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 6-coordinate geometry to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom. In the second Na site, Na(2) is bonded in a 6-coordinate geometry to one O(2), one O(3), two equivalent O(10), and two equivalent O(7) atoms. In the third Na site, Na(3) is bonded in a 7-coordinate geometry to one O(11), one O(12), one O(7), one O(8), one O(9), and two equivalent O(10) 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(5), one O(6), and two equivalent O(4) atoms to form distorted MnO6 octahedra that share corners with four equivalent P(1)O4 tetrahedra. In the second Mn site, Mn(2) is bonded to one O(11), one O(12), one O(8), one O(9), and two equivalent O(10) atoms to form distorted MnO6 octahedra that share corners with four 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(2), one O(3), and one O(7) atom. In the second C site, C(2) is bonded in a trigonal planar geometry to one O(1), one O(8), and one O(9) atom. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(5), one O(6), and two equivalent O(4) atoms to form PO4 tetrahedra that share corners with four equivalent Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 42-56°. In the second P site, P(2) is bonded to one O(11), one O(12), and two equivalent O(10) atoms to form PO4 tetrahedra that share corners with four equivalent Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 44-54°. 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(2), two equivalent Na(1), one Mn(1), and one C(1) atom. In the third O site, O(3) is bonded to one Na(2), two equivalent Na(1), one Mn(1), and one C(1) atom to form a mixture of distorted corner and edge-sharing ONa3MnC trigonal bipyramids. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one 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(1), and one P(1) atom. In the sixth O site, O(6) is bonded in a rectangular see-saw-like geometry to two equivalent Na(1), one Mn(1), and one P(1) atom. In the seventh O site, O(7) is bonded to two equivalent Na(2), two equivalent Na(3), and one C(1) atom to form distorted ONa4C trigonal bipyramids that share  a cornercorner with one O(3)Na3MnC trigonal bipyramid, corners with two equivalent O(7)Na4C trigonal bipyramids, corners with two equivalent O(8)Na2MnC trigonal pyramids, and  an edgeedge with one O(3)Na3MnC trigonal bipyramid. In the eighth O site, O(8) is bonded to two equivalent Na(3), one Mn(2), and one C(2) atom to form distorted corner-sharing ONa2MnC trigonal pyramids. In the ninth O site, O(9) is bonded in a rectangular see-saw-like geometry to two equivalent Na(3), one Mn(2), and one C(2) atom. In the tenth O site, O(10) is bonded in a 5-coordinate geometry to one Na(2), two equivalent Na(3), one Mn(2), and one P(2) 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(2) 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 6-coordinate geometry to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom. The Na(1)-O(1) bond length is 2.28 Å. The Na(1)-O(2) bond length is 2.57 Å. The Na(1)-O(3) bond length is 2.45 Å. The Na(1)-O(4) bond length is 2.53 Å. The Na(1)-O(5) bond length is 2.49 Å. The Na(1)-O(6) bond length is 2.34 Å. In the second Na site, Na(2) is bonded in a 6-coordinate geometry to one O(2), one O(3), two equivalent O(10), and two equivalent O(7) atoms. The Na(2)-O(2) bond length is 2.38 Å. The Na(2)-O(3) bond length is 2.52 Å. Both Na(2)-O(10) bond lengths are 2.53 Å. There is one shorter (2.53 Å) and one longer (2.72 Å) Na(2)-O(7) bond length. In the third Na site, Na(3) is bonded in a 7-coordinate geometry to one O(11), one O(12), one O(7), one O(8), one O(9), and two equivalent O(10) atoms. The Na(3)-O(11) bond length is 2.60 Å. The Na(3)-O(12) bond length is 2.34 Å. The Na(3)-O(7) bond length is 2.27 Å. The Na(3)-O(8) bond length is 2.47 Å. The Na(3)-O(9) bond length is 2.33 Å. There is one shorter (2.60 Å) and one longer (2.90 Å) Na(3)-O(10) bond length. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(2), one O(3), one O(5), one O(6), and two equivalent O(4) atoms to form distorted MnO6 octahedra that share corners with four equivalent P(1)O4 tetrahedra. The Mn(1)-O(2) bond length is 2.21 Å. The Mn(1)-O(3) bond length is 2.35 Å. The Mn(1)-O(5) bond length is 2.04 Å. The Mn(1)-O(6) bond length is 2.16 Å. Both Mn(1)-O(4) bond lengths are 2.07 Å. In the second Mn site, Mn(2) is bonded to one O(11), one O(12), one O(8), one O(9), and two equivalent O(10) atoms to form distorted MnO6 octahedra that share corners with four equivalent P(2)O4 tetrahedra. The Mn(2)-O(11) bond length is 2.03 Å. The Mn(2)-O(12) bond length is 2.15 Å. The Mn(2)-O(8) bond length is 2.09 Å. The Mn(2)-O(9) bond length is 2.23 Å. Both Mn(2)-O(10) bond lengths are 2.11 Å. There are two inequivalent C sites. In the first C site, C(1) is bonded in a trigonal planar geometry to one O(2), one O(3), and one O(7) atom. The C(1)-O(2) bond length is 1.31 Å. The C(1)-O(3) bond length is 1.30 Å. The C(1)-O(7) bond length is 1.29 Å. In the second C site, C(2) is bonded in a trigonal planar geometry to one O(1), one O(8), and one O(9) atom. The C(2)-O(1) bond length is 1.26 Å. The C(2)-O(8) bond length is 1.33 Å. The C(2)-O(9) bond length is 1.31 Å. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(5), one O(6), and two equivalent O(4) atoms to form PO4 tetrahedra that share corners with four equivalent Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 42-56°. The P(1)-O(5) bond length is 1.58 Å. The P(1)-O(6) bond length is 1.55 Å. Both P(1)-O(4) bond lengths are 1.56 Å. In the second P site, P(2) is bonded to one O(11), one O(12), and two equivalent O(10) atoms to form PO4 tetrahedra that share corners with four equivalent Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 44-54°. The P(2)-O(11) bond length is 1.58 Å. The P(2)-O(12) bond length is 1.54 Å. Both P(2)-O(10) 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(2), two equivalent Na(1), one Mn(1), and one C(1) atom. In the third O site, O(3) is bonded to one Na(2), two equivalent Na(1), one Mn(1), and one C(1) atom to form a mixture of distorted corner and edge-sharing ONa3MnC trigonal bipyramids. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one 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(1), and one P(1) atom. In the sixth O site, O(6) is bonded in a rectangular see-saw-like geometry to two equivalent Na(1), one Mn(1), and one P(1) atom. In the seventh O site, O(7) is bonded to two equivalent Na(2), two equivalent Na(3), and one C(1) atom to form distorted ONa4C trigonal bipyramids that share  a cornercorner with one O(3)Na3MnC trigonal bipyramid, corners with two equivalent O(7)Na4C trigonal bipyramids, corners with two equivalent O(8)Na2MnC trigonal pyramids, and  an edgeedge with one O(3)Na3MnC trigonal bipyramid. In the eighth O site, O(8) is bonded to two equivalent Na(3), one Mn(2), and one C(2) atom to form distorted corner-sharing ONa2MnC trigonal pyramids. In the ninth O site, O(9) is bonded in a rectangular see-saw-like geometry to two equivalent Na(3), one Mn(2), and one C(2) atom. In the tenth O site, O(10) is bonded in a 5-coordinate geometry to one Na(2), two equivalent Na(3), one Mn(2), and one P(2) 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(2) 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.