Ca3GaAs3 crystallizes in the orthorhombic Pnma space group. There are three inequivalent Ca sites. In the first Ca site, Ca(1) is bonded in a 7-coordinate geometry to two equivalent Ga(1), one As(3), two equivalent As(1), and two equivalent As(2) atoms. In the second Ca site, Ca(2) is bonded to one As(3), two equivalent As(2), and three equivalent As(1) atoms to form a mixture of distorted edge, face, and corner-sharing CaAs6 octahedra. The corner-sharing octahedral tilt angles range from 41-54°. In the third Ca site, Ca(3) is bonded to one As(1), two equivalent As(2), and three equivalent As(3) atoms to form a mixture of distorted edge, face, and corner-sharing CaAs6 octahedra. The corner-sharing octahedral tilt angles range from 41-54°. Ga(1) is bonded in a 6-coordinate geometry to two equivalent Ca(1), one As(1), one As(2), and two equivalent As(3) atoms. There are three inequivalent As sites. In the first As site, As(1) is bonded to one Ca(3), two equivalent Ca(1), three equivalent Ca(2), and one Ga(1) atom to form a mixture of distorted edge, face, and corner-sharing AsCa6Ga pentagonal bipyramids. In the second As site, As(2) is bonded to two equivalent Ca(1), two equivalent Ca(2), two equivalent Ca(3), and one Ga(1) atom to form a mixture of distorted edge, face, and corner-sharing AsCa6Ga pentagonal bipyramids. In the third As site, As(3) is bonded in a 7-coordinate geometry to one Ca(1), one Ca(2), three equivalent Ca(3), and two equivalent Ga(1) atoms.
Ca3GaAs3 crystallizes in the orthorhombic Pnma space group. There are three inequivalent Ca sites. In the first Ca site, Ca(1) is bonded in a 7-coordinate geometry to two equivalent Ga(1), one As(3), two equivalent As(1), and two equivalent As(2) atoms. Both Ca(1)-Ga(1) bond lengths are 3.10 Å. The Ca(1)-As(3) bond length is 2.96 Å. Both Ca(1)-As(1) bond lengths are 2.91 Å. Both Ca(1)-As(2) bond lengths are 3.03 Å. In the second Ca site, Ca(2) is bonded to one As(3), two equivalent As(2), and three equivalent As(1) atoms to form a mixture of distorted edge, face, and corner-sharing CaAs6 octahedra. The corner-sharing octahedral tilt angles range from 41-54°. The Ca(2)-As(3) bond length is 3.26 Å. Both Ca(2)-As(2) bond lengths are 3.11 Å. There are two shorter (2.96 Å) and one longer (3.04 Å) Ca(2)-As(1) bond length. In the third Ca site, Ca(3) is bonded to one As(1), two equivalent As(2), and three equivalent As(3) atoms to form a mixture of distorted edge, face, and corner-sharing CaAs6 octahedra. The corner-sharing octahedral tilt angles range from 41-54°. The Ca(3)-As(1) bond length is 3.35 Å. Both Ca(3)-As(2) bond lengths are 2.95 Å. There is one shorter (3.08 Å) and two longer (3.18 Å) Ca(3)-As(3) bond lengths. Ga(1) is bonded in a 6-coordinate geometry to two equivalent Ca(1), one As(1), one As(2), and two equivalent As(3) atoms. The Ga(1)-As(1) bond length is 2.53 Å. The Ga(1)-As(2) bond length is 2.51 Å. Both Ga(1)-As(3) bond lengths are 2.56 Å. There are three inequivalent As sites. In the first As site, As(1) is bonded to one Ca(3), two equivalent Ca(1), three equivalent Ca(2), and one Ga(1) atom to form a mixture of distorted edge, face, and corner-sharing AsCa6Ga pentagonal bipyramids. In the second As site, As(2) is bonded to two equivalent Ca(1), two equivalent Ca(2), two equivalent Ca(3), and one Ga(1) atom to form a mixture of distorted edge, face, and corner-sharing AsCa6Ga pentagonal bipyramids. In the third As site, As(3) is bonded in a 7-coordinate geometry to one Ca(1), one Ca(2), three equivalent Ca(3), and two equivalent Ga(1) atoms.