Li5Mn2P2(CO7)2 crystallizes in the monoclinic P2_1/m space group. 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(5), and two equivalent O(8) atoms. In the second Li site, Li(2) is bonded to one O(10), one O(2), one O(4), one O(8), and one O(9) atom to form distorted LiO5 trigonal bipyramids that share corners with two equivalent Mn(1)O6 octahedra,  a cornercorner with one P(2)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra,  an edgeedge with one Mn(2)O6 octahedra, and edges with two equivalent Li(2)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 64-84°. In the third Li site, Li(3) is bonded in a 5-coordinate geometry to one O(11), one O(12), one O(5), one O(6), and one O(7) atom. 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(4), and two equivalent O(7) atoms to form distorted MnO6 octahedra that share  a cornercorner with one P(2)O4 tetrahedra, corners with three equivalent P(1)O4 tetrahedra, and corners with four equivalent Li(2)O5 trigonal bipyramids. In the second Mn site, Mn(2) is bonded to one O(12), one O(3), one O(6), one O(9), and two equivalent O(8) atoms to form distorted MnO6 octahedra that share  a cornercorner with one P(1)O4 tetrahedra, corners with three equivalent P(2)O4 tetrahedra, and edges with two equivalent Li(2)O5 trigonal bipyramids. There are two inequivalent C sites. In the first C site, C(1) is bonded in a trigonal planar geometry to one O(1), one O(2), and one O(4) atom. In the second C site, C(2) is bonded in a trigonal planar geometry to one O(3), one O(5), and one O(6) atom. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(10), one O(9), and two equivalent O(7) atoms to form PO4 tetrahedra that share  a cornercorner with one Mn(2)O6 octahedra, corners with three equivalent Mn(1)O6 octahedra, and corners with four equivalent Li(2)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 45-63°. In the second P site, P(2) is bonded to one O(11), one O(12), and two equivalent O(8) atoms to form PO4 tetrahedra that share  a cornercorner with one Mn(1)O6 octahedra, corners with three equivalent Mn(2)O6 octahedra, and corners with two equivalent Li(2)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 47-60°. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a 2-coordinate geometry to one Li(1), one Mn(1), and one C(1) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to two equivalent Li(2) and one C(1) atom. In the third O site, O(3) is bonded in a distorted L-shaped geometry to one Mn(2) and one C(2) atom. In the fourth O site, O(4) is bonded to two equivalent Li(2), one Mn(1), and one C(1) atom to form a mixture of distorted corner and edge-sharing OLi2MnC trigonal pyramids. In the fifth O site, O(5) is bonded to one Li(1), two equivalent Li(3), and one C(2) atom to form a mixture of corner and edge-sharing OLi3C tetrahedra. In the sixth O site, O(6) is bonded in a 4-coordinate geometry to two equivalent Li(3), one Mn(2), and one C(2) atom. In the seventh O site, O(7) is bonded in a distorted trigonal planar geometry to one Li(3), one Mn(1), and one P(1) atom. In the eighth O site, O(8) is bonded to one Li(1), one Li(2), one Mn(2), and one P(2) atom to form distorted OLi2MnP trigonal pyramids that share  a cornercorner with one O(10)Li2MnP tetrahedra,  a cornercorner with one O(5)Li3C tetrahedra, corners with two equivalent O(12)Li2MnP tetrahedra,  a cornercorner with one O(4)Li2MnC trigonal pyramid,  a cornercorner with one O(11)Li2MnP trigonal pyramid,  a cornercorner with one O(8)Li2MnP trigonal pyramid,  an edgeedge with one O(8)Li2MnP trigonal pyramid, and  an edgeedge with one O(9)Li2MnP trigonal pyramid. In the ninth O site, O(9) is bonded to two equivalent Li(2), one Mn(2), and one P(1) atom to form distorted OLi2MnP trigonal pyramids that share  a cornercorner with one O(12)Li2MnP tetrahedra, corners with three equivalent O(10)Li2MnP tetrahedra,  an edgeedge with one O(4)Li2MnC trigonal pyramid, and edges with two equivalent O(8)Li2MnP trigonal pyramids. In the tenth O site, O(10) is bonded to two equivalent Li(2), one Mn(1), and one P(1) atom to form OLi2MnP tetrahedra that share  a cornercorner with one O(11)Li2MnP trigonal pyramid, corners with two equivalent O(8)Li2MnP trigonal pyramids, corners with three equivalent O(4)Li2MnC trigonal pyramids, and corners with three equivalent O(9)Li2MnP trigonal pyramids. In the eleventh O site, O(11) is bonded to two equivalent Li(3), one Mn(1), and one P(2) atom to form distorted OLi2MnP trigonal pyramids that share  a cornercorner with one O(10)Li2MnP tetrahedra, corners with two equivalent O(5)Li3C tetrahedra, corners with three equivalent O(12)Li2MnP tetrahedra,  a cornercorner with one O(4)Li2MnC trigonal pyramid, and corners with two equivalent O(8)Li2MnP trigonal pyramids. In the twelfth O site, O(12) is bonded to two equivalent Li(3), one Mn(2), and one P(2) atom to form distorted OLi2MnP tetrahedra that share  a cornercorner with one O(9)Li2MnP trigonal pyramid, corners with three equivalent O(11)Li2MnP trigonal pyramids, corners with four equivalent O(8)Li2MnP trigonal pyramids, and  an edgeedge with one O(5)Li3C tetrahedra.
Li5Mn2P2(CO7)2 crystallizes in the monoclinic P2_1/m space group. 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(5), and two equivalent O(8) atoms. The Li(1)-O(1) bond length is 1.93 Å. The Li(1)-O(5) bond length is 2.01 Å. Both Li(1)-O(8) bond lengths are 2.24 Å. In the second Li site, Li(2) is bonded to one O(10), one O(2), one O(4), one O(8), and one O(9) atom to form distorted LiO5 trigonal bipyramids that share corners with two equivalent Mn(1)O6 octahedra,  a cornercorner with one P(2)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra,  an edgeedge with one Mn(2)O6 octahedra, and edges with two equivalent Li(2)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 64-84°. The Li(2)-O(10) bond length is 2.25 Å. The Li(2)-O(2) bond length is 2.00 Å. The Li(2)-O(4) bond length is 2.29 Å. The Li(2)-O(8) bond length is 2.29 Å. The Li(2)-O(9) bond length is 2.20 Å. In the third Li site, Li(3) is bonded in a 5-coordinate geometry to one O(11), one O(12), one O(5), one O(6), and one O(7) atom. The Li(3)-O(11) bond length is 2.23 Å. The Li(3)-O(12) bond length is 2.29 Å. The Li(3)-O(5) bond length is 2.04 Å. The Li(3)-O(6) bond length is 2.36 Å. The Li(3)-O(7) bond length is 2.08 Å. 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(4), and two equivalent O(7) atoms to form distorted MnO6 octahedra that share  a cornercorner with one P(2)O4 tetrahedra, corners with three equivalent P(1)O4 tetrahedra, and corners with four equivalent Li(2)O5 trigonal bipyramids. The Mn(1)-O(1) bond length is 2.35 Å. The Mn(1)-O(10) bond length is 2.17 Å. The Mn(1)-O(11) bond length is 2.10 Å. The Mn(1)-O(4) bond length is 2.08 Å. Both Mn(1)-O(7) bond lengths are 2.01 Å. In the second Mn site, Mn(2) is bonded to one O(12), one O(3), one O(6), one O(9), and two equivalent O(8) atoms to form distorted MnO6 octahedra that share  a cornercorner with one P(1)O4 tetrahedra, corners with three equivalent P(2)O4 tetrahedra, and edges with two equivalent Li(2)O5 trigonal bipyramids. The Mn(2)-O(12) bond length is 2.17 Å. The Mn(2)-O(3) bond length is 2.29 Å. The Mn(2)-O(6) bond length is 2.16 Å. The Mn(2)-O(9) bond length is 2.14 Å. Both Mn(2)-O(8) bond lengths are 2.04 Å. There are two inequivalent C sites. In the first C site, C(1) is bonded in a trigonal planar geometry to one O(1), one O(2), and one O(4) atom. The C(1)-O(1) bond length is 1.30 Å. The C(1)-O(2) bond length is 1.28 Å. The C(1)-O(4) bond length is 1.33 Å. In the second C site, C(2) is bonded in a trigonal planar geometry to one O(3), one O(5), and one O(6) atom. The C(2)-O(3) bond length is 1.27 Å. The C(2)-O(5) bond length is 1.31 Å. The C(2)-O(6) bond length is 1.33 Å. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(10), one O(9), and two equivalent O(7) atoms to form PO4 tetrahedra that share  a cornercorner with one Mn(2)O6 octahedra, corners with three equivalent Mn(1)O6 octahedra, and corners with four equivalent Li(2)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 45-63°. The P(1)-O(10) bond length is 1.56 Å. The P(1)-O(9) bond length is 1.56 Å. Both P(1)-O(7) bond lengths are 1.55 Å. In the second P site, P(2) is bonded to one O(11), one O(12), and two equivalent O(8) atoms to form PO4 tetrahedra that share  a cornercorner with one Mn(1)O6 octahedra, corners with three equivalent Mn(2)O6 octahedra, and corners with two equivalent Li(2)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 47-60°. The P(2)-O(11) bond length is 1.55 Å. The P(2)-O(12) bond length is 1.55 Å. Both P(2)-O(8) bond lengths are 1.56 Å. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a 2-coordinate geometry to one Li(1), one Mn(1), and one C(1) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to two equivalent Li(2) and one C(1) atom. In the third O site, O(3) is bonded in a distorted L-shaped geometry to one Mn(2) and one C(2) atom. In the fourth O site, O(4) is bonded to two equivalent Li(2), one Mn(1), and one C(1) atom to form a mixture of distorted corner and edge-sharing OLi2MnC trigonal pyramids. In the fifth O site, O(5) is bonded to one Li(1), two equivalent Li(3), and one C(2) atom to form a mixture of corner and edge-sharing OLi3C tetrahedra. In the sixth O site, O(6) is bonded in a 4-coordinate geometry to two equivalent Li(3), one Mn(2), and one C(2) atom. In the seventh O site, O(7) is bonded in a distorted trigonal planar geometry to one Li(3), one Mn(1), and one P(1) atom. In the eighth O site, O(8) is bonded to one Li(1), one Li(2), one Mn(2), and one P(2) atom to form distorted OLi2MnP trigonal pyramids that share  a cornercorner with one O(10)Li2MnP tetrahedra,  a cornercorner with one O(5)Li3C tetrahedra, corners with two equivalent O(12)Li2MnP tetrahedra,  a cornercorner with one O(4)Li2MnC trigonal pyramid,  a cornercorner with one O(11)Li2MnP trigonal pyramid,  a cornercorner with one O(8)Li2MnP trigonal pyramid,  an edgeedge with one O(8)Li2MnP trigonal pyramid, and  an edgeedge with one O(9)Li2MnP trigonal pyramid. In the ninth O site, O(9) is bonded to two equivalent Li(2), one Mn(2), and one P(1) atom to form distorted OLi2MnP trigonal pyramids that share  a cornercorner with one O(12)Li2MnP tetrahedra, corners with three equivalent O(10)Li2MnP tetrahedra,  an edgeedge with one O(4)Li2MnC trigonal pyramid, and edges with two equivalent O(8)Li2MnP trigonal pyramids. In the tenth O site, O(10) is bonded to two equivalent Li(2), one Mn(1), and one P(1) atom to form OLi2MnP tetrahedra that share  a cornercorner with one O(11)Li2MnP trigonal pyramid, corners with two equivalent O(8)Li2MnP trigonal pyramids, corners with three equivalent O(4)Li2MnC trigonal pyramids, and corners with three equivalent O(9)Li2MnP trigonal pyramids. In the eleventh O site, O(11) is bonded to two equivalent Li(3), one Mn(1), and one P(2) atom to form distorted OLi2MnP trigonal pyramids that share  a cornercorner with one O(10)Li2MnP tetrahedra, corners with two equivalent O(5)Li3C tetrahedra, corners with three equivalent O(12)Li2MnP tetrahedra,  a cornercorner with one O(4)Li2MnC trigonal pyramid, and corners with two equivalent O(8)Li2MnP trigonal pyramids. In the twelfth O site, O(12) is bonded to two equivalent Li(3), one Mn(2), and one P(2) atom to form distorted OLi2MnP tetrahedra that share  a cornercorner with one O(9)Li2MnP trigonal pyramid, corners with three equivalent O(11)Li2MnP trigonal pyramids, corners with four equivalent O(8)Li2MnP trigonal pyramids, and  an edgeedge with one O(5)Li3C tetrahedra.