Synthesis, crystal structure, and second-order optical nonlinearity of bis(2-chlorobenzaldehyde thiosemicarbazone)cadmium halides (CdL(2)X(2); X=Br, I)

被引:208
作者
Tian, YP
Duan, CY
Zhao, CY
You, XZ
Mak, TCW
Zhang, ZY
机构
[1] NANJING UNIV, STATE KEY LAB COORDINAT CHEM, INST COORDINAT CHEM, NANJING 210093, PEOPLES R CHINA
[2] CHINESE UNIV HONG KONG, DEPT CHEM, HONG KONG, HONG KONG
关键词
D O I
10.1021/ic9603870
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
The new Schiff base ligand 2-chlorobenzaldehyde thiosemicarbazone (L, 1) has been synthesized and characterized by spectral techniques and single-crystal X-ray analysis. Crystals of 1 are monoclinic, space group P2(1)/n with a = 12.964(4) Angstrom, b = 5.131(5) Angstrom, c = 4.970(1) Angstrom, beta = 94.32(2)degrees, and Z = 4. The thiosemicarbazone moiety adopts a configuration with N(1) cis to N(3) and places the E configuration about both the bonds C(1)-N(2) and C(2)-N(3). The monodentate behavior of the neutral ligand (L) has been investigated in two cadmium halides CdL(2) Br-2 (2) and CdL(2)I(2) (3). Compound 2 crystallizes in space group Cc with a = 8.175(1) Angstrom, b = 14.176(1) Angstrom, c = 21.073(1) Angstrom, beta = 94.02(1)degrees, and Z = 4. Compound 3 crystallizes in space group <P(1)over bar> with a = 10.9577(1) Angstrom, b = 16.174(1) Angstrom, c = 7.878(1) Angstrom, alpha = 100.50(1)degrees, beta = 109.39(1)degrees, gamma = 83.67(1)degrees, and Z = 2. The coordination geometry about the cadmium(II) atom in compound 2 conforms to a tetrahedral configuration with two sulfur atoms from two unequivalent neutral ligands and two bromide atoms. Whereas the coordination geometry about the cadmium(II) atom in compound 3 is (4 + 1) distorted trigonal bipyramidal with two iodide atoms and one sulfur atom in the equatorial plane, the other thiosemicarbazone sulfur and the iodide atom I(1a) of an adjacent moiety occupy the axial positions. Compound 2 exhibits powder SHG efficiencies ca. 20 times that of urea, whereas compound 3 does not exhibit any SHG efficiency. Theory and experiment suggested that intermolecular contact is the main factor controlling the SHG efficiencies of compounds.
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页码:1247 / 1252
页数:6
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