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Roodt, Andreas

Steyl, Gideon

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metal-organic papersm1212 Steyl and Roodt  [Rh(C7H5O2)(C18H15As)(CO)] doi:10.1107/S1600536805015679 Acta Cryst. (2005). E61, m1212–m1214Acta Crystallographica Section EStructure ReportsOnlineISSN 1600-5368Carbonyl(triphenylarsine)(tropolonato)rhodium(I)Gideon Steyla andAndreas Roodtb*aDepartment of Chemistry and Biochemistry,University of Johannesburg, Johannesburg 2006,South Africa, and bDepartment of Chemistry,Free State University, Bloemfontein 9300, SouthAfricaCorrespondence e-mail:roodta.sci@mail.uovs.ac.zaKey indicatorsSingle-crystal X-ray studyT = 295 KMean (C–C) = 0.016 A˚R factor = 0.070wR factor = 0.186Data-to-parameter ratio = 16.3For details of how these key indicators wereautomatically derived from the article, seehttp://journals.iucr.org/e.# 2005 International Union of CrystallographyPrinted in Great Britain – all rights reservedThe title complex, [Rh(C7H5O2)(C18H15As)(CO)], has adistorted square-planar geometry. The most important bonddistances and angles include Rh—C = 1.788 (10) A˚, Rh—O(trans to CO) = 2.039 (6) A˚, Rh—O(trans to As) =2.059 (6) A˚, Rh—As = 2.3507 (13) A˚, O—Rh—O = 78.1 (2)and O—C—C—O = 3.4 (12). The short interplanar distancesbetween the tropolonate ligands [3.57 (5) A˚] and phenylgroups [3.51 (5) A˚] of neighbouring molecules indicate –stacking interactions, which stabilize the crystal packing.CommentThe first known structure of a group 15 rhodium tropolonate(Trop) compound was reported for the analogous triphenyl-phosphine derivative (Leipoldt et al., 1980) of the titlecompound. The current structure investigation was under-taken to evaluate the role that the other group 15 ligands playin affecting the solid-state behaviour of these complexes, sinceonly a small number of phosphine complexes are known todate containing tropolone ligands (Steyl et al., 2001; Steyl &Roodt, 2003, Crous et al., 2005). In this paper, we present thecrystal structure of the title compound, (I) (Fig. 1).In (I), the Rh—O bond lengths of 2.039 (6) and 2.059 (6) A˚,and the O—Rh—O bite angle of 78.1 (2) (Table 1) arecomparable with those observed in the phosphine derivative(Leipoldt et al., 1980), viz. 2.034 (7) and 2.081 (7) A˚, and77.8 (3), respectively. The tropolone ring system has adistorted geometry, confirmed by the non-zero torsion anglesO11—C1—C2—O12 [3.4 (12)] and C7—C1—C2—C3[9.7 (16)], and by the C—C bond distances in the seven-membered ring (Table 1). The Rh atom is slightly elevated by0.0481 (8) A˚ above the plane defined by the four ligand donoratoms of the square-planar coordination (C01, As1, O12 andO11). Intramolecular C—H  O hydrogen bonding isobserved in (I) (Table 2). The shortest intermolecular contact[H13  H36(x + 1, y, z) = 2.495 (8) A˚] illustrates the efficientpacking in the unit cell. Due to the efficient packing of thesystem, intermolecular interactions, with a C  O distance of3.42 (2) A˚ and a C—H  O angle of 140.5 (8), are observed(C4—H4  O01).Although (I) crystallizes in a similar fashion (square-planarconfiguration) as [Rh(L,L0-Bid)CO(PPh3)] (L,L0-Bid = - andReceived 9 May 2005Accepted 17 May 2005Online 28 May 2005-diketone) complexes (Leipoldt et al., 1980; Steyl & Roodt,2003; Crous et al., 2005), the effective and Tolman cone angles(Tolman, 1977; Otto et al., 2000) of the triphenylarsine ligandin (I) are significantly larger than those in the related struc-tures (Table 3). The Rh—As—C angles lie in the range 110–121 (Table 1); this can be attributed to the – stackinginteraction between the C31–C36 and symmetry-related[symmetry code: (2  x, y, 1  z)] phenyl rings, with aninterplanar distance of 3.51 (5) A˚. The half-angle contributionof the arsine derivative is ca 5 greater than that in the relatedcomplexes known to date (Table 3). The – interaction isalso observed for the C1–C7 tropolone and symmetry-related[symmetry code: (2  x, 1  y, z)] ring systems (Fig. 2), withan interplanar distance of 3.57 (3) A˚. The dihedral anglebetween the C1–C7 and C31–C36 planes is 89.8 (3). In thephosphine derivative (crystallized under similar conditions),where no – stacking interactions are observed for either thetropolone ring or phenyl rings, the O—C—C—O and C—C—C—C torsion angles of 1.6 and 2.8, respectively, demon-strate significantly less distortion compared with (I).Theoretical calculations were employed to determine theextent of the packing effect on the system compared to theoptimized gas-phase structure. The geometry of (I) was opti-mized with no restraints using Gaussian03W B3LYP/Lan2DZ(Frisch et al., 2003) and characterized as a minimum from thevibrational analysis. The overlay of the calculated and solidstate structures is in a good agreement (0.3 A˚; Pretorius et al.,2004), with the largest differences observed in the distortion ofthe tropolonato ring system as well as small torsion anglechanges in the phenyl rings.ExperimentalThe title compound, (I), was synthesized by dissolving[Rh(Trop)(CO)2] (10 mg, 0.036 mmol) in the minimum amount ofacetone (10 ml), adding 1.1 equivalents of AsPh3 (11.6 mg,0.038 mmol) and allowing crystallization to occur under slowevaporation (ca 1 h). IR: CO 1969 cm1, 1H NMR (CDCl3,300 MHz):  7.64 (m), 7.39 (m).Crystal data[Rh(C7H5O2)(C18H15As)(CO)]Mr = 558.25Triclinic, P1a = 8.996 (5) A˚b = 9.387 (5) A˚c = 14.137 (5) A˚ = 96.550 (5) = 103.623 (5) = 101.722 (5)V = 1119.5 (9) A˚3Z = 2Dx = 1.656 Mg m3Mo K radiationCell parameters from 1266reflections = 2.5–22.1	 = 2.25 mm1T = 295 (2) KBlock, orange0.15  0.14  0.08 mmData collectionBruker SMART CCD area-detectordiffractometer! scansAbsorption correction: multi-scan(SADABS; Sheldrick, 1998)Tmin = 0.729, Tmax = 0.8407120 measured reflections4552 independent reflections2446 reflections with I > 2(I)Rint = 0.063max = 26.4h = 11 ! 10k = 11 ! 11l = 17 ! 17RefinementRefinement on F 2R[F 2 > 2(F 2)] = 0.070wR(F 2) = 0.186S = 0.924552 reflections280 parametersH-atom parameters constrainedw = 1/[2(Fo2) + (0.1006P)2]where P = (Fo2 + 2Fc2)/3(/)max < 0.001max = 1.63 e A˚3min = 1.49 e A˚3metal-organic papersActa Cryst. (2005). E61, m1212–m1214 Steyl and Roodt  [Rh(C7H5O2)(C18H15As)(CO)] m1213Figure 1View of (I), showing the numbering scheme and displacement ellipsoidsdrawn at the 30% probability level. H atoms have been omitted forclarity. The numbering for the other atoms in the rings followsconsecutively from those shown.Figure 2The packing of (I) showing – stacking interactions (dashed lines). Hatoms have been omitted for clarity. [Symmetry codes: (i) 2  x, 1  y,1  z; (ii) 2  x, 1  y, z].Table 1Selected geometric parameters (A˚, ).Rh—C01 1.788 (10)Rh—O11 2.039 (6)Rh—O12 2.059 (6)Rh—As1 2.3507 (13)O12—C2 1.266 (11)C01—O01 1.151 (11)C1—O11 1.309 (10)C1—C7 1.392 (13)C1—C2 1.470 (13)C7—C6 1.393 (13)C2—C3 1.403 (12)C5—C6 1.349 (14)C5—C4 1.368 (15)C3—C4 1.385 (14)O11—Rh—O12 78.1 (2)C31—As1—Rh 109.7 (2)C21—As1—Rh 120.8 (3)C11—As1—Rh 117.6 (3)O01—C01—Rh 177.0 (10)C01—Rh—As1—C31 110.7 (4)C01—Rh—As1—C21 8.7 (4)C01—Rh—As1—C11 133.9 (5)O11—C1—C2—O12 3.4 (12)C7—C1—C2—C3 9.7 (16)Table 2Hydrogen-bonding geometry (A˚, ).D—H  A D—H H  A D  A D—H  AC12—H12  O11 0.93 2.30 3.152 (13) 152Table 3Effective and Tolman angles () for [Rh(X)(AsPh3)n(CO)] compounds.Compound Effective cone anglea Tolman cone anglebRh(Trop)CO(AsPh3)c 156 159Rh(TFBA)CO(AsPh3)d 152 154Rh(DBBT)CO(AsPh3)e 145 149Rh(H2O)CO(AsPh3)2f 151 152Notes: (a) Otto et al. (2000); (b) Tolman (1977); (c) present study; (d) Ebenebe et al.(1996); (e) Kemp et al. (1996); (f) Hursthouse et al. (1995).All H atoms were positioned geometrically and allowed to ride ontheir parent atoms, with C—H = 0.93 A˚ and Uiso(H) = 1.2Ueq of theparent atom. The highest and lowest electron-density peaks are 0.98and 0.91 A˚, respectively, from atom Rh.Data collection: SMART-NT (Bruker, 1998); cell refinement:SAINT-Plus (Bruker, 1999); data reduction: SAINT-Plus andSHELXTL (Bruker, 1998); program(s) used to solve structure:SHELXS97 (Sheldrick, 1997); program(s) used to refine structure:SHELXL97 (Sheldrick, 1997); molecular graphics: DIAMOND(Brandenburg, 2000); software used to prepare material for publi-cation: SHELXL97.Financial assistance from the University of Johannesburg isgratefully acknowledged. The University of the Witwatersrand(Professor D. Levendis, Dr D. Billing and Mr M. Fernandez) isacknowledged for the use of its diffractometer, while Mr A.Muller is thanked for the data collection. Part of this materialis based on the work supported by the South African NationalResearch Foundation (NRF) under grant number GUN2053397. Opinions, findings, conclusions or recommendationsexpressed in this material are those of the authors and do notnecessarily reflect the views of the NRF.ReferencesBrandenburg, K. (2000). DIAMOND. Release 2.1e. Crystal Impact GbR,Postfach 1251, D-53002, Bonn, Germany.Bruker (1998). SMART-NT (Version 5.050) and SHELXTL. Bruker AXSInc., Madison, Wisconsin, USA.Bruker (1999). SAINT-Plus (including XPREP). Version 6.02 (includingXPREP). Bruker AXS Inc., Madison, Wisconsin, USA.Crous, R., Datt, M., Foster, D., Bennie, L., Steenkamp, C., Huyser, J., Kirsten,L., Steyl, G. & Roodt, A. (2005). J. Chem. Soc. Dalton Trans. pp. 1108–1116.Ebenebe, P., Basson, S. S. & Purcell, W. (1996). Rhodium Express, pp. 11–16.Frisch, M. J., Trucks, G. W., Schlegel, H. B., Scuseria, G. E., Robb, M. A.,Cheeseman, J. R., Montgomery, J. A. Jr, Vreven, T., Kudin, K. N., Burant, J.C., Millam, J. M., Iyengar, S. S., Tomasi, J., Barone, V., Mennucci, B. et al.(2003). GAUSSIAN03. Version 6. Revision B.05. Gaussian Inc., Pittsburgh,PA, USA.Hursthouse, M. B., Malik, K. M. A., Evans, E. W., Howlader, M. B. H. & Atlay,M. T. (1995). Acta Cryst. C51, 1782–1784.Kemp, G., Roodt, A., Purcell, W. & Koch, K. R. (1996). Rhodium Express, pp.17–21.Leipoldt, J. G., Bok, L. D. C., Basson, S. S. & Meyer, H. (1980). Inorg. Chim.Acta, 42, 105–108.Otto, S., Roodt, A. & Smith, J. (2000). Inorg. Chim. Acta, 303, 295–299.Pretorius, M., Williams, D. B. G., Roodt, A. & Muller, A. (2004). Acta Cryst.C60, o384–o386.Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University ofGo¨ttingen, Germany.Sheldrick, G. M. (1998). SADABS. University of Go¨ttingen, Germany.Steyl, G., Otto, S. & Roodt, A. (2001). Acta Cryst. E57, m352–m354.Steyl, G. & Roodt, A. (2003). Acta Cryst. C59, o525–o527.Tolman, C. A. (1977). Chem. Rev. 77, 313–348.metal-organic papersm1214 Steyl and Roodt  [Rh(C7H5O2)(C18H15As)(CO)] Acta Cryst. (2005). E61, m1212–m1214

Carbonyl(triphenylarsine)(tropolonato)rhodium(I)

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Carbonyl(triphenylarsine)(tropolonato)rhodium(I)

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