Li6VCoP2(CO7)2 crystallizes in the monoclinic Pm space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded in a 4-coordinate geometry to one O(10), one O(2), and two equivalent O(11) atoms. In the second Li site, Li(2) is bonded in a 4-coordinate geometry to one O(1), one O(9), and two equivalent O(12) atoms. In the third Li site, Li(3) is bonded to one O(11), one O(2), one O(3), one O(4), and one O(5) atom to form LiO5 trigonal bipyramids that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one Co(1)O6 octahedra,  a cornercorner with one P(2)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra,  an edgeedge with one V(1)O6 octahedra, and edges with two equivalent Li(3)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 66-88°. In the fourth Li site, Li(4) is bonded to one O(12), one O(6), one O(7), one O(8), and one O(9) atom to form distorted LiO5 trigonal bipyramids that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one Co(1)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra,  an edgeedge with one Co(1)O6 octahedra, and edges with two equivalent Li(4)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 66-86°. V(1) is bonded to one O(1), one O(3), one O(4), one O(6), and two equivalent O(11) atoms to form distorted VO6 octahedra that share corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, corners with two equivalent Li(3)O5 trigonal bipyramids, corners with two equivalent Li(4)O5 trigonal bipyramids, and edges with two equivalent Li(3)O5 trigonal bipyramids. Co(1) is bonded to one O(10), one O(5), one O(7), one O(8), and two equivalent O(12) atoms to form distorted CoO6 octahedra that share corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, corners with two equivalent Li(3)O5 trigonal bipyramids, corners with two equivalent Li(4)O5 trigonal bipyramids, and edges with two equivalent Li(4)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(3), and one O(9) atom. In the second C site, C(2) is bonded in a trigonal planar geometry to one O(10), one O(2), and one O(8) atom. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(5), one O(7), and two equivalent O(11) atoms to form PO4 tetrahedra that share corners with two equivalent V(1)O6 octahedra, corners with two equivalent Co(1)O6 octahedra, corners with two equivalent Li(4)O5 trigonal bipyramids, and corners with four equivalent Li(3)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(4), one O(6), and two equivalent O(12) atoms to form PO4 tetrahedra that share corners with two equivalent V(1)O6 octahedra, corners with two equivalent Co(1)O6 octahedra, corners with two equivalent Li(3)O5 trigonal bipyramids, and corners with four equivalent Li(4)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 42-62°. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Li(2), one V(1), and one C(1) atom. In the second O site, O(2) is bonded to one Li(1), two equivalent Li(3), and one C(2) atom to form OLi3C tetrahedra that share  a cornercorner with one O(8)Li2CoC trigonal pyramid, corners with two equivalent O(3)Li2VC trigonal pyramids, corners with two equivalent O(4)Li2VP trigonal pyramids, corners with four equivalent O(11)Li2VP trigonal pyramids, and  an edgeedge with one O(5)Li2CoP tetrahedra. In the third O site, O(3) is bonded to two equivalent Li(3), one V(1), and one C(1) atom to form distorted OLi2VC trigonal pyramids that share  a cornercorner with one O(6)Li2VP tetrahedra,  a cornercorner with one O(9)Li3C tetrahedra, corners with two equivalent O(5)Li2CoP tetrahedra, corners with two equivalent O(2)Li3C tetrahedra,  a cornercorner with one O(4)Li2VP trigonal pyramid, corners with four equivalent O(11)Li2VP trigonal pyramids, and  an edgeedge with one O(4)Li2VP trigonal pyramid. In the fourth O site, O(4) is bonded to two equivalent Li(3), one V(1), and one P(2) atom to form distorted OLi2VP trigonal pyramids that share corners with two equivalent O(5)Li2CoP tetrahedra, corners with two equivalent O(6)Li2VP tetrahedra, corners with two equivalent O(2)Li3C tetrahedra,  a cornercorner with one O(3)Li2VC trigonal pyramid, corners with two equivalent O(12)Li2CoP trigonal pyramids,  an edgeedge with one O(3)Li2VC trigonal pyramid, and edges with two equivalent O(11)Li2VP trigonal pyramids. In the fifth O site, O(5) is bonded to two equivalent Li(3), one Co(1), and one P(1) atom to form distorted OLi2CoP tetrahedra that share  a cornercorner with one O(8)Li2CoC trigonal pyramid, corners with two equivalent O(12)Li2CoP trigonal pyramids, corners with two equivalent O(7)Li2CoP trigonal pyramids, corners with two equivalent O(3)Li2VC trigonal pyramids, corners with two equivalent O(4)Li2VP trigonal pyramids, corners with four equivalent O(11)Li2VP trigonal pyramids, and  an edgeedge with one O(2)Li3C tetrahedra. In the sixth O site, O(6) is bonded to two equivalent Li(4), one V(1), and one P(2) atom to form OLi2VP tetrahedra that share  a cornercorner with one O(3)Li2VC trigonal pyramid, corners with two equivalent O(8)Li2CoC trigonal pyramids, corners with two equivalent O(7)Li2CoP trigonal pyramids, corners with two equivalent O(11)Li2VP trigonal pyramids, corners with two equivalent O(4)Li2VP trigonal pyramids, corners with four equivalent O(12)Li2CoP trigonal pyramids, and  an edgeedge with one O(9)Li3C tetrahedra. In the seventh O site, O(7) is bonded to two equivalent Li(4), one Co(1), and one P(1) atom to form distorted OLi2CoP trigonal pyramids that share corners with two equivalent O(5)Li2CoP tetrahedra, corners with two equivalent O(6)Li2VP tetrahedra, corners with two equivalent O(9)Li3C tetrahedra,  a cornercorner with one O(8)Li2CoC trigonal pyramid, corners with two equivalent O(11)Li2VP trigonal pyramids,  an edgeedge with one O(8)Li2CoC trigonal pyramid, and edges with two equivalent O(12)Li2CoP trigonal pyramids. In the eighth O site, O(8) is bonded to two equivalent Li(4), one Co(1), and one C(2) atom to form distorted OLi2CoC trigonal pyramids that share  a cornercorner with one O(5)Li2CoP tetrahedra,  a cornercorner with one O(2)Li3C tetrahedra, corners with two equivalent O(6)Li2VP tetrahedra, corners with two equivalent O(9)Li3C tetrahedra,  a cornercorner with one O(7)Li2CoP trigonal pyramid, corners with four equivalent O(12)Li2CoP trigonal pyramids, and  an edgeedge with one O(7)Li2CoP trigonal pyramid. In the ninth O site, O(9) is bonded to one Li(2), two equivalent Li(4), and one C(1) atom to form OLi3C tetrahedra that share  a cornercorner with one O(3)Li2VC trigonal pyramid, corners with two equivalent O(8)Li2CoC trigonal pyramids, corners with two equivalent O(7)Li2CoP trigonal pyramids, corners with four equivalent O(12)Li2CoP trigonal pyramids, and  an edgeedge with one O(6)Li2VP tetrahedra. In the tenth O site, O(10) is bonded in a 3-coordinate geometry to one Li(1), one Co(1), and one C(2) atom. In the eleventh O site, O(11) is bonded to one Li(1), one Li(3), one V(1), and one P(1) atom to form distorted OLi2VP trigonal pyramids that share  a cornercorner with one O(6)Li2VP tetrahedra, corners with two equivalent O(5)Li2CoP tetrahedra, corners with two equivalent O(2)Li3C tetrahedra,  a cornercorner with one O(7)Li2CoP trigonal pyramid,  a cornercorner with one O(11)Li2VP trigonal pyramid, corners with two equivalent O(3)Li2VC trigonal pyramids,  an edgeedge with one O(11)Li2VP trigonal pyramid, and  an edgeedge with one O(4)Li2VP trigonal pyramid. In the twelfth O site, O(12) is bonded to one Li(2), one Li(4), one Co(1), and one P(2) atom to form distorted OLi2CoP trigonal pyramids that share  a cornercorner with one O(5)Li2CoP tetrahedra, corners with two equivalent O(6)Li2VP tetrahedra, corners with two equivalent O(9)Li3C tetrahedra,  a cornercorner with one O(12)Li2CoP trigonal pyramid,  a cornercorner with one O(4)Li2VP trigonal pyramid, corners with two equivalent O(8)Li2CoC trigonal pyramids,  an edgeedge with one O(12)Li2CoP trigonal pyramid, and  an edgeedge with one O(7)Li2CoP trigonal pyramid.
Li6VCoP2(CO7)2 crystallizes in the monoclinic Pm space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded in a 4-coordinate geometry to one O(10), one O(2), and two equivalent O(11) atoms. The Li(1)-O(10) bond length is 1.91 Å. The Li(1)-O(2) bond length is 2.01 Å. Both Li(1)-O(11) bond lengths are 2.12 Å. In the second Li site, Li(2) is bonded in a 4-coordinate geometry to one O(1), one O(9), and two equivalent O(12) atoms. The Li(2)-O(1) bond length is 1.91 Å. The Li(2)-O(9) bond length is 2.01 Å. Both Li(2)-O(12) bond lengths are 2.13 Å. In the third Li site, Li(3) is bonded to one O(11), one O(2), one O(3), one O(4), and one O(5) atom to form LiO5 trigonal bipyramids that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one Co(1)O6 octahedra,  a cornercorner with one P(2)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra,  an edgeedge with one V(1)O6 octahedra, and edges with two equivalent Li(3)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 66-88°. The Li(3)-O(11) bond length is 2.15 Å. The Li(3)-O(2) bond length is 2.15 Å. The Li(3)-O(3) bond length is 2.27 Å. The Li(3)-O(4) bond length is 2.20 Å. The Li(3)-O(5) bond length is 2.20 Å. In the fourth Li site, Li(4) is bonded to one O(12), one O(6), one O(7), one O(8), and one O(9) atom to form distorted LiO5 trigonal bipyramids that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one Co(1)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra,  an edgeedge with one Co(1)O6 octahedra, and edges with two equivalent Li(4)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 66-86°. The Li(4)-O(12) bond length is 2.15 Å. The Li(4)-O(6) bond length is 2.19 Å. The Li(4)-O(7) bond length is 2.19 Å. The Li(4)-O(8) bond length is 2.26 Å. The Li(4)-O(9) bond length is 2.14 Å. V(1) is bonded to one O(1), one O(3), one O(4), one O(6), and two equivalent O(11) atoms to form distorted VO6 octahedra that share corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, corners with two equivalent Li(3)O5 trigonal bipyramids, corners with two equivalent Li(4)O5 trigonal bipyramids, and edges with two equivalent Li(3)O5 trigonal bipyramids. The V(1)-O(1) bond length is 2.24 Å. The V(1)-O(3) bond length is 2.21 Å. The V(1)-O(4) bond length is 2.15 Å. The V(1)-O(6) bond length is 2.20 Å. Both V(1)-O(11) bond lengths are 2.09 Å. Co(1) is bonded to one O(10), one O(5), one O(7), one O(8), and two equivalent O(12) atoms to form distorted CoO6 octahedra that share corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, corners with two equivalent Li(3)O5 trigonal bipyramids, corners with two equivalent Li(4)O5 trigonal bipyramids, and edges with two equivalent Li(4)O5 trigonal bipyramids. The Co(1)-O(10) bond length is 2.26 Å. The Co(1)-O(5) bond length is 2.14 Å. The Co(1)-O(7) bond length is 2.11 Å. The Co(1)-O(8) bond length is 2.14 Å. Both Co(1)-O(12) bond lengths are 2.07 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(9) atom. The C(1)-O(1) bond length is 1.30 Å. The C(1)-O(3) bond length is 1.31 Å. The C(1)-O(9) bond length is 1.29 Å. In the second C site, C(2) is bonded in a trigonal planar geometry to one O(10), one O(2), and one O(8) atom. The C(2)-O(10) bond length is 1.29 Å. The C(2)-O(2) bond length is 1.30 Å. The C(2)-O(8) bond length is 1.31 Å. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(5), one O(7), and two equivalent O(11) atoms to form PO4 tetrahedra that share corners with two equivalent V(1)O6 octahedra, corners with two equivalent Co(1)O6 octahedra, corners with two equivalent Li(4)O5 trigonal bipyramids, and corners with four equivalent Li(3)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 42-60°. The P(1)-O(5) bond length is 1.57 Å. The P(1)-O(7) bond length is 1.54 Å. Both P(1)-O(11) bond lengths are 1.56 Å. In the second P site, P(2) is bonded to one O(4), one O(6), and two equivalent O(12) atoms to form PO4 tetrahedra that share corners with two equivalent V(1)O6 octahedra, corners with two equivalent Co(1)O6 octahedra, corners with two equivalent Li(3)O5 trigonal bipyramids, and corners with four equivalent Li(4)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 42-62°. The P(2)-O(4) bond length is 1.54 Å. The P(2)-O(6) bond length is 1.56 Å. Both P(2)-O(12) bond lengths are 1.56 Å. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Li(2), one V(1), and one C(1) atom. In the second O site, O(2) is bonded to one Li(1), two equivalent Li(3), and one C(2) atom to form OLi3C tetrahedra that share  a cornercorner with one O(8)Li2CoC trigonal pyramid, corners with two equivalent O(3)Li2VC trigonal pyramids, corners with two equivalent O(4)Li2VP trigonal pyramids, corners with four equivalent O(11)Li2VP trigonal pyramids, and  an edgeedge with one O(5)Li2CoP tetrahedra. In the third O site, O(3) is bonded to two equivalent Li(3), one V(1), and one C(1) atom to form distorted OLi2VC trigonal pyramids that share  a cornercorner with one O(6)Li2VP tetrahedra,  a cornercorner with one O(9)Li3C tetrahedra, corners with two equivalent O(5)Li2CoP tetrahedra, corners with two equivalent O(2)Li3C tetrahedra,  a cornercorner with one O(4)Li2VP trigonal pyramid, corners with four equivalent O(11)Li2VP trigonal pyramids, and  an edgeedge with one O(4)Li2VP trigonal pyramid. In the fourth O site, O(4) is bonded to two equivalent Li(3), one V(1), and one P(2) atom to form distorted OLi2VP trigonal pyramids that share corners with two equivalent O(5)Li2CoP tetrahedra, corners with two equivalent O(6)Li2VP tetrahedra, corners with two equivalent O(2)Li3C tetrahedra,  a cornercorner with one O(3)Li2VC trigonal pyramid, corners with two equivalent O(12)Li2CoP trigonal pyramids,  an edgeedge with one O(3)Li2VC trigonal pyramid, and edges with two equivalent O(11)Li2VP trigonal pyramids. In the fifth O site, O(5) is bonded to two equivalent Li(3), one Co(1), and one P(1) atom to form distorted OLi2CoP tetrahedra that share  a cornercorner with one O(8)Li2CoC trigonal pyramid, corners with two equivalent O(12)Li2CoP trigonal pyramids, corners with two equivalent O(7)Li2CoP trigonal pyramids, corners with two equivalent O(3)Li2VC trigonal pyramids, corners with two equivalent O(4)Li2VP trigonal pyramids, corners with four equivalent O(11)Li2VP trigonal pyramids, and  an edgeedge with one O(2)Li3C tetrahedra. In the sixth O site, O(6) is bonded to two equivalent Li(4), one V(1), and one P(2) atom to form OLi2VP tetrahedra that share  a cornercorner with one O(3)Li2VC trigonal pyramid, corners with two equivalent O(8)Li2CoC trigonal pyramids, corners with two equivalent O(7)Li2CoP trigonal pyramids, corners with two equivalent O(11)Li2VP trigonal pyramids, corners with two equivalent O(4)Li2VP trigonal pyramids, corners with four equivalent O(12)Li2CoP trigonal pyramids, and  an edgeedge with one O(9)Li3C tetrahedra. In the seventh O site, O(7) is bonded to two equivalent Li(4), one Co(1), and one P(1) atom to form distorted OLi2CoP trigonal pyramids that share corners with two equivalent O(5)Li2CoP tetrahedra, corners with two equivalent O(6)Li2VP tetrahedra, corners with two equivalent O(9)Li3C tetrahedra,  a cornercorner with one O(8)Li2CoC trigonal pyramid, corners with two equivalent O(11)Li2VP trigonal pyramids,  an edgeedge with one O(8)Li2CoC trigonal pyramid, and edges with two equivalent O(12)Li2CoP trigonal pyramids. In the eighth O site, O(8) is bonded to two equivalent Li(4), one Co(1), and one C(2) atom to form distorted OLi2CoC trigonal pyramids that share  a cornercorner with one O(5)Li2CoP tetrahedra,  a cornercorner with one O(2)Li3C tetrahedra, corners with two equivalent O(6)Li2VP tetrahedra, corners with two equivalent O(9)Li3C tetrahedra,  a cornercorner with one O(7)Li2CoP trigonal pyramid, corners with four equivalent O(12)Li2CoP trigonal pyramids, and  an edgeedge with one O(7)Li2CoP trigonal pyramid. In the ninth O site, O(9) is bonded to one Li(2), two equivalent Li(4), and one C(1) atom to form OLi3C tetrahedra that share  a cornercorner with one O(3)Li2VC trigonal pyramid, corners with two equivalent O(8)Li2CoC trigonal pyramids, corners with two equivalent O(7)Li2CoP trigonal pyramids, corners with four equivalent O(12)Li2CoP trigonal pyramids, and  an edgeedge with one O(6)Li2VP tetrahedra. In the tenth O site, O(10) is bonded in a 3-coordinate geometry to one Li(1), one Co(1), and one C(2) atom. In the eleventh O site, O(11) is bonded to one Li(1), one Li(3), one V(1), and one P(1) atom to form distorted OLi2VP trigonal pyramids that share  a cornercorner with one O(6)Li2VP tetrahedra, corners with two equivalent O(5)Li2CoP tetrahedra, corners with two equivalent O(2)Li3C tetrahedra,  a cornercorner with one O(7)Li2CoP trigonal pyramid,  a cornercorner with one O(11)Li2VP trigonal pyramid, corners with two equivalent O(3)Li2VC trigonal pyramids,  an edgeedge with one O(11)Li2VP trigonal pyramid, and  an edgeedge with one O(4)Li2VP trigonal pyramid. In the twelfth O site, O(12) is bonded to one Li(2), one Li(4), one Co(1), and one P(2) atom to form distorted OLi2CoP trigonal pyramids that share  a cornercorner with one O(5)Li2CoP tetrahedra, corners with two equivalent O(6)Li2VP tetrahedra, corners with two equivalent O(9)Li3C tetrahedra,  a cornercorner with one O(12)Li2CoP trigonal pyramid,  a cornercorner with one O(4)Li2VP trigonal pyramid, corners with two equivalent O(8)Li2CoC trigonal pyramids,  an edgeedge with one O(12)Li2CoP trigonal pyramid, and  an edgeedge with one O(7)Li2CoP trigonal pyramid.