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The square-planar RhI complex, [Rh(trop)(PFcPh2)(CO)] (tropH = 2-hydroxy-2,4,6-cyclo­heptatrienone, C7H6O2, and PFcPh2 = ferrocenyl­di­phenyl­phosphine, C22H19FeP), contains a five-membered chelate ring. The most important bond lengths and angles include Rh-O 2.0838 (14) Å (trans to P) and Rh-O 2.0487 (14) Å (trans to CO), Rh-P 2.2395 (5) Å, Rh-C 1.803 (2) Å, and O-Rh-O 77.56 (6)° and P-Rh-C 89.73 (7)°.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801011448/tk6032sup1.cif
Contains datablocks I, RHFCTR

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536801011448/tk6032Isup2.hkl
Contains datablock I

CCDC reference: 170868

Key indicators

  • Single-crystal X-ray study
  • T = 293 K
  • Mean [sigma](C-C) = 0.004 Å
  • Disorder in main residue
  • R factor = 0.026
  • wR factor = 0.062
  • Data-to-parameter ratio = 16.7

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


Yellow Alert Alert Level C:
PLAT_301 Alert C Main Residue Disorder ........................ 12.00 Perc.
0 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
1 Alert Level C = Please check

Comment top

A large number of rhodium(I) complexes are known, of which many involve π-bonding ligands such as CO, phosphines and arenes. A subset of these compounds includes β-diketonate and tropolonate. In this paper, we report the structure of [Rh(trop)(CO)(PFcPh2)], (I), as another complex in this series containing a ferrocenyl-functionalized tertiary phosphine.

The title compound crystallizes as a distorted square-planar moiety (Fig. 1) with the most important bond distances and angles given in Table 1. The efficient packing in the crystal structure is illustrated by the closest intermolecular contact of 2.91 Å between the rhodium centre and H43b(1.5 - x, -0.5 + y, 1.5 - z).

The Rh—P bond of 2.2395 (5) Å is comparable with that found in the corresponding [Rh(trop)(CO)(PPh3)] and [Rh(cupf)(CO)(PPh3)] (cupf = N-hydroxy-N-nitrosobenzeneaminato-O,O') complexes, see Table 2. The Rh—O2 bond is significantly longer than the Rh—O3 bond due to the larger trans influence of PFcPh2 compared with CO. The small steric demand of the tropolonate ligand is illustrated by the small O2—Rh—O3 bite angle of 77.56 (6)° and the consequent O3—Rh—P, O2—Rh—C1 and P—Rh—C1 coordination angles of 96.75 (4), 95.98 (8) and 89.73 (7)°, respectively. To date, [Rh(cupf)(CO)(PPh3)] is the only analogous complex, containing a five-membered O,O-chelate, for which a smaller O—Rh—O bite angle has been reported (Basson et al., 1986), see Table 2. A slight elongation is observed in the Rh—O2 and Rh—O3 bonds compared with similar complexes. The RhI centre is only slightly displaced by a distance of 0.0308 (8) Å from the plane defined by the four donor atoms of the respective ligands.

The variation in electron density of the RhI centre as a function of the substituent X on the tertiary aryl phosphine PX3 is illustrated by the slight decrease of the carbonyl stretching frequency. This arises as an increase in the electron density on the rhodium centre results in increased back donation to the carbonyl C atom which in turn lowers ν(CO). This is illustrated for both the solid-state and liquid-state data presented in Table 3, which are in agreement with the trend in basicity of the tertiary phospines as reflected in the respective pKa values.

It was reported Steyn et al. (1997) and extended to a wider range by Roodt & Steyn (2000) that the first order Rh—P coupling constants, 1J(Rh—P), in rhodium–phosphine complexes, determined from 31P NMR, enable good estimations of the Rh—P bond strength. Although small, a tendency is observed in Table 3, indicating PFcPh2 to be better electron donating than PPh3, and comparable to P(p—CH3—Ph)3.

The torsion angles of -72.3 (2) and -63.5 (6)° for Rh—P—C31—C41a and Rh—P—C31—C41b illustrate the different orientations of the ferrocenyl moiety (see Experimental), and is also related to the solid-state steric demand of the PFcPh2 ligand (Otto et al., 2000). In this regard, effective (using the actual Rh—P bond distance) and Tolman-cone angles (using a Rh—P bond distance of 2.28 Å; Tolman, 1977) of 171.2 and 169.8° for orientation β1, and 167.4 and 166.1° for orientation β2, were calculated.

Experimental top

[Rh(trop)(CO)2] (Leipoldt et al., 1980) (10 mg, 0.036 mmol) was dissolved in warm acetone (ca 4 ml, 313 K), PFcPh2 (Sollot et al., 1963) (10 mg, 0.027 mmol) was added as the solid, and the solution was filtered. Cooling to room temperature and slow evaporation of the solvent yielded crystals suitable for X-ray analysis. Yield: quantitative based on the phosphine. Spectral data, IR (KBr): ν(CO) 1965 cm-1, (CH2Cl2) ν(CO) 1974 cm-1. 1H NMR (CDCl3, 300 MHz): 4.43 (q, 4H), 4.22 (s, 5H), 7.3 (m, 15H). 31P NMR (CDCl3, 121.497 MHz): 41.21 (d), 1J(Rh—P) 174 Hz.

Refinement top

Some disorder was identified in the β-cyclopentadienyl ring (β1: C41A–C45A; β2: C41B—C45B). Statistical averaging and similar displacement parameters for each paired set of C atoms resolved the disorder of the system, significantly decreasing the reliability index, R, from 0.058 to 0.036. H atoms were placed in idealized positions using a riding model and thermal movement refined using an overall equivalent isotropic displacement parameter.

Computing details top

Data collection: SMART (Siemens, 1995); cell refinement: SMART; data reduction: SHELXTL (Siemens, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: DIAMOND (Brandenburg, 1999); software used to prepare material for publication: SHELXL97.

Figures top
[Figure 1] Fig. 1. The structure of (I) showing the numbering scheme and displacement ellipsoids (30% probability; Brandenburg, 1999). The first digit refers to the number of the ring and the second to the number of the C atom in the ring. H atoms have been omitted for clarity.
carbonyl(tropolonato)(ferrocenyldiphenylphosphine)rhodium(I) top
Crystal data top
[Rh(C7H5O2)(C22H19FeP)(CO)]F(000) = 1256
Mr = 622.22Dx = 1.629 Mg m3
Dm = 1.630 Mg m3
Dm measured by flotation in aqueous KI
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
a = 11.3122 (7) ÅCell parameters from 6239 reflections
b = 16.2035 (9) Åθ = 2.8–28.3°
c = 14.2663 (8) ŵ = 1.32 mm1
β = 104.046 (10)°T = 293 K
V = 2536.8 (3) Å3Prism, orange
Z = 40.30 × 0.26 × 0.20 mm
Data collection top
Siemens SMART CCD 1K
diffractometer
6239 independent reflections
Radiation source: fine-focus sealed tube5239 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.025
Detector resolution: 512 x 512 pixels mm-1θmax = 28.3°, θmin = 5.6°
ω scansh = 1515
Absorption correction: empirical (using intensity measurements)
(SADABS; Sheldrick, 1996)
k = 2121
Tmin = 0.694, Tmax = 0.779l = 1918
27848 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.026Hydrogen site location: riding model
wR(F2) = 0.062H-atom parameters constrained
S = 1.08 w = 1/[σ2(Fo2) + (0.0258P)2 + 0.9003P]
where P = (Fo2 + 2Fc2)/3
6239 reflections(Δ/σ)max = 0.035
373 parametersΔρmax = 0.26 e Å3
42 restraintsΔρmin = 0.38 e Å3
Crystal data top
[Rh(C7H5O2)(C22H19FeP)(CO)]V = 2536.8 (3) Å3
Mr = 622.22Z = 4
Monoclinic, P21/nMo Kα radiation
a = 11.3122 (7) ŵ = 1.32 mm1
b = 16.2035 (9) ÅT = 293 K
c = 14.2663 (8) Å0.30 × 0.26 × 0.20 mm
β = 104.046 (10)°
Data collection top
Siemens SMART CCD 1K
diffractometer
6239 independent reflections
Absorption correction: empirical (using intensity measurements)
(SADABS; Sheldrick, 1996)
5239 reflections with I > 2σ(I)
Tmin = 0.694, Tmax = 0.779Rint = 0.025
27848 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.02642 restraints
wR(F2) = 0.062H-atom parameters constrained
S = 1.08Δρmax = 0.26 e Å3
6239 reflectionsΔρmin = 0.38 e Å3
373 parameters
Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. Cone angles are calculated assuming a 1.2 Å radius for hydrogen atoms.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Rh0.570333 (12)0.409827 (10)0.619893 (10)0.03996 (5)
Fe0.74080 (2)0.609115 (18)0.83402 (2)0.04377 (8)
P0.54850 (4)0.43830 (3)0.76838 (4)0.04003 (11)
O30.75679 (13)0.40344 (11)0.65573 (11)0.0603 (4)
O20.60919 (13)0.38214 (10)0.48790 (10)0.0518 (3)
C30.80659 (19)0.39383 (14)0.58372 (16)0.0508 (5)
C40.9331 (2)0.3953 (2)0.6029 (2)0.0735 (8)
H40.97170.40360.66760.0797 (19)*
C51.0116 (2)0.3864 (2)0.5430 (2)0.0904 (10)
H51.09410.38930.57350.0797 (19)*
C60.9857 (3)0.3742 (2)0.4466 (3)0.0949 (11)
H61.05210.36830.41940.0797 (19)*
C70.8722 (3)0.3695 (2)0.3838 (2)0.0856 (9)
H70.87240.36320.31900.0797 (19)*
C80.7586 (2)0.37284 (19)0.40271 (18)0.0693 (7)
H80.69410.36820.34830.0797 (19)*
C20.72321 (19)0.38201 (13)0.49018 (15)0.0481 (5)
C10.40782 (19)0.41923 (13)0.57321 (15)0.0463 (4)
O10.30587 (14)0.42580 (11)0.53975 (14)0.0673 (5)
C110.39501 (18)0.42413 (14)0.78808 (15)0.0485 (5)
C120.3303 (2)0.48760 (17)0.81636 (17)0.0583 (6)
H120.36290.54060.82380.0797 (19)*
C130.2156 (2)0.4727 (2)0.83403 (19)0.0737 (8)
H130.17280.51580.85350.0797 (19)*
C140.1669 (2)0.3961 (2)0.8230 (2)0.0800 (9)
H140.09140.38620.83600.0797 (19)*
C150.2293 (3)0.3326 (2)0.7924 (2)0.0861 (9)
H150.19470.28030.78320.0797 (19)*
C160.3433 (2)0.34595 (18)0.7751 (2)0.0715 (7)
H160.38500.30260.75490.0797 (19)*
C210.64010 (18)0.37610 (13)0.86772 (15)0.0446 (4)
C220.6066 (2)0.36832 (16)0.95464 (17)0.0611 (6)
H220.53600.39390.96240.0797 (19)*
C230.6775 (3)0.32272 (17)1.03030 (18)0.0680 (7)
H230.65440.31801.08830.0797 (19)*
C240.7821 (2)0.28451 (16)1.01927 (18)0.0655 (6)
H240.83020.25461.07000.0797 (19)*
C250.8149 (2)0.29079 (17)0.93319 (19)0.0663 (6)
H250.88490.26440.92540.0797 (19)*
C260.7444 (2)0.33635 (15)0.85749 (16)0.0546 (5)
H260.76760.34020.79940.0797 (19)*
C310.58254 (16)0.54313 (12)0.80681 (13)0.0404 (4)
C320.57133 (17)0.61243 (13)0.74251 (15)0.0456 (4)
H320.55350.60990.67540.0797 (19)*
C330.5922 (2)0.68529 (14)0.79899 (17)0.0544 (5)
H330.59020.73880.77510.0797 (19)*
C340.6165 (2)0.66308 (15)0.89754 (17)0.0571 (5)
H340.63280.69940.94960.0797 (19)*
C350.6116 (2)0.57584 (14)0.90337 (15)0.0510 (5)
H350.62500.54500.96000.0797 (19)*
C41A0.8865 (12)0.5283 (8)0.8392 (11)0.062 (2)0.611 (18)
H41A0.88510.47090.84060.0797 (19)*0.611 (18)
C42A0.8684 (8)0.5789 (9)0.7561 (7)0.065 (3)0.611 (18)
H42A0.85080.56040.69250.0797 (19)*0.611 (18)
C43A0.8815 (8)0.6607 (8)0.7854 (13)0.075 (4)0.611 (18)
H43A0.87510.70570.74390.0797 (19)*0.611 (18)
C44A0.9055 (9)0.6660 (7)0.8855 (14)0.083 (5)0.611 (18)
H44A0.91780.71430.92190.0797 (19)*0.611 (18)
C45A0.9078 (14)0.5839 (10)0.9223 (7)0.078 (4)0.611 (18)
H45A0.92050.56880.98690.0797 (19)*0.611 (18)
C45B0.899 (2)0.5532 (14)0.898 (2)0.106 (9)0.389 (18)
H45B0.91220.50950.94140.0797 (19)*0.389 (18)
C41B0.8744 (17)0.5460 (12)0.807 (3)0.097 (11)0.389 (18)
H41B0.86260.49600.77380.0797 (19)*0.389 (18)
C42B0.8681 (13)0.6206 (19)0.7645 (11)0.080 (7)0.389 (18)
H42B0.85390.62980.69840.0797 (19)*0.389 (18)
C44B0.9024 (18)0.637 (2)0.9232 (12)0.090 (8)0.389 (18)
H44B0.91320.65960.98480.0797 (19)*0.389 (18)
C43B0.8859 (17)0.6805 (10)0.8337 (17)0.065 (5)0.389 (18)
H43B0.88700.73730.82450.0797 (19)*0.389 (18)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Rh0.03272 (7)0.04817 (9)0.03841 (8)0.00099 (6)0.00753 (6)0.00086 (6)
Fe0.03644 (14)0.05011 (17)0.04330 (15)0.00207 (11)0.00686 (12)0.00505 (12)
P0.0332 (2)0.0491 (3)0.0382 (2)0.00113 (19)0.00939 (19)0.0018 (2)
O30.0360 (7)0.1023 (13)0.0419 (8)0.0010 (8)0.0081 (6)0.0028 (8)
O20.0423 (7)0.0705 (10)0.0411 (7)0.0096 (7)0.0070 (6)0.0053 (7)
C30.0398 (10)0.0653 (14)0.0485 (11)0.0043 (9)0.0132 (9)0.0126 (10)
C40.0407 (11)0.121 (2)0.0595 (15)0.0028 (13)0.0142 (11)0.0178 (15)
C50.0461 (13)0.145 (3)0.087 (2)0.0077 (16)0.0303 (14)0.032 (2)
C60.0714 (19)0.137 (3)0.093 (2)0.0220 (19)0.0523 (18)0.029 (2)
C70.088 (2)0.115 (3)0.0670 (17)0.0249 (19)0.0440 (16)0.0135 (17)
C80.0665 (15)0.0939 (19)0.0499 (13)0.0203 (14)0.0190 (12)0.0007 (13)
C20.0489 (11)0.0523 (12)0.0447 (11)0.0119 (9)0.0141 (9)0.0057 (9)
C10.0453 (11)0.0448 (11)0.0483 (11)0.0002 (8)0.0105 (9)0.0013 (9)
O10.0363 (8)0.0780 (12)0.0812 (12)0.0024 (7)0.0021 (8)0.0043 (9)
C110.0358 (9)0.0680 (14)0.0415 (10)0.0044 (9)0.0092 (8)0.0078 (9)
C120.0432 (11)0.0782 (16)0.0555 (13)0.0026 (11)0.0160 (10)0.0039 (11)
C130.0408 (12)0.121 (2)0.0628 (15)0.0057 (14)0.0189 (11)0.0026 (15)
C140.0399 (12)0.141 (3)0.0603 (15)0.0135 (15)0.0144 (11)0.0204 (17)
C150.0575 (15)0.099 (2)0.100 (2)0.0277 (16)0.0151 (15)0.0195 (18)
C160.0528 (13)0.0746 (17)0.0884 (19)0.0130 (12)0.0195 (13)0.0047 (15)
C210.0424 (10)0.0455 (11)0.0438 (10)0.0032 (8)0.0063 (8)0.0028 (8)
C220.0608 (14)0.0721 (16)0.0539 (13)0.0085 (12)0.0205 (11)0.0155 (11)
C230.0788 (17)0.0744 (17)0.0511 (14)0.0045 (14)0.0162 (12)0.0173 (12)
C240.0721 (16)0.0589 (14)0.0548 (14)0.0028 (12)0.0053 (12)0.0104 (11)
C250.0580 (14)0.0723 (16)0.0635 (15)0.0187 (12)0.0050 (12)0.0023 (12)
C260.0530 (12)0.0621 (14)0.0476 (12)0.0082 (10)0.0101 (10)0.0014 (10)
C310.0347 (9)0.0490 (11)0.0386 (9)0.0000 (8)0.0111 (7)0.0020 (8)
C320.0363 (9)0.0561 (12)0.0424 (10)0.0052 (8)0.0058 (8)0.0048 (9)
C330.0485 (11)0.0504 (12)0.0643 (14)0.0055 (9)0.0137 (10)0.0031 (10)
C340.0572 (13)0.0621 (14)0.0561 (13)0.0060 (10)0.0215 (11)0.0124 (11)
C350.0539 (12)0.0614 (13)0.0410 (10)0.0080 (10)0.0177 (9)0.0007 (9)
C41A0.042 (4)0.054 (4)0.094 (6)0.010 (3)0.026 (4)0.013 (4)
C42A0.049 (3)0.083 (8)0.073 (4)0.002 (5)0.035 (3)0.004 (4)
C43A0.048 (4)0.067 (7)0.118 (12)0.002 (5)0.034 (7)0.025 (7)
C44A0.040 (3)0.073 (6)0.124 (12)0.009 (4)0.002 (8)0.029 (8)
C45A0.057 (5)0.103 (11)0.064 (3)0.025 (8)0.007 (3)0.002 (6)
C45B0.051 (6)0.081 (13)0.16 (2)0.013 (10)0.013 (16)0.036 (13)
C41B0.040 (5)0.050 (10)0.19 (3)0.002 (6)0.015 (15)0.008 (12)
C42B0.056 (5)0.12 (2)0.072 (6)0.010 (14)0.032 (4)0.035 (13)
C44B0.043 (6)0.15 (2)0.071 (7)0.014 (11)0.002 (6)0.007 (12)
C43B0.051 (7)0.058 (6)0.093 (15)0.015 (5)0.028 (9)0.010 (7)
Geometric parameters (Å, º) top
Rh—C11.803 (2)C21—C221.387 (3)
Rh—O32.0487 (14)C22—C231.391 (3)
Rh—O22.0838 (14)C22—H220.9300
Rh—P2.2395 (5)C23—C241.377 (4)
Fe—C352.026 (2)C23—H230.9300
Fe—C312.0400 (19)C24—C251.370 (4)
Fe—C322.041 (2)C24—H240.9300
Fe—C342.045 (2)C25—C261.389 (3)
Fe—C332.047 (2)C25—H250.9300
P—C311.798 (2)C26—H260.9300
P—C111.8394 (19)C31—C321.436 (3)
P—C211.840 (2)C31—C351.438 (3)
O3—C31.295 (3)C32—C331.416 (3)
O2—C21.282 (2)C32—H320.9300
C3—C41.390 (3)C33—C341.412 (3)
C3—C21.448 (3)C33—H330.9300
C4—C51.381 (3)C34—C351.418 (3)
C4—H40.9300C34—H340.9300
C5—C61.350 (5)C35—H350.9300
C5—H50.9300C41A—C42A1.414 (13)
C6—C71.378 (5)C41A—C45A1.463 (19)
C6—H60.9300C41A—H41A0.9300
C7—C81.377 (4)C42A—C43A1.387 (10)
C7—H70.9300C42A—H42A0.9300
C8—C21.408 (3)C43A—C44A1.390 (11)
C8—H80.9300C43A—H43A0.9300
C1—O11.141 (2)C44A—C45A1.428 (14)
C11—C121.378 (3)C44A—H44A0.9300
C11—C161.389 (3)C45A—H45A0.9300
C12—C131.401 (3)C45B—C41B1.26 (3)
C12—H120.9300C45B—C44B1.41 (3)
C13—C141.352 (4)C45B—H45B0.9300
C13—H130.9300C41B—C42B1.35 (2)
C14—C151.377 (5)C41B—H41B0.9300
C14—H140.9300C42B—C43B1.364 (17)
C15—C161.387 (4)C42B—H42B0.9300
C15—H150.9300C44B—C43B1.43 (2)
C16—H160.9300C44B—H44B0.9300
C21—C261.383 (3)C43B—H43B0.9300
C1—Rh—O3172.71 (8)C24—C23—H23120.0
C1—Rh—O295.98 (8)C22—C23—H23120.0
O3—Rh—O277.56 (6)C25—C24—C23119.7 (2)
C1—Rh—P89.73 (7)C25—C24—H24120.1
O3—Rh—P96.75 (4)C23—C24—H24120.1
O2—Rh—P174.29 (4)C24—C25—C26120.5 (2)
C35—Fe—C3141.40 (8)C24—C25—H25119.8
C35—Fe—C3269.06 (9)C26—C25—H25119.8
C31—Fe—C3241.20 (8)C21—C26—C25120.6 (2)
C35—Fe—C3440.76 (9)C21—C26—H26119.7
C31—Fe—C3469.04 (8)C25—C26—H26119.7
C32—Fe—C3468.41 (9)C32—C31—C35106.73 (18)
C35—Fe—C3368.46 (9)C32—C31—P124.39 (15)
C31—Fe—C3368.83 (9)C35—C31—P128.53 (15)
C32—Fe—C3340.54 (9)C32—C31—Fe69.46 (11)
C34—Fe—C3340.37 (9)C35—C31—Fe68.79 (11)
C31—P—C11102.22 (9)P—C31—Fe131.79 (10)
C31—P—C21104.11 (9)C33—C32—C31108.16 (18)
C11—P—C21100.95 (9)C33—C32—Fe69.96 (12)
C31—P—Rh114.74 (6)C31—C32—Fe69.34 (11)
C11—P—Rh116.34 (7)C33—C32—H32125.9
C21—P—Rh116.42 (7)C31—C32—H32125.9
C3—O3—Rh115.32 (13)Fe—C32—H32126.4
C2—O2—Rh114.13 (13)C34—C33—C32108.6 (2)
O3—C3—C4117.8 (2)C34—C33—Fe69.72 (13)
O3—C3—C2115.82 (18)C32—C33—Fe69.51 (12)
C4—C3—C2126.3 (2)C34—C33—H33125.7
C5—C4—C3131.5 (3)C32—C33—H33125.7
C5—C4—H4114.3Fe—C33—H33126.7
C3—C4—H4114.3C33—C34—C35108.2 (2)
C6—C5—C4129.2 (3)C33—C34—Fe69.91 (12)
C6—C5—H5115.4C35—C34—Fe68.92 (12)
C4—C5—H5115.4C33—C34—H34125.9
C5—C6—C7127.5 (3)C35—C34—H34125.9
C5—C6—H6116.2Fe—C34—H34126.8
C7—C6—H6116.2C34—C35—C31108.33 (19)
C6—C7—C8129.5 (3)C34—C35—Fe70.32 (12)
C6—C7—H7115.2C31—C35—Fe69.80 (11)
C8—C7—H7115.2C34—C35—H35125.8
C7—C8—C2131.1 (3)C31—C35—H35125.8
C7—C8—H8114.4Fe—C35—H35125.6
C2—C8—H8114.4C42A—C41A—C45A106.5 (10)
O2—C2—C8118.6 (2)C42A—C41A—H41A126.7
O2—C2—C3116.70 (18)C45A—C41A—H41A126.8
C8—C2—C3124.7 (2)C41A—C42A—C43A108.6 (10)
O1—C1—Rh177.0 (2)C41A—C42A—H42A125.7
C12—C11—C16118.9 (2)C43A—C42A—H42A125.7
C12—C11—P122.65 (17)C44A—C43A—C42A110.4 (9)
C16—C11—P118.42 (18)C44A—C43A—H43A124.8
C11—C12—C13120.3 (3)C42A—C43A—H43A124.8
C11—C12—H12119.9C43A—C44A—C45A107.6 (7)
C13—C12—H12119.9C43A—C44A—H44A126.2
C14—C13—C12120.4 (3)C45A—C44A—H44A126.2
C14—C13—H13119.8C41A—C45A—C44A106.9 (8)
C12—C13—H13119.8C41A—C45A—H45A126.5
C13—C14—C15119.7 (2)C44A—C45A—H45A126.6
C13—C14—H14120.1C41B—C45B—C44B109.9 (16)
C15—C14—H14120.1C41B—C45B—H45B125.0
C14—C15—C16120.7 (3)C44B—C45B—H45B125.1
C14—C15—H15119.6C45B—C41B—C42B110.6 (17)
C16—C15—H15119.6C45B—C41B—H41B124.7
C15—C16—C11119.8 (3)C42B—C41B—H41B124.6
C15—C16—H16120.1C43B—C42B—C41B109.4 (16)
C11—C16—H16120.1C43B—C42B—H42B125.2
C26—C21—C22118.5 (2)C41B—C42B—H42B125.3
C26—C21—P120.62 (16)C45B—C44B—C43B104.8 (18)
C22—C21—P120.88 (16)C45B—C44B—H44B127.5
C21—C22—C23120.7 (2)C43B—C44B—H44B127.6
C21—C22—H22119.6C42B—C43B—C44B105.1 (17)
C23—C22—H22119.6C42B—C43B—H43B127.5
C24—C23—C22120.0 (2)C44B—C43B—H43B127.4
Rh—P—C31—C41A72.3 (2)C42B—C43B—C34—C3361.3 (18)
Rh—P—C31—C41B63.5 (6)C43A—C44A—C34—C3318.4 (8)
C45B—C41B—C32—C3158.6 (16)C43B—C44B—C35—C3458.1 (19)
C41A—C42A—C32—C3116.1 (10)C44A—C45A—C35—C3417.8 (9)
C41B—C42B—C33—C3260.6 (17)C44B—C45B—C31—C3553.6 (18)
C42A—C43A—C33—C3216.6 (8)C45A—C41A—C31—C3516.1 (8)

Experimental details

Crystal data
Chemical formula[Rh(C7H5O2)(C22H19FeP)(CO)]
Mr622.22
Crystal system, space groupMonoclinic, P21/n
Temperature (K)293
a, b, c (Å)11.3122 (7), 16.2035 (9), 14.2663 (8)
β (°) 104.046 (10)
V3)2536.8 (3)
Z4
Radiation typeMo Kα
µ (mm1)1.32
Crystal size (mm)0.30 × 0.26 × 0.20
Data collection
DiffractometerSiemens SMART CCD 1K
diffractometer
Absorption correctionEmpirical (using intensity measurements)
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.694, 0.779
No. of measured, independent and
observed [I > 2σ(I)] reflections
27848, 6239, 5239
Rint0.025
(sin θ/λ)max1)0.667
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.026, 0.062, 1.08
No. of reflections6239
No. of parameters373
No. of restraints42
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.26, 0.38

Computer programs: SMART (Siemens, 1995), SMART, SHELXTL (Siemens, 1995), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), DIAMOND (Brandenburg, 1999), SHELXL97.

Selected geometric parameters (Å, º) top
Rh—C11.803 (2)Rh—P2.2395 (5)
Rh—O32.0487 (14)C1—O11.141 (2)
Rh—O22.0838 (14)
C1—Rh—O3172.71 (8)O3—Rh—P96.75 (4)
C1—Rh—O295.98 (8)O2—Rh—P174.29 (4)
O3—Rh—O277.56 (6)O1—C1—Rh177.0 (2)
C1—Rh—P89.73 (7)
Rh—P—C31—C41A72.3 (2)Rh—P—C31—C41B63.5 (6)
Comparative X-ray data for [Rh(O,O-Bidi)(CO)(L)] complexes top
ComplexRh-O3aRh-O2bRh-PO3-Rh-O2
[Rh(trop)(CO)(PFcPh2)]c2.0487 (14)2.0838 (14)2.2395 (5)77.56 (6)
[Rh(trop)(CO)(PPh3)]d2.034 (7)2.081 (7)2.232 (2)77.8 (3)
[Rh(cupf)(CO)(PPh3)]e2.024 (6)2.063 (6)2.232 (3)76.6 (3)
Notes: (i) bidentate oxygen ligand forming five membered chelate, (a) oxygen atom trans to the carbonyl, (b) oxygen atom trans to the phosphine, (c) present study, (d) Leipoldt et al. (1980), (e) Basson et al. (1986),
Comparative spectroscopic data for [Rh(trop)(CO)(L)] complexes top
Lν(CO) (KBr/cm-1)ν(CO) (CH2Cl2/cm-1)1J(Rh-P) (Hz)pKaa
P(p-CH3-Ph)3196619731753.84
PFcPh219651974174
PPh3197419751732.73
P(p-F-Ph)3197519761721.97
Notes: (a) Wilkinson (1987).
 

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