A comprehensive characterization of thiophosgene in the solid state.

IF 1.3 3区化学 Q3 CHEMISTRY, MULTIDISCIPLINARY

Acta crystallographica Section B, Structural science, crystal engineering and materials Pub Date : 2024-10-01 Epub Date: 2024-09-05 DOI:10.1107/S2052520624007583

Frank Tambornino, Sven Ringelband, Stewart F Parker, Christopher M Howard, Dominic Fortes

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Abstract

Thiophosgene is one of the principal C=S building blocks in synthetic chemistry. At room temperature, thiophosgene is a red liquid. While its properties in the liquid and gaseous states are well known, a comprehensive characterization of thiophosgene in its solid state is presented here. Differential scanning calorimetry shows that thiophosgene forms a supercooled melt before rapidly crystallizing. Its melting point is 231.85 K (-41.3 °C). At 80 K, thiophosgene crystallizes in space group P6₃/m [No. 174, a = b = 5.9645 (2), c = 6.2835 (3) Å, V = 193.59 (2) Å³]. The molecule shows a distinct rotational disorder: all S and Cl positions are of mixed occupancy and the disorder does not resolve at temperatures as low as 10 K, as was shown by neutron powder diffraction. Infrared, Raman and inelastic neutron scattering spectra were collected and assigned with the aid of quantum chemical calculations. A larger ordered structural model allowed for better agreement between the measured and calculated spectra, further indicating that disorder is an inherent feature of solid-state thiophosgene.

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固态硫代磷酰氯的综合表征。

硫代磷酰氯是合成化学中主要的 C=S 结构单元之一。在室温下，硫代磷炔是一种红色液体。虽然它在液态和气态下的特性已广为人知，但这里介绍的是硫代磷气在固态下的综合特性。差示扫描量热法显示，硫代磷酰氯在快速结晶之前会形成过冷熔体。其熔点为 231.85 K（-41.3 °C）。在 80 K 的温度下，硫代磷炔在空间群 P63/m 中结晶[编号 174，a = b = 5.9645 (2)，c = 6.2835 (3)埃，V = 193.59 (2)埃3]。正如中子粉末衍射所显示的那样，该分子显示出明显的旋转无序：所有 S 和 Cl 的位置都是混合占据的，而且在低至 10 K 的温度下，这种无序也无法消除。在量子化学计算的帮助下，收集并分配了红外线、拉曼和非弹性中子散射光谱。较大的有序结构模型使得测量和计算光谱之间的一致性更好，进一步表明无序是固态硫代磷气的固有特征。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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来源期刊

Acta crystallographica Section B, Structural science, crystal engineering and materials CHEMISTRY, MULTIDISCIPLINARYCRYSTALLOGRAPH-CRYSTALLOGRAPHY

CiteScore

3.60

自引率

5.30%

发文量

期刊介绍： Acta Crystallographica Section B: Structural Science, Crystal Engineering and Materials publishes scientific articles related to the structural science of compounds and materials in the widest sense. Knowledge of the arrangements of atoms, including their temporal variations and dependencies on temperature and pressure, is often the key to understanding physical and chemical phenomena and is crucial for the design of new materials and supramolecular devices. Acta Crystallographica B is the forum for the publication of such contributions. Scientific developments based on experimental studies as well as those based on theoretical approaches, including crystal-structure prediction, structure-property relations and the use of databases of crystal structures, are published.