Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801014568/ob6068sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536801014568/ob60681sup2.hkl |
CCDC reference: 175335
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.016 Å
- Disorder in solvent or counterion
- R factor = 0.065
- wR factor = 0.182
- Data-to-parameter ratio = 9.5
checkCIF results
No syntax errors found ADDSYM reports no extra symmetry
Alert Level A:
THETM_01 Alert A The value of sine(theta_max)/wavelength is less than 0.550 Calculated sin(theta_max)/wavelength = 0.5378
Alert Level C:
ABSTM_02 Alert C The ratio of expected to reported Tmax/Tmin(RR') is < 0.90 Tmin and Tmax reported: 0.448 0.898 Tmin' and Tmax expected: 0.581 0.898 RR' = 0.771 Please check that your absorption correction is appropriate. REFNR_01 Alert C Ratio of reflections to parameters is < 10 for a centrosymmetric structure sine(theta)/lambda 0.5378 Proportion of unique data used 0.9987 Ratio reflections to parameters 9.5200 PLAT_302 Alert C Anion/Solvent Disorder ....................... 36.00 Perc. General Notes
ABSTY_01 Extra text has been found in the _exptl_absorpt_correction_type field, which should be only a single keyword. A literature citation should be included in the _exptl_absorpt_process_details field.
1 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
3 Alert Level C = Please check
Reaction of RhCl3 with meso-2,3,7,11,12-pentamethyl-3,7,11,17-tetra- azabicyclo[11.3.1]heptadeca-1(17),13,15-triene in MeOH, followed by addition of PF6-. Crystals of (1) were grown from CH3NO2 solution. Elemental analysis, found: C 35.9, H 5.17, N 8.5%; calculated for C18H32Cl2F6N4PRh: C 34.6, H 5.17, N 9.0%.
The primary absorption correction was semi-empirical (North et al., 1968), supplemented by calculated corrections (Walker & Stuart, 1983). The largest residuals in the final ΔF synthesis lie near the metal atom. There is disorder in the equatorial F atoms of the anion which was modelled by allowing two orientations for each of these four atoms, F2—F5. Extensive restraints were applied to P–F distances, F—P—F angles and anisotropic displacement parameters. The occupancies of these orientations refined to 0.50 (3), indicating that they are equally occupied, and so all were set equal to 0.5. H atoms were placed geometrically and refining riding on their parent C atoms at distances of 0.93, 0.96, 0.97 and 0.98 Å for aromatic, methine, methylene and methyl groups, respectively, with Uiso(H) = xUeq(C), where x = 1.5 for methyl H atoms and 1.2 for all others.
Data collection: CAD-4 Software (Enraf-Nonius, 1989); cell refinement: CAD-4 Software; data reduction: CADABS (Gould & Smith, 1986); program(s) used to solve structure: SHELX76 (Sheldrick, 1976); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL/PC (Sheldrick, 1994); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2001).
[RhCl2(C18H32N4)]PF6 | Z = 2 |
Mr = 623.26 | F(000) = 632 |
Triclinic, P1 | Dx = 1.741 Mg m−3 |
a = 7.949 (5) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 11.067 (5) Å | Cell parameters from 19 reflections |
c = 14.116 (5) Å | θ = 12–13° |
α = 74.22 (5)° | µ = 1.07 mm−1 |
β = 86.26 (5)° | T = 293 K |
γ = 84.67 (5)° | Lath, yellow |
V = 1188.7 (10) Å3 | 0.5 × 0.2 × 0.1 mm |
Enraf-Nonius CAD-4 diffractometer | 2378 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.00 |
Graphite monochromator | θmax = 22.5°, θmin = 2.1° |
ω–2θ scans | h = −8→8 |
Absorption correction: ψ scans; part of the refinement model (ΔF) (North et al., 1968; Walker & Stuart, 1983) | k = −11→11 |
Tmin = 0.448, Tmax = 0.898 | l = 0→15 |
3098 measured reflections | 2 standard reflections every 60 reflections |
3098 independent reflections | intensity decay: 3% |
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)] = 0.065 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.182 | H-atom parameters constrained |
S = 1.00 | w = 1/[σ2(Fo2) + (0.149P)2] where P = (Fo2 + 2Fc2)/3 |
3094 reflections | (Δ/σ)max = 0.003 |
325 parameters | Δρmax = 1.92 e Å−3 |
360 restraints | Δρmin = −1.77 e Å−3 |
[RhCl2(C18H32N4)]PF6 | γ = 84.67 (5)° |
Mr = 623.26 | V = 1188.7 (10) Å3 |
Triclinic, P1 | Z = 2 |
a = 7.949 (5) Å | Mo Kα radiation |
b = 11.067 (5) Å | µ = 1.07 mm−1 |
c = 14.116 (5) Å | T = 293 K |
α = 74.22 (5)° | 0.5 × 0.2 × 0.1 mm |
β = 86.26 (5)° |
Enraf-Nonius CAD-4 diffractometer | 2378 reflections with I > 2σ(I) |
Absorption correction: ψ scans; part of the refinement model (ΔF) (North et al., 1968; Walker & Stuart, 1983) | Rint = 0.00 |
Tmin = 0.448, Tmax = 0.898 | θmax = 22.5° |
3098 measured reflections | 2 standard reflections every 60 reflections |
3098 independent reflections | intensity decay: 3% |
R[F2 > 2σ(F2)] = 0.065 | 360 restraints |
wR(F2) = 0.182 | H-atom parameters constrained |
S = 1.00 | Δρmax = 1.92 e Å−3 |
3094 reflections | Δρmin = −1.77 e Å−3 |
325 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. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Rh | 0.09546 (7) | 0.23461 (6) | 0.21425 (5) | 0.0284 (3) | |
Cl1 | 0.2853 (3) | 0.1324 (2) | 0.33661 (18) | 0.0466 (6) | |
Cl2 | −0.1108 (3) | 0.3363 (2) | 0.10132 (18) | 0.0469 (6) | |
N3 | 0.1235 (9) | 0.4127 (7) | 0.2420 (6) | 0.0413 (16) | |
N7 | 0.2980 (8) | 0.2396 (7) | 0.1060 (6) | 0.0447 (17) | |
N11 | 0.0066 (9) | 0.0580 (7) | 0.2113 (6) | 0.0420 (16) | |
N17 | −0.0790 (8) | 0.2230 (7) | 0.3208 (5) | 0.0344 (15) | |
C1 | −0.1075 (11) | 0.3213 (8) | 0.3597 (7) | 0.044 (2) | |
C2 | 0.0294 (13) | 0.4128 (9) | 0.3393 (8) | 0.052 (2) | |
H2 | −0.0280 | 0.4971 | 0.3310 | 0.062* | |
C2A | 0.1309 (17) | 0.3866 (11) | 0.4284 (9) | 0.073 (3) | |
H2A1 | 0.2170 | 0.4448 | 0.4171 | 0.110* | |
H2A2 | 0.1827 | 0.3021 | 0.4421 | 0.110* | |
H2A3 | 0.0585 | 0.3958 | 0.4835 | 0.110* | |
C3N | 0.0398 (14) | 0.5275 (9) | 0.1698 (9) | 0.058 (3) | |
H3N1 | −0.0781 | 0.5166 | 0.1674 | 0.087* | |
H3N2 | 0.0929 | 0.5366 | 0.1054 | 0.087* | |
H3N3 | 0.0520 | 0.6015 | 0.1910 | 0.087* | |
C4 | 0.3075 (13) | 0.4366 (10) | 0.2398 (8) | 0.056 (2) | |
H4A | 0.3626 | 0.3728 | 0.2923 | 0.067* | |
H4B | 0.3158 | 0.5177 | 0.2524 | 0.067* | |
C5 | 0.3994 (12) | 0.4356 (10) | 0.1433 (9) | 0.062 (3) | |
H5A | 0.3297 | 0.4841 | 0.0900 | 0.074* | |
H5B | 0.5029 | 0.4772 | 0.1387 | 0.074* | |
C6 | 0.4430 (11) | 0.3071 (11) | 0.1291 (9) | 0.059 (3) | |
H6A | 0.4940 | 0.2545 | 0.1884 | 0.071* | |
H6B | 0.5282 | 0.3140 | 0.0759 | 0.071* | |
C7N | 0.2509 (13) | 0.3016 (11) | 0.0029 (7) | 0.061 (3) | |
H7NA | 0.2014 | 0.3853 | −0.0015 | 0.091* | |
H7NB | 0.1707 | 0.2539 | −0.0163 | 0.091* | |
H7NC | 0.3501 | 0.3055 | −0.0400 | 0.091* | |
C8 | 0.3750 (12) | 0.1091 (10) | 0.1117 (9) | 0.060 (3) | |
H8A | 0.4341 | 0.0790 | 0.1727 | 0.072* | |
H8B | 0.4592 | 0.1146 | 0.0581 | 0.072* | |
C9 | 0.2582 (14) | 0.0116 (11) | 0.1074 (9) | 0.067 (3) | |
H9A | 0.1843 | 0.0470 | 0.0529 | 0.080* | |
H9B | 0.3254 | −0.0597 | 0.0933 | 0.080* | |
C10 | 0.1506 (14) | −0.0353 (9) | 0.1994 (9) | 0.057 (2) | |
H10A | 0.1057 | −0.1131 | 0.1977 | 0.069* | |
H10B | 0.2207 | −0.0535 | 0.2561 | 0.069* | |
C11N | −0.1140 (14) | 0.0651 (10) | 0.1309 (9) | 0.062 (3) | |
H111 | −0.2084 | 0.1242 | 0.1355 | 0.094* | |
H112 | −0.1536 | −0.0165 | 0.1386 | 0.094* | |
H113 | −0.0564 | 0.0919 | 0.0677 | 0.094* | |
C12 | −0.0983 (12) | 0.0120 (9) | 0.3079 (8) | 0.049 (2) | |
H12 | −0.1951 | −0.0266 | 0.2919 | 0.059* | |
C12A | −0.0088 (14) | −0.0868 (9) | 0.3910 (8) | 0.061 (3) | |
H121 | 0.0367 | −0.1571 | 0.3672 | 0.091* | |
H122 | −0.0882 | −0.1151 | 0.4450 | 0.091* | |
H123 | 0.0813 | −0.0503 | 0.4128 | 0.091* | |
C13 | −0.1693 (10) | 0.1245 (9) | 0.3439 (7) | 0.0420 (19) | |
C14 | −0.3077 (12) | 0.1216 (11) | 0.4091 (8) | 0.062 (3) | |
H14 | −0.3725 | 0.0525 | 0.4268 | 0.074* | |
C15 | −0.3471 (12) | 0.2223 (12) | 0.4469 (8) | 0.061 (3) | |
H15 | −0.4432 | 0.2236 | 0.4879 | 0.074* | |
C16 | −0.2456 (13) | 0.3232 (11) | 0.4248 (8) | 0.060 (3) | |
H16 | −0.2697 | 0.3900 | 0.4530 | 0.072* | |
P | 0.4075 (3) | 0.2810 (2) | 0.7110 (2) | 0.0533 (7) | |
F1 | 0.3713 (8) | 0.4012 (6) | 0.7469 (6) | 0.102 (3) | |
F2 | 0.483 (3) | 0.3606 (9) | 0.6136 (8) | 0.185 (12) | 0.50 |
F3 | 0.5818 (13) | 0.2598 (12) | 0.7555 (16) | 0.196 (12) | 0.50 |
F4 | 0.2326 (15) | 0.3034 (14) | 0.6664 (16) | 0.157 (11) | 0.50 |
F5 | 0.332 (3) | 0.2024 (9) | 0.8085 (8) | 0.168 (11) | 0.50 |
F2' | 0.450 (3) | 0.2057 (11) | 0.8163 (7) | 0.205 (13) | 0.50 |
F3' | 0.2197 (11) | 0.2543 (14) | 0.7345 (17) | 0.155 (11) | 0.50 |
F4' | 0.5934 (10) | 0.3083 (14) | 0.6880 (15) | 0.115 (8) | 0.50 |
F5' | 0.364 (3) | 0.3566 (13) | 0.6064 (6) | 0.154 (9) | 0.50 |
F6 | 0.4437 (10) | 0.1610 (6) | 0.6750 (7) | 0.137 (4) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Rh | 0.0221 (4) | 0.0299 (4) | 0.0347 (5) | −0.0043 (3) | 0.0019 (3) | −0.0112 (3) |
Cl1 | 0.0393 (12) | 0.0457 (13) | 0.0563 (16) | 0.0019 (10) | −0.0134 (11) | −0.0153 (12) |
Cl2 | 0.0362 (11) | 0.0530 (14) | 0.0478 (15) | −0.0005 (10) | −0.0068 (10) | −0.0072 (11) |
N3 | 0.042 (4) | 0.038 (4) | 0.046 (4) | −0.010 (3) | 0.002 (3) | −0.014 (3) |
N7 | 0.032 (3) | 0.057 (4) | 0.047 (4) | −0.007 (3) | 0.013 (3) | −0.018 (4) |
N11 | 0.042 (4) | 0.035 (4) | 0.053 (4) | −0.003 (3) | −0.008 (3) | −0.017 (3) |
N17 | 0.024 (3) | 0.041 (4) | 0.040 (4) | −0.006 (3) | 0.004 (3) | −0.014 (3) |
C1 | 0.045 (5) | 0.038 (5) | 0.039 (5) | 0.010 (3) | 0.006 (4) | −0.001 (4) |
C2 | 0.064 (6) | 0.039 (5) | 0.058 (5) | −0.001 (4) | 0.007 (4) | −0.026 (4) |
C2A | 0.099 (9) | 0.073 (8) | 0.058 (6) | −0.028 (7) | 0.001 (6) | −0.029 (6) |
C3N | 0.072 (6) | 0.034 (5) | 0.069 (7) | −0.002 (4) | −0.002 (5) | −0.014 (5) |
C4 | 0.054 (5) | 0.055 (6) | 0.067 (7) | −0.032 (4) | 0.000 (4) | −0.022 (5) |
C5 | 0.044 (5) | 0.064 (6) | 0.080 (8) | −0.028 (5) | 0.009 (5) | −0.019 (6) |
C6 | 0.028 (4) | 0.079 (6) | 0.072 (7) | −0.011 (4) | 0.007 (4) | −0.023 (6) |
C7N | 0.052 (6) | 0.092 (8) | 0.035 (5) | −0.002 (5) | 0.016 (4) | −0.017 (5) |
C8 | 0.043 (5) | 0.070 (6) | 0.069 (8) | 0.015 (4) | 0.005 (5) | −0.029 (5) |
C9 | 0.070 (7) | 0.065 (6) | 0.073 (8) | 0.015 (5) | 0.000 (5) | −0.040 (6) |
C10 | 0.074 (6) | 0.031 (5) | 0.073 (7) | 0.008 (4) | −0.009 (5) | −0.026 (5) |
C11N | 0.063 (6) | 0.057 (7) | 0.071 (7) | −0.010 (5) | −0.028 (5) | −0.017 (6) |
C12 | 0.042 (5) | 0.040 (5) | 0.063 (6) | −0.019 (4) | −0.011 (4) | −0.003 (4) |
C12A | 0.075 (7) | 0.045 (6) | 0.059 (7) | −0.011 (5) | −0.011 (5) | −0.002 (5) |
C13 | 0.032 (4) | 0.052 (5) | 0.036 (5) | −0.011 (3) | 0.000 (3) | 0.000 (4) |
C14 | 0.039 (5) | 0.070 (7) | 0.067 (8) | −0.012 (4) | 0.007 (4) | −0.002 (5) |
C15 | 0.031 (5) | 0.095 (7) | 0.049 (7) | 0.001 (4) | 0.013 (4) | −0.009 (5) |
C16 | 0.048 (5) | 0.077 (7) | 0.054 (7) | 0.014 (4) | 0.007 (4) | −0.024 (6) |
P | 0.0528 (15) | 0.0430 (15) | 0.067 (2) | −0.0049 (11) | 0.0085 (13) | −0.0223 (13) |
F1 | 0.082 (5) | 0.090 (5) | 0.166 (8) | −0.006 (4) | −0.005 (5) | −0.090 (5) |
F2 | 0.31 (3) | 0.105 (12) | 0.124 (15) | −0.08 (2) | 0.128 (17) | −0.024 (11) |
F3 | 0.101 (10) | 0.034 (9) | 0.44 (4) | −0.004 (7) | −0.145 (16) | −0.013 (14) |
F4 | 0.116 (14) | 0.15 (2) | 0.25 (3) | 0.031 (11) | −0.109 (17) | −0.119 (19) |
F5 | 0.29 (3) | 0.169 (14) | 0.072 (11) | −0.17 (2) | 0.051 (12) | −0.035 (9) |
F2' | 0.26 (3) | 0.218 (17) | 0.069 (8) | 0.15 (2) | 0.036 (12) | 0.013 (8) |
F3' | 0.071 (9) | 0.105 (15) | 0.32 (3) | −0.043 (9) | 0.093 (15) | −0.131 (19) |
F4' | 0.046 (6) | 0.088 (15) | 0.22 (2) | −0.011 (7) | 0.005 (9) | −0.061 (15) |
F5' | 0.154 (18) | 0.211 (16) | 0.073 (8) | 0.087 (18) | −0.026 (11) | −0.027 (8) |
F6 | 0.124 (6) | 0.083 (5) | 0.234 (10) | −0.029 (4) | 0.073 (7) | −0.105 (6) |
Rh—Cl1 | 2.345 (3) | C7N—H7NB | 0.9600 |
Rh—Cl2 | 2.349 (3) | C7N—H7NC | 0.9600 |
Rh—N3 | 2.145 (7) | C8—C9 | 1.503 (16) |
Rh—N7 | 2.140 (7) | C8—H8A | 0.9700 |
Rh—N11 | 2.150 (7) | C8—H8B | 0.9700 |
Rh—N17 | 1.964 (7) | C9—C10 | 1.504 (16) |
N3—C4 | 1.507 (12) | C9—H9A | 0.9700 |
N3—C2 | 1.521 (13) | C9—H9B | 0.9700 |
N3—C3N | 1.524 (12) | C10—H10A | 0.9700 |
N7—C7N | 1.486 (13) | C10—H10B | 0.9700 |
N7—C8 | 1.499 (12) | C11N—H111 | 0.9600 |
N7—C6 | 1.528 (12) | C11N—H112 | 0.9600 |
N11—C10 | 1.501 (12) | C11N—H113 | 0.9600 |
N11—C11N | 1.514 (12) | C12—C13 | 1.518 (14) |
N11—C12 | 1.539 (13) | C12—C12A | 1.531 (14) |
N17—C13 | 1.316 (11) | C12—H12 | 0.9800 |
N17—C1 | 1.342 (11) | C12A—H121 | 0.9600 |
C1—C16 | 1.387 (13) | C12A—H122 | 0.9600 |
C1—C2 | 1.516 (14) | C12A—H123 | 0.9600 |
C2—C2A | 1.485 (16) | C13—C14 | 1.385 (14) |
C2—H2 | 0.9800 | C14—C15 | 1.364 (16) |
C2A—H2A1 | 0.9600 | C14—H14 | 0.9300 |
C2A—H2A2 | 0.9600 | C15—C16 | 1.393 (16) |
C2A—H2A3 | 0.9600 | C15—H15 | 0.9300 |
C3N—H3N1 | 0.9600 | C16—H16 | 0.9300 |
C3N—H3N2 | 0.9600 | P—F1 | 1.545 (5) |
C3N—H3N3 | 0.9600 | P—F2 | 1.537 (7) |
C4—C5 | 1.507 (15) | P—F3 | 1.530 (7) |
C4—H4A | 0.9700 | P—F4 | 1.535 (7) |
C4—H4B | 0.9700 | P—F5 | 1.534 (7) |
C5—C6 | 1.495 (15) | P—F6 | 1.543 (5) |
C5—H5A | 0.9700 | P—F2' | 1.537 (7) |
C5—H5B | 0.9700 | P—F3' | 1.546 (7) |
C6—H6A | 0.9700 | P—F4' | 1.532 (7) |
C6—H6B | 0.9700 | P—F5' | 1.530 (7) |
C7N—H7NA | 0.9600 | ||
Cl1—Rh—Cl2 | 175.61 (8) | H7NA—C7N—H7NC | 109.5 |
Cl1—Rh—N3 | 91.1 (2) | H7NB—C7N—H7NC | 109.5 |
Cl1—Rh—N7 | 88.9 (2) | N7—C8—C9 | 117.5 (8) |
Cl1—Rh—N11 | 91.3 (2) | N7—C8—H8A | 107.9 |
Cl1—Rh—N17 | 86.9 (2) | C9—C8—H8A | 107.9 |
Cl2—Rh—N3 | 88.3 (2) | N7—C8—H8B | 107.9 |
Cl2—Rh—N7 | 95.4 (2) | C9—C8—H8B | 107.9 |
Cl2—Rh—N11 | 88.2 (2) | H8A—C8—H8B | 107.2 |
Cl2—Rh—N17 | 88.7 (2) | C10—C9—C8 | 115.1 (10) |
N3—Rh—N7 | 97.9 (3) | C10—C9—H9A | 108.5 |
N3—Rh—N11 | 164.5 (3) | C8—C9—H9A | 108.5 |
N3—Rh—N17 | 82.5 (3) | C10—C9—H9B | 108.5 |
N7—Rh—N11 | 97.5 (3) | C8—C9—H9B | 108.5 |
N7—Rh—N17 | 175.9 (3) | H9A—C9—H9B | 107.5 |
N11—Rh—N17 | 82.3 (3) | N11—C10—C9 | 112.6 (8) |
C4—N3—C2 | 113.8 (8) | N11—C10—H10A | 109.1 |
C4—N3—C3N | 105.9 (7) | C9—C10—H10A | 109.1 |
C2—N3—C3N | 103.1 (7) | N11—C10—H10B | 109.1 |
C4—N3—Rh | 111.0 (6) | C9—C10—H10B | 109.1 |
C2—N3—Rh | 107.3 (5) | H10A—C10—H10B | 107.8 |
C3N—N3—Rh | 115.7 (6) | N11—C11N—H111 | 109.5 |
C7N—N7—C8 | 108.8 (8) | N11—C11N—H112 | 109.5 |
C7N—N7—C6 | 107.9 (8) | H111—C11N—H112 | 109.5 |
C8—N7—C6 | 103.9 (7) | N11—C11N—H113 | 109.5 |
C7N—N7—Rh | 114.9 (6) | H111—C11N—H113 | 109.5 |
C8—N7—Rh | 110.4 (6) | H112—C11N—H113 | 109.5 |
C6—N7—Rh | 110.3 (6) | C13—C12—C12A | 110.2 (9) |
C10—N11—C11N | 106.6 (8) | C13—C12—N11 | 109.3 (7) |
C10—N11—C12 | 112.4 (7) | C12A—C12—N11 | 116.3 (8) |
C11N—N11—C12 | 104.5 (7) | C13—C12—H12 | 106.8 |
C10—N11—Rh | 111.5 (6) | C12A—C12—H12 | 106.8 |
C11N—N11—Rh | 115.5 (6) | N11—C12—H12 | 106.8 |
C12—N11—Rh | 106.4 (5) | C12—C12A—H121 | 109.5 |
C13—N17—C1 | 124.2 (8) | C12—C12A—H122 | 109.5 |
C13—N17—Rh | 118.1 (6) | H121—C12A—H122 | 109.5 |
C1—N17—Rh | 117.5 (6) | C12—C12A—H123 | 109.5 |
N17—C1—C16 | 118.5 (9) | H121—C12A—H123 | 109.5 |
N17—C1—C2 | 116.1 (8) | H122—C12A—H123 | 109.5 |
C16—C1—C2 | 124.9 (9) | N17—C13—C14 | 119.4 (10) |
C2A—C2—C1 | 108.4 (9) | N17—C13—C12 | 116.5 (8) |
C2A—C2—N3 | 117.6 (9) | C14—C13—C12 | 123.5 (9) |
C1—C2—N3 | 110.1 (8) | C15—C14—C13 | 118.6 (10) |
C2A—C2—H2 | 106.7 | C15—C14—H14 | 120.7 |
C1—C2—H2 | 106.7 | C13—C14—H14 | 120.7 |
N3—C2—H2 | 106.7 | C14—C15—C16 | 121.0 (9) |
C2—C2A—H2A1 | 109.5 | C14—C15—H15 | 119.5 |
C2—C2A—H2A2 | 109.5 | C16—C15—H15 | 119.5 |
H2A1—C2A—H2A2 | 109.5 | C1—C16—C15 | 118.2 (10) |
C2—C2A—H2A3 | 109.5 | C1—C16—H16 | 120.9 |
H2A1—C2A—H2A3 | 109.5 | C15—C16—H16 | 120.9 |
H2A2—C2A—H2A3 | 109.5 | F3—P—F5 | 90.1 (4) |
N3—C3N—H3N1 | 109.5 | F5'—P—F4' | 90.0 (4) |
N3—C3N—H3N2 | 109.5 | F3—P—F2 | 89.9 (4) |
H3N1—C3N—H3N2 | 109.5 | F5—P—F2 | 179.6 (5) |
N3—C3N—H3N3 | 109.5 | F3—P—F1 | 89.7 (3) |
H3N1—C3N—H3N3 | 109.5 | F5'—P—F1 | 90.1 (5) |
H3N2—C3N—H3N3 | 109.5 | F5—P—F1 | 90.1 (4) |
N3—C4—C5 | 113.2 (8) | F4'—P—F1 | 90.9 (4) |
N3—C4—H4A | 108.9 | F2—P—F1 | 89.5 (3) |
C5—C4—H4A | 108.9 | F3—P—F6 | 90.4 (3) |
N3—C4—H4B | 108.9 | F5'—P—F6 | 89.8 (6) |
C5—C4—H4B | 108.9 | F5—P—F6 | 89.9 (3) |
H4A—C4—H4B | 107.7 | F4'—P—F6 | 89.2 (5) |
C6—C5—C4 | 114.5 (9) | F2—P—F6 | 90.5 (4) |
C6—C5—H5A | 108.6 | F1—P—F6 | 179.9 (5) |
C4—C5—H5A | 108.6 | F3—P—F4 | 179.5 (4) |
C6—C5—H5B | 108.6 | F5—P—F4 | 90.1 (4) |
C4—C5—H5B | 108.6 | F2—P—F4 | 89.9 (4) |
H5A—C5—H5B | 107.6 | F1—P—F4 | 89.9 (4) |
C5—C6—N7 | 116.8 (8) | F6—P—F4 | 90.1 (3) |
C5—C6—H6A | 108.1 | F5'—P—F2' | 179.6 (6) |
N7—C6—H6A | 108.1 | F4'—P—F2' | 90.1 (4) |
C5—C6—H6B | 108.1 | F1—P—F2' | 89.6 (4) |
N7—C6—H6B | 108.1 | F6—P—F2' | 90.5 (6) |
H6A—C6—H6B | 107.3 | F5'—P—F3' | 90.0 (4) |
N7—C7N—H7NA | 109.5 | F4'—P—F3' | 179.6 (6) |
N7—C7N—H7NB | 109.5 | F1—P—F3' | 88.7 (4) |
H7NA—C7N—H7NB | 109.5 | F6—P—F3' | 91.3 (5) |
N7—C7N—H7NC | 109.5 | F2'—P—F3' | 89.9 (4) |
C13—N17—C1—C16 | −3.4 (13) | C11N—N11—C10—C9 | 68.6 (11) |
C13—N17—C1—C2 | 168.4 (8) | C12—N11—C10—C9 | −177.5 (8) |
N17—C1—C2—C2A | −101.6 (10) | C8—C9—C10—N11 | 75.4 (12) |
C16—C1—C2—C2A | 69.6 (12) | C10—N11—C12—C13 | 148.7 (8) |
N17—C1—C2—N3 | 28.3 (11) | C11N—N11—C12—C13 | −96.2 (8) |
C16—C1—C2—N3 | −160.6 (9) | C10—N11—C12—C12A | 23.1 (11) |
C4—N3—C2—C2A | −22.8 (12) | C11N—N11—C12—C12A | 138.3 (9) |
C3N—N3—C2—C2A | −137.0 (9) | C1—N17—C13—C14 | 2.9 (14) |
C4—N3—C2—C1 | −147.6 (8) | C1—N17—C13—C12 | −168.4 (8) |
C3N—N3—C2—C1 | 98.2 (8) | C12A—C12—C13—N17 | 99.2 (10) |
C2—N3—C4—C5 | 179.6 (8) | N11—C12—C13—N17 | −29.8 (11) |
C3N—N3—C4—C5 | −67.8 (11) | C12A—C12—C13—C14 | −71.8 (12) |
N3—C4—C5—C6 | −76.6 (12) | N11—C12—C13—C14 | 159.2 (9) |
C4—C5—C6—N7 | 74.3 (12) | N17—C13—C14—C15 | 0.6 (15) |
C7N—N7—C6—C5 | 73.0 (11) | C12—C13—C14—C15 | 171.3 (9) |
C8—N7—C6—C5 | −171.5 (9) | C13—C14—C15—C16 | −3.4 (16) |
C7N—N7—C8—C9 | −74.1 (12) | N17—C1—C16—C15 | 0.4 (14) |
C6—N7—C8—C9 | 171.1 (10) | C2—C1—C16—C15 | −170.6 (10) |
N7—C8—C9—C10 | −74.0 (14) | C14—C15—C16—C1 | 2.9 (16) |
Experimental details
Crystal data | |
Chemical formula | [RhCl2(C18H32N4)]PF6 |
Mr | 623.26 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 293 |
a, b, c (Å) | 7.949 (5), 11.067 (5), 14.116 (5) |
α, β, γ (°) | 74.22 (5), 86.26 (5), 84.67 (5) |
V (Å3) | 1188.7 (10) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 1.07 |
Crystal size (mm) | 0.5 × 0.2 × 0.1 |
Data collection | |
Diffractometer | Enraf-Nonius CAD-4 diffractometer |
Absorption correction | ψ scans; part of the refinement model (ΔF) (North et al., 1968; Walker & Stuart, 1983) |
Tmin, Tmax | 0.448, 0.898 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3098, 3098, 2378 |
Rint | 0.00 |
θmax (°) | 22.5 |
(sin θ/λ)max (Å−1) | 0.538 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.065, 0.182, 1.00 |
No. of reflections | 3094 |
No. of parameters | 325 |
No. of restraints | 360 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 1.92, −1.77 |
Computer programs: CAD-4 Software (Enraf-Nonius, 1989), CAD-4 Software, CADABS (Gould & Smith, 1986), SHELX76 (Sheldrick, 1976), SHELXL97 (Sheldrick, 1997), SHELXTL/PC (Sheldrick, 1994), SHELXL97 and PLATON (Spek, 2001).
Rh—Cl1 | 2.345 (3) | Rh—N7 | 2.140 (7) |
Rh—Cl2 | 2.349 (3) | Rh—N11 | 2.150 (7) |
Rh—N3 | 2.145 (7) | Rh—N17 | 1.964 (7) |
Cl1—Rh—Cl2 | 175.61 (8) | Cl2—Rh—N17 | 88.7 (2) |
Cl1—Rh—N3 | 91.1 (2) | N3—Rh—N7 | 97.9 (3) |
Cl1—Rh—N7 | 88.9 (2) | N3—Rh—N11 | 164.5 (3) |
Cl1—Rh—N11 | 91.3 (2) | N3—Rh—N17 | 82.5 (3) |
Cl1—Rh—N17 | 86.9 (2) | N7—Rh—N11 | 97.5 (3) |
Cl2—Rh—N3 | 88.3 (2) | N7—Rh—N17 | 175.9 (3) |
Cl2—Rh—N7 | 95.4 (2) | N11—Rh—N17 | 82.3 (3) |
Cl2—Rh—N11 | 88.2 (2) |
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The distortions from ideal octahedral coordination on the metal centre in the title complex, (1), are seen in the cis and trans angles subtended at that centre, which range from 82.3 (3) to 97.9 (3)° and from 164.5 (3) to 175.9 (3)°, respectively. The bonds to Rh formed by the two chloride ligands are equivalent, as are the three bonds from the sp3 nitrogen donors N3, N7 and N11. The Rh—N17 distance is much shorter, reflecting the sp2 hybridization of this donor atom. The four N atoms are not coplanar [mean r.m.s. deviation from the N4 best plane is 0.065 (8) Å] and this effect is represented in the 29° twists of N3 and N11 from the plane of the pyridyl ring. The metal ion lies 0.013 (3) Å out of the N4 plane, in the direction of Cl2. These observations suggest that with an ionic radius of 0.805 Å (Shannon, 1976), the RhIII ion is somewhat large for the macrocyclic cavity and the observed distortions are a mechanism to accommodate this misfit. A non-crystallographic mirror plane bisects the cation, passing through C15, N17, Rh, Cl1, Cl2, N7 and C7N (Fig. 1).
Complexes of second-row transition metals with the 2,3,7,11,12-pentamethyl- 3,7,11,17-tetra-azabicyclo(11.3.1)heptadeca-1(17),13,15-triene ligand are rare, the only structurally characterized example of which we are aware being the trans-isocyanatooxoruthenium(IV) complex, (2) (Che et al., 1989). However, a number of complexes of first-row elements are known, for example with cobalt(II) (Che et al., 1986) and nickel(II) (Che et al., 1988) and there are a large number of complexes with ligands having different functionalization of the 3,7,11,17-tetra-azabicyclo[11.3.1]heptadeca-1(17),13,15-triene backbone, for example, carbonylchloro[cis-2,7,12-trimethyl-3,7,11,17-tetra- azabicyclo[11.3.1]heptadeca-1(17),13,15-triene-κN3,κN7,κN11,κN17]- ruthenium(II) tetraphenylborate (Blake et al., 1986).