Na5Mn2P2(CO7)2 crystallizes in the monoclinic P2_1/m space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded in a distorted hexagonal planar geometry to one O(1), one O(2), one O(3), one O(6), and two equivalent O(8) atoms. In the second Na site, Na(2) is bonded in a 6-coordinate geometry to one O(10), one O(2), one O(3), one O(6), one O(7), and one O(9) atom. In the third Na site, Na(3) is bonded in a 7-coordinate geometry to one O(1), one O(11), one O(12), one O(4), one O(5), one O(7), and one O(8) atom. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(10), one O(3), one O(5), one O(9), and two equivalent O(7) atoms to form distorted MnO6 octahedra that share  a cornercorner with one P(2)O4 tetrahedra and corners with three equivalent P(1)O4 tetrahedra. In the second Mn site, Mn(2) is bonded to one O(11), one O(12), one O(4), one O(6), and two equivalent O(8) atoms to form distorted MnO6 octahedra that share  a cornercorner with one P(1)O4 tetrahedra and corners with three equivalent P(2)O4 tetrahedra. There are two inequivalent C sites. In the first C site, C(1) is bonded in a trigonal planar geometry to one O(1), one O(3), and one O(5) atom. In the second C site, C(2) is bonded in a trigonal planar geometry to one O(2), one O(4), and one O(6) atom. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(10), one O(11), and two equivalent O(7) atoms to form PO4 tetrahedra that share  a cornercorner with one Mn(2)O6 octahedra and corners with three equivalent Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 42-57°. In the second P site, P(2) is bonded to one O(12), one O(9), and two equivalent O(8) atoms to form PO4 tetrahedra that share  a cornercorner with one Mn(1)O6 octahedra and corners with three equivalent Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 45-55°. There are twelve inequivalent O sites. In the first O site, O(1) is bonded to one Na(1), two equivalent Na(3), and one C(1) atom to form distorted ONa3C trigonal pyramids that share  a cornercorner with one O(6)Na3MnC trigonal bipyramid,  a cornercorner with one O(2)Na3C trigonal pyramid, and  an edgeedge with one O(3)Na3MnC trigonal bipyramid. In the second O site, O(2) is bonded to one Na(1), two equivalent Na(2), and one C(2) atom to form distorted ONa3C trigonal pyramids that share corners with two equivalent O(6)Na3MnC trigonal bipyramids, corners with three equivalent O(3)Na3MnC trigonal bipyramids,  a cornercorner with one O(1)Na3C trigonal pyramid, and  an edgeedge with one O(6)Na3MnC trigonal bipyramid. In the third O site, O(3) is bonded to one Na(1), two equivalent Na(2), one Mn(1), and one C(1) atom to form distorted ONa3MnC trigonal bipyramids that share corners with three equivalent O(2)Na3C trigonal pyramids,  an edgeedge with one O(1)Na3C trigonal pyramid, and  a faceface with one O(6)Na3MnC trigonal bipyramid. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to two equivalent Na(3), one Mn(2), and one C(2) atom. In the fifth O site, O(5) is bonded in a distorted rectangular see-saw-like geometry to two equivalent Na(3), one Mn(1), and one C(1) atom. In the sixth O site, O(6) is bonded to one Na(1), two equivalent Na(2), one Mn(2), and one C(2) atom to form distorted ONa3MnC trigonal bipyramids that share  a cornercorner with one O(1)Na3C trigonal pyramid, corners with two equivalent O(2)Na3C trigonal pyramids,  an edgeedge with one O(2)Na3C trigonal pyramid, and  a faceface with one O(3)Na3MnC trigonal bipyramid. In the seventh O site, O(7) is bonded in a 4-coordinate geometry to one Na(2), one Na(3), one Mn(1), and one P(1) atom. In the eighth O site, O(8) is bonded in a 4-coordinate geometry to one Na(1), one Na(3), one Mn(2), and one P(2) atom. In the ninth O site, O(9) is bonded in a 4-coordinate geometry to two equivalent Na(2), one Mn(1), and one P(2) atom. In the tenth O site, O(10) is bonded in a distorted rectangular see-saw-like geometry to two equivalent Na(2), one Mn(1), and one P(1) atom. In the eleventh O site, O(11) is bonded in a 4-coordinate geometry to two equivalent Na(3), one Mn(2), and one P(1) atom. In the twelfth O site, O(12) is bonded in a rectangular see-saw-like geometry to two equivalent Na(3), one Mn(2), and one P(2) atom.
Na5Mn2P2(CO7)2 crystallizes in the monoclinic P2_1/m space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded in a distorted hexagonal planar geometry to one O(1), one O(2), one O(3), one O(6), and two equivalent O(8) atoms. The Na(1)-O(1) bond length is 2.51 Å. The Na(1)-O(2) bond length is 2.48 Å. The Na(1)-O(3) bond length is 2.48 Å. The Na(1)-O(6) bond length is 2.57 Å. Both Na(1)-O(8) bond lengths are 2.52 Å. In the second Na site, Na(2) is bonded in a 6-coordinate geometry to one O(10), one O(2), one O(3), one O(6), one O(7), and one O(9) atom. The Na(2)-O(10) bond length is 2.35 Å. The Na(2)-O(2) bond length is 2.30 Å. The Na(2)-O(3) bond length is 2.47 Å. The Na(2)-O(6) bond length is 2.47 Å. The Na(2)-O(7) bond length is 2.47 Å. The Na(2)-O(9) bond length is 2.53 Å. In the third Na site, Na(3) is bonded in a 7-coordinate geometry to one O(1), one O(11), one O(12), one O(4), one O(5), one O(7), and one O(8) atom. The Na(3)-O(1) bond length is 2.28 Å. The Na(3)-O(11) bond length is 2.56 Å. The Na(3)-O(12) bond length is 2.41 Å. The Na(3)-O(4) bond length is 2.62 Å. The Na(3)-O(5) bond length is 2.34 Å. The Na(3)-O(7) bond length is 2.87 Å. The Na(3)-O(8) bond length is 2.71 Å. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(10), one O(3), one O(5), one O(9), and two equivalent O(7) atoms to form distorted MnO6 octahedra that share  a cornercorner with one P(2)O4 tetrahedra and corners with three equivalent P(1)O4 tetrahedra. The Mn(1)-O(10) bond length is 2.17 Å. The Mn(1)-O(3) bond length is 2.12 Å. The Mn(1)-O(5) bond length is 2.33 Å. The Mn(1)-O(9) bond length is 2.04 Å. Both Mn(1)-O(7) bond lengths are 2.10 Å. In the second Mn site, Mn(2) is bonded to one O(11), one O(12), one O(4), one O(6), and two equivalent O(8) atoms to form distorted MnO6 octahedra that share  a cornercorner with one P(1)O4 tetrahedra and corners with three equivalent P(2)O4 tetrahedra. The Mn(2)-O(11) bond length is 2.07 Å. The Mn(2)-O(12) bond length is 2.19 Å. The Mn(2)-O(4) bond length is 2.16 Å. The Mn(2)-O(6) bond length is 2.35 Å. Both Mn(2)-O(8) bond lengths are 2.13 Å. There are two inequivalent C sites. In the first C site, C(1) is bonded in a trigonal planar geometry to one O(1), one O(3), and one O(5) atom. The C(1)-O(1) bond length is 1.28 Å. The C(1)-O(3) bond length is 1.33 Å. The C(1)-O(5) bond length is 1.29 Å. In the second C site, C(2) is bonded in a trigonal planar geometry to one O(2), one O(4), and one O(6) atom. The C(2)-O(2) bond length is 1.28 Å. The C(2)-O(4) bond length is 1.31 Å. The C(2)-O(6) bond length is 1.31 Å. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(10), one O(11), and two equivalent O(7) atoms to form PO4 tetrahedra that share  a cornercorner with one Mn(2)O6 octahedra and corners with three equivalent Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 42-57°. The P(1)-O(10) bond length is 1.55 Å. The P(1)-O(11) bond length is 1.57 Å. Both P(1)-O(7) bond lengths are 1.55 Å. In the second P site, P(2) is bonded to one O(12), one O(9), and two equivalent O(8) atoms to form PO4 tetrahedra that share  a cornercorner with one Mn(1)O6 octahedra and corners with three equivalent Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 45-55°. The P(2)-O(12) bond length is 1.55 Å. The P(2)-O(9) bond length is 1.58 Å. Both P(2)-O(8) bond lengths are 1.56 Å. There are twelve inequivalent O sites. In the first O site, O(1) is bonded to one Na(1), two equivalent Na(3), and one C(1) atom to form distorted ONa3C trigonal pyramids that share  a cornercorner with one O(6)Na3MnC trigonal bipyramid,  a cornercorner with one O(2)Na3C trigonal pyramid, and  an edgeedge with one O(3)Na3MnC trigonal bipyramid. In the second O site, O(2) is bonded to one Na(1), two equivalent Na(2), and one C(2) atom to form distorted ONa3C trigonal pyramids that share corners with two equivalent O(6)Na3MnC trigonal bipyramids, corners with three equivalent O(3)Na3MnC trigonal bipyramids,  a cornercorner with one O(1)Na3C trigonal pyramid, and  an edgeedge with one O(6)Na3MnC trigonal bipyramid. In the third O site, O(3) is bonded to one Na(1), two equivalent Na(2), one Mn(1), and one C(1) atom to form distorted ONa3MnC trigonal bipyramids that share corners with three equivalent O(2)Na3C trigonal pyramids,  an edgeedge with one O(1)Na3C trigonal pyramid, and  a faceface with one O(6)Na3MnC trigonal bipyramid. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to two equivalent Na(3), one Mn(2), and one C(2) atom. In the fifth O site, O(5) is bonded in a distorted rectangular see-saw-like geometry to two equivalent Na(3), one Mn(1), and one C(1) atom. In the sixth O site, O(6) is bonded to one Na(1), two equivalent Na(2), one Mn(2), and one C(2) atom to form distorted ONa3MnC trigonal bipyramids that share  a cornercorner with one O(1)Na3C trigonal pyramid, corners with two equivalent O(2)Na3C trigonal pyramids,  an edgeedge with one O(2)Na3C trigonal pyramid, and  a faceface with one O(3)Na3MnC trigonal bipyramid. In the seventh O site, O(7) is bonded in a 4-coordinate geometry to one Na(2), one Na(3), one Mn(1), and one P(1) atom. In the eighth O site, O(8) is bonded in a 4-coordinate geometry to one Na(1), one Na(3), one Mn(2), and one P(2) atom. In the ninth O site, O(9) is bonded in a 4-coordinate geometry to two equivalent Na(2), one Mn(1), and one P(2) atom. In the tenth O site, O(10) is bonded in a distorted rectangular see-saw-like geometry to two equivalent Na(2), one Mn(1), and one P(1) atom. In the eleventh O site, O(11) is bonded in a 4-coordinate geometry to two equivalent Na(3), one Mn(2), and one P(1) atom. In the twelfth O site, O(12) is bonded in a rectangular see-saw-like geometry to two equivalent Na(3), one Mn(2), and one P(2) atom.