CdGa4As4S is Stannite-like structured and crystallizes in the trigonal R3m space group. Cd(1) is bonded to one As(1) and three equivalent S(1) atoms to form CdAsS3 tetrahedra that share corners with three equivalent Ga(4)As3S tetrahedra, corners with three equivalent Ga(1)As4 tetrahedra, and corners with six equivalent Cd(1)AsS3 tetrahedra. There are four inequivalent Ga sites. In the first Ga site, Ga(1) is bonded to one As(2) and three equivalent As(1) atoms to form GaAs4 tetrahedra that share corners with three equivalent Cd(1)AsS3 tetrahedra, corners with three equivalent Ga(2)As4 tetrahedra, and corners with six equivalent Ga(1)As4 tetrahedra. In the second Ga site, Ga(2) is bonded to one As(3) and three equivalent As(2) atoms to form corner-sharing GaAs4 tetrahedra. In the third Ga site, Ga(3) is bonded to one As(4) and three equivalent As(3) atoms to form GaAs4 tetrahedra that share corners with three equivalent Ga(4)As3S tetrahedra, corners with three equivalent Ga(2)As4 tetrahedra, and corners with six equivalent Ga(3)As4 tetrahedra. In the fourth Ga site, Ga(4) is bonded to three equivalent As(4) and one S(1) atom to form GaAs3S tetrahedra that share corners with three equivalent Cd(1)AsS3 tetrahedra, corners with three equivalent Ga(3)As4 tetrahedra, and corners with six equivalent Ga(4)As3S tetrahedra. There are four inequivalent As sites. In the first As site, As(1) is bonded to one Cd(1) and three equivalent Ga(1) atoms to form AsCdGa3 tetrahedra that share corners with three equivalent As(2)Ga4 tetrahedra, corners with three equivalent S(1)Cd3Ga tetrahedra, and corners with six equivalent As(1)CdGa3 tetrahedra. In the second As site, As(2) is bonded to one Ga(1) and three equivalent Ga(2) atoms to form AsGa4 tetrahedra that share corners with three equivalent As(1)CdGa3 tetrahedra, corners with three equivalent As(3)Ga4 tetrahedra, and corners with six equivalent As(2)Ga4 tetrahedra. In the third As site, As(3) is bonded to one Ga(2) and three equivalent Ga(3) atoms to form corner-sharing AsGa4 tetrahedra. In the fourth As site, As(4) is bonded to one Ga(3) and three equivalent Ga(4) atoms to form AsGa4 tetrahedra that share corners with three equivalent As(3)Ga4 tetrahedra, corners with three equivalent S(1)Cd3Ga tetrahedra, and corners with six equivalent As(4)Ga4 tetrahedra. S(1) is bonded to three equivalent Cd(1) and one Ga(4) atom to form SCd3Ga tetrahedra that share corners with three equivalent As(1)CdGa3 tetrahedra, corners with three equivalent As(4)Ga4 tetrahedra, and corners with six equivalent S(1)Cd3Ga tetrahedra.
CdGa4As4S is Stannite-like structured and crystallizes in the trigonal R3m space group. Cd(1) is bonded to one As(1) and three equivalent S(1) atoms to form CdAsS3 tetrahedra that share corners with three equivalent Ga(4)As3S tetrahedra, corners with three equivalent Ga(1)As4 tetrahedra, and corners with six equivalent Cd(1)AsS3 tetrahedra. The Cd(1)-As(1) bond length is 2.61 Å. All Cd(1)-S(1) bond lengths are 2.59 Å. There are four inequivalent Ga sites. In the first Ga site, Ga(1) is bonded to one As(2) and three equivalent As(1) atoms to form GaAs4 tetrahedra that share corners with three equivalent Cd(1)AsS3 tetrahedra, corners with three equivalent Ga(2)As4 tetrahedra, and corners with six equivalent Ga(1)As4 tetrahedra. The Ga(1)-As(2) bond length is 2.49 Å. All Ga(1)-As(1) bond lengths are 2.49 Å. In the second Ga site, Ga(2) is bonded to one As(3) and three equivalent As(2) atoms to form corner-sharing GaAs4 tetrahedra. The Ga(2)-As(3) bond length is 2.50 Å. All Ga(2)-As(2) bond lengths are 2.50 Å. In the third Ga site, Ga(3) is bonded to one As(4) and three equivalent As(3) atoms to form GaAs4 tetrahedra that share corners with three equivalent Ga(4)As3S tetrahedra, corners with three equivalent Ga(2)As4 tetrahedra, and corners with six equivalent Ga(3)As4 tetrahedra. The Ga(3)-As(4) bond length is 2.50 Å. All Ga(3)-As(3) bond lengths are 2.50 Å. In the fourth Ga site, Ga(4) is bonded to three equivalent As(4) and one S(1) atom to form GaAs3S tetrahedra that share corners with three equivalent Cd(1)AsS3 tetrahedra, corners with three equivalent Ga(3)As4 tetrahedra, and corners with six equivalent Ga(4)As3S tetrahedra. All Ga(4)-As(4) bond lengths are 2.49 Å. The Ga(4)-S(1) bond length is 2.33 Å. There are four inequivalent As sites. In the first As site, As(1) is bonded to one Cd(1) and three equivalent Ga(1) atoms to form AsCdGa3 tetrahedra that share corners with three equivalent As(2)Ga4 tetrahedra, corners with three equivalent S(1)Cd3Ga tetrahedra, and corners with six equivalent As(1)CdGa3 tetrahedra. In the second As site, As(2) is bonded to one Ga(1) and three equivalent Ga(2) atoms to form AsGa4 tetrahedra that share corners with three equivalent As(1)CdGa3 tetrahedra, corners with three equivalent As(3)Ga4 tetrahedra, and corners with six equivalent As(2)Ga4 tetrahedra. In the third As site, As(3) is bonded to one Ga(2) and three equivalent Ga(3) atoms to form corner-sharing AsGa4 tetrahedra. In the fourth As site, As(4) is bonded to one Ga(3) and three equivalent Ga(4) atoms to form AsGa4 tetrahedra that share corners with three equivalent As(3)Ga4 tetrahedra, corners with three equivalent S(1)Cd3Ga tetrahedra, and corners with six equivalent As(4)Ga4 tetrahedra. S(1) is bonded to three equivalent Cd(1) and one Ga(4) atom to form SCd3Ga tetrahedra that share corners with three equivalent As(1)CdGa3 tetrahedra, corners with three equivalent As(4)Ga4 tetrahedra, and corners with six equivalent S(1)Cd3Ga tetrahedra.