KNa3WO5 crystallizes in the monoclinic C2/m space group. K(1) is bonded in a distorted body-centered cubic geometry to two equivalent O(3), two equivalent O(4), and four equivalent O(1) atoms. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded to one O(3), one O(4), and three equivalent O(2) atoms to form distorted NaO5 trigonal bipyramids that share  a cornercorner with one Na(2)O5 trigonal bipyramid,  a cornercorner with one W(1)O5 trigonal bipyramid, corners with four equivalent Na(1)O5 trigonal bipyramids, edges with two equivalent Na(1)O5 trigonal bipyramids, edges with two equivalent Na(2)O5 trigonal bipyramids, and edges with two equivalent W(1)O5 trigonal bipyramids. In the second Na site, Na(2) is bonded to one O(1), one O(3), one O(4), and two equivalent O(2) atoms to form NaO5 trigonal bipyramids that share corners with two equivalent Na(1)O5 trigonal bipyramids, corners with five equivalent W(1)O5 trigonal bipyramids, and edges with four equivalent Na(1)O5 trigonal bipyramids. W(1) is bonded to one O(1), one O(3), one O(4), and two equivalent O(2) atoms to form WO5 trigonal bipyramids that share corners with two equivalent Na(1)O5 trigonal bipyramids, corners with five equivalent Na(2)O5 trigonal bipyramids, and edges with four equivalent Na(1)O5 trigonal bipyramids. There are four inequivalent O sites. In the first O site, O(1) is bonded to four equivalent K(1), one Na(2), and one W(1) atom to form distorted OK4NaW octahedra that share corners with four equivalent O(3)K2Na3W octahedra, corners with four equivalent O(4)K2Na3W octahedra, corners with four equivalent O(1)K4NaW octahedra, corners with four equivalent O(2)Na4W trigonal bipyramids, edges with four equivalent O(1)K4NaW octahedra, faces with two equivalent O(3)K2Na3W octahedra, and faces with two equivalent O(4)K2Na3W octahedra. The corner-sharing octahedral tilt angles range from 12-67°. In the second O site, O(2) is bonded to one Na(2), three equivalent Na(1), and one W(1) atom to form ONa4W trigonal bipyramids that share  a cornercorner with one O(3)K2Na3W octahedra,  a cornercorner with one O(4)K2Na3W octahedra, corners with two equivalent O(1)K4NaW octahedra, corners with four equivalent O(2)Na4W trigonal bipyramids, edges with two equivalent O(3)K2Na3W octahedra, edges with two equivalent O(4)K2Na3W octahedra, and edges with two equivalent O(2)Na4W trigonal bipyramids. The corner-sharing octahedral tilt angles range from 54-63°. In the third O site, O(3) is bonded to two equivalent K(1), one Na(2), two equivalent Na(1), and one W(1) atom to form distorted OK2Na3W octahedra that share corners with four equivalent O(4)K2Na3W octahedra, corners with four equivalent O(1)K4NaW octahedra, corners with two equivalent O(2)Na4W trigonal bipyramids,  an edgeedge with one O(3)K2Na3W octahedra, edges with two equivalent O(4)K2Na3W octahedra, edges with four equivalent O(2)Na4W trigonal bipyramids, and faces with two equivalent O(1)K4NaW octahedra. The corner-sharing octahedral tilt angles range from 2-67°. In the fourth O site, O(4) is bonded to two equivalent K(1), one Na(2), two equivalent Na(1), and one W(1) atom to form distorted OK2Na3W octahedra that share corners with four equivalent O(3)K2Na3W octahedra, corners with four equivalent O(1)K4NaW octahedra, corners with two equivalent O(2)Na4W trigonal bipyramids,  an edgeedge with one O(4)K2Na3W octahedra, edges with two equivalent O(3)K2Na3W octahedra, edges with four equivalent O(2)Na4W trigonal bipyramids, and faces with two equivalent O(1)K4NaW octahedra. The corner-sharing octahedral tilt angles range from 2-66°.
KNa3WO5 crystallizes in the monoclinic C2/m space group. K(1) is bonded in a distorted body-centered cubic geometry to two equivalent O(3), two equivalent O(4), and four equivalent O(1) atoms. Both K(1)-O(3) bond lengths are 2.96 Å. Both K(1)-O(4) bond lengths are 2.89 Å. There are two shorter (2.96 Å) and two longer (3.01 Å) K(1)-O(1) bond lengths. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded to one O(3), one O(4), and three equivalent O(2) atoms to form distorted NaO5 trigonal bipyramids that share  a cornercorner with one Na(2)O5 trigonal bipyramid,  a cornercorner with one W(1)O5 trigonal bipyramid, corners with four equivalent Na(1)O5 trigonal bipyramids, edges with two equivalent Na(1)O5 trigonal bipyramids, edges with two equivalent Na(2)O5 trigonal bipyramids, and edges with two equivalent W(1)O5 trigonal bipyramids. The Na(1)-O(3) bond length is 2.31 Å. The Na(1)-O(4) bond length is 2.30 Å. There are a spread of Na(1)-O(2) bond distances ranging from 2.33-2.40 Å. In the second Na site, Na(2) is bonded to one O(1), one O(3), one O(4), and two equivalent O(2) atoms to form NaO5 trigonal bipyramids that share corners with two equivalent Na(1)O5 trigonal bipyramids, corners with five equivalent W(1)O5 trigonal bipyramids, and edges with four equivalent Na(1)O5 trigonal bipyramids. The Na(2)-O(1) bond length is 2.32 Å. The Na(2)-O(3) bond length is 2.60 Å. The Na(2)-O(4) bond length is 2.69 Å. Both Na(2)-O(2) bond lengths are 2.38 Å. W(1) is bonded to one O(1), one O(3), one O(4), and two equivalent O(2) atoms to form WO5 trigonal bipyramids that share corners with two equivalent Na(1)O5 trigonal bipyramids, corners with five equivalent Na(2)O5 trigonal bipyramids, and edges with four equivalent Na(1)O5 trigonal bipyramids. The W(1)-O(1) bond length is 1.86 Å. The W(1)-O(3) bond length is 1.94 Å. The W(1)-O(4) bond length is 1.94 Å. Both W(1)-O(2) bond lengths are 1.90 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded to four equivalent K(1), one Na(2), and one W(1) atom to form distorted OK4NaW octahedra that share corners with four equivalent O(3)K2Na3W octahedra, corners with four equivalent O(4)K2Na3W octahedra, corners with four equivalent O(1)K4NaW octahedra, corners with four equivalent O(2)Na4W trigonal bipyramids, edges with four equivalent O(1)K4NaW octahedra, faces with two equivalent O(3)K2Na3W octahedra, and faces with two equivalent O(4)K2Na3W octahedra. The corner-sharing octahedral tilt angles range from 12-67°. In the second O site, O(2) is bonded to one Na(2), three equivalent Na(1), and one W(1) atom to form ONa4W trigonal bipyramids that share  a cornercorner with one O(3)K2Na3W octahedra,  a cornercorner with one O(4)K2Na3W octahedra, corners with two equivalent O(1)K4NaW octahedra, corners with four equivalent O(2)Na4W trigonal bipyramids, edges with two equivalent O(3)K2Na3W octahedra, edges with two equivalent O(4)K2Na3W octahedra, and edges with two equivalent O(2)Na4W trigonal bipyramids. The corner-sharing octahedral tilt angles range from 54-63°. In the third O site, O(3) is bonded to two equivalent K(1), one Na(2), two equivalent Na(1), and one W(1) atom to form distorted OK2Na3W octahedra that share corners with four equivalent O(4)K2Na3W octahedra, corners with four equivalent O(1)K4NaW octahedra, corners with two equivalent O(2)Na4W trigonal bipyramids,  an edgeedge with one O(3)K2Na3W octahedra, edges with two equivalent O(4)K2Na3W octahedra, edges with four equivalent O(2)Na4W trigonal bipyramids, and faces with two equivalent O(1)K4NaW octahedra. The corner-sharing octahedral tilt angles range from 2-67°. In the fourth O site, O(4) is bonded to two equivalent K(1), one Na(2), two equivalent Na(1), and one W(1) atom to form distorted OK2Na3W octahedra that share corners with four equivalent O(3)K2Na3W octahedra, corners with four equivalent O(1)K4NaW octahedra, corners with two equivalent O(2)Na4W trigonal bipyramids,  an edgeedge with one O(4)K2Na3W octahedra, edges with two equivalent O(3)K2Na3W octahedra, edges with four equivalent O(2)Na4W trigonal bipyramids, and faces with two equivalent O(1)K4NaW octahedra. The corner-sharing octahedral tilt angles range from 2-66°.