ZnB2Bi2O7 crystallizes in the orthorhombic Pba2 space group. Zn(1) is bonded to one O(3), one O(4), one O(6), and one O(7) atom to form ZnO4 tetrahedra that share corners with two equivalent B(1)O4 tetrahedra. There are two inequivalent B sites. In the first B site, B(1) is bonded to one O(2), one O(5), one O(6), and one O(7) atom to form BO4 tetrahedra that share  a cornercorner with one B(1)O4 tetrahedra and corners with two equivalent Zn(1)O4 tetrahedra. In the second B site, B(2) is bonded in a trigonal planar geometry to one O(1), one O(3), and one O(8) atom. There are two inequivalent Bi sites. In the first Bi site, Bi(1) is bonded in a 6-coordinate geometry to one O(2), one O(3), one O(4), one O(5), one O(7), and one O(8) atom. In the second Bi site, Bi(2) is bonded in a 6-coordinate geometry to one O(1), one O(4), one O(5), one O(6), one O(7), and one O(8) atom. There are eight inequivalent O sites. In the first O site, O(7) is bonded in a 4-coordinate geometry to one Zn(1), one B(1), one Bi(1), and one Bi(2) atom. In the second O site, O(8) is bonded in a distorted single-bond geometry to one B(2), one Bi(1), and one Bi(2) atom. In the third O site, O(1) is bonded in a distorted bent 120 degrees geometry to two equivalent B(2) and two equivalent Bi(2) atoms. In the fourth O site, O(2) is bonded in a bent 150 degrees geometry to two equivalent B(1) and two equivalent Bi(1) atoms. In the fifth O site, O(3) is bonded in a 3-coordinate geometry to one Zn(1), one B(2), and one Bi(1) atom. In the sixth O site, O(4) is bonded in a trigonal planar geometry to one Zn(1), one Bi(1), and one Bi(2) atom. In the seventh O site, O(5) is bonded in a distorted single-bond geometry to one B(1), one Bi(1), and one Bi(2) atom. In the eighth O site, O(6) is bonded in a distorted trigonal planar geometry to one Zn(1), one B(1), and one Bi(2) atom.
ZnB2Bi2O7 crystallizes in the orthorhombic Pba2 space group. Zn(1) is bonded to one O(3), one O(4), one O(6), and one O(7) atom to form ZnO4 tetrahedra that share corners with two equivalent B(1)O4 tetrahedra. The Zn(1)-O(3) bond length is 1.96 Å. The Zn(1)-O(4) bond length is 1.93 Å. The Zn(1)-O(6) bond length is 1.94 Å. The Zn(1)-O(7) bond length is 1.94 Å. There are two inequivalent B sites. In the first B site, B(1) is bonded to one O(2), one O(5), one O(6), and one O(7) atom to form BO4 tetrahedra that share  a cornercorner with one B(1)O4 tetrahedra and corners with two equivalent Zn(1)O4 tetrahedra. The B(1)-O(2) bond length is 1.48 Å. The B(1)-O(5) bond length is 1.46 Å. The B(1)-O(6) bond length is 1.50 Å. The B(1)-O(7) bond length is 1.52 Å. In the second B site, B(2) is bonded in a trigonal planar geometry to one O(1), one O(3), and one O(8) atom. The B(2)-O(1) bond length is 1.42 Å. The B(2)-O(3) bond length is 1.35 Å. The B(2)-O(8) bond length is 1.35 Å. There are two inequivalent Bi sites. In the first Bi site, Bi(1) is bonded in a 6-coordinate geometry to one O(2), one O(3), one O(4), one O(5), one O(7), and one O(8) atom. The Bi(1)-O(2) bond length is 2.66 Å. The Bi(1)-O(3) bond length is 2.50 Å. The Bi(1)-O(4) bond length is 2.18 Å. The Bi(1)-O(5) bond length is 2.42 Å. The Bi(1)-O(7) bond length is 2.26 Å. The Bi(1)-O(8) bond length is 2.35 Å. In the second Bi site, Bi(2) is bonded in a 6-coordinate geometry to one O(1), one O(4), one O(5), one O(6), one O(7), and one O(8) atom. The Bi(2)-O(1) bond length is 2.76 Å. The Bi(2)-O(4) bond length is 2.16 Å. The Bi(2)-O(5) bond length is 2.29 Å. The Bi(2)-O(6) bond length is 2.18 Å. The Bi(2)-O(7) bond length is 2.66 Å. The Bi(2)-O(8) bond length is 2.52 Å. There are eight inequivalent O sites. In the first O site, O(7) is bonded in a 4-coordinate geometry to one Zn(1), one B(1), one Bi(1), and one Bi(2) atom. In the second O site, O(8) is bonded in a distorted single-bond geometry to one B(2), one Bi(1), and one Bi(2) atom. In the third O site, O(1) is bonded in a distorted bent 120 degrees geometry to two equivalent B(2) and two equivalent Bi(2) atoms. In the fourth O site, O(2) is bonded in a bent 150 degrees geometry to two equivalent B(1) and two equivalent Bi(1) atoms. In the fifth O site, O(3) is bonded in a 3-coordinate geometry to one Zn(1), one B(2), and one Bi(1) atom. In the sixth O site, O(4) is bonded in a trigonal planar geometry to one Zn(1), one Bi(1), and one Bi(2) atom. In the seventh O site, O(5) is bonded in a distorted single-bond geometry to one B(1), one Bi(1), and one Bi(2) atom. In the eighth O site, O(6) is bonded in a distorted trigonal planar geometry to one Zn(1), one B(1), and one Bi(2) atom.