BiCu2PO6 crystallizes in the orthorhombic Pnma space group. There are two inequivalent Cu sites. In the first Cu site, Cu(1) is bonded to one O(1), two equivalent O(2), and two equivalent O(4) atoms to form distorted CuO5 trigonal bipyramids that share corners with two equivalent Cu(2)O5 square pyramids, corners with three equivalent P(1)O4 tetrahedra, and  an edgeedge with one Cu(2)O5 square pyramid. In the second Cu site, Cu(2) is bonded to one O(3), two equivalent O(2), and two equivalent O(4) atoms to form distorted CuO5 square pyramids that share corners with three equivalent P(1)O4 tetrahedra, corners with two equivalent Cu(1)O5 trigonal bipyramids, and  an edgeedge with one Cu(1)O5 trigonal bipyramid. Bi(1) is bonded in a 5-coordinate geometry to one O(3) and four equivalent O(4) atoms. P(1) is bonded to one O(1), one O(3), and two equivalent O(2) atoms to form PO4 tetrahedra that share corners with three equivalent Cu(2)O5 square pyramids and corners with three equivalent Cu(1)O5 trigonal bipyramids. There are four inequivalent O sites. In the first O site, O(1) is bonded in a distorted single-bond geometry to one Cu(1) and one P(1) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Cu(1), one Cu(2), and one P(1) atom. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to one Cu(2), one Bi(1), and one P(1) atom. In the fourth O site, O(4) is bonded to one Cu(1), one Cu(2), and two equivalent Bi(1) atoms to form a mixture of corner and edge-sharing OCu2Bi2 tetrahedra.
BiCu2PO6 crystallizes in the orthorhombic Pnma space group. There are two inequivalent Cu sites. In the first Cu site, Cu(1) is bonded to one O(1), two equivalent O(2), and two equivalent O(4) atoms to form distorted CuO5 trigonal bipyramids that share corners with two equivalent Cu(2)O5 square pyramids, corners with three equivalent P(1)O4 tetrahedra, and  an edgeedge with one Cu(2)O5 square pyramid. The Cu(1)-O(1) bond length is 2.45 Å. Both Cu(1)-O(2) bond lengths are 2.02 Å. Both Cu(1)-O(4) bond lengths are 1.93 Å. In the second Cu site, Cu(2) is bonded to one O(3), two equivalent O(2), and two equivalent O(4) atoms to form distorted CuO5 square pyramids that share corners with three equivalent P(1)O4 tetrahedra, corners with two equivalent Cu(1)O5 trigonal bipyramids, and  an edgeedge with one Cu(1)O5 trigonal bipyramid. The Cu(2)-O(3) bond length is 2.26 Å. Both Cu(2)-O(2) bond lengths are 2.06 Å. Both Cu(2)-O(4) bond lengths are 1.94 Å. Bi(1) is bonded in a 5-coordinate geometry to one O(3) and four equivalent O(4) atoms. The Bi(1)-O(3) bond length is 2.44 Å. There are two shorter (2.24 Å) and two longer (2.43 Å) Bi(1)-O(4) bond lengths. P(1) is bonded to one O(1), one O(3), and two equivalent O(2) atoms to form PO4 tetrahedra that share corners with three equivalent Cu(2)O5 square pyramids and corners with three equivalent Cu(1)O5 trigonal bipyramids. The P(1)-O(1) bond length is 1.53 Å. The P(1)-O(3) bond length is 1.54 Å. Both P(1)-O(2) bond lengths are 1.57 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded in a distorted single-bond geometry to one Cu(1) and one P(1) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Cu(1), one Cu(2), and one P(1) atom. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to one Cu(2), one Bi(1), and one P(1) atom. In the fourth O site, O(4) is bonded to one Cu(1), one Cu(2), and two equivalent Bi(1) atoms to form a mixture of corner and edge-sharing OCu2Bi2 tetrahedra.