Can. J. Chem. 62, 891 (1984).The preparation, magnetic and thermal properties, electronic and infrared spectra. and molecular structure of poly-bis(pdi-n-hexylphosphinato)copper(II) are described. Crystals of the compound are triclinic, a = 9.800(3), b = 12.336(6), c = 13.352(8) A, a = 88.53(3), P = 74.02(4), y = 82.33(3)", Z = 2, space group P I . The structure was solved by Patterson and Fourier syntheses and was refined by full-matrix least-squares procedures to R = 0.045 and R,,. = 0.056 for 3095 reflections with I 2 3o(I). The crystal structure of C U [ (~-C~H ,~)~P O~]~ consists of well-separated infinite chains of centrosymmetric spiro-fused eight-membered rings propagating along the crystallographic a axis.The magnetic susceptibility of C U [ (~-C~H , ,~)~P O~]~ was studied over the temperature range 4.2 to 300 K. The compound shows ferromagnetic behaviour and the data have been successfully analyzed according to the isotropic Heisenberg model for linear chains with g = 2.16 and J = 2.58 cm-'. For comparison, the magnetic susceptibilities of CU[(C,H~),PO,]~ and C U [ (~-C , H~) , P O~]~ have also been measured over the range 4.2 to 300 K. The butyl derivative shows ferromagnetic exchange with g = 2.16 and J = 2.22 cm-' while the ethyl derivative is antiferromagnetic with g = 2.19 and -J = 1.27 cm-'. The structural details of all three compounds are examined in the light of the differing magnetic properties. . Can. J. Chem. 62, 891 (1984). On dCcrit les propriCtts magnCtiques et thermales, les spectres Clectronique et infrarouge, et la structure molCculaire de poly-bis(p-!i-n-hexyle phosphinato) cuivre(I1). Les cristaux sont tricliniques, a 9,800(3), b = 12,336(6), c = L3,352(8) A, a = 88,53(3), P = 74,02(4), y = 82,33(3)", Z = 2, groupe d'espace P I . On a rCsolu la structure par les syntheses de Patterson et de Fourier et on l'a affinCe par la mCthode des moindres carrCs (matrice entiere) jusqu'a des valeurs de R = 0,045 et R,,. = 0,056 pour 3095 reflexions avec I 2 3u(1). La structure du cristal de consiste en chainons, infinis et bien stpares, des cycles de huit membres, centrosymmetriques et spiro-fustes, qui sont propages suivant l'axe c . On a Ctudit la susceptibilitC magnitique dans I'intervalle de tempkrature de 4.2 i 300 K. La composC prCsente les proprittts ferromagnktiques et on a analyst les donntes d'aprbs la modble isotropique de Heisenberg pour les chainons lintaires, avec g = 2,16 et J = 2,58 cm-'. Par comparaison, les susceptibilitCs magnktiques de C U [ ( C , H~)~P O~]~ et de C U [ (~-C~H~)~P O~]~ ont t t t mesurCs aussi dans I'intervalle 4,2 a 300 K. Le dCrivatif butylique exhibe 1'Cchange ferromagnttique, avec g = 2,16 et J = 2,22 cm-', tandis que le dtrivatif CthylC est antiferromagnttique avec g = 2.19 et -J = 1,27 cm-'. On a examine les particularitCs structurales de tous les trois composCs en vue des proprittks magnttiques difftrentes. IntroductionSingle crystal X-ray diffraction studies on C U [ ( C~H~)~P O~]~ (1) and CU[(~-C,H,)~PO~]~ (2) have shown them to be polymeric with we...

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. Can. J. Chem. 63, I1 l l (1985). Phosphinates of copper(l1) of the type C U ( R~P O~)~ where R is n-octyl, n-decyl, and n-dodecyl have been synthesized and characterized by differential scanning calorimetry, vibrational and electronic spectroscopy, and variable temperature (300 to 4.2 K) magnetic susceptibility studies. Each of these compounds was obtained in distinct a and P structural forms. All materials appear to have the double phosphinate bridged extended chain structure and the magnetic data have been successfully analyzed according to the isotropic Heisenberg model for linear chains. The a forms exhibit antiferromagnetic behaviour with J values of -25, -29, and -29 cm-' for the octyl, decyl, and dodecyl derivatives respectively. The P forms are ferromagnetic and have corresponding J values of 1.8, 2

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