NaWO2Cl2 crystallizes in the orthorhombic Amm2 space group. Na(1) is bonded to two equivalent Cl(2) and four equivalent Cl(1) atoms to form distorted NaCl6 pentagonal pyramids that share corners with six equivalent W(1)Cl2O4 octahedra, corners with four equivalent Na(1)Cl6 pentagonal pyramids, edges with two equivalent Na(1)Cl6 pentagonal pyramids, and faces with two equivalent Na(1)Cl6 pentagonal pyramids. The corner-sharing octahedral tilt angles range from 44-72°. W(1) is bonded to two equivalent O(1), two equivalent O(2), one Cl(1), and one Cl(2) atom to form distorted WCl2O4 octahedra that share corners with four equivalent W(1)Cl2O4 octahedra and corners with six equivalent Na(1)Cl6 pentagonal pyramids. The corner-sharing octahedral tilt angles range from 2-3°. There are two inequivalent O sites. In the first O site, O(1) is bonded in a linear geometry to two equivalent W(1) atoms. In the second O site, O(2) is bonded in a linear geometry to two equivalent W(1) atoms. There are two inequivalent Cl sites. In the first Cl site, Cl(1) is bonded to four equivalent Na(1) and one W(1) atom to form a mixture of distorted edge and corner-sharing ClNa4W trigonal bipyramids. In the second Cl site, Cl(2) is bonded in a distorted T-shaped geometry to two equivalent Na(1) and one W(1) atom.
NaWO2Cl2 crystallizes in the orthorhombic Amm2 space group. Na(1) is bonded to two equivalent Cl(2) and four equivalent Cl(1) atoms to form distorted NaCl6 pentagonal pyramids that share corners with six equivalent W(1)Cl2O4 octahedra, corners with four equivalent Na(1)Cl6 pentagonal pyramids, edges with two equivalent Na(1)Cl6 pentagonal pyramids, and faces with two equivalent Na(1)Cl6 pentagonal pyramids. The corner-sharing octahedral tilt angles range from 44-72°. Both Na(1)-Cl(2) bond lengths are 2.82 Å. All Na(1)-Cl(1) bond lengths are 2.90 Å. W(1) is bonded to two equivalent O(1), two equivalent O(2), one Cl(1), and one Cl(2) atom to form distorted WCl2O4 octahedra that share corners with four equivalent W(1)Cl2O4 octahedra and corners with six equivalent Na(1)Cl6 pentagonal pyramids. The corner-sharing octahedral tilt angles range from 2-3°. Both W(1)-O(1) bond lengths are 1.95 Å. Both W(1)-O(2) bond lengths are 1.94 Å. The W(1)-Cl(1) bond length is 2.55 Å. The W(1)-Cl(2) bond length is 2.45 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded in a linear geometry to two equivalent W(1) atoms. In the second O site, O(2) is bonded in a linear geometry to two equivalent W(1) atoms. There are two inequivalent Cl sites. In the first Cl site, Cl(1) is bonded to four equivalent Na(1) and one W(1) atom to form a mixture of distorted edge and corner-sharing ClNa4W trigonal bipyramids. In the second Cl site, Cl(2) is bonded in a distorted T-shaped geometry to two equivalent Na(1) and one W(1) atom.