NaLi5Fe2P2(CO7)2 crystallizes in the monoclinic Pc space group. Na(1) is bonded in a 5-coordinate geometry to one O(1), one O(3), one O(5), one O(6), and one O(7) atom. There are five inequivalent Li sites. In the first Li site, Li(1) is bonded in a 4-coordinate geometry to one O(1), one O(13), one O(4), and one O(5) atom. In the second Li site, Li(2) is bonded to one O(1), one O(3), one O(4), one O(6), and one O(7) atom to form distorted LiO5 trigonal bipyramids that share  a cornercorner with one Fe(1)O6 octahedra,  a cornercorner with one Fe(2)O6 octahedra,  a cornercorner with one P(2)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, and  an edgeedge with one Fe(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 64-89°. In the third Li site, Li(3) is bonded to one O(11), one O(12), one O(14), one O(8), and one O(9) atom to form distorted LiO5 trigonal bipyramids that share  a cornercorner with one Fe(1)O6 octahedra,  a cornercorner with one Fe(2)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra,  an edgeedge with one Fe(2)O6 octahedra, and edges with two equivalent Li(4)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 69-87°. In the fourth Li site, Li(4) is bonded to one O(10), one O(12), one O(14), one O(8), and one O(9) atom to form LiO5 trigonal bipyramids that share  a cornercorner with one Fe(1)O6 octahedra,  a cornercorner with one Fe(2)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra,  an edgeedge with one Fe(2)O6 octahedra, and edges with two equivalent Li(3)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 69-85°. In the fifth Li site, Li(5) is bonded in a 4-coordinate geometry to one O(10), one O(11), one O(14), and one O(2) atom. There are two inequivalent Fe sites. In the first Fe site, Fe(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 distorted FeO6 octahedra that share corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra,  a cornercorner with one Li(2)O5 trigonal bipyramid,  a cornercorner with one Li(3)O5 trigonal bipyramid,  a cornercorner with one Li(4)O5 trigonal bipyramid, and  an edgeedge with one Li(2)O5 trigonal bipyramid. In the second Fe site, Fe(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 FeO6 octahedra that share corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra,  a cornercorner with one Li(2)O5 trigonal bipyramid,  a cornercorner with one Li(3)O5 trigonal bipyramid,  a cornercorner with one Li(4)O5 trigonal bipyramid,  an edgeedge with one Li(3)O5 trigonal bipyramid, and  an edgeedge with one Li(4)O5 trigonal bipyramid. 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 Fe(1)O6 octahedra, corners with two equivalent Fe(2)O6 octahedra,  a cornercorner with one Li(3)O5 trigonal bipyramid,  a cornercorner with one Li(4)O5 trigonal bipyramid, and corners with two equivalent Li(2)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 42-60°. 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 Fe(1)O6 octahedra, corners with two equivalent Fe(2)O6 octahedra,  a cornercorner with one Li(2)O5 trigonal bipyramid, corners with two equivalent Li(3)O5 trigonal bipyramids, and corners with two equivalent Li(4)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 42-61°. There are fourteen inequivalent O sites. In the first O site, O(1) is bonded to one Na(1), one Li(1), one Li(2), and one C(2) atom to form a mixture of distorted edge and corner-sharing ONaLi2C tetrahedra. In the second O site, O(2) is bonded in a distorted bent 120 degrees geometry to one Li(5), one Fe(1), and one C(1) atom. In the third O site, O(3) is bonded in a 1-coordinate geometry to one Na(1), one Li(2), one Fe(1), and one C(1) atom. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to one Li(1), one Li(2), one Fe(1), and one P(1) atom. In the fifth O site, O(5) is bonded to one Na(1), one Li(1), one Fe(1), and one P(1) atom to form distorted ONaLiFeP trigonal pyramids that share  a cornercorner with one O(8)Li2FeP tetrahedra,  a cornercorner with one O(9)Li2FeP tetrahedra, corners with two equivalent O(1)NaLi2C tetrahedra, and corners with two equivalent O(6)NaLiFeP tetrahedra. In the sixth O site, O(6) is bonded to one Na(1), one Li(2), one Fe(2), and one P(1) atom to form distorted ONaLiFeP tetrahedra that share  a cornercorner with one O(10)Li2FeP tetrahedra, corners with two equivalent O(8)Li2FeP tetrahedra, corners with two equivalent O(5)NaLiFeP trigonal pyramids, and  an edgeedge with one O(1)NaLi2C tetrahedra. In the seventh O site, O(7) is bonded in a 4-coordinate geometry to one Na(1), one Li(2), one Fe(1), and one P(2) atom. In the eighth O site, O(8) is bonded to one Li(3), one Li(4), one Fe(2), and one P(1) atom to form distorted OLi2FeP tetrahedra that share corners with two equivalent O(9)Li2FeP tetrahedra, corners with two equivalent O(14)Li3C tetrahedra, corners with two equivalent O(6)NaLiFeP tetrahedra,  a cornercorner with one O(5)NaLiFeP trigonal pyramid, and  an edgeedge with one O(10)Li2FeP tetrahedra. In the ninth O site, O(9) is bonded to one Li(3), one Li(4), one Fe(1), and one P(2) atom to form distorted OLi2FeP tetrahedra that share corners with two equivalent O(10)Li2FeP tetrahedra, corners with two equivalent O(8)Li2FeP tetrahedra,  a cornercorner with one O(5)NaLiFeP trigonal pyramid, and  an edgeedge with one O(14)Li3C tetrahedra. In the tenth O site, O(10) is bonded to one Li(4), one Li(5), one Fe(2), and one P(2) atom to form distorted OLi2FeP tetrahedra that share  a cornercorner with one O(6)NaLiFeP tetrahedra, corners with two equivalent O(9)Li2FeP tetrahedra, corners with two equivalent O(14)Li3C tetrahedra, and  an edgeedge with one O(8)Li2FeP tetrahedra. In the eleventh O site, O(11) is bonded in a 4-coordinate geometry to one Li(3), one Li(5), one Fe(2), and one P(2) atom. In the twelfth O site, O(12) is bonded in a 4-coordinate geometry to one Li(3), one Li(4), one Fe(2), and one C(2) atom. In the thirteenth O site, O(13) is bonded in a 3-coordinate geometry to one Li(1), one Fe(2), and one C(2) atom. In the fourteenth O site, O(14) is bonded to one Li(3), one Li(4), one Li(5), and one C(1) atom to form a mixture of edge and corner-sharing OLi3C tetrahedra.
NaLi5Fe2P2(CO7)2 crystallizes in the monoclinic Pc space group. Na(1) is bonded in a 5-coordinate geometry to one O(1), one O(3), one O(5), one O(6), and one O(7) atom. The Na(1)-O(1) bond length is 2.31 Å. The Na(1)-O(3) bond length is 2.29 Å. The Na(1)-O(5) bond length is 2.32 Å. The Na(1)-O(6) bond length is 2.43 Å. The Na(1)-O(7) bond length is 2.38 Å. There are five inequivalent Li sites. In the first Li site, Li(1) is bonded in a 4-coordinate geometry to one O(1), one O(13), one O(4), and one O(5) atom. The Li(1)-O(1) bond length is 2.00 Å. The Li(1)-O(13) bond length is 1.94 Å. The Li(1)-O(4) bond length is 2.20 Å. The Li(1)-O(5) bond length is 2.22 Å. In the second Li site, Li(2) is bonded to one O(1), one O(3), one O(4), one O(6), and one O(7) atom to form distorted LiO5 trigonal bipyramids that share  a cornercorner with one Fe(1)O6 octahedra,  a cornercorner with one Fe(2)O6 octahedra,  a cornercorner with one P(2)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, and  an edgeedge with one Fe(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 64-89°. The Li(2)-O(1) bond length is 2.03 Å. The Li(2)-O(3) bond length is 2.48 Å. The Li(2)-O(4) bond length is 2.28 Å. The Li(2)-O(6) bond length is 2.09 Å. The Li(2)-O(7) bond length is 2.06 Å. In the third Li site, Li(3) is bonded to one O(11), one O(12), one O(14), one O(8), and one O(9) atom to form distorted LiO5 trigonal bipyramids that share  a cornercorner with one Fe(1)O6 octahedra,  a cornercorner with one Fe(2)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra,  an edgeedge with one Fe(2)O6 octahedra, and edges with two equivalent Li(4)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 69-87°. The Li(3)-O(11) bond length is 2.07 Å. The Li(3)-O(12) bond length is 2.49 Å. The Li(3)-O(14) bond length is 2.07 Å. The Li(3)-O(8) bond length is 2.24 Å. The Li(3)-O(9) bond length is 2.16 Å. In the fourth Li site, Li(4) is bonded to one O(10), one O(12), one O(14), one O(8), and one O(9) atom to form LiO5 trigonal bipyramids that share  a cornercorner with one Fe(1)O6 octahedra,  a cornercorner with one Fe(2)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra,  an edgeedge with one Fe(2)O6 octahedra, and edges with two equivalent Li(3)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 69-85°. The Li(4)-O(10) bond length is 2.20 Å. The Li(4)-O(12) bond length is 2.30 Å. The Li(4)-O(14) bond length is 2.11 Å. The Li(4)-O(8) bond length is 2.16 Å. The Li(4)-O(9) bond length is 2.23 Å. In the fifth Li site, Li(5) is bonded in a 4-coordinate geometry to one O(10), one O(11), one O(14), and one O(2) atom. The Li(5)-O(10) bond length is 2.12 Å. The Li(5)-O(11) bond length is 2.42 Å. The Li(5)-O(14) bond length is 2.03 Å. The Li(5)-O(2) bond length is 1.94 Å. There are two inequivalent Fe sites. In the first Fe site, Fe(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 distorted FeO6 octahedra that share corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra,  a cornercorner with one Li(2)O5 trigonal bipyramid,  a cornercorner with one Li(3)O5 trigonal bipyramid,  a cornercorner with one Li(4)O5 trigonal bipyramid, and  an edgeedge with one Li(2)O5 trigonal bipyramid. The Fe(1)-O(2) bond length is 2.38 Å. The Fe(1)-O(3) bond length is 2.19 Å. The Fe(1)-O(4) bond length is 2.08 Å. The Fe(1)-O(5) bond length is 2.07 Å. The Fe(1)-O(7) bond length is 2.18 Å. The Fe(1)-O(9) bond length is 2.19 Å. In the second Fe site, Fe(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 FeO6 octahedra that share corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra,  a cornercorner with one Li(2)O5 trigonal bipyramid,  a cornercorner with one Li(3)O5 trigonal bipyramid,  a cornercorner with one Li(4)O5 trigonal bipyramid,  an edgeedge with one Li(3)O5 trigonal bipyramid, and  an edgeedge with one Li(4)O5 trigonal bipyramid. The Fe(2)-O(10) bond length is 2.09 Å. The Fe(2)-O(11) bond length is 2.07 Å. The Fe(2)-O(12) bond length is 2.18 Å. The Fe(2)-O(13) bond length is 2.32 Å. The Fe(2)-O(6) bond length is 2.15 Å. The Fe(2)-O(8) bond length is 2.18 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 1.29 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 1.29 Å. The C(2)-O(12) bond length is 1.31 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 Fe(1)O6 octahedra, corners with two equivalent Fe(2)O6 octahedra,  a cornercorner with one Li(3)O5 trigonal bipyramid,  a cornercorner with one Li(4)O5 trigonal bipyramid, and corners with two equivalent Li(2)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 42-60°. The P(1)-O(4) bond length is 1.57 Å. The P(1)-O(5) bond length is 1.56 Å. The P(1)-O(6) bond length is 1.56 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(7), and one O(9) atom to form PO4 tetrahedra that share corners with two equivalent Fe(1)O6 octahedra, corners with two equivalent Fe(2)O6 octahedra,  a cornercorner with one Li(2)O5 trigonal bipyramid, corners with two equivalent Li(3)O5 trigonal bipyramids, and corners with two equivalent Li(4)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 42-61°. The P(2)-O(10) bond length is 1.57 Å. The P(2)-O(11) bond length is 1.56 Å. The P(2)-O(7) bond length is 1.54 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 to one Na(1), one Li(1), one Li(2), and one C(2) atom to form a mixture of distorted edge and corner-sharing ONaLi2C tetrahedra. In the second O site, O(2) is bonded in a distorted bent 120 degrees geometry to one Li(5), one Fe(1), and one C(1) atom. In the third O site, O(3) is bonded in a 1-coordinate geometry to one Na(1), one Li(2), one Fe(1), and one C(1) atom. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to one Li(1), one Li(2), one Fe(1), and one P(1) atom. In the fifth O site, O(5) is bonded to one Na(1), one Li(1), one Fe(1), and one P(1) atom to form distorted ONaLiFeP trigonal pyramids that share  a cornercorner with one O(8)Li2FeP tetrahedra,  a cornercorner with one O(9)Li2FeP tetrahedra, corners with two equivalent O(1)NaLi2C tetrahedra, and corners with two equivalent O(6)NaLiFeP tetrahedra. In the sixth O site, O(6) is bonded to one Na(1), one Li(2), one Fe(2), and one P(1) atom to form distorted ONaLiFeP tetrahedra that share  a cornercorner with one O(10)Li2FeP tetrahedra, corners with two equivalent O(8)Li2FeP tetrahedra, corners with two equivalent O(5)NaLiFeP trigonal pyramids, and  an edgeedge with one O(1)NaLi2C tetrahedra. In the seventh O site, O(7) is bonded in a 4-coordinate geometry to one Na(1), one Li(2), one Fe(1), and one P(2) atom. In the eighth O site, O(8) is bonded to one Li(3), one Li(4), one Fe(2), and one P(1) atom to form distorted OLi2FeP tetrahedra that share corners with two equivalent O(9)Li2FeP tetrahedra, corners with two equivalent O(14)Li3C tetrahedra, corners with two equivalent O(6)NaLiFeP tetrahedra,  a cornercorner with one O(5)NaLiFeP trigonal pyramid, and  an edgeedge with one O(10)Li2FeP tetrahedra. In the ninth O site, O(9) is bonded to one Li(3), one Li(4), one Fe(1), and one P(2) atom to form distorted OLi2FeP tetrahedra that share corners with two equivalent O(10)Li2FeP tetrahedra, corners with two equivalent O(8)Li2FeP tetrahedra,  a cornercorner with one O(5)NaLiFeP trigonal pyramid, and  an edgeedge with one O(14)Li3C tetrahedra. In the tenth O site, O(10) is bonded to one Li(4), one Li(5), one Fe(2), and one P(2) atom to form distorted OLi2FeP tetrahedra that share  a cornercorner with one O(6)NaLiFeP tetrahedra, corners with two equivalent O(9)Li2FeP tetrahedra, corners with two equivalent O(14)Li3C tetrahedra, and  an edgeedge with one O(8)Li2FeP tetrahedra. In the eleventh O site, O(11) is bonded in a 4-coordinate geometry to one Li(3), one Li(5), one Fe(2), and one P(2) atom. In the twelfth O site, O(12) is bonded in a 4-coordinate geometry to one Li(3), one Li(4), one Fe(2), and one C(2) atom. In the thirteenth O site, O(13) is bonded in a 3-coordinate geometry to one Li(1), one Fe(2), and one C(2) atom. In the fourteenth O site, O(14) is bonded to one Li(3), one Li(4), one Li(5), and one C(1) atom to form a mixture of edge and corner-sharing OLi3C tetrahedra.