Solvothermal Synthesis and Crystal Structure of Mn 2 (C 5 H 14 N 2 )Sb 2 S 5 : A New Member of the Mn 2 (L)Sb 2 S 5 Family (L is an Organic Structure Director)

The new compound Mn 2 (C 5 H 14 N 2 )Sb 2 S 5 (C 5 H 14 N 2 = 1,3‐diaminopentane, DAPE) was prepared under solvothermal conditions using the elements as starting materials. The compound crystallizes in the orthorhombic space group Pbca with the lattice parameters a = 12.620(3), b = 11.877(2) and c = 21.814(4) Å. The primary building units are trigonal SbS 3 pyramids and distorted MnS 6 and MnS 4 N 2 octahedra. These primary building blocks are joined to form Mn 2 Sb 2 S 4 hetero‐cubane units which are then connected via common corners, edges and faces thus forming a second type of hetero‐cubane. The hetero‐cubanes are condensed into layers within the (001) plane. The connection mode yields ellipsoidal pores within the layers with dimensions of about 9·7.5Å. The N atoms of the structure directing amines are exclusively bound to one of the two crystallographically independent Mn 2+ cations and they point into the pores and between the layers separating the layers from each other. The interlayer separation measures about 6.7Å. Whereas the MnS 6 octahedron shows only a moderate distortion the MnS 4 N 2 octahedron is severely distorted with a remarkable long Mn‐S bond length of 2.968Å.