Acta Cryst. (2012). E68, m1451-m1452 [ doi:10.1107/S1600536812044893 ]
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2O,O')dicarbonylrhodium(I)In the title compound, [Rh(C10H9O2)(CO)2], a distorted square-planar coordination geometry is observed around the RhI atom, formed by the O atoms of the bidentate ligand and two C atoms from the carbonyl ligands. The RhI atom is displaced from the plane through the surrounding atoms by 0.017 Å. In the crystal, C-H
O interaction is observed between a methyl group of the bidentate ligand and a carbonyl O atom. Metallophilic interactions [3.308 (3) and 3.461 (3) Å] between neighbouring RhI atoms are encountered in the crystal, resulting in the formation of a metal chain along the b-axis direction.
[RhCl(CO)2]2 was prepared in situ by refluxing RhCl3.3H2O (0.1014 g, 0.385 mmol) in 2 ml DMF for 30 min. 1-Phenyl-1,3-butanedione (0.0906 g, 0.905 mmol) was added to the cooled DMF solution of [RhCl(CO)2]2. The orange product was precipitated with ice-water and isolated by centrifuge. Recrystallization from diethyl ether yielded pleochroic orange-red crystals suitable for X-ray diffraction. IR (ATR, cm-1): νCO, sym 2066 s, νCO, asym 1999 s.
The methyl and aromatic H atoms were placed in geometrically idealized positions and constrained to ride on their parent atoms, with C—H = 0.95 and 0.98 Å and Uiso(H) = 1.5Ueq(carrier C) and 1.2Ueq(carrier C), respectively. The highest residual electron density was located 0.04 Å from C12 and the deepest hole was 0.17 Å from O4.
Data collection: APEX2 (Bruker, 2011); cell refinement: SAINT-Plus (Bruker, 2008); data reduction: SAINT-Plus (Bruker, 2008); program(s) used to solve structure: SIR2002 (Burla et al., 2003) and SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: Mercury (Macrae et al., 2008); software used to prepare material for publication: WinGX (Farrugia, 1999), publCIF (Westrip, 2010), PARST (Nardelli, 1995) and PLATON (Spek, 2009).
![[Figure 1]](./bh2458fig1thm.gif)
| Fig. 1. Molecular structure of the title compound. Displacement ellipsoids are drawn at the 50% probability level. |
![[Figure 2]](./bh2458fig2thm.gif)
| Fig. 2. The metallophilic Rh···Rh interactions result in the formation of a 1D metal chain along the b-axis. |
| [Rh(C10H9O2)(CO)2] | F(000) = 632 |
| Mr = 320.1 | Dx = 1.864 Mg m−3 |
| Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: -P 2ybc | Cell parameters from 7402 reflections |
| a = 7.5887 (2) Å | θ = 2.7–28.3° |
| b = 6.7522 (1) Å | µ = 1.50 mm−1 |
| c = 22.5299 (5) Å | T = 100 K |
| β = 98.850 (1)° | Needle, orange |
| V = 1140.70 (4) Å3 | 0.19 × 0.09 × 0.05 mm |
| Z = 4 |
| Bruker APEXII KappaCCD diffractometer | 2827 independent reflections |
| Radiation source: fine-focus sealed tube | 2494 reflections with I > 2σ(I) |
| Graphite monochromator | Rint = 0.020 |
| Detector resolution: 512 pixels mm-1 | θmax = 28.3°, θmin = 1.8° |
| φ and ω scans | h = −10→10 |
| Absorption correction: multi-scan (SADABS; Bruker, 2008) | k = −9→8 |
| Tmin = 0.851, Tmax = 0.928 | l = −29→30 |
| 15332 measured reflections |
| Refinement on F2 | Primary atom site location: structure-invariant direct methods |
| Least-squares matrix: full | Secondary atom site location: difference Fourier map |
| R[F2 > 2σ(F2)] = 0.018 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.048 | H-atom parameters constrained |
| S = 1.08 | w = 1/[σ2(Fo2) + (0.0197P)2 + 0.986P] where P = (Fo2 + 2Fc2)/3 |
| 2827 reflections | (Δ/σ)max = 0.002 |
| 154 parameters | Δρmax = 0.56 e Å−3 |
| 0 restraints | Δρmin = −0.44 e Å−3 |
| 0 constraints |
| [Rh(C10H9O2)(CO)2] | V = 1140.70 (4) Å3 |
| Mr = 320.1 | Z = 4 |
| Monoclinic, P21/c | Mo Kα radiation |
| a = 7.5887 (2) Å | µ = 1.50 mm−1 |
| b = 6.7522 (1) Å | T = 100 K |
| c = 22.5299 (5) Å | 0.19 × 0.09 × 0.05 mm |
| β = 98.850 (1)° |
| Bruker APEXII KappaCCD diffractometer | 2827 independent reflections |
| Absorption correction: multi-scan (SADABS; Bruker, 2008) | 2494 reflections with I > 2σ(I) |
| Tmin = 0.851, Tmax = 0.928 | Rint = 0.020 |
| 15332 measured reflections | θmax = 28.3° |
| R[F2 > 2σ(F2)] = 0.018 | H-atom parameters constrained |
| wR(F2) = 0.048 | Δρmax = 0.56 e Å−3 |
| S = 1.08 | Δρmin = −0.44 e Å−3 |
| 2827 reflections | Absolute structure: ? |
| 154 parameters | Flack parameter: ? |
| 0 restraints | Rogers parameter: ? |
| x | y | z | Uiso*/Ueq | Occ. (<1) | |
| C1 | −0.0248 (2) | 0.2092 (2) | 0.36980 (7) | 0.0130 (3) | |
| C2 | 0.1566 (2) | 0.1653 (2) | 0.37257 (7) | 0.0156 (3) | |
| H2 | 0.1964 | 0.1341 | 0.3357 | 0.019* | |
| C3 | 0.2848 (2) | 0.1629 (2) | 0.42418 (8) | 0.0157 (3) | |
| C4 | −0.1396 (2) | 0.2156 (2) | 0.30958 (7) | 0.0132 (3) | |
| C5 | −0.0945 (2) | 0.1102 (2) | 0.26078 (7) | 0.0162 (3) | |
| H5 | 0.0096 | 0.0299 | 0.2658 | 0.019* | |
| C6 | −0.2006 (2) | 0.1218 (3) | 0.20490 (8) | 0.0174 (3) | |
| H6 | −0.1681 | 0.0505 | 0.1719 | 0.021* | |
| C7 | −0.3540 (2) | 0.2371 (2) | 0.19702 (8) | 0.0171 (3) | |
| H7 | −0.4262 | 0.2448 | 0.1587 | 0.02* | |
| C8 | −0.4015 (2) | 0.3411 (3) | 0.24546 (8) | 0.0170 (3) | |
| H8 | −0.5067 | 0.4195 | 0.2403 | 0.02* | |
| C9 | −0.2949 (2) | 0.3305 (2) | 0.30142 (7) | 0.0150 (3) | |
| H9 | −0.3278 | 0.4019 | 0.3344 | 0.018* | |
| C10 | 0.4773 (2) | 0.1331 (3) | 0.41774 (8) | 0.0201 (4) | |
| H10A | 0.5507 | 0.1351 | 0.4575 | 0.03* | 0.5 |
| H10B | 0.5155 | 0.2396 | 0.393 | 0.03* | 0.5 |
| H10C | 0.4912 | 0.0052 | 0.3984 | 0.03* | 0.5 |
| H10D | 0.4876 | 0.1182 | 0.3751 | 0.03* | 0.5 |
| H10E | 0.5227 | 0.0136 | 0.4396 | 0.03* | 0.5 |
| H10F | 0.5471 | 0.2481 | 0.4342 | 0.03* | 0.5 |
| C11 | −0.1975 (2) | 0.3058 (3) | 0.53050 (7) | 0.0170 (3) | |
| C12 | 0.1228 (2) | 0.2372 (2) | 0.58225 (8) | 0.0177 (3) | |
| O1 | −0.10332 (17) | 0.25034 (16) | 0.41481 (5) | 0.0152 (2) | |
| O2 | 0.25558 (16) | 0.18797 (19) | 0.47805 (5) | 0.0170 (2) | |
| O3 | −0.32389 (17) | 0.3454 (2) | 0.54935 (6) | 0.0240 (3) | |
| O4 | 0.19329 (19) | 0.23292 (19) | 0.63064 (6) | 0.0245 (3) | |
| Rh1 | 0.013973 (17) | 0.244320 (18) | 0.503043 (5) | 0.01307 (5) |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| C1 | 0.0169 (8) | 0.0101 (7) | 0.0118 (7) | −0.0026 (6) | 0.0018 (6) | 0.0010 (6) |
| C2 | 0.0181 (8) | 0.0165 (8) | 0.0127 (8) | −0.0007 (6) | 0.0040 (6) | 0.0006 (6) |
| C3 | 0.0172 (8) | 0.0140 (8) | 0.0160 (8) | −0.0023 (6) | 0.0028 (6) | 0.0020 (6) |
| C4 | 0.0157 (8) | 0.0130 (7) | 0.0108 (7) | −0.0020 (6) | 0.0018 (6) | 0.0010 (6) |
| C5 | 0.0181 (8) | 0.0160 (8) | 0.0146 (8) | 0.0024 (6) | 0.0026 (6) | 0.0001 (6) |
| C6 | 0.0230 (9) | 0.0169 (8) | 0.0124 (8) | 0.0005 (7) | 0.0033 (7) | −0.0023 (6) |
| C7 | 0.0204 (8) | 0.0172 (8) | 0.0126 (8) | −0.0014 (6) | −0.0006 (6) | 0.0018 (6) |
| C8 | 0.0169 (8) | 0.0163 (8) | 0.0174 (8) | 0.0024 (6) | 0.0014 (7) | 0.0014 (6) |
| C9 | 0.0178 (8) | 0.0141 (8) | 0.0138 (8) | −0.0003 (6) | 0.0044 (6) | −0.0012 (6) |
| C10 | 0.0148 (8) | 0.0282 (9) | 0.0170 (8) | −0.0028 (7) | 0.0019 (7) | 0.0007 (7) |
| C11 | 0.0239 (9) | 0.0163 (8) | 0.0100 (8) | −0.0033 (7) | 0.0000 (7) | −0.0002 (6) |
| C12 | 0.0198 (8) | 0.0142 (8) | 0.0192 (9) | −0.0039 (6) | 0.0038 (7) | −0.0002 (6) |
| O1 | 0.0166 (6) | 0.0180 (6) | 0.0111 (6) | −0.0011 (4) | 0.0021 (5) | −0.0002 (4) |
| O2 | 0.0159 (6) | 0.0216 (6) | 0.0135 (6) | −0.0026 (5) | 0.0020 (5) | 0.0011 (5) |
| O3 | 0.0240 (7) | 0.0308 (7) | 0.0183 (6) | 0.0009 (6) | 0.0063 (5) | −0.0014 (6) |
| O4 | 0.0306 (8) | 0.0264 (7) | 0.0143 (6) | −0.0057 (5) | −0.0033 (6) | 0.0003 (5) |
| Rh1 | 0.01542 (8) | 0.01454 (7) | 0.00917 (7) | −0.00290 (5) | 0.00160 (5) | 0.00006 (5) |
| C1—O1 | 1.283 (2) | C8—C9 | 1.391 (2) |
| C1—C2 | 1.399 (2) | C8—H8 | 0.95 |
| C1—C4 | 1.496 (2) | C9—H9 | 0.95 |
| C2—C3 | 1.397 (2) | C10—H10A | 0.98 |
| C2—H2 | 0.95 | C10—H10B | 0.98 |
| C3—O2 | 1.278 (2) | C10—H10C | 0.98 |
| C3—C10 | 1.504 (2) | C10—H10D | 0.98 |
| C4—C5 | 1.396 (2) | C10—H10E | 0.98 |
| C4—C9 | 1.400 (2) | C10—H10F | 0.98 |
| C5—C6 | 1.388 (2) | C11—O3 | 1.139 (2) |
| C5—H5 | 0.95 | C11—Rh1 | 1.8539 (18) |
| C6—C7 | 1.389 (2) | C12—O4 | 1.138 (2) |
| C6—H6 | 0.95 | C12—Rh1 | 1.8480 (19) |
| C7—C8 | 1.391 (2) | O1—Rh1 | 2.0498 (12) |
| C7—H7 | 0.95 | O2—Rh1 | 2.0349 (12) |
| O1—C1—C2 | 125.71 (15) | H10A—C10—H10B | 109.5 |
| O1—C1—C4 | 115.70 (15) | C3—C10—H10C | 109.5 |
| C2—C1—C4 | 118.57 (15) | H10A—C10—H10C | 109.5 |
| C3—C2—C1 | 126.44 (15) | H10B—C10—H10C | 109.5 |
| C3—C2—H2 | 116.8 | C3—C10—H10D | 109.5 |
| C1—C2—H2 | 116.8 | H10A—C10—H10D | 141.1 |
| O2—C3—C2 | 126.05 (16) | H10B—C10—H10D | 56.3 |
| O2—C3—C10 | 114.98 (15) | H10C—C10—H10D | 56.3 |
| C2—C3—C10 | 118.95 (15) | C3—C10—H10E | 109.5 |
| C5—C4—C9 | 118.87 (15) | H10A—C10—H10E | 56.3 |
| C5—C4—C1 | 121.36 (15) | H10B—C10—H10E | 141.1 |
| C9—C4—C1 | 119.77 (15) | H10C—C10—H10E | 56.3 |
| C6—C5—C4 | 120.47 (16) | H10D—C10—H10E | 109.5 |
| C6—C5—H5 | 119.8 | C3—C10—H10F | 109.5 |
| C4—C5—H5 | 119.8 | H10A—C10—H10F | 56.3 |
| C5—C6—C7 | 120.36 (16) | H10B—C10—H10F | 56.3 |
| C5—C6—H6 | 119.8 | H10C—C10—H10F | 141.1 |
| C7—C6—H6 | 119.8 | H10D—C10—H10F | 109.5 |
| C6—C7—C8 | 119.72 (16) | H10E—C10—H10F | 109.5 |
| C6—C7—H7 | 120.1 | O3—C11—Rh1 | 177.49 (15) |
| C8—C7—H7 | 120.1 | O4—C12—Rh1 | 178.55 (17) |
| C9—C8—C7 | 120.02 (16) | C1—O1—Rh1 | 125.23 (11) |
| C9—C8—H8 | 120 | C3—O2—Rh1 | 125.64 (11) |
| C7—C8—H8 | 120 | C12—Rh1—C11 | 87.98 (8) |
| C8—C9—C4 | 120.54 (15) | C12—Rh1—O2 | 88.54 (7) |
| C8—C9—H9 | 119.7 | C11—Rh1—O2 | 175.85 (6) |
| C4—C9—H9 | 119.7 | C12—Rh1—O1 | 179.13 (6) |
| C3—C10—H10A | 109.5 | C11—Rh1—O1 | 92.88 (6) |
| C3—C10—H10B | 109.5 | O2—Rh1—O1 | 90.61 (5) |
| D—H···A | D—H | H···A | D···A | D—H···A |
| C10—H10A···O3i | 0.98 | 2.57 | 3.427 (2) | 146 |
| Symmetry code: (i) x+1, y, z. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| C10—H10A···O3i | 0.98 | 2.57 | 3.427 (2) | 146.4 |
| Symmetry code: (i) x+1, y, z. |
Financial assistance from the University of the Free State Strategic Academic Cluster Initiative (Materials and Nanosciences), SASOL and the South African National Research Foundation (SA-NRF/THRIP) is gratefully acknowledged.
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Rhodium is one of the most studied transition metals due to its importance in various applications including catalysis and biological activity (Dutta & Singh, 1994). It is widely recognized as a good catalyst for several industrial processes such as the Monsanto process (Paulik & Roth, 1968) and hydroformylation (Evans et al., 1968). In turn, rhodium dicarbonyl complexes of the type [Rh(L,L')(CO)2] where (L,L') represents a mono-anionic bidentate ligand have been widely studied as catalyst precursors (Brink et al., 2010).
The structural analysis of the title complex was undertaken to obtain a better understanding of the rhodium-ligand interactions in this type of compound and as a partial study of the effects that the different substituents in non-symmetrical β-diketones have on the kinetics of substitution reactions of these complexes.
Metallophilicity has been defined as the interaction between electron densities of large metal centres with an associated energy in the same order as hydrogen-bonding (Doerrer, 2010). These metallophilic interactions lead to the construction of 1D metal chains and have been widely recognized for other square-planar RhI molecules (Prater et al., 1999; Laurila et al., 2012; Real et al., 1989). The rhodium complex reported here showed stacking in such a way that the rhodium atoms of neighbouring molecules occupy the two remaining pseudo-octahedral positions almost perpendicular to the coordination polyhedron, with Rh···Rh distances of 3.308 (3) and 3.461 (3) Å respectively (see Figure 2). These values are slightly longer than the Rh···Rh distances reported for [Rh(acac)(CO)2] (3.253 and 3.271 Å, Huq & Skapski, 1974). For the benzoyl-1,1,1-trifluoroacetonatodicarbonylrhodium(I) complex these distances were reported as 3.537 Å (Leipoldt et al., 1977). The metallophilic interactions result in the formation of a 1D metal chain along the b-axis in the unit cell. This is consistent with the [Rh(acac)(CO)2] complex and benzoyl-1,1,1-trifluoroacetonatodicarbonylrhodium(I), that also displayed chain growth along the shortest unit cell axis.
A substitutional disorder over two positions was observed for the hydrogen atoms of the methyl group on the pentenone backbone. Intermolecular C10—H10C···O3 hydrogen bonding in the order of 3.427 Å was observed with one of the carbonyl moieties.