Solvothermal Syntheses, Crystal Structures of Two New Thioantimonates(III) of the Mn₂(L)Sb₂S₅ Family with L = Diethylenetriamine and N-Methyl-1,3-Diaminopropane and a Study of the Magnetic Properties of Four Compounds of the Series

Abstract

The two new compounds Mn2(L)Sb2S5 (L = diethylenetriamine = DIEN, N-methyl-1,3- diaminopropane = MDAP) were prepared under solvothermal conditions using the elements as starting materials. Both compounds crystallise in the monoclinic space group P21/c with the lattice parameters a=10.669(7), b=12.805(2), c=12.072(1)Å , β =115.786(7)°,V =1485.1(4) Å3 for L = DIEN and a = 10.1859(7), b = 12.7806(6), c = 12.1256(8)Å , β = 110.173(8)°, V = 1481.7(2) Å3 for L = MDAP and Z = 4. The primary building units are SbS3 pyramids, MnS6 and MnS4N2 distorted octahedra. These primary building blocks are interconnected to form Mn2Sb2S4 hetero-cubane units. The hetero-cubanes share common corners, edges and faces thus forming a second heterocubane. These secondary building units are joined to form layers within the (100) plane. The connection mode yields ellipsoidal pores within the layers. The amines are exclusively bound to one of the two crystallographically independent Mn2+ cations and they point into the pores and between the layers separating the layers from each other. The interlayer separation and the size of the pores depend on the sterical requirements of the amine incorporated into the network. A pronounced distortion of the MnS4N2 octahedron results from a significant elongation of one Mn-S distance from 2.866 Å (L = methylamine, MA) to 3.185 Å for L = MDAP. The magnetic susceptibility curves are typical for low-dimensional antiferromagnetic materials and the large negative values for the Weiss constant Θ indicate strong antiferromagnetic exchange interactions. The magnetic properties are significantly influenced by the change of the Mn-S bonds introduced by the different amines. The compounds decompose at elevated temperatures with a two step reaction for L = MA and ethylenediamine and in a one step reaction for the bidentate acting amine molecules.

Synthesis, structure, and properties of a new manganese thioantimonate(III),

“…1, each Sb atom is coordinated to three S in a trigonal pyramid geometry. The Sb-S bond distances are in the range of 2.4070(8) (Sb(1)-S(2)) to 2.5364(8) (Sb(1)-S(3)) Å, being comparable to those found in other Mn 2 (L)Sb 2 S 5 compounds [22][23][24][25]. The Mn1 atom is chelated by one phen and coordinated by four sulfur atoms with Mn-N bond distances of 2.246(2) and 2.257(2) Å.…”

“…The Mn1 atom is chelated by one phen and coordinated by four sulfur atoms with Mn-N bond distances of 2.246(2) and 2.257(2) Å. The Mn-S bond distances are in the range 2.5510(9) (Mn(1)-S(1)) to 2.6239(9) (Mn(1)-S(5A)) Å, whereas the Mn2 atom is coordinated by six S atoms with the Mn-S bond distances spreading from 2.5422(10) (Mn(2)-S(5)) to 2.7115(9) (Mn(2)-S(4)) Å, which are the typical distances of Mn-N and Mn-S [22][23][24][25]. Obviously, the MnS 4 N 2 octahedron is severely distorted with axial angles ranging from 161.47(6)°to 177.69(7)°, however, those of MnS 6 octahedra are in the range from 175.71(3)°to 177.55(2)°.…”

Solvothermal Synthesis, Crystal Structure, and Thermal Stability of Three‐Layered Thioantimonate(III) Complexes: [Ni(C3H10N2)3]Sb4S7, [C4H14N2]Sb8S13·H2O, and [C6H18N2]Sb10S16·H2O

“…These values are normal and comparable to other thioantimonate(III) complexes. [13,35,36] The interconnection of primary building units (PBUs) Sb1S 4 , Sb2S 3 , Sb3S 3 , and Sb4S 4 results in an Sb 4 S 10 chain (Figure 2). Through sharing S1 and S2 atoms, four chains of this condense to an Sb 16 S 16 ring whose dimensions are about 8.1 ϫ 14.7 Å (measured from coordinate to coordinate); this is the largest pore in layered thioantiomonates by far.…”

Solvothermal syntheses, crystal structures, and properties of new lanthanide compounds based on tetraselenidoantimonate and tetraethylenepentamine mixed ligands

“…complexes ions [15][16][17][18][19][20][21][22][23]. Only a few ternary chalcogenidoantimonates integrated with TM were prepared in en and dien, and the examples include Cr(en) 2 SbS 3 [24], [Mn 2 (en) 2 (Sb 2 S 5 )] [25], [Mn 2 (dien)(Sb 2 S 5 )] [26], [Mn 4 (-en) 9 (SbSe 4 ) 4 ] 4- [27], [Mn 2 (SbSe 4 ) 2 (en) 4 (H 2 O)] 2- [28], and (dienH 3 )[(dienH)MnSb 8 S 15 ] H 2 O [29]. On the other hand, the TM n?…”