NaLi5Fe2P2(CO7)2 crystallizes in the monoclinic P2_1 space group. Na(1) is bonded in a 7-coordinate geometry to one O(13), one O(14), one O(2), one O(3), one O(6), one O(7), and one O(9) atom. There are five inequivalent Li sites. In the first Li site, Li(1) is bonded in a 5-coordinate geometry to one O(1), one O(4), one O(5), one O(7), and one O(8) atom. In the second Li site, Li(2) is bonded in a 4-coordinate geometry to one O(10), one O(2), one O(3), and one O(9) atom. In the third Li site, Li(3) is bonded to one O(1), one O(11), one O(12), one O(5), and one O(9) atom to form distorted LiO5 trigonal bipyramids that share corners with two equivalent Fe(1)O6 octahedra,  a cornercorner with one P(2)O4 tetrahedra, corners with two equivalent P(1)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 66-90°. In the fourth Li site, Li(4) is bonded to one O(1), one O(10), one O(11), one O(12), and one O(5) atom to form distorted LiO5 trigonal bipyramids that share corners with two equivalent Fe(1)O6 octahedra,  a cornercorner with one P(2)O4 tetrahedra, corners with two equivalent P(1)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 63-90°. In the fifth Li site, Li(5) is bonded to one O(13), one O(14), one O(2), one O(6), and one O(8) atom to form distorted LiO5 trigonal bipyramids that share corners with two equivalent Fe(2)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, and  an edgeedge with one Fe(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 65-85°. There are two inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to one O(11), one O(14), one O(3), one O(5), one O(7), and one O(8) atom to form distorted FeO6 octahedra that share  a cornercorner with one P(2)O4 tetrahedra, corners with three equivalent P(1)O4 tetrahedra, corners with two equivalent Li(3)O5 trigonal bipyramids, corners with two equivalent Li(4)O5 trigonal bipyramids, and  an edgeedge with one Li(5)O5 trigonal bipyramid. In the second Fe site, Fe(2) is bonded to one O(10), one O(12), one O(13), one O(4), one O(6), and one O(9) atom to form distorted FeO6 octahedra that share  a cornercorner with one P(1)O4 tetrahedra, corners with three equivalent P(2)O4 tetrahedra, corners with two equivalent Li(5)O5 trigonal bipyramids,  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(1), 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(2), 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(11), one O(12), one O(7), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one Fe(2)O6 octahedra, corners with three equivalent Fe(1)O6 octahedra,  a cornercorner with one Li(5)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 43-64°. In the second P site, P(2) is bonded to one O(10), one O(13), one O(14), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one Fe(1)O6 octahedra, corners with three 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(5)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 45-59°. There are fourteen inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(3), one Li(4), and one C(1) atom to form OLi3C tetrahedra that share corners with two equivalent O(5)Li3FeC trigonal bipyramids,  a cornercorner with one O(8)Li2FeP trigonal pyramid, corners with two equivalent O(12)Li2FeP trigonal pyramids,  an edgeedge with one O(11)Li2FeP tetrahedra, and  an edgeedge with one O(5)Li3FeC trigonal bipyramid. In the second O site, O(2) is bonded to one Na(1), one Li(2), one Li(5), and one C(2) atom to form distorted ONaLi2C tetrahedra that share  a cornercorner with one O(8)Li2FeP trigonal pyramid and  an edgeedge with one O(13)NaLiFeP tetrahedra. In the third O site, O(3) is bonded in a 2-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 distorted bent 120 degrees geometry to one Li(1), one Fe(2), and one C(2) atom. In the fifth O site, O(5) is bonded to one Li(1), one Li(3), one Li(4), one Fe(1), and one C(1) atom to form distorted OLi3FeC trigonal bipyramids that share corners with two equivalent O(1)Li3C tetrahedra, corners with three equivalent O(11)Li2FeP tetrahedra, corners with two equivalent O(8)Li2FeP trigonal pyramids,  an edgeedge with one O(1)Li3C tetrahedra, and  an edgeedge with one O(12)Li2FeP trigonal pyramid. In the sixth O site, O(6) is bonded in a 4-coordinate geometry to one Na(1), one Li(5), one Fe(2), and one C(2) atom. In the seventh O site, O(7) is bonded in a 4-coordinate geometry to one Na(1), one Li(1), one Fe(1), and one P(1) atom. In the eighth O site, O(8) is bonded to one Li(1), one Li(5), one Fe(1), and one P(1) atom to form distorted OLi2FeP trigonal pyramids that share  a cornercorner with one O(1)Li3C tetrahedra,  a cornercorner with one O(2)NaLi2C tetrahedra,  a cornercorner with one O(13)NaLiFeP tetrahedra, corners with two equivalent O(11)Li2FeP tetrahedra, corners with two equivalent O(5)Li3FeC trigonal bipyramids, and  a cornercorner with one O(12)Li2FeP trigonal pyramid. In the ninth O site, O(9) is bonded in a 4-coordinate geometry to one Na(1), one Li(2), one Li(3), one Fe(2), and one P(2) atom. In the tenth O site, O(10) is bonded in a 4-coordinate geometry to one Li(2), one Li(4), one Fe(2), and one P(2) atom. In the eleventh O site, O(11) is bonded to one Li(3), one Li(4), one Fe(1), and one P(1) atom to form OLi2FeP tetrahedra that share corners with three equivalent O(5)Li3FeC trigonal bipyramids, corners with two equivalent O(8)Li2FeP trigonal pyramids, corners with three equivalent O(12)Li2FeP trigonal pyramids, and  an edgeedge with one O(1)Li3C tetrahedra. In the twelfth O site, O(12) is bonded to one Li(3), one Li(4), one Fe(2), and one P(1) atom to form distorted OLi2FeP trigonal pyramids that share  a cornercorner with one O(13)NaLiFeP tetrahedra, corners with two equivalent O(1)Li3C tetrahedra, corners with three equivalent O(11)Li2FeP tetrahedra,  a cornercorner with one O(8)Li2FeP trigonal pyramid, and  an edgeedge with one O(5)Li3FeC trigonal bipyramid. In the thirteenth O site, O(13) is bonded to one Na(1), one Li(5), one Fe(2), and one P(2) atom to form distorted ONaLiFeP tetrahedra that share  a cornercorner with one O(12)Li2FeP trigonal pyramid,  a cornercorner with one O(8)Li2FeP trigonal pyramid, and  an edgeedge with one O(2)NaLi2C tetrahedra. In the fourteenth O site, O(14) is bonded in a distorted rectangular see-saw-like geometry to one Na(1), one Li(5), one Fe(1), and one P(2) atom.
NaLi5Fe2P2(CO7)2 crystallizes in the monoclinic P2_1 space group. Na(1) is bonded in a 7-coordinate geometry to one O(13), one O(14), one O(2), one O(3), one O(6), one O(7), and one O(9) atom. The Na(1)-O(13) bond length is 2.46 Å. The Na(1)-O(14) bond length is 2.34 Å. The Na(1)-O(2) bond length is 2.29 Å. The Na(1)-O(3) bond length is 2.75 Å. The Na(1)-O(6) bond length is 2.33 Å. The Na(1)-O(7) bond length is 2.36 Å. The Na(1)-O(9) bond length is 2.82 Å. There are five inequivalent Li sites. In the first Li site, Li(1) is bonded in a 5-coordinate geometry to one O(1), one O(4), one O(5), one O(7), and one O(8) atom. The Li(1)-O(1) bond length is 2.06 Å. The Li(1)-O(4) bond length is 1.96 Å. The Li(1)-O(5) bond length is 2.44 Å. The Li(1)-O(7) bond length is 2.35 Å. The Li(1)-O(8) bond length is 2.23 Å. In the second Li site, Li(2) is bonded in a 4-coordinate geometry to one O(10), one O(2), one O(3), and one O(9) atom. The Li(2)-O(10) bond length is 2.33 Å. The Li(2)-O(2) bond length is 2.03 Å. The Li(2)-O(3) bond length is 1.97 Å. The Li(2)-O(9) bond length is 2.17 Å. In the third Li site, Li(3) is bonded to one O(1), one O(11), one O(12), one O(5), and one O(9) atom to form distorted LiO5 trigonal bipyramids that share corners with two equivalent Fe(1)O6 octahedra,  a cornercorner with one P(2)O4 tetrahedra, corners with two equivalent P(1)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 66-90°. The Li(3)-O(1) bond length is 2.05 Å. The Li(3)-O(11) bond length is 2.19 Å. The Li(3)-O(12) bond length is 2.16 Å. The Li(3)-O(5) bond length is 2.45 Å. The Li(3)-O(9) bond length is 2.29 Å. In the fourth Li site, Li(4) is bonded to one O(1), one O(10), one O(11), one O(12), and one O(5) atom to form distorted LiO5 trigonal bipyramids that share corners with two equivalent Fe(1)O6 octahedra,  a cornercorner with one P(2)O4 tetrahedra, corners with two equivalent P(1)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 63-90°. The Li(4)-O(1) bond length is 2.06 Å. The Li(4)-O(10) bond length is 2.06 Å. The Li(4)-O(11) bond length is 2.11 Å. The Li(4)-O(12) bond length is 2.26 Å. The Li(4)-O(5) bond length is 2.48 Å. In the fifth Li site, Li(5) is bonded to one O(13), one O(14), one O(2), one O(6), and one O(8) atom to form distorted LiO5 trigonal bipyramids that share corners with two equivalent Fe(2)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, and  an edgeedge with one Fe(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 65-85°. The Li(5)-O(13) bond length is 2.12 Å. The Li(5)-O(14) bond length is 2.07 Å. The Li(5)-O(2) bond length is 2.02 Å. The Li(5)-O(6) bond length is 2.38 Å. The Li(5)-O(8) bond length is 2.21 Å. There are two inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to one O(11), one O(14), one O(3), one O(5), one O(7), and one O(8) atom to form distorted FeO6 octahedra that share  a cornercorner with one P(2)O4 tetrahedra, corners with three equivalent P(1)O4 tetrahedra, corners with two equivalent Li(3)O5 trigonal bipyramids, corners with two equivalent Li(4)O5 trigonal bipyramids, and  an edgeedge with one Li(5)O5 trigonal bipyramid. The Fe(1)-O(11) bond length is 2.13 Å. The Fe(1)-O(14) bond length is 2.16 Å. The Fe(1)-O(3) bond length is 2.34 Å. The Fe(1)-O(5) bond length is 2.22 Å. The Fe(1)-O(7) bond length is 2.06 Å. The Fe(1)-O(8) bond length is 2.07 Å. In the second Fe site, Fe(2) is bonded to one O(10), one O(12), one O(13), one O(4), one O(6), and one O(9) atom to form distorted FeO6 octahedra that share  a cornercorner with one P(1)O4 tetrahedra, corners with three equivalent P(2)O4 tetrahedra, corners with two equivalent Li(5)O5 trigonal bipyramids,  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 2.07 Å. The Fe(2)-O(12) bond length is 2.16 Å. The Fe(2)-O(13) bond length is 2.15 Å. The Fe(2)-O(4) bond length is 2.35 Å. The Fe(2)-O(6) bond length is 2.18 Å. The Fe(2)-O(9) bond length is 2.09 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(3), and one O(5) atom. The C(1)-O(1) bond length is 1.30 Å. The C(1)-O(3) bond length is 1.30 Å. The C(1)-O(5) bond length is 1.31 Å. In the second C site, C(2) is bonded in a trigonal planar geometry to one O(2), one O(4), and one O(6) atom. The C(2)-O(2) bond length is 1.29 Å. The C(2)-O(4) bond length is 1.30 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(11), one O(12), one O(7), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one Fe(2)O6 octahedra, corners with three equivalent Fe(1)O6 octahedra,  a cornercorner with one Li(5)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 43-64°. The P(1)-O(11) bond length is 1.56 Å. The P(1)-O(12) bond length is 1.55 Å. The P(1)-O(7) bond length is 1.55 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(13), one O(14), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one Fe(1)O6 octahedra, corners with three 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(5)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 45-59°. The P(2)-O(10) bond length is 1.56 Å. The P(2)-O(13) bond length is 1.56 Å. The P(2)-O(14) bond length is 1.55 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 to one Li(1), one Li(3), one Li(4), and one C(1) atom to form OLi3C tetrahedra that share corners with two equivalent O(5)Li3FeC trigonal bipyramids,  a cornercorner with one O(8)Li2FeP trigonal pyramid, corners with two equivalent O(12)Li2FeP trigonal pyramids,  an edgeedge with one O(11)Li2FeP tetrahedra, and  an edgeedge with one O(5)Li3FeC trigonal bipyramid. In the second O site, O(2) is bonded to one Na(1), one Li(2), one Li(5), and one C(2) atom to form distorted ONaLi2C tetrahedra that share  a cornercorner with one O(8)Li2FeP trigonal pyramid and  an edgeedge with one O(13)NaLiFeP tetrahedra. In the third O site, O(3) is bonded in a 2-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 distorted bent 120 degrees geometry to one Li(1), one Fe(2), and one C(2) atom. In the fifth O site, O(5) is bonded to one Li(1), one Li(3), one Li(4), one Fe(1), and one C(1) atom to form distorted OLi3FeC trigonal bipyramids that share corners with two equivalent O(1)Li3C tetrahedra, corners with three equivalent O(11)Li2FeP tetrahedra, corners with two equivalent O(8)Li2FeP trigonal pyramids,  an edgeedge with one O(1)Li3C tetrahedra, and  an edgeedge with one O(12)Li2FeP trigonal pyramid. In the sixth O site, O(6) is bonded in a 4-coordinate geometry to one Na(1), one Li(5), one Fe(2), and one C(2) atom. In the seventh O site, O(7) is bonded in a 4-coordinate geometry to one Na(1), one Li(1), one Fe(1), and one P(1) atom. In the eighth O site, O(8) is bonded to one Li(1), one Li(5), one Fe(1), and one P(1) atom to form distorted OLi2FeP trigonal pyramids that share  a cornercorner with one O(1)Li3C tetrahedra,  a cornercorner with one O(2)NaLi2C tetrahedra,  a cornercorner with one O(13)NaLiFeP tetrahedra, corners with two equivalent O(11)Li2FeP tetrahedra, corners with two equivalent O(5)Li3FeC trigonal bipyramids, and  a cornercorner with one O(12)Li2FeP trigonal pyramid. In the ninth O site, O(9) is bonded in a 4-coordinate geometry to one Na(1), one Li(2), one Li(3), one Fe(2), and one P(2) atom. In the tenth O site, O(10) is bonded in a 4-coordinate geometry to one Li(2), one Li(4), one Fe(2), and one P(2) atom. In the eleventh O site, O(11) is bonded to one Li(3), one Li(4), one Fe(1), and one P(1) atom to form OLi2FeP tetrahedra that share corners with three equivalent O(5)Li3FeC trigonal bipyramids, corners with two equivalent O(8)Li2FeP trigonal pyramids, corners with three equivalent O(12)Li2FeP trigonal pyramids, and  an edgeedge with one O(1)Li3C tetrahedra. In the twelfth O site, O(12) is bonded to one Li(3), one Li(4), one Fe(2), and one P(1) atom to form distorted OLi2FeP trigonal pyramids that share  a cornercorner with one O(13)NaLiFeP tetrahedra, corners with two equivalent O(1)Li3C tetrahedra, corners with three equivalent O(11)Li2FeP tetrahedra,  a cornercorner with one O(8)Li2FeP trigonal pyramid, and  an edgeedge with one O(5)Li3FeC trigonal bipyramid. In the thirteenth O site, O(13) is bonded to one Na(1), one Li(5), one Fe(2), and one P(2) atom to form distorted ONaLiFeP tetrahedra that share  a cornercorner with one O(12)Li2FeP trigonal pyramid,  a cornercorner with one O(8)Li2FeP trigonal pyramid, and  an edgeedge with one O(2)NaLi2C tetrahedra. In the fourteenth O site, O(14) is bonded in a distorted rectangular see-saw-like geometry to one Na(1), one Li(5), one Fe(1), and one P(2) atom.