NiBiAsO5 crystallizes in the triclinic P-1 space group. Ni(1) is bonded to one O(2), one O(3), one O(4), one O(5), and two equivalent O(1) atoms to form NiO6 octahedra that share corners with four equivalent As(1)O4 tetrahedra and  an edgeedge with one Ni(1)O6 octahedra. Bi(1) is bonded in a 5-coordinate geometry to one O(2), one O(3), one O(4), and two equivalent O(1) atoms. As(1) is bonded to one O(2), one O(3), one O(4), and one O(5) atom to form AsO4 tetrahedra that share corners with four equivalent Ni(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 49-57°. There are five inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Ni(1) and two equivalent Bi(1) atoms to form edge-sharing ONi2Bi2 tetrahedra. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Ni(1), one Bi(1), and one As(1) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Ni(1), one Bi(1), and one As(1) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one Ni(1), one Bi(1), and one As(1) atom. In the fifth O site, O(5) is bonded in a bent 120 degrees geometry to one Ni(1) and one As(1) atom.
NiBiAsO5 crystallizes in the triclinic P-1 space group. Ni(1) is bonded to one O(2), one O(3), one O(4), one O(5), and two equivalent O(1) atoms to form NiO6 octahedra that share corners with four equivalent As(1)O4 tetrahedra and  an edgeedge with one Ni(1)O6 octahedra. The Ni(1)-O(2) bond length is 2.06 Å. The Ni(1)-O(3) bond length is 2.06 Å. The Ni(1)-O(4) bond length is 2.13 Å. The Ni(1)-O(5) bond length is 2.04 Å. There is one shorter (2.03 Å) and one longer (2.11 Å) Ni(1)-O(1) bond length. Bi(1) is bonded in a 5-coordinate geometry to one O(2), one O(3), one O(4), and two equivalent O(1) atoms. The Bi(1)-O(2) bond length is 2.32 Å. The Bi(1)-O(3) bond length is 2.32 Å. The Bi(1)-O(4) bond length is 2.42 Å. There is one shorter (2.13 Å) and one longer (2.25 Å) Bi(1)-O(1) bond length. As(1) is bonded to one O(2), one O(3), one O(4), and one O(5) atom to form AsO4 tetrahedra that share corners with four equivalent Ni(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 49-57°. The As(1)-O(2) bond length is 1.71 Å. The As(1)-O(3) bond length is 1.70 Å. The As(1)-O(4) bond length is 1.72 Å. The As(1)-O(5) bond length is 1.69 Å. There are five inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Ni(1) and two equivalent Bi(1) atoms to form edge-sharing ONi2Bi2 tetrahedra. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Ni(1), one Bi(1), and one As(1) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Ni(1), one Bi(1), and one As(1) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one Ni(1), one Bi(1), and one As(1) atom. In the fifth O site, O(5) is bonded in a bent 120 degrees geometry to one Ni(1) and one As(1) atom.