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Muller, Alfred

Roodt, Andreas

English

University of Johannesburg Institutional Repository

metal-organic compoundsm266 # 2004 International Union of Crystallography DOI: 10.1107/S0108270104009096 Acta Cryst. (2004). C60, m266±m268cis-Diphenylbis(1,3,5-triaza-7-phosphaadamantane-jP)-platinum(II)Alfred Muller and Andreas Roodt*Department of Chemistry and Biochemistry, Rand Afrikaans University, AucklandPark, Johannesburg, South Africa 2006Correspondence e-mail: aroo@rau.ac.zaReceived 23 March 2004Accepted 16 April 2004Online 22 May 2004The structure of the title compound, [Pt(C6H5)2(C6H12N3P)2]or [Pt(Ph)2(PTA)2] (where Ph is phenyl and PTA is 1,3,5-triaza-7-phosphaadamantane), is discussed. Selected geom-etric parameters are: PtÐP = 2.2888 (16) and 2.2944 (17) AÊ ,PtÐC = 2.052 (5) and 2.064 (6) AÊ , CÐPtÐC = 84.6 (2) andPÐPtÐP = 99.28 (6). The effective cone angle for the PTAligands was calculated as 113.CommentThe 1,3,5-triaza-7-phosphaadamantane ligand (PTA) hasattracted much attention due to its unique characteristic ofenabling the preparation of water-soluble complexes withoutthe complication of introducing a charged species into thecomplex. Numerous PTA complexes exhibiting catalyticactivity have been reported (Darensbourg et al., 1997, 1999;Alyea et al., 1993; JooÂ et al., 1996).We report here the structure of the title cis-diphenyl-bis(PTA)platinum(II) complex, (I), as part of our systematicinvestigation into the basic coordination modes and solutionproperties of these complexes. Compound (I) is the ®rstexample of a PtII square-planar diphenyl complex with a cisgeometry containing non-bridged phosphine ligands(Cambridge Structural Database, Version 5.25; Allen, 2002).Similar diphenylplatinum complexes with a trans conforma-tion are known (Incarvito et al., 1999; Ertl et al., 1982). Theformation of the cis complex may be ascribed either todifferent synthetic routes or to the small steric demand of thePTA ligand (Daigle et al., 1998; Otto & Roodt, 2001), whichenables the more sterically demanding cis conformationtypically found for two strong cis ligands.The Pt atom of (I) lies on a general position in the asym-metric unit and the coordination polyhedron shows a slightlydistorted square-planar arrangement (Table 1). The phenylrings are almost perpendicular to the coordination plane ofthe Pt atom [dihedral angle = 85.2 (2) for the C41-phenyl and86.1 (2) for the C31-phenyl]. This perpendicular conforma-tion allows more space for the PTA ligands, resulting in quite asmall bite angle of 84.6 (2) for C41ÐPtÐC31, compared with99.28 (6) for P1ÐPtÐP2.The orientation of the PTA ligands is best described by thetorsion angles, which were calculated using the methylenesubstituent on the phosphine closest to the metal coordinationplane. Two signi®cantly different values [28.8 (3) for C41ÐPtÐP1ÐC12 and 15.5 (3) for C31ÐPtÐP2ÐC22], wereobtained, and may possibly be the result of steric and packingeffects.The most widely used method for determining ligand stericbehaviour at a metal centre utilizes the Tolman cone angle(Tolman, 1977), using an MÐP bond distance of 2.28 AÊ , a CÐH bond distance of 0.97 AÊ and 1.2 AÊ as the van der Waalsradius of hydrogen. For the calculation of effective coneangles, the PtÐP bond distances determined from the crys-tallographic data were used (Otto et al., 2000). The value of113 obtained from effective cone-angle calculations for (I) isin agreement with the previous values, again illustrating therigidness of PTA (Meij et al., 2002).High Ueq(max)/Ueq(min) values are observed for atomslying on the periphery of the molecule in both the phenyl andActa Crystallographica Section CCrystal StructureCommunicationsISSN 0108-2701Figure 1The structure of (I), showing the atom-numbering scheme anddisplacement ellipsoids at the 30% probability level.the phosphine parts, indicating some freedom of packing inthese regions. This may also explain some observed short CÐC distances (Albertsson et al., 1980).Relatively few structures of the form cis-[M(X)2(PTA)2](where M is Pd or Pt and X is an anionic substituent) areknown. These are compared with (I) in Table 2, clearlyshowing the higher steric demand of Clÿ compared with theC6H5ÿ ligand, with ca 5 differences for both the PÐMÐP andXÐMÐX angles. Larger effective cone angles (E) are notedfor the chloro complexes, indicating the weaker trans in¯uenceof Clÿ compared with PTA. This can also be correlated withthe respective MÐX and MÐP bond distances.It is interesting to note that, in a comparison with othersubstituted aryl ligands (Table 3), the CÐMÐC angles do notdiffer signi®cantly, even though phosphines with various stericdemands were used. The exception is the case of the stronglyelectron-withdrawing (and bulky) C6F5ÿ group, where differ-ences of ca 5 for both the PÐMÐP and XÐMÐX angleswere again noted.Experimental[Pt(Ph)2(cod)] (cod is 4-1,5-cyclooctadiene) was prepared accordingto the literature procedure of Clark & Manzer (1973). To a solution of[Pt(Ph)2(cod)] (50 mg, 0.11 mmol) in dichloromethane (10 ml) wasadded PTA (34 mg, 0.22 mmol) dissolved in methanol (10 ml).Crystals of (I) suitable for X-ray analysis separated from the solutionover a period of a few hours in quantitative yield. Spectroscopic data:31P{H} NMR (CDCl3): ÿ77.2 p.p.m. (1JPtÐP = 1560 Hz).Crystal data[Pt(C6H5)2(C6H12N3P)2]Mr = 663.6Triclinic, P1a = 9.616 (5) AÊb = 10.395 (5) AÊc = 12.477 (5) AÊ = 86.112 (5) = 83.778 (5) = 88.080 (5)V = 1236.5 (10) AÊ 3Z = 2Dx = 1.782 Mg mÿ3Mo K radiationCell parameters from 3164re¯ections = 2±24 = 5.83 mmÿ1T = 293 (2) KNeedle, colourless0.22  0.06  0.04 mmData collectionBruker SMART CCD 1K area-detector diffractometer! scansAbsorption correction: multi-scan(SADABS; Bruker, 1998)Tmin = 0.69, Tmax = 0.7712 595 measured re¯ections7326 independent re¯ections4483 re¯ections with I > 2(I)Rint = 0.048max = 31.6h = ÿ14! 14k = ÿ12! 15l = ÿ17! 18Re®nementRe®nement on F 2R(F ) = 0.045wR(F 2) = 0.083S = 0.887326 re¯ections298 parametersH-atom parameters constrainedw = 1/[2(Fo2) + (0.0291P)2]where P = (Fo2 + 2Fc2)/3(/)max = 0.001max = 0.99 e AÊÿ3min = ÿ0.72 e AÊ ÿ3The aromatic and methylene H atoms were placed in geometricallyidealized positions (CÐH = 0.97±0.98 AÊ ) and constrained to ride ontheir parent atoms, with Uiso(H) = 1.2Ueq(C).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 & Berndt, 2001); software used to prepare material forpublication: WinGX (Farrugia, 1999).Acta Cryst. (2004). C60, m266±m268 Muller and Roodt  [Pt(C6H5)2(C6H12N3P)2] m267metal-organic compoundsTable 1Selected geometric parameters (AÊ , ).PtÐC31 2.052 (5)PtÐC41 2.064 (6)PtÐP1 2.2888 (16)PtÐP2 2.2944 (17)C31ÐPtÐC41 84.6 (2)C31ÐPtÐP1 171.24 (15)C41ÐPtÐP1 86.71 (15)C31ÐPtÐP2 89.40 (15)C41ÐPtÐP2 173.77 (15)P1ÐPtÐP2 99.28 (6)C12ÐP1ÐC11 97.1 (3)C12ÐP1ÐC13 97.2 (3)C11ÐP1ÐC13 97.9 (3)C21ÐP2ÐC23 98.4 (3)C21ÐP2ÐC22 97.8 (3)C23ÐP2ÐC22 96.7 (3)Table 2Comparative geometrical data for cis-[M(X)2(PTA)2] complexes (AÊ ,).M(X) MÐP MÐX PÐMÐP XÐMÐX EPt(Ph)a 2.2888 (16) 2.052 (5) 99.28 (6) 84.6 (2) 1132.2944 (17) 2.064 (6) 113Pt(Cl)b 2.2240 (12) 2.3490 (13) 94.26 (4) 87.24 (5) 1162.2284 (12) 2.3712 (13) 1172.2229 (13) 2.3473 (12) 94.68 (5) 87.06 (5) 1162.2300 (12) 2.3663 (13) 116Pt(Cl)c² 2.218 (5) 2.358 (5) 94.3 86.2 (2) 117Pd(Cl)d 2.242 2.373 93.58 (5) 88.95 1162.255 2.347 1152.251 2.347 93.25 (5) 89.15 1172.239 2.378 116Pd(Cl)c 2.226 (5) 2.363 (5) 94.4 (2) 90.2 (2) 1172.264 (6) 2.360 (5) 117Notes: (a) this work; (b) Otto et al. (1998); (c) Darensbourg et al. (1997); (d) Alyea et al.(1998). ² Protonated form of PTA.Table 3Comparative geometrical data for cis-[Pt(X)2(PR3)2] complexes (AÊ ,).2-TolPh = o-tolylphenyl; DP(2-PE) = diphenyl(2-phenylethynyl); DP(3,3-DMB) = diphenyl(3,3-dimethylbutynyl); DP(2pTet) = diphenyl(2-p-tolyl)-ethynyl; 2-NPh = 2-nitrophenyl; 7-MeNap = 7-methyl-1-naphthyl; 2-OMePh =2-methoxyphenyl; 3,5-DAMPh = 3,5-bis(diethylaminomethyl)phenyl.Pt(X)(PR3) MÐP MÐX PÐMÐP CÐMÐC E(Ph)(PTA)a 2.2888 (16) 2.052 (5) 99.28 (6) 84.6 (2) 1132.2944 (17) 2.064 (6) 113(2-TolPh)(PEt3)b² 2.317 (2) 2.058 (10) 100.0 (1) 83.9 (3) 1452.330 (2) 2.091 (6) 140(C6F5)[DP(2-PEPh)]c 2.310 2.070 92.86 85.83 148(C6F5)[DP(3,3-DMBPh)]c 2.294 2.050 95.02 84.24 1512.297 2.059 149(C6F5)[DP(2pTet)]c 2.315 2.068 93.28 85.78 1512.285 2.109 149(2-NPh)(PPh3)d 2.332 2.061 100.37 82.88 ³2.313 2.061(7-MeNap)(PPh3)e 2.34 (1) 2.08 (2) 99.8 (2) 85.2 (7) ³2.32 (1) 2.08 (2)(2-OMePh)(PPh3)e 2.309 2.033 100.87 81.56 ³2.313 2.033(3,5-DAMPh)(PEt3)f 2.305 2.071 100.17 82.55 1502.317 2.058 144Notes: (a) this work; (b) Rieger et al. (1993); (c) Ara et al. (2002); (d) Brune et al. (1984);(e) Debaerdemaeker et al. (1987); (f) James et al. (1996). ² Anti isomer. ³ H atomsnot included in the structure extracted from the CSD (Allen, 2002).metal-organic compoundsm268 Muller and Roodt  [Pt(C6H5)2(C6H12N3P)2] Acta Cryst. (2004). C60, m266±m268Financial assistance from Sasol, the Research Funds ofRAU and the Swedish International Development Coopera-tion Agency are gratefully acknowledged. Lund University(Professor AÊ . Oskarsson) is thanked for the use of itsdiffractometer. Part of this material is based on worksupported by the South African National Research Founda-tion under grant No. GUN 2053397. Opinions, ®ndings,conclusions or recommendations expressed in this materialare those of the authors and do not necessarily re¯ect theviews of the NRF.Supplementary data for this paper are available from the IUCr electronicarchives (Reference: TR1089). 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cis-Diphenylbis(1,3,5-triaza-7-phosphaadamantane-ĸP)-platinum(II)

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cis-Diphenylbis(1,3,5-triaza-7-phosphaadamantane-ĸP)-platinum(II)

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