Na3Mn2P2(CO7)2 crystallizes in the monoclinic Pc 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(6), and one O(7) atom. In the second Na site, Na(2) is bonded in a 6-coordinate geometry to one O(10), one O(12), one O(13), one O(14), one O(8), and one O(9) atom. In the third Na site, Na(3) is bonded in a 6-coordinate geometry to one O(11), one O(12), one O(13), one O(14), one O(8), and one O(9) atom. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(2), one O(3), one O(4), one O(5), one O(7), and one O(9) atom to form 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(12), one O(13), one O(6), and one O(8) atom to form 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(14), 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(12), and one O(13) atom. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(4), one O(5), one O(6), and one O(8) atom 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 38-45°. In the second P site, P(2) is bonded to one O(10), one O(11), one O(7), and one O(9) atom 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 37-47°. There are fourteen inequivalent O sites. In the first O site, O(1) is bonded in a distorted bent 150 degrees geometry to one Na(1) and one C(2) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Na(1), one Mn(1), and one C(1) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Na(1), one Mn(1), and one C(1) atom. 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 bent 150 degrees geometry to one Mn(1) and one P(1) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one Na(1), one Mn(2), and one P(1) atom. In the seventh O site, O(7) is bonded in a 3-coordinate geometry to one Na(1), one Mn(1), and one P(2) atom. In the eighth O site, O(8) is bonded in a distorted rectangular see-saw-like geometry to one Na(2), one Na(3), one Mn(2), and one P(1) atom. In the ninth O site, O(9) is bonded in a 4-coordinate geometry to one Na(2), one Na(3), one Mn(1), and one P(2) atom. In the tenth O site, O(10) is bonded in a 3-coordinate geometry to one Na(2), 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(3), one Mn(2), and one P(2) atom. In the twelfth O site, O(12) is bonded in a distorted trigonal pyramidal geometry to one Na(2), one Na(3), one Mn(2), and one C(2) atom. In the thirteenth O site, O(13) 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 fourteenth O site, O(14) is bonded in a 3-coordinate geometry to one Na(2), one Na(3), and one C(1) atom.
Na3Mn2P2(CO7)2 crystallizes in the monoclinic Pc 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(6), and one O(7) atom. The Na(1)-O(1) bond length is 2.25 Å. The Na(1)-O(2) bond length is 2.54 Å. The Na(1)-O(3) bond length is 2.43 Å. The Na(1)-O(4) bond length is 2.49 Å. The Na(1)-O(6) bond length is 2.64 Å. The Na(1)-O(7) bond length is 2.45 Å. In the second Na site, Na(2) is bonded in a 6-coordinate geometry to one O(10), one O(12), one O(13), one O(14), one O(8), and one O(9) atom. The Na(2)-O(10) bond length is 2.52 Å. The Na(2)-O(12) bond length is 2.35 Å. The Na(2)-O(13) bond length is 2.45 Å. The Na(2)-O(14) bond length is 2.27 Å. The Na(2)-O(8) bond length is 2.45 Å. The Na(2)-O(9) bond length is 2.74 Å. In the third Na site, Na(3) is bonded in a 6-coordinate geometry to one O(11), one O(12), one O(13), one O(14), one O(8), and one O(9) atom. The Na(3)-O(11) bond length is 2.55 Å. The Na(3)-O(12) bond length is 2.34 Å. The Na(3)-O(13) bond length is 2.44 Å. The Na(3)-O(14) bond length is 2.28 Å. The Na(3)-O(8) bond length is 2.45 Å. The Na(3)-O(9) bond length is 2.77 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(4), one O(5), one O(7), and one O(9) atom to form 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 2.01 Å. The Mn(1)-O(3) bond length is 2.01 Å. The Mn(1)-O(4) bond length is 2.11 Å. The Mn(1)-O(5) bond length is 2.01 Å. The Mn(1)-O(7) bond length is 1.99 Å. The Mn(1)-O(9) bond length is 2.00 Å. In the second Mn site, Mn(2) is bonded to one O(10), one O(11), one O(12), one O(13), one O(6), and one O(8) atom to form 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 2.07 Å. The Mn(2)-O(11) bond length is 2.07 Å. The Mn(2)-O(12) bond length is 2.04 Å. The Mn(2)-O(13) bond length is 2.01 Å. The Mn(2)-O(6) bond length is 1.93 Å. The Mn(2)-O(8) bond length is 2.01 Å. There are two inequivalent C sites. In the first C site, C(1) is bonded in a trigonal planar geometry to one O(14), one O(2), and one O(3) atom. The C(1)-O(14) bond length is 1.25 Å. The C(1)-O(2) bond length is 1.31 Å. The C(1)-O(3) bond length is 1.32 Å. In the second C site, C(2) is bonded in a trigonal planar geometry to one O(1), one O(12), and one O(13) atom. The C(2)-O(1) bond length is 1.22 Å. The C(2)-O(12) bond length is 1.33 Å. The C(2)-O(13) bond length is 1.33 Å. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(4), one O(5), one O(6), and one O(8) atom 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 38-45°. The P(1)-O(4) bond length is 1.55 Å. The P(1)-O(5) bond length is 1.53 Å. The P(1)-O(6) bond length is 1.57 Å. The P(1)-O(8) bond length is 1.56 Å. In the second P site, P(2) is bonded to one O(10), one O(11), one O(7), and one O(9) atom 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 37-47°. The P(2)-O(10) bond length is 1.55 Å. The P(2)-O(11) bond length is 1.55 Å. The P(2)-O(7) bond length is 1.54 Å. The P(2)-O(9) bond length is 1.57 Å. There are fourteen inequivalent O sites. In the first O site, O(1) is bonded in a distorted bent 150 degrees geometry to one Na(1) and one C(2) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Na(1), one Mn(1), and one C(1) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Na(1), one Mn(1), and one C(1) atom. 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 bent 150 degrees geometry to one Mn(1) and one P(1) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one Na(1), one Mn(2), and one P(1) atom. In the seventh O site, O(7) is bonded in a 3-coordinate geometry to one Na(1), one Mn(1), and one P(2) atom. In the eighth O site, O(8) is bonded in a distorted rectangular see-saw-like geometry to one Na(2), one Na(3), one Mn(2), and one P(1) atom. In the ninth O site, O(9) is bonded in a 4-coordinate geometry to one Na(2), one Na(3), one Mn(1), and one P(2) atom. In the tenth O site, O(10) is bonded in a 3-coordinate geometry to one Na(2), 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(3), one Mn(2), and one P(2) atom. In the twelfth O site, O(12) is bonded in a distorted trigonal pyramidal geometry to one Na(2), one Na(3), one Mn(2), and one C(2) atom. In the thirteenth O site, O(13) 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 fourteenth O site, O(14) is bonded in a 3-coordinate geometry to one Na(2), one Na(3), and one C(1) atom.