Na5Mn2P2(CO7)2 crystallizes in the monoclinic Pm space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded in a 7-coordinate geometry to one O(1), one O(2), one O(3), one O(5), one O(6), and two equivalent O(4) atoms. In the second Na site, Na(2) is bonded in a 7-coordinate geometry to one O(10), one O(11), one O(12), one O(7), one O(8), and two equivalent O(9) atoms. In the third Na site, Na(3) is bonded in a 6-coordinate geometry to one O(2), one O(3), two equivalent O(12), and two equivalent O(9) atoms. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(2), one O(3), one O(6), one O(8), and two equivalent O(4) atoms to form distorted MnO6 octahedra that share corners with two equivalent P(1)O4 tetrahedra and corners with two equivalent P(2)O4 tetrahedra. In the second Mn site, Mn(2) is bonded to one O(10), one O(11), one O(5), one O(7), and two equivalent O(9) atoms to form distorted MnO6 octahedra that share corners with two equivalent P(1)O4 tetrahedra and corners with two 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(12), one O(2), and one O(3) atom. In the second C site, C(2) is bonded in a trigonal planar geometry to one O(1), one O(10), and one O(11) atom. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(5), one O(7), and two equivalent O(4) atoms to form PO4 tetrahedra that share corners with two equivalent Mn(1)O6 octahedra and corners with two equivalent Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 40-49°. In the second P site, P(2) is bonded to one O(6), one O(8), and two equivalent O(9) atoms to form PO4 tetrahedra that share corners with two equivalent Mn(1)O6 octahedra and corners with two equivalent Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 44-60°. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to two equivalent Na(1) and one C(2) atom. In the second O site, O(2) is bonded in a 5-coordinate geometry to one Na(3), two equivalent Na(1), one Mn(1), and one C(1) atom. In the third O site, O(3) is bonded to one Na(3), two equivalent Na(1), one Mn(1), and one C(1) atom to form distorted corner-sharing ONa3MnC trigonal bipyramids. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to two equivalent Na(1), one Mn(1), and one P(1) atom. In the fifth O site, O(5) is bonded in a 4-coordinate geometry to two equivalent Na(1), one Mn(2), and one P(1) atom. In the sixth O site, O(6) is bonded in a distorted rectangular see-saw-like geometry to two equivalent Na(1), one Mn(1), and one P(2) atom. In the seventh O site, O(7) is bonded in a distorted rectangular see-saw-like geometry to two equivalent Na(2), one Mn(2), and one P(1) atom. In the eighth O site, O(8) is bonded to two equivalent Na(2), one Mn(1), and one P(2) atom to form distorted ONa2MnP tetrahedra that share  a cornercorner with one O(3)Na3MnC trigonal bipyramid and corners with two equivalent O(10)Na2MnC trigonal pyramids. In the ninth O site, O(9) is bonded in a 4-coordinate geometry to one Na(3), two equivalent Na(2), one Mn(2), and one P(2) atom. In the tenth O site, O(10) is bonded to two equivalent Na(2), one Mn(2), and one C(2) atom to form distorted corner-sharing ONa2MnC trigonal pyramids. In the eleventh O site, O(11) is bonded in a distorted rectangular see-saw-like geometry to two equivalent Na(2), one Mn(2), and one C(2) atom. In the twelfth O site, O(12) is bonded in a 5-coordinate geometry to two equivalent Na(2), two equivalent Na(3), and one C(1) atom.
Na5Mn2P2(CO7)2 crystallizes in the monoclinic Pm space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded in a 7-coordinate geometry to one O(1), one O(2), one O(3), one O(5), one O(6), and two equivalent O(4) atoms. The Na(1)-O(1) bond length is 2.39 Å. The Na(1)-O(2) bond length is 2.56 Å. The Na(1)-O(3) bond length is 2.47 Å. The Na(1)-O(5) bond length is 2.64 Å. The Na(1)-O(6) bond length is 2.41 Å. There is one shorter (2.59 Å) and one longer (2.89 Å) Na(1)-O(4) bond length. In the second Na site, Na(2) is bonded in a 7-coordinate geometry to one O(10), one O(11), one O(12), one O(7), one O(8), and two equivalent O(9) atoms. The Na(2)-O(10) bond length is 2.41 Å. The Na(2)-O(11) bond length is 2.53 Å. The Na(2)-O(12) bond length is 2.30 Å. The Na(2)-O(7) bond length is 2.38 Å. The Na(2)-O(8) bond length is 2.42 Å. There is one shorter (2.50 Å) and one longer (2.90 Å) Na(2)-O(9) bond length. In the third Na site, Na(3) is bonded in a 6-coordinate geometry to one O(2), one O(3), two equivalent O(12), and two equivalent O(9) atoms. The Na(3)-O(2) bond length is 2.35 Å. The Na(3)-O(3) bond length is 2.53 Å. There is one shorter (2.47 Å) and one longer (2.73 Å) Na(3)-O(12) bond length. Both Na(3)-O(9) bond lengths are 2.52 Å. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(2), one O(3), one O(6), one O(8), and two equivalent O(4) atoms to form distorted MnO6 octahedra that share corners with two equivalent P(1)O4 tetrahedra and corners with two equivalent P(2)O4 tetrahedra. The Mn(1)-O(2) bond length is 2.31 Å. The Mn(1)-O(3) bond length is 2.35 Å. The Mn(1)-O(6) bond length is 2.19 Å. The Mn(1)-O(8) bond length is 2.13 Å. Both Mn(1)-O(4) bond lengths are 2.17 Å. In the second Mn site, Mn(2) is bonded to one O(10), one O(11), one O(5), one O(7), and two equivalent O(9) atoms to form distorted MnO6 octahedra that share corners with two equivalent P(1)O4 tetrahedra and corners with two equivalent P(2)O4 tetrahedra. The Mn(2)-O(10) bond length is 2.17 Å. The Mn(2)-O(11) bond length is 2.00 Å. The Mn(2)-O(5) bond length is 1.96 Å. The Mn(2)-O(7) bond length is 2.05 Å. Both Mn(2)-O(9) bond lengths are 2.19 Å. There are two inequivalent C sites. In the first C site, C(1) is bonded in a trigonal planar geometry to one O(12), one O(2), and one O(3) atom. The C(1)-O(12) bond length is 1.30 Å. The C(1)-O(2) bond length is 1.30 Å. The C(1)-O(3) bond length is 1.30 Å. In the second C site, C(2) is bonded in a trigonal planar geometry to one O(1), one O(10), and one O(11) atom. The C(2)-O(1) bond length is 1.25 Å. The C(2)-O(10) bond length is 1.31 Å. The C(2)-O(11) bond length is 1.33 Å. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(5), one O(7), and two equivalent O(4) atoms to form PO4 tetrahedra that share corners with two equivalent Mn(1)O6 octahedra and corners with two equivalent Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 40-49°. The P(1)-O(5) bond length is 1.60 Å. The P(1)-O(7) bond length is 1.57 Å. Both P(1)-O(4) bond lengths are 1.53 Å. In the second P site, P(2) is bonded to one O(6), one O(8), and two equivalent O(9) atoms to form PO4 tetrahedra that share corners with two equivalent Mn(1)O6 octahedra and corners with two equivalent Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 44-60°. The P(2)-O(6) bond length is 1.55 Å. The P(2)-O(8) bond length is 1.56 Å. Both P(2)-O(9) bond lengths are 1.56 Å. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to two equivalent Na(1) and one C(2) atom. In the second O site, O(2) is bonded in a 5-coordinate geometry to one Na(3), two equivalent Na(1), one Mn(1), and one C(1) atom. In the third O site, O(3) is bonded to one Na(3), two equivalent Na(1), one Mn(1), and one C(1) atom to form distorted corner-sharing ONa3MnC trigonal bipyramids. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to two equivalent Na(1), one Mn(1), and one P(1) atom. In the fifth O site, O(5) is bonded in a 4-coordinate geometry to two equivalent Na(1), one Mn(2), and one P(1) atom. In the sixth O site, O(6) is bonded in a distorted rectangular see-saw-like geometry to two equivalent Na(1), one Mn(1), and one P(2) atom. In the seventh O site, O(7) is bonded in a distorted rectangular see-saw-like geometry to two equivalent Na(2), one Mn(2), and one P(1) atom. In the eighth O site, O(8) is bonded to two equivalent Na(2), one Mn(1), and one P(2) atom to form distorted ONa2MnP tetrahedra that share  a cornercorner with one O(3)Na3MnC trigonal bipyramid and corners with two equivalent O(10)Na2MnC trigonal pyramids. In the ninth O site, O(9) is bonded in a 4-coordinate geometry to one Na(3), two equivalent Na(2), one Mn(2), and one P(2) atom. In the tenth O site, O(10) is bonded to two equivalent Na(2), one Mn(2), and one C(2) atom to form distorted corner-sharing ONa2MnC trigonal pyramids. In the eleventh O site, O(11) is bonded in a distorted rectangular see-saw-like geometry to two equivalent Na(2), one Mn(2), and one C(2) atom. In the twelfth O site, O(12) is bonded in a 5-coordinate geometry to two equivalent Na(2), two equivalent Na(3), and one C(1) atom.