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Muller, Afred

Roodt, Andreas

Steyl, Gideon

English

University of Johannesburg Institutional Repository

Triferrocenylphosphine oxide mono-hydrateAlfred Muller, Gideon Steyl and Andreas Roodt*Department of Chemistry and Biochemistry, Rand Afrikaans University, AucklandPark, Johannesburg, South Africa 2006Correspondence e-mail: aroo@rau.ac.zaReceived 30 April 2004Accepted 18 June 2004Online 21 July 2004The title compound, [Fe3(C5H5)3(C15H12OP)]H2O or Fc3PO-H2O, was obtained as red crystals from the Friedel±Craftsalkylation reaction of PCl3 and ferrocene. Torsion angles(O PÐCÐFe/C) range fromÿ45.39 (9) toÿ56.11 (14). Thestructure is stabilized by intermolecular hydrogen bonds[H  O = 2.10 (3) and 2.00 (4) AÊ ], forming dimeric structuresbetween pairs of O PFc3 and water molecules. A theoreticalTolman cone angle of 211 was calculated.CommentAs part of a systematic investigation into the steric demand ofphosphine ligands in various model Pt-group metal complexes,we have unexpectedly isolated crystals of triferrocenyl-phosphine oxide (Fc3P O), (I), previously reported but notstructurally characterized by Sollot & Howard (1962). Theyellow crystalline solid obtained was at ®rst thought to beunoxidized PFc3, and was tested in reaction with[Rh(Cl)(CO)2]2 in an attempt to synthesize the well known[MCl(CO)(XY3)2] Vaska-type complexes (M is Rh or Ir, X is P,As or Sb, and Y is aryl or alkyl), which often crystallize withease. However, no reaction was observed (IR and 31P NMRspectroscopy) and crystals, now red in colour, were isolatedfrom the mixture. The spectroscopic data of these were similarto those of the yellow crystalline compound (see Experi-mental). The change in colour can probably be attributed tothe variation in solvent between the two synthetic steps,resulting in different packing effects.Compound (I) (Fig. 1) is one of the few structures char-acterized to date containing the PFc3 moiety [CambridgeStructural Database (CSD), Version 5.25 of 2004; Allen, 2002].Usually, ferrocenyl fragments possess geometric parameterssimilar to those of ferrocene and its derivatives. In the case of(I), all the cyclopentadienyl (Cp) rings are planar to within0.003 AÊ and the interplanar angles are 3.53 (19), 2.37 (12) and2.19 (12) for the Fe1, Fe2 and Fe3 moieties, respectively.Furthermore, the Cp rings in each ferrocenyl moiety have analmost eclipsed conformation.Pairs of O PFc3 molecules are linked via OÐH  Ohydrogen bonds to water molecules, forming a dimeric struc-ture around an inversion centre (Table 2 and Fig. 2). Thisinteraction creates channels along the c axis (Fig. 2). The useof water as a hydrogen bridge in the solid state in phosphineoxide compounds is not uncommon, but few form dimericstructures in the unit cell (ca 10% in the CSD). Thesecompounds mostly consist of either ferrocene or electron-donating (Krauss et al., 2001) functionalized variationsthereof. Thus, electron-rich phosphorus(V) oxides might assistin the formation of dimeric structures. The same hydrogen-bonding pattern is observed for the structure ofO PFc2EtH2O (Durfey et al., 2002).metal-organic compoundsm386 # 2004 International Union of Crystallography DOI: 10.1107/S0108270104014908 Acta Cryst. (2004). C60, m386±m388Acta Crystallographica Section CCrystal StructureCommunicationsISSN 0108-2701Figure 2A packing diagram for (I), illustrating the interactions between pairs ofO PFc3 and water molecules.Figure 1The structure of (I), showing the atom-numbering scheme anddisplacement ellipsoids at the 30% probability level. H atoms have beenomitted for clarity. For the C atoms, the ®rst digit indicates the ringnumber and the second digit indicates the number of the atom in the ring.The conformation of the ferrocene substituents in (I) can bedescribed by the torsion angles between the O P moiety andferrocene, which are compared in Table 3 with those of othercompounds containing PFc3 fragments. It is important to notethat none of the compounds has torsion angles close to 0,illustrating few or no intramolecular interactions betweenXÐP and ferrocene, which was postulated as an option for apossible geometrical conformation of (I) (Sollot & Howard,1962). The ferrocenyl moieties are staggered in such a way thatatoms O1 and P are both above the plane formed by the threeFe atoms [1.8424 (16) and 0.3499 (5) AÊ for O1 and P, respec-tively].Three different methods have been investigated to estimatethe torsion angles of the ferrocenyl moiety for comparisonwith reported torsion angles in the literature (Steyl et al.,2001). These include OÐPÐCg1ÐCg2, OÐPÐCÐFe andOÐPÐCÐC (Cg is the centroid of ring 1 or 2). The torsionangles OÐPÐCg1ÐCg2 and OÐPÐCÐFe yield similarvalues, while the other method gives ca 5 difference, becauseof the almost eclipsed conformation of the Cp rings.The most widely used parameter to de®ne the stericdemand of tertiary phosphines is the Tolman cone angle (T),which was calculated as described previously (Tolman, 1977;Otto et al., 2000). A modi®ed structure of (I) was used tocalculate a reasonable value for the expected Tolman coneangle, by incorporating a dummy atom 2.28 AÊ from the Patom. A somewhat larger value of 211 was obtained for (I)compared with the other known PFc3 structures (Table 3).This value may not necessarily be a true re¯ection of the stericin¯uence on a given metal centre, since the ¯exibility offerrocenyl moieties around the PÐC bond can signi®cantlyaffect this value. This was found previously with similar ¯ex-ible phosphines, e.g. tribenzylphosphine (Muller et al., 2002)and ferrocenyldiphenylphosphine (Otto et al., 2000). Thestructures of IÐPFc3 and H2C PFc3 are examples where theferrocenyl fragments have different orientations with respectto the XÐP moieties (torsion angles given in Table 3) but stillpossess similar cone angles.ExperimentalThe title compound was prepared according to a modi®ed version ofthe published procedure of Sollot & Howard (1962). Ferrocene (30 g,0.16 mol) and freshly sublimed AlCl3 (4.33 g, 0.032 mol) were addedto degassed heptane (100 ml) in a vessel equipped with a re¯uxcondenser and a dropping funnel containing PCl3 (2.84 ml,0.03262 mol) in degassed heptane (100 ml). The solution in thedropping funnel was added to the mixture over a period of 1 h, afterwhich the mixture was re¯uxed (ca 373 K) for 24 h. The mixture wasthen decanted and the remaining solids extracted successively withhot benzene and water. The combined benzene extracts were dried(Na2SO4) and the remaining solid puri®ed by column chromatog-raphy [acetone±CHCl3, 1:4; RF(O PFc3) = 0.3]. Puri®ed (I) crys-tallized as yellow crystals by slow evaporation from the acetone±chloroform solution (yield 0.5 g, 2.6%). Red crystals of (I) wereobtained from the reaction of [Rh(Cl)(CO)2]2 and (I) (1:4 molarratio) in dichloromethane. Spectroscopic data, 1H NMR (CDCl3,300 MHz): 4.08 p.p.m. (d, 27 H); 31P{H} NMR (CDCl3, 121.46 MHz):30.3 p.p.m. (s).Crystal data[Fe3(C5H5)3(C15H12OP)]H2OMr = 620.05Triclinic, P1a = 10.010 (2) AÊb = 11.900 (2) AÊc = 11.920 (2) AÊ = 76.51 (3) = 70.23 (3) = 78.13 (3)V = 1286.8 (5) AÊ 3Z = 2Dx = 1.60 Mg mÿ3Dm = 1.585 Mg mÿ3Dm measured by ¯otation inaqueous NaIMo K radiationCell parameters from 966re¯ections = 3±28 = 1.76 mmÿ1T = 293 (2) KCuboid, red0.40  0.24  0.18 mmData collectionBruker SMART 1K CCD area-detector diffractometer! scansAbsorption correction: multi-scan(SADABS; Bruker, 1998)Tmin = 0.583, Tmax = 0.7288973 measured re¯ections6181 independent re¯ections5233 re¯ections with I > 2(I)Rint = 0.015max = 28.3h = ÿ10! 13k = ÿ15! 15l = ÿ15! 15Re®nementRe®nement on F 2R(F ) = 0.028wR(F 2) = 0.073S = 1.036181 re¯ections333 parametersH atoms treated by a mixture ofindependent and constrainedre®nementw = 1/[2(Fo2) + (0.0338P)2+ 0.4474P]where P = (Fo2 + 2Fc2)/3(/)max = 0.001max = 0.39 e AÊÿ3min = ÿ0.47 e AÊ ÿ3Aromatic H atoms were placed in geometrically idealized posi-tions (CÐH = 0.97±0.98 AÊ ) and constrained to ride on their parentatoms, with Uiso(H) = 1.2Ueq(C). The positions of the water H atomswere determined from a Fourier difference map and their coordinateswere re®ned isotropically.Data collection: SMART-NT (Bruker, 1998); cell re®nement:SAINT-Plus (Bruker, 1999); data reduction: SAINT-Plus andXPREP (Bruker, 1999); program(s) used to solve structure: SIR97(Altomare et al., 1999); program(s) used to re®ne structure:SHELXL97 (Sheldrick, 1997); molecular graphics: DIAMOND(Brandenburg, 2001); software used to prepare material for publi-cation: WinGX (Farrugia, 1999).metal-organic compoundsActa Cryst. (2004). C60, m386±m388 Muller, Steyl and Roodt  [Fe3(C5H5)3(C15H12OP)]H2O m387Table 1Selected geometric parameters (AÊ , ).PÐO1 1.4941 (15)PÐC31 1.7846 (19)PÐC51 1.7872 (17)PÐC11 1.7879 (18)O1ÐPÐC31 114.50 (9)O1ÐPÐC51 113.87 (9)O1ÐPÐC11 113.96 (8)C21ÐC11ÐPÐO1 ÿ45.39 (9)C41ÐC31ÐPÐO1 ÿ51.27 (10)C61ÐC51ÐPÐO1 ÿ50.69 (10)Fe1ÐC11ÐPÐO1 ÿ49.29 (13)Fe2ÐC31ÐPÐO1 ÿ56.11 (14)Fe3ÐC51ÐPÐO1 ÿ54.49 (14)Table 2Hydrogen-bonding geometry (AÊ , ).DÐH  A DÐH H  A D  A DÐH  AO2ÐH1  O1 0.75 (3) 2.10 (3) 2.843 (3) 167 (3)O2ÐH2  O1i 0.86 (4) 2.00 (4) 2.860 (3) 178 (4)Symmetry code: (i) 1ÿ x; 1ÿ y; 1ÿ z.Financial assistance from the South Africa NRF, SASOL,and RAU is acknowledged, and the University of theWitwatersrand (Professor D. Levendis and Dr D. Billing) isthanked for the use of its diffractometer. Part of this materialis based on work supported by the South African NationalResearch Foundation under grant No. GUN 2053397.Opinions, ®ndings, conclusions or recommendations expressedin this material are those of the authors and do not necessarilyre¯ect the views of the NRF.Supplementary data for this paper are available from the IUCr electronicarchives (Reference: JZ1629). Services for accessing these data aredescribed at the back of the journal.ReferencesAllen, F. H. (2002). Acta Cryst. B58, 380±388.Altomare, A., Burla, M. C., Camalli, M., Cascarano, G., Giacovazzo, C.,Guagliardi, A., Moliterni, A. G. G., Polidori, G. & Spagna, R. (1999). J.Appl. Cryst. 32, 115±119.Brandenburg, K. (2001). DIAMOND. Release 2.1e. Crystal Impact GbR,Bonn, Germany.Bruker (1998). SADABS (Version 2004/1) and SMART-NT (Version 5.050).Bruker AXS Inc., Madison, Wisconsin, USA.Bruker (1999). SAINT-Plus. Version 6.02 (including XPREP). Bruker AXSInc., Madison, Wisconsin, USA.Durfey, D. A., Kirss, R. U., Churchill, M. R., Keil, K. M. & Feighery, W. (2002).Synth. React. Inorg. Met. Org. Chem. 32, 97±115.Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837±838.Gridunova, G. V., Shklover, V. E., Struchkov, Yu. T., Vil'chevskaya, V. D.,Podobedova, N. L. & Krylova, A. I. (1982). J. Organomet. Chem. 238, 297±305.Krauss, B., Mugge, C., Ziemer, B., Zschunke, A. & Krech, F. (2001). Z. Anorg.Allg. Chem. 627, 1542±1552.Muller, A. J., Roodt, A., Otto, S., Oskarsson, AÊ . & Yong, S. (2002). Acta Cryst.E58, m715±m717.Otto, S., Roodt, A. & Smith, J. (2000). Inorg. Chim. Acta, 303, 295±299.Schmidbaur, H., Jeong, J., Schier, A., Graf, W., Wilkinson, D. L. & Muller, G.(1989). New J. Chem. (Nouv. J. Chim.), 13, 341±352.Sheldrick, G. M. (1997). SHELXL97. University of GoÈ ttingen, Germany.Sollot, G. P. & Howard, E. (1962). J. Org. Chem. 27, 4034±4040.Steyl, G., Otto, S. & Roodt, A. (2001). Acta Cryst. E57, m352±m354.Tolman, C. A. (1977). Chem. Rev. 77, 313±348.metal-organic compoundsm388 Muller, Steyl and Roodt  [Fe3(C5H5)3(C15H12OP)]H2O Acta Cryst. (2004). C60, m386±m388Table 3Comparative geometrical data for XPFc3 (, AÊ ).tor1 = XÐPÐCg1ÐCg2; tor2 = XÐPÐCÐFe; tor3 = XÐPÐCÐC; T is theTolman cone angle (Tolman, 1977); Cg is the centroid of ring 1 or 2.X FeÐX tor1 tor2 tor3 T ReferenceO 1.4941 (15) ÿ47.6 ÿ49.3 ÿ45.4 211 aÿ55.2 ÿ56.2 ÿ51.3ÿ54.6 ÿ54.4 ÿ50.6I 2.426 (12) ÿ46.3 ÿ47.3 ÿ45.4 198 bÿ162.0 ÿ161.2 ÿ167.6ÿ49.2 ÿ49.3 ÿ52.0CH2 1.630 56.3 57.2 51.5 200 c63.5 62.7 58.864.5 64.3 61.3References: (a) this work; (b) Gridunova et al. (1982); (c) Schmidbaur et al. (1989).

Triferrocenylphosphine oxide mono-hydrate

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Triferrocenylphosphine oxide mono-hydrate

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