Na3Li3Mn2P2(CO7)2 crystallizes in the triclinic P1 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(12), one O(13), one O(4), one O(5), and two equivalent O(1) atoms. In the second Na site, Na(2) is bonded in a 7-coordinate geometry to one O(1), one O(2), one O(3), one O(6), one O(7), and two equivalent O(4) atoms. In the third Na site, Na(3) is bonded in a 7-coordinate geometry to one O(12), one O(13), one O(14), one O(8), one O(9), and two equivalent O(10) atoms. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded in a 4-coordinate geometry to one O(1), one O(3), one O(5), one O(6), and one O(7) atom. In the second Li site, Li(2) is bonded in a 4-coordinate geometry to one O(11), one O(14), one O(8), and one O(9) atom. In the third Li site, Li(3) is bonded in a 5-coordinate geometry to one O(10), one O(11), one O(14), one O(2), and one O(3) atom. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded in a 6-coordinate geometry to one O(2), one O(3), one O(4), one O(5), one O(7), and one O(9) atom. 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 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(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(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 55-65°. 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(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 48-50°. There are fourteen inequivalent O sites. In the first O site, O(1) is bonded in a 5-coordinate geometry to one Na(2), two equivalent Na(1), one Li(1), and one C(2) atom. In the second O site, O(2) is bonded in a 2-coordinate geometry to one Na(2), one Li(3), one Mn(1), and one C(1) atom. In the third O site, O(3) is bonded in a 5-coordinate geometry to one Na(2), one Li(1), one Li(3), one Mn(1), and one C(1) atom. In the fourth O site, O(4) is bonded in a 5-coordinate geometry to one Na(1), two equivalent Na(2), one Mn(1), and one P(1) atom. In the fifth O site, O(5) is bonded to one Na(1), one Li(1), one Mn(1), and one P(1) atom to form distorted corner-sharing ONaLiMnP trigonal pyramids. In the sixth O site, O(6) is bonded to one Na(2), one Li(1), one Mn(2), and one P(1) atom to form distorted ONaLiMnP tetrahedra that share  a cornercorner with one O(11)Li2MnP trigonal pyramid and corners with two equivalent O(5)NaLiMnP trigonal pyramids. In the seventh O site, O(7) is bonded in a 4-coordinate geometry to one Na(2), one Li(1), one Mn(1), and one P(2) atom. In the eighth O site, O(8) is bonded in a 4-coordinate geometry to one Na(3), one Li(2), one Mn(2), and one P(1) atom. In the ninth O site, O(9) is bonded to one Na(3), one Li(2), one Mn(1), and one P(2) atom to form distorted ONaLiMnP tetrahedra that share  a cornercorner with one O(5)NaLiMnP trigonal pyramid, corners with two equivalent O(11)Li2MnP trigonal pyramids, and  an edgeedge with one O(14)NaLi2C tetrahedra. In the tenth O site, O(10) is bonded in a 5-coordinate geometry to two equivalent Na(3), one Li(3), one Mn(2), and one P(2) atom. In the eleventh O site, O(11) is bonded to one Li(2), one Li(3), one Mn(2), and one P(2) atom to form distorted OLi2MnP trigonal pyramids that share  a cornercorner with one O(6)NaLiMnP tetrahedra, corners with two equivalent O(14)NaLi2C tetrahedra, and corners with two equivalent O(9)NaLiMnP tetrahedra. In the twelfth O site, O(12) is bonded in a 1-coordinate geometry to one Na(1), one Na(3), one Mn(2), and one C(2) atom. In the thirteenth O site, O(13) is bonded in a 1-coordinate geometry to one Na(1), one Na(3), one Mn(2), and one C(2) atom. In the fourteenth O site, O(14) is bonded to one Na(3), one Li(2), one Li(3), and one C(1) atom to form distorted ONaLi2C tetrahedra that share corners with two equivalent O(11)Li2MnP trigonal pyramids and  an edgeedge with one O(9)NaLiMnP tetrahedra.
Na3Li3Mn2P2(CO7)2 crystallizes in the triclinic P1 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(12), one O(13), one O(4), one O(5), and two equivalent O(1) atoms. The Na(1)-O(12) bond length is 2.43 Å. The Na(1)-O(13) bond length is 2.24 Å. The Na(1)-O(4) bond length is 2.42 Å. The Na(1)-O(5) bond length is 2.44 Å. There is one shorter (2.40 Å) and one longer (2.69 Å) Na(1)-O(1) bond length. In the second Na site, Na(2) is bonded in a 7-coordinate geometry to one O(1), one O(2), one O(3), one O(6), one O(7), and two equivalent O(4) atoms. The Na(2)-O(1) bond length is 2.33 Å. The Na(2)-O(2) bond length is 2.61 Å. The Na(2)-O(3) bond length is 2.45 Å. The Na(2)-O(6) bond length is 2.47 Å. The Na(2)-O(7) bond length is 2.38 Å. There is one shorter (2.49 Å) and one longer (2.78 Å) Na(2)-O(4) bond length. In the third Na site, Na(3) is bonded in a 7-coordinate geometry to one O(12), one O(13), one O(14), one O(8), one O(9), and two equivalent O(10) atoms. The Na(3)-O(12) bond length is 2.43 Å. The Na(3)-O(13) bond length is 2.53 Å. The Na(3)-O(14) bond length is 2.34 Å. The Na(3)-O(8) bond length is 2.35 Å. The Na(3)-O(9) bond length is 2.46 Å. There is one shorter (2.49 Å) and one longer (2.75 Å) Na(3)-O(10) bond length. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded in a 4-coordinate geometry to one O(1), one O(3), one O(5), one O(6), and one O(7) atom. The Li(1)-O(1) bond length is 2.06 Å. The Li(1)-O(3) bond length is 2.63 Å. The Li(1)-O(5) bond length is 2.10 Å. The Li(1)-O(6) bond length is 2.10 Å. The Li(1)-O(7) bond length is 2.21 Å. In the second Li site, Li(2) is bonded in a 4-coordinate geometry to one O(11), one O(14), one O(8), and one O(9) atom. The Li(2)-O(11) bond length is 2.12 Å. The Li(2)-O(14) bond length is 2.08 Å. The Li(2)-O(8) bond length is 2.18 Å. The Li(2)-O(9) bond length is 2.11 Å. In the third Li site, Li(3) is bonded in a 5-coordinate geometry to one O(10), one O(11), one O(14), one O(2), and one O(3) atom. The Li(3)-O(10) bond length is 2.30 Å. The Li(3)-O(11) bond length is 2.36 Å. The Li(3)-O(14) bond length is 2.10 Å. The Li(3)-O(2) bond length is 2.04 Å. The Li(3)-O(3) bond length is 2.56 Å. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded in a 6-coordinate geometry to one O(2), one O(3), one O(4), one O(5), one O(7), and one O(9) atom. The Mn(1)-O(2) bond length is 2.60 Å. The Mn(1)-O(3) bond length is 2.21 Å. The Mn(1)-O(4) bond length is 2.17 Å. The Mn(1)-O(5) bond length is 2.15 Å. The Mn(1)-O(7) bond length is 2.19 Å. The Mn(1)-O(9) bond length is 2.12 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 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 2.19 Å. The Mn(2)-O(11) bond length is 2.16 Å. The Mn(2)-O(12) bond length is 2.31 Å. The Mn(2)-O(13) bond length is 2.29 Å. The Mn(2)-O(6) bond length is 2.14 Å. The Mn(2)-O(8) bond length is 2.21 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 1.30 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(12), and one O(13) atom. The C(2)-O(1) bond length is 1.30 Å. The C(2)-O(12) bond length is 1.30 Å. The C(2)-O(13) bond length is 1.30 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(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 55-65°. The P(1)-O(4) bond length is 1.56 Å. The P(1)-O(5) bond length is 1.56 Å. The P(1)-O(6) bond length is 1.57 Å. The P(1)-O(8) bond length is 1.55 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(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 48-50°. The P(2)-O(10) bond length is 1.56 Å. The P(2)-O(11) bond length is 1.56 Å. The P(2)-O(7) bond length is 1.56 Å. The P(2)-O(9) bond length is 1.56 Å. There are fourteen inequivalent O sites. In the first O site, O(1) is bonded in a 5-coordinate geometry to one Na(2), two equivalent Na(1), one Li(1), and one C(2) atom. In the second O site, O(2) is bonded in a 2-coordinate geometry to one Na(2), one Li(3), one Mn(1), and one C(1) atom. In the third O site, O(3) is bonded in a 5-coordinate geometry to one Na(2), one Li(1), one Li(3), one Mn(1), and one C(1) atom. In the fourth O site, O(4) is bonded in a 5-coordinate geometry to one Na(1), two equivalent Na(2), one Mn(1), and one P(1) atom. In the fifth O site, O(5) is bonded to one Na(1), one Li(1), one Mn(1), and one P(1) atom to form distorted corner-sharing ONaLiMnP trigonal pyramids. In the sixth O site, O(6) is bonded to one Na(2), one Li(1), one Mn(2), and one P(1) atom to form distorted ONaLiMnP tetrahedra that share  a cornercorner with one O(11)Li2MnP trigonal pyramid and corners with two equivalent O(5)NaLiMnP trigonal pyramids. In the seventh O site, O(7) is bonded in a 4-coordinate geometry to one Na(2), one Li(1), one Mn(1), and one P(2) atom. In the eighth O site, O(8) is bonded in a 4-coordinate geometry to one Na(3), one Li(2), one Mn(2), and one P(1) atom. In the ninth O site, O(9) is bonded to one Na(3), one Li(2), one Mn(1), and one P(2) atom to form distorted ONaLiMnP tetrahedra that share  a cornercorner with one O(5)NaLiMnP trigonal pyramid, corners with two equivalent O(11)Li2MnP trigonal pyramids, and  an edgeedge with one O(14)NaLi2C tetrahedra. In the tenth O site, O(10) is bonded in a 5-coordinate geometry to two equivalent Na(3), one Li(3), one Mn(2), and one P(2) atom. In the eleventh O site, O(11) is bonded to one Li(2), one Li(3), one Mn(2), and one P(2) atom to form distorted OLi2MnP trigonal pyramids that share  a cornercorner with one O(6)NaLiMnP tetrahedra, corners with two equivalent O(14)NaLi2C tetrahedra, and corners with two equivalent O(9)NaLiMnP tetrahedra. In the twelfth O site, O(12) is bonded in a 1-coordinate geometry to one Na(1), one Na(3), one Mn(2), and one C(2) atom. In the thirteenth O site, O(13) is bonded in a 1-coordinate geometry to one Na(1), one Na(3), one Mn(2), and one C(2) atom. In the fourteenth O site, O(14) is bonded to one Na(3), one Li(2), one Li(3), and one C(1) atom to form distorted ONaLi2C tetrahedra that share corners with two equivalent O(11)Li2MnP trigonal pyramids and  an edgeedge with one O(9)NaLiMnP tetrahedra.