Ba2LaAg5S6 crystallizes in the monoclinic C2/m space group. Ba(1) is bonded in a 7-coordinate geometry to two equivalent S(1), two equivalent S(2), and three equivalent S(3) atoms. La(1) is bonded to two equivalent S(1) and four equivalent S(3) atoms to form LaS6 octahedra that share corners with two equivalent Ag(1)S4 trigonal pyramids, edges with two equivalent La(1)S6 octahedra, and edges with four equivalent Ag(2)S4 tetrahedra. There are three inequivalent Ag sites. In the first Ag site, Ag(1) is bonded to one S(1) and three equivalent S(2) atoms to form distorted AgS4 trigonal pyramids that share  a cornercorner with one La(1)S6 octahedra, corners with five equivalent Ag(2)S4 tetrahedra, corners with two equivalent Ag(1)S4 trigonal pyramids, and edges with two equivalent Ag(1)S4 trigonal pyramids. The corner-sharing octahedral tilt angles are 5°. In the second Ag site, Ag(2) is bonded to one S(2), one S(3), and two equivalent S(1) atoms to form distorted AgS4 tetrahedra that share corners with two equivalent Ag(2)S4 tetrahedra, corners with five equivalent Ag(1)S4 trigonal pyramids, and edges with two equivalent La(1)S6 octahedra. In the third Ag site, Ag(3) is bonded in a linear geometry to two equivalent S(2) atoms. There are three inequivalent S sites. In the first S site, S(1) is bonded to two equivalent Ba(1), one La(1), one Ag(1), and two equivalent Ag(2) atoms to form SBa2LaAg3 octahedra that share  a cornercorner with one S(1)Ba2LaAg3 octahedra, corners with two equivalent S(3)Ba3La2Ag octahedra, edges with two equivalent S(1)Ba2LaAg3 octahedra, and edges with five equivalent S(3)Ba3La2Ag octahedra. The corner-sharing octahedral tilt angles range from 0-26°. In the second S site, S(2) is bonded in a 7-coordinate geometry to two equivalent Ba(1), one Ag(2), one Ag(3), and three equivalent Ag(1) atoms. In the third S site, S(3) is bonded to three equivalent Ba(1), two equivalent La(1), and one Ag(2) atom to form distorted SBa3La2Ag octahedra that share corners with two equivalent S(1)Ba2LaAg3 octahedra, corners with two equivalent S(3)Ba3La2Ag octahedra, edges with five equivalent S(1)Ba2LaAg3 octahedra, and edges with five equivalent S(3)Ba3La2Ag octahedra. The corner-sharing octahedral tilt angles range from 0-26°.
Ba2LaAg5S6 crystallizes in the monoclinic C2/m space group. Ba(1) is bonded in a 7-coordinate geometry to two equivalent S(1), two equivalent S(2), and three equivalent S(3) atoms. Both Ba(1)-S(1) bond lengths are 3.22 Å. Both Ba(1)-S(2) bond lengths are 3.24 Å. There is one shorter (3.25 Å) and two longer (3.32 Å) Ba(1)-S(3) bond lengths. La(1) is bonded to two equivalent S(1) and four equivalent S(3) atoms to form LaS6 octahedra that share corners with two equivalent Ag(1)S4 trigonal pyramids, edges with two equivalent La(1)S6 octahedra, and edges with four equivalent Ag(2)S4 tetrahedra. Both La(1)-S(1) bond lengths are 2.90 Å. All La(1)-S(3) bond lengths are 2.93 Å. There are three inequivalent Ag sites. In the first Ag site, Ag(1) is bonded to one S(1) and three equivalent S(2) atoms to form distorted AgS4 trigonal pyramids that share  a cornercorner with one La(1)S6 octahedra, corners with five equivalent Ag(2)S4 tetrahedra, corners with two equivalent Ag(1)S4 trigonal pyramids, and edges with two equivalent Ag(1)S4 trigonal pyramids. The corner-sharing octahedral tilt angles are 5°. The Ag(1)-S(1) bond length is 2.60 Å. There are two shorter (2.64 Å) and one longer (2.91 Å) Ag(1)-S(2) bond length. In the second Ag site, Ag(2) is bonded to one S(2), one S(3), and two equivalent S(1) atoms to form distorted AgS4 tetrahedra that share corners with two equivalent Ag(2)S4 tetrahedra, corners with five equivalent Ag(1)S4 trigonal pyramids, and edges with two equivalent La(1)S6 octahedra. The Ag(2)-S(2) bond length is 2.74 Å. The Ag(2)-S(3) bond length is 2.59 Å. Both Ag(2)-S(1) bond lengths are 2.61 Å. In the third Ag site, Ag(3) is bonded in a linear geometry to two equivalent S(2) atoms. Both Ag(3)-S(2) bond lengths are 2.41 Å. There are three inequivalent S sites. In the first S site, S(1) is bonded to two equivalent Ba(1), one La(1), one Ag(1), and two equivalent Ag(2) atoms to form SBa2LaAg3 octahedra that share  a cornercorner with one S(1)Ba2LaAg3 octahedra, corners with two equivalent S(3)Ba3La2Ag octahedra, edges with two equivalent S(1)Ba2LaAg3 octahedra, and edges with five equivalent S(3)Ba3La2Ag octahedra. The corner-sharing octahedral tilt angles range from 0-26°. In the second S site, S(2) is bonded in a 7-coordinate geometry to two equivalent Ba(1), one Ag(2), one Ag(3), and three equivalent Ag(1) atoms. In the third S site, S(3) is bonded to three equivalent Ba(1), two equivalent La(1), and one Ag(2) atom to form distorted SBa3La2Ag octahedra that share corners with two equivalent S(1)Ba2LaAg3 octahedra, corners with two equivalent S(3)Ba3La2Ag octahedra, edges with five equivalent S(1)Ba2LaAg3 octahedra, and edges with five equivalent S(3)Ba3La2Ag octahedra. The corner-sharing octahedral tilt angles range from 0-26°.