由 [MS4]2- 阴离子稳定的双(4-氨基吡啶)和双(2-氨基-6-甲基吡啶)阳离子：合成、晶体结构、Hirshfeld 表面分析和硫转移反应

IF 2.4 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Polyhedron Pub Date : 2024-10-28 DOI:10.1016/j.poly.2024.117272

Milagrina D’Souza , Nikita N. Harmalkar , Vishnu R. Chari , Beena K. Vernekar , Sunder N. Dhuri

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引用次数: 0

摘要

采用著名的碱促进阳离子交换法合成了四种新的有机四硫代金铵盐：(4-氨基吡啶鎓)2[MoS4]-H2O 1、(4-氨基吡啶鎓)2[WS4]-H2O 2、(2-氨基-6-甲基吡啶鎓)2[MoS4] 3 和 (2-氨基-6-甲基吡啶鎓)2[WS4] 4。所有化合物都通过元素分析、红外/拉曼/紫外-可见光谱、热重分析和 X 射线晶体学进行了表征。1 和 2 的结构由独特的四面体 [MoS4]2- 和 [WS4]2- 二价离子组成，它们通过晶体学上独立的 4-aminopyridinium 单价离子实现电荷平衡。此外，这两种化合物都有一个晶格水分子，这有助于提高其结构的整体稳定性。在化合物 3 和 4 中，1 和 2 中的 4-氨基吡啶鎓被 2-氨基-6-甲基吡啶鎓阳离子取代，并且缺少晶格水。在 1 和 2 中观察到不同的 H 键相互作用，即 NH⋯S、CH⋯S、NH⋯O 和 OH⋯O，而在 3 和 4 中则减少为两种，即 NH⋯S 和 CH⋯S。在 1 和 2 中，源自晶格水的弱相互作用（NH⋯O 和 OH⋯O）进一步将阳离子与 [MoS4]2- 和 [WS4]2- 阴离子相互连接，形成扩展网络。为了了解分子间相互作用在 1-4 结构中的重要性，我们进行了 Hirshfeld 表面分析。得出了 1-4 号化合物结构中的富集比（E）。测试了化合物 1-4 的硫转移能力。只有化合物 1 在与 1,3-二溴丙烷反应时形成了主要的二硫产物。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

Bis(4-aminopyridinium) and bis(2-amino-6-methylpyridinium) cations stabilised by [MS4]2− anions: Synthesis, crystal structures, Hirshfeld surface analysis and sulfur transfer reactions

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Bis(4-aminopyridinium) and bis(2-amino-6-methylpyridinium) cations stabilised by [MS4]2− anions: Synthesis, crystal structures, Hirshfeld surface analysis and sulfur transfer reactions

Four new organic ammonium tetrasulfidometallates: (4-aminopyridinium)₂[MoS₄]·H₂O 1, (4-aminopyridinium)₂[WS₄]·H₂O 2, (2-amino-6-methylpyridinium)₂[MoS₄] 3, and (2-amino-6-methylpyridinium)₂[WS₄] 4 have been synthesized by a well-known base promoted cation exchange method. All compounds were characterized by elemental analysis, IR/Raman/UV–Vis spectroscopy, thermogravimetric analysis, and X-ray crystallography. The structures of 1 and 2 consist of unique tetrahedral [MoS₄]²⁻ and [WS₄]²⁻ dianions, which are charge-balanced by crystallographically independent 4-aminopyridinium monocations. Additionally, both have a lattice water molecule, which contributes to the overall stability of their structures. In compounds 3 and 4, 4-aminopyridinium of 1 and 2 are replaced by 2-amino-6-methylpyridinium cation and lack lattice water. The different H-bonding interactions viz NH⋯S, CH⋯S, NH⋯O and OH⋯O are observed in 1 and 2, which are reduced to two viz. NH⋯S and CH⋯S in 3 and 4. The weak interactions (NH⋯O and OH⋯O) originating from lattice water further interlink cations with [MoS₄]²⁻ and [WS₄]²⁻ anions forming extended networks in 1 and 2. To understand the importance of intermolecular interactions in the structures of 1–4, the Hirshfeld surface analyses were performed. The enrichment ratio (E) in the structures of compounds 1–4 was obtained. Compounds 1–4 were tested for their sulfur transfer ability. Only compound 1 showed a predominant disulfide product formation in reaction with 1,3-dibromopropane.

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来源期刊

Polyhedron 化学-晶体学

CiteScore

4.90

自引率

7.70%

发文量

515

审稿时长

2 months

期刊介绍： Polyhedron publishes original, fundamental, experimental and theoretical work of the highest quality in all the major areas of inorganic chemistry. This includes synthetic chemistry, coordination chemistry, organometallic chemistry, bioinorganic chemistry, and solid-state and materials chemistry. Papers should be significant pieces of work, and all new compounds must be appropriately characterized. The inclusion of single-crystal X-ray structural data is strongly encouraged, but papers reporting only the X-ray structure determination of a single compound will usually not be considered. Papers on solid-state or materials chemistry will be expected to have a significant molecular chemistry component (such as the synthesis and characterization of the molecular precursors and/or a systematic study of the use of different precursors or reaction conditions) or demonstrate a cutting-edge application (for example inorganic materials for energy applications). Papers dealing only with stability constants are not considered.