Cs5SiAs3 crystallizes in the orthorhombic Pnma space group. There are five inequivalent Cs sites. In the first Cs site, Cs(1) is bonded in a 5-coordinate geometry to two equivalent As(3) and three equivalent As(1) atoms. In the second Cs site, Cs(2) is bonded in a 3-coordinate geometry to one As(3), two equivalent As(1), and two equivalent As(2) atoms. In the third Cs site, Cs(3) is bonded in a 3-coordinate geometry to one As(3) and two equivalent As(2) atoms. In the fourth Cs site, Cs(4) is bonded in a 4-coordinate geometry to one As(3) and three equivalent As(1) atoms. In the fifth Cs site, Cs(5) is bonded in a 4-coordinate geometry to one As(1), one As(2), and two equivalent As(3) atoms. Si(1) is bonded in a trigonal planar geometry to one As(1), one As(2), and one As(3) atom. There are three inequivalent As sites. In the first As site, As(1) is bonded in a 10-coordinate geometry to one Cs(5), two equivalent Cs(2), three equivalent Cs(1), three equivalent Cs(4), and one Si(1) atom. In the second As site, As(2) is bonded in a 1-coordinate geometry to one Cs(5), two equivalent Cs(2), two equivalent Cs(3), and one Si(1) atom. In the third As site, As(3) is bonded in a 1-coordinate geometry to one Cs(2), one Cs(3), one Cs(4), two equivalent Cs(1), two equivalent Cs(5), and one Si(1) atom.
Cs5SiAs3 crystallizes in the orthorhombic Pnma space group. There are five inequivalent Cs sites. In the first Cs site, Cs(1) is bonded in a 5-coordinate geometry to two equivalent As(3) and three equivalent As(1) atoms. Both Cs(1)-As(3) bond lengths are 3.87 Å. There is one shorter (3.70 Å) and two longer (3.78 Å) Cs(1)-As(1) bond lengths. In the second Cs site, Cs(2) is bonded in a 3-coordinate geometry to one As(3), two equivalent As(1), and two equivalent As(2) atoms. The Cs(2)-As(3) bond length is 3.63 Å. Both Cs(2)-As(1) bond lengths are 3.97 Å. Both Cs(2)-As(2) bond lengths are 3.71 Å. In the third Cs site, Cs(3) is bonded in a 3-coordinate geometry to one As(3) and two equivalent As(2) atoms. The Cs(3)-As(3) bond length is 3.77 Å. Both Cs(3)-As(2) bond lengths are 3.80 Å. In the fourth Cs site, Cs(4) is bonded in a 4-coordinate geometry to one As(3) and three equivalent As(1) atoms. The Cs(4)-As(3) bond length is 3.98 Å. There are two shorter (3.93 Å) and one longer (3.95 Å) Cs(4)-As(1) bond length. In the fifth Cs site, Cs(5) is bonded in a 4-coordinate geometry to one As(1), one As(2), and two equivalent As(3) atoms. The Cs(5)-As(1) bond length is 3.63 Å. The Cs(5)-As(2) bond length is 3.74 Å. Both Cs(5)-As(3) bond lengths are 3.72 Å. Si(1) is bonded in a trigonal planar geometry to one As(1), one As(2), and one As(3) atom. The Si(1)-As(1) bond length is 2.30 Å. The Si(1)-As(2) bond length is 2.31 Å. The Si(1)-As(3) bond length is 2.29 Å. There are three inequivalent As sites. In the first As site, As(1) is bonded in a 10-coordinate geometry to one Cs(5), two equivalent Cs(2), three equivalent Cs(1), three equivalent Cs(4), and one Si(1) atom. In the second As site, As(2) is bonded in a 1-coordinate geometry to one Cs(5), two equivalent Cs(2), two equivalent Cs(3), and one Si(1) atom. In the third As site, As(3) is bonded in a 1-coordinate geometry to one Cs(2), one Cs(3), one Cs(4), two equivalent Cs(1), two equivalent Cs(5), and one Si(1) atom.