LiEu3SiO4Cl3 crystallizes in the orthorhombic Pmna space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in an octahedral geometry to two equivalent Cl(1) and four equivalent Cl(2) atoms. In the second Li site, Li(2) is bonded in a distorted square co-planar geometry to two equivalent O(1) and two equivalent O(2) atoms. There are three inequivalent Eu sites. In the first Eu site, Eu(1) is bonded in a 8-coordinate geometry to two equivalent O(1), two equivalent O(3), two equivalent Cl(1), and two equivalent Cl(2) atoms. In the second Eu site, Eu(2) is bonded in a 8-coordinate geometry to one O(1), one O(2), two equivalent O(3), and four equivalent Cl(2) atoms. In the third Eu site, Eu(3) is bonded in a 8-coordinate geometry to two equivalent O(2), two equivalent O(3), two equivalent Cl(1), and two equivalent Cl(2) atoms. Si(1) is bonded in a tetrahedral geometry to one O(1), one O(2), and two equivalent O(3) atoms. There are three inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Li(2), one Eu(2), two equivalent Eu(1), and one Si(1) atom. In the second O site, O(2) is bonded in a 5-coordinate geometry to one Li(2), one Eu(2), two equivalent Eu(3), and one Si(1) atom. In the third O site, O(3) is bonded in a 4-coordinate geometry to one Eu(1), one Eu(2), one Eu(3), and one Si(1) atom. There are two inequivalent Cl sites. In the first Cl site, Cl(1) is bonded to one Li(1), two equivalent Eu(1), and two equivalent Eu(3) atoms to form a mixture of distorted corner and edge-sharing ClLiEu4 square pyramids. In the second Cl site, Cl(2) is bonded in a 5-coordinate geometry to one Li(1), one Eu(1), one Eu(3), and two equivalent Eu(2) atoms.
LiEu3SiO4Cl3 crystallizes in the orthorhombic Pmna space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in an octahedral geometry to two equivalent Cl(1) and four equivalent Cl(2) atoms. Both Li(1)-Cl(1) bond lengths are 2.54 Å. All Li(1)-Cl(2) bond lengths are 2.71 Å. In the second Li site, Li(2) is bonded in a distorted square co-planar geometry to two equivalent O(1) and two equivalent O(2) atoms. Both Li(2)-O(1) bond lengths are 1.93 Å. Both Li(2)-O(2) bond lengths are 2.25 Å. There are three inequivalent Eu sites. In the first Eu site, Eu(1) is bonded in a 8-coordinate geometry to two equivalent O(1), two equivalent O(3), two equivalent Cl(1), and two equivalent Cl(2) atoms. Both Eu(1)-O(1) bond lengths are 2.94 Å. Both Eu(1)-O(3) bond lengths are 2.42 Å. Both Eu(1)-Cl(1) bond lengths are 3.05 Å. Both Eu(1)-Cl(2) bond lengths are 2.97 Å. In the second Eu site, Eu(2) is bonded in a 8-coordinate geometry to one O(1), one O(2), two equivalent O(3), and four equivalent Cl(2) atoms. The Eu(2)-O(1) bond length is 2.47 Å. The Eu(2)-O(2) bond length is 2.52 Å. Both Eu(2)-O(3) bond lengths are 2.61 Å. There are two shorter (3.15 Å) and two longer (3.24 Å) Eu(2)-Cl(2) bond lengths. In the third Eu site, Eu(3) is bonded in a 8-coordinate geometry to two equivalent O(2), two equivalent O(3), two equivalent Cl(1), and two equivalent Cl(2) atoms. Both Eu(3)-O(2) bond lengths are 2.76 Å. Both Eu(3)-O(3) bond lengths are 2.44 Å. Both Eu(3)-Cl(1) bond lengths are 3.23 Å. Both Eu(3)-Cl(2) bond lengths are 2.96 Å. Si(1) is bonded in a tetrahedral geometry to one O(1), one O(2), and two equivalent O(3) atoms. The Si(1)-O(1) bond length is 1.65 Å. The Si(1)-O(2) bond length is 1.65 Å. Both Si(1)-O(3) bond lengths are 1.65 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Li(2), one Eu(2), two equivalent Eu(1), and one Si(1) atom. In the second O site, O(2) is bonded in a 5-coordinate geometry to one Li(2), one Eu(2), two equivalent Eu(3), and one Si(1) atom. In the third O site, O(3) is bonded in a 4-coordinate geometry to one Eu(1), one Eu(2), one Eu(3), and one Si(1) atom. There are two inequivalent Cl sites. In the first Cl site, Cl(1) is bonded to one Li(1), two equivalent Eu(1), and two equivalent Eu(3) atoms to form a mixture of distorted corner and edge-sharing ClLiEu4 square pyramids. In the second Cl site, Cl(2) is bonded in a 5-coordinate geometry to one Li(1), one Eu(1), one Eu(3), and two equivalent Eu(2) atoms.