Institut für Anorganische Chemie, Christian-Albrechts-Universität zu Kiel, Max-Eyth-Strasse 2, D-24118 Kiel, Germany.
Inorg Chem. 2010 Feb 15;49(4):1651-7. doi: 10.1021/ic902053b.
The title compound Mn(3)Sb(2)S(6)(C(6)H(18)N(4)) (C(6)H(18)N(4) = triethylenetetramine) was obtained under solvothermal conditions by reacting Mn, Sb, S, and the amine at 140 degrees C for 7 days. The compound crystallizes in the triclinic space group P1 with a = 6.645(1) A, b = 8.667(1) A, c = 9.660(1) A, alpha = 90.82(2) degrees , beta = 109.70(2) degrees , gamma = 110.68(2) degrees , Z = 1, and V = 484.4(1) A(3). The Mn(4)Sb(2)S(6) double-heterocubane unit is the main motif in the structure of the title compound, which results from the interconnection of two SbS(3) trigonal pyramids, two MnS(6) octahedra, and two MnS(4)N(2) octahedra. The two N atoms completing the environment of the latter Mn(2+) ions belong to the tetradentate amine; i.e., the amine acts in a bidentate manner. The Mn(4)Sb(2)S(6) groups are joined by corner sharing of the MnS(6) octahedra, yielding one-dimensional linear Mn(3)Sb(2)S(6) rods along [100]. The two other N atoms of the amine molecule act in a bidentate manner to Mn(2+) ions of neighboring rods, thus producing layers within the (010) plane. Within the rods, the arrangement of the Mn(2+) ions in triangles leads to a chain of Mn(2+) diamonds connected via opposite corners. For the magnetic properties, each edge connecting the Mn(2+) ions represents a superexchange path due to coupling of the Mn(2+) centers via S bridges. The resulting Mn(2+) triangles give rise to substantial competing interaction and magnetic frustration. Below about 100 K, a gradual buildup of short-range antiferromagnetic correlations is observed. At lower temperatures, long-range antiferromagnetic interactions occur with T(N) = 2.90 K, as indicated by a lambda-type anomaly in the heat capacity curve. The analysis of the magnetic and heat capacity data evidences that the magnetic properties are essentially determined by the one-dimensional character of the Mn(3)Sb(2)S(6) chain. In addition, significant magnetic frustration due to the arrangement of the Mn(2+) ions in a triangular configuration cannot be neglected.
标题化合物 Mn(3)Sb(2)S(6)(C(6)H(18)N(4))(C(6)H(18)N(4) = 三乙烯四胺)是在溶剂热条件下，通过在 140°C 下反应 Mn、Sb、S 和胺 7 天而得到的。该化合物在三斜空间群 P1 中结晶，晶胞参数为 a = 6.645(1)A，b = 8.667(1)A，c = 9.660(1)A，alpha = 90.82(2)°，beta = 109.70(2)°，gamma = 110.68(2)°，Z = 1，V = 484.4(1)A(3)。Mn(4)Sb(2)S(6) 双异核立方烷单元是标题化合物结构的主要特征，它是由两个 SbS(3)三角锥、两个 MnS(6)八面体和两个 MnS(4)N(2)八面体相互连接而成的。完成后者 Mn(2+)离子环境的两个 N 原子属于四齿胺; 即，胺以双齿方式作用。Mn(4)Sb(2)S(6)基团通过 MnS(6)八面体的角共享连接，从而在[100]方向上生成一维线性 Mn(3)Sb(2)S(6)棒。胺分子的另外两个 N 原子以双齿方式与相邻棒的 Mn(2+)离子作用，从而在(010)平面内产生层。在棒内，Mn(2+)离子的排列成三角形导致通过对角连接的 Mn(2+)钻石链。对于磁性性质，由于 S 桥连接 Mn(2+)中心，连接 Mn(2+)离子的每个边缘都代表一个超交换路径。由此产生的 Mn(2+)三角形导致了大量的竞争相互作用和磁挫折。在 100 K 以下，观察到短程反铁磁相关的逐渐建立。在较低温度下，通过热容曲线中的 lambda 型异常，发生长程反铁磁相互作用，T(N) = 2.90 K。磁性和热容数据的分析表明，磁性性质主要由 Mn(3)Sb(2)S(6)链的一维性质决定。此外，由于 Mn(2+)离子呈三角形排列而产生的显著磁挫折也不容忽视。
