Na2SmCl5 crystallizes in the orthorhombic Pnma space group. Na(1) is bonded in a 8-coordinate geometry to two equivalent Cl(1), two equivalent Cl(2), two equivalent Cl(3), and two equivalent Cl(4) atoms. Sm(1) is bonded to one Cl(1), one Cl(3), one Cl(4), and four equivalent Cl(2) atoms to form distorted edge-sharing SmCl7 pentagonal bipyramids. There are four inequivalent Cl sites. In the first Cl site, Cl(1) is bonded in a 5-coordinate geometry to four equivalent Na(1) and one Sm(1) atom. In the second Cl site, Cl(2) is bonded to two equivalent Na(1) and two equivalent Sm(1) atoms to form ClNa2Sm2 trigonal pyramids that share corners with four equivalent Cl(3)Na4Sm square pyramids, corners with two equivalent Cl(4)Na4Sm trigonal bipyramids, corners with six equivalent Cl(2)Na2Sm2 trigonal pyramids,  an edgeedge with one Cl(3)Na4Sm square pyramid, edges with two equivalent Cl(4)Na4Sm trigonal bipyramids, and  an edgeedge with one Cl(2)Na2Sm2 trigonal pyramid. In the third Cl site, Cl(3) is bonded to four equivalent Na(1) and one Sm(1) atom to form ClNa4Sm square pyramids that share corners with four equivalent Cl(4)Na4Sm trigonal bipyramids, corners with eight equivalent Cl(2)Na2Sm2 trigonal pyramids, edges with two equivalent Cl(3)Na4Sm square pyramids,  an edgeedge with one Cl(4)Na4Sm trigonal bipyramid, edges with two equivalent Cl(2)Na2Sm2 trigonal pyramids, and  a faceface with one Cl(4)Na4Sm trigonal bipyramid. In the fourth Cl site, Cl(4) is bonded to four equivalent Na(1) and one Sm(1) atom to form distorted ClNa4Sm trigonal bipyramids that share corners with four equivalent Cl(3)Na4Sm square pyramids, corners with four equivalent Cl(4)Na4Sm trigonal bipyramids, corners with four equivalent Cl(2)Na2Sm2 trigonal pyramids,  an edgeedge with one Cl(3)Na4Sm square pyramid, edges with four equivalent Cl(2)Na2Sm2 trigonal pyramids, and  a faceface with one Cl(3)Na4Sm square pyramid.
Na2SmCl5 crystallizes in the orthorhombic Pnma space group. Na(1) is bonded in a 8-coordinate geometry to two equivalent Cl(1), two equivalent Cl(2), two equivalent Cl(3), and two equivalent Cl(4) atoms. There is one shorter (2.95 Å) and one longer (3.32 Å) Na(1)-Cl(1) bond length. There is one shorter (2.96 Å) and one longer (3.01 Å) Na(1)-Cl(2) bond length. Both Na(1)-Cl(3) bond lengths are 3.01 Å. There is one shorter (2.93 Å) and one longer (3.09 Å) Na(1)-Cl(4) bond length. Sm(1) is bonded to one Cl(1), one Cl(3), one Cl(4), and four equivalent Cl(2) atoms to form distorted edge-sharing SmCl7 pentagonal bipyramids. The Sm(1)-Cl(1) bond length is 2.74 Å. The Sm(1)-Cl(3) bond length is 2.77 Å. The Sm(1)-Cl(4) bond length is 2.76 Å. There are two shorter (2.72 Å) and two longer (2.81 Å) Sm(1)-Cl(2) bond lengths. There are four inequivalent Cl sites. In the first Cl site, Cl(1) is bonded in a 5-coordinate geometry to four equivalent Na(1) and one Sm(1) atom. In the second Cl site, Cl(2) is bonded to two equivalent Na(1) and two equivalent Sm(1) atoms to form ClNa2Sm2 trigonal pyramids that share corners with four equivalent Cl(3)Na4Sm square pyramids, corners with two equivalent Cl(4)Na4Sm trigonal bipyramids, corners with six equivalent Cl(2)Na2Sm2 trigonal pyramids,  an edgeedge with one Cl(3)Na4Sm square pyramid, edges with two equivalent Cl(4)Na4Sm trigonal bipyramids, and  an edgeedge with one Cl(2)Na2Sm2 trigonal pyramid. In the third Cl site, Cl(3) is bonded to four equivalent Na(1) and one Sm(1) atom to form ClNa4Sm square pyramids that share corners with four equivalent Cl(4)Na4Sm trigonal bipyramids, corners with eight equivalent Cl(2)Na2Sm2 trigonal pyramids, edges with two equivalent Cl(3)Na4Sm square pyramids,  an edgeedge with one Cl(4)Na4Sm trigonal bipyramid, edges with two equivalent Cl(2)Na2Sm2 trigonal pyramids, and  a faceface with one Cl(4)Na4Sm trigonal bipyramid. In the fourth Cl site, Cl(4) is bonded to four equivalent Na(1) and one Sm(1) atom to form distorted ClNa4Sm trigonal bipyramids that share corners with four equivalent Cl(3)Na4Sm square pyramids, corners with four equivalent Cl(4)Na4Sm trigonal bipyramids, corners with four equivalent Cl(2)Na2Sm2 trigonal pyramids,  an edgeedge with one Cl(3)Na4Sm square pyramid, edges with four equivalent Cl(2)Na2Sm2 trigonal pyramids, and  a faceface with one Cl(3)Na4Sm square pyramid.