Na2EuCl5 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. Eu(1) is bonded to one Cl(1), one Cl(2), one Cl(3), and four equivalent Cl(4) atoms to form distorted edge-sharing EuCl7 pentagonal bipyramids. There are four inequivalent Cl sites. In the first Cl site, Cl(1) is bonded to four equivalent Na(1) and one Eu(1) atom to form ClNa4Eu square pyramids that share corners with four equivalent Cl(3)Na4Eu trigonal bipyramids, corners with eight equivalent Cl(4)Na2Eu2 trigonal pyramids, edges with two equivalent Cl(1)Na4Eu square pyramids,  an edgeedge with one Cl(3)Na4Eu trigonal bipyramid, edges with two equivalent Cl(4)Na2Eu2 trigonal pyramids, and  a faceface with one Cl(3)Na4Eu trigonal bipyramid. In the second Cl site, Cl(2) is bonded in a 5-coordinate geometry to four equivalent Na(1) and one Eu(1) atom. In the third Cl site, Cl(3) is bonded to four equivalent Na(1) and one Eu(1) atom to form ClNa4Eu trigonal bipyramids that share corners with four equivalent Cl(1)Na4Eu square pyramids, corners with four equivalent Cl(3)Na4Eu trigonal bipyramids, corners with four equivalent Cl(4)Na2Eu2 trigonal pyramids,  an edgeedge with one Cl(1)Na4Eu square pyramid, edges with four equivalent Cl(4)Na2Eu2 trigonal pyramids, and  a faceface with one Cl(1)Na4Eu square pyramid. In the fourth Cl site, Cl(4) is bonded to two equivalent Na(1) and two equivalent Eu(1) atoms to form distorted ClNa2Eu2 trigonal pyramids that share corners with four equivalent Cl(1)Na4Eu square pyramids, corners with two equivalent Cl(3)Na4Eu trigonal bipyramids, corners with six equivalent Cl(4)Na2Eu2 trigonal pyramids,  an edgeedge with one Cl(1)Na4Eu square pyramid, edges with two equivalent Cl(3)Na4Eu trigonal bipyramids, and  an edgeedge with one Cl(4)Na2Eu2 trigonal pyramid.
Na2EuCl5 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 (3.05 Å) and one longer (3.09 Å) Na(1)-Cl(1) bond length. There is one shorter (3.12 Å) and one longer (3.34 Å) Na(1)-Cl(2) bond length. There is one shorter (3.06 Å) and one longer (3.17 Å) Na(1)-Cl(3) bond length. There is one shorter (3.12 Å) and one longer (3.16 Å) Na(1)-Cl(4) bond length. Eu(1) is bonded to one Cl(1), one Cl(2), one Cl(3), and four equivalent Cl(4) atoms to form distorted edge-sharing EuCl7 pentagonal bipyramids. The Eu(1)-Cl(1) bond length is 2.89 Å. The Eu(1)-Cl(2) bond length is 2.80 Å. The Eu(1)-Cl(3) bond length is 2.84 Å. There are two shorter (2.81 Å) and two longer (2.87 Å) Eu(1)-Cl(4) bond lengths. There are four inequivalent Cl sites. In the first Cl site, Cl(1) is bonded to four equivalent Na(1) and one Eu(1) atom to form ClNa4Eu square pyramids that share corners with four equivalent Cl(3)Na4Eu trigonal bipyramids, corners with eight equivalent Cl(4)Na2Eu2 trigonal pyramids, edges with two equivalent Cl(1)Na4Eu square pyramids,  an edgeedge with one Cl(3)Na4Eu trigonal bipyramid, edges with two equivalent Cl(4)Na2Eu2 trigonal pyramids, and  a faceface with one Cl(3)Na4Eu trigonal bipyramid. In the second Cl site, Cl(2) is bonded in a 5-coordinate geometry to four equivalent Na(1) and one Eu(1) atom. In the third Cl site, Cl(3) is bonded to four equivalent Na(1) and one Eu(1) atom to form ClNa4Eu trigonal bipyramids that share corners with four equivalent Cl(1)Na4Eu square pyramids, corners with four equivalent Cl(3)Na4Eu trigonal bipyramids, corners with four equivalent Cl(4)Na2Eu2 trigonal pyramids,  an edgeedge with one Cl(1)Na4Eu square pyramid, edges with four equivalent Cl(4)Na2Eu2 trigonal pyramids, and  a faceface with one Cl(1)Na4Eu square pyramid. In the fourth Cl site, Cl(4) is bonded to two equivalent Na(1) and two equivalent Eu(1) atoms to form distorted ClNa2Eu2 trigonal pyramids that share corners with four equivalent Cl(1)Na4Eu square pyramids, corners with two equivalent Cl(3)Na4Eu trigonal bipyramids, corners with six equivalent Cl(4)Na2Eu2 trigonal pyramids,  an edgeedge with one Cl(1)Na4Eu square pyramid, edges with two equivalent Cl(3)Na4Eu trigonal bipyramids, and  an edgeedge with one Cl(4)Na2Eu2 trigonal pyramid.