Na5Mn2P2(CO7)2 crystallizes in the triclinic P-1 space group. There are five inequivalent Na sites. In the first Na site, Na(1) is bonded in a 6-coordinate geometry to one O(1), one O(10), one O(11), one O(13), one O(2), and one O(3) atom. In the second Na site, Na(2) is bonded to one O(12), one O(14), one O(4), one O(5), one O(9), and two equivalent O(8) atoms to form distorted NaO7 pentagonal bipyramids that share  a cornercorner with one Mn(1)O6 octahedra, corners with two equivalent Na(2)O7 pentagonal bipyramids,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra,  an edgeedge with one Mn(2)O6 octahedra,  an edgeedge with one P(2)O4 tetrahedra, and  a faceface with one Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles are 64°. In the third Na site, Na(3) is bonded in a 7-coordinate geometry to one O(10), one O(11), one O(14), one O(3), one O(5), and two equivalent O(7) atoms. In the fourth Na site, Na(4) is bonded in a 6-coordinate geometry to one O(12), one O(13), one O(2), one O(4), one O(6), and one O(9) atom. In the fifth Na site, Na(5) is bonded in a 6-coordinate geometry to one O(12), one O(7), one O(8), one O(9), and two equivalent O(14) atoms. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(1), one O(10), one O(11), one O(3), one O(5), and one O(7) atom to form distorted MnO6 octahedra that share  a cornercorner with one Na(2)O7 pentagonal bipyramid,  a cornercorner with one P(1)O4 tetrahedra, and corners with three equivalent P(2)O4 tetrahedra. In the second Mn site, Mn(2) is bonded to one O(12), one O(2), one O(4), one O(6), one O(8), and one O(9) atom to form distorted MnO6 octahedra that share  a cornercorner with one P(2)O4 tetrahedra, corners with three equivalent P(1)O4 tetrahedra,  an edgeedge with one Na(2)O7 pentagonal bipyramid, and  a faceface with one Na(2)O7 pentagonal bipyramid. There are two inequivalent C sites. In the first C site, C(1) is bonded in a trigonal planar geometry to one O(10), one O(11), and one O(13) atom. In the second C site, C(2) is bonded in a trigonal planar geometry to one O(12), one O(14), and one O(9) atom. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(2), one O(4), and one O(6) atom to form PO4 tetrahedra that share  a cornercorner with one Mn(1)O6 octahedra, corners with three equivalent Mn(2)O6 octahedra, and  a cornercorner with one Na(2)O7 pentagonal bipyramid. The corner-sharing octahedral tilt angles range from 42-59°. In the second P site, P(2) is bonded to one O(3), one O(5), one O(7), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one Mn(2)O6 octahedra, corners with three equivalent Mn(1)O6 octahedra,  a cornercorner with one Na(2)O7 pentagonal bipyramid, and  an edgeedge with one Na(2)O7 pentagonal bipyramid. The corner-sharing octahedral tilt angles range from 43-53°. There are fourteen inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Na(1), one Mn(1), and one P(1) atom. In the second O site, O(2) is bonded to one Na(1), one Na(4), one Mn(2), and one P(1) atom to form distorted ONa2MnP tetrahedra that share corners with two equivalent O(9)Na3MnC trigonal bipyramids and  a cornercorner with one O(10)Na2MnC trigonal pyramid. In the third O site, O(3) is bonded in a distorted rectangular see-saw-like geometry to one Na(1), one Na(3), one Mn(1), and one P(2) atom. In the fourth O site, O(4) is bonded in a distorted rectangular see-saw-like geometry to one Na(2), one Na(4), one Mn(2), and one P(1) atom. In the fifth O site, O(5) is bonded in a 4-coordinate geometry to one Na(2), one Na(3), one Mn(1), and one P(2) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one Na(4), one Mn(2), and one P(1) atom. In the seventh O site, O(7) is bonded in a 5-coordinate geometry to one Na(5), two equivalent Na(3), one Mn(1), and one P(2) atom. In the eighth O site, O(8) is bonded in a 5-coordinate geometry to one Na(5), two equivalent Na(2), one Mn(2), and one P(2) atom. In the ninth O site, O(9) is bonded to one Na(2), one Na(4), one Na(5), one Mn(2), and one C(2) atom to form distorted corner-sharing ONa3MnC trigonal bipyramids. In the tenth O site, O(10) is bonded to one Na(1), one Na(3), one Mn(1), and one C(1) 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 one Na(1), one Na(3), one Mn(1), and one C(1) atom. In the twelfth O site, O(12) is bonded in a 5-coordinate geometry to one Na(2), one Na(4), one Na(5), one Mn(2), and one C(2) atom. In the thirteenth O site, O(13) is bonded in a 3-coordinate geometry to one Na(1), one Na(4), and one C(1) atom. In the fourteenth O site, O(14) is bonded in a 5-coordinate geometry to one Na(2), one Na(3), two equivalent Na(5), and one C(2) atom.
Na5Mn2P2(CO7)2 crystallizes in the triclinic P-1 space group. There are five inequivalent Na sites. In the first Na site, Na(1) is bonded in a 6-coordinate geometry to one O(1), one O(10), one O(11), one O(13), one O(2), and one O(3) atom. The Na(1)-O(1) bond length is 2.49 Å. The Na(1)-O(10) bond length is 2.38 Å. The Na(1)-O(11) bond length is 2.50 Å. The Na(1)-O(13) bond length is 2.28 Å. The Na(1)-O(2) bond length is 2.48 Å. The Na(1)-O(3) bond length is 2.49 Å. In the second Na site, Na(2) is bonded to one O(12), one O(14), one O(4), one O(5), one O(9), and two equivalent O(8) atoms to form distorted NaO7 pentagonal bipyramids that share  a cornercorner with one Mn(1)O6 octahedra, corners with two equivalent Na(2)O7 pentagonal bipyramids,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra,  an edgeedge with one Mn(2)O6 octahedra,  an edgeedge with one P(2)O4 tetrahedra, and  a faceface with one Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles are 64°. The Na(2)-O(12) bond length is 2.55 Å. The Na(2)-O(14) bond length is 2.29 Å. The Na(2)-O(4) bond length is 2.27 Å. The Na(2)-O(5) bond length is 2.56 Å. The Na(2)-O(9) bond length is 2.44 Å. There is one shorter (2.61 Å) and one longer (2.83 Å) Na(2)-O(8) bond length. In the third Na site, Na(3) is bonded in a 7-coordinate geometry to one O(10), one O(11), one O(14), one O(3), one O(5), and two equivalent O(7) atoms. The Na(3)-O(10) bond length is 2.33 Å. The Na(3)-O(11) bond length is 2.46 Å. The Na(3)-O(14) bond length is 2.28 Å. The Na(3)-O(3) bond length is 2.34 Å. The Na(3)-O(5) bond length is 2.61 Å. There is one shorter (2.61 Å) and one longer (2.86 Å) Na(3)-O(7) bond length. In the fourth Na site, Na(4) is bonded in a 6-coordinate geometry to one O(12), one O(13), one O(2), one O(4), one O(6), and one O(9) atom. The Na(4)-O(12) bond length is 2.64 Å. The Na(4)-O(13) bond length is 2.29 Å. The Na(4)-O(2) bond length is 2.44 Å. The Na(4)-O(4) bond length is 2.38 Å. The Na(4)-O(6) bond length is 2.47 Å. The Na(4)-O(9) bond length is 2.50 Å. In the fifth Na site, Na(5) is bonded in a 6-coordinate geometry to one O(12), one O(7), one O(8), one O(9), and two equivalent O(14) atoms. The Na(5)-O(12) bond length is 2.34 Å. The Na(5)-O(7) bond length is 2.53 Å. The Na(5)-O(8) bond length is 2.50 Å. The Na(5)-O(9) bond length is 2.52 Å. There is one shorter (2.48 Å) and one longer (2.75 Å) Na(5)-O(14) bond length. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(1), one O(10), one O(11), one O(3), one O(5), and one O(7) atom to form distorted MnO6 octahedra that share  a cornercorner with one Na(2)O7 pentagonal bipyramid,  a cornercorner with one P(1)O4 tetrahedra, and corners with three equivalent P(2)O4 tetrahedra. The Mn(1)-O(1) bond length is 2.05 Å. The Mn(1)-O(10) bond length is 2.24 Å. The Mn(1)-O(11) bond length is 2.01 Å. The Mn(1)-O(3) bond length is 2.14 Å. The Mn(1)-O(5) bond length is 1.98 Å. The Mn(1)-O(7) bond length is 2.14 Å. In the second Mn site, Mn(2) is bonded to one O(12), one O(2), one O(4), one O(6), one O(8), and one O(9) atom to form distorted MnO6 octahedra that share  a cornercorner with one P(2)O4 tetrahedra, corners with three equivalent P(1)O4 tetrahedra,  an edgeedge with one Na(2)O7 pentagonal bipyramid, and  a faceface with one Na(2)O7 pentagonal bipyramid. The Mn(2)-O(12) bond length is 2.33 Å. The Mn(2)-O(2) bond length is 2.12 Å. The Mn(2)-O(4) bond length is 2.18 Å. The Mn(2)-O(6) bond length is 2.12 Å. The Mn(2)-O(8) bond length is 2.22 Å. The Mn(2)-O(9) bond length is 2.38 Å. There are two inequivalent C sites. In the first C site, C(1) is bonded in a trigonal planar geometry to one O(10), one O(11), and one O(13) atom. The C(1)-O(10) bond length is 1.30 Å. The C(1)-O(11) bond length is 1.34 Å. The C(1)-O(13) bond length is 1.26 Å. In the second C site, C(2) is bonded in a trigonal planar geometry to one O(12), one O(14), and one O(9) atom. The C(2)-O(12) bond length is 1.30 Å. The C(2)-O(14) bond length is 1.30 Å. The C(2)-O(9) bond length is 1.30 Å. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(2), one O(4), and one O(6) atom to form PO4 tetrahedra that share  a cornercorner with one Mn(1)O6 octahedra, corners with three equivalent Mn(2)O6 octahedra, and  a cornercorner with one Na(2)O7 pentagonal bipyramid. The corner-sharing octahedral tilt angles range from 42-59°. The P(1)-O(1) bond length is 1.56 Å. The P(1)-O(2) bond length is 1.57 Å. The P(1)-O(4) bond length is 1.56 Å. The P(1)-O(6) bond length is 1.54 Å. In the second P site, P(2) is bonded to one O(3), one O(5), one O(7), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one Mn(2)O6 octahedra, corners with three equivalent Mn(1)O6 octahedra,  a cornercorner with one Na(2)O7 pentagonal bipyramid, and  an edgeedge with one Na(2)O7 pentagonal bipyramid. The corner-sharing octahedral tilt angles range from 43-53°. The P(2)-O(3) bond length is 1.54 Å. The P(2)-O(5) bond length is 1.59 Å. The P(2)-O(7) bond length is 1.56 Å. The P(2)-O(8) bond length is 1.55 Å. There are fourteen inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Na(1), one Mn(1), and one P(1) atom. In the second O site, O(2) is bonded to one Na(1), one Na(4), one Mn(2), and one P(1) atom to form distorted ONa2MnP tetrahedra that share corners with two equivalent O(9)Na3MnC trigonal bipyramids and  a cornercorner with one O(10)Na2MnC trigonal pyramid. In the third O site, O(3) is bonded in a distorted rectangular see-saw-like geometry to one Na(1), one Na(3), one Mn(1), and one P(2) atom. In the fourth O site, O(4) is bonded in a distorted rectangular see-saw-like geometry to one Na(2), one Na(4), one Mn(2), and one P(1) atom. In the fifth O site, O(5) is bonded in a 4-coordinate geometry to one Na(2), one Na(3), one Mn(1), and one P(2) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one Na(4), one Mn(2), and one P(1) atom. In the seventh O site, O(7) is bonded in a 5-coordinate geometry to one Na(5), two equivalent Na(3), one Mn(1), and one P(2) atom. In the eighth O site, O(8) is bonded in a 5-coordinate geometry to one Na(5), two equivalent Na(2), one Mn(2), and one P(2) atom. In the ninth O site, O(9) is bonded to one Na(2), one Na(4), one Na(5), one Mn(2), and one C(2) atom to form distorted corner-sharing ONa3MnC trigonal bipyramids. In the tenth O site, O(10) is bonded to one Na(1), one Na(3), one Mn(1), and one C(1) 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 one Na(1), one Na(3), one Mn(1), and one C(1) atom. In the twelfth O site, O(12) is bonded in a 5-coordinate geometry to one Na(2), one Na(4), one Na(5), one Mn(2), and one C(2) atom. In the thirteenth O site, O(13) is bonded in a 3-coordinate geometry to one Na(1), one Na(4), and one C(1) atom. In the fourteenth O site, O(14) is bonded in a 5-coordinate geometry to one Na(2), one Na(3), two equivalent Na(5), and one C(2) atom.