Second harmonic generation of eta(5)-monocyclopentadienyl ruthenium p-benzonitrile derivatives by Kurtz powder technique. Crystal and molecular structure determinations of [Ru(eta(5)-C5H5)((+)-DIOP)(p-NCC6H4NO2)][X], X = PF6-, CF3SO3- and [RU(eta(5)-C5H5)((+)-DIOP)(NCCH3)][PF6]

A new series of salts [RuCp(PP)(p-N dropC(CH=CH)(n)C6H4R)][X] (PP = ((+)-DI OP. DPPE: n = 0, 1: R = CH3,Br, OCH3, NH2, N(CH3)(2), C6H5 and NO2: X = PF6 -, CF3SO3-) were synthesised and the second harmonic generation (SHG) effic iencies were measured by Kurtz powder technique in order to better understa nd the relationship between structural features and solid state packing wit h SHG properties. A structural study of [RuCp((+)-DIOP)(p-N drop CC6H4NO2)] [X]. X = PF6. CF3SO3- by X-ray diffraction showed crystallisation on accent ric groups. The PF, salt crystallised in a triclinic space group P1 showing perfect parallel alignment of the molecular dipoles. The CF3SO3 salt cryst allised in a monoclinic space group P2(1) and shows an angle of 73.8 degree s between the molecular dipoles in the unit cell. Complex [RuCp(( +)-DIOP)( p-N drop CCH3)][PF6]. studied for comparison, crystallises in the C222(1) s pace group and shows eight molecules per unit cell randomly orientated. Com parison of the Ru-N and N dropC distances between the three compounds are i n agreement with metal-nitrile bonding suggested by the spectroscopic data. (C) 2001 Elsevier Science B.V. All rights reserved.