RbAg2(AsSe2)3 crystallizes in the monoclinic P2_1/c space group. Rb(1) is bonded in a 12-coordinate geometry to one As(1), one As(2), one As(3), one Se(1), one Se(4), one Se(5), two equivalent Se(2), two equivalent Se(3), and two equivalent Se(6) atoms. There are two inequivalent Ag sites. In the first Ag site, Ag(1) is bonded in a 3-coordinate geometry to one Se(1), one Se(5), and two equivalent Se(4) atoms. In the second Ag site, Ag(2) is bonded in a 3-coordinate geometry to one Se(1), one Se(4), one Se(5), and one Se(6) atom. There are three inequivalent As sites. In the first As site, As(1) is bonded in a distorted trigonal non-coplanar geometry to one Rb(1), one Se(2), one Se(5), and one Se(6) atom. In the second As site, As(2) is bonded in a distorted trigonal non-coplanar geometry to one Rb(1), one Se(1), one Se(2), and one Se(3) atom. In the third As site, As(3) is bonded in a distorted trigonal non-coplanar geometry to one Rb(1), one Se(3), one Se(4), and one Se(6) atom. There are six inequivalent Se sites. In the first Se site, Se(6) is bonded in a 5-coordinate geometry to two equivalent Rb(1), one Ag(2), one As(1), and one As(3) atom. In the second Se site, Se(1) is bonded to one Rb(1), one Ag(1), one Ag(2), and one As(2) atom to form a mixture of distorted edge and corner-sharing SeRbAg2As tetrahedra. In the third Se site, Se(2) is bonded to two equivalent Rb(1), one As(1), and one As(2) atom to form distorted SeRb2As2 trigonal pyramids that share corners with three equivalent Se(1)RbAg2As tetrahedra, corners with two equivalent Se(2)Rb2As2 trigonal pyramids, corners with three equivalent Se(3)Rb2As2 trigonal pyramids, and  an edgeedge with one Se(3)Rb2As2 trigonal pyramid. In the fourth Se site, Se(3) is bonded to two equivalent Rb(1), one As(2), and one As(3) atom to form distorted SeRb2As2 trigonal pyramids that share  a cornercorner with one Se(1)RbAg2As tetrahedra, corners with two equivalent Se(3)Rb2As2 trigonal pyramids, corners with three equivalent Se(2)Rb2As2 trigonal pyramids,  an edgeedge with one Se(1)RbAg2As tetrahedra, and  an edgeedge with one Se(2)Rb2As2 trigonal pyramid. In the fifth Se site, Se(4) is bonded in a 5-coordinate geometry to one Rb(1), one Ag(2), two equivalent Ag(1), and one As(3) atom. In the sixth Se site, Se(5) is bonded in a distorted rectangular see-saw-like geometry to one Rb(1), one Ag(1), one Ag(2), and one As(1) atom.
RbAg2(AsSe2)3 crystallizes in the monoclinic P2_1/c space group. Rb(1) is bonded in a 12-coordinate geometry to one As(1), one As(2), one As(3), one Se(1), one Se(4), one Se(5), two equivalent Se(2), two equivalent Se(3), and two equivalent Se(6) atoms. The Rb(1)-As(1) bond length is 4.12 Å. The Rb(1)-As(2) bond length is 4.04 Å. The Rb(1)-As(3) bond length is 3.98 Å. The Rb(1)-Se(1) bond length is 3.71 Å. The Rb(1)-Se(4) bond length is 3.94 Å. The Rb(1)-Se(5) bond length is 3.79 Å. There is one shorter (3.58 Å) and one longer (3.94 Å) Rb(1)-Se(2) bond length. There is one shorter (3.86 Å) and one longer (3.88 Å) Rb(1)-Se(3) bond length. There is one shorter (3.64 Å) and one longer (3.83 Å) Rb(1)-Se(6) bond length. There are two inequivalent Ag sites. In the first Ag site, Ag(1) is bonded in a 3-coordinate geometry to one Se(1), one Se(5), and two equivalent Se(4) atoms. The Ag(1)-Se(1) bond length is 2.59 Å. The Ag(1)-Se(5) bond length is 2.57 Å. There is one shorter (2.83 Å) and one longer (3.24 Å) Ag(1)-Se(4) bond length. In the second Ag site, Ag(2) is bonded in a 3-coordinate geometry to one Se(1), one Se(4), one Se(5), and one Se(6) atom. The Ag(2)-Se(1) bond length is 2.60 Å. The Ag(2)-Se(4) bond length is 2.57 Å. The Ag(2)-Se(5) bond length is 2.72 Å. The Ag(2)-Se(6) bond length is 3.38 Å. There are three inequivalent As sites. In the first As site, As(1) is bonded in a distorted trigonal non-coplanar geometry to one Rb(1), one Se(2), one Se(5), and one Se(6) atom. The As(1)-Se(2) bond length is 2.45 Å. The As(1)-Se(5) bond length is 2.35 Å. The As(1)-Se(6) bond length is 2.43 Å. In the second As site, As(2) is bonded in a distorted trigonal non-coplanar geometry to one Rb(1), one Se(1), one Se(2), and one Se(3) atom. The As(2)-Se(1) bond length is 2.37 Å. The As(2)-Se(2) bond length is 2.42 Å. The As(2)-Se(3) bond length is 2.44 Å. In the third As site, As(3) is bonded in a distorted trigonal non-coplanar geometry to one Rb(1), one Se(3), one Se(4), and one Se(6) atom. The As(3)-Se(3) bond length is 2.43 Å. The As(3)-Se(4) bond length is 2.36 Å. The As(3)-Se(6) bond length is 2.45 Å. There are six inequivalent Se sites. In the first Se site, Se(6) is bonded in a 5-coordinate geometry to two equivalent Rb(1), one Ag(2), one As(1), and one As(3) atom. In the second Se site, Se(1) is bonded to one Rb(1), one Ag(1), one Ag(2), and one As(2) atom to form a mixture of distorted edge and corner-sharing SeRbAg2As tetrahedra. In the third Se site, Se(2) is bonded to two equivalent Rb(1), one As(1), and one As(2) atom to form distorted SeRb2As2 trigonal pyramids that share corners with three equivalent Se(1)RbAg2As tetrahedra, corners with two equivalent Se(2)Rb2As2 trigonal pyramids, corners with three equivalent Se(3)Rb2As2 trigonal pyramids, and  an edgeedge with one Se(3)Rb2As2 trigonal pyramid. In the fourth Se site, Se(3) is bonded to two equivalent Rb(1), one As(2), and one As(3) atom to form distorted SeRb2As2 trigonal pyramids that share  a cornercorner with one Se(1)RbAg2As tetrahedra, corners with two equivalent Se(3)Rb2As2 trigonal pyramids, corners with three equivalent Se(2)Rb2As2 trigonal pyramids,  an edgeedge with one Se(1)RbAg2As tetrahedra, and  an edgeedge with one Se(2)Rb2As2 trigonal pyramid. In the fifth Se site, Se(4) is bonded in a 5-coordinate geometry to one Rb(1), one Ag(2), two equivalent Ag(1), and one As(3) atom. In the sixth Se site, Se(5) is bonded in a distorted rectangular see-saw-like geometry to one Rb(1), one Ag(1), one Ag(2), and one As(1) atom.