Cr4ZnO6 crystallizes in the orthorhombic Cmcm space group. There are two inequivalent Cr sites. In the first Cr site, Cr(1) is bonded to one O(2), two equivalent O(1), and three equivalent O(3) atoms to form CrO6 octahedra that share corners with two equivalent Cr(1)O6 octahedra, corners with two equivalent Cr(2)O6 octahedra, corners with two equivalent Zn(1)O6 pentagonal pyramids, edges with five equivalent Cr(1)O6 octahedra, and edges with five equivalent Cr(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-12°. In the second Cr site, Cr(2) is bonded to one O(1), one O(4), two equivalent O(2), and two equivalent O(3) atoms to form CrO6 octahedra that share corners with two equivalent Cr(1)O6 octahedra, corners with two equivalent Cr(2)O6 octahedra, corners with four equivalent Zn(1)O6 pentagonal pyramids, edges with two equivalent Cr(2)O6 octahedra, edges with five equivalent Cr(1)O6 octahedra, and  an edgeedge with one Zn(1)O6 pentagonal pyramid. The corner-sharing octahedral tilt angles range from 0-61°. Zn(1) is bonded to two equivalent O(4) and four equivalent O(2) atoms to form distorted ZnO6 pentagonal pyramids that share corners with four equivalent Cr(1)O6 octahedra, corners with eight equivalent Cr(2)O6 octahedra, edges with two equivalent Cr(2)O6 octahedra, and faces with two equivalent Zn(1)O6 pentagonal pyramids. The corner-sharing octahedral tilt angles range from 25-75°. There are four inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Cr(2) and four equivalent Cr(1) atoms to form OCr6 octahedra that share corners with four equivalent O(3)Cr5 square pyramids, corners with two equivalent O(4)Zn2Cr2 tetrahedra, edges with two equivalent O(1)Cr6 octahedra, edges with six equivalent O(3)Cr5 square pyramids, and edges with four equivalent O(2)Zn2Cr3 trigonal bipyramids. In the second O site, O(2) is bonded to one Cr(1), two equivalent Cr(2), and two equivalent Zn(1) atoms to form distorted OZn2Cr3 trigonal bipyramids that share corners with five equivalent O(3)Cr5 square pyramids, corners with four equivalent O(4)Zn2Cr2 tetrahedra, corners with two equivalent O(2)Zn2Cr3 trigonal bipyramids, edges with two equivalent O(1)Cr6 octahedra,  an edgeedge with one O(3)Cr5 square pyramid,  an edgeedge with one O(4)Zn2Cr2 tetrahedra, and edges with three equivalent O(2)Zn2Cr3 trigonal bipyramids. In the third O site, O(3) is bonded to two equivalent Cr(2) and three equivalent Cr(1) atoms to form OCr5 square pyramids that share corners with two equivalent O(1)Cr6 octahedra, corners with two equivalent O(4)Zn2Cr2 tetrahedra, corners with five equivalent O(2)Zn2Cr3 trigonal bipyramids, edges with three equivalent O(1)Cr6 octahedra, edges with four equivalent O(3)Cr5 square pyramids, and  an edgeedge with one O(2)Zn2Cr3 trigonal bipyramid. The corner-sharing octahedral tilt angles are 6°. In the fourth O site, O(4) is bonded to two equivalent Cr(2) and two equivalent Zn(1) atoms to form OZn2Cr2 tetrahedra that share corners with two equivalent O(1)Cr6 octahedra, corners with four equivalent O(3)Cr5 square pyramids, corners with two equivalent O(4)Zn2Cr2 tetrahedra, corners with eight equivalent O(2)Zn2Cr3 trigonal bipyramids, and edges with two equivalent O(2)Zn2Cr3 trigonal bipyramids. The corner-sharing octahedral tilt angles are 6°.
Cr4ZnO6 crystallizes in the orthorhombic Cmcm space group. There are two inequivalent Cr sites. In the first Cr site, Cr(1) is bonded to one O(2), two equivalent O(1), and three equivalent O(3) atoms to form CrO6 octahedra that share corners with two equivalent Cr(1)O6 octahedra, corners with two equivalent Cr(2)O6 octahedra, corners with two equivalent Zn(1)O6 pentagonal pyramids, edges with five equivalent Cr(1)O6 octahedra, and edges with five equivalent Cr(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-12°. The Cr(1)-O(2) bond length is 2.01 Å. Both Cr(1)-O(1) bond lengths are 2.15 Å. There is one shorter (2.09 Å) and two longer (2.18 Å) Cr(1)-O(3) bond lengths. In the second Cr site, Cr(2) is bonded to one O(1), one O(4), two equivalent O(2), and two equivalent O(3) atoms to form CrO6 octahedra that share corners with two equivalent Cr(1)O6 octahedra, corners with two equivalent Cr(2)O6 octahedra, corners with four equivalent Zn(1)O6 pentagonal pyramids, edges with two equivalent Cr(2)O6 octahedra, edges with five equivalent Cr(1)O6 octahedra, and  an edgeedge with one Zn(1)O6 pentagonal pyramid. The corner-sharing octahedral tilt angles range from 0-61°. The Cr(2)-O(1) bond length is 2.30 Å. The Cr(2)-O(4) bond length is 2.05 Å. Both Cr(2)-O(2) bond lengths are 2.06 Å. Both Cr(2)-O(3) bond lengths are 2.11 Å. Zn(1) is bonded to two equivalent O(4) and four equivalent O(2) atoms to form distorted ZnO6 pentagonal pyramids that share corners with four equivalent Cr(1)O6 octahedra, corners with eight equivalent Cr(2)O6 octahedra, edges with two equivalent Cr(2)O6 octahedra, and faces with two equivalent Zn(1)O6 pentagonal pyramids. The corner-sharing octahedral tilt angles range from 25-75°. Both Zn(1)-O(4) bond lengths are 2.06 Å. All Zn(1)-O(2) bond lengths are 2.38 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Cr(2) and four equivalent Cr(1) atoms to form OCr6 octahedra that share corners with four equivalent O(3)Cr5 square pyramids, corners with two equivalent O(4)Zn2Cr2 tetrahedra, edges with two equivalent O(1)Cr6 octahedra, edges with six equivalent O(3)Cr5 square pyramids, and edges with four equivalent O(2)Zn2Cr3 trigonal bipyramids. In the second O site, O(2) is bonded to one Cr(1), two equivalent Cr(2), and two equivalent Zn(1) atoms to form distorted OZn2Cr3 trigonal bipyramids that share corners with five equivalent O(3)Cr5 square pyramids, corners with four equivalent O(4)Zn2Cr2 tetrahedra, corners with two equivalent O(2)Zn2Cr3 trigonal bipyramids, edges with two equivalent O(1)Cr6 octahedra,  an edgeedge with one O(3)Cr5 square pyramid,  an edgeedge with one O(4)Zn2Cr2 tetrahedra, and edges with three equivalent O(2)Zn2Cr3 trigonal bipyramids. In the third O site, O(3) is bonded to two equivalent Cr(2) and three equivalent Cr(1) atoms to form OCr5 square pyramids that share corners with two equivalent O(1)Cr6 octahedra, corners with two equivalent O(4)Zn2Cr2 tetrahedra, corners with five equivalent O(2)Zn2Cr3 trigonal bipyramids, edges with three equivalent O(1)Cr6 octahedra, edges with four equivalent O(3)Cr5 square pyramids, and  an edgeedge with one O(2)Zn2Cr3 trigonal bipyramid. The corner-sharing octahedral tilt angles are 6°. In the fourth O site, O(4) is bonded to two equivalent Cr(2) and two equivalent Zn(1) atoms to form OZn2Cr2 tetrahedra that share corners with two equivalent O(1)Cr6 octahedra, corners with four equivalent O(3)Cr5 square pyramids, corners with two equivalent O(4)Zn2Cr2 tetrahedra, corners with eight equivalent O(2)Zn2Cr3 trigonal bipyramids, and edges with two equivalent O(2)Zn2Cr3 trigonal bipyramids. The corner-sharing octahedral tilt angles are 6°.