TY - JOUR
T1 - Structural variations of praseodymium(III) benzoate derivative complexes with dimethylformamide
AU - Zhou, Xianju
AU - Wong, Wing Tak
AU - Hau, Sam C.K.
AU - Tanner, Peter A.
N1 - Funding Information:
We are indebted to Ms. Wang Yan Ming, Dr. Chris S.K. Mak and Dr. Lin-Ping Zhang for technical assistance in the early stages of this project, and to The Chinese University of Hong Kong and The University of Hong Kong for X-ray data collection. We thank Professor T.C.W. Mak for useful comments on the manuscript. We thank Professor P.C. Junk for sending reprints of his works. X.Z. acknowledges the National Natural Science Foundation of China grant No. 10704090 for financial support.
PY - 2015/3/9
Y1 - 2015/3/9
N2 - Eight- or nine-coordinated trivalent praseodymium complexes derived from para-substituted benzoic acids have been synthesized by the reaction of hydrated Pr(OH)3 with 4-XC6H4CO2H, where X = OMe, H, Cl, NO2, OH, NH2 or F, in dimethylformamide [DMF, (CH3)2NCHO], and eight single crystal X-ray structures have been determined. For the substituted systems studied, dimeric units hydrogen-bonded into chains or networks are observed in complexes comprising electron-donating groups X, whereas electron-withdrawing groups X form polymeric complexes. However, the steric effect of the ligand and the coordination of solvated molecules also play roles in determining the coordination polyhedra. The coordination geometry of the carboxylate ligand in these complexes is restricted to three types: bidentate chelating (η2); bridging bidentate (μ-η1:η1 (O,O′)) and bridging chelating tridentate (μ-η2:η1). Two geometrical isomers, of [Pr(C6H5COO)3(DMF)(H2O)]2, designated as a and b, crystallize in the same monoclinic space group but differ in the arrangement of C6H5COO and DMF ligands in their coordination polyhedra. The packing of isomer a is more efficient than that of b, resulting in a smaller unit-cell volume of about 50 Å3. Although functional group fingerprints from the p-substitution moieties are well-identified in the vibrational spectra of the complexes, reasons are provided to explain why the correlation between carboxyl group ligation and spectra cannot be readily made.
AB - Eight- or nine-coordinated trivalent praseodymium complexes derived from para-substituted benzoic acids have been synthesized by the reaction of hydrated Pr(OH)3 with 4-XC6H4CO2H, where X = OMe, H, Cl, NO2, OH, NH2 or F, in dimethylformamide [DMF, (CH3)2NCHO], and eight single crystal X-ray structures have been determined. For the substituted systems studied, dimeric units hydrogen-bonded into chains or networks are observed in complexes comprising electron-donating groups X, whereas electron-withdrawing groups X form polymeric complexes. However, the steric effect of the ligand and the coordination of solvated molecules also play roles in determining the coordination polyhedra. The coordination geometry of the carboxylate ligand in these complexes is restricted to three types: bidentate chelating (η2); bridging bidentate (μ-η1:η1 (O,O′)) and bridging chelating tridentate (μ-η2:η1). Two geometrical isomers, of [Pr(C6H5COO)3(DMF)(H2O)]2, designated as a and b, crystallize in the same monoclinic space group but differ in the arrangement of C6H5COO and DMF ligands in their coordination polyhedra. The packing of isomer a is more efficient than that of b, resulting in a smaller unit-cell volume of about 50 Å3. Although functional group fingerprints from the p-substitution moieties are well-identified in the vibrational spectra of the complexes, reasons are provided to explain why the correlation between carboxyl group ligation and spectra cannot be readily made.
KW - Benzoate complex
KW - Crystal structure
KW - Packing isomers
KW - Praseodymium
KW - Vibrational spectra
UR - http://www.scopus.com/inward/record.url?scp=84921458724&partnerID=8YFLogxK
U2 - 10.1016/j.poly.2014.12.007
DO - 10.1016/j.poly.2014.12.007
M3 - Journal article
AN - SCOPUS:84921458724
SN - 0277-5387
VL - 88
SP - 138
EP - 148
JO - Polyhedron
JF - Polyhedron
ER -