Na2Co(SO6)2 crystallizes in the monoclinic P2_1/c space group. Na(1) is bonded to one O(1), one O(2), one O(4), one O(6), and two equivalent O(3) atoms to form NaO6 octahedra that share corners with two equivalent Co(1)O6 octahedra, corners with four equivalent S(1)O4 tetrahedra, and  an edgeedge with one Na(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 38-51°. Co(1) is bonded to two equivalent O(2), two equivalent O(5), and two equivalent O(6) atoms to form CoO6 octahedra that share corners with four equivalent Na(1)O6 octahedra and corners with two equivalent S(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 38-51°. S(1) is bonded to one O(1), one O(3), one O(4), and one O(5) atom to form SO4 tetrahedra that share  a cornercorner with one Co(1)O6 octahedra and corners with four equivalent Na(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 38-56°. There are six inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to one Na(1) and one S(1) atom. In the second O site, O(2) is bonded in a distorted bent 120 degrees geometry to one Na(1) and one Co(1) atom. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to two equivalent Na(1) and one S(1) atom. In the fourth O site, O(4) is bonded in a bent 150 degrees geometry to one Na(1) and one S(1) atom. In the fifth O site, O(5) is bonded in a bent 120 degrees geometry to one Co(1) and one S(1) atom. In the sixth O site, O(6) is bonded in a distorted bent 150 degrees geometry to one Na(1) and one Co(1) atom.
Na2Co(SO6)2 crystallizes in the monoclinic P2_1/c space group. Na(1) is bonded to one O(1), one O(2), one O(4), one O(6), and two equivalent O(3) atoms to form NaO6 octahedra that share corners with two equivalent Co(1)O6 octahedra, corners with four equivalent S(1)O4 tetrahedra, and  an edgeedge with one Na(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 38-51°. The Na(1)-O(1) bond length is 2.35 Å. The Na(1)-O(2) bond length is 2.57 Å. The Na(1)-O(4) bond length is 2.41 Å. The Na(1)-O(6) bond length is 2.45 Å. There is one shorter (2.38 Å) and one longer (2.40 Å) Na(1)-O(3) bond length. Co(1) is bonded to two equivalent O(2), two equivalent O(5), and two equivalent O(6) atoms to form CoO6 octahedra that share corners with four equivalent Na(1)O6 octahedra and corners with two equivalent S(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 38-51°. Both Co(1)-O(2) bond lengths are 1.76 Å. Both Co(1)-O(5) bond lengths are 2.00 Å. Both Co(1)-O(6) bond lengths are 1.76 Å. S(1) is bonded to one O(1), one O(3), one O(4), and one O(5) atom to form SO4 tetrahedra that share  a cornercorner with one Co(1)O6 octahedra and corners with four equivalent Na(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 38-56°. The S(1)-O(1) bond length is 1.47 Å. The S(1)-O(3) bond length is 1.48 Å. The S(1)-O(4) bond length is 1.46 Å. The S(1)-O(5) bond length is 1.54 Å. There are six inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to one Na(1) and one S(1) atom. In the second O site, O(2) is bonded in a distorted bent 120 degrees geometry to one Na(1) and one Co(1) atom. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to two equivalent Na(1) and one S(1) atom. In the fourth O site, O(4) is bonded in a bent 150 degrees geometry to one Na(1) and one S(1) atom. In the fifth O site, O(5) is bonded in a bent 120 degrees geometry to one Co(1) and one S(1) atom. In the sixth O site, O(6) is bonded in a distorted bent 150 degrees geometry to one Na(1) and one Co(1) atom.