六种聚(芳基亚磺酰基)和聚(芳基硫酰基)二茂铁的分子和晶体结构。

IF 0.7 4区 化学 Q4 CHEMISTRY, MULTIDISCIPLINARY Acta Crystallographica Section C Structural Chemistry Pub Date : 2024-11-01 Epub Date: 2024-10-04 DOI:10.1107/S2053229624009318
Tobias Blockhaus, Karlheinz Sünkel
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引用次数: 0

摘要

从 (对甲苯亚磺酰基)二茂铁 (1) 开始,得到了一个完整系列 [CpFe{C5H5-n(SOTol-p)n}] (n = 2-4) (2-4) 的混合物,其中包含所有区域异构体。经过色谱分离,得到了 1,2-双[(4-甲基苯)亚磺酰基]二茂铁 2a 和 1,3-双[(4-甲基苯)亚磺酰基]二茂铁 2b 的晶体,它们都是[Fe(C5H5)(C19H17O2S2)]、以及 1,2,3-三[(4-甲基苯)亚磺酰基]二茂铁[Fe(C5H5)(C26H23O3S3)]3a 和 1,2,3,4-四[(4-甲基苯)亚磺酰基]二茂铁乙酸乙酯 0.75 溶剂,即[Fe(C5H5)(C33H29O4S4)]-0.75C4H8O2,4。我们将它们的分子结构和晶体结构相互进行了比较,并与迄今为止尚未报道的相关 1,2-双(苯硫基)二茂铁 [Fe(C5H5)(C17H13S2)], 5 和 1,2,3,4-四(苯硫基)二茂铁 [Fe(C5H5)(C29H21S4)], 6 的结构进行了比较。在所有的亚磺酰基结构中,除四取代基 4 外,S=O 基团的 O 原子都位于赤道位置。这些化合物的所有烯环(除 4 中的一个环外)都位于远离铁原子的轴向位置,大部分与环戊二烯环的平面呈近乎垂直的方向。晶体中主要的分子间相互作用是 C-H...H-C、C-H...π 和 C-H...O,而 C-H...S(除四硫化合物 6 外)的重要性要小得多。Hirshfeld 分析表明,分散项在所有六种化合物的相互作用能中都占主导地位。一般来说,计算得出的总相互作用能随着取代基数目的增加而增加,并且亚磺酰基的相互作用能高于硫酰基。
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Molecular and crystal structures of six poly(arylsulfinyl)- and poly(arylsulfanyl)ferrocenes.

Starting from (p-tolylsulfinyl)ferrocene (1), a mixture of the complete series [CpFe{C5H5-n(SOTol-p)n}] (n = 2-4) (2-4) in all regioisomers was obtained. After chromatographic separation, crystals of 1,2-bis[(4-methylbenzene)sulfinyl]ferrocene, 2a, and 1,3-bis[(4-methylbenzene)sulfinyl]ferrocene, 2b, both [Fe(C5H5)(C19H17O2S2)], as well as of 1,2,3-tris[(4-methylbenzene)sulfinyl]ferrocene, [Fe(C5H5)(C26H23O3S3)], 3a, and 1,2,3,4-tetrakis[(4-methylbenzene)sulfinyl]ferrocene ethyl acetate 0.75-solvate, [Fe(C5H5)(C33H29O4S4)]·0.75C4H8O2, 4, could be isolated. Their molecular and crystal structures are compared with each other and also with the so far unreported structures of related 1,2-bis(phenylsulfanyl)ferrocene, [Fe(C5H5)(C17H13S2)], 5, and 1,2,3,4-tetrakis(phenylsulfanyl)ferrocene, [Fe(C5H5)(C29H21S4)], 6. In all the sulfinyl structures, the O atoms of the S=O groups are in equatorial positions, except for that in tetrasubstituted 4. All the arene rings of these compounds (except for one ring in 4) are in axial positions directed away from the Fe atom, mostly in a near perpendicular orientation with respect to the plane of the cyclopentadienyl ring. The main intermolecular interactions in the crystals are C-H...H-C, C-H...π and C-H...O, while C-H...S interactions are much less important, except for tetrasulfanyl compound 6. π-π interactions (intramolecular) are only important in compound 3a. Hirshfeld analysis shows that dispersion terms are dominant for the interaction energies of all six compounds. In general, the calculated total interaction energies increase with increasing number of substituents and are higher for the sulfinyl than for the sulfanyl groups.

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来源期刊
Acta Crystallographica Section C Structural Chemistry
Acta Crystallographica Section C Structural Chemistry CHEMISTRY, MULTIDISCIPLINARYCRYSTALLOGRAPH-CRYSTALLOGRAPHY
CiteScore
1.60
自引率
12.50%
发文量
148
期刊介绍: Acta Crystallographica Section C: Structural Chemistry is continuing its transition to a journal that publishes exciting science with structural content, in particular, important results relating to the chemical sciences. Section C is the journal of choice for the rapid publication of articles that highlight interesting research facilitated by the determination, calculation or analysis of structures of any type, other than macromolecular structures. Articles that emphasize the science and the outcomes that were enabled by the study are particularly welcomed. Authors are encouraged to include mainstream science in their papers, thereby producing manuscripts that are substantial scientific well-rounded contributions that appeal to a broad community of readers and increase the profile of the authors.
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