首页> 外文期刊>Zeitschrift fur Anorganische und Allgemeine Chemie >The novel alkali sulfidoferrates K_9[FeIIIS_4](S_2)S, (K/Rb)_6[Fe~(III) _2S_6], Rb_8[Fe~(III) _4S_(10)], and K_7[Fe~(II/III)S_2]_5 [Die neuen Alkalimetall-Sulfidoferrate K_9[Fe~(III)S_4](S_2)S, (K/Rb)_6[Fe~(III) _2S_6], Rb_8[Fe~(III) _4S _(10)] und K_7[Fe~(II/III)S_2]_5]
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The novel alkali sulfidoferrates K_9[FeIIIS_4](S_2)S, (K/Rb)_6[Fe~(III) _2S_6], Rb_8[Fe~(III) _4S_(10)], and K_7[Fe~(II/III)S_2]_5 [Die neuen Alkalimetall-Sulfidoferrate K_9[Fe~(III)S_4](S_2)S, (K/Rb)_6[Fe~(III) _2S_6], Rb_8[Fe~(III) _4S _(10)] und K_7[Fe~(II/III)S_2]_5]

机译:新型碱金属亚铁酸盐K_9 [FeIIIS_4](S_2)S,(K / Rb)_6 [Fe〜(III)_2S_6],Rb_8 [Fe〜(III)_4S_(10)]和K_7 [Fe〜(II / III) )S_2] _5 [Die neuen Alkalimetall-Sulfidoferrate K_9 [Fe〜(III)S_4](S_2)S,(K / Rb)_6 [Fe〜(III)_2S_6],Rb_8 [Fe〜(III)_4S _(10 )]和K_7 [Fe〜(II / III)S_2] _5]

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摘要

A series of new potassium and rubidium sulfido ferrates were synthesized from iron and sulfur using elemental potassium and Rb_2S as alkali element sources. The structures of all title compounds were determined by means of single-crystal X-ray data. Isolated ortho anions [Fe~(III)S _4]~(5-), together with disulfide and sulfide anions, are the structure elements in K_9[FeS_4](S_2)S (monoclinic, space group P2_1/c, a = 1068.58(2), b = 787.480(10), c = 2372.96(3) pm, β = 102.9670(10)°, Z = 4, R_1 = 0.0325). The diferrates A_6[Fe~(III) _2S_6], among which only the sodium and the cesium salts were known so far, contain dimers of two edge-sharing [FeS_4] tetrahedra. The potassium and the monoclinic form of the rubidium compound (monoclinic, space group P2_1/c, a = 772.50(1)/796.06(5), b = 1251.24(2)/1291.35(8), c = 1002.80(1)/1032.40(6) pm, β = 127.5260(10)/127.163(4), Z = 2, R_1 = 0.0356/0.0466) crystallize with the Cs_3GaSe_3 structure type. The second, orthorhombic form of Rb_6[Fe~(III) _2S_6] is isotypic to the cesium ferrate (orthorhombic, space group Cmca, a = 1884.36(3), b = 695.660(10), c = 1296.09(2) pm, Z = 4, R_1 = 0.0220) forming the Ba_3AlSb_3 structure type. The rubidium ferrate Rb_8[Fe_4S_(10)] crystallizes with a new structure type (triclinic, space group P1, a = 744.65(3), b = 851.21(3), c = 1042.77(4) pm, α = 77.990(2), β = 85.244(2) γ = 81.051(2)°, Z = 1, R_1 = 0.0537). The structure exhibits novel tetrameres [Fe _4S_(10)]~(8-) of edge-sharing tetrahedra, which represent segments of the well-known chain compounds A[FeS_2]. K _7[Fe~(II/III)S_2]_5 (monoclinic, space group C2/c, a = 2790.1(3), b = 1153.74(13), c = 720.17(8) pm, β = 102.746(8)°, Z = 4, R_1 = 0.0407) exhibits SiS_2 analogous chains of edge-sharing [FeS4] tetrahedra and contains iron in oxidation states II and III in a 2:3 ratio. This compound is an interesting "intermediate" inbetween the ferrate(III) K[Fe~(III)S _2] and K_3[Fe~(II/III)S_2]_2, with a 1:1 ratio of Fe~(II):Fe~(III).
机译:以元素钾和Rb_2S为碱金属源,由铁和硫合成了一系列新的高铁酸钾和rub高铁酸盐。所有标题化合物的结构均通过单晶X射线数据确定。分离的原阴离子[Fe〜(III)S _4]〜(5-)与二硫化物和硫化物阴离子一起构成K_9 [FeS_4](S_2)S(单斜晶系,空间群P2_1 / c,a = 1068.58)中的结构元素(2),b = 787.480(10),c = 2372.96(3)pm,β= 102.9670(10)°,Z = 4,R_1 = 0.0325)。迄今仅已知钠盐和铯盐的二价铁A_6 [Fe〜(III)_2S_6]包含两个边缘共享[FeS_4]四面体的二聚体。 id化合物的钾和单斜晶形式(单斜晶,空间群P2_1 / c,a = 772.50(1)/796.06(5),b = 1251.24(2)/1291.35(8),c = 1002.80(1)/ 1032.40(6)pm,β= 127.5260(10)/127.163(4),Z = 2,R_1 = 0.0356 / 0.0466)以Cs_3GaSe_3结构类型结晶。 Rb_6 [Fe〜(III)_2S_6]的第二种斜方晶型与高铁酸铯同型(斜方晶系Cmca,a = 1884.36(3),b = 695.660(10),c = 1296.09(2)pm, Z = 4,R_1 = 0.0220)形成Ba_3AlSb_3结构类型。高铁rub Rb_8 [Fe_4S_(10)]以新的结构类型结晶(三斜晶系,空间群P1,a = 744.65(3),b = 851.21(3),c = 1042.77(4)pm,α= 77.990(2 ),β= 85.244(2)γ= 81.051(2)°,Z = 1,R_1 = 0.0537)。该结构表现出新的边缘共享四面体的四氢化物[Fe _4S_(10)]〜(8-),它们代表众所周知的链化合物A [FeS_2]的片段。 K _7 [Fe〜(II / III)S_2] _5(单斜晶系,空间群C2 / c,a = 2790.1(3),b = 1153.74(13),c = 720.17(8)pm,β= 102.746(8) °,Z = 4,R_1 = 0.0407)具有SiS_2相似的边缘共享[FeS4]四面体链,并以2:3的比例包含处于氧化态II和III的铁。该化合物是高铁酸盐(III)K [Fe〜(III)S _2]和K_3 [Fe〜(II / III)S_2] _2之间有趣的“中间体”,Fe〜(II)的比例为1:1 :Fe〜(III)。

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