Na3Mn2P2(CO7)2 crystallizes in the monoclinic P2_1 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(11), one O(12), one O(2), one O(3), one O(6), and one O(8) atom. In the second Na site, Na(2) is bonded in a 7-coordinate geometry to one O(1), one O(13), one O(14), one O(4), one O(5), 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(10), one O(13), one O(14), one O(4), one O(5), and one O(8) atom. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(12), one O(13), one O(3), one O(5), one O(7), and one O(8) atom to form 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(10), one O(11), one O(14), one O(4), one O(6), and one O(9) atom to form 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(2), 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(1), 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(13), one O(14), one O(7), and one O(8) atom 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 40-48°. In the second P site, P(2) is bonded to one O(10), one O(11), one O(12), and one O(9) atom 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 39-48°. There are fourteen inequivalent O sites. In the first O site, O(1) is bonded in a distorted T-shaped geometry to one Na(2), one Na(3), and one C(2) atom. In the second O site, O(2) is bonded in a distorted bent 120 degrees geometry to one Na(1) and one C(1) atom. In the third O site, O(3) is bonded in a distorted T-shaped geometry to one Na(1), one Mn(1), and one C(1) atom. In the fourth O site, O(4) is bonded in a distorted rectangular see-saw-like geometry to one Na(2), one Na(3), one Mn(2), and one C(2) atom. In the fifth O site, O(5) is bonded in a distorted trigonal pyramidal geometry to one Na(2), one Na(3), one Mn(1), and one C(1) atom. In the sixth O site, O(6) is bonded in a distorted T-shaped geometry to one Na(1), one Mn(2), and one C(2) atom. In the seventh O site, O(7) is bonded in a 2-coordinate geometry to one Na(2), one Mn(1), and one P(1) atom. In the eighth O site, O(8) is bonded in a 3-coordinate geometry to one Na(1), one Na(3), one Mn(1), and one P(1) atom. In the ninth O site, O(9) is bonded in a 3-coordinate geometry to one Na(2), one Mn(2), and one P(2) atom. In the tenth O site, O(10) is bonded in a 3-coordinate geometry to one Na(3), one Mn(2), and one P(2) atom. In the eleventh O site, O(11) is bonded in a 3-coordinate geometry to one Na(1), one Mn(2), and one P(2) atom. In the twelfth O site, O(12) is bonded in a 3-coordinate geometry to one Na(1), one Mn(1), and one P(2) atom. In the thirteenth O site, O(13) is bonded in a 4-coordinate geometry to one Na(2), one Na(3), one Mn(1), and one P(1) atom. In the fourteenth O site, O(14) is bonded in a rectangular see-saw-like geometry to one Na(2), one Na(3), one Mn(2), and one P(1) atom.
Na3Mn2P2(CO7)2 crystallizes in the monoclinic P2_1 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(11), one O(12), one O(2), one O(3), one O(6), and one O(8) atom. The Na(1)-O(11) bond length is 2.64 Å. The Na(1)-O(12) bond length is 2.44 Å. The Na(1)-O(2) bond length is 2.22 Å. The Na(1)-O(3) bond length is 2.47 Å. The Na(1)-O(6) bond length is 2.39 Å. The Na(1)-O(8) bond length is 2.50 Å. In the second Na site, Na(2) is bonded in a 7-coordinate geometry to one O(1), one O(13), one O(14), one O(4), one O(5), one O(7), and one O(9) atom. The Na(2)-O(1) bond length is 2.25 Å. The Na(2)-O(13) bond length is 2.68 Å. The Na(2)-O(14) bond length is 2.41 Å. The Na(2)-O(4) bond length is 2.45 Å. The Na(2)-O(5) bond length is 2.34 Å. The Na(2)-O(7) bond length is 2.80 Å. The Na(2)-O(9) bond length is 2.51 Å. In the third Na site, Na(3) is bonded in a 7-coordinate geometry to one O(1), one O(10), one O(13), one O(14), one O(4), one O(5), and one O(8) atom. The Na(3)-O(1) bond length is 2.26 Å. The Na(3)-O(10) bond length is 2.50 Å. The Na(3)-O(13) bond length is 2.64 Å. The Na(3)-O(14) bond length is 2.40 Å. The Na(3)-O(4) bond length is 2.47 Å. The Na(3)-O(5) bond length is 2.34 Å. The Na(3)-O(8) bond length is 2.91 Å. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(12), one O(13), one O(3), one O(5), one O(7), and one O(8) atom to form 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(12) bond length is 1.96 Å. The Mn(1)-O(13) bond length is 2.00 Å. The Mn(1)-O(3) bond length is 2.00 Å. The Mn(1)-O(5) bond length is 2.03 Å. The Mn(1)-O(7) bond length is 2.03 Å. The Mn(1)-O(8) bond length is 2.09 Å. In the second Mn site, Mn(2) is bonded to one O(10), one O(11), one O(14), one O(4), one O(6), and one O(9) atom to form 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(10) bond length is 2.08 Å. The Mn(2)-O(11) bond length is 1.94 Å. The Mn(2)-O(14) bond length is 2.07 Å. The Mn(2)-O(4) bond length is 2.01 Å. The Mn(2)-O(6) bond length is 2.06 Å. The Mn(2)-O(9) bond length is 2.05 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(5) atom. The C(1)-O(2) bond length is 1.23 Å. The C(1)-O(3) bond length is 1.32 Å. The C(1)-O(5) bond length is 1.34 Å. In the second C site, C(2) is bonded in a trigonal planar geometry to one O(1), one O(4), and one O(6) atom. The C(2)-O(1) bond length is 1.24 Å. The C(2)-O(4) bond length is 1.33 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(13), one O(14), one O(7), and one O(8) atom 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 40-48°. The P(1)-O(13) bond length is 1.58 Å. The P(1)-O(14) bond length is 1.55 Å. The P(1)-O(7) bond length is 1.54 Å. The P(1)-O(8) bond length is 1.54 Å. In the second P site, P(2) is bonded to one O(10), one O(11), one O(12), and one O(9) atom 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 39-48°. The P(2)-O(10) bond length is 1.55 Å. The P(2)-O(11) bond length is 1.56 Å. The P(2)-O(12) bond length is 1.55 Å. The P(2)-O(9) bond length is 1.55 Å. There are fourteen inequivalent O sites. In the first O site, O(1) is bonded in a distorted T-shaped geometry to one Na(2), one Na(3), and one C(2) atom. In the second O site, O(2) is bonded in a distorted bent 120 degrees geometry to one Na(1) and one C(1) atom. In the third O site, O(3) is bonded in a distorted T-shaped geometry to one Na(1), one Mn(1), and one C(1) atom. In the fourth O site, O(4) is bonded in a distorted rectangular see-saw-like geometry to one Na(2), one Na(3), one Mn(2), and one C(2) atom. In the fifth O site, O(5) is bonded in a distorted trigonal pyramidal geometry to one Na(2), one Na(3), one Mn(1), and one C(1) atom. In the sixth O site, O(6) is bonded in a distorted T-shaped geometry to one Na(1), one Mn(2), and one C(2) atom. In the seventh O site, O(7) is bonded in a 2-coordinate geometry to one Na(2), one Mn(1), and one P(1) atom. In the eighth O site, O(8) is bonded in a 3-coordinate geometry to one Na(1), one Na(3), one Mn(1), and one P(1) atom. In the ninth O site, O(9) is bonded in a 3-coordinate geometry to one Na(2), one Mn(2), and one P(2) atom. In the tenth O site, O(10) is bonded in a 3-coordinate geometry to one Na(3), one Mn(2), and one P(2) atom. In the eleventh O site, O(11) is bonded in a 3-coordinate geometry to one Na(1), one Mn(2), and one P(2) atom. In the twelfth O site, O(12) is bonded in a 3-coordinate geometry to one Na(1), one Mn(1), and one P(2) atom. In the thirteenth O site, O(13) is bonded in a 4-coordinate geometry to one Na(2), one Na(3), one Mn(1), and one P(1) atom. In the fourteenth O site, O(14) is bonded in a rectangular see-saw-like geometry to one Na(2), one Na(3), one Mn(2), and one P(1) atom.