Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807052920/bg3061sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807052920/bg3061Isup2.hkl |
CCDC reference: 667247
Key indicators
- Single-crystal X-ray study
- T = 150 K
- Mean (C-C) = 0.003 Å
- R factor = 0.016
- wR factor = 0.035
- Data-to-parameter ratio = 22.9
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X) Rh1 - Cl1 .. 5.13 su PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X) Rh1 - N1 .. 5.43 su PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X) Rh2 - Cl2 .. 8.03 su
Alert level G REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is correct. If it is not, please give the correct count in the _publ_section_exptl_refinement section of the submitted CIF. From the CIF: _diffrn_reflns_theta_max 28.70 From the CIF: _reflns_number_total 7489 Count of symmetry unique reflns 3809 Completeness (_total/calc) 196.61% TEST3: Check Friedels for noncentro structure Estimate of Friedel pairs measured 3680 Fraction of Friedel pairs measured 0.966 Are heavy atom types Z>Si present yes PLAT791_ALERT_1_G Confirm the Absolute Configuration of N1 = . R PLAT791_ALERT_1_G Confirm the Absolute Configuration of N2 = . R PLAT791_ALERT_1_G Confirm the Absolute Configuration of C4 = . S PLAT791_ALERT_1_G Confirm the Absolute Configuration of C18 = . S PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 3
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 3 ALERT level C = Check and explain 6 ALERT level G = General alerts; check 4 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 3 ALERT type 2 Indicator that the structure model may be wrong or deficient 1 ALERT type 3 Indicator that the structure quality may be low 1 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
For structurally related rhodium complexes with various chiral and achiral β-amino alcohol ligands, see Dahlenburg et al. (2007).
Compound (I) was prepared by the bridge-opening reaction of [{Rh(η4-C8H12)}2(µ-Cl)2] with (S)-2-methoxymethylpyrrolidine, similar to the procedure previously communicated for the syntheses of a number of chlorido(η4-1,5-cyclooctadiene)rhodium(I) derivatives bearing diverse N-bonded β-amino alcohol ligands (Dahlenburg et al., 2007). The specimen used for the X-ray diffraction study was collected from a partially evaporated NMR sample in CDCl3 solution.
Carbon-and nitrogen-bound H atoms were positioned geometrically (C—H = 0.95–0.99 Å; N—H = 0.93 Å) and refined using appropriate riding models. All hydrogen Uiso values were fixed at 1.2 times Ueq of the preceding carrier atom.
Chlorido(η4-1,5-cyclooctadiene)[κN-(S)-2-methoxymethylpyrrolidine]rhodium(I), [Rh(Cl)(η4-C8H12){(S)-C6H13NO}] (I), represents the O-methylated analogue of the previously described prolinol complexes [Rh(Cl)(η4-C8H12){(R)-C5H11NO}] and [Rh(Cl)(η4-C8H12){(S)-C5H11NO}] which themselves belong to a family of catalytically attractive rhodium compounds containing β-amino alcohol ligands (Dahlenburg et al., 2007). Complex (I) crystallizes from CDCl3 in the triclinic space group P1 with two independent moieties per cell.
Not unexpectedly, neither the Rh—Cl distances nor the Rh—N bond lengths deviate significantly from the corresponding dimensions observed fo closely related chlorido rhodium complexes in the literature possessing N-bonded ethanolamine, valinol, prolinol, and norephedrine ligands [Rh—Cl = 2.381 → 2.398 Å and Rh—N = 2.127→ 2.137 Å] (Dahlenburg et al., 2007).
In the solid state the individual complexes of (I) are assembled through N—H···Cl hydrogen bonds (Table 2). The (R)-enantiomer of the parent prolinol compound [Rh(Cl)(η4-C8H12)(C5H11NO)] shows similar N—H···Cl (and O—H···Cl) hydrogen-bonding between two crystallographically independent molecules (Dahlenburg et al., 2007).
For structurally related rhodium complexes with various chiral and achiral β-amino alcohol ligands, see Dahlenburg et al. (2007).
Data collection: COLLECT (Bruker, 2002); cell refinement: EVALCCD (Duisenberg et al., 2003); data reduction: EVALCCD (Duisenberg et al., 2003); program(s) used to solve structure: SHELXTL-NT (Bruker, 2002); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).
Fig. 1. Structures of the two crystallographically independent molecules of (I). Displacement ellipsoids are drawn at the 50% probability level. |
[RhCl(C8H12)(C6H13NO)] | Z = 2 |
Mr = 361.71 | F(000) = 372 |
Triclinic, P1 | Dx = 1.622 Mg m−3 |
Hall symbol: P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 6.5499 (2) Å | Cell parameters from 98 reflections |
b = 6.6563 (2) Å | θ = 6.0–20.0° |
c = 18.8540 (7) Å | µ = 1.32 mm−1 |
α = 92.253 (3)° | T = 150 K |
β = 95.026 (3)° | Plate, yellow |
γ = 114.841 (2)° | 0.25 × 0.18 × 0.10 mm |
V = 740.44 (4) Å3 |
Bruker–Nonius KappaCCD diffractometer | 7489 independent reflections |
Radiation source: fine-focus sealed tube | 7246 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.019 |
Detector resolution: 9 pixels mm-1 | θmax = 28.7°, θmin = 3.3° |
ω–rotations with 1.70 ° and 76 sec per frame scans | h = −8→8 |
Absorption correction: multi-scan (SADABS; Bruker, 2002) | k = −8→8 |
Tmin = 0.730, Tmax = 0.880 | l = −25→25 |
19576 measured reflections |
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)] = 0.016 | H-atom parameters constrained |
wR(F2) = 0.035 | w = 1/[σ2(Fo2) + (0.0125P)2 + 0.1842P] where P = (Fo2 + 2Fc2)/3 |
S = 1.06 | (Δ/σ)max = 0.002 |
7489 reflections | Δρmax = 0.37 e Å−3 |
327 parameters | Δρmin = −0.35 e Å−3 |
3 restraints | Absolute structure: Flack (1983) |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: −0.013 (13) |
[RhCl(C8H12)(C6H13NO)] | γ = 114.841 (2)° |
Mr = 361.71 | V = 740.44 (4) Å3 |
Triclinic, P1 | Z = 2 |
a = 6.5499 (2) Å | Mo Kα radiation |
b = 6.6563 (2) Å | µ = 1.32 mm−1 |
c = 18.8540 (7) Å | T = 150 K |
α = 92.253 (3)° | 0.25 × 0.18 × 0.10 mm |
β = 95.026 (3)° |
Bruker–Nonius KappaCCD diffractometer | 7489 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2002) | 7246 reflections with I > 2σ(I) |
Tmin = 0.730, Tmax = 0.880 | Rint = 0.019 |
19576 measured reflections |
R[F2 > 2σ(F2)] = 0.016 | H-atom parameters constrained |
wR(F2) = 0.035 | Δρmax = 0.37 e Å−3 |
S = 1.06 | Δρmin = −0.35 e Å−3 |
7489 reflections | Absolute structure: Flack (1983) |
327 parameters | Absolute structure parameter: −0.013 (13) |
3 restraints |
Refinement. 3690 Friedel pairs were used in the refinement of the Flack parameter. |
x | y | z | Uiso*/Ueq | ||
Rh1 | 0.084451 (15) | 0.914650 (14) | 0.609209 (7) | 0.01109 (4) | |
Cl1 | 0.20120 (12) | 0.67363 (10) | 0.67548 (3) | 0.02427 (14) | |
N1 | 0.2502 (3) | 1.1749 (3) | 0.69167 (8) | 0.0131 (3) | |
H1 | 0.2092 | 1.2887 | 0.6803 | 0.016* | |
O1 | −0.0795 (3) | 1.0168 (3) | 0.84488 (8) | 0.0287 (4) | |
C1 | 0.5026 (3) | 1.2725 (3) | 0.69824 (10) | 0.0180 (4) | |
H1A | 0.5599 | 1.3537 | 0.6561 | 0.022* | |
H1B | 0.5570 | 1.1549 | 0.7026 | 0.022* | |
C2 | 0.5807 (3) | 1.4316 (3) | 0.76628 (11) | 0.0217 (4) | |
H2A | 0.6092 | 1.5844 | 0.7549 | 0.026* | |
H2B | 0.7209 | 1.4340 | 0.7916 | 0.026* | |
C3 | 0.3818 (3) | 1.3363 (3) | 0.81205 (10) | 0.0210 (4) | |
H3A | 0.4312 | 1.2943 | 0.8580 | 0.025* | |
H3B | 0.3209 | 1.4465 | 0.8220 | 0.025* | |
C4 | 0.2023 (3) | 1.1302 (4) | 0.76651 (10) | 0.0142 (4) | |
H4A | 0.2276 | 0.9970 | 0.7788 | 0.017* | |
C5 | −0.0394 (3) | 1.0849 (4) | 0.77490 (10) | 0.0178 (4) | |
H5A | −0.0633 | 1.2207 | 0.7686 | 0.021* | |
H5B | −0.1442 | 0.9663 | 0.7387 | 0.021* | |
C6 | −0.2952 (4) | 0.9857 (4) | 0.86247 (12) | 0.0254 (4) | |
H6A | −0.3208 | 0.9189 | 0.9081 | 0.038* | |
H6B | −0.4116 | 0.8871 | 0.8250 | 0.038* | |
H6C | −0.3029 | 1.1295 | 0.8665 | 0.038* | |
C7 | 0.0141 (3) | 0.7171 (3) | 0.50952 (10) | 0.0179 (4) | |
H7A | 0.1378 | 0.6841 | 0.5249 | 0.021* | |
C8 | −0.1764 (3) | 0.6376 (3) | 0.54673 (10) | 0.0177 (4) | |
H8A | −0.1753 | 0.5469 | 0.5843 | 0.021* | |
C9 | −0.3832 (3) | 0.6819 (3) | 0.53303 (12) | 0.0229 (4) | |
H9A | −0.4747 | 0.6343 | 0.5735 | 0.028* | |
H9B | −0.4764 | 0.5903 | 0.4894 | 0.028* | |
C10 | −0.3300 (3) | 0.9254 (3) | 0.52363 (12) | 0.0219 (4) | |
H10A | −0.3216 | 0.9514 | 0.4724 | 0.026* | |
H10B | −0.4537 | 0.9584 | 0.5394 | 0.026* | |
C11 | −0.1070 (3) | 1.0805 (3) | 0.56654 (11) | 0.0165 (4) | |
H11A | −0.1115 | 1.1258 | 0.6146 | 0.020* | |
C12 | 0.1055 (3) | 1.1619 (3) | 0.54041 (10) | 0.0155 (4) | |
H12A | 0.2311 | 1.2644 | 0.5717 | 0.019* | |
C13 | 0.1534 (4) | 1.1028 (3) | 0.46791 (10) | 0.0213 (4) | |
H13A | 0.3187 | 1.1521 | 0.4682 | 0.026* | |
H13B | 0.1049 | 1.1838 | 0.4322 | 0.026* | |
C14 | 0.0326 (4) | 0.8540 (3) | 0.44560 (11) | 0.0238 (4) | |
H14A | −0.1211 | 0.8179 | 0.4219 | 0.029* | |
H14B | 0.1170 | 0.8144 | 0.4107 | 0.029* | |
Rh2 | 0.094539 (15) | 0.761289 (15) | 0.114302 (7) | 0.01106 (4) | |
Cl2 | −0.21538 (8) | 0.68239 (9) | 0.18309 (3) | 0.02146 (10) | |
N2 | 0.2549 (3) | 0.6455 (3) | 0.19530 (9) | 0.0143 (3) | |
H2 | 0.3952 | 0.6673 | 0.1815 | 0.017* | |
O2 | 0.5079 (2) | 1.0692 (2) | 0.34836 (7) | 0.0215 (3) | |
C15 | 0.1275 (3) | 0.4022 (3) | 0.20168 (11) | 0.0198 (4) | |
H15A | 0.1370 | 0.3147 | 0.1594 | 0.024* | |
H15B | −0.0339 | 0.3633 | 0.2063 | 0.024* | |
C16 | 0.2431 (4) | 0.3587 (4) | 0.26888 (11) | 0.0248 (4) | |
H16A | 0.3738 | 0.3297 | 0.2580 | 0.030* | |
H16B | 0.1360 | 0.2297 | 0.2912 | 0.030* | |
C17 | 0.3211 (4) | 0.5724 (3) | 0.31814 (11) | 0.0235 (4) | |
H17A | 0.4806 | 0.6220 | 0.3388 | 0.028* | |
H17B | 0.2254 | 0.5483 | 0.3576 | 0.028* | |
C18 | 0.2969 (3) | 0.7465 (3) | 0.27071 (9) | 0.0149 (3) | |
H18A | 0.1607 | 0.7682 | 0.2819 | 0.018* | |
C19 | 0.4995 (3) | 0.9695 (3) | 0.27987 (10) | 0.0183 (4) | |
H19A | 0.6400 | 0.9502 | 0.2758 | 0.022* | |
H19B | 0.4847 | 1.0644 | 0.2425 | 0.022* | |
C20 | 0.7024 (4) | 1.2750 (4) | 0.36377 (12) | 0.0264 (4) | |
H20A | 0.6966 | 1.3446 | 0.4099 | 0.040* | |
H20B | 0.7055 | 1.3735 | 0.3262 | 0.040* | |
H20C | 0.8392 | 1.2488 | 0.3659 | 0.040* | |
C21 | −0.1169 (3) | 0.7272 (3) | 0.01827 (10) | 0.0168 (4) | |
H21A | −0.2417 | 0.6306 | 0.0408 | 0.020* | |
C22 | −0.0168 (4) | 0.9508 (4) | 0.04382 (14) | 0.0185 (5) | |
H22A | −0.0744 | 0.9937 | 0.0834 | 0.022* | |
C23 | 0.1775 (4) | 1.1297 (3) | 0.01277 (11) | 0.0234 (4) | |
H23A | 0.1619 | 1.2711 | 0.0173 | 0.028* | |
H23B | 0.1697 | 1.0881 | −0.0387 | 0.028* | |
C24 | 0.4096 (4) | 1.1644 (3) | 0.05044 (12) | 0.0244 (4) | |
H24A | 0.5235 | 1.2168 | 0.0161 | 0.029* | |
H24B | 0.4556 | 1.2818 | 0.0902 | 0.029* | |
C25 | 0.4086 (3) | 0.9560 (3) | 0.07954 (10) | 0.0181 (4) | |
H25A | 0.4751 | 0.9678 | 0.1273 | 0.022* | |
C26 | 0.3173 (3) | 0.7468 (3) | 0.04160 (10) | 0.0169 (4) | |
H26A | 0.3207 | 0.6251 | 0.0656 | 0.020* | |
C27 | 0.2129 (3) | 0.7032 (4) | −0.03583 (11) | 0.0210 (4) | |
H27A | 0.2477 | 0.5885 | −0.0601 | 0.025* | |
H27B | 0.2814 | 0.8411 | −0.0603 | 0.025* | |
C28 | −0.0445 (4) | 0.6248 (4) | −0.04210 (11) | 0.0195 (4) | |
H28A | −0.0959 | 0.6644 | −0.0882 | 0.023* | |
H28B | −0.1185 | 0.4610 | −0.0420 | 0.023* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Rh1 | 0.01358 (9) | 0.00928 (8) | 0.01085 (8) | 0.00528 (7) | 0.00132 (6) | 0.00121 (6) |
Cl1 | 0.0390 (3) | 0.0184 (3) | 0.0208 (3) | 0.0188 (3) | −0.0037 (2) | 0.0012 (2) |
N1 | 0.0149 (7) | 0.0133 (7) | 0.0125 (7) | 0.0072 (6) | 0.0014 (6) | 0.0026 (6) |
O1 | 0.0225 (8) | 0.0499 (10) | 0.0204 (7) | 0.0196 (7) | 0.0088 (6) | 0.0144 (7) |
C1 | 0.0147 (8) | 0.0203 (9) | 0.0174 (9) | 0.0060 (7) | 0.0018 (7) | 0.0006 (7) |
C2 | 0.0181 (9) | 0.0188 (10) | 0.0235 (10) | 0.0044 (8) | −0.0007 (8) | −0.0036 (8) |
C3 | 0.0201 (9) | 0.0253 (10) | 0.0161 (9) | 0.0092 (8) | −0.0008 (7) | −0.0040 (8) |
C4 | 0.0168 (9) | 0.0160 (10) | 0.0114 (9) | 0.0085 (8) | 0.0006 (7) | 0.0031 (7) |
C5 | 0.0171 (9) | 0.0231 (10) | 0.0140 (9) | 0.0091 (8) | 0.0021 (7) | 0.0032 (8) |
C6 | 0.0226 (10) | 0.0322 (12) | 0.0246 (10) | 0.0129 (9) | 0.0106 (8) | 0.0070 (9) |
C7 | 0.0212 (9) | 0.0145 (9) | 0.0152 (9) | 0.0053 (8) | 0.0021 (7) | −0.0023 (7) |
C8 | 0.0193 (9) | 0.0110 (8) | 0.0175 (9) | 0.0021 (7) | −0.0009 (7) | −0.0004 (7) |
C9 | 0.0152 (9) | 0.0183 (10) | 0.0287 (11) | 0.0009 (8) | 0.0009 (8) | 0.0019 (8) |
C10 | 0.0167 (9) | 0.0228 (10) | 0.0259 (10) | 0.0089 (8) | −0.0022 (8) | 0.0030 (8) |
C11 | 0.0172 (9) | 0.0145 (9) | 0.0202 (10) | 0.0092 (8) | 0.0008 (8) | 0.0052 (8) |
C12 | 0.0192 (9) | 0.0125 (8) | 0.0137 (8) | 0.0059 (7) | 0.0001 (7) | 0.0041 (7) |
C13 | 0.0228 (10) | 0.0235 (10) | 0.0165 (9) | 0.0077 (8) | 0.0055 (8) | 0.0073 (8) |
C14 | 0.0297 (11) | 0.0233 (10) | 0.0146 (9) | 0.0070 (9) | 0.0061 (8) | 0.0008 (8) |
Rh2 | 0.00948 (8) | 0.01340 (8) | 0.01073 (8) | 0.00511 (7) | 0.00209 (6) | 0.00113 (6) |
Cl2 | 0.0144 (2) | 0.0360 (3) | 0.0181 (2) | 0.0139 (2) | 0.00577 (17) | 0.00443 (19) |
N2 | 0.0146 (8) | 0.0178 (8) | 0.0128 (8) | 0.0088 (7) | 0.0032 (6) | 0.0012 (6) |
O2 | 0.0210 (7) | 0.0207 (7) | 0.0169 (7) | 0.0040 (6) | 0.0009 (5) | −0.0041 (5) |
C15 | 0.0245 (10) | 0.0155 (9) | 0.0197 (9) | 0.0097 (8) | −0.0005 (8) | −0.0005 (7) |
C16 | 0.0330 (12) | 0.0209 (10) | 0.0244 (10) | 0.0152 (9) | 0.0014 (9) | 0.0052 (8) |
C17 | 0.0299 (11) | 0.0212 (10) | 0.0183 (9) | 0.0105 (9) | −0.0015 (8) | 0.0035 (8) |
C18 | 0.0146 (8) | 0.0192 (9) | 0.0123 (8) | 0.0084 (7) | 0.0018 (7) | 0.0001 (7) |
C19 | 0.0208 (9) | 0.0179 (9) | 0.0173 (9) | 0.0094 (8) | 0.0028 (7) | −0.0002 (7) |
C20 | 0.0235 (10) | 0.0200 (10) | 0.0290 (11) | 0.0050 (8) | −0.0063 (9) | −0.0043 (8) |
C21 | 0.0163 (9) | 0.0189 (9) | 0.0136 (8) | 0.0063 (7) | −0.0011 (7) | 0.0025 (7) |
C22 | 0.0223 (11) | 0.0187 (12) | 0.0160 (10) | 0.0106 (10) | −0.0004 (8) | 0.0016 (9) |
C23 | 0.0339 (11) | 0.0130 (9) | 0.0204 (10) | 0.0075 (8) | 0.0003 (8) | 0.0038 (7) |
C24 | 0.0234 (10) | 0.0158 (9) | 0.0250 (10) | −0.0009 (8) | 0.0049 (8) | 0.0022 (8) |
C25 | 0.0128 (8) | 0.0214 (10) | 0.0159 (9) | 0.0027 (7) | 0.0045 (7) | 0.0021 (7) |
C26 | 0.0158 (9) | 0.0207 (9) | 0.0170 (9) | 0.0088 (8) | 0.0087 (7) | 0.0054 (7) |
C27 | 0.0261 (11) | 0.0213 (10) | 0.0163 (9) | 0.0098 (9) | 0.0082 (8) | 0.0003 (8) |
C28 | 0.0250 (11) | 0.0172 (11) | 0.0124 (9) | 0.0059 (9) | −0.0014 (8) | 0.0003 (8) |
Rh1—N1 | 2.1236 (15) | Rh2—N2 | 2.1263 (15) |
Rh1—Cl1 | 2.3960 (6) | Rh2—Cl2 | 2.3870 (5) |
Rh1—C11 | 2.1199 (17) | Rh2—C25 | 2.0985 (18) |
Rh1—C12 | 2.1021 (17) | Rh2—C26 | 2.1154 (18) |
Rh1—C7 | 2.1491 (19) | Rh2—C21 | 2.1242 (18) |
Rh1—C8 | 2.1300 (19) | Rh2—C22 | 2.150 (2) |
N1—C4 | 1.487 (2) | N2—C15 | 1.494 (2) |
N1—C1 | 1.492 (2) | N2—C18 | 1.500 (2) |
N1—H1 | 0.9300 | N2—H2 | 0.9300 |
O1—C6 | 1.411 (2) | O2—C19 | 1.415 (2) |
O1—C5 | 1.422 (2) | O2—C20 | 1.422 (3) |
C1—C2 | 1.534 (3) | C15—C16 | 1.519 (3) |
C1—H1A | 0.9900 | C15—H15A | 0.9900 |
C1—H1B | 0.9900 | C15—H15B | 0.9900 |
C2—C3 | 1.546 (3) | C16—C17 | 1.533 (3) |
C2—H2A | 0.9900 | C16—H16A | 0.9900 |
C2—H2B | 0.9900 | C16—H16B | 0.9900 |
C3—C4 | 1.542 (3) | C17—C18 | 1.542 (3) |
C3—H3A | 0.9900 | C17—H17A | 0.9900 |
C3—H3B | 0.9900 | C17—H17B | 0.9900 |
C4—C5 | 1.506 (3) | C18—C19 | 1.510 (3) |
C4—H4A | 1.0000 | C18—H18A | 1.0000 |
C5—H5A | 0.9900 | C19—H19A | 0.9900 |
C5—H5B | 0.9900 | C19—H19B | 0.9900 |
C6—H6A | 0.9800 | C20—H20A | 0.9800 |
C6—H6B | 0.9800 | C20—H20B | 0.9800 |
C6—H6C | 0.9800 | C20—H20C | 0.9800 |
C7—C8 | 1.399 (3) | C21—C22 | 1.395 (3) |
C7—C14 | 1.522 (3) | C21—C28 | 1.514 (3) |
C7—H7A | 0.9500 | C21—H21A | 0.9500 |
C8—C9 | 1.506 (3) | C22—C23 | 1.514 (3) |
C8—H8A | 0.9500 | C22—H22A | 0.9500 |
C9—C10 | 1.529 (3) | C23—C24 | 1.540 (3) |
C9—H9A | 0.9900 | C23—H23A | 0.9900 |
C9—H9B | 0.9900 | C23—H23B | 0.9900 |
C10—C11 | 1.521 (3) | C24—C25 | 1.510 (3) |
C10—H10A | 0.9900 | C24—H24A | 0.9900 |
C10—H10B | 0.9900 | C24—H24B | 0.9900 |
C11—C12 | 1.407 (3) | C25—C26 | 1.398 (3) |
C11—H11A | 0.9500 | C25—H25A | 0.9500 |
C12—C13 | 1.503 (3) | C26—C27 | 1.519 (3) |
C12—H12A | 0.9500 | C26—H26A | 0.9500 |
C13—C14 | 1.527 (3) | C27—C28 | 1.533 (3) |
C13—H13A | 0.9900 | C27—H27A | 0.9900 |
C13—H13B | 0.9900 | C27—H27B | 0.9900 |
C14—H14A | 0.9900 | C28—H28A | 0.9900 |
C14—H14B | 0.9900 | C28—H28B | 0.9900 |
C12—Rh1—C11 | 38.94 (7) | C25—Rh2—C26 | 38.76 (8) |
C12—Rh1—N1 | 87.10 (7) | C25—Rh2—C21 | 98.69 (7) |
C11—Rh1—N1 | 90.70 (7) | C26—Rh2—C21 | 82.18 (7) |
C12—Rh1—C8 | 98.37 (7) | C25—Rh2—N2 | 90.73 (7) |
C11—Rh1—C8 | 82.13 (8) | C26—Rh2—N2 | 90.97 (7) |
N1—Rh1—C8 | 160.31 (7) | C21—Rh2—N2 | 154.68 (7) |
C12—Rh1—C7 | 81.99 (7) | C25—Rh2—C22 | 82.24 (9) |
C11—Rh1—C7 | 90.51 (8) | C26—Rh2—C22 | 90.28 (9) |
N1—Rh1—C7 | 161.01 (7) | C21—Rh2—C22 | 38.08 (8) |
C8—Rh1—C7 | 38.17 (7) | N2—Rh2—C22 | 167.08 (8) |
C12—Rh1—Cl1 | 158.38 (6) | C25—Rh2—Cl2 | 156.03 (6) |
C11—Rh1—Cl1 | 162.67 (6) | C26—Rh2—Cl2 | 165.20 (6) |
N1—Rh1—Cl1 | 90.47 (4) | C21—Rh2—Cl2 | 91.21 (5) |
C8—Rh1—Cl1 | 91.09 (5) | N2—Rh2—Cl2 | 89.43 (5) |
C7—Rh1—Cl1 | 93.97 (6) | C22—Rh2—Cl2 | 92.63 (7) |
C4—N1—C1 | 102.50 (14) | C15—N2—C18 | 103.84 (14) |
C4—N1—Rh1 | 119.03 (12) | C15—N2—Rh2 | 112.21 (12) |
C1—N1—Rh1 | 114.78 (11) | C18—N2—Rh2 | 119.48 (12) |
C4—N1—H1 | 106.6 | C15—N2—H2 | 106.9 |
C1—N1—H1 | 106.6 | C18—N2—H2 | 106.9 |
Rh1—N1—H1 | 106.6 | Rh2—N2—H2 | 106.9 |
C6—O1—C5 | 113.45 (15) | C19—O2—C20 | 111.74 (16) |
N1—C1—C2 | 104.90 (15) | N2—C15—C16 | 104.54 (16) |
N1—C1—H1A | 110.8 | N2—C15—H15A | 110.8 |
C2—C1—H1A | 110.8 | C16—C15—H15A | 110.8 |
N1—C1—H1B | 110.8 | N2—C15—H15B | 110.8 |
C2—C1—H1B | 110.8 | C16—C15—H15B | 110.8 |
H1A—C1—H1B | 108.8 | H15A—C15—H15B | 108.9 |
C1—C2—C3 | 104.37 (16) | C15—C16—C17 | 104.50 (16) |
C1—C2—H2A | 110.9 | C15—C16—H16A | 110.9 |
C3—C2—H2A | 110.9 | C17—C16—H16A | 110.9 |
C1—C2—H2B | 110.9 | C15—C16—H16B | 110.9 |
C3—C2—H2B | 110.9 | C17—C16—H16B | 110.9 |
H2A—C2—H2B | 108.9 | H16A—C16—H16B | 108.9 |
C4—C3—C2 | 104.89 (16) | C16—C17—C18 | 105.80 (16) |
C4—C3—H3A | 110.8 | C16—C17—H17A | 110.6 |
C2—C3—H3A | 110.8 | C18—C17—H17A | 110.6 |
C4—C3—H3B | 110.8 | C16—C17—H17B | 110.6 |
C2—C3—H3B | 110.8 | C18—C17—H17B | 110.6 |
H3A—C3—H3B | 108.8 | H17A—C17—H17B | 108.7 |
N1—C4—C5 | 110.67 (15) | N2—C18—C19 | 110.83 (15) |
N1—C4—C3 | 104.52 (15) | N2—C18—C17 | 105.67 (15) |
C5—C4—C3 | 114.78 (18) | C19—C18—C17 | 114.30 (16) |
N1—C4—H4A | 108.9 | N2—C18—H18A | 108.6 |
C5—C4—H4A | 108.9 | C19—C18—H18A | 108.6 |
C3—C4—H4A | 108.9 | C17—C18—H18A | 108.6 |
O1—C5—C4 | 107.16 (15) | O2—C19—C18 | 107.61 (15) |
O1—C5—H5A | 110.3 | O2—C19—H19A | 110.2 |
C4—C5—H5A | 110.3 | C18—C19—H19A | 110.2 |
O1—C5—H5B | 110.3 | O2—C19—H19B | 110.2 |
C4—C5—H5B | 110.3 | C18—C19—H19B | 110.2 |
H5A—C5—H5B | 108.5 | H19A—C19—H19B | 108.5 |
O1—C6—H6A | 109.5 | O2—C20—H20A | 109.5 |
O1—C6—H6B | 109.5 | O2—C20—H20B | 109.5 |
H6A—C6—H6B | 109.5 | H20A—C20—H20B | 109.5 |
O1—C6—H6C | 109.5 | O2—C20—H20C | 109.5 |
H6A—C6—H6C | 109.5 | H20A—C20—H20C | 109.5 |
H6B—C6—H6C | 109.5 | H20B—C20—H20C | 109.5 |
C8—C7—C14 | 123.11 (18) | C22—C21—C28 | 125.83 (19) |
C8—C7—Rh1 | 70.17 (11) | C22—C21—Rh2 | 71.97 (13) |
C14—C7—Rh1 | 112.11 (13) | C28—C21—Rh2 | 109.72 (13) |
C8—C7—H7A | 118.4 | C22—C21—H21A | 117.1 |
C14—C7—H7A | 118.4 | C28—C21—H21A | 117.1 |
Rh1—C7—H7A | 87.8 | Rh2—C21—H21A | 88.2 |
C7—C8—C9 | 126.34 (17) | C21—C22—C23 | 124.4 (2) |
C7—C8—Rh1 | 71.66 (11) | C21—C22—Rh2 | 69.95 (12) |
C9—C8—Rh1 | 109.19 (13) | C23—C22—Rh2 | 112.47 (16) |
C7—C8—H8A | 116.8 | C21—C22—H22A | 117.8 |
C9—C8—H8A | 116.8 | C23—C22—H22A | 117.8 |
Rh1—C8—H8A | 89.1 | Rh2—C22—H22A | 87.6 |
C8—C9—C10 | 113.95 (16) | C22—C23—C24 | 112.19 (17) |
C8—C9—H9A | 108.8 | C22—C23—H23A | 109.2 |
C10—C9—H9A | 108.8 | C24—C23—H23A | 109.2 |
C8—C9—H9B | 108.8 | C22—C23—H23B | 109.2 |
C10—C9—H9B | 108.8 | C24—C23—H23B | 109.2 |
H9A—C9—H9B | 107.7 | H23A—C23—H23B | 107.9 |
C11—C10—C9 | 111.37 (16) | C25—C24—C23 | 112.97 (16) |
C11—C10—H10A | 109.4 | C25—C24—H24A | 109.0 |
C9—C10—H10A | 109.4 | C23—C24—H24A | 109.0 |
C11—C10—H10B | 109.4 | C25—C24—H24B | 109.0 |
C9—C10—H10B | 109.4 | C23—C24—H24B | 109.0 |
H10A—C10—H10B | 108.0 | H24A—C24—H24B | 107.8 |
C12—C11—C10 | 124.88 (19) | C26—C25—C24 | 124.98 (18) |
C12—C11—Rh1 | 69.85 (10) | C26—C25—Rh2 | 71.28 (10) |
C10—C11—Rh1 | 113.50 (13) | C24—C25—Rh2 | 110.91 (13) |
C12—C11—H11A | 117.6 | C26—C25—H25A | 117.5 |
C10—C11—H11A | 117.6 | C24—C25—H25A | 117.5 |
Rh1—C11—H11A | 86.6 | Rh2—C25—H25A | 87.8 |
C11—C12—C13 | 126.47 (18) | C25—C26—C27 | 123.65 (18) |
C11—C12—Rh1 | 71.21 (10) | C25—C26—Rh2 | 69.96 (10) |
C13—C12—Rh1 | 110.29 (13) | C27—C26—Rh2 | 113.19 (13) |
C11—C12—H12A | 116.8 | C25—C26—H26A | 118.2 |
C13—C12—H12A | 116.8 | C27—C26—H26A | 118.2 |
Rh1—C12—H12A | 88.4 | Rh2—C26—H26A | 86.9 |
C12—C13—C14 | 112.74 (16) | C26—C27—C28 | 111.86 (16) |
C12—C13—H13A | 109.0 | C26—C27—H27A | 109.2 |
C14—C13—H13A | 109.0 | C28—C27—H27A | 109.2 |
C12—C13—H13B | 109.0 | C26—C27—H27B | 109.2 |
C14—C13—H13B | 109.0 | C28—C27—H27B | 109.2 |
H13A—C13—H13B | 107.8 | H27A—C27—H27B | 107.9 |
C7—C14—C13 | 111.54 (16) | C21—C28—C27 | 112.25 (17) |
C7—C14—H14A | 109.3 | C21—C28—H28A | 109.2 |
C13—C14—H14A | 109.3 | C27—C28—H28A | 109.2 |
C7—C14—H14B | 109.3 | C21—C28—H28B | 109.2 |
C13—C14—H14B | 109.3 | C27—C28—H28B | 109.2 |
H14A—C14—H14B | 108.0 | H28A—C28—H28B | 107.9 |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···Cl1i | 0.93 | 2.59 | 3.4888 (16) | 163 |
N2—H2···Cl2ii | 0.93 | 2.51 | 3.4028 (16) | 162 |
Symmetry codes: (i) x, y+1, z; (ii) x+1, y, z. |
Experimental details
Crystal data | |
Chemical formula | [RhCl(C8H12)(C6H13NO)] |
Mr | 361.71 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 150 |
a, b, c (Å) | 6.5499 (2), 6.6563 (2), 18.8540 (7) |
α, β, γ (°) | 92.253 (3), 95.026 (3), 114.841 (2) |
V (Å3) | 740.44 (4) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 1.32 |
Crystal size (mm) | 0.25 × 0.18 × 0.10 |
Data collection | |
Diffractometer | Bruker–Nonius KappaCCD |
Absorption correction | Multi-scan (SADABS; Bruker, 2002) |
Tmin, Tmax | 0.730, 0.880 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 19576, 7489, 7246 |
Rint | 0.019 |
(sin θ/λ)max (Å−1) | 0.676 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.016, 0.035, 1.06 |
No. of reflections | 7489 |
No. of parameters | 327 |
No. of restraints | 3 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.37, −0.35 |
Absolute structure | Flack (1983) |
Absolute structure parameter | −0.013 (13) |
Computer programs: COLLECT (Bruker, 2002), EVALCCD (Duisenberg et al., 2003), SHELXTL-NT (Bruker, 2002), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).
Rh1—N1 | 2.1236 (15) | Rh2—N2 | 2.1263 (15) |
Rh1—Cl1 | 2.3960 (6) | Rh2—Cl2 | 2.3870 (5) |
Rh1—C11 | 2.1199 (17) | Rh2—C25 | 2.0985 (18) |
Rh1—C12 | 2.1021 (17) | Rh2—C26 | 2.1154 (18) |
Rh1—C7 | 2.1491 (19) | Rh2—C21 | 2.1242 (18) |
Rh1—C8 | 2.1300 (19) | Rh2—C22 | 2.150 (2) |
N1—Rh1—Cl1 | 90.47 (4) | N2—Rh2—Cl2 | 89.43 (5) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···Cl1i | 0.93 | 2.59 | 3.4888 (16) | 162.8 |
N2—H2···Cl2ii | 0.93 | 2.51 | 3.4028 (16) | 161.5 |
Symmetry codes: (i) x, y+1, z; (ii) x+1, y, z. |
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Chlorido(η4-1,5-cyclooctadiene)[κN-(S)-2-methoxymethylpyrrolidine]rhodium(I), [Rh(Cl)(η4-C8H12){(S)-C6H13NO}] (I), represents the O-methylated analogue of the previously described prolinol complexes [Rh(Cl)(η4-C8H12){(R)-C5H11NO}] and [Rh(Cl)(η4-C8H12){(S)-C5H11NO}] which themselves belong to a family of catalytically attractive rhodium compounds containing β-amino alcohol ligands (Dahlenburg et al., 2007). Complex (I) crystallizes from CDCl3 in the triclinic space group P1 with two independent moieties per cell.
Not unexpectedly, neither the Rh—Cl distances nor the Rh—N bond lengths deviate significantly from the corresponding dimensions observed fo closely related chlorido rhodium complexes in the literature possessing N-bonded ethanolamine, valinol, prolinol, and norephedrine ligands [Rh—Cl = 2.381 → 2.398 Å and Rh—N = 2.127→ 2.137 Å] (Dahlenburg et al., 2007).
In the solid state the individual complexes of (I) are assembled through N—H···Cl hydrogen bonds (Table 2). The (R)-enantiomer of the parent prolinol compound [Rh(Cl)(η4-C8H12)(C5H11NO)] shows similar N—H···Cl (and O—H···Cl) hydrogen-bonding between two crystallographically independent molecules (Dahlenburg et al., 2007).