Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536802019980/cf6218sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536802019980/cf6218Isup2.hkl |
CCDC reference: 202284
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.010 Å
- R factor = 0.048
- wR factor = 0.091
- Data-to-parameter ratio = 10.1
checkCIF results
No syntax errors found ADDSYM reports no extra symmetry
Alert Level A:
DIFF_020 Alert A _diffrn_standards_interval_count and _diffrn_standards_interval_time are missing. Number of measurements between standards or time (min) between standards. DIFF_022 Alert A _diffrn_standards_decay_% is missing Percentage decrease in standards intensity.
Alert Level B:
REFLT_03 From the CIF: _diffrn_reflns_theta_max 31.66 From the CIF: _reflns_number_total 11180 TEST2: Reflns within _diffrn_reflns_theta_max Count of symmetry unique reflns 12659 Completeness (_total/calc) 88.32% Alert B: < 90% complete (theta max?)
2 Alert Level A = Potentially serious problem
1 Alert Level B = Potential problem
0 Alert Level C = Please check
[RhCl(CO)2]2 (Lebedev National Rubber Research Institute) and PBz3 (Aldrich) were used as received. PBz3 (157 mg, 0.52 mmol), dissolved in acetone (5 ml), was added to a solution of [RhCl(CO)2]2 (50 mg, 0.13 mmol) in acetone (10 ml). Slow evaporation of the solution yielded yellow crystals suitable for X-ray analysis. 31P NMR (CDCl3): 18.1 p.p.m. [d, 1J(Rh–P) = 124 Hz]; IR (DCM), ν(CO): 1968 cm−1. Quantum chemical geometry optimizations were performed with the density-functional B—P86 method, as implemented in the Turbomole 5.5 software (Hertwig & Koch, 1997; Treutler & Ahlrichs, 1995). Basis sets at the def-SVP level were used for Rh, Cl and P, and at 6–31g* for the other atoms. Two starting structures, one direct from the crystal structure data and one modified with an anti conformation along the P···P axis, reproduced approximately the same final geometry of the complex in the gas phase. However, a starting structure with O—C—Rh—Cl rotated by approximately 180° compared to the crystal structure found a local minimum in this region, with a somewhat larger energy compared to the global minimum. Accurate energies were calculated with single-point calculations on the optimized structures, by the B3LYP method, and using basis sets def-TZVPP for Rh and def-TZVP for the other atoms, as implemented in Turbomole 5.5.
The first 50 frames of data were recollected at the end of the data collection to check for decay; none was found. Both the minimum and maximum residual electron densities lie within 1 Å of the Rh atom.
Data collection: SMART (Siemens, 1998); cell refinement: SAINT; data reduction: SAINT (Siemens, 1998); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: CRYSTALS (Watkin et al., 2001); molecular graphics: DIAMOND (Brandenburg & Berndt, 2000); software used to prepare material for publication: CRYSTALS.
Fig. 1. The molecular structure of (I), showing the atom-numbering scheme and displacement ellipsoids (30% probability). H atoms have been omitted for clarity. |
[RhCl(C21H21P)2(CO)] | Z = 2 |
Mr = 775.11 | F(000) = 800.000 |
Triclinic, P1 | Dx = 1.371 Mg m−3 |
Hall symbol: -P 1 | Melting point: not measured K |
a = 10.031 (1) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 10.165 (1) Å | Cell parameters from 1993 reflections |
c = 18.9910 (19) Å | θ = 2–21° |
α = 93.36 (3)° | µ = 0.64 mm−1 |
β = 90.37 (3)° | T = 293 K |
γ = 103.69 (3)° | Cuboid, yellow |
V = 1877.8 (4) Å3 | 0.09 × 0.08 × 0.03 mm |
Bruker SMART diffractometer | 4389 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.032 |
ω scans | θmax = 31.7°, θmin = 1.1° |
Absorption correction: multi-scan SADABS (Siemens, 1998) | h = −14→14 |
Tmin = 0.85, Tmax = 0.95 | k = −14→14 |
19116 measured reflections | l = −21→27 |
11180 independent reflections |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.048 | H-atom parameters constrained |
wR(F2) = 0.091 | w = 1/[σ2(Fo2) + (0.0462P)2] where P = (Fo2 + 2Fc2)/3 |
S = 0.88 | (Δ/σ)max < 0.001 |
4389 reflections | Δρmax = 0.78 e Å−3 |
433 parameters | Δρmin = −0.50 e Å−3 |
[RhCl(C21H21P)2(CO)] | γ = 103.69 (3)° |
Mr = 775.11 | V = 1877.8 (4) Å3 |
Triclinic, P1 | Z = 2 |
a = 10.031 (1) Å | Mo Kα radiation |
b = 10.165 (1) Å | µ = 0.64 mm−1 |
c = 18.9910 (19) Å | T = 293 K |
α = 93.36 (3)° | 0.09 × 0.08 × 0.03 mm |
β = 90.37 (3)° |
Bruker SMART diffractometer | 11180 independent reflections |
Absorption correction: multi-scan SADABS (Siemens, 1998) | 4389 reflections with I > 2σ(I) |
Tmin = 0.85, Tmax = 0.95 | Rint = 0.032 |
19116 measured reflections |
R[F2 > 2σ(F2)] = 0.048 | 433 parameters |
wR(F2) = 0.091 | H-atom parameters constrained |
S = 0.88 | Δρmax = 0.78 e Å−3 |
4389 reflections | Δρmin = −0.50 e Å−3 |
x | y | z | Uiso*/Ueq | ||
P1 | 0.86236 (14) | 0.18462 (13) | 0.12054 (7) | 0.0350 | |
P2 | 0.90376 (16) | 0.25692 (15) | 0.36357 (8) | 0.0447 | |
Rh | 0.88696 (5) | 0.21895 (5) | 0.24206 (2) | 0.0376 | |
C1 | 0.9621 (6) | 0.0770 (6) | 0.2455 (3) | 0.0462 | |
O1 | 1.0123 (5) | −0.0146 (5) | 0.2480 (2) | 0.0773 | |
C13 | 0.7027 (5) | 0.0637 (5) | 0.0905 (3) | 0.0436 | |
C131 | 0.6815 (5) | −0.0726 (5) | 0.1212 (3) | 0.0388 | |
C136 | 0.6946 (6) | −0.1855 (6) | 0.0804 (3) | 0.0581 | |
C135 | 0.6788 (7) | −0.3097 (6) | 0.1107 (5) | 0.0784 | |
C134 | 0.6478 (7) | −0.3214 (8) | 0.1805 (5) | 0.0751 | |
C133 | 0.6309 (6) | −0.2110 (8) | 0.2199 (4) | 0.0667 | |
C132 | 0.6478 (6) | −0.0874 (6) | 0.1919 (3) | 0.0520 | |
C11 | 0.8541 (5) | 0.3351 (5) | 0.0722 (3) | 0.0406 | |
C111 | 0.8369 (6) | 0.3171 (5) | −0.0063 (3) | 0.0424 | |
C116 | 0.9502 (6) | 0.3275 (5) | −0.0498 (3) | 0.0473 | |
C115 | 0.9371 (7) | 0.3134 (6) | −0.1230 (3) | 0.0581 | |
C114 | 0.8080 (9) | 0.2865 (7) | −0.1539 (3) | 0.0711 | |
C113 | 0.6956 (7) | 0.2755 (7) | −0.1121 (4) | 0.0694 | |
C112 | 0.7084 (6) | 0.2902 (6) | −0.0396 (3) | 0.0558 | |
C12 | 0.9898 (5) | 0.1099 (5) | 0.0755 (3) | 0.0408 | |
C121 | 1.1392 (5) | 0.1662 (5) | 0.0967 (3) | 0.0404 | |
C122 | 1.2027 (6) | 0.3037 (6) | 0.0969 (3) | 0.0485 | |
C123 | 1.3410 (6) | 0.3505 (6) | 0.1145 (3) | 0.0603 | |
C124 | 1.4169 (6) | 0.2595 (8) | 0.1331 (4) | 0.0721 | |
C125 | 1.3558 (6) | 0.1230 (7) | 0.1325 (4) | 0.0724 | |
C126 | 1.2173 (6) | 0.0786 (6) | 0.1149 (3) | 0.0573 | |
C22 | 0.9754 (6) | 0.1367 (6) | 0.4126 (3) | 0.0471 | |
C221 | 1.0252 (6) | 0.1771 (5) | 0.4876 (3) | 0.0466 | |
C226 | 0.9353 (6) | 0.1775 (6) | 0.5436 (3) | 0.0551 | |
C225 | 0.9842 (8) | 0.2159 (7) | 0.6121 (3) | 0.0701 | |
C224 | 1.1217 (9) | 0.2526 (7) | 0.6257 (4) | 0.0789 | |
C223 | 1.2112 (7) | 0.2497 (7) | 0.5734 (4) | 0.0789 | |
C222 | 1.1630 (6) | 0.2112 (6) | 0.5042 (3) | 0.0610 | |
C23 | 0.7388 (6) | 0.2640 (6) | 0.4049 (3) | 0.0553 | |
C231 | 0.6183 (7) | 0.1462 (9) | 0.3861 (3) | 0.0670 | |
C232 | 0.5998 (8) | 0.0281 (9) | 0.4162 (5) | 0.0951 | |
C233 | 0.4885 (11) | −0.0784 (11) | 0.4002 (6) | 0.1341 | |
C234 | 0.3957 (14) | −0.0660 (17) | 0.3533 (7) | 0.1707 | |
C235 | 0.4062 (12) | 0.0493 (19) | 0.3216 (6) | 0.1776 | |
C236 | 0.520 (1) | 0.1611 (12) | 0.3371 (4) | 0.1243 | |
C21 | 1.0045 (7) | 0.4256 (6) | 0.3934 (3) | 0.0595 | |
C211 | 1.1560 (7) | 0.4591 (5) | 0.3764 (3) | 0.0543 | |
C216 | 1.2544 (8) | 0.4979 (7) | 0.4291 (3) | 0.0721 | |
C215 | 1.3903 (9) | 0.5295 (8) | 0.4146 (4) | 0.0873 | |
C214 | 1.4308 (8) | 0.5222 (8) | 0.3477 (5) | 0.0981 | |
C213 | 1.337 (1) | 0.4901 (9) | 0.2934 (4) | 0.1207 | |
C212 | 1.1984 (8) | 0.4570 (8) | 0.3086 (4) | 0.0946 | |
Cl | 0.78656 (19) | 0.40721 (17) | 0.24058 (8) | 0.0720 | |
H15 | 0.7042 | 0.0502 | 0.0380 | 0.0516* | |
H16 | 0.6238 | 0.1036 | 0.1042 | 0.0516* | |
H136 | 0.7153 | −0.1783 | 0.0291 | 0.0680* | |
H135 | 0.6908 | −0.3908 | 0.0813 | 0.0937* | |
H134 | 0.6374 | −0.4104 | 0.2022 | 0.0917* | |
H133 | 0.6056 | −0.2202 | 0.2706 | 0.0772* | |
H132 | 0.6359 | −0.0072 | 0.2223 | 0.0600* | |
H11 | 0.9420 | 0.4045 | 0.0828 | 0.0507* | |
H12 | 0.7755 | 0.3694 | 0.0908 | 0.0507* | |
H116 | 1.0441 | 0.3458 | −0.0275 | 0.0536* | |
H115 | 1.0202 | 0.3228 | −0.1528 | 0.0683* | |
H114 | 0.7965 | 0.2749 | −0.2065 | 0.0822* | |
H113 | 0.6020 | 0.2562 | −0.1348 | 0.0826* | |
H112 | 0.6243 | 0.2815 | −0.0105 | 0.0675* | |
H14 | 0.9667 | 0.0110 | 0.0840 | 0.0484* | |
H13 | 0.9808 | 0.1218 | 0.0240 | 0.0484* | |
H122 | 1.1480 | 0.3698 | 0.0843 | 0.0581* | |
H123 | 1.3860 | 0.4494 | 0.1135 | 0.0695* | |
H124 | 1.5160 | 0.2931 | 0.1471 | 0.0851* | |
H125 | 1.4106 | 0.0566 | 0.1445 | 0.0894* | |
H126 | 1.1728 | −0.0205 | 0.1156 | 0.0699* | |
H23 | 1.0549 | 0.1187 | 0.3855 | 0.0577* | |
H24 | 0.9021 | 0.0508 | 0.4137 | 0.0577* | |
H226 | 0.8338 | 0.1496 | 0.5341 | 0.0652* | |
H225 | 0.9182 | 0.2166 | 0.6515 | 0.0859* | |
H224 | 1.1564 | 0.2816 | 0.6751 | 0.0926* | |
H223 | 1.3120 | 0.2755 | 0.5842 | 0.0920* | |
H222 | 1.2304 | 0.2082 | 0.4658 | 0.0726* | |
H25 | 0.7532 | 0.2694 | 0.4572 | 0.0691* | |
H26 | 0.7137 | 0.3484 | 0.3905 | 0.0691* | |
H232 | 0.6694 | 0.0160 | 0.4517 | 0.1097* | |
H233 | 0.4777 | −0.1654 | 0.4242 | 0.1501* | |
H234 | 0.3166 | −0.1446 | 0.3413 | 0.1806* | |
H235 | 0.3334 | 0.0569 | 0.2868 | 0.2002* | |
H236 | 0.5294 | 0.2484 | 0.3134 | 0.1485* | |
H22 | 0.9971 | 0.4351 | 0.4458 | 0.0711* | |
H21 | 0.9626 | 0.4935 | 0.3712 | 0.0711* | |
H216 | 1.2253 | 0.5030 | 0.4792 | 0.0806* | |
H215 | 1.4601 | 0.5581 | 0.4538 | 0.0978* | |
H214 | 1.5311 | 0.5408 | 0.3373 | 0.1088* | |
H213 | 1.3679 | 0.4899 | 0.2433 | 0.1246* | |
H212 | 1.1286 | 0.4312 | 0.2691 | 0.1008* |
U11 | U22 | U33 | U12 | U13 | U23 | |
P1 | 0.0357 (9) | 0.0339 (8) | 0.0363 (9) | 0.0098 (7) | 0.0020 (7) | 0.0028 (7) |
P2 | 0.0577 (11) | 0.0422 (9) | 0.0360 (9) | 0.0167 (8) | −0.0030 (8) | −0.0019 (7) |
Rh | 0.0442 (3) | 0.0367 (3) | 0.0341 (3) | 0.0140 (2) | 0.0004 (2) | 0.00075 (18) |
C1 | 0.064 (4) | 0.050 (4) | 0.028 (3) | 0.018 (3) | 0.009 (3) | 0.013 (3) |
O1 | 0.112 (4) | 0.080 (3) | 0.062 (3) | 0.064 (3) | 0.013 (3) | 0.018 (2) |
C13 | 0.037 (3) | 0.047 (3) | 0.046 (3) | 0.008 (3) | 0.000 (3) | 0.004 (3) |
C131 | 0.028 (3) | 0.040 (3) | 0.045 (3) | 0.003 (3) | −0.003 (3) | 0.001 (3) |
C136 | 0.050 (4) | 0.055 (4) | 0.066 (4) | 0.006 (3) | 0.019 (3) | 0.002 (3) |
C135 | 0.056 (5) | 0.031 (4) | 0.148 (8) | 0.011 (3) | 0.026 (5) | 0.004 (4) |
C134 | 0.047 (4) | 0.071 (5) | 0.112 (7) | 0.011 (4) | 0.004 (4) | 0.050 (5) |
C133 | 0.049 (4) | 0.080 (5) | 0.064 (5) | −0.002 (4) | −0.011 (3) | 0.027 (4) |
C132 | 0.047 (4) | 0.055 (4) | 0.048 (4) | −0.002 (3) | −0.001 (3) | 0.010 (3) |
C11 | 0.046 (4) | 0.037 (3) | 0.041 (3) | 0.014 (3) | 0.003 (3) | 0.005 (3) |
C111 | 0.050 (4) | 0.030 (3) | 0.047 (4) | 0.009 (3) | −0.003 (3) | 0.008 (3) |
C116 | 0.045 (4) | 0.046 (3) | 0.044 (4) | −0.005 (3) | −0.003 (3) | 0.011 (3) |
C115 | 0.068 (5) | 0.057 (4) | 0.046 (4) | 0.007 (3) | 0.005 (3) | 0.008 (3) |
C114 | 0.104 (6) | 0.063 (5) | 0.039 (4) | 0.005 (4) | −0.019 (4) | 0.006 (3) |
C113 | 0.065 (5) | 0.070 (5) | 0.071 (5) | 0.010 (4) | −0.028 (4) | 0.014 (4) |
C112 | 0.037 (4) | 0.064 (4) | 0.069 (5) | 0.011 (3) | −0.000 (3) | 0.023 (3) |
C12 | 0.041 (3) | 0.041 (3) | 0.040 (3) | 0.009 (3) | 0.004 (3) | −0.000 (3) |
C121 | 0.037 (3) | 0.051 (4) | 0.034 (3) | 0.013 (3) | 0.009 (2) | −0.001 (3) |
C122 | 0.044 (4) | 0.044 (4) | 0.058 (4) | 0.011 (3) | −0.003 (3) | −0.003 (3) |
C123 | 0.047 (4) | 0.057 (4) | 0.071 (5) | 0.003 (3) | 0.001 (3) | −0.011 (3) |
C124 | 0.030 (4) | 0.096 (6) | 0.087 (5) | 0.012 (4) | 0.002 (3) | −0.006 (4) |
C125 | 0.038 (4) | 0.081 (5) | 0.105 (6) | 0.023 (4) | 0.012 (4) | 0.026 (4) |
C126 | 0.045 (4) | 0.060 (4) | 0.071 (5) | 0.017 (3) | 0.010 (3) | 0.014 (3) |
C22 | 0.054 (4) | 0.050 (4) | 0.039 (3) | 0.016 (3) | 0.000 (3) | 0.006 (3) |
C221 | 0.056 (4) | 0.036 (3) | 0.047 (4) | 0.009 (3) | −0.007 (3) | 0.006 (3) |
C226 | 0.058 (4) | 0.058 (4) | 0.047 (4) | 0.010 (3) | −0.009 (3) | 0.005 (3) |
C225 | 0.100 (6) | 0.072 (5) | 0.044 (4) | 0.031 (4) | −0.005 (4) | 0.003 (3) |
C224 | 0.100 (7) | 0.062 (5) | 0.070 (5) | 0.015 (5) | −0.043 (5) | −0.011 (4) |
C223 | 0.057 (5) | 0.078 (5) | 0.095 (6) | 0.003 (4) | −0.033 (4) | 0.009 (5) |
C222 | 0.049 (4) | 0.062 (4) | 0.072 (5) | 0.008 (3) | −0.008 (3) | 0.016 (3) |
C23 | 0.069 (5) | 0.063 (4) | 0.041 (4) | 0.031 (4) | 0.002 (3) | 0.001 (3) |
C231 | 0.052 (5) | 0.108 (6) | 0.043 (4) | 0.026 (4) | 0.007 (3) | −0.011 (4) |
C232 | 0.067 (6) | 0.079 (6) | 0.129 (8) | −0.002 (5) | −0.003 (5) | −0.005 (5) |
C233 | 0.090 (8) | 0.124 (9) | 0.166 (12) | −0.013 (7) | 0.021 (7) | −0.023 (8) |
C234 | 0.090 (9) | 0.260 (18) | 0.102 (11) | −0.059 (11) | 0.036 (8) | −0.079 (11) |
C235 | 0.055 (7) | 0.37 (2) | 0.081 (8) | −0.012 (11) | −0.012 (6) | 0.03 (1) |
C236 | 0.081 (7) | 0.216 (11) | 0.077 (6) | 0.028 (7) | 0.001 (5) | 0.040 (7) |
C21 | 0.082 (5) | 0.049 (4) | 0.047 (4) | 0.017 (4) | 0.000 (3) | −0.007 (3) |
C211 | 0.088 (5) | 0.031 (3) | 0.037 (4) | 0.003 (3) | −0.002 (3) | −0.006 (3) |
C216 | 0.094 (6) | 0.061 (5) | 0.047 (4) | −0.011 (4) | −0.009 (4) | 0.004 (3) |
C215 | 0.093 (7) | 0.084 (6) | 0.068 (6) | −0.015 (5) | −0.019 (5) | 0.018 (4) |
C214 | 0.076 (6) | 0.086 (6) | 0.112 (7) | −0.018 (5) | −0.007 (6) | −0.009 (5) |
C213 | 0.113 (8) | 0.140 (8) | 0.060 (5) | −0.060 (6) | 0.018 (5) | −0.030 (5) |
C212 | 0.089 (6) | 0.114 (7) | 0.050 (5) | −0.036 (5) | −0.009 (4) | −0.001 (4) |
Cl | 0.1119 (15) | 0.0718 (11) | 0.052 (1) | 0.0608 (11) | 0.0004 (9) | 0.0020 (8) |
Rh—P1 | 2.3164 (15) | C124—C125 | 1.377 (9) |
P1—C13 | 1.837 (5) | C124—H124 | 1.000 |
P1—C11 | 1.847 (5) | C125—C126 | 1.387 (8) |
P1—C12 | 1.827 (5) | C125—H125 | 1.001 |
Rh—P2 | 2.3156 (16) | C126—H126 | 1.002 |
P2—C22 | 1.849 (5) | C22—C221 | 1.506 (7) |
P2—C23 | 1.851 (6) | C22—H23 | 1.000 |
P2—C21 | 1.828 (6) | C22—H24 | 1.001 |
Rh—C1 | 1.783 (6) | C221—C226 | 1.399 (8) |
Rh—Cl | 2.3654 (15) | C221—C222 | 1.373 (8) |
C1—O1 | 1.162 (6) | C226—C225 | 1.388 (8) |
C13—C131 | 1.504 (7) | C226—H226 | 1.003 |
C13—H15 | 0.999 | C225—C224 | 1.360 (9) |
C13—H16 | 1.001 | C225—H225 | 1.003 |
C131—C136 | 1.379 (7) | C224—C223 | 1.35 (1) |
C131—C132 | 1.395 (7) | C224—H224 | 1.001 |
C136—C135 | 1.393 (8) | C223—C222 | 1.399 (9) |
C136—H136 | 1.002 | C223—H223 | 1.000 |
C135—C134 | 1.368 (9) | C222—H222 | 1.001 |
C135—H135 | 1.000 | C23—C231 | 1.511 (9) |
C134—C133 | 1.357 (9) | C23—H25 | 0.999 |
C134—H134 | 1.000 | C23—H26 | 1.001 |
C133—C132 | 1.367 (8) | C231—C232 | 1.333 (9) |
C133—H133 | 1.001 | C231—C236 | 1.39 (1) |
C132—H132 | 1.001 | C232—C233 | 1.377 (11) |
C11—C111 | 1.495 (7) | C232—H232 | 1.002 |
C11—H11 | 1.001 | C233—C234 | 1.316 (16) |
C11—H12 | 0.994 | C233—H233 | 1.003 |
C111—C116 | 1.397 (7) | C234—C235 | 1.33 (2) |
C111—C112 | 1.392 (7) | C234—H234 | 0.998 |
C116—C115 | 1.391 (7) | C235—C236 | 1.424 (15) |
C116—H116 | 1.001 | C235—H235 | 1.002 |
C115—C114 | 1.379 (9) | C236—H236 | 1.003 |
C115—H115 | 1.000 | C21—C211 | 1.518 (8) |
C114—C113 | 1.370 (9) | C21—H22 | 0.999 |
C114—H114 | 1.001 | C21—H21 | 0.999 |
C113—C112 | 1.379 (8) | C211—C216 | 1.374 (8) |
C113—H113 | 1.001 | C211—C212 | 1.358 (8) |
C112—H112 | 1.002 | C216—C215 | 1.36 (1) |
C12—C121 | 1.515 (7) | C216—H216 | 1.000 |
C12—H14 | 1.000 | C215—C214 | 1.34 (1) |
C12—H13 | 1.000 | C215—H215 | 1.000 |
C121—C122 | 1.392 (7) | C214—C213 | 1.36 (1) |
C121—C126 | 1.374 (7) | C214—H214 | 1.002 |
C122—C123 | 1.387 (7) | C213—C212 | 1.39 (1) |
C122—H122 | 1.001 | C213—H213 | 1.002 |
C123—C124 | 1.388 (8) | C212—H212 | 1.002 |
C123—H123 | 1.001 | ||
Rh—P1—C13 | 114.03 (17) | C123—C124—C125 | 120.1 (6) |
Rh—P1—C11 | 115.95 (17) | C123—C124—H124 | 120.0 |
C13—P1—C11 | 101.8 (2) | C125—C124—H124 | 119.9 |
Rh—P1—C12 | 116.38 (18) | C124—C125—C126 | 119.1 (6) |
C13—P1—C12 | 100.9 (2) | C124—C125—H125 | 120.5 |
C11—P1—C12 | 105.8 (2) | C126—C125—H125 | 120.4 |
Rh—P2—C22 | 116.59 (18) | C121—C126—C125 | 122.2 (6) |
Rh—P2—C23 | 113.43 (19) | C121—C126—H126 | 118.9 |
C22—P2—C23 | 106.6 (3) | C125—C126—H126 | 118.9 |
Rh—P2—C21 | 113.9 (2) | P2—C22—C221 | 118.5 (4) |
C22—P2—C21 | 105.5 (3) | P2—C22—H23 | 107.3 |
C23—P2—C21 | 99.0 (3) | C221—C22—H23 | 107.2 |
P1—Rh—P2 | 177.67 (6) | P2—C22—H24 | 107.2 |
P1—Rh—C1 | 90.54 (17) | C221—C22—H24 | 107.1 |
P2—Rh—C1 | 91.48 (17) | H23—C22—H24 | 109.4 |
P1—Rh—Cl | 90.86 (5) | C22—C221—C226 | 122.5 (5) |
P2—Rh—Cl | 87.11 (5) | C22—C221—C222 | 120.7 (6) |
C1—Rh—Cl | 178.55 (17) | C226—C221—C222 | 116.8 (6) |
Rh—C1—O1 | 179.3 (6) | C221—C226—C225 | 121.2 (6) |
P1—C13—C131 | 114.1 (4) | C221—C226—H226 | 119.4 |
P1—C13—H15 | 108.4 | C225—C226—H226 | 119.4 |
C131—C13—H15 | 108.3 | C226—C225—C224 | 119.9 (7) |
P1—C13—H16 | 108.3 | C226—C225—H225 | 120.1 |
C131—C13—H16 | 108.3 | C224—C225—H225 | 120.0 |
H15—C13—H16 | 109.5 | C225—C224—C223 | 120.5 (7) |
C13—C131—C136 | 121.1 (5) | C225—C224—H224 | 119.6 |
C13—C131—C132 | 120.4 (5) | C223—C224—H224 | 119.9 |
C136—C131—C132 | 118.5 (5) | C224—C223—C222 | 120.0 (7) |
C131—C136—C135 | 119.9 (6) | C224—C223—H223 | 119.8 |
C131—C136—H136 | 120.0 | C222—C223—H223 | 120.2 |
C135—C136—H136 | 120.1 | C221—C222—C223 | 121.5 (6) |
C136—C135—C134 | 120.6 (6) | C221—C222—H222 | 119.2 |
C136—C135—H135 | 119.7 | C223—C222—H222 | 119.3 |
C134—C135—H135 | 119.7 | P2—C23—C231 | 116.4 (4) |
C135—C134—C133 | 119.4 (6) | P2—C23—H25 | 107.8 |
C135—C134—H134 | 120.4 | C231—C23—H25 | 107.7 |
C133—C134—H134 | 120.2 | P2—C23—H26 | 107.7 |
C134—C133—C132 | 121.4 (7) | C231—C23—H26 | 107.6 |
C134—C133—H133 | 119.3 | H25—C23—H26 | 109.5 |
C132—C133—H133 | 119.3 | C23—C231—C232 | 122.5 (7) |
C131—C132—C133 | 120.2 (6) | C23—C231—C236 | 119.4 (8) |
C131—C132—H132 | 119.9 | C232—C231—C236 | 118.1 (8) |
C133—C132—H132 | 119.9 | C231—C232—C233 | 122.5 (9) |
P1—C11—C111 | 117.7 (3) | C231—C232—H232 | 118.9 |
P1—C11—H11 | 107.1 | C233—C232—H232 | 118.5 |
C111—C11—H11 | 107.1 | C232—C233—C234 | 120.0 (13) |
P1—C11—H12 | 107.4 | C232—C233—H233 | 120.2 |
C111—C11—H12 | 107.5 | C234—C233—H233 | 119.8 |
H11—C11—H12 | 109.9 | C233—C234—C235 | 121.0 (14) |
C11—C111—C116 | 121.1 (5) | C233—C234—H234 | 119.2 |
C11—C111—C112 | 122.1 (5) | C235—C234—H234 | 119.8 |
C116—C111—C112 | 116.8 (5) | C234—C235—C236 | 120.2 (13) |
C111—C116—C115 | 122.2 (5) | C234—C235—H235 | 119.6 |
C111—C116—H116 | 118.9 | C236—C235—H235 | 120.2 |
C115—C116—H116 | 118.9 | C231—C236—C235 | 118.1 (10) |
C116—C115—C114 | 119.2 (6) | C231—C236—H236 | 120.9 |
C116—C115—H115 | 120.4 | C235—C236—H236 | 120.9 |
C114—C115—H115 | 120.3 | P2—C21—C211 | 116.9 (4) |
C115—C114—C113 | 119.4 (6) | P2—C21—H22 | 107.5 |
C115—C114—H114 | 120.3 | C211—C21—H22 | 107.6 |
C113—C114—H114 | 120.3 | P2—C21—H21 | 107.5 |
C114—C113—C112 | 121.5 (6) | C211—C21—H21 | 107.6 |
C114—C113—H113 | 119.3 | H22—C21—H21 | 109.6 |
C112—C113—H113 | 119.2 | C21—C211—C216 | 120.9 (6) |
C111—C112—C113 | 120.9 (6) | C21—C211—C212 | 121.1 (6) |
C111—C112—H112 | 119.5 | C216—C211—C212 | 117.9 (7) |
C113—C112—H112 | 119.6 | C211—C216—C215 | 121.5 (7) |
P1—C12—C121 | 117.6 (4) | C211—C216—H216 | 119.2 |
P1—C12—H14 | 107.4 | C215—C216—H216 | 119.3 |
C121—C12—H14 | 107.4 | C216—C215—C214 | 119.9 (7) |
P1—C12—H13 | 107.4 | C216—C215—H215 | 120.1 |
C121—C12—H13 | 107.3 | C214—C215—H215 | 120.0 |
H14—C12—H13 | 109.5 | C215—C214—C213 | 120.9 (8) |
C12—C121—C122 | 122.7 (5) | C215—C214—H214 | 119.8 |
C12—C121—C126 | 119.3 (5) | C213—C214—H214 | 119.4 |
C122—C121—C126 | 118.0 (5) | C214—C213—C212 | 118.8 (7) |
C121—C122—C123 | 120.9 (5) | C214—C213—H213 | 120.6 |
C121—C122—H122 | 119.6 | C212—C213—H213 | 120.5 |
C123—C122—H122 | 119.5 | C211—C212—C213 | 120.9 (7) |
C122—C123—C124 | 119.7 (6) | C211—C212—H212 | 119.6 |
C122—C123—H123 | 120.2 | C213—C212—H212 | 119.6 |
C124—C123—H123 | 120.1 |
Experimental details
Crystal data | |
Chemical formula | [RhCl(C21H21P)2(CO)] |
Mr | 775.11 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 293 |
a, b, c (Å) | 10.031 (1), 10.165 (1), 18.9910 (19) |
α, β, γ (°) | 93.36 (3), 90.37 (3), 103.69 (3) |
V (Å3) | 1877.8 (4) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.64 |
Crystal size (mm) | 0.09 × 0.08 × 0.03 |
Data collection | |
Diffractometer | Bruker SMART diffractometer |
Absorption correction | Multi-scan SADABS (Siemens, 1998) |
Tmin, Tmax | 0.85, 0.95 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 19116, 11180, 4389 |
Rint | 0.032 |
(sin θ/λ)max (Å−1) | 0.739 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.048, 0.091, 0.88 |
No. of reflections | 4389 |
No. of parameters | 433 |
No. of restraints | ? |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.78, −0.50 |
Computer programs: SMART (Siemens, 1998), SAINT (Siemens, 1998), SIR92 (Altomare et al., 1994), CRYSTALS (Watkin et al., 2001), DIAMOND (Brandenburg & Berndt, 2000), CRYSTALS.
Rh—P1 | 2.3164 (15) | Rh—Cl | 2.3654 (15) |
Rh—P2 | 2.3156 (16) | C1—O1 | 1.162 (6) |
Rh—C1 | 1.783 (6) | ||
P1—Rh—P2 | 177.67 (6) | P2—Rh—Cl | 87.11 (5) |
P1—Rh—C1 | 90.54 (17) | C1—Rh—Cl | 178.55 (17) |
P2—Rh—C1 | 91.48 (17) | Rh—C1—O1 | 179.3 (6) |
P1—Rh—Cl | 90.86 (5) |
M(X) | θTor1(°) | θTor2(°) | θT(°) | θE(°) | Conformation | Reference |
Ni(Cl) | 1.72 (11) | -1.72 (11) | 167 | |||
14.05 (8) | -14.05 (8) | 162 | anti | i* | ||
Pd(I) | 0.8 (4) | -3.0 (4) | 157 | 155 | anti | ii |
Pd(CN) | 18.63 (5) | -18.63 (5) | 232 | 182 | anti | iii* |
Pd(N3) | 12.24 (5) | -12.24 (5) | 200 | 163 | anti | iii* |
Pt(Cl) | 1.6 (2) | -1.6 (2) | 164 | 162 | ||
1.08 (15) | -1.08 (15) | 160 | 160 | anti | ii | |
Pt(I) | -2.1 (3) | 3.9 (3) | 156 | 155 | ||
161 | 163 | anti | ii | |||
Pt(NCS) | -0.8 (2) | -15.2 (2) | 179 | 178 | ||
167 | 165 | gauche | ii | |||
Rh(CO)(Cl) | -1.6 (3) | -30.2 (3) | 170 | 171 | ||
172 | 173 | gauche | iv |
References: (i) Novoa de Armas et al. (2000); (ii) Johansson et al. (2002); (iii) Bendiksen et al. (1982); (iv) this work. * Calculated data extracted from CSD (Allen & Kennard, 1993). |
Complexes with the general formula trans-[MClXL2] (M = Rh, Ir, Pd, Pt; X = Me, CO; L = tertiary phosphine or arsine) often crystallize with the metal on a crystallographic centre of symmetry, thus imposing a disordered packing arrangement (Otto, 2001; Otto et al., 2000; Chen et al., 1991; Kuwabara & Bau, 1994). This study is part of an investigation aiming to elucidate the factors governing a disordered packing. It should also be noted that, to our knowledge, the title compound, (I), is the first reported rhodium structure containing the PBz3 ligand.
The Rh atom is in a general position and there is no disorder of the Cl—Rh—CO moiety. All angles within the Rh coordination sphere are close to those expected for a square-planar environment (Table 1). There are two intramolecular Rh···H agostic interactions, one on each side of the coordination plane, with Rh···H distances of 3.04 and 2.92 Å and H—Rh—P angles of 75 and 107°, respectively, giving a pseudo-octahedral environment around Rh. High anisotropy is observed for atoms C234 and C235, lying on the periphery of the molecule. This is the result of weak packing forces (H···H, H···C and one H···Cl), allowing for high flexibility of the PBz3 ligands, and is especially observed in one PBz3 ligand, indicating some freedom of packing in this region; it may also explain some observed short C···C distances (Albertsson et al., 1980). The Rh—P, Rh—Cl and Rh—CO bonds, together with bonds in the PBz3 ligand, are within normal ranges for this type of complex (Allen & Kennard, 1993).
The CH2 spacers between the P atom and phenyl rings in the PBz3 ligand introduce additional flexiblility compared to a PPh3 ligand. This increases the ligand cone angle size and is expected to influence, for example, the reactivity of the complex. The individual benzyl groups may have different orientations, resulting in variations in cone-angle sizes, as observed earlier (Ferguson et al., 1978). The most widely used method for describing ligand steric behaviour at a metal centre is the Tolman cone angle (Tolman, 1977), using an M—P bond distance of 2.28 Å, C—H bond distances of 0.97 Å, and 1.2 Å as the van der Waals radius of hydrogen. For the calculation of effective cone angles, actual Rh—P bond distances, as determined from crystallographic data, are used (Otto et al., 2000). Values obtained from effective cone-angle calculations for the title compound, 171 and 173°, are in agreement with the value of 165° proposed by Tolman (1977) for PBz3, and also correlate with recent work (Johansson et al., 2002), where an effective cone angle of 165±12° was postulated. Only one of the benzyl C atoms is used in the cone-angle calculation, while the phenyl rings of the other two substituents contribute to the large cone angle. The cone-angle values may not be a true indication of the ligand influence on the metal centre behaviour, since the phenyl rings used to calculate cone angles are not in the close vicinity of the metal. In Table 2, the title compound is compared with other closely related NiII, PdII and PtII complexes containing two of the bulky tribenzylphosphine ligands in a trans configuration. The Tolman (θT) and effective (θE) cone angles for (I) correlate with those calculated by Johannson et al. (2002), but deviate substantially from some other reported values (Bendiksen et al., 1982).
The two C—P—Rh—CO torsion angles, representing the least deviation from the coordination plane for the title compound, are −1.6 (3) and −30.2 (3)°, i.e. one P—C bond is close to the coordination plane for one of the ligands and one is slightly out of the plane for the other. This was previously observed in trans-[PtCl2(XPh3)2] (X = P, As) (Johansson et al., 2000; Johansson & Otto, 2000), trans-[MX2(PBz3)2] (M = Pt, X = Cl−, I−, NCS−; M = Pd, X = I−; Johansson et al., 2002), trans-[PtH(OPh)(PBz3)2] (Seligson et al., 1991) and [PdX2(PBz3)2] (X = N3−, CN−; Bendiksen et al., 1982). The orientation of the benzyl C atoms relative to the P—Rh—P axis are thus gauche. In previous studies, it was observed that the orientation of the benzyl C atoms relative to the P—M—P axis were anti, implying a pseudo-inversion centre in the complex, except in the case of trans-[Pt(NCS)2(PBz3)2], where a gauche comformation was also observed (Johansson et al., 2002). DFT calculations on the title complex in the gas phase result in C—P—Rh—CO torsion angles of −17.4 and 6.2°, which are fairly close to the observed values, implying that the conformation in the crystal structure is only slightly affected by the packing arrangement. A local minimum is also observed when the P—C bond is close to the coordination plane, but with the C—P—Rh—Cl torsion angles close to zero, i.e. Cl—Rh—CO is rotated by approximately 180° compared to the global minimum. The energy difference between the global and local minima is 18.5 kJ mol−1, which may be too large for a disordered packing for the title compound. The global minimum structure has one agostic interaction on one side of the coordination plane (Rh···H = 2.59 Å) and two on the other side (Rh···H = 3.05 and 3.12 Å). The calculations indicate interactions between the metal and the H atoms, since the Mulliken charges are 0.19 for these three H atoms, compared to 0.11 for H atoms further away.