Crystal Structure of Trans- [bis(2,5-dichlorophenylcyanamido) {N,N′-propanediylbis(2,3-butadien-2-imine-3-oxime)} Cobalt(III)], trans-[Co((DO)(DOH)pn)(2,5-Cl2pcyd)2]

Abstract

The first crystal structure of a phenylcyanamide cobaltoxime (cobaloxime) complex is reported. This compound is trans-[Co((DO)(DOH)pn)(2,5-Cl2pcyd)2], and consits of an imine-oxime equatorial ligand ((DO)(DOH)pn) and two 2,5-dichlorophenylcyanamide ligands in axial positions. Crystals of trans- [Co((DO)(DOH)pn)(2,5-Cl2pcyd)2] were grown by ether diffusion into an acetonitrile solution of the complex. Crystal structure of this complex is orthorhombic (space group: Pbca) with a = 13.6800, b = 13.7434, c = 29.892 Å, and Z = 8. The structure was refined by using 2946 independent reflections with I>2σ(I) to a R factor of 0.0606. Both phenylcyanamide ligands are coordinated to Co(III) through the terminal nitrile nitrogen of the cyanamide group. In addition, the cobalt(III)-cyanamide (Co(III)-N=C=N-ph) bond angle is significantly bent while the cyanamide group(N=C=N-) is largely coplanar with the phenyl ring. These geometries can be ascribed to the relative importance of p bonding.

Keywords


[1] Hadadzadeh H., Shamsipur M., Salimi A., Mousavi M.F., "Electrocatalytic ativity of cobaloxime complexes adsorbed on glassy carbon electrodes toward the reduction of dioxygen", J. Electroanal. Chem. 517 (2001) 37-44.

[2] Hadadzadeh H., Rezvani A.R., "Synthesis of novel mononuclear and dinuclear cobalt(III) complexes with cyanamide derivative ligands", J. Chem. Research No.3 (2002) 139-141.

[3] Hadadzadeh H., Amirnasr M., "Ligand field photoaquation reactions of trans- [Co((DO)(DOH)pn)(amine)Cl]PF6 complexes", Scientia Iranica 4 (1997) 125-130.

[4] Hadadzadeh H., Amirnasr M., "Synthesis and characterization of amine (chloro) cobaloxime derivatives, approximate values of the AOM parameter σ for the coordinated amines", J. Science 7 (1996) 164-168.

[5] Marzilli L.G., Yohannes P.G., Bresciani-Pahor N., Randaccio L., Zangrando E., "Organocobalt B12 models bearing axial substituents on a costa-type equatorial ligand: structural, rate and spectroscopic consequences", Inorg. Chem. 27 (1988) 4738-4744.

[6] Marzilli L.G., Pahor N.B., Zangrando E., Finke R.G., Myers S.A., "An assessment of the cis- influence in coenzyme B12 models", Inorg. Chim Acta. 107 (1985) 139-145.

[7] Marzilli L.G., Gerli A., "Costa-type B12 models: synthesis, structural characterization and electrochemistry of chloro derivatives", Inorg. Chem. 31 (1992) 1152-1160.

[8] Marzilli L.G., Polson M., Hansen L., Moore, S.J., Marzilli, P.A., "B12 models with highly distorted N4 equatorial ligation and a Co-C-N ring: Structural assessment of the steric influence of benzimidazole and imidazole axial ligands", Inorg. Chem. 36 (1997) 3854-3860.

[9] Marzilli L.G., Moore S.J., Kutikor A., Lachicotte R.J.L., "Methyl B12 models containing unsubstituted imidazole as an axial ligand investigated by structural and NMR spectroscopic methods", Inorg. Chem. 38 (1999) 768-776.

[10] Crutchley R.J., "Phenylcyanamide ligands and their metal complexes", Coord. Chem. Rev. 219-221 (2001) 125-155.

[11] Kabesova M., Boca R., Melnick M., Valigura D., Dunaj-jurco M., "Boding properties of thiocyanate groups in copper(II) complexes", Coord. Chem. Rev. 140 (1995) 115-135.

[12] Naklicki M.L., Crutchley R.J., "Coordination chemistry of neutral phenylcyanamide ligands bound to pentaammineruthenium(II)", Inorg. Chem. 28 (1989) 4226-4229.

[13] Crutchley R.J., Nakliki M.L., "Pentaammineruthenium(III) complexes of neutral and anionic (2,3-dichlorophenyl)cyanamide: spectroscopic analysis of ligand to metal gharge transfer", Inorg. Chem. 28 (1989) 1955-1958.

[14] Buchanan G.W., Crutchley R.J., "15N-NMR study of phenylcyanamides", Magn. Reson. Chem. 32 (1994) 552-258.

[15] Chisholm M.H., Folting K., Huffman J.C., Marchant N.S., "Notable features in the molecular structure of W2(OCH2-t-Bu)6(NCNMe2)3, Polyhedron", 3 (1984) 1033-1035.

[16] Rezvani A.R., Evans C.E.B., Crutchley R.J., "Strong metal-metal coupling in a dinuclear (terpyridine)ruthenium mixed-valence complex incorporating the bridging ligand 1,4-dicyanamidobenzene dianion", Inorg. Chem., 34 (1995) 4600-4604.

[17] Rezvani A.R., Bensimon C., Cromp B., Reber C., Greedan J.E., Kodratiev V.V., Crutchley R.J., "Inner coordination sphere control of metal-metal superexchange in ruthenium dimmers", Inorg. Chem. 36 (1997) 3322-3329.

[18] Rezvani A.R., Crutchley R.J., "Dependence of the Ru(III)-cyanamide chromophore on inner-spehere coordination: comparison of cis-[Ru(bpy)2 (pcyd)2]+and [Ru(NH3)5(pcyd)]2+complexes", Inorg. Chem. 33 (1994) 170-174.

[19] Rezvani A.R., Evans C.E.B., Naklicki M.L., White C.A., Kondratiev V.V., Crutchley R.J., "An investigation of superexchange in dinuclear mixed-valence ruthenium complexes", J. Am. Chem. Soc. 120 (1998) 13096-13103.

[20] Mosher P.J., Yap G.P.A., Crutchley R.J., "Influuence of the inner coordination sphere on the Ru(II)-cyanamide ligand to metal charge transfer chromophore", Inorg. Chem. 40 (2001) 550-553.

[21] Brader M.L., Ainscough E.W., Backer E.N., Brodie A.M., Ingham S.L., "Synthetic, spectroscopic, and X-ray crystallographic studies on phenylcyanamidocopper(II) complexes. The characterization of three different co-ordination modes for phenylcyanamide anions", J. Chem. Soc. Dalton Trans. (1990) 2785-2792.

[22] Aquino M.A.S., Crutchley R.J., Lee F.L., Gabe E.J., Bensimon C., "Structure of 1,4-benzenedicyanamide dianion derivatives", Acta Crystallogr. C49 (1993) 1543-1547.

[23] Evans C.E.B., Yap G.P.A., Crutchley R.J., "Comparison of hole transfer superexchange in dinuclear mixed-valence ruthenium complexes", Inorg. Chem. 37 (1998) 6161-6167.

[24] Hadadzadeh H., Rezvani A.R., "The electrochemical and spectroscopic studies of trans- [Co((DO)(DOH)pn)LL’] complexes", Iran J. Chem. & Chem. Eng. 21(2002) 21-27.

[25] Nakliki M.L., White C.A., Kondratiev V.V., Crutchley R.J., "Mono and dinuclear ruthenium(III) and ruthenium(IV) complexes of 1,4-dicyanamido-

2,5-dimethylbenzene dianion", Inorg. Chim. Acta 242 (1996) 63-69.

[26] Desjardins P., Yap G.P.A., Crutchley R.J., "Tetrakis(pyridine)ruthenium trans complexes of phenylcyanamide ligands", Inorg. Chem. 38 (1999) 5901-5905.

[27] Aquino M.A.S., Crutchley R.J., "A pentaamineruthenium mixed-valence complex with 1,4-dicyanamidobenzene dianion as bridging ligand", Inorg. Chem. 29(1990) 3641-3644.

[28] Letcher R.J., Zhang W., Bensimon C., Crutchley R.J., "1,3-Bis(2’-pyridylamino)isoindolinato)nickel(II) complexes of phenylcyanamido ligands", Inorg. Chim. Acta 210 (1993) 183-191.

[29] Zhang W., Bensimon C., Crutchley R.J., "(Terpyridine)palladium(II) complexes of phenylcyanamide ligands", Inorg. Chem. 32 (1993) 5808-5812.

[30] Brader M.L., Aniscough E.W., Baker E.N., Brodie A.M., "Copper(II) promoted desulphurization of N-phenylthiourea", Polyhedron 8 (1989) 2219-2221.

[31] Hadadzadeh H., Rezvani A.R., Patrick B., "Stucture and spectroscopic studies of cis-bis(bipyridine) cobalt(III) complexes of phenylcyanamide ligands", Inorg. Chim. Acta 336 (2002) 125-130.

[32] Derosa M.C., Crutchley R.J., "Semiconductor properties in an iodine-doped Pt(II) dinuclear complex", Inorg. Chem. 40 (2001) 1406-1407.

[33] Ainscough E.W., Backer E.N., Brader M.L., Brodie A.M., Ingham S.L., Waters J.M., Hanna J.V., Healy P.C., "Synthetic, spectroscopic and X-ray crystallographic studies on phenylcyanamidocopper(I) complexes", J. Chem. Soc. Dalton Trans. (1991) 1243-1250.

[34] Blessing R., "An empirical correction for absorption anisotropy", Acta Crystallogr. A51 (1995) 33-38.

[35] Sheldrick G.M., "SHELXTL 5.1", Bruker AXS Inc., Madison, WI (1997).

[36] Mosher P.J., Yap G. P. A., Crutchley R.J., "A donor-acceptor-donor bridging ligand in a class III mixed-valence complex", Inorg. Chem. 40 (2001) 1189-1195.

[37] Lever A.B.P., "Inorganic Electronic Spectroscopy", 2'nd ed. (1984) Elsevier, Amsterdam.