Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270102018747/jz1526sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270102018747/jz1526Isup2.hkl |
CCDC reference: 201248
NaI (17 mg, 0.113 mmol) was added to a nitrogen-flushed solution of the [Rh(µ-Cl)(CO)2]2 dimer (20 mg, 0.051 mmol) in acetone (5 ml). The reaction medium immediately took on a deep-red colour and was stirred for a further 5 min after addition. Stirring was discontinued and SbPh3 (126 mg, 0.357 mmol) dissolved in acetone (7 ml) was added carefully to avoid the least disturbance in the solution. Deep-red rectangles of (I) soon started separating from the solution. Yields > 80% based on Rh could be obtained. Spectroscopic analysis: IR (KBr, ν): 1977 cm-1 (CO); IR (dichloromethane, ν): 1978 cm-1 (CO).
H atoms were treated as riding, with C—H = 0.93 Å. Is this added text OK? Even though the structure contains solvent-accessible voids of 115 Å3, both the minimum and maximum residual electron density were smaller than 1 e Å-3, indicating that no molecular fragments remain unaccounted for.
Data collection: SMART (Siemens, 1995); cell refinement: SAINT (Siemens, 1995); data reduction: SAINT; 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.
[RhI(CO)(C18H15Sb)3] | Dx = 1.737 Mg m−3 |
Mr = 1316.97 | Mo Kα radiation, λ = 0.71073 Å |
Trigonal, P3 | Cell parameters from 4642 reflections |
a = 14.462 (2) Å | θ = 2.2–24.8° |
c = 13.902 (3) Å | µ = 2.56 mm−1 |
V = 2518.2 (7) Å3 | T = 293 K |
Z = 2 | Parallelepiped, dark red |
F(000) = 1268 | 0.29 × 0.10 × 0.08 mm |
Siemens SMART CCD area-detector diffractometer | 5324 independent reflections |
Radiation source: rotating anode | 2651 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.094 |
ω scans | θmax = 31.8°, θmin = 1.5° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −18→21 |
Tmin = 0.493, Tmax = 0.815 | k = −20→20 |
24940 measured reflections | l = −20→20 |
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)] = 0.031 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.056 | H-atom parameters constrained |
S = 0.86 | w = 1/[σ2(Fo2) + (0.0154P)2] where P = (Fo2 + 2Fc2)/3 |
5324 reflections | (Δ/σ)max = 0.003 |
185 parameters | Δρmax = 0.43 e Å−3 |
0 restraints | Δρmin = −0.67 e Å−3 |
[RhI(CO)(C18H15Sb)3] | Z = 2 |
Mr = 1316.97 | Mo Kα radiation |
Trigonal, P3 | µ = 2.56 mm−1 |
a = 14.462 (2) Å | T = 293 K |
c = 13.902 (3) Å | 0.29 × 0.10 × 0.08 mm |
V = 2518.2 (7) Å3 |
Siemens SMART CCD area-detector diffractometer | 5324 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 2651 reflections with I > 2σ(I) |
Tmin = 0.493, Tmax = 0.815 | Rint = 0.094 |
24940 measured reflections |
R[F2 > 2σ(F2)] = 0.031 | 0 restraints |
wR(F2) = 0.056 | H-atom parameters constrained |
S = 0.86 | Δρmax = 0.43 e Å−3 |
5324 reflections | Δρmin = −0.67 e Å−3 |
185 parameters |
Experimental. Data completeness of 99.3% was accomplished up to θ = 30.50°. The first 50 frames were recollected at the end of the data collection to check for decay, none being found. |
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. |
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. |
x | y | z | Uiso*/Ueq | ||
Rh | 0.3333 | 0.6667 | 0.28356 (3) | 0.03710 (11) | |
I | 0.3333 | 0.6667 | 0.08820 (3) | 0.05782 (12) | |
Sb | 0.184189 (16) | 0.467444 (16) | 0.281520 (16) | 0.04150 (7) | |
C1 | 0.3333 | 0.6667 | 0.4148 (4) | 0.0465 (14) | |
O | 0.3333 | 0.6667 | 0.4978 (3) | 0.0674 (12) | |
C11 | 0.1435 (2) | 0.3991 (3) | 0.4224 (2) | 0.0454 (8) | |
C12 | 0.1118 (3) | 0.4465 (3) | 0.4918 (3) | 0.0629 (10) | |
H12 | 0.1026 | 0.5037 | 0.4753 | 0.075 (3)* | |
C13 | 0.0941 (3) | 0.4097 (3) | 0.5844 (3) | 0.0716 (11) | |
H13 | 0.0710 | 0.4406 | 0.6300 | 0.075 (3)* | |
C14 | 0.1103 (3) | 0.3275 (4) | 0.6102 (3) | 0.0795 (13) | |
H14 | 0.0997 | 0.3039 | 0.6736 | 0.075 (3)* | |
C15 | 0.1416 (3) | 0.2803 (4) | 0.5434 (3) | 0.0788 (13) | |
H15 | 0.1521 | 0.2241 | 0.5607 | 0.075 (3)* | |
C16 | 0.1579 (3) | 0.3167 (3) | 0.4496 (3) | 0.0613 (10) | |
H16 | 0.1791 | 0.2841 | 0.4039 | 0.075 (3)* | |
C21 | 0.0271 (2) | 0.4102 (2) | 0.2246 (2) | 0.0441 (8) | |
C22 | 0.0133 (3) | 0.4108 (3) | 0.1265 (3) | 0.0616 (10) | |
H22 | 0.0722 | 0.4375 | 0.0859 | 0.075 (3)* | |
C23 | −0.0883 (3) | 0.3718 (3) | 0.0879 (3) | 0.0713 (11) | |
H23 | −0.0975 | 0.3719 | 0.0217 | 0.075 (3)* | |
C24 | −0.1749 (3) | 0.3331 (3) | 0.1484 (3) | 0.0668 (11) | |
H24 | −0.2429 | 0.3065 | 0.1226 | 0.075 (3)* | |
C25 | −0.1626 (3) | 0.3332 (3) | 0.2443 (3) | 0.0686 (11) | |
H25 | −0.2220 | 0.3070 | 0.2843 | 0.075 (3)* | |
C26 | −0.0614 (3) | 0.3724 (3) | 0.2840 (3) | 0.0563 (9) | |
H26 | −0.0532 | 0.3733 | 0.3504 | 0.075 (3)* | |
C31 | 0.2134 (2) | 0.3547 (2) | 0.2094 (2) | 0.0433 (8) | |
C32 | 0.3162 (3) | 0.3818 (3) | 0.1849 (2) | 0.0529 (9) | |
H32 | 0.3722 | 0.4494 | 0.2001 | 0.075 (3)* | |
C33 | 0.3375 (3) | 0.3095 (3) | 0.1379 (3) | 0.0692 (11) | |
H33 | 0.4076 | 0.3289 | 0.1227 | 0.075 (3)* | |
C34 | 0.2569 (4) | 0.2109 (3) | 0.1141 (3) | 0.0758 (12) | |
H34 | 0.2711 | 0.1629 | 0.0822 | 0.075 (3)* | |
C35 | 0.1556 (4) | 0.1834 (3) | 0.1373 (4) | 0.0951 (15) | |
H35 | 0.1000 | 0.1159 | 0.1213 | 0.075 (3)* | |
C36 | 0.1337 (3) | 0.2544 (3) | 0.1847 (3) | 0.0775 (12) | |
H36 | 0.0633 | 0.2337 | 0.2000 | 0.075 (3)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Rh | 0.03752 (16) | 0.03752 (16) | 0.0362 (3) | 0.01876 (8) | 0.000 | 0.000 |
I | 0.06804 (18) | 0.06804 (18) | 0.0374 (2) | 0.03402 (9) | 0.000 | 0.000 |
Sb | 0.03827 (13) | 0.03649 (13) | 0.04601 (13) | 0.01590 (11) | 0.00141 (11) | 0.00096 (11) |
C1 | 0.046 (2) | 0.046 (2) | 0.047 (4) | 0.0232 (11) | 0.000 | 0.000 |
O | 0.079 (2) | 0.079 (2) | 0.043 (3) | 0.0397 (10) | 0.000 | 0.000 |
C11 | 0.0371 (18) | 0.043 (2) | 0.049 (2) | 0.0145 (16) | 0.0028 (16) | 0.0047 (17) |
C12 | 0.068 (3) | 0.056 (2) | 0.054 (2) | 0.022 (2) | 0.011 (2) | 0.010 (2) |
C13 | 0.062 (3) | 0.081 (3) | 0.056 (3) | 0.024 (2) | 0.014 (2) | −0.003 (2) |
C14 | 0.055 (3) | 0.114 (4) | 0.056 (3) | 0.033 (3) | 0.005 (2) | 0.024 (3) |
C15 | 0.078 (3) | 0.104 (4) | 0.073 (3) | 0.059 (3) | 0.012 (2) | 0.037 (3) |
C16 | 0.054 (2) | 0.077 (3) | 0.063 (3) | 0.041 (2) | 0.011 (2) | 0.017 (2) |
C21 | 0.0385 (19) | 0.0349 (18) | 0.059 (2) | 0.0183 (15) | −0.0024 (18) | 0.0012 (16) |
C22 | 0.046 (2) | 0.069 (3) | 0.064 (3) | 0.024 (2) | −0.007 (2) | −0.006 (2) |
C23 | 0.072 (3) | 0.078 (3) | 0.066 (3) | 0.039 (2) | −0.020 (2) | −0.011 (2) |
C24 | 0.043 (2) | 0.059 (2) | 0.096 (3) | 0.024 (2) | −0.011 (2) | 0.011 (2) |
C25 | 0.040 (2) | 0.074 (3) | 0.089 (3) | 0.027 (2) | 0.006 (2) | 0.028 (2) |
C26 | 0.052 (2) | 0.059 (2) | 0.058 (2) | 0.027 (2) | 0.0014 (19) | 0.0108 (19) |
C31 | 0.044 (2) | 0.0398 (19) | 0.046 (2) | 0.0207 (17) | −0.0014 (16) | 0.0004 (16) |
C32 | 0.054 (2) | 0.047 (2) | 0.056 (2) | 0.0238 (18) | 0.0038 (19) | 0.0027 (18) |
C33 | 0.077 (3) | 0.075 (3) | 0.075 (3) | 0.053 (3) | 0.008 (2) | 0.005 (2) |
C34 | 0.104 (4) | 0.076 (3) | 0.075 (3) | 0.066 (3) | −0.010 (3) | −0.018 (2) |
C35 | 0.079 (3) | 0.053 (3) | 0.148 (5) | 0.028 (2) | −0.035 (3) | −0.047 (3) |
C36 | 0.049 (2) | 0.058 (3) | 0.122 (4) | 0.025 (2) | −0.010 (2) | −0.023 (2) |
Rh—C1 | 1.825 (6) | C21—C26 | 1.386 (4) |
Rh—Sbi | 2.5962 (4) | C22—C23 | 1.392 (5) |
Rh—Sb | 2.5962 (4) | C22—H22 | 0.9300 |
Rh—Sbii | 2.5962 (4) | C23—C24 | 1.374 (5) |
Rh—I | 2.7159 (8) | C23—H23 | 0.9300 |
Sb—C11 | 2.140 (3) | C24—C25 | 1.346 (5) |
Sb—C21 | 2.143 (3) | C24—H24 | 0.9300 |
Sb—C31 | 2.129 (3) | C25—C26 | 1.392 (4) |
C1—O | 1.153 (6) | C25—H25 | 0.9300 |
C11—C16 | 1.362 (4) | C26—H26 | 0.9300 |
C11—C12 | 1.387 (4) | C31—C36 | 1.370 (4) |
C12—C13 | 1.367 (5) | C31—C32 | 1.378 (4) |
C12—H12 | 0.9300 | C32—C33 | 1.392 (4) |
C13—C14 | 1.369 (5) | C32—H32 | 0.9300 |
C13—H13 | 0.9300 | C33—C34 | 1.356 (5) |
C14—C15 | 1.357 (5) | C33—H33 | 0.9300 |
C14—H14 | 0.9300 | C34—C35 | 1.351 (5) |
C15—C16 | 1.383 (5) | C34—H34 | 0.9300 |
C15—H15 | 0.9300 | C35—C36 | 1.384 (5) |
C16—H16 | 0.9300 | C35—H35 | 0.9300 |
C21—C22 | 1.379 (4) | C36—H36 | 0.9300 |
C1—Rh—Sbi | 90.626 (10) | C22—C21—Sb | 119.5 (2) |
C1—Rh—Sb | 90.626 (10) | C26—C21—Sb | 121.6 (3) |
Sbi—Rh—Sb | 120 | C21—C22—C23 | 120.3 (4) |
C1—Rh—Sbii | 90.626 (10) | C21—C22—H22 | 119.8 |
Sbi—Rh—Sbii | 120 | C23—C22—H22 | 119.8 |
Sb—Rh—Sbii | 120 | C24—C23—C22 | 119.5 (4) |
C1—Rh—I | 180 | C24—C23—H23 | 120.3 |
Sbi—Rh—I | 89.374 (10) | C22—C23—H23 | 120.3 |
Sb—Rh—I | 89.374 (10) | C25—C24—C23 | 120.9 (3) |
Sbii—Rh—I | 89.374 (10) | C25—C24—H24 | 119.6 |
C11—Sb—C21 | 99.57 (12) | C23—C24—H24 | 119.6 |
C11—Sb—C31 | 101.04 (12) | C24—C25—C26 | 120.3 (4) |
C21—Sb—C31 | 96.21 (12) | C24—C25—H25 | 119.9 |
C11—Sb—Rh | 112.73 (9) | C26—C25—H25 | 119.9 |
C21—Sb—Rh | 124.39 (8) | C21—C26—C25 | 120.0 (3) |
C31—Sb—Rh | 118.84 (8) | C21—C26—H26 | 120.0 |
O—C1—Rh | 180 | C25—C26—H26 | 120.0 |
C16—C11—C12 | 118.2 (3) | C36—C31—C32 | 117.2 (3) |
C16—C11—Sb | 122.1 (3) | C36—C31—Sb | 123.0 (3) |
C12—C11—Sb | 119.4 (3) | C32—C31—Sb | 119.8 (2) |
C13—C12—C11 | 120.4 (4) | C31—C32—C33 | 121.0 (3) |
C13—C12—H12 | 119.8 | C31—C32—H32 | 119.5 |
C11—C12—H12 | 119.8 | C33—C32—H32 | 119.5 |
C12—C13—C14 | 120.3 (4) | C34—C33—C32 | 120.5 (4) |
C12—C13—H13 | 119.8 | C34—C33—H33 | 119.8 |
C14—C13—H13 | 119.8 | C32—C33—H33 | 119.8 |
C15—C14—C13 | 120.2 (4) | C35—C34—C33 | 119.2 (4) |
C15—C14—H14 | 119.9 | C35—C34—H34 | 120.4 |
C13—C14—H14 | 119.9 | C33—C34—H34 | 120.4 |
C14—C15—C16 | 119.3 (4) | C34—C35—C36 | 120.8 (4) |
C14—C15—H15 | 120.3 | C34—C35—H35 | 119.6 |
C16—C15—H15 | 120.3 | C36—C35—H35 | 119.6 |
C11—C16—C15 | 121.6 (4) | C31—C36—C35 | 121.4 (4) |
C11—C16—H16 | 119.2 | C31—C36—H36 | 119.3 |
C15—C16—H16 | 119.2 | C35—C36—H36 | 119.3 |
C22—C21—C26 | 118.9 (3) | ||
I—Rh—Sb—C11 | 175.77 (10) | I—Rh—Sb—C31 | 57.89 (9) |
I—Rh—Sb—C21 | −63.88 (11) |
Symmetry codes: (i) −x+y, −x+1, z; (ii) −y+1, x−y+1, z. |
Experimental details
Crystal data | |
Chemical formula | [RhI(CO)(C18H15Sb)3] |
Mr | 1316.97 |
Crystal system, space group | Trigonal, P3 |
Temperature (K) | 293 |
a, c (Å) | 14.462 (2), 13.902 (3) |
V (Å3) | 2518.2 (7) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 2.56 |
Crystal size (mm) | 0.29 × 0.10 × 0.08 |
Data collection | |
Diffractometer | Siemens SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.493, 0.815 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 24940, 5324, 2651 |
Rint | 0.094 |
(sin θ/λ)max (Å−1) | 0.740 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.031, 0.056, 0.86 |
No. of reflections | 5324 |
No. of parameters | 185 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.43, −0.67 |
Computer programs: SMART (Siemens, 1995), SAINT (Siemens, 1995), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), DIAMOND (Brandenburg, 1999), SHELXL97.
Rh—C1 | 1.825 (6) | Sb—C21 | 2.143 (3) |
Rh—Sb | 2.5962 (4) | Sb—C31 | 2.129 (3) |
Rh—I | 2.7159 (8) | C1—O | 1.153 (6) |
Sb—C11 | 2.140 (3) | ||
C1—Rh—Sb | 90.626 (10) | C21—Sb—C31 | 96.21 (12) |
Sbi—Rh—Sb | 120 | C11—Sb—Rh | 112.73 (9) |
C1—Rh—I | 180 | C21—Sb—Rh | 124.39 (8) |
Sb—Rh—I | 89.374 (10) | C31—Sb—Rh | 118.84 (8) |
C11—Sb—C21 | 99.57 (12) | O—C1—Rh | 180 |
C11—Sb—C31 | 101.04 (12) | ||
I—Rh—Sb—C11 | 175.77 (10) | I—Rh—Sb—C31 | 57.89 (9) |
I—Rh—Sb—C21 | −63.88 (11) |
Symmetry code: (i) −x+y, −x+1, z. |
X | n | L | Rh-C1 (Å) | Rh-L (Å) | Rh-X (Å) | Reference |
Cl | 2 | Sb | 1.797 (13) | 2.5655 (2) | 2.315 (3) | (a) |
Cl | 3 | Sb | 1.875 (7) | 2.5981 (5) | 2.4094 (18) | (a) |
I | 2 | P | 1.81 (1) | 2.326 (2) | 2.683 (1) | (b) |
I | 3 | Sb | 1.825 (6) | 2.5962 (4) | 2.7159 (8) | (c) |
COCH3 | 3 | Sb | 1.91 (2) | 2.568 (2) | 2.095 (16) | (d) |
(a) Otto & Roodt (2002); (b) Basson et al. (1990); (c) this work; (d) Lamprecht et al. (1986) |
Although stibine complexes of Rh have been known since the 1950 s (Vallarino, 1957), surprisingly few crystallographic studies of these complexes have been reported to date. As has been pointed out in earlier investigations (Ugo et al., 1969; Otto & Roodt, 2002), several experimental problems may arise during the characterization of these complexes, making X-ray crystallography the method of choice. As part of our systematic investigation of these systems (Mzamane et al., 2001; Otto & Roodt, 2002), we obtained single crystals of trans-carbonyliodotris(triphenylstibine-κSb)rhodium(I), (I), and its crystal structure is presented here. \sch
Compound (I) (Fig. 1) crystallizes with an almost perfect trigonal-bipyramidal geometry in the trigonal space group P3. The packing in the crystal is governed by van der Waals forces alone; no significant intermolecular interactions are observed. The OC—Rh—I core is situated along the threefold rotation axis, resulting in three crystallographically equivalent SbPh3 ligands around the Rh atom with angles of exactly 120°. Accordingly, the OC—Rh—I core is exactly linear and the C1—Rh—Sb and I—Rh—Sb angles are close to 90°, at 90.626 (10) and 89.374 (10)°, respectively.
An I—Rh—Sb—C11 torsion angle of 175.77 (10)° indicates phenyl ring 1 (C11—C16) points almost directly towards the CO moiety, whereas rings 2 (C21—C26) and 3 (C31—C36) are staggered with respect to the Rh—I bond, with I—Rh—Sb—C21 and I—Rh—Sb—C31 torsion angles of -63.88 (11) and 57.89 (9)°, respectively. These specific geometric orientations may account for the observation that the SbPh3 ligands are marginally displaced towards the larger I ligand.
Based on molecular models, Tolman (1977) predicted that increasing the M—L or L—C (M is a metal, L is a ligand) bond lengths by 0.1 Å (for ligands containing other donor atoms than P) would result in a 3–5° decrease in the cone angle of the ligand. In this regard, the effective cone angle, as defined earlier (Otto et al., 2001), utilizes the observed Rh—Sb bond distance, and the cone angle for SbPh3 in (I) was calculated as 137°. This value is in excellent agreement with both Tolman's prediction and the average of 139° for six independent SbPh3 ligands obtained during a previous study (Otto & Roodt, 2002).
In Table 2, compound (I) is compared with related trans-[Rh(X)CO(LPh3)n] (n = 2 or 3, L is Sb or P) complexes from the literature, illustrating the effect of different X ligands on the geometric parameters of four- and five-coordinate SbPh3 complexes of RhI. From these data, it is clear that the Rh—Sb bond length of 2.5962 (4) Å in (I) is comparable with the value of 2.5981 (5) Å found in the analogous five-coordinate Cl complex, but is slightly longer than the values of 2.568 (2) Å in the acetyl complex and 2.5655 (2) Å in the four-coordinate Cl complex. Not many Rh—I bond distances are known for complexes of this kind, but the Rh—I bond length of 2.7159 (8) Å in (I) is considerably longer than the value of 2.683 (1) Å determined for trans-[RhI(CO)(PPh3)2] (Basson et al., 1990). This may be a result of the increased steric crowding in the five-coordinate complex or the increased electron density introduced by the three SbPh3 ligands. A similar observation was made in relation to the Rh—Cl bond distances of the four- and five-coordinate triphenylstibine complexes (Otto & Roodt, 2002) listed in Table 2, where an elongation of 2.315 (3)–2.4094 (18) Å was induced by the increase in coordination number.