Extending the Time:  Solvothermal Syntheses, Crystal Structures, and Properties of Two Non-isostructural Thioantimonates with the Composition [Mn(tren)]Sb₂S₄

Abstract

The two novel compounds, [Mn(tren)]Sb2S4 (1 and 2), were obtained by the reaction of elemental Mn, Sb, and S in aqueous solutions of tren (tren = tris(2-aminoethyl)amine, C6H18N4) after different reaction times. Compound 1 is formed up to a reaction time of 13 d, and an extension of the reaction time leads to the formation of 2. Both compounds crystallize in monoclinic space groups (1, P2(1)/c; 2, C2/c). In 1, the two unique SbS3 trigonal pyramids share a common S atom to form a Sb2S5 unit. Two S atoms of this group have a bond to Mn2+ yielding a MnSb2S3 heteroring in the boat conformation. The Sb2S5 moieties are joined via common corners into the final undulated [Sb2S4]2- anion which is directed along [001]. The structure of 2 contains the [Mn(tren)]2+ ion, one SbS3 pyramid, and a SbS4 unit. Two symmetry-related SbS4 groups share an edge, forming a Sb2S6 group containing a Sb2S2 ring. This group is joined via corners to two SbS3 pyramids on both sides producing a Sb4S4 ring. The Sb2S2 and Sb4S4 rings are condensed into the final [Sb2S4]2- anion which runs along [010]. The [Mn(tren)] groups are bound to the thioantimonate(III) backbone on opposite sides of the Sb4S4 ring, and a small MnSbS2 ring is formed. In both structures, weak S...H bonds are found which may contribute to the stability of the materials. The two compounds decompose in one step upon heating, and only MnS and Sb2S3 could be identified as the crystalline part of the decomposition products. Both compounds can also be prepared under solvothermal conditions using MnSb2S4 as starting material. Compounds 1 and 2 are obtained from this ternary material in a high yield.

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

“…The structure of compound 1 is composed of isolated [Ni(1,2-PDA) 3 ion is sixfold coordinated by six nitrogen atoms of bichelate 1,2-PDA ligands, which forms a distorted octahedron (Figure 1), as is suggested by the octahedral axial N-Ni-N trans angles between 171.6(4)°and 172.4(4)°. The Ni-N distances between 2.091(9) and 2.135(9) Å (Table 1) are comparable with those reported in the literature.…”

“…The design and synthesis of chalcogenidometalates have received considerable attention [1][2][3] during the past decades. To design and synthesize more compounds with various configurations, it is very important to understand which factors affect the structures of chalcogenidometalates.…”

“…[21][22][23][24][25][26][27][28][29][30][31][32] The solvothermal method was proven to be [ 16 heterorings resulted in an unprecedented framework of the five-atom thick Sb x S y n-layer. In 2, a new member of Sb n S n (n = 2, 3,4,8,16,30,31,32) heterocycles Sb 15 S 15 heteroring has been obtained as the first example. In compound 3, the most particular feature is that when the secondary Sb-S bonds are considered the Sb2 atom becomes sevenfold coordinated.…”

“…In this work, [Ni(1,2-PDA) 3 ]Sb 4 S 7 (1) is the first example of a thioantimonate(III) in which a 1,2-propanediamine complex of a transition metal serves as the counterion. As a result of the use of two N-substituted polyamines, N,Ndimethylethylenediamine and N,N-diethylethylenediamine, we successfully prepared two additional thioantimonate(III) complexes: [C 4 …”

Microwave‐Hydrothermal Synthesis of Nanostructured Zinc‐Copper Gallates

“…Among these techniques, hydrothermal syntheses are of special interest, because they can provide homogeneous phases and particle size distributions as well as tuneable particle morphologies in a single reaction step. [38][39][40][41][42] The production of metal oxides with microwave-assisted hydrothermal syntheses is even superior to conventional hydrothermal routes due to enhanced crystallization kinetics, shorter reaction times and energy saving through rapid heating of the entire reaction mixture. [43,44] Recently, the use of ionic liquids has opened up new preparative avenues [45] and microwave-hydrothermal technologies are likely to replace the conventional routes in future technical implementations.…”