Ni4As3S5 is Spinel-like structured and crystallizes in the trigonal R3 space group. There are two inequivalent Ni sites. In the first Ni site, Ni(1) is bonded to three equivalent As(1) and three equivalent S(2) atoms to form NiAs3S3 octahedra that share corners with twelve equivalent Ni(2)As2S4 octahedra, corners with three equivalent As(1)Ni3S tetrahedra, and corners with three equivalent S(2)Ni3As tetrahedra. The corner-sharing octahedral tilt angles range from 63-65°. In the second Ni site, Ni(2) is bonded to two equivalent As(1), one S(1), one S(3), and two equivalent S(2) atoms to form NiAs2S4 octahedra that share corners with four equivalent Ni(1)As3S3 octahedra, corners with eight equivalent Ni(2)As2S4 octahedra,  a cornercorner with one S(1)Ni3S tetrahedra,  a cornercorner with one S(3)Ni3S tetrahedra, corners with two equivalent As(1)Ni3S tetrahedra, and corners with two equivalent S(2)Ni3As tetrahedra. The corner-sharing octahedral tilt angles range from 63-66°. As(1) is bonded to one Ni(1), two equivalent Ni(2), and one S(2) atom to form AsNi3S tetrahedra that share  a cornercorner with one Ni(1)As3S3 octahedra, corners with two equivalent Ni(2)As2S4 octahedra, corners with two equivalent S(1)Ni3S tetrahedra, corners with two equivalent S(3)Ni3S tetrahedra, corners with four equivalent As(1)Ni3S tetrahedra, and corners with seven equivalent S(2)Ni3As tetrahedra. The corner-sharing octahedral tilt angles are 78°. There are three inequivalent S sites. In the first S site, S(1) is bonded to three equivalent Ni(2) and one S(3) atom to form distorted SNi3S tetrahedra that share corners with three equivalent Ni(2)As2S4 octahedra, corners with three equivalent S(3)Ni3S tetrahedra, corners with six equivalent As(1)Ni3S tetrahedra, and corners with six equivalent S(2)Ni3As tetrahedra. The corner-sharing octahedral tilt angles are 76°. In the second S site, S(2) is bonded to one Ni(1), two equivalent Ni(2), and one As(1) atom to form SNi3As tetrahedra that share  a cornercorner with one Ni(1)As3S3 octahedra, corners with two equivalent Ni(2)As2S4 octahedra, corners with two equivalent S(1)Ni3S tetrahedra, corners with two equivalent S(3)Ni3S tetrahedra, corners with four equivalent S(2)Ni3As tetrahedra, and corners with seven equivalent As(1)Ni3S tetrahedra. The corner-sharing octahedral tilt angles range from 77-80°. In the third S site, S(3) is bonded to three equivalent Ni(2) and one S(1) atom to form distorted SNi3S tetrahedra that share corners with three equivalent Ni(2)As2S4 octahedra, corners with three equivalent S(1)Ni3S tetrahedra, corners with six equivalent As(1)Ni3S tetrahedra, and corners with six equivalent S(2)Ni3As tetrahedra. The corner-sharing octahedral tilt angles are 76°.
Ni4As3S5 is Spinel-like structured and crystallizes in the trigonal R3 space group. There are two inequivalent Ni sites. In the first Ni site, Ni(1) is bonded to three equivalent As(1) and three equivalent S(2) atoms to form NiAs3S3 octahedra that share corners with twelve equivalent Ni(2)As2S4 octahedra, corners with three equivalent As(1)Ni3S tetrahedra, and corners with three equivalent S(2)Ni3As tetrahedra. The corner-sharing octahedral tilt angles range from 63-65°. All Ni(1)-As(1) bond lengths are 2.39 Å. All Ni(1)-S(2) bond lengths are 2.33 Å. In the second Ni site, Ni(2) is bonded to two equivalent As(1), one S(1), one S(3), and two equivalent S(2) atoms to form NiAs2S4 octahedra that share corners with four equivalent Ni(1)As3S3 octahedra, corners with eight equivalent Ni(2)As2S4 octahedra,  a cornercorner with one S(1)Ni3S tetrahedra,  a cornercorner with one S(3)Ni3S tetrahedra, corners with two equivalent As(1)Ni3S tetrahedra, and corners with two equivalent S(2)Ni3As tetrahedra. The corner-sharing octahedral tilt angles range from 63-66°. There is one shorter (2.39 Å) and one longer (2.41 Å) Ni(2)-As(1) bond length. The Ni(2)-S(1) bond length is 2.41 Å. The Ni(2)-S(3) bond length is 2.40 Å. There is one shorter (2.31 Å) and one longer (2.35 Å) Ni(2)-S(2) bond length. As(1) is bonded to one Ni(1), two equivalent Ni(2), and one S(2) atom to form AsNi3S tetrahedra that share  a cornercorner with one Ni(1)As3S3 octahedra, corners with two equivalent Ni(2)As2S4 octahedra, corners with two equivalent S(1)Ni3S tetrahedra, corners with two equivalent S(3)Ni3S tetrahedra, corners with four equivalent As(1)Ni3S tetrahedra, and corners with seven equivalent S(2)Ni3As tetrahedra. The corner-sharing octahedral tilt angles are 78°. The As(1)-S(2) bond length is 2.31 Å. There are three inequivalent S sites. In the first S site, S(1) is bonded to three equivalent Ni(2) and one S(3) atom to form distorted SNi3S tetrahedra that share corners with three equivalent Ni(2)As2S4 octahedra, corners with three equivalent S(3)Ni3S tetrahedra, corners with six equivalent As(1)Ni3S tetrahedra, and corners with six equivalent S(2)Ni3As tetrahedra. The corner-sharing octahedral tilt angles are 76°. The S(1)-S(3) bond length is 2.08 Å. In the second S site, S(2) is bonded to one Ni(1), two equivalent Ni(2), and one As(1) atom to form SNi3As tetrahedra that share  a cornercorner with one Ni(1)As3S3 octahedra, corners with two equivalent Ni(2)As2S4 octahedra, corners with two equivalent S(1)Ni3S tetrahedra, corners with two equivalent S(3)Ni3S tetrahedra, corners with four equivalent S(2)Ni3As tetrahedra, and corners with seven equivalent As(1)Ni3S tetrahedra. The corner-sharing octahedral tilt angles range from 77-80°. In the third S site, S(3) is bonded to three equivalent Ni(2) and one S(1) atom to form distorted SNi3S tetrahedra that share corners with three equivalent Ni(2)As2S4 octahedra, corners with three equivalent S(1)Ni3S tetrahedra, corners with six equivalent As(1)Ni3S tetrahedra, and corners with six equivalent S(2)Ni3As tetrahedra. The corner-sharing octahedral tilt angles are 76°.