Hirshfeld surface analysis of new organotin(IV)-phosphoramide complexes

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• 作者：Mehrdad Pourayoubi ; Samad Shoghpour Bayraq ; Atekeh Tarahhomi ; Marek Ne膷as ; Karla Fejfarov谩 ; Michal Du拧ek
• 关键词：Organotin(IV)-phosphoramide complexes ; Hirshfeld surfaces ; Two-dimensional fingerprint plots ; Crystal packing
• 刊名：Journal of Organometallic Chemistry
• 出版年：1 February, 2014
• 年：2014
• 卷：751
• 期：Complete
• 页码：508-518
• 全文大小：3112 K

文摘

Hirshfeld surfaces and two-dimensional fingerprint plots are used to study short intermolecular contacts in new organotin(IV)-phosphoramide complexes, (L¹)₂Cl₂Me₂Sn (1), (L²)Cl₂Me₂Sn (2) and (L³)₂Cl₂Me₂Sn (3) [L¹聽=聽(C₅H₉NH)₃PO, L²聽=聽[(CH₃)₃CNH][C₆H₅CH₂N(CH₃)]₂PO and L³聽=聽(3-F-C₆H₄C(O)NH)(N(CH₃)C₆H₁₁)₂PO]. The previously reported structure L³ is also analyzed for a comparison with the related complex, 3. While 2 and 3, respectively, contain one independent molecule and one-half of a molecule, the asymmetric unit of 1 is composed of three independent molecules with different conformations of ligands around the tin center but with very similar Hirshfeld surfaces and fingerprint plots. The Sn^IV coordination geometries are octahedral for 1 and 3 with cis-phosphoramides in each independent molecule of 1 and trans-phosphoramides in 3. For 2, the Sn^IV adopts a distorted trigonal bipyramidal environment with the axial positions occupied by the ligand phosphoramide and one Cl atom. Two-dimensional fingerprint plots of 1 and 2 show pairs of spikes attributed to the intermolecular H鈰疌l contacts including N-H鈰疌l hydrogen bonds. Two spikes found in 3 are much shorter comparing with 1 and 2 due to absence of the intermolecular N-H鈰疌l hydrogen bond and lower contribution of C-H鈰疌l contacts. In the ligand L³ the presence of N-H鈰疧P hydrogen bond is reflected as a deep-red area of Hirshfeld surfaces. Moreover, in fingerprint plot of L³ two intense spikes are observed related to the intermolecular H鈰疧 contacts including N-H鈰疧P hydrogen bond. The more shallow red spots on the Hirshfeld surface of 3 with respect to L³ are caused by absence of N-H鈰疧 hydrogen bond and the lower contribution of H鈰疧 contacts.