Re4As6S3 crystallizes in the trigonal R3m space group. There are two inequivalent Re sites. In the first Re site, Re(1) is bonded in a 6-coordinate geometry to three equivalent As(3) and three equivalent S(1) atoms. In the second Re site, Re(2) is bonded in a 6-coordinate geometry to one As(2), one As(4), two equivalent As(3), and two equivalent S(1) atoms. There are four inequivalent As sites. In the first As site, As(1) is bonded in a tetrahedral geometry to one As(2) and three equivalent As(3) atoms. In the second As site, As(2) is bonded to three equivalent Re(2) and one As(1) atom to form a mixture of distorted corner and edge-sharing AsRe3As tetrahedra. In the third As site, As(3) is bonded to one Re(1), two equivalent Re(2), and one As(1) atom to form a mixture of distorted corner and edge-sharing AsRe3As tetrahedra. In the fourth As site, As(4) is bonded in a 3-coordinate geometry to three equivalent Re(2) atoms. S(1) is bonded in a 3-coordinate geometry to one Re(1) and two equivalent Re(2) atoms.
Re4As6S3 crystallizes in the trigonal R3m space group. There are two inequivalent Re sites. In the first Re site, Re(1) is bonded in a 6-coordinate geometry to three equivalent As(3) and three equivalent S(1) atoms. All Re(1)-As(3) bond lengths are 2.64 Å. All Re(1)-S(1) bond lengths are 2.34 Å. In the second Re site, Re(2) is bonded in a 6-coordinate geometry to one As(2), one As(4), two equivalent As(3), and two equivalent S(1) atoms. The Re(2)-As(2) bond length is 2.62 Å. The Re(2)-As(4) bond length is 2.47 Å. Both Re(2)-As(3) bond lengths are 2.64 Å. Both Re(2)-S(1) bond lengths are 2.32 Å. There are four inequivalent As sites. In the first As site, As(1) is bonded in a tetrahedral geometry to one As(2) and three equivalent As(3) atoms. The As(1)-As(2) bond length is 2.45 Å. All As(1)-As(3) bond lengths are 2.46 Å. In the second As site, As(2) is bonded to three equivalent Re(2) and one As(1) atom to form a mixture of distorted corner and edge-sharing AsRe3As tetrahedra. In the third As site, As(3) is bonded to one Re(1), two equivalent Re(2), and one As(1) atom to form a mixture of distorted corner and edge-sharing AsRe3As tetrahedra. In the fourth As site, As(4) is bonded in a 3-coordinate geometry to three equivalent Re(2) atoms. S(1) is bonded in a 3-coordinate geometry to one Re(1) and two equivalent Re(2) atoms.