MgWO2 crystallizes in the triclinic P-1 space group. There are two inequivalent Mg sites. In the first Mg site, Mg(1) is bonded in a 6-coordinate geometry to two equivalent O(1), two equivalent O(3), and two equivalent O(4) atoms. In the second Mg site, Mg(2) is bonded to one O(3), two equivalent O(2), and two equivalent O(4) atoms to form distorted edge-sharing MgO5 trigonal bipyramids. There are two inequivalent W sites. In the first W site, W(1) is bonded in a square co-planar geometry to two equivalent O(1) and two equivalent O(3) atoms. In the second W site, W(2) is bonded in a 4-coordinate geometry to one O(1), one O(4), and two equivalent O(2) atoms. There are four inequivalent O sites. In the first O site, O(1) is bonded in a 5-coordinate geometry to two equivalent Mg(1), one W(2), and two equivalent W(1) atoms. In the second O site, O(2) is bonded to two equivalent Mg(2) and two equivalent W(2) atoms to form distorted OMg2W2 trigonal pyramids that share corners with four equivalent O(4)Mg4W square pyramids,  an edgeedge with one O(4)Mg4W square pyramid, and edges with two equivalent O(2)Mg2W2 trigonal pyramids. In the third O site, O(3) is bonded in a 5-coordinate geometry to one Mg(2), two equivalent Mg(1), and two equivalent W(1) atoms. In the fourth O site, O(4) is bonded to two equivalent Mg(1), two equivalent Mg(2), and one W(2) atom to form OMg4W square pyramids that share corners with four equivalent O(2)Mg2W2 trigonal pyramids, edges with two equivalent O(4)Mg4W square pyramids, and  an edgeedge with one O(2)Mg2W2 trigonal pyramid.
MgWO2 crystallizes in the triclinic P-1 space group. There are two inequivalent Mg sites. In the first Mg site, Mg(1) is bonded in a 6-coordinate geometry to two equivalent O(1), two equivalent O(3), and two equivalent O(4) atoms. There is one shorter (2.20 Å) and one longer (2.56 Å) Mg(1)-O(1) bond length. There is one shorter (2.11 Å) and one longer (2.20 Å) Mg(1)-O(3) bond length. There is one shorter (2.07 Å) and one longer (2.08 Å) Mg(1)-O(4) bond length. In the second Mg site, Mg(2) is bonded to one O(3), two equivalent O(2), and two equivalent O(4) atoms to form distorted edge-sharing MgO5 trigonal bipyramids. The Mg(2)-O(3) bond length is 2.00 Å. There is one shorter (2.12 Å) and one longer (2.13 Å) Mg(2)-O(2) bond length. There is one shorter (2.07 Å) and one longer (2.08 Å) Mg(2)-O(4) bond length. There are two inequivalent W sites. In the first W site, W(1) is bonded in a square co-planar geometry to two equivalent O(1) and two equivalent O(3) atoms. There is one shorter (2.16 Å) and one longer (2.18 Å) W(1)-O(1) bond length. There is one shorter (2.23 Å) and one longer (2.24 Å) W(1)-O(3) bond length. In the second W site, W(2) is bonded in a 4-coordinate geometry to one O(1), one O(4), and two equivalent O(2) atoms. The W(2)-O(1) bond length is 2.20 Å. The W(2)-O(4) bond length is 2.23 Å. There is one shorter (2.17 Å) and one longer (2.19 Å) W(2)-O(2) bond length. There are four inequivalent O sites. In the first O site, O(1) is bonded in a 5-coordinate geometry to two equivalent Mg(1), one W(2), and two equivalent W(1) atoms. In the second O site, O(2) is bonded to two equivalent Mg(2) and two equivalent W(2) atoms to form distorted OMg2W2 trigonal pyramids that share corners with four equivalent O(4)Mg4W square pyramids,  an edgeedge with one O(4)Mg4W square pyramid, and edges with two equivalent O(2)Mg2W2 trigonal pyramids. In the third O site, O(3) is bonded in a 5-coordinate geometry to one Mg(2), two equivalent Mg(1), and two equivalent W(1) atoms. In the fourth O site, O(4) is bonded to two equivalent Mg(1), two equivalent Mg(2), and one W(2) atom to form OMg4W square pyramids that share corners with four equivalent O(2)Mg2W2 trigonal pyramids, edges with two equivalent O(4)Mg4W square pyramids, and  an edgeedge with one O(2)Mg2W2 trigonal pyramid.