3) atom. In the tenth O site, O(10) is bonded in a distorted trigonal planar geometry to one V(3), one Cd(2), and one Cd(3) atom. In the eleventh O site, O(11) is bonded in a 3-coordinate geometry to one V(1), one Cd(3), and one Cd(4) atom. In the twelfth O site, O(12) is bonded in a 4-coordinate geometry to one K(1), one V(3), one Cd(1), and one Cd(4) atom.
KCd4(VO4)3 crystallizes in the monoclinic Cc space group. K(1) is bonded in a 6-coordinate geometry to one O(12), one O(5), two equivalent O(1), and two equivalent O(4) atoms. The K(1)-O(12) bond length is 3.02 Å. The K(1)-O(5) bond length is 3.02 Å. There is one shorter (2.70 Å) and one longer (2.80 Å) K(1)-O(1) bond length. There is one shorter (2.71 Å) and one longer (2.83 Å) K(1)-O(4) bond length. There are three inequivalent V sites. In the first V site, V(1) is bonded to one O(11), one O(3), one O(4), and one O(6) atom to form VO4 tetrahedra that share  a cornercorner with one Cd(3)O6 octahedra, corners with three equivalent Cd(4)O6 octahedra, and corners with two equivalent Cd(1)O6 pentagonal pyramids. The corner-sharing octahedral tilt angles range from 39-63°. The V(1)-O(11) bond length is 1.73 Å. The V(1)-O(3) bond length is 1.81 Å. The V(1)-O(4) bond length is 1.72 Å. The V(1)-O(6) bond length is 1.75 Å. In the second V site, V(2) is bonded to one O(1), one O(2), one O(8), and one O(9) atom to form VO4 tetrahedra that share  a cornercorner with one Cd(4)O6 octahedra, corners with three equivalent Cd(3)O6 octahedra, and corners with two equivalent Cd(1)O6 pentagonal pyramids. The corner-sharing octahedral tilt angles range from 41-66°. The V(2)-O(1) bond length is 1.72 Å. The V(2)-O(2) bond length is 1.78 Å. The V(2)-O(8) bond length is 1.74 Å. The V(2)-O(9) bond length is 1.77 Å. In the third V site, V(3) is bonded to one O(10), one O(12), one O(5), and one O(7) atom to form VO4 tetrahedra that share corners with two equivalent Cd(3)O6 octahedra, corners with two equivalent Cd(4)O6 octahedra, and corners with two equivalent Cd(1)O6 pentagonal pyramids. The corner-sharing octahedral tilt angles range from 53-62°. The V(3)-O(10) bond length is 1.75 Å. The V(3)-O(12) bond length is 1.74 Å. The V(3)-O(5) bond length is 1.75 Å. The V(3)-O(7) bond length is 1.77 Å. There are four inequivalent Cd sites. In the first Cd site, Cd(1) is bonded to one O(12), one O(2), one O(3), one O(5), one O(6), and one O(9) atom to form distorted CdO6 pentagonal pyramids that share corners with two equivalent V(1)O4 tetrahedra, corners with two equivalent V(2)O4 tetrahedra, corners with two equivalent V(3)O4 tetrahedra,  an edgeedge with one Cd(3)O6 octahedra, and  an edgeedge with one Cd(4)O6 octahedra. The Cd(1)-O(12) bond length is 2.44 Å. The Cd(1)-O(2) bond length is 2.35 Å. The Cd(1)-O(3) bond length is 2.45 Å. The Cd(1)-O(5) bond length is 2.36 Å. The Cd(1)-O(6) bond length is 2.34 Å. The Cd(1)-O(9) bond length is 2.34 Å. In the second Cd site, Cd(2) is bonded in a 5-coordinate geometry to one O(10), one O(2), one O(7), and two equivalent O(3) atoms. The Cd(2)-O(10) bond length is 2.33 Å. The Cd(2)-O(2) bond length is 2.34 Å. The Cd(2)-O(7) bond length is 2.32 Å. There is one shorter (2.40 Å) and one longer (2.54 Å) Cd(2)-O(3) bond length. In the third Cd site, Cd(3) is bonded to one O(1), one O(10), one O(11), one O(5), one O(8), and one O(9) atom to form CdO6 octahedra that share  a cornercorner with one V(1)O4 tetrahedra, corners with two equivalent V(3)O4 tetrahedra, corners with three equivalent V(2)O4 tetrahedra,  an edgeedge with one Cd(4)O6 octahedra, and  an edgeedge with one Cd(1)O6 pentagonal pyramid. The Cd(3)-O(1) bond length is 2.26 Å. The Cd(3)-O(10) bond length is 2.25 Å. The Cd(3)-O(11) bond length is 2.38 Å. The Cd(3)-O(5) bond length is 2.32 Å. The Cd(3)-O(8) bond length is 2.33 Å. The Cd(3)-O(9) bond length is 2.28 Å. In the fourth Cd site, Cd(4) is bonded to one O(11), one O(12), one O(4), one O(6), one O(7), and one O(8) atom to form CdO6 octahedra that share  a cornercorner with one V(2)O4 tetrahedra, corners with two equivalent V(3)O4 tetrahedra, corners with three equivalent V(1)O4 tetrahedra,  an edgeedge with one Cd(3)O6 octahedra, and  an edgeedge with one Cd(1)O6 pentagonal pyramid. The Cd(4)-O(11) bond length is 2.33 Å. The Cd(4)-O(12) bond length is 2.30 Å. The Cd(4)-O(4) bond length is 2.28 Å. The Cd(4)-O(6) bond length is 2.29 Å. The Cd(4)-O(7) bond length is 2.26 Å. The Cd(4)-O(8) bond length is 2.34 Å. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a 4-coordinate geometry to two equivalent K(1), one V(2), and one Cd(3) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one V(2), one Cd(1), and one Cd(2) atom. In the third O site, O(3) is bonded to one V(1), one Cd(1), and two equivalent Cd(2) atoms to form distorted corner-sharing OVCd3 tetrahedra. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to two equivalent K(1), one V(1), and one Cd(4) atom. In the fifth O site, O(5) is bonded in a 4-coordinate geometry to one K(1), one V(3), one Cd(1), and one Cd(3) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one V(1), one Cd(1), and one Cd(4) atom. In the seventh O site, O(7) is bonded in a distorted trigonal planar geometry to one V(3), one Cd(2), and one Cd(4) atom. In the eighth O site, O(8) is bonded in a 3-coordinate geometry to one V(2), one Cd(3), and one Cd(4) atom. In the ninth O site, O(9) is bonded in a 3-coordinate geometry to one V(2), one Cd(1), and one Cd(3) atom. In the tenth O site, O(10) is bonded in a distorted trigonal planar geometry to one V(3), one Cd(2), and one Cd(3) atom. In the eleventh O site, O(11) is bonded in a 3-coordinate geometry to one V(1), one Cd(3), and one Cd(4) atom. In the twelfth O site, O(12) is bonded in a 4-coordinate geometry to one K(1), one V(3), one Cd(1), and one Cd(4) atom.