Buy article online - an online subscription or single-article purchase is required to access this article.
A series of related acetylacetonate–carbonyl–rhodium compounds substituted by functionalized phosphines has been prepared in good to excellent yields by the reaction of [Rh(acac)(CO)
2] (acac is acetylacetonate) with the corresponding allyl-, cyanomethyl- or cyanoethyl-substituted phosphines. All compounds were fully characterized by
31P,
1H,
13C NMR and IR spectroscopy. The X-ray structures of (acetylacetonato-κ
2O,
O′)(
tert-butylphosphanedicarbonitrile-κ
P)carbonylrhodium(I), [Rh(C
5H
7O
2)(CO)(C
8H
13N
2)] or [Rh(acac)(CO)(
tBuP(CH
2CN)
2}] (
2b), (acetylacetonato-κ
2O,
O′)carbonyl[3-(diphenylphosphanyl)propanenitrile-κ
P]rhodium(I), [Rh(C
5H
7O
2)(C
15H
14N)(CO)] or [Rh(acac)(CO){Ph
2P(CH
2CH
2CN)}] (
2h), and (acetylacetonato-κ
2O,
O′)carbonyl[3-(di-
tert-butylphosphanyl)propanenitrile-κ
P]rhodium(I), [Rh(C
5H
7O
2)(C
11H
22N)(CO)] or [Rh(acac)(CO){
tBu
2P(CH
2CH
2CN)}] (
2i), showed a square-planar geometry around the Rh atom with a significant
trans influence over the acetylacetonate moiety, evidenced by long Rh—O bond lengths as expected for poor π-acceptor phosphines. The Rh—P distances displayed an inverse linear dependence with the coupling constants
JP-Rh and the IR ν(C
O) bands, which accounts for the Rh—P electronic bonding feature (poor π-acceptors) of these complexes. A combined study from density functional theory (DFT) calculations and an evaluation of the intramolecular H
Rh contacts from X-ray diffraction data allowed a comparison of the conformational preferences of these complexes in the solid state
versus the isolated compounds in the gas phase. For
2b,
2h and
2i, an energy-framework study evidenced that the crystal structures are mainly governed by dispersive energy. In fact, strong pairwise molecular dispersive interactions are responsible for the columnar arrangement observed in these complexes. A Hirshfeld surface analysis employing three-dimensional molecular surface contours and two-dimensional fingerprint plots indicated that the structures are stabilized by H
H, C
H, H
O, H
N and H
Rh intermolecular interactions.
Supporting information
CCDC references: 793226; 793227; 793228
Data collection: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1991) for (2b); CrystalClear (Rigaku/MSC, 2005) for (2h), (2i). Cell refinement: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1991) for (2b); CrystalClear (Rigaku/MSC, 2005) for (2h), (2i). Data reduction: TEXSAN (Molecular Structure Corporation, 1999) for (2b); CrystalClear (Rigaku/MSC, 2005) for (2h), (2i). For all structures, program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2015); software used to prepare material for publication: SHELXL2013 (Sheldrick, 2015).
(Acetylacetonato-
κ2O,
O')(
tert-butylphosphanedicarbonitrile-
κP)carbonylrhodium(I) (2b)
top
Crystal data top
[Rh(C5H7O2)(CO)(C8H13N2)] | Dx = 1.519 Mg m−3 |
Mr = 398.20 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, P212121 | Cell parameters from 25 reflections |
a = 11.972 (4) Å | θ = 28–36° |
b = 12.032 (5) Å | µ = 1.08 mm−1 |
c = 12.085 (5) Å | T = 298 K |
V = 1740.8 (11) Å3 | Prism |
Z = 4 | 0.36 × 0.34 × 0.30 mm |
F(000) = 808 | |
Data collection top
Rigaku AFC7S diffractometer | 2724 reflections with I > 2σ(I) |
Radiation source: Normal-focus sealed tube | Rint = 0.050 |
ω–2θ scans | θmax = 25.0°, θmin = 2.4° |
Absorption correction: ψ scan (North et al., 1968) | h = −3→14 |
Tmin = 0.655, Tmax = 0.714 | k = −4→14 |
4245 measured reflections | l = −4→14 |
2835 independent reflections | |
Refinement top
Refinement on F2 | Hydrogen site location: difference Fourier map |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.026 | w = 1/[σ2(Fo2) + (0.0463P)2 + 0.6003P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.074 | (Δ/σ)max < 0.001 |
S = 1.11 | Δρmax = 0.61 e Å−3 |
2835 reflections | Δρmin = −0.78 e Å−3 |
190 parameters | Absolute structure: Flack x determined using 1013 quotients [(I+)-(I-)]/[(I+)+(I-)]
(Parsons & Flack, 2004). |
0 restraints | Absolute structure parameter: −0.03 (4) |
Special details top
Experimental. 3 standard reflection, every 150 reflection, decay: none |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell esds are taken
into account individually in the estimation of esds in distances, angles
and torsion angles; correlations between esds in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell esds is used for estimating esds involving l.s. planes. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Rh1 | 0.39711 (3) | 0.27288 (3) | 0.17779 (3) | 0.04056 (14) | |
P1 | 0.40942 (10) | 0.37160 (10) | 0.33244 (10) | 0.0375 (3) | |
O1 | 0.5060 (3) | 0.3797 (3) | 0.1045 (3) | 0.0523 (9) | |
O2 | 0.3837 (4) | 0.1863 (3) | 0.0316 (3) | 0.0549 (9) | |
O3 | 0.2458 (5) | 0.1175 (5) | 0.2916 (4) | 0.0829 (15) | |
N1 | 0.4814 (6) | 0.3748 (7) | 0.6386 (5) | 0.092 (2) | |
N2 | 0.7008 (5) | 0.3071 (6) | 0.3924 (6) | 0.089 (2) | |
C1 | 0.5362 (5) | 0.3781 (5) | 0.0018 (4) | 0.0486 (13) | |
C2 | 0.4984 (5) | 0.3044 (5) | −0.0767 (4) | 0.0540 (14) | |
H2 | 0.5235 | 0.3161 | −0.1486 | 0.065* | |
C3 | 0.4272 (5) | 0.2147 (5) | −0.0616 (4) | 0.0521 (13) | |
C4 | 0.6169 (7) | 0.4666 (6) | −0.0292 (5) | 0.0712 (17) | |
H4A | 0.6340 | 0.5109 | 0.0347 | 0.107* | |
H4B | 0.5848 | 0.5130 | −0.0854 | 0.107* | |
H4C | 0.6842 | 0.4332 | −0.0568 | 0.107* | |
C5 | 0.3956 (8) | 0.1442 (6) | −0.1578 (5) | 0.082 (2) | |
H5A | 0.3457 | 0.0866 | −0.1337 | 0.123* | |
H5B | 0.4614 | 0.1114 | −0.1892 | 0.123* | |
H5C | 0.3591 | 0.1892 | −0.2125 | 0.123* | |
C6 | 0.3034 (5) | 0.1782 (5) | 0.2471 (5) | 0.0543 (13) | |
C7 | 0.3031 (5) | 0.4820 (5) | 0.3522 (5) | 0.0576 (14) | |
C8 | 0.3136 (7) | 0.5450 (8) | 0.4614 (6) | 0.092 (3) | |
H8A | 0.2562 | 0.6006 | 0.4656 | 0.138* | |
H8B | 0.3855 | 0.5801 | 0.4650 | 0.138* | |
H8C | 0.3057 | 0.4942 | 0.5221 | 0.138* | |
C9 | 0.1889 (6) | 0.4288 (8) | 0.3372 (9) | 0.102 (3) | |
H9A | 0.1319 | 0.4841 | 0.3465 | 0.153* | |
H9B | 0.1791 | 0.3713 | 0.3913 | 0.153* | |
H9C | 0.1837 | 0.3975 | 0.2643 | 0.153* | |
C10 | 0.3211 (8) | 0.5646 (6) | 0.2567 (6) | 0.089 (2) | |
H10A | 0.2680 | 0.6241 | 0.2626 | 0.133* | |
H10B | 0.3111 | 0.5270 | 0.1873 | 0.133* | |
H10C | 0.3955 | 0.5942 | 0.2606 | 0.133* | |
C11 | 0.4086 (5) | 0.2847 (5) | 0.4581 (4) | 0.0553 (14) | |
H11A | 0.3327 | 0.2599 | 0.4709 | 0.066* | |
H11B | 0.4536 | 0.2192 | 0.4439 | 0.066* | |
C12 | 0.4493 (6) | 0.3365 (6) | 0.5595 (5) | 0.0652 (17) | |
C13 | 0.5445 (4) | 0.4448 (5) | 0.3435 (4) | 0.0467 (12) | |
H13A | 0.5609 | 0.4816 | 0.2739 | 0.056* | |
H13B | 0.5397 | 0.5013 | 0.4005 | 0.056* | |
C14 | 0.6331 (5) | 0.3689 (6) | 0.3697 (5) | 0.0570 (15) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Rh1 | 0.0443 (2) | 0.0422 (2) | 0.03527 (19) | −0.00320 (18) | −0.00025 (17) | 0.00016 (17) |
P1 | 0.0373 (6) | 0.0417 (6) | 0.0336 (5) | 0.0001 (5) | 0.0005 (6) | 0.0028 (5) |
O1 | 0.061 (2) | 0.055 (2) | 0.0410 (18) | −0.0129 (19) | 0.0063 (17) | −0.0039 (18) |
O2 | 0.075 (2) | 0.0479 (18) | 0.0421 (18) | −0.012 (2) | −0.003 (2) | −0.0014 (16) |
O3 | 0.082 (3) | 0.082 (3) | 0.085 (3) | −0.034 (3) | 0.013 (3) | 0.007 (3) |
N1 | 0.113 (5) | 0.118 (6) | 0.045 (3) | −0.019 (5) | −0.016 (3) | 0.011 (3) |
N2 | 0.056 (3) | 0.109 (5) | 0.103 (5) | 0.017 (4) | −0.021 (3) | −0.008 (4) |
C1 | 0.053 (3) | 0.052 (3) | 0.041 (3) | 0.000 (3) | 0.010 (2) | 0.003 (2) |
C2 | 0.073 (4) | 0.056 (3) | 0.034 (2) | 0.005 (3) | 0.004 (2) | 0.001 (2) |
C3 | 0.069 (3) | 0.050 (3) | 0.038 (3) | 0.004 (3) | −0.006 (2) | 0.000 (2) |
C4 | 0.090 (5) | 0.068 (4) | 0.055 (3) | −0.013 (4) | 0.019 (4) | −0.002 (3) |
C5 | 0.121 (6) | 0.077 (4) | 0.048 (3) | −0.004 (5) | −0.009 (4) | −0.015 (3) |
C6 | 0.055 (3) | 0.055 (3) | 0.053 (3) | −0.013 (3) | −0.002 (3) | 0.002 (3) |
C7 | 0.051 (3) | 0.062 (3) | 0.059 (3) | 0.016 (3) | −0.006 (3) | −0.008 (3) |
C8 | 0.093 (5) | 0.113 (7) | 0.071 (4) | 0.044 (5) | −0.005 (4) | −0.032 (5) |
C9 | 0.046 (3) | 0.106 (6) | 0.154 (8) | 0.022 (4) | 0.002 (5) | −0.010 (7) |
C10 | 0.112 (6) | 0.072 (4) | 0.083 (5) | 0.038 (5) | −0.021 (5) | 0.009 (4) |
C11 | 0.059 (3) | 0.064 (3) | 0.042 (3) | −0.011 (3) | −0.001 (3) | 0.011 (3) |
C12 | 0.069 (4) | 0.084 (5) | 0.043 (3) | −0.010 (4) | 0.000 (3) | 0.020 (3) |
C13 | 0.048 (3) | 0.047 (3) | 0.045 (3) | −0.009 (2) | 0.001 (2) | 0.001 (2) |
C14 | 0.040 (3) | 0.076 (4) | 0.055 (3) | −0.005 (3) | −0.004 (2) | −0.006 (3) |
Geometric parameters (Å, º) top
Rh1—C6 | 1.805 (6) | C5—H5B | 0.9600 |
Rh1—O1 | 2.033 (4) | C5—H5C | 0.9600 |
Rh1—O2 | 2.057 (4) | C7—C9 | 1.520 (10) |
Rh1—P1 | 2.2194 (14) | C7—C8 | 1.528 (9) |
P1—C11 | 1.843 (5) | C7—C10 | 1.539 (9) |
P1—C13 | 1.846 (5) | C8—H8A | 0.9600 |
P1—C7 | 1.855 (6) | C8—H8B | 0.9600 |
O1—C1 | 1.294 (6) | C8—H8C | 0.9599 |
O2—C3 | 1.287 (7) | C9—H9A | 0.9600 |
O3—C6 | 1.140 (7) | C9—H9B | 0.9600 |
N1—C12 | 1.129 (9) | C9—H9C | 0.9600 |
N2—C14 | 1.133 (9) | C10—H10A | 0.9599 |
C1—C2 | 1.375 (8) | C10—H10B | 0.9600 |
C1—C4 | 1.486 (9) | C10—H10C | 0.9601 |
C2—C3 | 1.388 (8) | C11—C12 | 1.458 (9) |
C2—H2 | 0.9301 | C11—H11A | 0.9701 |
C3—C5 | 1.488 (8) | C11—H11B | 0.9701 |
C4—H4A | 0.9601 | C13—C14 | 1.435 (8) |
C4—H4B | 0.9601 | C13—H13A | 0.9700 |
C4—H4C | 0.9599 | C13—H13B | 0.9698 |
C5—H5A | 0.9600 | | |
| | | |
C6—Rh1—O1 | 178.0 (2) | C9—C7—C10 | 108.0 (6) |
C6—Rh1—O2 | 91.7 (2) | C8—C7—C10 | 108.4 (6) |
O1—Rh1—O2 | 89.78 (15) | C9—C7—P1 | 107.5 (5) |
C6—Rh1—P1 | 89.33 (18) | C8—C7—P1 | 114.2 (4) |
O1—Rh1—P1 | 89.18 (11) | C10—C7—P1 | 105.6 (4) |
O2—Rh1—P1 | 177.97 (11) | C7—C8—H8A | 109.5 |
C11—P1—C13 | 102.4 (3) | C7—C8—H8B | 109.4 |
C11—P1—C7 | 107.2 (3) | H8A—C8—H8B | 109.5 |
C13—P1—C7 | 104.5 (3) | C7—C8—H8C | 109.6 |
C11—P1—Rh1 | 112.9 (2) | H8A—C8—H8C | 109.5 |
C13—P1—Rh1 | 111.98 (18) | H8B—C8—H8C | 109.5 |
C7—P1—Rh1 | 116.48 (18) | C7—C9—H9A | 109.5 |
C1—O1—Rh1 | 126.0 (4) | C7—C9—H9B | 109.4 |
C3—O2—Rh1 | 125.9 (3) | H9A—C9—H9B | 109.5 |
O1—C1—C2 | 125.4 (5) | C7—C9—H9C | 109.5 |
O1—C1—C4 | 114.4 (5) | H9A—C9—H9C | 109.5 |
C2—C1—C4 | 120.2 (5) | H9B—C9—H9C | 109.5 |
C1—C2—C3 | 127.8 (5) | C7—C10—H10A | 109.5 |
C1—C2—H2 | 116.1 | C7—C10—H10B | 109.5 |
C3—C2—H2 | 116.1 | H10A—C10—H10B | 109.5 |
O2—C3—C2 | 124.8 (5) | C7—C10—H10C | 109.5 |
O2—C3—C5 | 115.5 (6) | H10A—C10—H10C | 109.5 |
C2—C3—C5 | 119.8 (5) | H10B—C10—H10C | 109.5 |
C1—C4—H4A | 109.5 | C12—C11—P1 | 116.6 (4) |
C1—C4—H4B | 109.5 | C12—C11—H11A | 108.1 |
H4A—C4—H4B | 109.5 | P1—C11—H11A | 108.1 |
C1—C4—H4C | 109.4 | C12—C11—H11B | 108.1 |
H4A—C4—H4C | 109.5 | P1—C11—H11B | 108.2 |
H4B—C4—H4C | 109.5 | H11A—C11—H11B | 107.3 |
C3—C5—H5A | 109.5 | N1—C12—C11 | 178.8 (8) |
C3—C5—H5B | 109.5 | C14—C13—P1 | 111.1 (4) |
H5A—C5—H5B | 109.5 | C14—C13—H13A | 109.4 |
C3—C5—H5C | 109.5 | P1—C13—H13A | 109.4 |
H5A—C5—H5C | 109.5 | C14—C13—H13B | 109.5 |
H5B—C5—H5C | 109.5 | P1—C13—H13B | 109.5 |
O3—C6—Rh1 | 178.9 (6) | H13A—C13—H13B | 108.0 |
C9—C7—C8 | 112.7 (6) | N2—C14—C13 | 177.9 (7) |
(Acetylacetonato-
κ2O,
O')]carbonyl[3-(diphenylphosphanyl)propanenitrile-
κPrhodium(I), (2h)
top
Crystal data top
[Rh(C5H7O2)(C15H14NP)(CO)] | F(000) = 952 |
Mr = 469.27 | Dx = 1.459 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 11.676 (4) Å | Cell parameters from 23386 reflections |
b = 15.666 (4) Å | θ = 2–25° |
c = 11.937 (4) Å | µ = 0.89 mm−1 |
β = 101.927 (8)° | T = 298 K |
V = 2136.4 (11) Å3 | Block, yellow |
Z = 4 | 0.50 × 0.45 × 0.35 mm |
Data collection top
Rigaku AFC-7S Mercury diffractometer | 4343 independent reflections |
Radiation source: fine-focus seal tube | 3661 reflections with I > 2σ(I) |
Detector resolution: 14.6306 pixels mm-1 | Rint = 0.029 |
ω scans | θmax = 28.1°, θmin = 2.2° |
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005) | h = −13→13 |
Tmin = 0.642, Tmax = 0.733 | k = −16→19 |
23386 measured reflections | l = −14→14 |
Refinement top
Refinement on F2 | 104 restraints |
Least-squares matrix: full | Hydrogen site location: mixed |
R[F2 > 2σ(F2)] = 0.034 | H-atom parameters constrained |
wR(F2) = 0.088 | w = 1/[σ2(Fo2) + (0.0421P)2 + 1.0006P] where P = (Fo2 + 2Fc2)/3 |
S = 1.08 | (Δ/σ)max = 0.002 |
4343 reflections | Δρmax = 0.74 e Å−3 |
301 parameters | Δρmin = −0.61 e Å−3 |
Special details top
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell esds are taken
into account individually in the estimation of esds in distances, angles
and torsion angles; correlations between esds in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell esds is used for estimating esds involving l.s. planes. |
Refinement. Intensity data were recorded at room temperature on a Rigaku
AFC-7S diffractometer using monochromated Mo Kα radiation (λ= 0.71073 Å).
The apparatus was configured with a fine-focus sealed tube and a scintillator
detector for data collection of 2b and a CCD mercury detector for
2h and 2i. Experimental details on unit cell and intensity
measurements can be found in the CIF files deposited with the Cambridge
Crystallographic Data Centre [CCDC 793226, 793227, 793228]. Crystal data,
intensity data collection parameters, and final refinement results are
summarized in Table 1. For 2h and 2i, an empirical absorption
correction multi-scan was applied to data using the CrystalClear
crystallographic software package ?(CrystalClear, 2005)?.
For 2b, a
semiempirical psi-scan absorption correction was applied ?(North et al.,
1968). The structures were solved by Direct
Methods and refined by
full-matrix least-squares on F2. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | Occ. (<1) |
Rh1 | 0.74701 (2) | 0.20421 (2) | 0.10036 (2) | 0.04352 (10) | |
P1 | 0.78345 (6) | 0.17911 (4) | 0.28775 (6) | 0.03969 (16) | |
O2 | 0.7114 (2) | 0.22219 (15) | −0.07578 (18) | 0.0607 (6) | |
O1 | 0.80710 (19) | 0.08437 (13) | 0.07647 (17) | 0.0578 (5) | |
O3 | 0.6495 (3) | 0.37253 (17) | 0.1389 (3) | 0.1012 (10) | |
N1 | 1.1467 (3) | −0.0185 (3) | 0.3857 (3) | 0.1013 (13) | |
C7 | 0.8542 (2) | 0.26134 (17) | 0.3849 (2) | 0.0442 (6) | |
C8 | 0.9039 (3) | 0.33200 (19) | 0.3434 (3) | 0.0570 (8) | |
H8 | 0.8952 | 0.3397 | 0.2649 | 0.068* | |
C9 | 0.9663 (3) | 0.3909 (2) | 0.4180 (4) | 0.0762 (11) | |
H9 | 1.0008 | 0.4376 | 0.3897 | 0.091* | |
C10 | 0.9773 (3) | 0.3805 (2) | 0.5336 (4) | 0.0843 (13) | |
H10 | 1.0184 | 0.4206 | 0.5837 | 0.101* | |
C11 | 0.9281 (3) | 0.3113 (2) | 0.5761 (3) | 0.0734 (11) | |
H11 | 0.9356 | 0.3050 | 0.6548 | 0.088* | |
C12 | 0.8674 (3) | 0.2509 (2) | 0.5025 (3) | 0.0558 (7) | |
H12 | 0.8355 | 0.2035 | 0.5316 | 0.067* | |
C13 | 0.8808 (3) | 0.08754 (17) | 0.3320 (3) | 0.0492 (7) | |
H13A | 0.8488 | 0.0375 | 0.2761 | 0.074* | |
H13B | 0.8860 | 0.0725 | 0.4170 | 0.074* | |
C14 | 1.0051 (3) | 0.1070 (2) | 0.3150 (3) | 0.0583 (8) | |
H14B | 1.0469 | 0.1621 | 0.3511 | 0.088* | |
H14A | 1.0021 | 0.1126 | 0.2260 | 0.088* | |
C15 | 1.0855 (3) | 0.0363 (2) | 0.3546 (3) | 0.0686 (9) | |
C3 | 0.7231 (3) | 0.1658 (3) | −0.1494 (3) | 0.0647 (9) | |
C2 | 0.7654 (3) | 0.0836 (3) | −0.1261 (3) | 0.0706 (10) | |
H2 | 0.7689 | 0.0494 | −0.1890 | 0.085* | |
C1 | 0.8029 (3) | 0.0471 (2) | −0.0195 (3) | 0.0592 (8) | |
C6 | 0.6884 (3) | 0.3077 (2) | 0.1246 (3) | 0.0613 (8) | |
C4 | 0.8444 (4) | −0.0439 (2) | −0.0091 (4) | 0.0852 (12) | |
H4A | 0.8500 | −0.0650 | −0.0833 | 0.128* | |
H4B | 0.7897 | −0.0781 | 0.0213 | 0.128* | |
H4C | 0.9198 | −0.0466 | 0.0413 | 0.128* | |
C5 | 0.6887 (4) | 0.1951 (3) | −0.2720 (3) | 0.0945 (14) | |
H5A | 0.7354 | 0.2435 | −0.2835 | 0.142* | |
H5B | 0.6075 | 0.2109 | −0.2886 | 0.142* | |
H5C | 0.7013 | 0.1496 | −0.3220 | 0.142* | |
C16A | 0.6522 (12) | 0.1593 (10) | 0.3447 (16) | 0.046 (3) | 0.53 (3) |
C17A | 0.5929 (12) | 0.2284 (10) | 0.3791 (17) | 0.051 (3) | 0.53 (3) |
H17A | 0.6226 | 0.2833 | 0.3767 | 0.061* | 0.53 (3) |
C18A | 0.4895 (10) | 0.2156 (13) | 0.4168 (11) | 0.061 (3) | 0.53 (3) |
H18A | 0.4524 | 0.2614 | 0.4438 | 0.073* | 0.53 (3) |
C19A | 0.4421 (9) | 0.1361 (15) | 0.4142 (10) | 0.066 (3) | 0.53 (3) |
H19A | 0.3718 | 0.1286 | 0.4380 | 0.079* | 0.53 (3) |
C20A | 0.4965 (12) | 0.0654 (10) | 0.3767 (13) | 0.069 (3) | 0.53 (3) |
H20A | 0.4636 | 0.0113 | 0.3755 | 0.083* | 0.53 (3) |
C21A | 0.6016 (14) | 0.0785 (10) | 0.3413 (17) | 0.055 (3) | 0.53 (3) |
H21A | 0.6387 | 0.0324 | 0.3148 | 0.066* | 0.53 (3) |
C16B | 0.6538 (12) | 0.1456 (13) | 0.3384 (16) | 0.043 (3) | 0.47 (3) |
C17B | 0.5876 (15) | 0.2031 (13) | 0.3849 (19) | 0.054 (3) | 0.47 (3) |
H17B | 0.6135 | 0.2592 | 0.3961 | 0.065* | 0.47 (3) |
C18B | 0.4829 (11) | 0.1800 (15) | 0.4155 (12) | 0.061 (3) | 0.47 (3) |
H18B | 0.4381 | 0.2197 | 0.4455 | 0.074* | 0.47 (3) |
C19B | 0.4486 (11) | 0.0969 (17) | 0.4000 (12) | 0.064 (4) | 0.47 (3) |
H19B | 0.3789 | 0.0799 | 0.4196 | 0.077* | 0.47 (3) |
C20B | 0.5146 (14) | 0.0373 (14) | 0.3559 (16) | 0.073 (4) | 0.47 (3) |
H20B | 0.4886 | −0.0188 | 0.3456 | 0.087* | 0.47 (3) |
C21B | 0.6188 (15) | 0.0606 (12) | 0.327 (2) | 0.056 (3) | 0.47 (3) |
H21B | 0.6649 | 0.0200 | 0.3006 | 0.067* | 0.47 (3) |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Rh1 | 0.05160 (16) | 0.04385 (15) | 0.03655 (14) | −0.00244 (9) | 0.01242 (10) | −0.00134 (8) |
P1 | 0.0429 (4) | 0.0402 (3) | 0.0364 (4) | −0.0009 (3) | 0.0093 (3) | −0.0016 (3) |
O2 | 0.0707 (15) | 0.0772 (14) | 0.0360 (11) | −0.0047 (11) | 0.0156 (10) | 0.0020 (10) |
O1 | 0.0692 (14) | 0.0551 (12) | 0.0505 (12) | 0.0037 (10) | 0.0156 (10) | −0.0105 (9) |
O3 | 0.136 (3) | 0.0571 (15) | 0.104 (2) | 0.0380 (16) | 0.0112 (19) | −0.0034 (14) |
N1 | 0.107 (3) | 0.117 (3) | 0.086 (2) | 0.062 (2) | 0.032 (2) | 0.018 (2) |
C7 | 0.0381 (14) | 0.0458 (15) | 0.0470 (16) | 0.0028 (11) | 0.0052 (12) | −0.0084 (12) |
C8 | 0.0522 (18) | 0.0448 (16) | 0.070 (2) | −0.0017 (13) | 0.0040 (15) | −0.0026 (14) |
C9 | 0.067 (2) | 0.0486 (19) | 0.101 (3) | −0.0068 (15) | −0.010 (2) | −0.0077 (18) |
C10 | 0.078 (3) | 0.062 (2) | 0.093 (3) | 0.0078 (18) | −0.029 (2) | −0.029 (2) |
C11 | 0.073 (2) | 0.078 (2) | 0.056 (2) | 0.0130 (19) | −0.0163 (18) | −0.0198 (17) |
C12 | 0.0550 (18) | 0.064 (2) | 0.0444 (17) | 0.0053 (14) | 0.0007 (13) | −0.0047 (13) |
C13 | 0.0592 (18) | 0.0413 (15) | 0.0487 (16) | 0.0041 (12) | 0.0145 (13) | 0.0026 (12) |
C14 | 0.0506 (17) | 0.0617 (19) | 0.064 (2) | 0.0124 (14) | 0.0159 (15) | 0.0083 (15) |
C15 | 0.068 (2) | 0.085 (2) | 0.056 (2) | 0.0253 (19) | 0.0202 (17) | −0.0003 (17) |
C3 | 0.058 (2) | 0.095 (3) | 0.0448 (18) | −0.0100 (18) | 0.0192 (15) | −0.0072 (17) |
C2 | 0.072 (2) | 0.090 (3) | 0.054 (2) | −0.0025 (19) | 0.0221 (17) | −0.0250 (18) |
C1 | 0.0506 (18) | 0.067 (2) | 0.063 (2) | −0.0069 (14) | 0.0199 (15) | −0.0211 (16) |
C6 | 0.076 (2) | 0.0571 (19) | 0.0480 (19) | 0.0058 (16) | 0.0059 (16) | 0.0052 (14) |
C4 | 0.091 (3) | 0.064 (2) | 0.104 (3) | 0.0005 (19) | 0.029 (2) | −0.031 (2) |
C5 | 0.117 (4) | 0.126 (4) | 0.042 (2) | 0.007 (3) | 0.019 (2) | −0.006 (2) |
C16A | 0.046 (5) | 0.056 (5) | 0.035 (6) | −0.001 (3) | 0.008 (4) | 0.001 (4) |
C17A | 0.042 (4) | 0.059 (6) | 0.052 (5) | −0.002 (4) | 0.013 (3) | −0.004 (5) |
C18A | 0.043 (4) | 0.075 (7) | 0.067 (5) | 0.001 (4) | 0.018 (3) | −0.003 (5) |
C19A | 0.053 (4) | 0.077 (8) | 0.070 (5) | −0.005 (5) | 0.019 (4) | 0.001 (5) |
C20A | 0.068 (6) | 0.065 (7) | 0.080 (7) | −0.005 (4) | 0.030 (4) | 0.008 (5) |
C21A | 0.062 (5) | 0.053 (5) | 0.054 (6) | 0.002 (4) | 0.020 (4) | 0.004 (4) |
C16B | 0.039 (5) | 0.059 (6) | 0.028 (6) | −0.005 (4) | −0.001 (4) | 0.002 (4) |
C17B | 0.049 (4) | 0.060 (7) | 0.055 (5) | −0.006 (4) | 0.013 (4) | 0.008 (6) |
C18B | 0.047 (5) | 0.071 (9) | 0.068 (5) | −0.005 (5) | 0.017 (4) | 0.008 (6) |
C19B | 0.052 (5) | 0.077 (9) | 0.065 (6) | −0.015 (5) | 0.016 (4) | 0.009 (6) |
C20B | 0.059 (5) | 0.081 (8) | 0.082 (7) | −0.019 (5) | 0.024 (4) | 0.004 (6) |
C21B | 0.051 (5) | 0.056 (6) | 0.063 (7) | −0.015 (4) | 0.017 (4) | 0.004 (5) |
Geometric parameters (Å, º) top
Rh1—C6 | 1.807 (3) | C3—C5 | 1.507 (5) |
Rh1—O1 | 2.045 (2) | C2—C1 | 1.381 (5) |
Rh1—O2 | 2.076 (2) | C2—H2 | 0.9300 |
Rh1—P1 | 2.2240 (10) | C1—C4 | 1.502 (5) |
Rh1—H14A | 3.3668 | C4—H4A | 0.9600 |
Rh1—H13A | 3.4068 | C4—H4B | 0.9600 |
P1—C7 | 1.814 (3) | C4—H4C | 0.9600 |
P1—C16B | 1.820 (9) | C5—H5A | 0.9600 |
P1—C16A | 1.828 (9) | C5—H5B | 0.9600 |
P1—C13 | 1.839 (3) | C5—H5C | 0.9600 |
O2—C3 | 1.273 (4) | C16A—C17A | 1.392 (10) |
O1—C1 | 1.278 (4) | C16A—C21A | 1.394 (10) |
O3—C6 | 1.139 (4) | C17A—C18A | 1.388 (10) |
N1—C15 | 1.130 (4) | C17A—H17A | 0.9300 |
C7—C8 | 1.388 (4) | C18A—C19A | 1.360 (11) |
C7—C12 | 1.391 (4) | C18A—H18A | 0.9300 |
C8—C9 | 1.381 (4) | C19A—C20A | 1.394 (11) |
C8—H8 | 0.9300 | C19A—H19A | 0.9300 |
C9—C10 | 1.369 (6) | C20A—C21A | 1.394 (10) |
C9—H9 | 0.9300 | C20A—H20A | 0.9300 |
C10—C11 | 1.373 (6) | C21A—H21A | 0.9300 |
C10—H10 | 0.9300 | C16B—C17B | 1.376 (11) |
C11—C12 | 1.382 (4) | C16B—C21B | 1.392 (11) |
C11—H11 | 0.9300 | C17B—C18B | 1.395 (11) |
C12—H12 | 0.9300 | C17B—H17B | 0.9300 |
C13—C14 | 1.536 (4) | C18B—C19B | 1.363 (12) |
C13—H13A | 1.0472 | C18B—H18B | 0.9300 |
C13—H13B | 1.0318 | C19B—C20B | 1.382 (12) |
C14—C15 | 1.465 (4) | C19B—H19B | 0.9300 |
C14—H14B | 1.0410 | C20B—C21B | 1.380 (11) |
C14—H14A | 1.0595 | C20B—H20B | 0.9300 |
C3—C2 | 1.387 (5) | C21B—H21B | 0.9300 |
| | | |
C6—Rh1—O1 | 177.17 (13) | O2—C3—C5 | 114.5 (4) |
C6—Rh1—O2 | 92.15 (13) | C2—C3—C5 | 119.3 (3) |
O1—Rh1—O2 | 89.19 (9) | C1—C2—C3 | 126.9 (3) |
C6—Rh1—P1 | 89.85 (11) | C1—C2—H2 | 116.5 |
O1—Rh1—P1 | 88.74 (6) | C3—C2—H2 | 116.5 |
O2—Rh1—P1 | 177.57 (6) | O1—C1—C2 | 125.7 (3) |
C6—Rh1—H14A | 129.8 | O1—C1—C4 | 114.0 (3) |
O1—Rh1—H14A | 51.2 | C2—C1—C4 | 120.3 (3) |
O2—Rh1—H14A | 118.8 | O3—C6—Rh1 | 178.8 (4) |
P1—Rh1—H14A | 60.6 | C1—C4—H4A | 109.5 |
C6—Rh1—H13A | 133.2 | C1—C4—H4B | 109.5 |
O1—Rh1—H13A | 45.2 | H4A—C4—H4B | 109.5 |
O2—Rh1—H13A | 134.3 | C1—C4—H4C | 109.5 |
P1—Rh1—H13A | 43.5 | H4A—C4—H4C | 109.5 |
H14A—Rh1—H13A | 40.1 | H4B—C4—H4C | 109.5 |
C7—P1—C16B | 107.0 (6) | C3—C5—H5A | 109.5 |
C7—P1—C16A | 100.9 (6) | C3—C5—H5B | 109.5 |
C7—P1—C13 | 101.38 (13) | H5A—C5—H5B | 109.5 |
C16B—P1—C13 | 100.8 (6) | C3—C5—H5C | 109.5 |
C16A—P1—C13 | 106.1 (6) | H5A—C5—H5C | 109.5 |
C7—P1—Rh1 | 118.97 (10) | H5B—C5—H5C | 109.5 |
C16B—P1—Rh1 | 112.7 (6) | C17A—C16A—C21A | 118.8 (8) |
C16A—P1—Rh1 | 113.8 (6) | C17A—C16A—P1 | 118.9 (10) |
C13—P1—Rh1 | 113.90 (10) | C21A—C16A—P1 | 121.7 (10) |
C3—O2—Rh1 | 125.3 (2) | C18A—C17A—C16A | 120.1 (9) |
C1—O1—Rh1 | 126.4 (2) | C18A—C17A—H17A | 119.9 |
C8—C7—C12 | 119.1 (3) | C16A—C17A—H17A | 119.9 |
C8—C7—P1 | 120.5 (2) | C19A—C18A—C17A | 120.1 (8) |
C12—C7—P1 | 120.2 (2) | C19A—C18A—H18A | 119.9 |
C9—C8—C7 | 120.5 (3) | C17A—C18A—H18A | 119.9 |
C9—C8—H8 | 119.7 | C18A—C19A—C20A | 121.6 (8) |
C7—C8—H8 | 119.7 | C18A—C19A—H19A | 119.2 |
C10—C9—C8 | 119.8 (4) | C20A—C19A—H19A | 119.2 |
C10—C9—H9 | 120.1 | C21A—C20A—C19A | 117.9 (9) |
C8—C9—H9 | 120.1 | C21A—C20A—H20A | 121.0 |
C9—C10—C11 | 120.5 (3) | C19A—C20A—H20A | 121.0 |
C9—C10—H10 | 119.7 | C16A—C21A—C20A | 121.2 (8) |
C11—C10—H10 | 119.7 | C16A—C21A—H21A | 119.4 |
C10—C11—C12 | 120.3 (4) | C20A—C21A—H21A | 119.4 |
C10—C11—H11 | 119.9 | C17B—C16B—C21B | 119.2 (9) |
C12—C11—H11 | 119.9 | C17B—C16B—P1 | 121.3 (10) |
C11—C12—C7 | 119.8 (3) | C21B—C16B—P1 | 119.5 (10) |
C11—C12—H12 | 120.1 | C16B—C17B—C18B | 122.1 (10) |
C7—C12—H12 | 120.1 | C16B—C17B—H17B | 118.9 |
C14—C13—P1 | 110.63 (19) | C18B—C17B—H17B | 118.9 |
C14—C13—H13A | 106.7 | C19B—C18B—C17B | 117.5 (10) |
P1—C13—H13A | 106.4 | C19B—C18B—H18B | 121.3 |
C14—C13—H13B | 108.1 | C17B—C18B—H18B | 121.3 |
P1—C13—H13B | 111.6 | C18B—C19B—C20B | 121.7 (9) |
H13A—C13—H13B | 113.3 | C18B—C19B—H19B | 119.2 |
C15—C14—C13 | 111.6 (3) | C20B—C19B—H19B | 119.2 |
C15—C14—H14B | 106.1 | C21B—C20B—C19B | 120.4 (10) |
C13—C14—H14B | 119.0 | C21B—C20B—H20B | 119.8 |
C15—C14—H14A | 105.8 | C19B—C20B—H20B | 119.8 |
C13—C14—H14A | 108.2 | C20B—C21B—C16B | 119.0 (10) |
H14B—C14—H14A | 105.1 | C20B—C21B—H21B | 120.5 |
N1—C15—C14 | 179.3 (4) | C16B—C21B—H21B | 120.5 |
O2—C3—C2 | 126.2 (3) | | |
(Acetylacetonato-
κ2O,
O')carbonyl[3-(di-
tert-butylphosphanyl)propanenitrile-
κP]rhodium(I) (2i)
top
Crystal data top
[Rh(C5H7O2)(C11H22N)(CO)] | F(000) = 888 |
Mr = 429.29 | Dx = 1.409 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 13.531 (3) Å | Cell parameters from 19824 reflections |
b = 12.450 (3) Å | θ = 27–3° |
c = 12.161 (2) Å | µ = 0.94 mm−1 |
β = 98.92 (3)° | T = 298 K |
V = 2024.0 (7) Å3 | Platelet, yellow |
Z = 4 | 0.50 × 0.15 × 0.10 mm |
Data collection top
Rigaku AFC-7S Mercury diffractometer | 3851 independent reflections |
Radiation source: fine-focus seal tube | 2307 reflections with I > 2σ(I) |
Detector resolution: 14.6306 pixels mm-1 | Rint = 0.090 |
ω scans | θmax = 27.7°, θmin = 1.5° |
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005) | h = −16→17 |
Tmin = 0.818, Tmax = 0.942 | k = −14→14 |
19824 measured reflections | l = −15→15 |
Refinement top
Refinement on F2 | 2 restraints |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.075 | H-atom parameters constrained |
wR(F2) = 0.178 | w = 1/[σ2(Fo2) + (0.0407P)2 + 8.7706P] where P = (Fo2 + 2Fc2)/3 |
S = 1.16 | (Δ/σ)max < 0.001 |
3851 reflections | Δρmax = 0.50 e Å−3 |
209 parameters | Δρmin = −0.84 e Å−3 |
Special details top
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell esds are taken
into account individually in the estimation of esds in distances, angles
and torsion angles; correlations between esds in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell esds is used for estimating esds involving l.s. planes. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Rh1 | 0.30329 (5) | 0.25416 (6) | 0.11383 (6) | 0.0480 (2) | |
P1 | 0.26047 (17) | 0.42905 (18) | 0.13165 (19) | 0.0447 (6) | |
O1 | 0.1572 (4) | 0.2136 (5) | 0.1180 (5) | 0.0557 (16) | |
O2 | 0.3358 (5) | 0.0914 (5) | 0.1043 (5) | 0.0588 (16) | |
O3 | 0.5129 (6) | 0.3017 (7) | 0.0906 (9) | 0.104 (3) | |
N1 | −0.0282 (8) | 0.3013 (8) | 0.3290 (9) | 0.084 (3) | |
C1 | 0.1179 (7) | 0.1187 (8) | 0.1135 (7) | 0.053 (2) | |
C2 | 0.1730 (7) | 0.0241 (8) | 0.1086 (7) | 0.054 (2) | |
H2 | 0.1374 | −0.0399 | 0.1075 | 0.065* | |
C3 | 0.2736 (8) | 0.0151 (8) | 0.1052 (8) | 0.059 (3) | |
C5 | 0.3200 (9) | −0.0967 (7) | 0.1058 (9) | 0.081 (3) | |
H5A | 0.3905 | −0.0903 | 0.1044 | 0.121* | |
H5B | 0.2893 | −0.1358 | 0.0414 | 0.121* | |
H5C | 0.3093 | −0.1343 | 0.1719 | 0.121* | |
C4 | 0.0102 (7) | 0.1157 (8) | 0.1149 (8) | 0.064 (3) | |
H4A | −0.0029 | 0.1320 | 0.1884 | 0.097* | |
H4B | −0.0149 | 0.0453 | 0.0938 | 0.097* | |
H4C | −0.0223 | 0.1677 | 0.0633 | 0.097* | |
C6 | 0.4299 (8) | 0.2876 (7) | 0.1024 (9) | 0.064 (3) | |
C13 | 0.1426 (6) | 0.4313 (7) | 0.1894 (7) | 0.051 (2) | |
H13A | 0.1236 | 0.5055 | 0.1985 | 0.061* | |
H13B | 0.0907 | 0.3984 | 0.1360 | 0.061* | |
C14 | 0.1466 (7) | 0.3732 (8) | 0.3019 (8) | 0.060 (3) | |
H14A | 0.1924 | 0.3130 | 0.3049 | 0.071* | |
H14B | 0.1719 | 0.4222 | 0.3617 | 0.071* | |
C15 | 0.0474 (8) | 0.3343 (8) | 0.3181 (9) | 0.060 (3) | |
C7 | 0.2243 (7) | 0.4954 (7) | −0.0091 (8) | 0.054 (2) | |
C8 | 0.1937 (10) | 0.6139 (8) | −0.0037 (10) | 0.090 (4) | |
H8A | 0.1768 | 0.6417 | −0.0778 | 0.136* | |
H8B | 0.2484 | 0.6543 | 0.0358 | 0.136* | |
H8C | 0.1368 | 0.6196 | 0.0343 | 0.136* | |
C9 | 0.3072 (8) | 0.4826 (9) | −0.0780 (9) | 0.077 (3) | |
H9A | 0.2882 | 0.5165 | −0.1490 | 0.116* | |
H9B | 0.3192 | 0.4076 | −0.0888 | 0.116* | |
H9C | 0.3671 | 0.5155 | −0.0401 | 0.116* | |
C10 | 0.1334 (7) | 0.4328 (9) | −0.0702 (8) | 0.069 (3) | |
H10A | 0.1128 | 0.4640 | −0.1423 | 0.103* | |
H10B | 0.0794 | 0.4365 | −0.0278 | 0.103* | |
H10C | 0.1518 | 0.3591 | −0.0785 | 0.103* | |
C11 | 0.3479 (7) | 0.5177 (8) | 0.2282 (8) | 0.056 (2) | |
C12 | 0.3935 (8) | 0.4479 (10) | 0.3277 (9) | 0.083 (3) | |
H12A | 0.4386 | 0.4905 | 0.3787 | 0.125* | |
H12B | 0.4293 | 0.3889 | 0.3016 | 0.125* | |
H12C | 0.3410 | 0.4207 | 0.3648 | 0.125* | |
C16 | 0.2922 (8) | 0.6120 (8) | 0.2739 (9) | 0.082 (3) | |
H16A | 0.3391 | 0.6551 | 0.3223 | 0.123* | |
H16B | 0.2425 | 0.5843 | 0.3148 | 0.123* | |
H16C | 0.2605 | 0.6552 | 0.2132 | 0.123* | |
C17 | 0.4337 (8) | 0.5603 (9) | 0.1733 (10) | 0.084 (4) | |
H17A | 0.4761 | 0.6049 | 0.2250 | 0.127* | |
H17B | 0.4073 | 0.6017 | 0.1088 | 0.127* | |
H17C | 0.4718 | 0.5011 | 0.1514 | 0.127* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Rh1 | 0.0480 (4) | 0.0411 (4) | 0.0564 (4) | −0.0046 (3) | 0.0129 (3) | 0.0005 (4) |
P1 | 0.0470 (13) | 0.0419 (13) | 0.0453 (13) | −0.0047 (10) | 0.0070 (10) | 0.0013 (11) |
O1 | 0.057 (4) | 0.044 (4) | 0.068 (4) | −0.014 (3) | 0.016 (3) | −0.005 (3) |
O2 | 0.065 (4) | 0.041 (4) | 0.072 (4) | 0.001 (3) | 0.015 (3) | −0.006 (3) |
O3 | 0.060 (5) | 0.081 (6) | 0.182 (9) | 0.002 (4) | 0.048 (6) | 0.026 (6) |
N1 | 0.090 (7) | 0.069 (6) | 0.106 (8) | 0.003 (5) | 0.056 (6) | −0.010 (6) |
C1 | 0.058 (6) | 0.057 (6) | 0.043 (5) | −0.018 (5) | 0.007 (5) | −0.002 (4) |
C2 | 0.068 (7) | 0.049 (6) | 0.043 (5) | −0.022 (5) | 0.001 (5) | −0.002 (4) |
C3 | 0.079 (7) | 0.048 (6) | 0.049 (6) | −0.005 (5) | 0.004 (5) | −0.007 (4) |
C5 | 0.107 (9) | 0.035 (5) | 0.097 (8) | 0.012 (5) | 0.005 (7) | −0.006 (5) |
C4 | 0.067 (7) | 0.055 (6) | 0.071 (7) | −0.009 (5) | 0.009 (5) | −0.014 (5) |
C6 | 0.061 (7) | 0.042 (5) | 0.089 (8) | 0.002 (5) | 0.016 (6) | 0.008 (5) |
C13 | 0.058 (5) | 0.045 (5) | 0.052 (5) | −0.002 (4) | 0.014 (5) | 0.000 (4) |
C14 | 0.060 (6) | 0.063 (6) | 0.058 (6) | 0.007 (5) | 0.013 (5) | 0.013 (5) |
C15 | 0.072 (7) | 0.053 (6) | 0.063 (7) | 0.010 (5) | 0.032 (6) | 0.002 (5) |
C7 | 0.063 (6) | 0.047 (5) | 0.052 (6) | 0.001 (4) | 0.011 (5) | 0.009 (4) |
C8 | 0.131 (11) | 0.054 (7) | 0.081 (8) | 0.013 (7) | 0.000 (7) | 0.017 (6) |
C9 | 0.088 (8) | 0.081 (8) | 0.066 (7) | −0.007 (6) | 0.024 (6) | 0.009 (6) |
C10 | 0.070 (7) | 0.083 (8) | 0.049 (6) | −0.005 (6) | −0.006 (5) | 0.000 (5) |
C11 | 0.055 (6) | 0.058 (6) | 0.052 (6) | −0.009 (5) | −0.001 (5) | −0.014 (5) |
C12 | 0.070 (7) | 0.111 (10) | 0.062 (7) | −0.014 (7) | −0.009 (6) | −0.001 (7) |
C16 | 0.092 (8) | 0.065 (7) | 0.087 (8) | −0.015 (6) | 0.010 (7) | −0.029 (6) |
C17 | 0.076 (7) | 0.086 (8) | 0.090 (8) | −0.038 (6) | 0.010 (6) | −0.015 (7) |
Geometric parameters (Å, º) top
Rh1—C6 | 1.790 (11) | C14—H14A | 0.9700 |
Rh1—O1 | 2.048 (6) | C14—H14B | 0.9700 |
Rh1—O2 | 2.081 (6) | C7—C9 | 1.510 (13) |
Rh1—P1 | 2.272 (2) | C7—C8 | 1.535 (13) |
P1—C13 | 1.840 (9) | C7—C10 | 1.545 (12) |
P1—C11 | 1.888 (9) | C8—H8A | 0.9600 |
P1—C7 | 1.896 (9) | C8—H8B | 0.9600 |
O1—C1 | 1.294 (10) | C8—H8C | 0.9600 |
O2—C3 | 1.271 (11) | C9—H9A | 0.9600 |
O3—C6 | 1.167 (11) | C9—H9B | 0.9600 |
N1—C15 | 1.129 (12) | C9—H9C | 0.9600 |
C1—C2 | 1.400 (13) | C10—H10A | 0.9600 |
C1—C4 | 1.460 (12) | C10—H10B | 0.9600 |
C2—C3 | 1.373 (13) | C10—H10C | 0.9600 |
C2—H2 | 0.9300 | C11—C17 | 1.521 (13) |
C3—C5 | 1.527 (13) | C11—C12 | 1.539 (13) |
C5—H5A | 0.9600 | C11—C16 | 1.544 (13) |
C5—H5B | 0.9600 | C12—H12A | 0.9600 |
C5—H5C | 0.9600 | C12—H12B | 0.9600 |
C4—H4A | 0.9600 | C12—H12C | 0.9600 |
C4—H4B | 0.9600 | C16—H16A | 0.9600 |
C4—H4C | 0.9600 | C16—H16B | 0.9600 |
C13—C14 | 1.541 (12) | C16—H16C | 0.9600 |
C13—H13A | 0.9700 | C17—H17A | 0.9600 |
C13—H13B | 0.9700 | C17—H17B | 0.9600 |
C14—C15 | 1.469 (14) | C17—H17C | 0.9600 |
| | | |
C6—Rh1—O1 | 176.9 (4) | C9—C7—C8 | 110.7 (9) |
C6—Rh1—O2 | 90.5 (4) | C9—C7—C10 | 106.5 (8) |
O1—Rh1—O2 | 88.6 (2) | C8—C7—C10 | 107.8 (8) |
C6—Rh1—P1 | 92.6 (3) | C9—C7—P1 | 110.2 (7) |
O1—Rh1—P1 | 88.41 (18) | C8—C7—P1 | 114.4 (7) |
O2—Rh1—P1 | 176.28 (19) | C10—C7—P1 | 106.8 (6) |
C13—P1—C11 | 104.5 (4) | C7—C8—H8A | 109.5 |
C13—P1—C7 | 102.7 (4) | C7—C8—H8B | 109.5 |
C11—P1—C7 | 110.8 (4) | H8A—C8—H8B | 109.5 |
C13—P1—Rh1 | 107.5 (3) | C7—C8—H8C | 109.5 |
C11—P1—Rh1 | 118.4 (3) | H8A—C8—H8C | 109.5 |
C7—P1—Rh1 | 111.5 (3) | H8B—C8—H8C | 109.5 |
C1—O1—Rh1 | 128.0 (6) | C7—C9—H9A | 109.5 |
C3—O2—Rh1 | 125.5 (6) | C7—C9—H9B | 109.5 |
O1—C1—C2 | 123.5 (8) | H9A—C9—H9B | 109.5 |
O1—C1—C4 | 115.3 (9) | C7—C9—H9C | 109.5 |
C2—C1—C4 | 121.2 (8) | H9A—C9—H9C | 109.5 |
C3—C2—C1 | 127.3 (9) | H9B—C9—H9C | 109.5 |
C3—C2—H2 | 116.3 | C7—C10—H10A | 109.5 |
C1—C2—H2 | 116.3 | C7—C10—H10B | 109.5 |
O2—C3—C2 | 127.0 (9) | H10A—C10—H10B | 109.5 |
O2—C3—C5 | 114.1 (9) | C7—C10—H10C | 109.5 |
C2—C3—C5 | 118.9 (9) | H10A—C10—H10C | 109.5 |
C3—C5—H5A | 109.5 | H10B—C10—H10C | 109.5 |
C3—C5—H5B | 109.5 | C17—C11—C12 | 107.5 (8) |
H5A—C5—H5B | 109.5 | C17—C11—C16 | 110.0 (9) |
C3—C5—H5C | 109.5 | C12—C11—C16 | 107.7 (8) |
H5A—C5—H5C | 109.5 | C17—C11—P1 | 112.2 (7) |
H5B—C5—H5C | 109.5 | C12—C11—P1 | 107.1 (7) |
C1—C4—H4A | 109.5 | C16—C11—P1 | 112.0 (6) |
C1—C4—H4B | 109.5 | C11—C12—H12A | 109.5 |
H4A—C4—H4B | 109.5 | C11—C12—H12B | 109.5 |
C1—C4—H4C | 109.5 | H12A—C12—H12B | 109.5 |
H4A—C4—H4C | 109.5 | C11—C12—H12C | 109.5 |
H4B—C4—H4C | 109.5 | H12A—C12—H12C | 109.5 |
O3—C6—Rh1 | 174.6 (10) | H12B—C12—H12C | 109.5 |
C14—C13—P1 | 114.7 (6) | C11—C16—H16A | 109.5 |
C14—C13—H13A | 108.6 | C11—C16—H16B | 109.5 |
P1—C13—H13A | 108.6 | H16A—C16—H16B | 109.5 |
C14—C13—H13B | 108.6 | C11—C16—H16C | 109.5 |
P1—C13—H13B | 108.6 | H16A—C16—H16C | 109.5 |
H13A—C13—H13B | 107.6 | H16B—C16—H16C | 109.5 |
C15—C14—C13 | 111.5 (8) | C11—C17—H17A | 109.5 |
C15—C14—H14A | 109.3 | C11—C17—H17B | 109.5 |
C13—C14—H14A | 109.3 | H17A—C17—H17B | 109.5 |
C15—C14—H14B | 109.3 | C11—C17—H17C | 109.5 |
C13—C14—H14B | 109.3 | H17A—C17—H17C | 109.5 |
H14A—C14—H14B | 108.0 | H17B—C17—H17C | 109.5 |
N1—C15—C14 | 177.8 (11) | | |
Selected 31P NMR, 1H NMR and IR values for 2a–2i top | δ31P | 1JP-Rh | CH3trans | CH3cis | IR ν(C≡O, cm-1) |
2a | 56.3 | 170.3 | 2.04 | 1.86 | 1961.8 |
2b | 61.9 | 174.5 | 2.08 | 1.94 | 1964.0 |
2c | 35.8 | 172.2 | 2.06 | 1.85 | 1969.1 |
2d | 39.6 | 188.1 | 2.10 | 1.94 | 1968.0 |
2e | 43.7 | 173.2 | 2.06 | 1.76 | 1967.7 |
2f | 45.0 | 178.6 | 2.13 | 1.94 | 1969.3 |
2g | 74.0 | 180.7 | 2.09 | 1.91 | 1968.5 |
2h | 46.0 | 174.0 | 2.10 | 1.90 | 1967.3 |
2i | 83.1 | 158.0 | 2.07 | 1.94 | 1927.9 |
Selected 13C NMR values for 2a–2i top | C≡O | 2JP-CO | 1JRh-CO | Ccis | Ctrans | CH3cis | CH3trans | 3JRh-CH3trans |
2a | 189.8 | 24.3 | 76.0 | 184.9 | 187.9 | 27.1 | 27.7 | - |
2b | 187.7 | - | - | 184.9 | 188.4 | 27.1 | 27.6 | 5.8 |
2c | 189.1 | 25.1 | 75.9 | 185.2 | 187.8 | 27.2 | 27.6 | 5.6 |
2d | 187.1 | 26.8 | 73.7 | 185.3 | 188.2 | 27.1 | 27.5 | 6.1 |
2e | 189.0 | 24.9 | 75.7 | 185.3 | 187.7 | 27.0 | 27.6 | 5.2 |
2f | 187.9 | - | - | 185.2 | 188.1 | 27.1 | 27.6 | - |
2g | 190.0 | 25.3 | 78.1 | 185.1 | 187.9 | 27.2 | 27.7 | 5.7 |
2h | 188.3 | 25.3 | 71.4 | 185.2 | 188.3 | 27.1 | 27.6 | 5.5 |
2i | 189.2 | 23.5 | 75.4 | 184.0 | 187.6 | 26.1 | 26.8 | 5.0 |
Selected bond lengths (Å) and angles (°) for 2a, 2b,
2c and 2i top | 2a | 2b | 2h | 2i |
Rh1—P1 | 2.2387 (8) | 2.2194 (9) | 2.2240 (10) | 2.272 (2) |
Rh1—O1 | 2.036 (2) | 2.033 (4) | 2.045 (2) | 2.048 (6) |
Rh1—O2 | 2.082 (2) | 2.057 (4) | 2.077 (2) | 2.081 (6) |
Rh1—C6(CO) | 1.797 (4) | 1.805 (6) | 1.807 (3) | 1.790 (11) |
O1—Rh1—O2 | 88.0 (1) | 89.8 (2) | 89.2 (1) | 88.6 (2) |
O1—Rh1—P1 | 88.2 (1) | 89.2 (1) | 88.7 (2) | 88.4 (2) |
O2—Rh1—P1 | 176.2 (1) | 177.9 (2) | 177.6 (1) | 176.3 (2) |
O1—Rh1—C6(CO) | 177.5 (1) | 178.0 (2) | 177.2 (1) | 176.9 (4) |
O2—Rh1—C6(CO) | 94.4 (1) | 91.7 (2) | 92.2 (1) | 90.5 (3) |
P1—Rh1—C6(CO) | 89.4 (1) | 89.3 (2) | 89.9 (1) | 92.6 (3) |
Distances and angles (Å, °) for the shortest C—H···Rh contacts
found in 2b, 2h and 2i top | | | From XRD data | From DFT calculation at B3YLP/DGDZVP | | |
Compound | The substituent on the phosphine ligand | Contact C—H···Rh | H···Rh | C—H···Rh | H···Rh | C—H···Rh |
2b | Cyanoalkyl | C11—H11B···Rh1 | 3.349 | 84.3 | 3.513 | 81.1 |
C13—H13A···Rh1 | 3.391 | 80.9 | 3.511 | 78.1 | | |
tert-Butyl | C9—H9C···Rh1 | 3.142 | 116.1 | 3.559 | 111.2 | |
C10—H10B···Rh1 | 3.228 | 115.9 | 3.068 | 112.4 | | |
2h | Cyanoalkyl | C13—H13A···Rh1 | 3.407 | 81.4 | 3.507 | 79.7 |
C14—H14A···Rh1 | 3.367 | 108.9 | 3.371 | 112.5 | | |
Phenyl | C8—H8···Rh1 | 3.155 | 118.2 | 3.125 | 117.7 | |
2i | Cyanoalkyl | C14—H14A···Rh1 | 3.044 | 123.0 | 3.214 | 116.7 |
tert-Butyl | C9—H9B···Rh1 | 3.152 | 116.7 | 3.147 | 115.5 | |
C10—H10C···Rh1 | 3.145 | 117.9 | 3.125 | 119.5 | | |
C12—H12B···Rh1 | 3.119 | 114.0 | 3.208 | 108.2 | | |
Comparison of 31P NMR, IR and structural selected data for a collection of Rh
complexes topEntry | [Rh(acac)(CO)P] | δ31P (ppm) | 1JP-Rh (Hz) | dRh-Ot (Å) | dRh-CO (Å) | dRh-P (Å) | νC≡O (cm-1) | Cone angle (°) |
1 | Ph3P | 48.6 | 180.0 | 2.087 | 1.801 | 2.244 | 1975 | 145a |
2 | Cy3P | 58.0 | 170.0 | 2.096 | 1.804 | 2.261 | 1945 | 170a |
3 | Cy2PhP | 59.0 | 168.3 | 2.078 | 1.797 | 2.243 | 1949 | 163a |
4 | CyPh2P | 53.3 | 171.3 | 2.076 | 1.802 | 2.233 | 1959 | 151a |
5 | 2a | 56.3 | 170.3 | 2.082 | 1.797 | 2.239 | 1961 | 118b |
6 | 2b | 61.9 | 174.5 | 2.057 | 1.805 | 2.219 | 1964 | 129b |
7 | 2h | 46.0 | 174.0 | 2.077 | 1.806 | 2.224 | 1967 | 122b |
8 | 2i | 83.1 | 158.0 | 2.081 | 1.790 | 2.272 | 1927 | 143b |
9 | (PhO)3P | 212.1 | 293.0 | 2.063 | 1.823 | 2.170 | 2006 | 136d |
10 | Py3P | 102.0 | 251.0 | 2.054 | 1.826 | 2.166 | 2012 | 141c |
References: (a) Tolman (1977)
(b) calculated in this work following the method by Müller & Mingos
1995);
(c Trzeciak et al. (1997);
(d) Simanko et al. (2000). |
Hydrogen-bond and short-contact geometry (Å, °) for
2b, 2h and 2i topCompound 2b | | | | | |
D—H···A | D—H | H···A | D···A | Angle | Symmetry code |
C11—H11A···N2 | 0.97 | 2.42 | 3.267 (9) | 145.0 | x-1/2, -y+1/2, -z+1 |
C13—H13A···O1 | 0.97 | 2.48 | 3.028 (6) | 116.0 | |
C2—H2···N1 | 0.97 | 2.71 | 3.549 (8) | 145.0 | x-1/2, -y+1/2, -z+1 |
C13—H13B···O2 | 0.97 | 2.54 | 3.385 (7) | 145.0 | -x+1, y+1/2, -z+1/2 |
| | | | | |
Short contacts | | | | | |
X—H···Cg | X—H | H···Cg | X···Cg | X—H···Cg | Symmetry code |
C8—H8a···Cg11 | 0.96 | 3.20 | 3.903 (9) | 145.5 | -x+1/2, -y+1, z+1/2 |
| | | | | |
Compound 2h | | | | | |
D—H···A | D—H | H···A | D···A | Angle | Symmetry code |
C14—H14b···O2 | 0.97 | 2.65 | 3.657 (6) | 161.6 | x-1/2, -y-1/2, z-1/2 |
| | | | | |
Short contacts | | | | | |
D—H···A | D—H | H···A | D···A | Angle | Symmetry code |
C4—H4b···Cg22 | 0.93 | 2.93 | 3.850 (7) | 161 | -x+3/2, y-1/2, -z+1/2 |
C11—H11a···Cg23 | 0.93 | 2.85 | 3.655 (6) | 146 | x+1/2, -y+1/2, z+1/2 |
C18—H18···Cg21 | | 2.96 | 3.850 (6) | 161 | x-1/2, -y+1/2, z+1/2 |
Rh1···Cg22 | | 4.05 | | | x+1/2, -y+1/2, z+1/2 |
| | | | | |
Compound 2i | | | | | |
D—H···A | D—H (Å) | H···A (Å) | D···A (Å) | Angle (°) | Symmetry code |
C13—H13B···O1 | 0.97 | 2.49 | 2.862 (11) | 102.0 | |
C14—H14A···O1 | 0.97 | 2.57 | 3.012 (12) | 108.0 | |
C2—H2···N1 | 0.93 | 2.65 | 3.545 (14) | 160.8 | -x, y-1/2, -z+1/2 |
C12—H12C···O2 | 0.97 | 2.93 | 3.603 (13) | 128.3 | x, -y+1/2, z+1/2 |
C9—H9A···C3(acac) | 0.97 | 2.99 | 3.809 (14) | 143.9 | x, y, z+1 |
C10—H10A···Cg(C1—C2) | 0.97 | 3.13 | 3.901 (12) | 138.9 | x, y, z+1 |
C14—H14B···Cg(Rh-acac) | 0.97 | 3.05 | 3.742 (9) | 129.9 | x, -y+1/2, z+1/2 |
Centroids: Cg(C1—C2) centroid between C1 and C2;
Cg(Rh-acac) Rh1/O1/C1/C2/C3/O2;
Cg11/Cg21 Rh1/O1/C1/C2/C3/O2;
Cg22 C7–C12;
Cg23 C16A–C21A; |
Subscribe to Acta Crystallographica Section C: Structural Chemistry
The full text of this article is available to subscribers to the journal.
If you have already registered and are using a computer listed in your registration details, please email
support@iucr.org for assistance.