KC4N3H6S crystallizes in the monoclinic C2/c space group. K(1) is bonded to one N(1), one N(2), one N(3), and three equivalent S(1) atoms to form distorted KS3N3 octahedra that share corners with two equivalent K(1)S3N3 octahedra,  a cornercorner with one C(4)H2N2 tetrahedra,  a cornercorner with one C(5)H2N2 tetrahedra, corners with two equivalent C(2)H2N2 tetrahedra, corners with two equivalent C(3)H2N2 tetrahedra, and edges with two equivalent K(1)S3N3 octahedra. The corner-sharing octahedral tilt angles are 14°. The K(1)-N(1) bond length is 2.74 Å. The K(1)-N(2) bond length is 2.86 Å. The K(1)-N(3) bond length is 2.89 Å. There is one shorter (3.28 Å) and two longer (3.30 Å) K(1)-S(1) bond lengths. There are five inequivalent C sites. In the first C site, C(3) is bonded to one N(2), one N(3), one H(3), and one H(4) atom to form CH2N2 tetrahedra that share corners with two equivalent K(1)S3N3 octahedra,  a cornercorner with one C(4)H2N2 tetrahedra,  a cornercorner with one C(5)H2N2 tetrahedra, and corners with two equivalent C(2)H2N2 tetrahedra. The corner-sharing octahedral tilt angles range from 64-65°. The C(3)-N(2) bond length is 1.48 Å. The C(3)-N(3) bond length is 1.48 Å. The C(3)-H(3) bond length is 1.10 Å. The C(3)-H(4) bond length is 1.10 Å. In the second C site, C(4) is bonded to two equivalent N(2) and two equivalent H(5) atoms to form CH2N2 tetrahedra that share corners with two equivalent K(1)S3N3 octahedra, corners with two equivalent C(2)H2N2 tetrahedra, and corners with two equivalent C(3)H2N2 tetrahedra. The corner-sharing octahedral tilt angles are 65°. Both C(4)-N(2) bond lengths are 1.48 Å. Both C(4)-H(5) bond lengths are 1.10 Å. In the third C site, C(5) is bonded to two equivalent N(3) and two equivalent H(6) atoms to form CH2N2 tetrahedra that share corners with two equivalent K(1)S3N3 octahedra, corners with two equivalent C(2)H2N2 tetrahedra, and corners with two equivalent C(3)H2N2 tetrahedra. The corner-sharing octahedral tilt angles are 65°. Both C(5)-N(3) bond lengths are 1.48 Å. Both C(5)-H(6) bond lengths are 1.10 Å. In the fourth C site, C(2) is bonded to one N(2); one N(3); and two equivalent H(1,2) atoms to form CH2N2 tetrahedra that share corners with two equivalent K(1)S3N3 octahedra,  a cornercorner with one C(4)H2N2 tetrahedra,  a cornercorner with one C(5)H2N2 tetrahedra, and corners with two equivalent C(3)H2N2 tetrahedra. The corner-sharing octahedral tilt angles range from 78-79°. The C(2)-N(2) bond length is 1.48 Å. The C(2)-N(3) bond length is 1.48 Å. Both C(2)-H(1,2) bond lengths are 1.10 Å. In the fifth C site, C(1) is bonded in a distorted single-bond geometry to one N(1) and one S(1) atom. The C(1)-N(1) bond length is 1.19 Å. The C(1)-S(1) bond length is 1.64 Å. There are three inequivalent N sites. In the first N site, N(1) is bonded in a distorted single-bond geometry to one K(1) and one C(1) atom. In the second N site, N(2) is bonded in a distorted trigonal non-coplanar geometry to one K(1), one C(2), one C(3), and one C(4) atom. In the third N site, N(3) is bonded in a distorted trigonal non-coplanar geometry to one K(1), one C(2), one C(3), and one C(5) atom. There are five inequivalent H sites. In the first H site, H(1,2) is bonded in a single-bond geometry to one C(2) atom. In the second H site, H(3) is bonded in a single-bond geometry to one C(3) atom. In the third H site, H(4) is bonded in a single-bond geometry to one C(3) atom. In the fourth H site, H(5) is bonded in a single-bond geometry to one C(4) atom. In the fifth H site, H(6) is bonded in a single-bond geometry to one C(5) atom. S(1) is bonded in a distorted see-saw-like geometry to three equivalent K(1) and one C(1) atom. Linkers: 2 C1N2CN3CN1CN(C2)C3. Metal clusters: 4 [K]. The MOF has largest included sphere 1.89 A, density 1.60 g/cm3, surface area 2461.71 m2/g, accessible volume 0.06 cm3/g