KNaV4H4O11 crystallizes in the monoclinic C2/c space group. K(1) is bonded in a 6-coordinate geometry to two equivalent O(4) and four equivalent O(5) atoms. Na(1) is bonded in a distorted pentagonal pyramidal geometry to two equivalent O(1), two equivalent O(2), and two equivalent O(6) atoms. There are two inequivalent V sites. In the first V site, V(1) is bonded in a 5-coordinate geometry to one O(2), one O(3), one O(4), and two equivalent O(1) atoms. In the second V site, V(2) is bonded in a 5-coordinate geometry to one O(1), one O(3), one O(5), and two equivalent O(2) atoms. There are two inequivalent H sites. In the first H site, H(1) is bonded in a single-bond geometry to one O(6) atom. In the second H site, H(2) is bonded in a single-bond geometry to one O(6) atom. There are six inequivalent O sites. In the first O site, O(1) is bonded to one Na(1), one V(2), and two equivalent V(1) atoms to form distorted ONaV3 tetrahedra that share  a cornercorner with one O(1)NaV3 tetrahedra, corners with two equivalent O(2)NaV3 tetrahedra,  a cornercorner with one O(3)V4 trigonal pyramid,  an edgeedge with one O(1)NaV3 tetrahedra, edges with two equivalent O(2)NaV3 tetrahedra, and  an edgeedge with one O(3)V4 trigonal pyramid. In the second O site, O(2) is bonded to one Na(1), one V(1), and two equivalent V(2) atoms to form distorted ONaV3 tetrahedra that share  a cornercorner with one O(2)NaV3 tetrahedra, corners with two equivalent O(1)NaV3 tetrahedra,  a cornercorner with one O(3)V4 trigonal pyramid,  an edgeedge with one O(2)NaV3 tetrahedra, edges with two equivalent O(1)NaV3 tetrahedra, and  an edgeedge with one O(3)V4 trigonal pyramid. In the third O site, O(3) is bonded to two equivalent V(1) and two equivalent V(2) atoms to form a mixture of distorted corner and edge-sharing OV4 trigonal pyramids. In the fourth O site, O(4) is bonded in a single-bond geometry to one K(1) and one V(1) atom. In the fifth O site, O(5) is bonded in a distorted single-bond geometry to two equivalent K(1) and one V(2) atom. In the sixth O site, O(6) is bonded in a distorted water-like geometry to one Na(1), one H(1), and one H(2) atom.
KNaV4H4O11 crystallizes in the monoclinic C2/c space group. K(1) is bonded in a 6-coordinate geometry to two equivalent O(4) and four equivalent O(5) atoms. Both K(1)-O(4) bond lengths are 2.97 Å. There are two shorter (2.75 Å) and two longer (2.83 Å) K(1)-O(5) bond lengths. Na(1) is bonded in a distorted pentagonal pyramidal geometry to two equivalent O(1), two equivalent O(2), and two equivalent O(6) atoms. Both Na(1)-O(1) bond lengths are 2.51 Å. Both Na(1)-O(2) bond lengths are 2.47 Å. Both Na(1)-O(6) bond lengths are 2.34 Å. There are two inequivalent V sites. In the first V site, V(1) is bonded in a 5-coordinate geometry to one O(2), one O(3), one O(4), and two equivalent O(1) atoms. The V(1)-O(2) bond length is 1.97 Å. The V(1)-O(3) bond length is 2.05 Å. The V(1)-O(4) bond length is 1.67 Å. There is one shorter (1.96 Å) and one longer (1.98 Å) V(1)-O(1) bond length. In the second V site, V(2) is bonded in a 5-coordinate geometry to one O(1), one O(3), one O(5), and two equivalent O(2) atoms. The V(2)-O(1) bond length is 1.97 Å. The V(2)-O(3) bond length is 2.06 Å. The V(2)-O(5) bond length is 1.66 Å. There is one shorter (1.97 Å) and one longer (1.99 Å) V(2)-O(2) bond length. There are two inequivalent H sites. In the first H site, H(1) is bonded in a single-bond geometry to one O(6) atom. The H(1)-O(6) bond length is 0.98 Å. In the second H site, H(2) is bonded in a single-bond geometry to one O(6) atom. The H(2)-O(6) bond length is 0.99 Å. There are six inequivalent O sites. In the first O site, O(1) is bonded to one Na(1), one V(2), and two equivalent V(1) atoms to form distorted ONaV3 tetrahedra that share  a cornercorner with one O(1)NaV3 tetrahedra, corners with two equivalent O(2)NaV3 tetrahedra,  a cornercorner with one O(3)V4 trigonal pyramid,  an edgeedge with one O(1)NaV3 tetrahedra, edges with two equivalent O(2)NaV3 tetrahedra, and  an edgeedge with one O(3)V4 trigonal pyramid. In the second O site, O(2) is bonded to one Na(1), one V(1), and two equivalent V(2) atoms to form distorted ONaV3 tetrahedra that share  a cornercorner with one O(2)NaV3 tetrahedra, corners with two equivalent O(1)NaV3 tetrahedra,  a cornercorner with one O(3)V4 trigonal pyramid,  an edgeedge with one O(2)NaV3 tetrahedra, edges with two equivalent O(1)NaV3 tetrahedra, and  an edgeedge with one O(3)V4 trigonal pyramid. In the third O site, O(3) is bonded to two equivalent V(1) and two equivalent V(2) atoms to form a mixture of distorted corner and edge-sharing OV4 trigonal pyramids. In the fourth O site, O(4) is bonded in a single-bond geometry to one K(1) and one V(1) atom. In the fifth O site, O(5) is bonded in a distorted single-bond geometry to two equivalent K(1) and one V(2) atom. In the sixth O site, O(6) is bonded in a distorted water-like geometry to one Na(1), one H(1), and one H(2) atom.