Na2MnCl4 crystallizes in the orthorhombic Pbam space group. Na(1) is bonded in a 6-coordinate geometry to two equivalent Cl(1) and four equivalent Cl(2) atoms. Mn(1) is bonded to two equivalent Cl(2) and four equivalent Cl(1) atoms to form edge-sharing MnCl6 octahedra. There are two inequivalent Cl sites. In the first Cl site, Cl(2) is bonded to four equivalent Na(1) and one Mn(1) atom to form distorted ClNa4Mn trigonal bipyramids that share corners with five equivalent Cl(2)Na4Mn trigonal bipyramids, corners with eight equivalent Cl(1)Na2Mn2 trigonal pyramids, edges with four equivalent Cl(2)Na4Mn trigonal bipyramids, and edges with two equivalent Cl(1)Na2Mn2 trigonal pyramids. In the second Cl site, Cl(1) is bonded to two equivalent Na(1) and two equivalent Mn(1) atoms to form distorted ClNa2Mn2 trigonal pyramids that share corners with eight equivalent Cl(2)Na4Mn trigonal bipyramids, corners with four equivalent Cl(1)Na2Mn2 trigonal pyramids, edges with two equivalent Cl(2)Na4Mn trigonal bipyramids, and edges with two equivalent Cl(1)Na2Mn2 trigonal pyramids.
Na2MnCl4 crystallizes in the orthorhombic Pbam space group. Na(1) is bonded in a 6-coordinate geometry to two equivalent Cl(1) and four equivalent Cl(2) atoms. There is one shorter (2.87 Å) and one longer (2.94 Å) Na(1)-Cl(1) bond length. There are two shorter (2.78 Å) and two longer (2.79 Å) Na(1)-Cl(2) bond lengths. Mn(1) is bonded to two equivalent Cl(2) and four equivalent Cl(1) atoms to form edge-sharing MnCl6 octahedra. Both Mn(1)-Cl(2) bond lengths are 2.49 Å. All Mn(1)-Cl(1) bond lengths are 2.58 Å. There are two inequivalent Cl sites. In the first Cl site, Cl(2) is bonded to four equivalent Na(1) and one Mn(1) atom to form distorted ClNa4Mn trigonal bipyramids that share corners with five equivalent Cl(2)Na4Mn trigonal bipyramids, corners with eight equivalent Cl(1)Na2Mn2 trigonal pyramids, edges with four equivalent Cl(2)Na4Mn trigonal bipyramids, and edges with two equivalent Cl(1)Na2Mn2 trigonal pyramids. In the second Cl site, Cl(1) is bonded to two equivalent Na(1) and two equivalent Mn(1) atoms to form distorted ClNa2Mn2 trigonal pyramids that share corners with eight equivalent Cl(2)Na4Mn trigonal bipyramids, corners with four equivalent Cl(1)Na2Mn2 trigonal pyramids, edges with two equivalent Cl(2)Na4Mn trigonal bipyramids, and edges with two equivalent Cl(1)Na2Mn2 trigonal pyramids.