BiMn2PO6 crystallizes in the orthorhombic Pnma space group. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(4), two equivalent O(1), and two equivalent O(3) atoms to form distorted MnO5 trigonal bipyramids that share corners with three equivalent P(1)O4 tetrahedra, corners with two equivalent Mn(2)O5 trigonal bipyramids, and  an edgeedge with one Mn(2)O5 trigonal bipyramid. In the second Mn site, Mn(2) is bonded to one O(2), two equivalent O(1), and two equivalent O(3) atoms to form distorted MnO5 trigonal bipyramids that share corners with three equivalent P(1)O4 tetrahedra, corners with two equivalent Mn(1)O5 trigonal bipyramids, and  an edgeedge with one Mn(1)O5 trigonal bipyramid. Bi(1) is bonded in a 4-coordinate geometry to four equivalent O(3) atoms. P(1) is bonded to one O(2), one O(4), and two equivalent O(1) atoms to form PO4 tetrahedra that share corners with three equivalent Mn(1)O5 trigonal bipyramids and corners with three equivalent Mn(2)O5 trigonal bipyramids. There are four inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one Mn(1), one Mn(2), and one P(1) atom. In the second O site, O(2) is bonded in a distorted bent 120 degrees geometry to one Mn(2) and one P(1) atom. In the third O site, O(3) is bonded to one Mn(1), one Mn(2), and two equivalent Bi(1) atoms to form a mixture of corner and edge-sharing OMn2Bi2 tetrahedra. In the fourth O site, O(4) is bonded in a linear geometry to one Mn(1) and one P(1) atom.
BiMn2PO6 crystallizes in the orthorhombic Pnma space group. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(4), two equivalent O(1), and two equivalent O(3) atoms to form distorted MnO5 trigonal bipyramids that share corners with three equivalent P(1)O4 tetrahedra, corners with two equivalent Mn(2)O5 trigonal bipyramids, and  an edgeedge with one Mn(2)O5 trigonal bipyramid. The Mn(1)-O(4) bond length is 2.12 Å. Both Mn(1)-O(1) bond lengths are 2.20 Å. Both Mn(1)-O(3) bond lengths are 2.15 Å. In the second Mn site, Mn(2) is bonded to one O(2), two equivalent O(1), and two equivalent O(3) atoms to form distorted MnO5 trigonal bipyramids that share corners with three equivalent P(1)O4 tetrahedra, corners with two equivalent Mn(1)O5 trigonal bipyramids, and  an edgeedge with one Mn(1)O5 trigonal bipyramid. The Mn(2)-O(2) bond length is 2.10 Å. Both Mn(2)-O(1) bond lengths are 2.19 Å. Both Mn(2)-O(3) bond lengths are 2.15 Å. Bi(1) is bonded in a 4-coordinate geometry to four equivalent O(3) atoms. There are two shorter (2.22 Å) and two longer (2.28 Å) Bi(1)-O(3) bond lengths. P(1) is bonded to one O(2), one O(4), and two equivalent O(1) atoms to form PO4 tetrahedra that share corners with three equivalent Mn(1)O5 trigonal bipyramids and corners with three equivalent Mn(2)O5 trigonal bipyramids. The P(1)-O(2) bond length is 1.55 Å. The P(1)-O(4) bond length is 1.54 Å. Both P(1)-O(1) bond lengths are 1.57 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one Mn(1), one Mn(2), and one P(1) atom. In the second O site, O(2) is bonded in a distorted bent 120 degrees geometry to one Mn(2) and one P(1) atom. In the third O site, O(3) is bonded to one Mn(1), one Mn(2), and two equivalent Bi(1) atoms to form a mixture of corner and edge-sharing OMn2Bi2 tetrahedra. In the fourth O site, O(4) is bonded in a linear geometry to one Mn(1) and one P(1) atom.