Zn3(AsO3)2 crystallizes in the orthorhombic Pbam space group. There are two inequivalent Zn sites. In the first Zn site, Zn(1) is bonded to two equivalent O(1) and two equivalent O(4) atoms to form a mixture of distorted corner and edge-sharing ZnO4 tetrahedra. In the second Zn site, Zn(2) is bonded to one O(1), one O(3), and two equivalent O(2) atoms to form corner-sharing ZnO4 tetrahedra. There are two inequivalent As sites. In the first As site, As(1) is bonded in a distorted trigonal non-coplanar geometry to one O(4) and two equivalent O(2) atoms. In the second As site, As(2) is bonded in a distorted T-shaped geometry to one O(3) and two equivalent O(1) atoms. There are four inequivalent O sites. In the first O site, O(3) is bonded in a trigonal planar geometry to two equivalent Zn(2) and one As(2) atom. In the second O site, O(4) is bonded in a distorted trigonal planar geometry to two equivalent Zn(1) and one As(1) atom. In the third O site, O(1) is bonded in a trigonal planar geometry to one Zn(1), one Zn(2), and one As(2) atom. In the fourth O site, O(2) is bonded in a trigonal planar geometry to two equivalent Zn(2) and one As(1) atom.
Zn3(AsO3)2 crystallizes in the orthorhombic Pbam space group. There are two inequivalent Zn sites. In the first Zn site, Zn(1) is bonded to two equivalent O(1) and two equivalent O(4) atoms to form a mixture of distorted corner and edge-sharing ZnO4 tetrahedra. Both Zn(1)-O(1) bond lengths are 1.94 Å. Both Zn(1)-O(4) bond lengths are 1.98 Å. In the second Zn site, Zn(2) is bonded to one O(1), one O(3), and two equivalent O(2) atoms to form corner-sharing ZnO4 tetrahedra. The Zn(2)-O(1) bond length is 1.96 Å. The Zn(2)-O(3) bond length is 1.98 Å. There is one shorter (1.95 Å) and one longer (1.96 Å) Zn(2)-O(2) bond length. There are two inequivalent As sites. In the first As site, As(1) is bonded in a distorted trigonal non-coplanar geometry to one O(4) and two equivalent O(2) atoms. The As(1)-O(4) bond length is 1.77 Å. Both As(1)-O(2) bond lengths are 1.78 Å. In the second As site, As(2) is bonded in a distorted T-shaped geometry to one O(3) and two equivalent O(1) atoms. The As(2)-O(3) bond length is 1.78 Å. Both As(2)-O(1) bond lengths are 1.78 Å. There are four inequivalent O sites. In the first O site, O(3) is bonded in a trigonal planar geometry to two equivalent Zn(2) and one As(2) atom. In the second O site, O(4) is bonded in a distorted trigonal planar geometry to two equivalent Zn(1) and one As(1) atom. In the third O site, O(1) is bonded in a trigonal planar geometry to one Zn(1), one Zn(2), and one As(2) atom. In the fourth O site, O(2) is bonded in a trigonal planar geometry to two equivalent Zn(2) and one As(1) atom.