Na4Co(MoO4)3 crystallizes in the monoclinic C2 space group. There are six inequivalent Na sites. In the first Na site, Na(1) is bonded in a rectangular see-saw-like geometry to two equivalent O(5) and two equivalent O(6) atoms. In the second Na site, Na(2) is bonded in a square co-planar geometry to two equivalent O(5) and two equivalent O(6) atoms. In the third Na site, Na(3) is bonded in a 6-coordinate geometry to one O(11), one O(12), two equivalent O(10), and two equivalent O(9) atoms. In the fourth Na site, Na(4) is bonded in a 6-coordinate geometry to two equivalent O(1), two equivalent O(10), and two equivalent O(3) atoms. In the fifth Na site, Na(5) is bonded in a 6-coordinate geometry to two equivalent O(2), two equivalent O(4), and two equivalent O(9) atoms. In the sixth Na site, Na(6) is bonded to one O(11), one O(2), one O(4), one O(5), one O(7), and one O(8) atom to form NaO6 octahedra that share  a cornercorner with one Mo(1)O4 tetrahedra,  a cornercorner with one Mo(2)O4 tetrahedra, corners with two equivalent Mo(3)O4 tetrahedra, corners with two equivalent Mo(4)O4 tetrahedra, and  an edgeedge with one Co(1)O6 octahedra. There are four inequivalent Mo sites. In the first Mo site, Mo(1) is bonded to two equivalent O(1) and two equivalent O(11) atoms to form MoO4 tetrahedra that share corners with two equivalent Na(6)O6 octahedra and corners with two equivalent Co(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 55-58°. In the second Mo site, Mo(2) is bonded to two equivalent O(12) and two equivalent O(2) atoms to form MoO4 tetrahedra that share corners with two equivalent Na(6)O6 octahedra and corners with two equivalent Co(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 53-62°. In the third Mo site, Mo(3) is bonded to one O(3), one O(5), one O(7), and one O(9) atom to form MoO4 tetrahedra that share corners with two equivalent Na(6)O6 octahedra and corners with two equivalent Co(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 35-63°. In the fourth Mo site, Mo(4) is bonded to one O(10), one O(4), one O(6), and one O(8) atom to form MoO4 tetrahedra that share corners with two equivalent Na(6)O6 octahedra and corners with two equivalent Co(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 45-55°. Co(1) is bonded to one O(1), one O(12), one O(3), one O(6), one O(7), and one O(8) atom to form CoO6 octahedra that share  a cornercorner with one Mo(1)O4 tetrahedra,  a cornercorner with one Mo(2)O4 tetrahedra, corners with two equivalent Mo(3)O4 tetrahedra, corners with two equivalent Mo(4)O4 tetrahedra, and  an edgeedge with one Na(6)O6 octahedra. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal non-coplanar geometry to one Na(4), one Mo(1), and one Co(1) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Na(5), one Na(6), and one Mo(2) atom. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to one Na(4), one Mo(3), and one Co(1) atom. In the fourth O site, O(4) is bonded in a distorted trigonal planar geometry to one Na(5), one Na(6), and one Mo(4) atom. In the fifth O site, O(5) is bonded to one Na(1), one Na(2), one Na(6), and one Mo(3) atom to form distorted ONa3Mo tetrahedra that share corners with two equivalent O(5)Na3Mo tetrahedra, corners with two equivalent O(6)Na2CoMo trigonal pyramids, and  an edgeedge with one O(6)Na2CoMo trigonal pyramid. In the sixth O site, O(6) is bonded to one Na(1), one Na(2), one Mo(4), and one Co(1) atom to form distorted ONa2CoMo trigonal pyramids that share corners with two equivalent O(5)Na3Mo tetrahedra, corners with two equivalent O(6)Na2CoMo trigonal pyramids, and  an edgeedge with one O(5)Na3Mo tetrahedra. In the seventh O site, O(7) is bonded in a 3-coordinate geometry to one Na(6), one Mo(3), and one Co(1) atom. In the eighth O site, O(8) is bonded in a distorted trigonal planar geometry to one Na(6), one Mo(4), and one Co(1) atom. In the ninth O site, O(9) is bonded in a rectangular see-saw-like geometry to one Na(5), two equivalent Na(3), and one Mo(3) atom. In the tenth O site, O(10) is bonded in a rectangular see-saw-like geometry to one Na(4), two equivalent Na(3), and one Mo(4) atom. In the eleventh O site, O(11) is bonded in a trigonal planar geometry to one Na(3), one Na(6), and one Mo(1) atom. In the twelfth O site, O(12) is bonded in a distorted trigonal planar geometry to one Na(3), one Mo(2), and one Co(1) atom.
Na4Co(MoO4)3 crystallizes in the monoclinic C2 space group. There are six inequivalent Na sites. In the first Na site, Na(1) is bonded in a rectangular see-saw-like geometry to two equivalent O(5) and two equivalent O(6) atoms. Both Na(1)-O(5) bond lengths are 2.44 Å. Both Na(1)-O(6) bond lengths are 2.63 Å. In the second Na site, Na(2) is bonded in a square co-planar geometry to two equivalent O(5) and two equivalent O(6) atoms. Both Na(2)-O(5) bond lengths are 2.58 Å. Both Na(2)-O(6) bond lengths are 2.63 Å. In the third Na site, Na(3) is bonded in a 6-coordinate geometry to one O(11), one O(12), two equivalent O(10), and two equivalent O(9) atoms. The Na(3)-O(11) bond length is 2.46 Å. The Na(3)-O(12) bond length is 2.68 Å. There is one shorter (2.55 Å) and one longer (2.62 Å) Na(3)-O(10) bond length. There is one shorter (2.49 Å) and one longer (2.71 Å) Na(3)-O(9) bond length. In the fourth Na site, Na(4) is bonded in a 6-coordinate geometry to two equivalent O(1), two equivalent O(10), and two equivalent O(3) atoms. Both Na(4)-O(1) bond lengths are 2.46 Å. Both Na(4)-O(10) bond lengths are 2.50 Å. Both Na(4)-O(3) bond lengths are 2.45 Å. In the fifth Na site, Na(5) is bonded in a 6-coordinate geometry to two equivalent O(2), two equivalent O(4), and two equivalent O(9) atoms. Both Na(5)-O(2) bond lengths are 2.39 Å. Both Na(5)-O(4) bond lengths are 2.39 Å. Both Na(5)-O(9) bond lengths are 2.58 Å. In the sixth Na site, Na(6) is bonded to one O(11), one O(2), one O(4), one O(5), one O(7), and one O(8) atom to form NaO6 octahedra that share  a cornercorner with one Mo(1)O4 tetrahedra,  a cornercorner with one Mo(2)O4 tetrahedra, corners with two equivalent Mo(3)O4 tetrahedra, corners with two equivalent Mo(4)O4 tetrahedra, and  an edgeedge with one Co(1)O6 octahedra. The Na(6)-O(11) bond length is 2.26 Å. The Na(6)-O(2) bond length is 2.30 Å. The Na(6)-O(4) bond length is 2.26 Å. The Na(6)-O(5) bond length is 2.34 Å. The Na(6)-O(7) bond length is 2.45 Å. The Na(6)-O(8) bond length is 2.30 Å. There are four inequivalent Mo sites. In the first Mo site, Mo(1) is bonded to two equivalent O(1) and two equivalent O(11) atoms to form MoO4 tetrahedra that share corners with two equivalent Na(6)O6 octahedra and corners with two equivalent Co(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 55-58°. Both Mo(1)-O(1) bond lengths are 1.84 Å. Both Mo(1)-O(11) bond lengths are 1.77 Å. In the second Mo site, Mo(2) is bonded to two equivalent O(12) and two equivalent O(2) atoms to form MoO4 tetrahedra that share corners with two equivalent Na(6)O6 octahedra and corners with two equivalent Co(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 53-62°. Both Mo(2)-O(12) bond lengths are 1.82 Å. Both Mo(2)-O(2) bond lengths are 1.78 Å. In the third Mo site, Mo(3) is bonded to one O(3), one O(5), one O(7), and one O(9) atom to form MoO4 tetrahedra that share corners with two equivalent Na(6)O6 octahedra and corners with two equivalent Co(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 35-63°. The Mo(3)-O(3) bond length is 1.81 Å. The Mo(3)-O(5) bond length is 1.80 Å. The Mo(3)-O(7) bond length is 1.81 Å. The Mo(3)-O(9) bond length is 1.79 Å. In the fourth Mo site, Mo(4) is bonded to one O(10), one O(4), one O(6), and one O(8) atom to form MoO4 tetrahedra that share corners with two equivalent Na(6)O6 octahedra and corners with two equivalent Co(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 45-55°. The Mo(4)-O(10) bond length is 1.78 Å. The Mo(4)-O(4) bond length is 1.78 Å. The Mo(4)-O(6) bond length is 1.84 Å. The Mo(4)-O(8) bond length is 1.81 Å. Co(1) is bonded to one O(1), one O(12), one O(3), one O(6), one O(7), and one O(8) atom to form CoO6 octahedra that share  a cornercorner with one Mo(1)O4 tetrahedra,  a cornercorner with one Mo(2)O4 tetrahedra, corners with two equivalent Mo(3)O4 tetrahedra, corners with two equivalent Mo(4)O4 tetrahedra, and  an edgeedge with one Na(6)O6 octahedra. The Co(1)-O(1) bond length is 2.04 Å. The Co(1)-O(12) bond length is 2.05 Å. The Co(1)-O(3) bond length is 2.14 Å. The Co(1)-O(6) bond length is 2.25 Å. The Co(1)-O(7) bond length is 2.19 Å. The Co(1)-O(8) bond length is 2.20 Å. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal non-coplanar geometry to one Na(4), one Mo(1), and one Co(1) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Na(5), one Na(6), and one Mo(2) atom. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to one Na(4), one Mo(3), and one Co(1) atom. In the fourth O site, O(4) is bonded in a distorted trigonal planar geometry to one Na(5), one Na(6), and one Mo(4) atom. In the fifth O site, O(5) is bonded to one Na(1), one Na(2), one Na(6), and one Mo(3) atom to form distorted ONa3Mo tetrahedra that share corners with two equivalent O(5)Na3Mo tetrahedra, corners with two equivalent O(6)Na2CoMo trigonal pyramids, and  an edgeedge with one O(6)Na2CoMo trigonal pyramid. In the sixth O site, O(6) is bonded to one Na(1), one Na(2), one Mo(4), and one Co(1) atom to form distorted ONa2CoMo trigonal pyramids that share corners with two equivalent O(5)Na3Mo tetrahedra, corners with two equivalent O(6)Na2CoMo trigonal pyramids, and  an edgeedge with one O(5)Na3Mo tetrahedra. In the seventh O site, O(7) is bonded in a 3-coordinate geometry to one Na(6), one Mo(3), and one Co(1) atom. In the eighth O site, O(8) is bonded in a distorted trigonal planar geometry to one Na(6), one Mo(4), and one Co(1) atom. In the ninth O site, O(9) is bonded in a rectangular see-saw-like geometry to one Na(5), two equivalent Na(3), and one Mo(3) atom. In the tenth O site, O(10) is bonded in a rectangular see-saw-like geometry to one Na(4), two equivalent Na(3), and one Mo(4) atom. In the eleventh O site, O(11) is bonded in a trigonal planar geometry to one Na(3), one Na(6), and one Mo(1) atom. In the twelfth O site, O(12) is bonded in a distorted trigonal planar geometry to one Na(3), one Mo(2), and one Co(1) atom.