Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270108026589/hj3081sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270108026589/hj3081Isup2.hkl |
CCDC reference: 707201
For related literature, see: Anada et al. (2004); Catino & Gorslund (2005); Catino et al. (2004); Catino, Nichols, Gorslund & Doyle (2005); Cotton et al. (2002); Davies & Beckwith (2003); Doyle (2006); Doyle et al. (1998); Fiori & Du Bois (2007); Forslund et al. (2005); Góis & Afonso (2004); Góis et al. (2007); Liang et al. (2006); Lou et al. (2005); Reddy & Davies (2006); Trindade et al. (2008); Wang et al. (2008); Washio et al. (2005).
Complex (III) (see scheme) (43 mg, 0.051 mmol) was suspended in dry tetrahydrofuran (THF; 1 ml), and phenyl lithium (27 µl, 0.051 mmol) was added at 193 K. The colour changed instantaneously from purple to orange. The mixture was stirred at room temperature for 12 h. After filtration, the solvent was removed under vacuum and fresh THF was added (1 ml). The solution was kept at 253 K to induce crystallization. X-ray diffraction analysis of the crude crystals formed allowed the identification of the bis-complex presented in this paper and the mono-complex with a molecule of THF attached to the vacant coordination site of the complex, previously reported by Trindade et al. (2008).
Distance restraints were applied to the C—C bonds of the solvent molecules, while similarity and pseudo-isotropic restraints were applied to the atomic displacement parameters of these atoms. H atoms were placed in calculated positions and allowed to ride on their parent C atoms, with C—H = 0.93 for aromatic H, 0.97 for methylene H, 0.98 for methine H and 0.96 Å for methyl H, and with Uiso(H) = ?.?Ueq(C). [Please complete].
Data collection: SMART (Bruker, 1997); cell refinement: SMART (Bruker, 1997); data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3.2 (Farrugia, 1997) and Mercury (Version 1.4; Macrae et al., 2006); software used to prepare material for publication: enCIFer (Allen et al., 2004).
[Rh2(C2H3O2O)4(C27H36N2)2]·4C4H8O | F(000) = 1596 |
Mr = 1507.56 | Dx = 1.268 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71069 Å |
a = 10.509 (4) Å | Cell parameters from 4779 reflections |
b = 33.708 (6) Å | θ = 2.2–27.5° |
c = 11.967 (3) Å | µ = 0.48 mm−1 |
β = 111.388 (6)° | T = 150 K |
V = 3947.2 (19) Å3 | Needle, orange |
Z = 2 | 0.30 × 0.15 × 0.15 mm |
Bruker SMART CCD area-detector diffractometer | 9028 independent reflections |
Radiation source: fine-focus sealed tube | 6488 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.082 |
ϕ and ω scans | θmax = 27.5°, θmin = 2.2° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2004) | h = −13→13 |
Tmin = 0.870, Tmax = 0.932 | k = −42→43 |
38595 measured reflections | l = −15→15 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.071 | H-atom parameters constrained |
wR(F2) = 0.151 | w = 1/[\s^2^(Fo^2^) + (0.0392P)^2^ + 9.4018P], P = (Fo^2^ + 2Fc^2^)/3 |
S = 1.17 | (Δ/σ)max = 0.001 |
9028 reflections | Δρmax = 0.88 e Å−3 |
438 parameters | Δρmin = −0.92 e Å−3 |
96 restraints | Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0050 (5) |
[Rh2(C2H3O2O)4(C27H36N2)2]·4C4H8O | V = 3947.2 (19) Å3 |
Mr = 1507.56 | Z = 2 |
Monoclinic, P21/c | Mo Kα radiation |
a = 10.509 (4) Å | µ = 0.48 mm−1 |
b = 33.708 (6) Å | T = 150 K |
c = 11.967 (3) Å | 0.30 × 0.15 × 0.15 mm |
β = 111.388 (6)° |
Bruker SMART CCD area-detector diffractometer | 9028 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2004) | 6488 reflections with I > 2σ(I) |
Tmin = 0.870, Tmax = 0.932 | Rint = 0.082 |
38595 measured reflections |
R[F2 > 2σ(F2)] = 0.071 | 96 restraints |
wR(F2) = 0.151 | H-atom parameters constrained |
S = 1.17 | Δρmax = 0.88 e Å−3 |
9028 reflections | Δρmin = −0.92 e Å−3 |
438 parameters |
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 | ||
Rh1 | 0.01080 (4) | 0.034797 (11) | 0.53295 (3) | 0.01975 (13) | |
O1 | 0.1527 (3) | −0.02478 (9) | 0.4158 (3) | 0.0266 (8) | |
O4 | 0.1722 (3) | 0.03923 (10) | 0.4756 (3) | 0.0275 (7) | |
O5 | −0.1208 (3) | 0.04861 (9) | 0.3645 (3) | 0.0262 (8) | |
O8 | −0.1411 (3) | −0.01525 (10) | 0.3038 (3) | 0.0272 (8) | |
C1 | −0.1674 (5) | 0.02118 (15) | 0.2897 (4) | 0.0248 (11) | |
C2 | −0.2653 (6) | 0.03345 (18) | 0.1664 (4) | 0.0416 (14) | |
H2A | −0.3212 | 0.0106 | 0.1265 | 0.062* | |
H2B | −0.2133 | 0.0429 | 0.1184 | 0.062* | |
H2C | −0.3248 | 0.0547 | 0.1746 | 0.062* | |
C7 | 0.2050 (5) | 0.00882 (14) | 0.4297 (4) | 0.0237 (10) | |
C8 | 0.3231 (5) | 0.01420 (17) | 0.3870 (5) | 0.0377 (13) | |
H8B | 0.3712 | −0.0111 | 0.3932 | 0.057* | |
H8A | 0.3865 | 0.0341 | 0.4370 | 0.057* | |
H8C | 0.2882 | 0.0231 | 0.3033 | 0.057* | |
C9 | 0.0348 (4) | 0.09825 (13) | 0.5935 (4) | 0.019 | |
C10 | 0.0335 (6) | 0.16534 (15) | 0.5912 (5) | 0.0351 (13) | |
H10 | 0.0129 | 0.1917 | 0.5626 | 0.042* | |
C11 | 0.1134 (6) | 0.15418 (15) | 0.7021 (4) | 0.0340 (13) | |
H11 | 0.1616 | 0.1711 | 0.7673 | 0.041* | |
C12 | −0.1031 (5) | 0.13345 (13) | 0.4044 (4) | 0.0229 (10) | |
C13 | −0.2448 (5) | 0.13589 (15) | 0.3780 (4) | 0.0282 (11) | |
C14 | −0.3289 (6) | 0.14240 (17) | 0.2596 (5) | 0.0400 (14) | |
H14 | −0.4248 | 0.1444 | 0.2398 | 0.048* | |
C15 | −0.2767 (6) | 0.14604 (17) | 0.1708 (5) | 0.0432 (15) | |
H15 | −0.3364 | 0.1512 | 0.0908 | 0.052* | |
C16 | −0.1379 (6) | 0.14233 (17) | 0.1964 (5) | 0.0403 (14) | |
H16 | −0.1029 | 0.1443 | 0.1338 | 0.048* | |
C17 | −0.0494 (6) | 0.13576 (15) | 0.3141 (4) | 0.0307 (12) | |
C18 | 0.1045 (6) | 0.13056 (19) | 0.3437 (5) | 0.0433 (15) | |
H18 | 0.1425 | 0.1156 | 0.4210 | 0.052* | |
C19 | 0.1760 (7) | 0.1702 (2) | 0.3617 (9) | 0.082 (3) | |
H19A | 0.1470 | 0.1845 | 0.2852 | 0.124* | |
H19B | 0.2751 | 0.1661 | 0.3911 | 0.124* | |
H19C | 0.1523 | 0.1858 | 0.4206 | 0.124* | |
C20 | 0.1346 (7) | 0.1067 (2) | 0.2485 (6) | 0.0591 (19) | |
H20A | 0.1093 | 0.1222 | 0.1744 | 0.089* | |
H20B | 0.0816 | 0.0820 | 0.2329 | 0.089* | |
H20C | 0.2323 | 0.1004 | 0.2769 | 0.089* | |
C21 | −0.3052 (6) | 0.1306 (2) | 0.4738 (5) | 0.0452 (15) | |
H21 | −0.2296 | 0.1234 | 0.5504 | 0.054* | |
C22 | −0.3718 (8) | 0.1684 (2) | 0.4950 (7) | 0.072 (2) | |
H22A | −0.3018 | 0.1889 | 0.5276 | 0.107* | |
H22B | −0.4168 | 0.1631 | 0.5523 | 0.107* | |
H22C | −0.4397 | 0.1776 | 0.4190 | 0.107* | |
C23 | −0.4089 (8) | 0.0969 (2) | 0.4407 (8) | 0.072 (2) | |
H23A | −0.4895 | 0.1048 | 0.3716 | 0.107* | |
H23B | −0.4361 | 0.0910 | 0.5090 | 0.107* | |
H23C | −0.3678 | 0.0733 | 0.4201 | 0.107* | |
C24 | 0.1878 (5) | 0.09154 (14) | 0.8112 (4) | 0.0229 (10) | |
C25 | 0.3279 (5) | 0.08820 (15) | 0.8430 (4) | 0.0279 (11) | |
C26 | 0.4023 (5) | 0.07276 (17) | 0.9558 (4) | 0.0363 (13) | |
H26 | 0.4989 | 0.0709 | 0.9816 | 0.044* | |
C27 | 0.3376 (6) | 0.06032 (18) | 1.0299 (5) | 0.0404 (14) | |
H27 | 0.3903 | 0.0505 | 1.1074 | 0.048* | |
C28 | 0.1980 (5) | 0.06164 (16) | 0.9945 (4) | 0.0318 (12) | |
H28 | 0.1552 | 0.0518 | 1.0465 | 0.038* | |
C29 | 0.1179 (5) | 0.07731 (14) | 0.8829 (4) | 0.0250 (10) | |
C30 | −0.0359 (5) | 0.07887 (16) | 0.8404 (4) | 0.0303 (11) | |
H30 | −0.0714 | 0.0764 | 0.7510 | 0.036* | |
C31 | −0.0859 (6) | 0.1185 (2) | 0.8697 (7) | 0.0607 (19) | |
H31A | −0.0556 | 0.1216 | 0.9570 | 0.091* | |
H31B | −0.1859 | 0.1194 | 0.8347 | 0.091* | |
H31C | −0.0483 | 0.1401 | 0.8363 | 0.091* | |
C32 | −0.0955 (6) | 0.0446 (2) | 0.8876 (6) | 0.0551 (18) | |
H32A | −0.0578 | 0.0196 | 0.8718 | 0.083* | |
H32B | −0.1951 | 0.0444 | 0.8473 | 0.083* | |
H32C | −0.0719 | 0.0478 | 0.9743 | 0.083* | |
C33 | 0.3996 (5) | 0.09949 (18) | 0.7576 (5) | 0.0378 (13) | |
H33 | 0.3286 | 0.1082 | 0.6799 | 0.045* | |
C34 | 0.4733 (6) | 0.0630 (2) | 0.7332 (6) | 0.0539 (18) | |
H34A | 0.5413 | 0.0536 | 0.8089 | 0.081* | |
H34B | 0.5189 | 0.0703 | 0.6779 | 0.081* | |
H34C | 0.4066 | 0.0419 | 0.6974 | 0.081* | |
C35 | 0.5007 (7) | 0.1337 (2) | 0.8065 (6) | 0.0603 (19) | |
H35A | 0.4525 | 0.1567 | 0.8220 | 0.090* | |
H35B | 0.5413 | 0.1408 | 0.7474 | 0.090* | |
H35C | 0.5729 | 0.1254 | 0.8813 | 0.090* | |
N1 | −0.0130 (4) | 0.13101 (11) | 0.5268 (3) | 0.0227 (9) | |
N2 | 0.1117 (4) | 0.11307 (11) | 0.7025 (3) | 0.0219 (8) | |
O10 | 0.3204 (9) | 0.1989 (2) | 0.9488 (6) | 0.120 (3) | |
C36 | 0.3768 (14) | 0.2346 (3) | 0.9723 (11) | 0.127 (4) | |
H36A | 0.3253 | 0.2533 | 0.9079 | 0.152* | |
H36B | 0.4720 | 0.2334 | 0.9752 | 0.152* | |
C37 | 0.3755 (14) | 0.2488 (3) | 1.0882 (9) | 0.129 (4) | |
H37A | 0.4670 | 0.2584 | 1.1402 | 0.155* | |
H37B | 0.3085 | 0.2706 | 1.0765 | 0.155* | |
C38 | 0.3359 (12) | 0.2141 (3) | 1.1403 (8) | 0.111 (3) | |
H38A | 0.2586 | 0.2204 | 1.1657 | 0.134* | |
H38B | 0.4135 | 0.2045 | 1.2108 | 0.134* | |
C39 | 0.2950 (11) | 0.1834 (3) | 1.0431 (8) | 0.096 (3) | |
H39A | 0.3484 | 0.1588 | 1.0712 | 0.115* | |
H39B | 0.1967 | 0.1771 | 1.0194 | 0.115* | |
O11 | −0.0364 (7) | 0.2529 (2) | 0.4568 (6) | 0.102 (2) | |
C40 | −0.0856 (11) | 0.2530 (3) | 0.3341 (8) | 0.097 (3) | |
H40A | −0.0769 | 0.2262 | 0.3038 | 0.116* | |
H40B | −0.0326 | 0.2718 | 0.3047 | 0.116* | |
C41 | −0.2275 (13) | 0.2647 (4) | 0.2917 (11) | 0.150 (5) | |
H41A | −0.2875 | 0.2423 | 0.2512 | 0.180* | |
H41B | −0.2445 | 0.2872 | 0.2347 | 0.180* | |
C43 | −0.1184 (17) | 0.2721 (3) | 0.4955 (9) | 0.136 (5) | |
H43A | −0.0798 | 0.2986 | 0.5243 | 0.163* | |
H43B | −0.1287 | 0.2577 | 0.5636 | 0.163* | |
C42 | −0.2515 (13) | 0.2765 (4) | 0.3996 (15) | 0.147 (5) | |
H42A | −0.2836 | 0.3043 | 0.3935 | 0.176* | |
H42B | −0.3202 | 0.2591 | 0.4133 | 0.176* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Rh1 | 0.0185 (2) | 0.0219 (2) | 0.01642 (18) | 0.00222 (17) | 0.00339 (13) | 0.00039 (16) |
O1 | 0.0267 (18) | 0.0208 (18) | 0.0358 (19) | −0.0014 (14) | 0.0153 (16) | −0.0039 (14) |
O4 | 0.0285 (18) | 0.0232 (18) | 0.0339 (18) | 0.0003 (15) | 0.0153 (15) | −0.0024 (15) |
O5 | 0.0263 (18) | 0.0259 (17) | 0.0134 (15) | 0.0045 (14) | −0.0082 (13) | 0.0014 (13) |
O8 | 0.0320 (19) | 0.0242 (18) | 0.0170 (15) | 0.0026 (15) | −0.0009 (14) | −0.0006 (14) |
C1 | 0.021 (2) | 0.031 (3) | 0.016 (2) | 0.001 (2) | −0.0010 (19) | −0.0013 (19) |
C2 | 0.046 (3) | 0.039 (3) | 0.025 (3) | 0.007 (3) | −0.006 (2) | 0.000 (3) |
C7 | 0.021 (2) | 0.028 (3) | 0.019 (2) | 0.005 (2) | 0.003 (2) | 0.002 (2) |
C8 | 0.029 (3) | 0.041 (3) | 0.047 (3) | −0.004 (3) | 0.019 (3) | −0.005 (3) |
C9 | 0.010 | 0.025 | 0.017 | 0.002 | −0.001 | 0.002 |
C10 | 0.043 (3) | 0.021 (3) | 0.032 (3) | −0.001 (2) | 0.003 (2) | −0.003 (2) |
C11 | 0.045 (3) | 0.023 (3) | 0.024 (2) | −0.002 (2) | 0.000 (2) | −0.005 (2) |
C12 | 0.031 (3) | 0.021 (2) | 0.016 (2) | 0.000 (2) | 0.007 (2) | −0.0015 (18) |
C13 | 0.027 (3) | 0.027 (3) | 0.026 (2) | 0.000 (2) | 0.005 (2) | 0.004 (2) |
C14 | 0.033 (3) | 0.043 (3) | 0.033 (3) | 0.001 (3) | −0.001 (2) | 0.006 (3) |
C15 | 0.051 (4) | 0.041 (3) | 0.025 (3) | 0.009 (3) | −0.001 (3) | 0.007 (2) |
C16 | 0.058 (4) | 0.041 (3) | 0.024 (3) | 0.008 (3) | 0.017 (3) | 0.003 (2) |
C17 | 0.038 (3) | 0.028 (3) | 0.028 (3) | 0.003 (2) | 0.014 (2) | 0.001 (2) |
C18 | 0.041 (3) | 0.062 (4) | 0.033 (3) | 0.009 (3) | 0.020 (3) | 0.005 (3) |
C19 | 0.043 (4) | 0.088 (6) | 0.129 (8) | −0.010 (4) | 0.045 (5) | −0.027 (5) |
C20 | 0.066 (5) | 0.075 (5) | 0.052 (4) | 0.024 (4) | 0.041 (4) | 0.012 (4) |
C21 | 0.024 (3) | 0.074 (4) | 0.038 (3) | 0.004 (3) | 0.012 (2) | 0.019 (3) |
C22 | 0.085 (6) | 0.081 (5) | 0.070 (5) | −0.003 (5) | 0.053 (5) | −0.011 (4) |
C23 | 0.057 (5) | 0.069 (5) | 0.102 (6) | −0.005 (4) | 0.045 (5) | 0.024 (5) |
C24 | 0.024 (3) | 0.028 (3) | 0.013 (2) | 0.004 (2) | 0.0037 (19) | −0.0023 (19) |
C25 | 0.024 (3) | 0.040 (3) | 0.018 (2) | 0.000 (2) | 0.005 (2) | −0.006 (2) |
C26 | 0.021 (3) | 0.055 (4) | 0.025 (3) | 0.008 (2) | 0.000 (2) | 0.002 (3) |
C27 | 0.037 (3) | 0.055 (4) | 0.022 (3) | 0.011 (3) | 0.002 (2) | 0.005 (2) |
C28 | 0.035 (3) | 0.041 (3) | 0.020 (2) | 0.006 (2) | 0.010 (2) | 0.004 (2) |
C29 | 0.028 (3) | 0.030 (3) | 0.017 (2) | 0.004 (2) | 0.006 (2) | −0.0021 (19) |
C30 | 0.020 (3) | 0.047 (3) | 0.024 (2) | 0.000 (2) | 0.009 (2) | 0.000 (2) |
C31 | 0.035 (4) | 0.075 (5) | 0.069 (5) | 0.015 (3) | 0.015 (3) | −0.013 (4) |
C32 | 0.040 (4) | 0.081 (5) | 0.043 (3) | −0.012 (3) | 0.014 (3) | 0.010 (3) |
C33 | 0.022 (3) | 0.063 (4) | 0.029 (3) | −0.001 (3) | 0.009 (2) | −0.002 (3) |
C34 | 0.041 (4) | 0.082 (5) | 0.043 (3) | 0.003 (3) | 0.021 (3) | −0.016 (3) |
C35 | 0.055 (4) | 0.075 (5) | 0.063 (4) | −0.021 (4) | 0.036 (4) | −0.011 (4) |
N1 | 0.025 (2) | 0.025 (2) | 0.0168 (18) | 0.0017 (17) | 0.0058 (17) | 0.0027 (17) |
N2 | 0.024 (2) | 0.025 (2) | 0.0109 (17) | 0.0044 (17) | −0.0004 (15) | 0.0024 (16) |
O10 | 0.181 (8) | 0.117 (6) | 0.064 (4) | −0.055 (5) | 0.045 (4) | −0.031 (4) |
C36 | 0.191 (12) | 0.076 (7) | 0.158 (11) | −0.021 (8) | 0.118 (10) | −0.005 (7) |
C37 | 0.198 (12) | 0.081 (7) | 0.084 (7) | −0.036 (8) | 0.021 (8) | −0.015 (6) |
C38 | 0.140 (9) | 0.136 (9) | 0.061 (6) | 0.009 (8) | 0.040 (6) | −0.004 (6) |
C39 | 0.116 (8) | 0.085 (6) | 0.082 (6) | −0.032 (6) | 0.031 (6) | −0.001 (5) |
O11 | 0.117 (6) | 0.089 (5) | 0.082 (5) | 0.021 (4) | 0.013 (4) | 0.008 (4) |
C40 | 0.145 (9) | 0.085 (6) | 0.065 (6) | 0.027 (6) | 0.044 (6) | 0.004 (5) |
C41 | 0.142 (11) | 0.119 (10) | 0.126 (10) | 0.024 (8) | −0.026 (9) | −0.010 (8) |
C43 | 0.264 (17) | 0.083 (7) | 0.079 (7) | 0.041 (9) | 0.084 (10) | 0.001 (6) |
C42 | 0.135 (10) | 0.127 (10) | 0.230 (15) | 0.065 (8) | 0.127 (10) | 0.076 (10) |
Rh1—O5 | 2.040 (3) | C24—C25 | 1.385 (7) |
Rh1—O8i | 2.043 (3) | C24—C29 | 1.401 (7) |
Rh1—O1i | 2.052 (3) | C24—N2 | 1.449 (6) |
Rh1—O4 | 2.054 (3) | C25—C26 | 1.391 (7) |
Rh1—C9 | 2.243 (5) | C25—C33 | 1.522 (7) |
Rh1—Rh1i | 2.4589 (8) | C26—C27 | 1.365 (8) |
O1—C7 | 1.244 (6) | C26—H26 | 0.9500 |
O1—Rh1i | 2.052 (3) | C27—C28 | 1.372 (8) |
O4—C7 | 1.269 (6) | C27—H27 | 0.9500 |
O5—C1 | 1.255 (6) | C28—C29 | 1.397 (6) |
O8—C1 | 1.256 (6) | C28—H28 | 0.9500 |
O8—Rh1i | 2.043 (3) | C29—C30 | 1.508 (7) |
C1—C2 | 1.517 (6) | C30—C32 | 1.517 (8) |
C2—H2A | 0.9800 | C30—C31 | 1.523 (8) |
C2—H2B | 0.9800 | C30—H30 | 1.0000 |
C2—H2C | 0.9800 | C31—H31A | 0.9800 |
C7—C8 | 1.516 (7) | C31—H31B | 0.9800 |
C8—H8B | 0.9800 | C31—H31C | 0.9800 |
C8—H8A | 0.9800 | C32—H32A | 0.9800 |
C8—H8C | 0.9800 | C32—H32B | 0.9800 |
C9—N1 | 1.348 (6) | C32—H32C | 0.9800 |
C9—N2 | 1.354 (5) | C33—C35 | 1.531 (8) |
C10—C11 | 1.340 (7) | C33—C34 | 1.537 (8) |
C10—N1 | 1.377 (6) | C33—H33 | 1.0000 |
C10—H10 | 0.9500 | C34—H34A | 0.9800 |
C11—N2 | 1.386 (6) | C34—H34B | 0.9800 |
C11—H11 | 0.9500 | C34—H34C | 0.9800 |
C12—C17 | 1.392 (7) | C35—H35A | 0.9800 |
C12—C13 | 1.407 (7) | C35—H35B | 0.9800 |
C12—N1 | 1.428 (6) | C35—H35C | 0.9800 |
C13—C14 | 1.387 (7) | O10—C36 | 1.325 (11) |
C13—C21 | 1.510 (7) | O10—C39 | 1.356 (10) |
C14—C15 | 1.367 (8) | C36—C37 | 1.472 (11) |
C14—H14 | 0.9500 | C36—H36A | 0.9900 |
C15—C16 | 1.382 (8) | C36—H36B | 0.9900 |
C15—H15 | 0.9500 | C37—C38 | 1.457 (11) |
C16—C17 | 1.393 (7) | C37—H37A | 0.9900 |
C16—H16 | 0.9500 | C37—H37B | 0.9900 |
C17—C18 | 1.534 (8) | C38—C39 | 1.496 (10) |
C18—C19 | 1.510 (10) | C38—H38A | 0.9900 |
C18—C20 | 1.519 (8) | C38—H38B | 0.9900 |
C18—H18 | 1.0000 | C39—H39A | 0.9900 |
C19—H19A | 0.9800 | C39—H39B | 0.9900 |
C19—H19B | 0.9800 | O11—C43 | 1.291 (12) |
C19—H19C | 0.9800 | O11—C40 | 1.367 (10) |
C20—H20A | 0.9800 | C40—C41 | 1.444 (12) |
C20—H20B | 0.9800 | C40—H40A | 0.9900 |
C20—H20C | 0.9800 | C40—H40B | 0.9900 |
C21—C22 | 1.519 (9) | C41—C42 | 1.458 (13) |
C21—C23 | 1.522 (9) | C41—H41A | 0.9900 |
C21—H21 | 1.0000 | C41—H41B | 0.9900 |
C22—H22A | 0.9800 | C43—C42 | 1.458 (13) |
C22—H22B | 0.9800 | C43—H43A | 0.9900 |
C22—H22C | 0.9800 | C43—H43B | 0.9900 |
C23—H23A | 0.9800 | C42—H42A | 0.9900 |
C23—H23B | 0.9800 | C42—H42B | 0.9900 |
C23—H23C | 0.9800 | ||
O5—Rh1—O8i | 174.33 (13) | C26—C25—C33 | 120.3 (5) |
O5—Rh1—O1i | 89.62 (14) | C27—C26—C25 | 120.6 (5) |
O8i—Rh1—O1i | 90.17 (14) | C27—C26—H26 | 119.7 |
O5—Rh1—O4 | 89.89 (14) | C25—C26—H26 | 119.7 |
O8i—Rh1—O4 | 89.76 (14) | C26—C27—C28 | 121.3 (5) |
O1i—Rh1—O4 | 174.42 (13) | C26—C27—H27 | 119.3 |
O5—Rh1—C9 | 93.30 (14) | C28—C27—H27 | 119.3 |
O8i—Rh1—C9 | 92.36 (14) | C27—C28—C29 | 120.7 (5) |
O1i—Rh1—C9 | 93.91 (14) | C27—C28—H28 | 119.6 |
O4—Rh1—C9 | 91.67 (15) | C29—C28—H28 | 119.6 |
O5—Rh1—Rh1i | 87.18 (9) | C28—C29—C24 | 116.6 (5) |
O8i—Rh1—Rh1i | 87.15 (9) | C28—C29—C30 | 122.2 (4) |
O1i—Rh1—Rh1i | 87.11 (9) | C24—C29—C30 | 121.2 (4) |
O4—Rh1—Rh1i | 87.32 (9) | C29—C30—C32 | 112.6 (5) |
C9—Rh1—Rh1i | 178.87 (11) | C29—C30—C31 | 111.7 (5) |
C7—O1—Rh1i | 119.2 (3) | C32—C30—C31 | 111.0 (5) |
C7—O4—Rh1 | 118.3 (3) | C29—C30—H30 | 107.0 |
C1—O5—Rh1 | 118.9 (3) | C32—C30—H30 | 107.0 |
C1—O8—Rh1i | 118.8 (3) | C31—C30—H30 | 107.0 |
O5—C1—O8 | 127.9 (4) | C30—C31—H31A | 109.5 |
O5—C1—C2 | 116.3 (4) | C30—C31—H31B | 109.5 |
O8—C1—C2 | 115.8 (4) | H31A—C31—H31B | 109.5 |
C1—C2—H2A | 109.5 | C30—C31—H31C | 109.5 |
C1—C2—H2B | 109.5 | H31A—C31—H31C | 109.5 |
H2A—C2—H2B | 109.5 | H31B—C31—H31C | 109.5 |
C1—C2—H2C | 109.5 | C30—C32—H32A | 109.5 |
H2A—C2—H2C | 109.5 | C30—C32—H32B | 109.5 |
H2B—C2—H2C | 109.5 | H32A—C32—H32B | 109.5 |
O1—C7—O4 | 128.1 (5) | C30—C32—H32C | 109.5 |
O1—C7—C8 | 116.1 (4) | H32A—C32—H32C | 109.5 |
O4—C7—C8 | 115.8 (4) | H32B—C32—H32C | 109.5 |
C7—C8—H8B | 109.5 | C25—C33—C35 | 112.1 (5) |
C7—C8—H8A | 109.5 | C25—C33—C34 | 109.5 (5) |
H8B—C8—H8A | 109.5 | C35—C33—C34 | 110.3 (5) |
C7—C8—H8C | 109.5 | C25—C33—H33 | 108.3 |
H8B—C8—H8C | 109.5 | C35—C33—H33 | 108.3 |
H8A—C8—H8C | 109.5 | C34—C33—H33 | 108.3 |
N1—C9—N2 | 103.3 (4) | C33—C34—H34A | 109.5 |
N1—C9—Rh1 | 128.0 (3) | C33—C34—H34B | 109.5 |
N2—C9—Rh1 | 128.4 (3) | H34A—C34—H34B | 109.5 |
C11—C10—N1 | 106.5 (4) | C33—C34—H34C | 109.5 |
C11—C10—H10 | 126.7 | H34A—C34—H34C | 109.5 |
N1—C10—H10 | 126.7 | H34B—C34—H34C | 109.5 |
C10—C11—N2 | 106.3 (4) | C33—C35—H35A | 109.5 |
C10—C11—H11 | 126.9 | C33—C35—H35B | 109.5 |
N2—C11—H11 | 126.9 | H35A—C35—H35B | 109.5 |
C17—C12—C13 | 121.2 (4) | C33—C35—H35C | 109.5 |
C17—C12—N1 | 119.7 (5) | H35A—C35—H35C | 109.5 |
C13—C12—N1 | 119.1 (4) | H35B—C35—H35C | 109.5 |
C14—C13—C12 | 117.8 (5) | C9—N1—C10 | 112.2 (4) |
C14—C13—C21 | 120.4 (5) | C9—N1—C12 | 128.3 (4) |
C12—C13—C21 | 121.7 (4) | C10—N1—C12 | 119.5 (4) |
C15—C14—C13 | 121.4 (5) | C9—N2—C11 | 111.7 (4) |
C15—C14—H14 | 119.3 | C9—N2—C24 | 128.3 (4) |
C13—C14—H14 | 119.3 | C11—N2—C24 | 120.0 (4) |
C14—C15—C16 | 120.6 (5) | C36—O10—C39 | 112.4 (8) |
C14—C15—H15 | 119.7 | O10—C36—C37 | 109.8 (8) |
C16—C15—H15 | 119.7 | O10—C36—H36A | 109.7 |
C15—C16—C17 | 120.0 (5) | C37—C36—H36A | 109.7 |
C15—C16—H16 | 120.0 | O10—C36—H36B | 109.7 |
C17—C16—H16 | 120.0 | C37—C36—H36B | 109.7 |
C12—C17—C16 | 118.9 (5) | H36A—C36—H36B | 108.2 |
C12—C17—C18 | 120.4 (5) | C38—C37—C36 | 104.1 (8) |
C16—C17—C18 | 120.7 (5) | C38—C37—H37A | 110.9 |
C19—C18—C20 | 110.3 (6) | C36—C37—H37A | 110.9 |
C19—C18—C17 | 111.1 (5) | C38—C37—H37B | 110.9 |
C20—C18—C17 | 112.2 (5) | C36—C37—H37B | 110.9 |
C19—C18—H18 | 107.7 | H37A—C37—H37B | 109.0 |
C20—C18—H18 | 107.7 | C37—C38—C39 | 105.6 (8) |
C17—C18—H18 | 107.7 | C37—C38—H38A | 110.6 |
C18—C19—H19A | 109.5 | C39—C38—H38A | 110.6 |
C18—C19—H19B | 109.5 | C37—C38—H38B | 110.6 |
H19A—C19—H19B | 109.5 | C39—C38—H38B | 110.6 |
C18—C19—H19C | 109.5 | H38A—C38—H38B | 108.8 |
H19A—C19—H19C | 109.5 | O10—C39—C38 | 107.1 (8) |
H19B—C19—H19C | 109.5 | O10—C39—H39A | 110.3 |
C18—C20—H20A | 109.5 | C38—C39—H39A | 110.3 |
C18—C20—H20B | 109.5 | O10—C39—H39B | 110.3 |
H20A—C20—H20B | 109.5 | C38—C39—H39B | 110.3 |
C18—C20—H20C | 109.5 | H39A—C39—H39B | 108.6 |
H20A—C20—H20C | 109.5 | C43—O11—C40 | 110.0 (8) |
H20B—C20—H20C | 109.5 | O11—C40—C41 | 108.5 (9) |
C13—C21—C22 | 112.0 (5) | O11—C40—H40A | 110.0 |
C13—C21—C23 | 110.5 (6) | C41—C40—H40A | 110.0 |
C22—C21—C23 | 109.9 (6) | O11—C40—H40B | 110.0 |
C13—C21—H21 | 108.1 | C41—C40—H40B | 110.0 |
C22—C21—H21 | 108.1 | H40A—C40—H40B | 108.4 |
C23—C21—H21 | 108.1 | C40—C41—C42 | 104.6 (9) |
C21—C22—H22A | 109.5 | C40—C41—H41A | 110.8 |
C21—C22—H22B | 109.5 | C42—C41—H41A | 110.8 |
H22A—C22—H22B | 109.5 | C40—C41—H41B | 110.8 |
C21—C22—H22C | 109.5 | C42—C41—H41B | 110.8 |
H22A—C22—H22C | 109.5 | H41A—C41—H41B | 108.9 |
H22B—C22—H22C | 109.5 | O11—C43—C42 | 110.1 (9) |
C21—C23—H23A | 109.5 | O11—C43—H43A | 109.6 |
C21—C23—H23B | 109.5 | C42—C43—H43A | 109.6 |
H23A—C23—H23B | 109.5 | O11—C43—H43B | 109.6 |
C21—C23—H23C | 109.5 | C42—C43—H43B | 109.6 |
H23A—C23—H23C | 109.5 | H43A—C43—H43B | 108.2 |
H23B—C23—H23C | 109.5 | C43—C42—C41 | 104.1 (9) |
C25—C24—C29 | 123.1 (4) | C43—C42—H42A | 110.9 |
C25—C24—N2 | 118.1 (4) | C41—C42—H42A | 110.9 |
C29—C24—N2 | 118.7 (4) | C43—C42—H42B | 110.9 |
C24—C25—C26 | 117.5 (5) | C41—C42—H42B | 110.9 |
C24—C25—C33 | 122.2 (4) | H42A—C42—H42B | 109.0 |
Symmetry code: (i) −x, −y, −z+1. |
Experimental details
Crystal data | |
Chemical formula | [Rh2(C2H3O2O)4(C27H36N2)2]·4C4H8O |
Mr | 1507.56 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 150 |
a, b, c (Å) | 10.509 (4), 33.708 (6), 11.967 (3) |
β (°) | 111.388 (6) |
V (Å3) | 3947.2 (19) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.48 |
Crystal size (mm) | 0.30 × 0.15 × 0.15 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2004) |
Tmin, Tmax | 0.870, 0.932 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 38595, 9028, 6488 |
Rint | 0.082 |
(sin θ/λ)max (Å−1) | 0.650 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.071, 0.151, 1.17 |
No. of reflections | 9028 |
No. of parameters | 438 |
No. of restraints | 96 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.88, −0.92 |
Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 2008), ORTEP-3.2 (Farrugia, 1997) and Mercury (Version 1.4; Macrae et al., 2006), enCIFer (Allen et al., 2004).
THF solvate (this work) | Toluene solvate (Góis et al., 2007) | |
C9-N1-C12-C17 | -92.5 (6) | -98.3 (4) |
C9-N1-C12-C13 | 91.3 (6) | 85.3 (4) |
C9-N2-C24-C25 | 101.9 (6) | 99.8 (4) |
C9-N2-C24-C29 | -82.0 (6) | -84.0 (4) |
C36-N3-C39-C40 | * 101.9 (6) | 93.7 (4) |
C36-N3-C39-C44 | * -82.0 (6) | -89.8 (4) |
C36-N4-C51-C52 | * 91.3 (6) | 87.5 (4) |
C36-N4-C51-C56 | * -92.5 (6) | -96.7 (4) |
N1-C12-C13-C21 | -8.2 (7) | -8.1 (5) |
N1-C12-C17-C18 | 7.6 (7) | 9.9 (5) |
N2-C24-C25-C33 | -11.4 (7) | -10.1 (5) |
N2-C24-C29-C30 | 8.8 (7) | 8.4 (5) |
N3-C39-C40-C48 | * -11.4 (7) | -7.1 (5) |
N3-C39-C44-C45 | * 8.8 (7) | 6.9 (5) |
N4-C51-C56-C57 | * 7.6 (7) | 9.9 (5) |
N4-C51-C52-C60 | * -8.2 (7) | -8.9 (5) |
* Values obtained by symmetry. |
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In the last two decades the family of dirhodium(II) complexes has attracted considerable interest from the organic chemistry community since they are able to catalyse efficiently some remarkable transformations, such as: intramolecular and intermolecular C—H bond activation with RhII carbenoids (Davies & Beckwith, 2003; Doyle, 2006; Góis & Afonso, 2004); C—H bond amination with RhII nitrenoids; oxidations; cycloadditions and a variety of ylide-based transformations (see, for example, Catino et al., 2004; Catino, Nichols, Choi et al., 2005 or Catino, Nichols, Gorslund & Doyle, 2005 ?; Liang et al., 2006; Reddy & Davies, 2006; Fiori & Du Bois, 2007; Anada et al., 2004; Forslund et al., 2005; Washio et al., 2005; Wang et al., 2008; Catino, Gorslund et al., 2005). More recently, we have successfully been able to prepare and fully characterize stable complexes of Rh2(OAc)4 with one and two NHCs [Please define] attached at the axial positions. These complexes proved to be excellent catalysts for aldehyde arylation reactions with boronic acids (Góis et al., 2007; Trindade et al., 2008).
Dirhodium(II) complexes have an intermetallic bond, two axial ligands (normally solvent molecules), and four bridging ligands which are responsible for controlling the electrophilicity and asymmetry of the complex (Doyle et al., 1998; Lou et al., 2005; Cotton et al., 2002). Unlike bridging ligands, the axial ligands are considered to be labile (weakly bonded) and could easily be displaced by other molecules.
The previously reported complex Rh2(OAc)4(NHC)2 (Góis et al., 2007), (II), was obtained as a toluene solvate with a stoichiometry of three molecules of solvent to one molecule of dirhodium(II) (diRh) complex (Fig. 1a). More recently, we obtained a new solvate, (I), with tetrahydrofuran (THF). In this case, the asymmetric unit consists of two crystallographically independent THF molecules and half a complex molecule residing on an inversion centre (Fig. 1b).
In both solvates, no classical hydrogen bonds were found, but the supramolecular arrangements are indeed very different, due to the distinct interactions with the solvent molecules. On the whole, the two diRh complex molecules retain their conformation, as can be seen in Fig. 2 and sustained by the small differences in torsion angle values presented in Table 1.
In the toluene solvate, (II), previously reported by us (Góis et al., 2007), there are no short contacts between the diRh complex molecules; they all interact via C—H···π interactions with solvent molecules, which behave as linkers. The linking between two complex molecules is achieved through two toluene molecules, A and B (Fig. 3a), which interact further with the remaining solvent molecule, C. The diRh complex molecules interact in two different modes with the solvent molecules. Toluene molecule A interacts with a neighbouring diisopropylphenyl ring (Cg1, defined by atoms C24–C29) [C65—H65···Cg1i, H65···Cg1i = 2.79 Å, C65···Cg1i = 3.716 (8) Å and C65—H65···Cg1i = 175°; symmetry code: (i) x, 1+y, z], while the other interaction is through a C atom of an imidazole-2-ylidene group and the ring of toluene molecule B (Cg2, defined by atoms C70–C76) [C37—H37···Cg2, 2.67 Å, 3.449 (4) Å and 142°].
The toluene molecules do not have the same orientation: the dihedral angles between the planes of solvent molecules A and B, B and C, and A and C are 86.1 (3), 78.2 (3) and 32.3 (4)°, respectively. This relative positioning of the solvent molecules is due to the C—H···π interactions established among them (Fig. 3a): toluene molecules A and B interact through C75—H75···Cg3 (where Cg3 is the ring defined by atoms C63–C69) [2.77 Å, 3.688 (6) Å and 168°]; molecules B and C are linked via C71—H71···Cg4 (where Cg4 is the ring defined by atoms C77–C83) [2.73 Å, 3.587 (6) Å and 154°].
In a view along a (Fig. 3b), it is possible to see that, along b, the diRh complex molecules are intercalated by groups of the three independent toluene molecules, forming chains with a repeat motif of diRh complex molecule–group of toluene molecules–diRh complex molecule. On the other hand, diRh complex molecules align along the bc diagonal.
The THF solvate, (I), presents a very different supramolecular arrangement compared with the toluene solvate, resulting in very different crystal packing for the two structures. In this new derivative, not only do the solvent molecules interact differently with the organometallic moieties, but they also do not interpose with the diRh complex molecules, resulting in a `pseudo-polymer' array of diRh complex molecules aligning along a (Fig. 4a). However, even though the diRh complex molecules do not interact with each other directly, they are much closer to each other (shortest intermolecular distance of 2.34 Å) than in the crystal packing of the toluene solvate (2.77 Å).
Each solvent molecule establishes a short-contact interaction involving different H atoms from the five-membered ring of the imidazol-2-ylidene group of the diRh complex, resulting in its association with two THF molecules through C10—H10···O11 [2.37 Å, 3.313 (9) Å and 169°] and C11—H11···O10 [2.39 Å, 3.322 (9) Å and 165°] interactions (Fig. 4b).
In Fig. 4(c), chains of alternating diRh complex and THF molecules are visible along b. The diRh complex `pseudo-polymer' array aligned along a is once again observed, as well as an interesting THF motif intercalating consecutive complex molecules.
As discussed above, the supramolecular assemblies in both solvates compared in this paper are completely different and the space filling is achieved in two distinct modes, even though they both result in similar packing efficiencies, with a slightly higher value (64.8%) in the THF solvate than in the toluene solvate (62.8%).