Zn3In2O6 is Aluminum carbonitride-like structured and crystallizes in the trigonal R3m space group. There are three inequivalent Zn sites. In the first Zn site, Zn(1) is bonded to one O(5) and three equivalent O(1) atoms to form ZnO4 tetrahedra that share corners with three equivalent In(1)O6 octahedra, corners with six equivalent Zn(1)O4 tetrahedra, and corners with three equivalent In(2)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles are 62°. In the second Zn site, Zn(2) is bonded to one O(6) and three equivalent O(2) atoms to form ZnO4 tetrahedra that share corners with three equivalent In(1)O6 octahedra, corners with three equivalent Zn(3)O4 tetrahedra, and corners with six equivalent Zn(2)O4 tetrahedra. The corner-sharing octahedral tilt angles are 63°. In the third Zn site, Zn(3) is bonded to one O(2) and three equivalent O(4) atoms to form ZnO4 tetrahedra that share corners with three equivalent Zn(2)O4 tetrahedra, corners with six equivalent Zn(3)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 three equivalent O(5) and three equivalent O(6) atoms to form InO6 octahedra that share corners with three equivalent Zn(1)O4 tetrahedra, corners with three equivalent Zn(2)O4 tetrahedra, and edges with six equivalent In(1)O6 octahedra. In the second In site, In(2) is bonded to one O(1), one O(4), and three equivalent O(3) atoms to form InO5 trigonal bipyramids that share corners with three equivalent Zn(1)O4 tetrahedra, corners with three equivalent Zn(3)O4 tetrahedra, and corners with six equivalent In(2)O5 trigonal bipyramids. There are six inequivalent O sites. In the first O site, O(1) is bonded to three equivalent Zn(1) and one In(2) atom to form OZn3In tetrahedra that share  a cornercorner with one O(4)Zn3In tetrahedra, corners with three equivalent O(5)ZnIn3 tetrahedra, and corners with six equivalent O(1)Zn3In tetrahedra. In the second O site, O(2) is bonded to one Zn(3) and three equivalent Zn(2) atoms to form OZn4 tetrahedra that share corners with three equivalent O(4)Zn3In tetrahedra, corners with three equivalent O(6)ZnIn3 tetrahedra, and corners with six equivalent O(2)Zn4 tetrahedra. In the third O site, O(3) is bonded in a trigonal planar geometry to three equivalent In(2) atoms. In the fourth O site, O(4) is bonded to three equivalent Zn(3) and one In(2) atom to form OZn3In tetrahedra that share  a cornercorner with one O(1)Zn3In tetrahedra, corners with three equivalent O(2)Zn4 tetrahedra, and corners with six equivalent O(4)Zn3In tetrahedra. In the fifth O site, O(5) 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)Zn3In tetrahedra, corners with three equivalent O(6)ZnIn3 tetrahedra, corners with six equivalent O(5)ZnIn3 tetrahedra, and edges with three equivalent O(6)ZnIn3 tetrahedra. In the sixth O site, O(6) is bonded to one Zn(2) and three equivalent In(1) atoms to form OZnIn3 tetrahedra that share corners with three equivalent O(2)Zn4 tetrahedra, corners with three equivalent O(5)ZnIn3 tetrahedra, corners with six equivalent O(6)ZnIn3 tetrahedra, and edges with three equivalent O(5)ZnIn3 tetrahedra.
Zn3In2O6 is Aluminum carbonitride-like structured and crystallizes in the trigonal R3m space group. There are three inequivalent Zn sites. In the first Zn site, Zn(1) is bonded to one O(5) and three equivalent O(1) atoms to form ZnO4 tetrahedra that share corners with three equivalent In(1)O6 octahedra, corners with six equivalent Zn(1)O4 tetrahedra, and corners with three equivalent In(2)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles are 62°. The Zn(1)-O(5) bond length is 1.97 Å. All Zn(1)-O(1) bond lengths are 2.09 Å. In the second Zn site, Zn(2) is bonded to one O(6) and three equivalent O(2) atoms to form ZnO4 tetrahedra that share corners with three equivalent In(1)O6 octahedra, corners with three equivalent Zn(3)O4 tetrahedra, and corners with six equivalent Zn(2)O4 tetrahedra. The corner-sharing octahedral tilt angles are 63°. The Zn(2)-O(6) bond length is 2.00 Å. All Zn(2)-O(2) bond lengths are 2.06 Å. In the third Zn site, Zn(3) is bonded to one O(2) and three equivalent O(4) atoms to form ZnO4 tetrahedra that share corners with three equivalent Zn(2)O4 tetrahedra, corners with six equivalent Zn(3)O4 tetrahedra, and corners with three equivalent In(2)O5 trigonal bipyramids. The Zn(3)-O(2) bond length is 2.01 Å. All Zn(3)-O(4) bond lengths are 2.07 Å. There are two inequivalent In sites. In the first In site, In(1) is bonded to three equivalent O(5) and three equivalent O(6) atoms to form InO6 octahedra that share corners with three equivalent Zn(1)O4 tetrahedra, corners with three equivalent Zn(2)O4 tetrahedra, and edges with six equivalent In(1)O6 octahedra. All In(1)-O(5) bond lengths are 2.26 Å. All In(1)-O(6) bond lengths are 2.24 Å. In the second In site, In(2) is bonded to one O(1), one O(4), and three equivalent O(3) atoms to form InO5 trigonal bipyramids that share corners with three equivalent Zn(1)O4 tetrahedra, corners with three equivalent Zn(3)O4 tetrahedra, and corners with six equivalent In(2)O5 trigonal bipyramids. The In(2)-O(1) bond length is 2.20 Å. The In(2)-O(4) bond length is 2.24 Å. All In(2)-O(3) bond lengths are 2.00 Å. There are six inequivalent O sites. In the first O site, O(1) is bonded to three equivalent Zn(1) and one In(2) atom to form OZn3In tetrahedra that share  a cornercorner with one O(4)Zn3In tetrahedra, corners with three equivalent O(5)ZnIn3 tetrahedra, and corners with six equivalent O(1)Zn3In tetrahedra. In the second O site, O(2) is bonded to one Zn(3) and three equivalent Zn(2) atoms to form OZn4 tetrahedra that share corners with three equivalent O(4)Zn3In tetrahedra, corners with three equivalent O(6)ZnIn3 tetrahedra, and corners with six equivalent O(2)Zn4 tetrahedra. In the third O site, O(3) is bonded in a trigonal planar geometry to three equivalent In(2) atoms. In the fourth O site, O(4) is bonded to three equivalent Zn(3) and one In(2) atom to form OZn3In tetrahedra that share  a cornercorner with one O(1)Zn3In tetrahedra, corners with three equivalent O(2)Zn4 tetrahedra, and corners with six equivalent O(4)Zn3In tetrahedra. In the fifth O site, O(5) 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)Zn3In tetrahedra, corners with three equivalent O(6)ZnIn3 tetrahedra, corners with six equivalent O(5)ZnIn3 tetrahedra, and edges with three equivalent O(6)ZnIn3 tetrahedra. In the sixth O site, O(6) is bonded to one Zn(2) and three equivalent In(1) atoms to form OZnIn3 tetrahedra that share corners with three equivalent O(2)Zn4 tetrahedra, corners with three equivalent O(5)ZnIn3 tetrahedra, corners with six equivalent O(6)ZnIn3 tetrahedra, and edges with three equivalent O(5)ZnIn3 tetrahedra.