Mn3Co4P6(HO6)4 crystallizes in the triclinic P-1 space group. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to two equivalent O(10), two equivalent O(3), and two equivalent O(8) atoms to form MnO6 octahedra that share corners with two equivalent Co(1)O6 octahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, corners with two equivalent P(3)O4 tetrahedra, and corners with two equivalent Mn(2)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles are 63°. In the second Mn site, Mn(2) is bonded to one O(1), one O(10), one O(2), one O(4), and one O(7) atom to form MnO5 trigonal bipyramids that share  a cornercorner with one Mn(1)O6 octahedra,  a cornercorner with one P(2)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(3)O4 tetrahedra,  an edgeedge with one Co(1)O6 octahedra, and  an edgeedge with one Co(2)O6 octahedra. The corner-sharing octahedral tilt angles are 70°. There are two inequivalent Co sites. In the first Co site, Co(1) is bonded to one O(1), one O(2), one O(8), one O(9), and two equivalent O(11) atoms to form CoO6 octahedra that share  a cornercorner with one Mn(1)O6 octahedra,  a cornercorner with one P(3)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, corners with three equivalent P(2)O4 tetrahedra,  an edgeedge with one Co(1)O6 octahedra, and  an edgeedge with one Mn(2)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles are 63°. In the second Co site, Co(2) is bonded to one O(12), one O(4), one O(5), one O(7), and two equivalent O(6) atoms to form CoO6 octahedra that share corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, corners with two equivalent P(3)O4 tetrahedra,  an edgeedge with one Co(2)O6 octahedra, and  an edgeedge with one Mn(2)O5 trigonal bipyramid. There are three inequivalent P sites. In the first P site, P(1) is bonded to one O(2), one O(4), one O(5), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one Mn(1)O6 octahedra, corners with two equivalent Co(1)O6 octahedra, corners with two equivalent Co(2)O6 octahedra, and corners with two equivalent Mn(2)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 41-60°. In the second P site, P(2) is bonded to one O(1), one O(11), one O(3), and one O(6) atom to form PO4 tetrahedra that share  a cornercorner with one Mn(1)O6 octahedra, corners with two equivalent Co(2)O6 octahedra, corners with three equivalent Co(1)O6 octahedra, and  a cornercorner with one Mn(2)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 30-54°. In the third P site, P(3) is bonded to one O(10), one O(12), one O(7), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one Mn(1)O6 octahedra,  a cornercorner with one Co(1)O6 octahedra, corners with two equivalent Co(2)O6 octahedra, and corners with two equivalent Mn(2)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 32-57°. There are two inequivalent H sites. In the first H site, H(1) is bonded in a linear geometry to one O(3) and one O(5) atom. In the second H site, H(2) is bonded in a linear geometry to one O(12) and one O(9) atom. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one Mn(2), one Co(1), and one P(2) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Mn(2), one Co(1), and one P(1) atom. In the third O site, O(3) is bonded in a distorted T-shaped geometry to one Mn(1), one P(2), and one H(1) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one Mn(2), one Co(2), and one P(1) atom. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to one Co(2), one P(1), and one H(1) atom. In the sixth O site, O(6) is bonded in a distorted trigonal planar geometry to two equivalent Co(2) and one P(2) atom. In the seventh O site, O(7) is bonded in a distorted trigonal planar geometry to one Mn(2), one Co(2), and one P(3) atom. In the eighth O site, O(8) is bonded in a trigonal planar geometry to one Mn(1), one Co(1), and one P(1) atom. In the ninth O site, O(9) is bonded in a distorted trigonal planar geometry to one Co(1), one P(3), and one H(2) atom. In the tenth O site, O(10) is bonded in a distorted trigonal planar geometry to one Mn(1), one Mn(2), and one P(3) atom. In the eleventh O site, O(11) is bonded in a 3-coordinate geometry to two equivalent Co(1) and one P(2) atom. In the twelfth O site, O(12) is bonded in a 3-coordinate geometry to one Co(2), one P(3), and one H(2) atom.
Mn3Co4P6(HO6)4 crystallizes in the triclinic P-1 space group. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to two equivalent O(10), two equivalent O(3), and two equivalent O(8) atoms to form MnO6 octahedra that share corners with two equivalent Co(1)O6 octahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, corners with two equivalent P(3)O4 tetrahedra, and corners with two equivalent Mn(2)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles are 63°. Both Mn(1)-O(10) bond lengths are 2.27 Å. Both Mn(1)-O(3) bond lengths are 2.17 Å. Both Mn(1)-O(8) bond lengths are 2.23 Å. In the second Mn site, Mn(2) is bonded to one O(1), one O(10), one O(2), one O(4), and one O(7) atom to form MnO5 trigonal bipyramids that share  a cornercorner with one Mn(1)O6 octahedra,  a cornercorner with one P(2)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(3)O4 tetrahedra,  an edgeedge with one Co(1)O6 octahedra, and  an edgeedge with one Co(2)O6 octahedra. The corner-sharing octahedral tilt angles are 70°. The Mn(2)-O(1) bond length is 2.12 Å. The Mn(2)-O(10) bond length is 2.16 Å. The Mn(2)-O(2) bond length is 2.15 Å. The Mn(2)-O(4) bond length is 2.22 Å. The Mn(2)-O(7) bond length is 2.17 Å. There are two inequivalent Co sites. In the first Co site, Co(1) is bonded to one O(1), one O(2), one O(8), one O(9), and two equivalent O(11) atoms to form CoO6 octahedra that share  a cornercorner with one Mn(1)O6 octahedra,  a cornercorner with one P(3)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, corners with three equivalent P(2)O4 tetrahedra,  an edgeedge with one Co(1)O6 octahedra, and  an edgeedge with one Mn(2)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles are 63°. The Co(1)-O(1) bond length is 2.15 Å. The Co(1)-O(2) bond length is 2.22 Å. The Co(1)-O(8) bond length is 2.12 Å. The Co(1)-O(9) bond length is 2.10 Å. There is one shorter (2.09 Å) and one longer (2.11 Å) Co(1)-O(11) bond length. In the second Co site, Co(2) is bonded to one O(12), one O(4), one O(5), one O(7), and two equivalent O(6) atoms to form CoO6 octahedra that share corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, corners with two equivalent P(3)O4 tetrahedra,  an edgeedge with one Co(2)O6 octahedra, and  an edgeedge with one Mn(2)O5 trigonal bipyramid. The Co(2)-O(12) bond length is 2.18 Å. The Co(2)-O(4) bond length is 2.11 Å. The Co(2)-O(5) bond length is 2.13 Å. The Co(2)-O(7) bond length is 2.12 Å. There is one shorter (2.07 Å) and one longer (2.11 Å) Co(2)-O(6) bond length. There are three inequivalent P sites. In the first P site, P(1) is bonded to one O(2), one O(4), one O(5), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one Mn(1)O6 octahedra, corners with two equivalent Co(1)O6 octahedra, corners with two equivalent Co(2)O6 octahedra, and corners with two equivalent Mn(2)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 41-60°. The P(1)-O(2) bond length is 1.54 Å. The P(1)-O(4) bond length is 1.54 Å. The P(1)-O(5) bond length is 1.60 Å. The P(1)-O(8) bond length is 1.56 Å. In the second P site, P(2) is bonded to one O(1), one O(11), one O(3), and one O(6) atom to form PO4 tetrahedra that share  a cornercorner with one Mn(1)O6 octahedra, corners with two equivalent Co(2)O6 octahedra, corners with three equivalent Co(1)O6 octahedra, and  a cornercorner with one Mn(2)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 30-54°. The P(2)-O(1) bond length is 1.55 Å. The P(2)-O(11) bond length is 1.55 Å. The P(2)-O(3) bond length is 1.56 Å. The P(2)-O(6) bond length is 1.56 Å. In the third P site, P(3) is bonded to one O(10), one O(12), one O(7), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one Mn(1)O6 octahedra,  a cornercorner with one Co(1)O6 octahedra, corners with two equivalent Co(2)O6 octahedra, and corners with two equivalent Mn(2)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 32-57°. The P(3)-O(10) bond length is 1.54 Å. The P(3)-O(12) bond length is 1.61 Å. The P(3)-O(7) bond length is 1.55 Å. The P(3)-O(9) bond length is 1.53 Å. There are two inequivalent H sites. In the first H site, H(1) is bonded in a linear geometry to one O(3) and one O(5) atom. The H(1)-O(3) bond length is 1.40 Å. The H(1)-O(5) bond length is 1.07 Å. In the second H site, H(2) is bonded in a linear geometry to one O(12) and one O(9) atom. The H(2)-O(12) bond length is 1.03 Å. The H(2)-O(9) bond length is 1.59 Å. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one Mn(2), one Co(1), and one P(2) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Mn(2), one Co(1), and one P(1) atom. In the third O site, O(3) is bonded in a distorted T-shaped geometry to one Mn(1), one P(2), and one H(1) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one Mn(2), one Co(2), and one P(1) atom. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to one Co(2), one P(1), and one H(1) atom. In the sixth O site, O(6) is bonded in a distorted trigonal planar geometry to two equivalent Co(2) and one P(2) atom. In the seventh O site, O(7) is bonded in a distorted trigonal planar geometry to one Mn(2), one Co(2), and one P(3) atom. In the eighth O site, O(8) is bonded in a trigonal planar geometry to one Mn(1), one Co(1), and one P(1) atom. In the ninth O site, O(9) is bonded in a distorted trigonal planar geometry to one Co(1), one P(3), and one H(2) atom. In the tenth O site, O(10) is bonded in a distorted trigonal planar geometry to one Mn(1), one Mn(2), and one P(3) atom. In the eleventh O site, O(11) is bonded in a 3-coordinate geometry to two equivalent Co(1) and one P(2) atom. In the twelfth O site, O(12) is bonded in a 3-coordinate geometry to one Co(2), one P(3), and one H(2) atom.