Synthesis, Crystal Structure, and Second-Order Optical Nonlinearity of Bis(2-chlorobenzaldehyde thiosemicarbazone)cadmium Halides (CdL2X2; X = Br, I)
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- 作者：Yu-peng Tian ; Chun-ying Duan ; Cun-yuan Zhao ; Xiao-zeng You ; Thomas C. W. Mak ; and Ze-ying Zhang
- 刊名：Inorganic Chemistry
- 出版年：1997
- 出版时间：March 12, 1997
- 年：1997
- 卷：36
- 期：6
- 页码：1247 - 1252
- 全文大小：140K
- 年卷期：v.36,no.6(March 12, 1997)
- ISSN：1520-510X
文摘
The new Schiff base ligand 2-chlorobenzaldehyde thiosemicarbazone(L, 1) has been synthesized and characterizedby spectral techniques and single-crystal X-ray analysis. Crystalsof 1 are monoclinic, space groupP21/n witha = 12.964(4) Å, b = 5.131(5) Å,c = 4.970(1) Å, 
= 94.32(2)
,and Z = 4. The thiosemicarbazone moietyadopts a configuration with N(1) cis to N(3) and places theE configuration about both the bonds C(1)-N(2)andC(2)-N(3). The monodentate behavior of the neutral ligand (L)has been investigated in two cadmium halidesCdL2 Br2 (2) andCdL2I2 (3). Compound2 crystallizes in space group Cc witha = 8.175(1) Å, b =14.176(1)Å, c = 21.073(1) Å, =94.02(1), and Z = 4. Compound 3crystallizes in space group P
with a =10.9577(1)Å, b = 16.174(1) Å, c = 7.878(1)Å, 
= 100.50(1), = 109.39(1),
= 83.67(1), and Z = 2. Thecoordinationgeometry about the cadmium(II) atom in compound 2conforms to a tetrahedral configuration with two sulfuratoms from two unequivalent neutral ligands and two bromide atoms.Whereas the coordination geometry aboutthe cadmium(II) atom in compound 3 is (4 + 1)distorted trigonal bipyramidal with two iodide atoms andonesulfur atom in the equatorial plane, the other thiosemicarbazone sulfurand the iodide atom I(1a) of an adjacentmoiety occupy the axial positions. Compound 2 exhibitspowder SHG efficiencies ca. 20 times that ofurea,whereas compound 3 does not exhibit any SHG efficiency.Theory and experiment suggested that intermolecularcontact is the main factor controlling the SHG efficiencies ofcompounds.
= 94.32(2),and Z = 4. The thiosemicarbazone moietyadopts a configuration with N(1) cis to N(3) and places theE configuration about both the bonds C(1)-N(2)andC(2)-N(3). The monodentate behavior of the neutral ligand (L)has been investigated in two cadmium halidesCdL2 Br2 (2) andCdL2I2 (3). Compound2 crystallizes in space group Cc witha = 8.175(1) Å, b =14.176(1)Å, c = 21.073(1) Å, =94.02(1), and Z = 4. Compound 3crystallizes in space group P with a =10.9577(1)Å, b = 16.174(1) Å, c = 7.878(1)Å, = 100.50(1), = 109.39(1), = 83.67(1), and Z = 2. Thecoordinationgeometry about the cadmium(II) atom in compound 2conforms to a tetrahedral configuration with two sulfuratoms from two unequivalent neutral ligands and two bromide atoms.Whereas the coordination geometry aboutthe cadmium(II) atom in compound 3 is (4 + 1)distorted trigonal bipyramidal with two iodide atoms andonesulfur atom in the equatorial plane, the other thiosemicarbazone sulfurand the iodide atom I(1a) of an adjacentmoiety occupy the axial positions. Compound 2 exhibitspowder SHG efficiencies ca. 20 times that ofurea,whereas compound 3 does not exhibit any SHG efficiency.Theory and experiment suggested that intermolecularcontact is the main factor controlling the SHG efficiencies ofcompounds.