Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536805030461/om6262sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536805030461/om6262Isup2.hkl |
CCDC reference: 287692
Key indicators
- Single-crystal X-ray study
- T = 183 K
- Mean (C-C) = 0.007 Å
- R factor = 0.039
- wR factor = 0.107
- Data-to-parameter ratio = 24.0
checkCIF/PLATON results
No syntax errors found Datablock: I
Alert level B PLAT242_ALERT_2_B Check Low Ueq as Compared to Neighbors for C8
Alert level C PLAT220_ALERT_2_C Large Non-Solvent C Ueq(max)/Ueq(min) ... 2.82 Ratio PLAT230_ALERT_2_C Hirshfeld Test Diff for C8 - C10 .. 5.01 su PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X) Ru - C2 .. 5.57 su PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X) Ru - C7 .. 6.22 su PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for Rh PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C3 PLAT366_ALERT_2_C Short? C(sp?)-C(sp?) Bond C12 - C13 ... 1.39 Ang. PLAT366_ALERT_2_C Short? C(sp?)-C(sp?) Bond C16 - C17 ... 1.38 Ang. PLAT480_ALERT_4_C Long H...A H-Bond Reported H11C .. CL .. 2.93 Ang. PLAT601_ALERT_2_C Structure Contains Solvent Accessible VOIDS of . 35.00 A 3
0 ALERT level A = In general: serious problem 1 ALERT level B = Potentially serious problem 10 ALERT level C = Check and explain 0 ALERT level G = General alerts; check 0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 10 ALERT type 2 Indicator that the structure model may be wrong or deficient 0 ALERT type 3 Indicator that the structure quality may be low 1 ALERT type 4 Improvement, methodology, query or suggestion
[Rh(cod)Cl]2 (3.2 mg, 0.007 mmol) in dry dichloromethane was added to a solution of trans-[Ru(tBuNC)4(CN)2] water solvate (6.6 mg, 0.013 mmol) in dichloromethane. After stirring for 15 min, the solvent was removed in vacuo, producing a yellow powder of the title compound. Recrystallization from dichloromethane yielded yellow prismatic crystals suitable for this X-ray diffraction study. IR (KBr, cm−1): ν(CH3) 2980 (s), 2934 (m), ν(CN) 2224 (m), ν(NC) 2169 (vs), 2174 (s), 2118 (m), δ(CH) 1457 (m), δ(CMe3) 1399 (w), 1372 (s); MS (micro-ESI in dichloromethane/methanol) [m/z, (%)]: 943 (32) {[Ru(tBuNC)4(CN)2]Rh2(cod)2Cl}+, 697 (100) {[Ru(tBuNC) 4(CN)2]Rh(cod)}+.
All H atoms were placed in idealized positions (C—H = 0.98–1.00 Å) and were refined with Uiso(H) values of 1.2 or 1.5 times Ueq(C). Please check data in CIF; C—H distances are given twice for C4–C6 but not at all for C9–C11.
Data collection: COLLECT (Nonius, 1998); cell refinement: DENZO (Otwinowski & Minor, 1997); data reduction: DENZO; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP (Siemens, 1990); software used to prepare material for publication: SHELXL97.
[Rh2Ru(CN)2Cl2(C8H12)2(C5H9N)4] | F(000) = 1992 |
Mr = 978.71 | Dx = 1.389 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C2yc | Cell parameters from 4052 reflections |
a = 21.7982 (5) Å | θ = 3.3–27.5° |
b = 11.3347 (4) Å | µ = 1.16 mm−1 |
c = 21.4881 (8) Å | T = 183 K |
β = 118.189 (2)° | Prism, yellow |
V = 4679.5 (3) Å3 | 0.03 × 0.03 × 0.02 mm |
Z = 4 |
Nonius KappaCCD diffractometer | 4052 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.041 |
Graphite monochromator | θmax = 27.5°, θmin = 3.3° |
ϕ and ω scans | h = −28→28 |
16239 measured reflections | k = −13→14 |
5332 independent reflections | l = −25→27 |
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)] = 0.039 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.107 | H-atom parameters constrained |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0599P)2 + 3.4513P] where P = (Fo2 + 2Fc2)/3 |
5332 reflections | (Δ/σ)max = 0.008 |
222 parameters | Δρmax = 1.17 e Å−3 |
0 restraints | Δρmin = −0.68 e Å−3 |
[Rh2Ru(CN)2Cl2(C8H12)2(C5H9N)4] | V = 4679.5 (3) Å3 |
Mr = 978.71 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 21.7982 (5) Å | µ = 1.16 mm−1 |
b = 11.3347 (4) Å | T = 183 K |
c = 21.4881 (8) Å | 0.03 × 0.03 × 0.02 mm |
β = 118.189 (2)° |
Nonius KappaCCD diffractometer | 4052 reflections with I > 2σ(I) |
16239 measured reflections | Rint = 0.041 |
5332 independent reflections |
R[F2 > 2σ(F2)] = 0.039 | 0 restraints |
wR(F2) = 0.107 | H-atom parameters constrained |
S = 1.03 | Δρmax = 1.17 e Å−3 |
5332 reflections | Δρmin = −0.68 e Å−3 |
222 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. The structure determination was performed on a Enraf–Nonius Kappa CCD diffractometer, crystal detector distance 25 mm, using graphite monochromated Mo—Kα radiation. The crystal was mounted in a stream of cold nitrogen. Data were corrected for Lorentz and polarization effects but not for absorption. The structure was solved by direct methods and refined by full-matrix least squares techniques against F2 using the programme packages SHELXS (Sheldrick, 1990) and SHELXL97 (Sheldrick, 1997). Computation of the structure and drawing of the molecular as well as crystal structure was acomplished with the programme XP (Siemens Inc., 1990). 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 | 0.214768 (13) | 0.26195 (3) | 0.206642 (13) | 0.03460 (11) | |
Ru | 0.0000 | 0.30911 (3) | 0.2500 | 0.03082 (12) | |
Cl | 0.13491 (5) | 0.19688 (10) | 0.09197 (5) | 0.0528 (3) | |
N1 | 0.13375 (16) | 0.2924 (3) | 0.22730 (17) | 0.0424 (7) | |
N2 | 0.06527 (15) | 0.1318 (3) | 0.37701 (16) | 0.0406 (7) | |
N3 | 0.06698 (15) | 0.4930 (3) | 0.37428 (16) | 0.0405 (7) | |
C1 | 0.08690 (19) | 0.3030 (3) | 0.23686 (18) | 0.0367 (8) | |
C2 | 0.04166 (17) | 0.1902 (3) | 0.32815 (19) | 0.0357 (8) | |
C3 | 0.08718 (18) | 0.0589 (3) | 0.44061 (19) | 0.0405 (8) | |
C4 | 0.1571 (2) | 0.0076 (4) | 0.4598 (3) | 0.0706 (14) | |
H4A | 0.1535 | −0.0444 | 0.4217 | 0.106* | |
H4B | 0.1737 | −0.0377 | 0.5036 | 0.106* | |
H4C | 0.1900 | 0.0715 | 0.4665 | 0.106* | |
C5 | 0.0314 (2) | −0.0343 (5) | 0.4228 (3) | 0.0741 (15) | |
H5A | 0.0298 | −0.0856 | 0.3853 | 0.111* | |
H5B | −0.0139 | 0.0041 | 0.4066 | 0.111* | |
H5C | 0.0422 | −0.0816 | 0.4649 | 0.111* | |
C6 | 0.0904 (3) | 0.1391 (5) | 0.4986 (2) | 0.0765 (14) | |
H6A | 0.0440 | 0.1712 | 0.4848 | 0.115* | |
H6B | 0.1228 | 0.2041 | 0.5060 | 0.115* | |
H6C | 0.1064 | 0.0940 | 0.5424 | 0.115* | |
C7 | 0.04236 (16) | 0.4296 (3) | 0.32708 (19) | 0.0357 (7) | |
C8 | 0.09163 (17) | 0.5680 (3) | 0.43617 (19) | 0.0369 (8) | |
C9 | 0.0298 (2) | 0.6175 (6) | 0.4393 (3) | 0.092 (2) | |
H9A | 0.0030 | 0.6666 | 0.3975 | 0.137* | |
H9B | 0.0453 | 0.6657 | 0.4820 | 0.137* | |
H9C | 0.0005 | 0.5529 | 0.4404 | 0.137* | |
C10 | 0.1319 (3) | 0.4911 (5) | 0.5030 (3) | 0.0904 (18) | |
H10A | 0.1730 | 0.4569 | 0.5024 | 0.136* | |
H10B | 0.1016 | 0.4276 | 0.5035 | 0.136* | |
H10C | 0.1467 | 0.5401 | 0.5452 | 0.136* | |
C11 | 0.1405 (4) | 0.6602 (5) | 0.4348 (3) | 0.101 (2) | |
H11A | 0.1162 | 0.7091 | 0.3924 | 0.151* | |
H11B | 0.1804 | 0.6216 | 0.4340 | 0.151* | |
H11C | 0.1569 | 0.7099 | 0.4769 | 0.151* | |
C12 | 0.2812 (2) | 0.2407 (5) | 0.3149 (2) | 0.0603 (13) | |
H12A | 0.2565 | 0.2281 | 0.3434 | 0.072* | |
C13 | 0.28347 (19) | 0.3577 (5) | 0.2968 (2) | 0.0616 (14) | |
H13A | 0.2599 | 0.4139 | 0.3146 | 0.074* | |
C14 | 0.3441 (2) | 0.4108 (5) | 0.2903 (3) | 0.0796 (17) | |
H14A | 0.3498 | 0.4944 | 0.3054 | 0.096* | |
H14B | 0.3874 | 0.3684 | 0.3223 | 0.096* | |
C15 | 0.3340 (2) | 0.4043 (5) | 0.2158 (3) | 0.0696 (14) | |
H15A | 0.3801 | 0.3991 | 0.2175 | 0.084* | |
H15B | 0.3114 | 0.4779 | 0.1906 | 0.084* | |
C16 | 0.2899 (2) | 0.2994 (4) | 0.1742 (2) | 0.0479 (9) | |
H16A | 0.2707 | 0.3065 | 0.1219 | 0.057* | |
C17 | 0.29952 (19) | 0.1843 (4) | 0.1987 (2) | 0.0476 (10) | |
H17A | 0.2852 | 0.1236 | 0.1605 | 0.057* | |
C18 | 0.3574 (2) | 0.1440 (5) | 0.2694 (2) | 0.0666 (13) | |
H18A | 0.3708 | 0.0623 | 0.2649 | 0.080* | |
H18B | 0.3986 | 0.1951 | 0.2829 | 0.080* | |
C19 | 0.3361 (2) | 0.1481 (6) | 0.3268 (2) | 0.0792 (16) | |
H19A | 0.3779 | 0.1642 | 0.3724 | 0.095* | |
H19B | 0.3180 | 0.0696 | 0.3303 | 0.095* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Rh | 0.03264 (16) | 0.04679 (19) | 0.02301 (16) | 0.00258 (11) | 0.01202 (11) | −0.00204 (11) |
Ru | 0.0351 (2) | 0.0313 (2) | 0.0279 (2) | 0.000 | 0.01643 (16) | 0.000 |
Cl | 0.0589 (6) | 0.0628 (6) | 0.0247 (5) | −0.0115 (5) | 0.0099 (4) | −0.0035 (4) |
N1 | 0.0358 (15) | 0.0553 (19) | 0.0370 (17) | 0.0010 (14) | 0.0179 (13) | −0.0006 (15) |
N2 | 0.0454 (16) | 0.0392 (17) | 0.0356 (17) | 0.0022 (13) | 0.0178 (14) | 0.0041 (14) |
N3 | 0.0430 (16) | 0.0402 (17) | 0.0404 (18) | −0.0009 (13) | 0.0215 (14) | −0.0041 (15) |
C1 | 0.0389 (18) | 0.0389 (19) | 0.0298 (18) | 0.0018 (15) | 0.0141 (15) | 0.0002 (15) |
C2 | 0.0370 (17) | 0.0381 (19) | 0.036 (2) | −0.0005 (15) | 0.0204 (15) | −0.0032 (16) |
C3 | 0.0406 (18) | 0.044 (2) | 0.0321 (19) | 0.0001 (15) | 0.0133 (15) | 0.0091 (16) |
C4 | 0.058 (3) | 0.075 (3) | 0.080 (3) | 0.020 (2) | 0.033 (2) | 0.035 (3) |
C5 | 0.067 (3) | 0.077 (3) | 0.053 (3) | −0.022 (2) | 0.007 (2) | 0.024 (2) |
C6 | 0.104 (4) | 0.080 (4) | 0.046 (3) | 0.003 (3) | 0.035 (3) | −0.002 (3) |
C7 | 0.0353 (17) | 0.0368 (18) | 0.039 (2) | 0.0015 (14) | 0.0205 (15) | 0.0029 (16) |
C8 | 0.0375 (17) | 0.0359 (18) | 0.038 (2) | −0.0023 (14) | 0.0184 (15) | −0.0071 (15) |
C9 | 0.059 (3) | 0.126 (5) | 0.090 (4) | −0.011 (3) | 0.035 (3) | −0.056 (4) |
C10 | 0.116 (4) | 0.072 (3) | 0.055 (3) | 0.008 (3) | 0.018 (3) | −0.005 (3) |
C11 | 0.160 (6) | 0.089 (4) | 0.099 (5) | −0.068 (4) | 0.098 (5) | −0.046 (4) |
C12 | 0.044 (2) | 0.105 (4) | 0.023 (2) | 0.012 (2) | 0.0081 (17) | −0.006 (2) |
C13 | 0.039 (2) | 0.101 (4) | 0.039 (2) | −0.007 (2) | 0.0125 (17) | −0.035 (2) |
C14 | 0.047 (2) | 0.099 (4) | 0.087 (4) | −0.020 (3) | 0.027 (2) | −0.047 (3) |
C15 | 0.054 (3) | 0.077 (3) | 0.089 (4) | −0.016 (2) | 0.044 (3) | −0.016 (3) |
C16 | 0.046 (2) | 0.064 (3) | 0.042 (2) | −0.0018 (19) | 0.0282 (18) | −0.0070 (19) |
C17 | 0.044 (2) | 0.062 (3) | 0.042 (2) | 0.0102 (18) | 0.0253 (18) | −0.0059 (19) |
C18 | 0.051 (2) | 0.083 (3) | 0.061 (3) | 0.022 (2) | 0.022 (2) | 0.001 (3) |
C19 | 0.054 (3) | 0.132 (5) | 0.039 (3) | 0.029 (3) | 0.012 (2) | 0.018 (3) |
Rh—N1 | 2.043 (3) | C6—H6C | 0.9800 |
Rh—C12 | 2.093 (4) | C9—H9A | 0.9800 |
Rh—C16 | 2.105 (4) | C9—H9B | 0.9800 |
Rh—C13 | 2.106 (4) | C9—H9C | 0.9800 |
Rh—C17 | 2.125 (3) | C10—H10A | 0.9800 |
Rh—Cl | 2.3651 (9) | C10—H10B | 0.9800 |
Ru—C7 | 2.004 (4) | C10—H10C | 0.9800 |
Ru—C7i | 2.004 (4) | C11—H11A | 0.9800 |
Ru—C2 | 2.005 (4) | C11—H11B | 0.9800 |
Ru—C2i | 2.005 (4) | C11—H11C | 0.9800 |
Ru—C1 | 2.044 (4) | C12—C13 | 1.389 (7) |
Ru—C1i | 2.044 (4) | C12—C19 | 1.520 (6) |
N1—C1 | 1.139 (5) | C12—H12A | 1.0000 |
N2—C2 | 1.138 (4) | C13—C14 | 1.519 (6) |
N2—C3 | 1.470 (4) | C13—H13A | 1.0000 |
N3—C7 | 1.148 (4) | C14—C15 | 1.511 (7) |
N3—C8 | 1.451 (4) | C14—H14A | 0.9900 |
C3—C4 | 1.497 (5) | C14—H14B | 0.9900 |
C3—C6 | 1.518 (6) | C15—C16 | 1.524 (6) |
C3—C5 | 1.518 (5) | C15—H15A | 0.9900 |
C8—C9 | 1.490 (6) | C15—H15B | 0.9900 |
C8—C11 | 1.503 (6) | C16—C17 | 1.386 (6) |
C8—C10 | 1.549 (6) | C16—H16A | 1.0000 |
C4—H4A | 0.9800 | C17—C18 | 1.516 (6) |
C4—H4B | 0.9800 | C17—H17A | 1.0000 |
C4—H4C | 0.9800 | C18—C19 | 1.509 (7) |
C5—H5A | 0.9800 | C18—H18A | 0.9900 |
C5—H5B | 0.9800 | C18—H18B | 0.9900 |
C5—H5C | 0.9800 | C19—H19A | 0.9900 |
C6—H6A | 0.9800 | C19—H19B | 0.9900 |
C6—H6B | 0.9800 | ||
N1—Rh—C12 | 89.62 (16) | C8—C9—H9A | 109.5 |
N1—Rh—C16 | 157.77 (16) | C8—C9—H9B | 109.5 |
C12—Rh—C16 | 98.82 (18) | H9A—C9—H9B | 109.5 |
N1—Rh—C13 | 91.42 (14) | C8—C9—H9C | 109.5 |
C12—Rh—C13 | 38.64 (19) | H9A—C9—H9C | 109.5 |
C16—Rh—C13 | 82.80 (16) | H9B—C9—H9C | 109.5 |
N1—Rh—C17 | 163.92 (15) | C8—C10—H10A | 109.5 |
C12—Rh—C17 | 82.55 (16) | C8—C10—H10B | 109.5 |
C16—Rh—C17 | 38.25 (17) | H10A—C10—H10B | 109.5 |
C13—Rh—C17 | 91.18 (16) | C8—C10—H10C | 109.5 |
N1—Rh—Cl | 89.58 (9) | H10A—C10—H10C | 109.5 |
C12—Rh—Cl | 154.69 (15) | H10B—C10—H10C | 109.5 |
C16—Rh—Cl | 91.29 (12) | C8—C11—H11A | 109.5 |
C13—Rh—Cl | 166.66 (16) | C8—C11—H11B | 109.5 |
C17—Rh—Cl | 91.53 (11) | H11A—C11—H11B | 109.5 |
C7—Ru—C7i | 94.1 (2) | C8—C11—H11C | 109.5 |
C7—Ru—C2 | 85.22 (14) | H11A—C11—H11C | 109.5 |
C7i—Ru—C2 | 178.92 (14) | H11B—C11—H11C | 109.5 |
C7—Ru—C2i | 178.92 (14) | C13—C12—C19 | 125.2 (5) |
C7i—Ru—C2i | 85.22 (14) | C13—C12—Rh | 71.2 (2) |
C2—Ru—C2i | 95.5 (2) | C19—C12—Rh | 110.1 (3) |
C7—Ru—C1 | 92.40 (13) | C13—C12—H12A | 114.1 |
C7i—Ru—C1 | 90.24 (13) | C19—C12—H12A | 114.1 |
C2—Ru—C1 | 90.60 (14) | Rh—C12—H12A | 114.1 |
C2i—Ru—C1 | 86.80 (14) | C12—C13—C14 | 123.5 (4) |
C7—Ru—C1i | 90.23 (13) | C12—C13—Rh | 70.2 (2) |
C7i—Ru—C1i | 92.39 (13) | C14—C13—Rh | 113.0 (3) |
C2—Ru—C1i | 86.81 (14) | C12—C13—H13A | 114.2 |
C2i—Ru—C1i | 90.60 (14) | C14—C13—H13A | 114.2 |
C1—Ru—C1i | 176.1 (2) | Rh—C13—H13A | 114.2 |
C1—N1—Rh | 175.8 (3) | C15—C14—C13 | 112.4 (3) |
C2—N2—C3 | 172.4 (4) | C15—C14—H14A | 109.1 |
C7—N3—C8 | 173.0 (3) | C13—C14—H14A | 109.1 |
N1—C1—Ru | 175.3 (3) | C15—C14—H14B | 109.1 |
N2—C2—Ru | 172.9 (3) | C13—C14—H14B | 109.1 |
N2—C3—C4 | 108.4 (3) | H14A—C14—H14B | 107.9 |
N2—C3—C6 | 107.2 (3) | C14—C15—C16 | 113.3 (4) |
C4—C3—C6 | 111.2 (4) | C14—C15—H15A | 108.9 |
N2—C3—C5 | 106.7 (3) | C16—C15—H15A | 108.9 |
C4—C3—C5 | 113.0 (4) | C14—C15—H15B | 108.9 |
C6—C3—C5 | 110.2 (4) | C16—C15—H15B | 108.9 |
C3—C4—H4A | 109.5 | H15A—C15—H15B | 107.7 |
C3—C4—H4B | 109.5 | C17—C16—C15 | 124.9 (4) |
H4A—C4—H4B | 109.5 | C17—C16—Rh | 71.7 (2) |
C3—C4—H4C | 109.5 | C15—C16—Rh | 109.7 (3) |
H4A—C4—H4C | 109.5 | C17—C16—H16A | 114.2 |
H4B—C4—H4C | 109.5 | C15—C16—H16A | 114.2 |
C3—C5—H5A | 109.5 | Rh—C16—H16A | 114.2 |
C3—C5—H5B | 109.5 | C16—C17—C18 | 124.7 (4) |
H5A—C5—H5B | 109.5 | C16—C17—Rh | 70.1 (2) |
C3—C5—H5C | 109.5 | C18—C17—Rh | 112.8 (3) |
H5A—C5—H5C | 109.5 | C16—C17—H17A | 113.8 |
H5B—C5—H5C | 109.5 | C18—C17—H17A | 113.8 |
C3—C6—H6A | 109.5 | Rh—C17—H17A | 113.8 |
C3—C6—H6B | 109.5 | C19—C18—C17 | 112.2 (3) |
H6A—C6—H6B | 109.5 | C19—C18—H18A | 109.2 |
C3—C6—H6C | 109.5 | C17—C18—H18A | 109.2 |
H6A—C6—H6C | 109.5 | C19—C18—H18B | 109.2 |
H6B—C6—H6C | 109.5 | C17—C18—H18B | 109.2 |
N3—C7—Ru | 175.5 (3) | H18A—C18—H18B | 107.9 |
N3—C8—C9 | 108.1 (3) | C18—C19—C12 | 113.9 (4) |
N3—C8—C11 | 110.4 (3) | C18—C19—H19A | 108.8 |
C9—C8—C11 | 113.9 (4) | C12—C19—H19A | 108.8 |
N3—C8—C10 | 108.7 (3) | C18—C19—H19B | 108.8 |
C9—C8—C10 | 107.4 (4) | C12—C19—H19B | 108.8 |
C11—C8—C10 | 108.2 (4) | H19A—C19—H19B | 107.7 |
Symmetry code: (i) −x, y, −z+1/2. |
D—H···A | H···A | D···A | D—H···A |
C9—H9B···Clii | 2.73 | 3.652 (5) | 156 |
C5—H5C···Cliii | 2.84 | 3.736 (5) | 153 |
C11—H11C···Clii | 2.93 | 3.800 (5) | 149 |
Symmetry codes: (ii) x, −y+1, z+1/2; (iii) x, −y, z+1/2. |
Experimental details
Crystal data | |
Chemical formula | [Rh2Ru(CN)2Cl2(C8H12)2(C5H9N)4] |
Mr | 978.71 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 183 |
a, b, c (Å) | 21.7982 (5), 11.3347 (4), 21.4881 (8) |
β (°) | 118.189 (2) |
V (Å3) | 4679.5 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.16 |
Crystal size (mm) | 0.03 × 0.03 × 0.02 |
Data collection | |
Diffractometer | Nonius KappaCCD diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 16239, 5332, 4052 |
Rint | 0.041 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.039, 0.107, 1.03 |
No. of reflections | 5332 |
No. of parameters | 222 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 1.17, −0.68 |
Computer programs: COLLECT (Nonius, 1998), DENZO (Otwinowski & Minor, 1997), DENZO, SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), XP (Siemens, 1990), SHELXL97.
Rh—N1 | 2.043 (3) | Ru—C2 | 2.005 (4) |
Rh—C12 | 2.093 (4) | Ru—C1 | 2.044 (4) |
Rh—C16 | 2.105 (4) | N1—C1 | 1.139 (5) |
Rh—C13 | 2.106 (4) | N2—C2 | 1.138 (4) |
Rh—C17 | 2.125 (3) | N3—C7 | 1.148 (4) |
Rh—Cl | 2.3651 (9) | C12—C13 | 1.389 (7) |
Ru—C7 | 2.004 (4) | C16—C17 | 1.386 (6) |
N1—Rh—C12 | 89.62 (16) | C7—Ru—C2i | 178.92 (14) |
N1—Rh—C16 | 157.77 (16) | C7i—Ru—C2i | 85.22 (14) |
C12—Rh—C16 | 98.82 (18) | C2—Ru—C2i | 95.5 (2) |
N1—Rh—C13 | 91.42 (14) | C7—Ru—C1 | 92.40 (13) |
C12—Rh—C13 | 38.64 (19) | C7i—Ru—C1 | 90.24 (13) |
C16—Rh—C13 | 82.80 (16) | C2—Ru—C1 | 90.60 (14) |
N1—Rh—C17 | 163.92 (15) | C2i—Ru—C1 | 86.80 (14) |
C12—Rh—C17 | 82.55 (16) | C7—Ru—C1i | 90.23 (13) |
C16—Rh—C17 | 38.25 (17) | C7i—Ru—C1i | 92.39 (13) |
C13—Rh—C17 | 91.18 (16) | C2—Ru—C1i | 86.81 (14) |
N1—Rh—Cl | 89.58 (9) | C2i—Ru—C1i | 90.60 (14) |
C12—Rh—Cl | 154.69 (15) | C1—Ru—C1i | 176.1 (2) |
C16—Rh—Cl | 91.29 (12) | C1—N1—Rh | 175.8 (3) |
C13—Rh—Cl | 166.66 (16) | C2—N2—C3 | 172.4 (4) |
C17—Rh—Cl | 91.53 (11) | C7—N3—C8 | 173.0 (3) |
C7—Ru—C7i | 94.1 (2) | N1—C1—Ru | 175.3 (3) |
C7—Ru—C2 | 85.22 (14) | N2—C2—Ru | 172.9 (3) |
C7i—Ru—C2 | 178.92 (14) | N3—C7—Ru | 175.5 (3) |
Symmetry code: (i) −x, y, −z+1/2. |
D—H···A | H···A | D···A | D—H···A |
C9—H9B···Clii | 2.733 | 3.652 (5) | 156 |
C5—H5C···Cliii | 2.835 | 3.736 (5) | 153 |
C11—H11C···Clii | 2.929 | 3.800 (5) | 149 |
Symmetry codes: (ii) x, −y+1, z+1/2; (iii) x, −y, z+1/2. |
The title compound, (I), is the first structually characterized example of a compound with an Rh and an Ru atom being bridged by a cyanide ligand.
Recently, some of us published the facile synthesis of cis- and trans-[Ru(CNtBu)4(CN)2] from Ru3(CO)12 and tert-butylisocyanide by the reductive cleavage of isocyanide ligands and the concomitant oxidation of the Ru atoms (Imhof & Dönnecke, 2003). In the meantime we were able to transfer this reaction principle to other transition metal carbonyls and we are actually investigating the potential of this cyano complex to produce cyanide-bridged coordination polymers with a controllable three-dimensional arrangement of the metal centers. Since the resulting coordination polymers often show very complex magnetic and electronic properties, we were looking for a way to produce trinuclear cutouts of the polymer chains in order to investigate the communication between the metal centers in these trinuclear complexes hopefully enabling us to also understand the properties of the polymers.
The reaction of [Rh(cod)Cl]2 with trans-[Ru(CNtBu)4(CN)2] in dry dichloromethane leads to the almost quantitative formation of (I). The cleavage of chloro bridges by Lewis bases is a commonly known process (Cotton et al., 1999). With this reaction it becomes evident that cyano ligands that are already coordinated to a transition metal still are basic enough to induce the cleavage of chloro bridges.
The molecular structure of (I) is presented in Fig. 1; the most important bond lengths and angles are given in Table 1. The central Ru ion is situated on a crystallographic twofold axis, resulting in a nearly perfect octahedral coordination sphere assembled by the four isocyanide ligands and the two cyano groups. The cyanide groups act as bridging ligands between the Ru and Rh centers. Owing to the symmetry of the molecule the chloro(cod)rhodium subunits exhibit a trans configuration relative to each other. The Rh atoms show a square-planar ligand environment built up of the N atom of the bridging cyanide, the chloro ligand and the centers of the olefinic double bonds (C12═C13 and C16═C17). The deviations from this plane are well below 0.1 Å.
A Cambridge Structural Database (Version 5.26 of November 2004; Allen, 2002) search found 15 structurally characterized compounds in which rhodium ions are coordinated to cyanide bridging two transition metals and in which the rhodium centers are connected to the N atom of the bridging ligand. The compounds may be divided into two basic groups concerning the arrangement of the metal atoms. There are cyclic structures consisting of four metals with all metal ions being connected by bridging cyanide groups. These compounds have been described for Rh atoms only (Kalb et al., 1982; Klausmeyer et al., 1998) or for combinations of rhodium with platinum (Fornies et al., 2004). In addition, there has been a report concerning a metallocycle of Rh atoms bridged by only two cyanide groups, which therefore exhibits two metal–metal bonds (Martinez et al., 1991). Three-dimensional arrangements of rhodium ions bridged by cyanide ligands have been described in terms of a cubic structure (Klausmeyer et al., 1998) and as a oligomer with seven rhodium centers, which is best described as a cube with one missing corner (Contakes et al., 1998). All other structures reported so far are linear coordination complexes, either being discrete dinuclear (Atkinson et al., 1993; Bezrukova et al., 1993) or trinuclear (Deeming et al., 1988; Atkinson et al., 1993) compounds. There have also been reports about coordination polymers, which were synthesized from rhodium carboxylates and hexacyanoferrate (Kim et al., 2001), hexacyanocobaltate (Lu et al., 1996) or [(η5-C5H5)Ir(CO)3] (Contakes et al., 2000). The title compound is the first structurally characterized compound with an Rh and an Ru atom being bridged by a cyanide ligand.
The crystal structure of the title compound is shown in Fig. 2; the shortest intermolecular contacts are presented in Table 2. Infinite chains of the trinuclear complex units are built up by C—H···Cl hydrogen bonds (Desiraju & Steiner, 1999) between the chloro ligands and an H atom of one of the isocyanide ligands of a neighboring molecule and vice versa. These infinite chains are interconnected in a three-dimensional arrangement by additional C—H···Cl contacts, which have been omitted from Fig. 2 for the sake of clarity (Table 2).