Anion Induced Formation of Supramolecular Associations Involving Lone pair鈭捪€ and Anion鈭捪€ Interactions in Co(II) Malonate Complexes: Experimental Observations, Hirshfeld Surface Analyses and DFT Stud
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- 作者：Prankrishna Manna ; Saikat Kumar Seth ; Amrita Das ; Joanna Hemming ; Richard Prendergast ; Madeleine Helliwell ; Somnath Ray Choudhury ; Antonio Frontera ; Subrata Mukhopadhyay
- 刊名：Inorganic Chemistry
- 出版年：2012
- 出版时间：March 19, 2012
- 年：2012
- 卷：51
- 期：6
- 页码：3557-3571
- 全文大小：1042K
- 年卷期：v.51,no.6(March 19, 2012)
- ISSN：1520-510X
文摘
Three Co(II)鈥搈alonate complexes, namely, (C5H7N2)4[Co(C3H2O4)2(H2O)2](NO3)2 (1), (C5H7N2)4[Co(C3H2O4)2(H2O)2](ClO4)2 (2), and (C5H7N2)4[Co(C3H2O4)2(H2O)2](PF6)2 (3) [C5H7N2 = protonated 2-aminopyridine, C3H4O4 = malonic acid, NO3鈥?/sup> = nitrate, ClO4鈥?/sup> = perchlorate, PF6鈥?/sup> = hexafluorophosphate], have been synthesized from purely aqueous media, and their crystal structures have been determined by single crystal X-ray diffraction. A thorough analysis of Hirshfeld surfaces and fingerprint plots facilitates a comparison of intermolecular interactions in 1鈥?b>3, which are crucial in building supramolecular architectures. When these complexes are structurally compared with their previously reported analogous Ni(II) or Mg(II) compounds, a very interesting feature regarding the role of counteranions has emerged. This phenomenon can be best described as anion-induced formation of extended supramolecular networks of the type lone pair鈭捪€/蟺鈥撓€/蟺鈥揳nion鈭捪€/蟺鈥搇one pair and lone pair鈭捪€/蟺鈥撓€/蟺鈥揳nion involving various weak forces like lone pair鈭捪€, 蟺鈥撓€, and anion鈭捪€ interactions. The strength of these 蟺 contacts has been estimated using DFT calculations (M06/6-31+G*), and the formation energy of the supramolecular networks has been also evaluated. The influence of the anion (NO3鈥?/sup>, ClO4鈥?/sup>, and PF6鈥?/sup>) on the total interaction energy of the assembly is also studied.