Versatility of Thiosemicarbazones in the Construction of Monomers, Dimers and Hydrogen-Bonded Networks of Silver(I) Complexes
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- 作者：Tarlok S. Lobana ; Sonia Khanna ; Rekha Sharma ; Geeta Hundal ; Razia Sultana ; Manisha Chaudhary ; R. J. Butcher ; A. Castineiras
- 刊名：Crystal Growth & Design
- 出版年：2008
- 出版时间：April 2008
- 年：2008
- 卷：8
- 期：4
- 页码：1203 - 1212
- 全文大小：3648K
- 年卷期：v.8,no.4(April 2008)
- ISSN：1528-7505
文摘
Reactions of thiosemicarbazones {R1R2C2
N3-N2(H)-C1(S)-N1H2}, a multidonor class of ligands, with silver(I) halides in the presence of PPh3 have yielded a variety of compounds, viz.: (i) halogen-bridged dimers, [Ag2(μ-X)2(η1-S-Haptsc)2(PPh3)2] (R1 = Ph, R2 = Me, Haptsc, X = Cl (1); Br (2)), [Ag2(μ-Br)2(η1-S-Hbtsc)2(PPh3)2] (R1 = Ph, R2 = H, Hbtsc (3)), [Ag2(μ-Br)2(η1-S-Hactsc)2(PPh3)2] (R1 = R2 = Me, Hactsc (4)); (ii) sulfur-bridged dimers, [Ag2Br2(μ-S-Hptsc)2(PPh3)2]·2H2O (R1 = pyrrole, R2 = H, Hptsc (5)), and [Ag2Cl2(μ-S-Httsc)2(PPh3)2]·2CH3CN (R1 = thiophene, R2 = H, Httsc (6)), and (iii) monomers, [AgX(η1-S-Hpytsc)(PPh3)2]·CH3CN (R1 = pyridine, R2 = H, Hpytsc, X = Br (7); Cl (8)). In contrast, silver(I) nitrate has formed only sulfur-bridged dimers, [Ag2(η1-N-μ-S-Hftsc)2(Ph3P)2](NO3)2 (9) (R1 = furan, R2 = H, Hftsc), and [Ag2(η1-S-Hptsc)2(μ-S-Hptsc)2(Ph3P)2](NO3)2·2CHCl3 (10) (R1 = pyrrole, R2 = H, Hptsc) (Hpytsc = pyridine-2-carbaldehyde thiosemicarbazone, Hptsc = pyrrole-2-carbaldehyde thiosemicarbazone, Httsc = thiophene-2-carbaldehyde thiosemicarbazone, Hftsc = furan-2-carbaldehyde thiosemicarbazone, Hbtsc = benzaldehyde thiosemicarbazone, Hactsc = acetone thiosemicarbazone, and Haptsc = acetophenone thiosemicarbazone). Complexes 1−10 are the first examples exhibiting new bonding modes (η1-S, μ-S, and μ-S-η1-N3) in silver(I)-thiosemicarbazone chemistry. The substituents at C2 carbon appear to have significant influence on the nature of bonding in the complexes. The intermolecular interactions such as, NH···X (X = S, Br, Cl, O), CH···π and CH···X (X = S, Cl) have led to the formation of one- and two-dimensional (1D and 2D) networks. Interestingly, a novel feature is that some of the 2D networks encapsulate organic molecules in the voids.
N3-N2(H)-C1(S)-N1H2}, a multidonor class of ligands, with silver(I) halides in the presence of PPh3 have yielded a variety of compounds, viz.: (i) halogen-bridged dimers, [Ag2(μ-X)2(η1-S-Haptsc)2(PPh3)2] (R1 = Ph, R2 = Me, Haptsc, X = Cl (1); Br (2)), [Ag2(μ-Br)2(η1-S-Hbtsc)2(PPh3)2] (R1 = Ph, R2 = H, Hbtsc (3)), [Ag2(μ-Br)2(η1-S-Hactsc)2(PPh3)2] (R1 = R2 = Me, Hactsc (4)); (ii) sulfur-bridged dimers, [Ag2Br2(μ-S-Hptsc)2(PPh3)2]·2H2O (R1 = pyrrole, R2 = H, Hptsc (5)), and [Ag2Cl2(μ-S-Httsc)2(PPh3)2]·2CH3CN (R1 = thiophene, R2 = H, Httsc (6)), and (iii) monomers, [AgX(η1-S-Hpytsc)(PPh3)2]·CH3CN (R1 = pyridine, R2 = H, Hpytsc, X = Br (7); Cl (8)). In contrast, silver(I) nitrate has formed only sulfur-bridged dimers, [Ag2(η1-N-μ-S-Hftsc)2(Ph3P)2](NO3)2 (9) (R1 = furan, R2 = H, Hftsc), and [Ag2(η1-S-Hptsc)2(μ-S-Hptsc)2(Ph3P)2](NO3)2·2CHCl3 (10) (R1 = pyrrole, R2 = H, Hptsc) (Hpytsc = pyridine-2-carbaldehyde thiosemicarbazone, Hptsc = pyrrole-2-carbaldehyde thiosemicarbazone, Httsc = thiophene-2-carbaldehyde thiosemicarbazone, Hftsc = furan-2-carbaldehyde thiosemicarbazone, Hbtsc = benzaldehyde thiosemicarbazone, Hactsc = acetone thiosemicarbazone, and Haptsc = acetophenone thiosemicarbazone). Complexes 1−10 are the first examples exhibiting new bonding modes (η1-S, μ-S, and μ-S-η1-N3) in silver(I)-thiosemicarbazone chemistry. The substituents at C2 carbon appear to have significant influence on the nature of bonding in the complexes. The intermolecular interactions such as, NH···X (X = S, Br, Cl, O), CH···π and CH···X (X = S, Cl) have led to the formation of one- and two-dimensional (1D and 2D) networks. Interestingly, a novel feature is that some of the 2D networks encapsulate organic molecules in the voids.