Ni3(BiO2)10 crystallizes in the monoclinic C2 space group. There are two inequivalent Ni sites. In the first Ni site, Ni(1) is bonded to two equivalent O(6) and two equivalent O(9) atoms to form NiO4 tetrahedra that share corners with two equivalent Bi(2)O5 square pyramids, corners with two equivalent Bi(4)O5 square pyramids, and corners with two equivalent Bi(5)O5 square pyramids. In the second Ni site, Ni(2) is bonded in a see-saw-like geometry to one O(4), one O(5), one O(7), and one O(8) atom. There are five inequivalent Bi sites. In the first Bi site, Bi(1) is bonded in a 5-coordinate geometry to one O(4), one O(6), one O(7), and two equivalent O(2) atoms. In the second Bi site, Bi(2) is bonded to one O(1), one O(10), one O(4), one O(5), and one O(6) atom to form distorted BiO5 square pyramids that share corners with two equivalent Bi(5)O5 square pyramids,  a cornercorner with one Ni(1)O4 tetrahedra, and  an edgeedge with one Bi(4)O5 square pyramid. In the third Bi site, Bi(3) is bonded in a 5-coordinate geometry to one O(1), one O(3), one O(6), one O(7), and one O(8) atom. In the fourth Bi site, Bi(4) is bonded to one O(1), one O(2), one O(3), one O(5), and one O(9) atom to form distorted BiO5 square pyramids that share corners with two equivalent Bi(5)O5 square pyramids,  a cornercorner with one Ni(1)O4 tetrahedra, and  an edgeedge with one Bi(2)O5 square pyramid. In the fifth Bi site, Bi(5) is bonded to one O(3), one O(8), one O(9), and two equivalent O(10) atoms to form distorted BiO5 square pyramids that share corners with two equivalent Bi(2)O5 square pyramids, corners with two equivalent Bi(4)O5 square pyramids,  a cornercorner with one Ni(1)O4 tetrahedra, and  an edgeedge with one Bi(5)O5 square pyramid. There are ten inequivalent O sites. In the first O site, O(6) is bonded to one Ni(1), one Bi(1), one Bi(2), and one Bi(3) atom to form distorted corner-sharing ONiBi3 tetrahedra. In the second O site, O(7) is bonded in a trigonal non-coplanar geometry to one Ni(2), one Bi(1), and one Bi(3) atom. In the third O site, O(8) is bonded in a distorted trigonal non-coplanar geometry to one Ni(2), one Bi(3), and one Bi(5) atom. In the fourth O site, O(9) is bonded in a distorted trigonal non-coplanar geometry to one Ni(1), one Bi(4), and one Bi(5) atom. In the fifth O site, O(10) is bonded in a distorted trigonal non-coplanar geometry to one Bi(2) and two equivalent Bi(5) atoms. In the sixth O site, O(1) is bonded in a distorted trigonal non-coplanar geometry to one Bi(2), one Bi(3), and one Bi(4) atom. In the seventh O site, O(2) is bonded in a distorted trigonal non-coplanar geometry to one Bi(4) and two equivalent Bi(1) atoms. In the eighth O site, O(3) is bonded in a trigonal planar geometry to one Bi(3), one Bi(4), and one Bi(5) atom. In the ninth O site, O(4) is bonded in a trigonal planar geometry to one Ni(2), one Bi(1), and one Bi(2) atom. In the tenth O site, O(5) is bonded in a 3-coordinate geometry to one Ni(2), one Bi(2), and one Bi(4) atom.
Ni3(BiO2)10 crystallizes in the monoclinic C2 space group. There are two inequivalent Ni sites. In the first Ni site, Ni(1) is bonded to two equivalent O(6) and two equivalent O(9) atoms to form NiO4 tetrahedra that share corners with two equivalent Bi(2)O5 square pyramids, corners with two equivalent Bi(4)O5 square pyramids, and corners with two equivalent Bi(5)O5 square pyramids. Both Ni(1)-O(6) bond lengths are 1.89 Å. Both Ni(1)-O(9) bond lengths are 1.87 Å. In the second Ni site, Ni(2) is bonded in a see-saw-like geometry to one O(4), one O(5), one O(7), and one O(8) atom. The Ni(2)-O(4) bond length is 2.03 Å. The Ni(2)-O(5) bond length is 1.92 Å. The Ni(2)-O(7) bond length is 2.18 Å. The Ni(2)-O(8) bond length is 1.96 Å. There are five inequivalent Bi sites. In the first Bi site, Bi(1) is bonded in a 5-coordinate geometry to one O(4), one O(6), one O(7), and two equivalent O(2) atoms. The Bi(1)-O(4) bond length is 2.22 Å. The Bi(1)-O(6) bond length is 2.55 Å. The Bi(1)-O(7) bond length is 2.13 Å. There is one shorter (2.25 Å) and one longer (2.61 Å) Bi(1)-O(2) bond length. In the second Bi site, Bi(2) is bonded to one O(1), one O(10), one O(4), one O(5), and one O(6) atom to form distorted BiO5 square pyramids that share corners with two equivalent Bi(5)O5 square pyramids,  a cornercorner with one Ni(1)O4 tetrahedra, and  an edgeedge with one Bi(4)O5 square pyramid. The Bi(2)-O(1) bond length is 2.62 Å. The Bi(2)-O(10) bond length is 2.10 Å. The Bi(2)-O(4) bond length is 2.21 Å. The Bi(2)-O(5) bond length is 2.24 Å. The Bi(2)-O(6) bond length is 2.47 Å. In the third Bi site, Bi(3) is bonded in a 5-coordinate geometry to one O(1), one O(3), one O(6), one O(7), and one O(8) atom. The Bi(3)-O(1) bond length is 2.14 Å. The Bi(3)-O(3) bond length is 2.31 Å. The Bi(3)-O(6) bond length is 2.72 Å. The Bi(3)-O(7) bond length is 2.27 Å. The Bi(3)-O(8) bond length is 2.42 Å. In the fourth Bi site, Bi(4) is bonded to one O(1), one O(2), one O(3), one O(5), and one O(9) atom to form distorted BiO5 square pyramids that share corners with two equivalent Bi(5)O5 square pyramids,  a cornercorner with one Ni(1)O4 tetrahedra, and  an edgeedge with one Bi(2)O5 square pyramid. The Bi(4)-O(1) bond length is 2.24 Å. The Bi(4)-O(2) bond length is 2.10 Å. The Bi(4)-O(3) bond length is 2.22 Å. The Bi(4)-O(5) bond length is 2.55 Å. The Bi(4)-O(9) bond length is 2.53 Å. In the fifth Bi site, Bi(5) is bonded to one O(3), one O(8), one O(9), and two equivalent O(10) atoms to form distorted BiO5 square pyramids that share corners with two equivalent Bi(2)O5 square pyramids, corners with two equivalent Bi(4)O5 square pyramids,  a cornercorner with one Ni(1)O4 tetrahedra, and  an edgeedge with one Bi(5)O5 square pyramid. The Bi(5)-O(3) bond length is 2.26 Å. The Bi(5)-O(8) bond length is 2.10 Å. The Bi(5)-O(9) bond length is 2.52 Å. There is one shorter (2.26 Å) and one longer (2.57 Å) Bi(5)-O(10) bond length. There are ten inequivalent O sites. In the first O site, O(6) is bonded to one Ni(1), one Bi(1), one Bi(2), and one Bi(3) atom to form distorted corner-sharing ONiBi3 tetrahedra. In the second O site, O(7) is bonded in a trigonal non-coplanar geometry to one Ni(2), one Bi(1), and one Bi(3) atom. In the third O site, O(8) is bonded in a distorted trigonal non-coplanar geometry to one Ni(2), one Bi(3), and one Bi(5) atom. In the fourth O site, O(9) is bonded in a distorted trigonal non-coplanar geometry to one Ni(1), one Bi(4), and one Bi(5) atom. In the fifth O site, O(10) is bonded in a distorted trigonal non-coplanar geometry to one Bi(2) and two equivalent Bi(5) atoms. In the sixth O site, O(1) is bonded in a distorted trigonal non-coplanar geometry to one Bi(2), one Bi(3), and one Bi(4) atom. In the seventh O site, O(2) is bonded in a distorted trigonal non-coplanar geometry to one Bi(4) and two equivalent Bi(1) atoms. In the eighth O site, O(3) is bonded in a trigonal planar geometry to one Bi(3), one Bi(4), and one Bi(5) atom. In the ninth O site, O(4) is bonded in a trigonal planar geometry to one Ni(2), one Bi(1), and one Bi(2) atom. In the tenth O site, O(5) is bonded in a 3-coordinate geometry to one Ni(2), one Bi(2), and one Bi(4) atom.