Zn4In2O7 crystallizes in the hexagonal P6_3/mmc space group. There are two inequivalent Zn sites. In the first Zn site, Zn(1) is bonded to one O(2) and three equivalent O(1) atoms to form ZnO4 tetrahedra that share corners with three equivalent In(1)O6 octahedra, corners with three equivalent Zn(2)O4 tetrahedra, and corners with six equivalent Zn(1)O4 tetrahedra. The corner-sharing octahedral tilt angles are 62°. In the second Zn site, Zn(2) is bonded to one O(1) and three equivalent O(3) atoms to form ZnO4 tetrahedra that share corners with three equivalent Zn(1)O4 tetrahedra, corners with six equivalent Zn(2)O4 tetrahedra, and corners with three equivalent In(2)O5 trigonal bipyramids. There are two inequivalent In sites. In the first In site, In(1) is bonded to six equivalent O(2) atoms to form InO6 octahedra that share corners with six equivalent Zn(1)O4 tetrahedra and edges with six equivalent In(1)O6 octahedra. In the second In site, In(2) is bonded to two equivalent O(3) and three equivalent O(4) atoms to form InO5 trigonal bipyramids that share corners with six equivalent Zn(2)O4 tetrahedra and corners with six equivalent In(2)O5 trigonal bipyramids. There are four inequivalent O sites. In the first O site, O(1) is bonded to one Zn(2) and three equivalent Zn(1) atoms to form OZn4 tetrahedra that share corners with three equivalent O(3)Zn3In tetrahedra, corners with three equivalent O(2)ZnIn3 tetrahedra, and corners with six equivalent O(1)Zn4 tetrahedra. In the second O site, O(2) is bonded to one Zn(1) and three equivalent In(1) atoms to form distorted OZnIn3 tetrahedra that share corners with three equivalent O(1)Zn4 tetrahedra, corners with nine equivalent O(2)ZnIn3 tetrahedra, and edges with three equivalent O(2)ZnIn3 tetrahedra. In the third O site, O(3) is bonded to three equivalent Zn(2) and one In(2) atom to form OZn3In tetrahedra that share corners with three equivalent O(1)Zn4 tetrahedra and corners with seven equivalent O(3)Zn3In tetrahedra. In the fourth O site, O(4) is bonded in a trigonal planar geometry to three equivalent In(2) atoms.
Zn4In2O7 crystallizes in the hexagonal P6_3/mmc space group. There are two inequivalent Zn sites. In the first Zn site, Zn(1) is bonded to one O(2) and three equivalent O(1) atoms to form ZnO4 tetrahedra that share corners with three equivalent In(1)O6 octahedra, corners with three equivalent Zn(2)O4 tetrahedra, and corners with six equivalent Zn(1)O4 tetrahedra. The corner-sharing octahedral tilt angles are 62°. The Zn(1)-O(2) bond length is 1.99 Å. All Zn(1)-O(1) bond lengths are 2.06 Å. In the second Zn site, Zn(2) is bonded to one O(1) and three equivalent O(3) atoms to form ZnO4 tetrahedra that share corners with three equivalent Zn(1)O4 tetrahedra, corners with six equivalent Zn(2)O4 tetrahedra, and corners with three equivalent In(2)O5 trigonal bipyramids. The Zn(2)-O(1) bond length is 1.99 Å. All Zn(2)-O(3) bond lengths are 2.07 Å. There are two inequivalent In sites. In the first In site, In(1) is bonded to six equivalent O(2) atoms to form InO6 octahedra that share corners with six equivalent Zn(1)O4 tetrahedra and edges with six equivalent In(1)O6 octahedra. All In(1)-O(2) bond lengths are 2.25 Å. In the second In site, In(2) is bonded to two equivalent O(3) and three equivalent O(4) atoms to form InO5 trigonal bipyramids that share corners with six equivalent Zn(2)O4 tetrahedra and corners with six equivalent In(2)O5 trigonal bipyramids. Both In(2)-O(3) bond lengths are 2.22 Å. All In(2)-O(4) bond lengths are 1.98 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded to one Zn(2) and three equivalent Zn(1) atoms to form OZn4 tetrahedra that share corners with three equivalent O(3)Zn3In tetrahedra, corners with three equivalent O(2)ZnIn3 tetrahedra, and corners with six equivalent O(1)Zn4 tetrahedra. In the second O site, O(2) is bonded to one Zn(1) and three equivalent In(1) atoms to form distorted OZnIn3 tetrahedra that share corners with three equivalent O(1)Zn4 tetrahedra, corners with nine equivalent O(2)ZnIn3 tetrahedra, and edges with three equivalent O(2)ZnIn3 tetrahedra. In the third O site, O(3) is bonded to three equivalent Zn(2) and one In(2) atom to form OZn3In tetrahedra that share corners with three equivalent O(1)Zn4 tetrahedra and corners with seven equivalent O(3)Zn3In tetrahedra. In the fourth O site, O(4) is bonded in a trigonal planar geometry to three equivalent In(2) atoms.