Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807044716/zl2063sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807044716/zl2063Isup2.hkl |
CCDC reference: 663628
Key indicators
- Single-crystal X-ray study
- T = 193 K
- Mean (C-C) = 0.004 Å
- Disorder in solvent or counterion
- R factor = 0.037
- wR factor = 0.100
- Data-to-parameter ratio = 16.6
checkCIF/PLATON results
No syntax errors found
Alert level B PLAT432_ALERT_2_B Short Inter X...Y Contact C11 .. F23 .. 2.82 Ang. PLAT432_ALERT_2_B Short Inter X...Y Contact C11 .. F4 .. 2.83 Ang. PLAT432_ALERT_2_B Short Inter X...Y Contact C15 .. F16 .. 2.83 Ang.
Alert level C PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ .... ? PLAT244_ALERT_4_C Low 'Solvent' Ueq as Compared to Neighbors for P1 PLAT244_ALERT_4_C Low 'Solvent' Ueq as Compared to Neighbors for P3 PLAT244_ALERT_4_C Low 'Solvent' Ueq as Compared to Neighbors for P5 PLAT244_ALERT_4_C Low 'Solvent' Ueq as Compared to Neighbors for P2 PLAT244_ALERT_4_C Low 'Solvent' Ueq as Compared to Neighbors for P4 PLAT302_ALERT_4_C Anion/Solvent Disorder ......................... 40.00 Perc. PLAT432_ALERT_2_C Short Inter X...Y Contact C13 .. F28 .. 2.96 Ang. PLAT432_ALERT_2_C Short Inter X...Y Contact C17 .. F30 .. 2.89 Ang.
Alert level G PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 241
0 ALERT level A = In general: serious problem 3 ALERT level B = Potentially serious problem 9 ALERT level C = Check and explain 1 ALERT level G = General alerts; check 1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 5 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 6 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
[Cp*Rh(NCMe)3](PF6)2 was prepared according to literature methods (White et al., 1992). The compound was synthesized by dissolving 95 mg (0.15 mmol) [Cp*Rh(NCMe)3](PF6)2 and 35 mg (0.44 mmol) pyrimidine in 2 ml MeCN. Yellow crystals were grown at room temperature by vapor diffusion of diethylether into an acetonitrile solution.
The proposed model includes multiple disordered sites for the two anions. Disordered anion moieties were refined as rigid, idealized groups with similar amplitude restraints imposed on displacement parameters for overlapping sites separated by less than Van der Waals radii using an effective standard deviation of 0.01 Å. The single idealized group refinement for the first set converged with some principal mean square atomic displacements that differed by as much as a factor of ten and some that were nearly isotropic. This suggested that a single rigid body with anisotropic displacement parameters was a poor fit to the observed data. In addition, residual electron density in excess of 2 e/Å3 from a subsequent difference Fourier map clearly indicated multiple potential surfaces for this anion. After refining two rigid groups (P1, P3) for the first set, residual density from a subsequent difference Fourier map indicated reasonable atomic positions for a third group. The proposed model for the second anion set (P2, P4) was developed simultaneously in a like manner. Methyl H atom positions, R—CH3, were optimized by rotation about R—C bonds with idealized C—H, R—H and H···H distances. Remaining H atoms were included as riding idealized contributors. Methyl H atom U's were assigned as 1.5 times Ueq of the carrier atom; remaining H atom U's were assigned as 1.2 times the carrier Ueq.
While pyrimidine and pyrimidine derivatives are biologically relevant, only 120 crystal structures with metal–pyrimidine bonds have been reported, none of which contain Cp co-ligands (Barnett et al., 2005; Nedelec & Rochon, 2001; and Sharma et al., 1998). Here we report the crystal structure of [Cp*Rh(NCMe)2(N2C4H4)](PF6)2 as an unique half-sandwich pyrimidine adduct. The Rh—N distance for the two acetonitrile ligands are 2.093 (2) and 2.109 (2) Å. The coordinated pyrimidine has a longer Rh—N distance of 2.148 (2) Å. The N—Rh—N angles are slightly contracted ranging from 86.05 (9) to 88.74 (10)°.
For selected literature on metal–pyrimidine complexes, see: Barnett et al. (2005); Nedelec & Rochon (2001); Sharma et al. (1998). For the synthesis of [Cp*Rh(NCMe)3](PF6)2, see: White et al. (1992).
Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXTL (Bruker, 2005); program(s) used to refine structure: SHELXTL (Bruker, 2005); molecular graphics: SHELXTL (Bruker, 2005); software used to prepare material for publication: XCIF (Bruker, 2005).
[Rh(C10H15)(C4H4N2)(C2H3N)2](PF6)2 | F(000) = 2752 |
Mr = 690.27 | Dx = 1.770 Mg m−3 |
Orthorhombic, Pbca | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ac 2ab | Cell parameters from 9298 reflections |
a = 14.4046 (8) Å | θ = 2.2–30.7° |
b = 14.7669 (7) Å | µ = 0.89 mm−1 |
c = 24.3537 (13) Å | T = 193 K |
V = 5180.3 (5) Å3 | Prism, yellow |
Z = 8 | 0.36 × 0.36 × 0.32 mm |
Bruker Kappa APEXII CCD diffractometer | 7612 independent reflections |
Radiation source: fine-focus sealed tube | 6384 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.026 |
profile data from φ and ω scans | θmax = 30.1°, θmin = 1.7° |
Absorption correction: integration (SHELXTL and XPREP; Bruker, 2005) | h = −20→19 |
Tmin = 0.625, Tmax = 0.813 | k = −20→20 |
93720 measured reflections | l = −34→34 |
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)] = 0.037 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.100 | H-atom parameters not refined |
S = 1.04 | w = 1/[σ2(Fo2) + (0.0435P)2 + 9.0148P] where P = (Fo2 + 2Fc2)/3 |
7612 reflections | (Δ/σ)max = 0.017 |
459 parameters | Δρmax = 0.93 e Å−3 |
241 restraints | Δρmin = −0.72 e Å−3 |
[Rh(C10H15)(C4H4N2)(C2H3N)2](PF6)2 | V = 5180.3 (5) Å3 |
Mr = 690.27 | Z = 8 |
Orthorhombic, Pbca | Mo Kα radiation |
a = 14.4046 (8) Å | µ = 0.89 mm−1 |
b = 14.7669 (7) Å | T = 193 K |
c = 24.3537 (13) Å | 0.36 × 0.36 × 0.32 mm |
Bruker Kappa APEXII CCD diffractometer | 7612 independent reflections |
Absorption correction: integration (SHELXTL and XPREP; Bruker, 2005) | 6384 reflections with I > 2σ(I) |
Tmin = 0.625, Tmax = 0.813 | Rint = 0.026 |
93720 measured reflections |
R[F2 > 2σ(F2)] = 0.037 | 241 restraints |
wR(F2) = 0.100 | H-atom parameters not refined |
S = 1.04 | Δρmax = 0.93 e Å−3 |
7612 reflections | Δρmin = −0.72 e Å−3 |
459 parameters |
Experimental. One distinct cell was identified using APEX2 (Bruker, 2004). Five frame series were integrated and filtered for statistical outliers using SAINT (Bruker, 2005) then corrected for absorption by integration using SHELXTL/XPREP (Bruker, 2005) before using SAINT/SADABS (Bruker, 2005) to sort, merge, and scale the combined data. No decay correction was applied. |
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. Structure was phased by direct methods. Systematic conditions suggested the unambiguous space group. The space group choice was confirmed by successful convergence of the full-matrix least-squares refinement on F2. The highest peaks in the final difference Fourier map were in the vicinity of atoms F7 and F3; the final map had no other significant features. A final analysis of variance between observed and calculated structure factors showed no dependence on amplitude or resolution. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Rh1 | 0.568281 (13) | 0.322308 (12) | 0.639265 (8) | 0.02201 (6) | |
C1 | 0.59292 (19) | 0.43808 (17) | 0.69007 (11) | 0.0269 (5) | |
C2 | 0.68007 (17) | 0.39330 (16) | 0.67877 (10) | 0.0239 (5) | |
C3 | 0.67538 (19) | 0.30338 (17) | 0.70001 (11) | 0.0275 (5) | |
C4 | 0.5845 (2) | 0.2917 (2) | 0.72445 (11) | 0.0318 (6) | |
C5 | 0.53674 (19) | 0.3764 (2) | 0.72025 (11) | 0.0315 (5) | |
C6 | 0.5700 (3) | 0.5338 (2) | 0.67585 (15) | 0.0435 (7) | |
H6A | 0.5898 | 0.5737 | 0.7057 | 0.065* | |
H6B | 0.5028 | 0.5396 | 0.6705 | 0.065* | |
H6C | 0.6022 | 0.5508 | 0.6419 | 0.065* | |
C7 | 0.7606 (2) | 0.4361 (2) | 0.65047 (12) | 0.0353 (6) | |
H7A | 0.7996 | 0.4672 | 0.6775 | 0.053* | |
H7B | 0.7381 | 0.4799 | 0.6234 | 0.053* | |
H7C | 0.7972 | 0.3893 | 0.6319 | 0.053* | |
C8 | 0.7502 (2) | 0.2337 (2) | 0.69899 (14) | 0.0441 (7) | |
H8A | 0.7795 | 0.2301 | 0.7353 | 0.066* | |
H8B | 0.7969 | 0.2505 | 0.6716 | 0.066* | |
H8C | 0.7235 | 0.1747 | 0.6895 | 0.066* | |
C9 | 0.5515 (3) | 0.2092 (3) | 0.75445 (17) | 0.0576 (10) | |
H9A | 0.5662 | 0.2151 | 0.7936 | 0.086* | |
H9B | 0.5826 | 0.1555 | 0.7396 | 0.086* | |
H9C | 0.4843 | 0.2030 | 0.7498 | 0.086* | |
C10 | 0.4433 (2) | 0.3962 (3) | 0.74368 (15) | 0.0548 (10) | |
H10A | 0.4492 | 0.4088 | 0.7830 | 0.082* | |
H10B | 0.4026 | 0.3438 | 0.7383 | 0.082* | |
H10C | 0.4167 | 0.4491 | 0.7251 | 0.082* | |
N1 | 0.42867 (16) | 0.31056 (16) | 0.61660 (11) | 0.0320 (5) | |
C11 | 0.3546 (2) | 0.30076 (18) | 0.60177 (12) | 0.0319 (5) | |
C12 | 0.2609 (2) | 0.2874 (2) | 0.58173 (15) | 0.0462 (8) | |
H12A | 0.2424 | 0.3395 | 0.5593 | 0.069* | |
H12B | 0.2184 | 0.2814 | 0.6129 | 0.069* | |
H12C | 0.2585 | 0.2322 | 0.5594 | 0.069* | |
C13 | 0.6125 (2) | 0.42360 (19) | 0.52430 (11) | 0.0337 (6) | |
N2 | 0.59482 (18) | 0.38485 (16) | 0.56298 (9) | 0.0317 (5) | |
C14 | 0.6351 (3) | 0.4750 (3) | 0.47474 (13) | 0.0520 (9) | |
H14A | 0.6240 | 0.5396 | 0.4813 | 0.078* | |
H14B | 0.5958 | 0.4543 | 0.4444 | 0.078* | |
H14C | 0.7005 | 0.4656 | 0.4653 | 0.078* | |
N3 | 0.58730 (16) | 0.19358 (15) | 0.59979 (10) | 0.0280 (4) | |
C15 | 0.6593 (2) | 0.17756 (19) | 0.56566 (12) | 0.0345 (6) | |
H15 | 0.7032 | 0.2250 | 0.5610 | 0.041* | |
N4 | 0.67417 (19) | 0.10158 (18) | 0.53820 (11) | 0.0402 (6) | |
C16 | 0.6122 (2) | 0.0354 (2) | 0.54516 (14) | 0.0408 (7) | |
H16 | 0.6202 | −0.0196 | 0.5255 | 0.049* | |
C17 | 0.5376 (2) | 0.0438 (2) | 0.57957 (15) | 0.0415 (7) | |
H17 | 0.4949 | −0.0045 | 0.5847 | 0.050* | |
C18 | 0.5271 (2) | 0.12540 (19) | 0.60656 (13) | 0.0353 (6) | |
H18 | 0.4758 | 0.1334 | 0.6306 | 0.042* | |
P1 | 0.4462 (3) | 0.2436 (2) | 0.43923 (14) | 0.0403 (15) | 0.408 (5) |
F1 | 0.3842 (4) | 0.3239 (3) | 0.4127 (3) | 0.081 (2) | 0.408 (5) |
F2 | 0.5083 (4) | 0.1632 (3) | 0.4658 (3) | 0.090 (2) | 0.408 (5) |
F3 | 0.4497 (4) | 0.1931 (4) | 0.38019 (18) | 0.072 (2) | 0.408 (5) |
F4 | 0.4428 (5) | 0.2940 (4) | 0.49825 (19) | 0.076 (2) | 0.408 (5) |
F5 | 0.3525 (3) | 0.1885 (3) | 0.4546 (2) | 0.0509 (17) | 0.408 (5) |
F6 | 0.5400 (3) | 0.2986 (4) | 0.4238 (3) | 0.078 (2) | 0.408 (5) |
P2 | 0.28776 (14) | 0.02841 (15) | 0.67394 (8) | 0.0362 (6) | 0.588 (5) |
F7 | 0.18034 (15) | 0.0385 (4) | 0.65521 (14) | 0.0862 (18) | 0.588 (5) |
F8 | 0.39517 (16) | 0.0183 (3) | 0.69267 (14) | 0.0647 (14) | 0.588 (5) |
F9 | 0.2574 (3) | 0.0414 (2) | 0.73750 (9) | 0.0506 (13) | 0.588 (5) |
F10 | 0.3182 (2) | 0.0155 (3) | 0.61038 (9) | 0.0713 (17) | 0.588 (5) |
F11 | 0.3014 (3) | 0.13688 (15) | 0.66808 (17) | 0.0900 (18) | 0.588 (5) |
F12 | 0.2742 (3) | −0.08006 (16) | 0.67979 (17) | 0.0821 (15) | 0.588 (5) |
P3 | 0.4535 (4) | 0.2487 (3) | 0.43830 (17) | 0.034 (3) | 0.304 (4) |
F13 | 0.4356 (6) | 0.3326 (5) | 0.4798 (3) | 0.061 (2) | 0.304 (4) |
F14 | 0.4713 (6) | 0.1648 (4) | 0.3967 (3) | 0.055 (2) | 0.304 (4) |
F15 | 0.3741 (5) | 0.2876 (5) | 0.3975 (3) | 0.077 (2) | 0.304 (4) |
F16 | 0.5329 (5) | 0.2098 (6) | 0.4791 (3) | 0.099 (3) | 0.304 (4) |
F17 | 0.3759 (5) | 0.1897 (5) | 0.4705 (3) | 0.080 (3) | 0.304 (4) |
F18 | 0.5311 (5) | 0.3078 (5) | 0.4061 (3) | 0.083 (3) | 0.304 (4) |
P4 | 0.2829 (2) | 0.04411 (19) | 0.66883 (12) | 0.0334 (7) | 0.412 (5) |
F19 | 0.2476 (4) | 0.0260 (3) | 0.73103 (13) | 0.0478 (17) | 0.412 (5) |
F20 | 0.3182 (3) | 0.0622 (3) | 0.60663 (13) | 0.0514 (16) | 0.412 (5) |
F21 | 0.1967 (3) | 0.1128 (4) | 0.6591 (2) | 0.087 (2) | 0.412 (5) |
F22 | 0.3690 (4) | −0.0246 (4) | 0.6786 (2) | 0.090 (2) | 0.412 (5) |
F23 | 0.2198 (4) | −0.0395 (4) | 0.6474 (2) | 0.088 (2) | 0.412 (5) |
F24 | 0.3460 (4) | 0.1277 (3) | 0.6903 (2) | 0.079 (2) | 0.412 (5) |
P5 | 0.4569 (3) | 0.2483 (3) | 0.44008 (16) | 0.028 (2) | 0.288 (4) |
F25 | 0.4469 (6) | 0.2722 (6) | 0.37544 (17) | 0.085 (2) | 0.288 (4) |
F26 | 0.4668 (6) | 0.2243 (6) | 0.50474 (18) | 0.094 (2) | 0.288 (4) |
F27 | 0.3520 (4) | 0.2086 (5) | 0.4403 (3) | 0.057 (2) | 0.288 (4) |
F28 | 0.5617 (4) | 0.2879 (6) | 0.4399 (4) | 0.090 (3) | 0.288 (4) |
F29 | 0.4174 (6) | 0.3477 (4) | 0.4557 (4) | 0.077 (3) | 0.288 (4) |
F30 | 0.4963 (6) | 0.1488 (4) | 0.4244 (4) | 0.082 (2) | 0.288 (4) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Rh1 | 0.02173 (10) | 0.02244 (10) | 0.02185 (10) | −0.00308 (7) | −0.00013 (7) | 0.00192 (6) |
C1 | 0.0279 (12) | 0.0266 (11) | 0.0262 (12) | 0.0018 (9) | −0.0002 (10) | −0.0038 (9) |
C2 | 0.0234 (11) | 0.0271 (11) | 0.0212 (10) | −0.0023 (9) | −0.0004 (9) | −0.0015 (9) |
C3 | 0.0292 (13) | 0.0275 (11) | 0.0259 (12) | 0.0013 (9) | −0.0046 (10) | 0.0012 (9) |
C4 | 0.0334 (14) | 0.0382 (14) | 0.0237 (12) | −0.0083 (11) | −0.0022 (10) | 0.0078 (10) |
C5 | 0.0244 (12) | 0.0458 (15) | 0.0242 (12) | −0.0021 (11) | 0.0030 (10) | −0.0020 (11) |
C6 | 0.054 (2) | 0.0292 (14) | 0.0475 (18) | 0.0098 (13) | −0.0076 (15) | −0.0049 (13) |
C7 | 0.0292 (14) | 0.0434 (15) | 0.0332 (14) | −0.0106 (12) | 0.0028 (11) | −0.0006 (11) |
C8 | 0.0438 (17) | 0.0386 (15) | 0.0498 (18) | 0.0137 (13) | −0.0116 (15) | −0.0009 (13) |
C9 | 0.068 (2) | 0.058 (2) | 0.047 (2) | −0.0242 (19) | −0.0037 (18) | 0.0267 (18) |
C10 | 0.0317 (16) | 0.091 (3) | 0.0420 (18) | 0.0036 (17) | 0.0129 (14) | −0.0070 (19) |
N1 | 0.0289 (12) | 0.0328 (11) | 0.0342 (12) | −0.0012 (9) | −0.0028 (9) | 0.0024 (9) |
C11 | 0.0314 (14) | 0.0301 (12) | 0.0343 (14) | −0.0025 (10) | −0.0041 (11) | 0.0027 (10) |
C12 | 0.0342 (16) | 0.0484 (17) | 0.056 (2) | −0.0040 (14) | −0.0166 (15) | 0.0043 (15) |
C13 | 0.0392 (15) | 0.0328 (13) | 0.0290 (13) | −0.0071 (11) | −0.0004 (11) | −0.0003 (10) |
N2 | 0.0364 (12) | 0.0327 (11) | 0.0260 (11) | −0.0072 (10) | −0.0013 (9) | 0.0011 (9) |
C14 | 0.071 (2) | 0.0529 (19) | 0.0322 (16) | −0.0148 (18) | 0.0076 (16) | 0.0122 (14) |
N3 | 0.0289 (11) | 0.0249 (9) | 0.0302 (11) | −0.0024 (8) | −0.0014 (9) | −0.0007 (8) |
C15 | 0.0324 (14) | 0.0336 (13) | 0.0376 (15) | −0.0033 (11) | 0.0032 (12) | −0.0026 (11) |
N4 | 0.0398 (14) | 0.0374 (13) | 0.0434 (14) | 0.0025 (11) | 0.0020 (11) | −0.0061 (11) |
C16 | 0.0440 (17) | 0.0309 (13) | 0.0475 (18) | 0.0039 (12) | −0.0075 (14) | −0.0073 (12) |
C17 | 0.0397 (16) | 0.0274 (13) | 0.057 (2) | −0.0057 (12) | −0.0040 (15) | −0.0009 (13) |
C18 | 0.0339 (14) | 0.0285 (12) | 0.0435 (16) | −0.0052 (11) | 0.0011 (12) | 0.0020 (11) |
P1 | 0.048 (3) | 0.036 (2) | 0.037 (3) | −0.0051 (19) | −0.012 (2) | −0.0006 (19) |
F1 | 0.085 (4) | 0.055 (4) | 0.103 (5) | 0.004 (3) | −0.015 (4) | 0.031 (4) |
F2 | 0.092 (4) | 0.069 (4) | 0.108 (5) | 0.019 (3) | −0.065 (4) | 0.008 (4) |
F3 | 0.078 (4) | 0.085 (5) | 0.053 (4) | 0.003 (4) | 0.001 (3) | −0.022 (4) |
F4 | 0.096 (4) | 0.084 (5) | 0.047 (4) | −0.017 (4) | −0.004 (3) | −0.027 (3) |
F5 | 0.056 (3) | 0.050 (3) | 0.046 (4) | −0.019 (3) | −0.010 (3) | 0.015 (3) |
F6 | 0.042 (3) | 0.077 (4) | 0.116 (6) | −0.037 (3) | 0.013 (4) | −0.015 (4) |
P2 | 0.0333 (11) | 0.0463 (10) | 0.0290 (9) | −0.0026 (8) | −0.0009 (7) | 0.0082 (8) |
F7 | 0.038 (2) | 0.173 (5) | 0.048 (2) | 0.005 (3) | −0.0042 (17) | 0.030 (3) |
F8 | 0.0369 (19) | 0.106 (4) | 0.051 (2) | −0.013 (2) | −0.0052 (17) | 0.023 (2) |
F9 | 0.064 (3) | 0.049 (2) | 0.038 (2) | −0.006 (2) | 0.005 (2) | 0.0008 (18) |
F10 | 0.054 (2) | 0.130 (5) | 0.0303 (19) | −0.007 (3) | 0.0069 (17) | 0.004 (2) |
F11 | 0.136 (5) | 0.051 (2) | 0.083 (4) | 0.003 (3) | 0.022 (3) | 0.032 (2) |
F12 | 0.101 (4) | 0.059 (2) | 0.087 (3) | −0.018 (2) | 0.021 (3) | −0.020 (2) |
P3 | 0.035 (4) | 0.032 (4) | 0.036 (4) | −0.011 (3) | −0.003 (4) | −0.005 (3) |
F13 | 0.081 (5) | 0.062 (5) | 0.040 (5) | 0.012 (4) | −0.014 (4) | −0.021 (4) |
F14 | 0.084 (6) | 0.026 (3) | 0.056 (5) | 0.008 (3) | −0.007 (4) | −0.012 (3) |
F15 | 0.082 (5) | 0.064 (5) | 0.085 (5) | 0.007 (4) | −0.037 (4) | 0.014 (4) |
F16 | 0.102 (5) | 0.098 (5) | 0.098 (5) | 0.031 (5) | −0.041 (4) | 0.000 (5) |
F17 | 0.077 (5) | 0.083 (5) | 0.078 (6) | −0.022 (4) | 0.000 (5) | 0.012 (4) |
F18 | 0.075 (5) | 0.073 (5) | 0.101 (6) | −0.009 (4) | 0.008 (5) | 0.004 (5) |
P4 | 0.0357 (15) | 0.0394 (12) | 0.0251 (13) | −0.0036 (10) | −0.0032 (10) | 0.0008 (10) |
F19 | 0.059 (4) | 0.064 (4) | 0.020 (2) | −0.018 (3) | −0.002 (2) | 0.000 (2) |
F20 | 0.044 (3) | 0.079 (4) | 0.032 (3) | −0.009 (3) | 0.004 (2) | −0.006 (3) |
F21 | 0.071 (4) | 0.116 (5) | 0.074 (4) | 0.032 (4) | 0.023 (3) | 0.032 (4) |
F22 | 0.080 (5) | 0.119 (5) | 0.070 (4) | 0.050 (4) | −0.006 (4) | 0.010 (4) |
F23 | 0.109 (5) | 0.094 (4) | 0.062 (4) | −0.064 (4) | 0.012 (4) | −0.014 (3) |
F24 | 0.093 (5) | 0.088 (5) | 0.056 (4) | −0.055 (4) | 0.026 (4) | −0.020 (3) |
P5 | 0.031 (3) | 0.025 (3) | 0.028 (3) | 0.008 (3) | −0.009 (3) | −0.005 (3) |
F25 | 0.096 (5) | 0.092 (5) | 0.068 (4) | 0.002 (5) | −0.004 (4) | 0.023 (4) |
F26 | 0.099 (5) | 0.113 (5) | 0.070 (4) | 0.010 (5) | −0.031 (4) | 0.012 (4) |
F27 | 0.044 (4) | 0.067 (5) | 0.060 (5) | −0.018 (4) | −0.005 (3) | 0.000 (4) |
F28 | 0.059 (5) | 0.098 (5) | 0.112 (7) | −0.007 (5) | 0.001 (5) | −0.029 (5) |
F29 | 0.092 (5) | 0.060 (4) | 0.078 (6) | 0.020 (4) | 0.000 (5) | −0.023 (5) |
F30 | 0.101 (5) | 0.052 (4) | 0.092 (5) | 0.020 (4) | −0.007 (5) | −0.004 (4) |
Rh1—N1 | 2.093 (2) | C14—H14C | 0.9800 |
Rh1—N2 | 2.110 (2) | N3—C18 | 1.339 (3) |
Rh1—C4 | 2.136 (3) | N3—C15 | 1.350 (4) |
Rh1—C1 | 2.140 (2) | C15—N4 | 1.324 (4) |
Rh1—N3 | 2.148 (2) | C15—H15 | 0.9500 |
Rh1—C2 | 2.149 (2) | N4—C16 | 1.335 (4) |
Rh1—C3 | 2.156 (3) | C16—C17 | 1.368 (5) |
Rh1—C5 | 2.176 (3) | C16—H16 | 0.9500 |
C1—C5 | 1.423 (4) | C17—C18 | 1.381 (4) |
C1—C2 | 1.445 (4) | C17—H17 | 0.9500 |
C1—C6 | 1.492 (4) | C18—H18 | 0.9500 |
C2—C3 | 1.427 (3) | P1—F4 | 1.6199 |
C2—C7 | 1.490 (4) | P1—F6 | 1.6199 |
C3—C4 | 1.448 (4) | P1—F5 | 1.6200 |
C3—C8 | 1.491 (4) | P1—F1 | 1.6201 |
C4—C5 | 1.432 (4) | P1—F3 | 1.6201 |
C4—C9 | 1.498 (4) | P1—F2 | 1.6202 |
C5—C10 | 1.491 (4) | P2—F10 | 1.6198 |
C6—H6A | 0.9800 | P2—F7 | 1.6199 |
C6—H6B | 0.9800 | P2—F8 | 1.6200 |
C6—H6C | 0.9800 | P2—F12 | 1.6200 |
C7—H7A | 0.9800 | P2—F11 | 1.6200 |
C7—H7B | 0.9800 | P2—F9 | 1.6200 |
C7—H7C | 0.9800 | P3—F16 | 1.6199 |
C8—H8A | 0.9800 | P3—F13 | 1.6199 |
C8—H8B | 0.9800 | P3—F18 | 1.6200 |
C8—H8C | 0.9800 | P3—F17 | 1.6201 |
C9—H9A | 0.9800 | P3—F14 | 1.6201 |
C9—H9B | 0.9800 | P3—F15 | 1.6202 |
C9—H9C | 0.9800 | P4—F23 | 1.6199 |
C10—H10A | 0.9800 | P4—F21 | 1.6200 |
C10—H10B | 0.9800 | P4—F22 | 1.6200 |
C10—H10C | 0.9800 | P4—F20 | 1.6200 |
N1—C11 | 1.136 (4) | P4—F19 | 1.6200 |
C11—C12 | 1.449 (4) | P4—F24 | 1.6201 |
C12—H12A | 0.9800 | P5—F25 | 1.6198 |
C12—H12B | 0.9800 | P5—F27 | 1.6198 |
C12—H12C | 0.9800 | P5—F30 | 1.6199 |
C13—N2 | 1.131 (4) | P5—F28 | 1.6200 |
C13—C14 | 1.462 (4) | P5—F29 | 1.6201 |
C14—H14A | 0.9800 | P5—F26 | 1.6202 |
C14—H14B | 0.9800 | ||
N1—Rh1—N2 | 88.75 (10) | C13—C14—H14A | 109.5 |
N1—Rh1—C4 | 110.11 (10) | C13—C14—H14B | 109.5 |
N2—Rh1—C4 | 158.14 (10) | H14A—C14—H14B | 109.5 |
N1—Rh1—C1 | 112.22 (10) | C13—C14—H14C | 109.5 |
N2—Rh1—C1 | 97.43 (9) | H14A—C14—H14C | 109.5 |
C4—Rh1—C1 | 65.76 (11) | H14B—C14—H14C | 109.5 |
N1—Rh1—N3 | 86.05 (9) | C18—N3—C15 | 116.2 (2) |
N2—Rh1—N3 | 88.29 (9) | C18—N3—Rh1 | 121.9 (2) |
C4—Rh1—N3 | 103.49 (10) | C15—N3—Rh1 | 121.91 (18) |
C1—Rh1—N3 | 160.86 (10) | N4—C15—N3 | 125.7 (3) |
N1—Rh1—C2 | 151.48 (10) | N4—C15—H15 | 117.1 |
N2—Rh1—C2 | 92.57 (9) | N3—C15—H15 | 117.1 |
C4—Rh1—C2 | 65.57 (10) | C15—N4—C16 | 116.7 (3) |
C1—Rh1—C2 | 39.38 (10) | N4—C16—C17 | 122.5 (3) |
N3—Rh1—C2 | 122.45 (9) | N4—C16—H16 | 118.8 |
N1—Rh1—C3 | 149.10 (10) | C17—C16—H16 | 118.8 |
N2—Rh1—C3 | 122.10 (10) | C16—C17—C18 | 117.2 (3) |
C4—Rh1—C3 | 39.44 (10) | C16—C17—H17 | 121.4 |
C1—Rh1—C3 | 65.67 (10) | C18—C17—H17 | 121.4 |
N3—Rh1—C3 | 95.81 (9) | N3—C18—C17 | 121.8 (3) |
C2—Rh1—C3 | 38.71 (9) | N3—C18—H18 | 119.1 |
N1—Rh1—C5 | 93.95 (10) | C17—C18—H18 | 119.1 |
N2—Rh1—C5 | 132.47 (11) | F4—P1—F6 | 90.0 |
C4—Rh1—C5 | 38.77 (11) | F4—P1—F5 | 90.0 |
C1—Rh1—C5 | 38.48 (10) | F6—P1—F5 | 180.0 |
N3—Rh1—C5 | 139.24 (10) | F4—P1—F1 | 90.0 |
C2—Rh1—C5 | 64.63 (10) | F6—P1—F1 | 90.0 |
C3—Rh1—C5 | 64.85 (10) | F5—P1—F1 | 90.0 |
C5—C1—C2 | 107.4 (2) | F4—P1—F3 | 180.0 |
C5—C1—C6 | 126.9 (3) | F6—P1—F3 | 90.0 |
C2—C1—C6 | 125.6 (3) | F5—P1—F3 | 90.0 |
C5—C1—Rh1 | 72.13 (15) | F1—P1—F3 | 90.0 |
C2—C1—Rh1 | 70.64 (14) | F4—P1—F2 | 90.0 |
C6—C1—Rh1 | 125.8 (2) | F6—P1—F2 | 90.0 |
C3—C2—C1 | 108.4 (2) | F5—P1—F2 | 90.0 |
C3—C2—C7 | 126.8 (2) | F1—P1—F2 | 180.0 |
C1—C2—C7 | 124.8 (2) | F3—P1—F2 | 90.0 |
C3—C2—Rh1 | 70.90 (14) | F10—P2—F7 | 90.0 |
C1—C2—Rh1 | 69.98 (14) | F10—P2—F8 | 90.0 |
C7—C2—Rh1 | 125.68 (18) | F7—P2—F8 | 180.0 |
C2—C3—C4 | 107.6 (2) | F10—P2—F12 | 90.0 |
C2—C3—C8 | 127.0 (3) | F7—P2—F12 | 90.0 |
C4—C3—C8 | 125.3 (3) | F8—P2—F12 | 90.0 |
C2—C3—Rh1 | 70.39 (14) | F10—P2—F11 | 90.0 |
C4—C3—Rh1 | 69.56 (15) | F7—P2—F11 | 90.0 |
C8—C3—Rh1 | 126.6 (2) | F8—P2—F11 | 90.0 |
C5—C4—C3 | 107.5 (2) | F12—P2—F11 | 180.0 |
C5—C4—C9 | 126.4 (3) | F10—P2—F9 | 180.0 |
C3—C4—C9 | 125.7 (3) | F7—P2—F9 | 90.0 |
C5—C4—Rh1 | 72.12 (15) | F8—P2—F9 | 90.0 |
C3—C4—Rh1 | 71.00 (15) | F12—P2—F9 | 90.0 |
C9—C4—Rh1 | 127.7 (2) | F11—P2—F9 | 90.0 |
C1—C5—C4 | 108.8 (2) | F16—P3—F13 | 90.0 |
C1—C5—C10 | 125.9 (3) | F16—P3—F18 | 90.0 |
C4—C5—C10 | 125.3 (3) | F13—P3—F18 | 90.0 |
C1—C5—Rh1 | 69.39 (14) | F16—P3—F17 | 90.0 |
C4—C5—Rh1 | 69.11 (15) | F13—P3—F17 | 90.0 |
C10—C5—Rh1 | 127.4 (2) | F18—P3—F17 | 180.0 |
C1—C6—H6A | 109.5 | F16—P3—F14 | 90.0 |
C1—C6—H6B | 109.5 | F13—P3—F14 | 180.0 |
H6A—C6—H6B | 109.5 | F18—P3—F14 | 90.0 |
C1—C6—H6C | 109.5 | F17—P3—F14 | 90.0 |
H6A—C6—H6C | 109.5 | F16—P3—F15 | 180.0 |
H6B—C6—H6C | 109.5 | F13—P3—F15 | 90.0 |
C2—C7—H7A | 109.5 | F18—P3—F15 | 90.0 |
C2—C7—H7B | 109.5 | F17—P3—F15 | 90.0 |
H7A—C7—H7B | 109.5 | F14—P3—F15 | 90.0 |
C2—C7—H7C | 109.5 | F23—P4—F21 | 90.0 |
H7A—C7—H7C | 109.5 | F23—P4—F22 | 90.0 |
H7B—C7—H7C | 109.5 | F21—P4—F22 | 180.0 |
C3—C8—H8A | 109.5 | F23—P4—F20 | 90.0 |
C3—C8—H8B | 109.5 | F21—P4—F20 | 90.0 |
H8A—C8—H8B | 109.5 | F22—P4—F20 | 90.0 |
C3—C8—H8C | 109.5 | F23—P4—F19 | 90.0 |
H8A—C8—H8C | 109.5 | F21—P4—F19 | 90.0 |
H8B—C8—H8C | 109.5 | F22—P4—F19 | 90.0 |
C4—C9—H9A | 109.5 | F20—P4—F19 | 180.0 |
C4—C9—H9B | 109.5 | F23—P4—F24 | 180.0 |
H9A—C9—H9B | 109.5 | F21—P4—F24 | 90.0 |
C4—C9—H9C | 109.5 | F22—P4—F24 | 90.0 |
H9A—C9—H9C | 109.5 | F20—P4—F24 | 90.0 |
H9B—C9—H9C | 109.5 | F19—P4—F24 | 90.0 |
C5—C10—H10A | 109.5 | F25—P5—F27 | 90.0 |
C5—C10—H10B | 109.5 | F25—P5—F30 | 90.0 |
H10A—C10—H10B | 109.5 | F27—P5—F30 | 90.0 |
C5—C10—H10C | 109.5 | F25—P5—F28 | 90.0 |
H10A—C10—H10C | 109.5 | F27—P5—F28 | 180.0 |
H10B—C10—H10C | 109.5 | F30—P5—F28 | 90.0 |
C11—N1—Rh1 | 175.8 (3) | F25—P5—F29 | 90.0 |
N1—C11—C12 | 178.7 (4) | F27—P5—F29 | 90.0 |
C11—C12—H12A | 109.5 | F30—P5—F29 | 180.0 |
C11—C12—H12B | 109.5 | F28—P5—F29 | 90.0 |
H12A—C12—H12B | 109.5 | F25—P5—F26 | 180.0 |
C11—C12—H12C | 109.5 | F27—P5—F26 | 90.0 |
H12A—C12—H12C | 109.5 | F30—P5—F26 | 90.0 |
H12B—C12—H12C | 109.5 | F28—P5—F26 | 90.0 |
N2—C13—C14 | 179.1 (3) | F29—P5—F26 | 90.0 |
C13—N2—Rh1 | 174.6 (2) |
Experimental details
Crystal data | |
Chemical formula | [Rh(C10H15)(C4H4N2)(C2H3N)2](PF6)2 |
Mr | 690.27 |
Crystal system, space group | Orthorhombic, Pbca |
Temperature (K) | 193 |
a, b, c (Å) | 14.4046 (8), 14.7669 (7), 24.3537 (13) |
V (Å3) | 5180.3 (5) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 0.89 |
Crystal size (mm) | 0.36 × 0.36 × 0.32 |
Data collection | |
Diffractometer | Bruker Kappa APEXII CCD |
Absorption correction | Integration (SHELXTL and XPREP; Bruker, 2005) |
Tmin, Tmax | 0.625, 0.813 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 93720, 7612, 6384 |
Rint | 0.026 |
(sin θ/λ)max (Å−1) | 0.706 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.037, 0.100, 1.04 |
No. of reflections | 7612 |
No. of parameters | 459 |
No. of restraints | 241 |
H-atom treatment | H-atom parameters not refined |
Δρmax, Δρmin (e Å−3) | 0.93, −0.72 |
Computer programs: APEX2 (Bruker, 2004), SAINT (Bruker, 2005), SHELXTL (Bruker, 2005), XCIF (Bruker, 2005).
Rh1—N1 | 2.093 (2) | Rh1—N3 | 2.148 (2) |
Rh1—N2 | 2.110 (2) | Rh1—C2 | 2.149 (2) |
Rh1—C4 | 2.136 (3) | Rh1—C3 | 2.156 (3) |
Rh1—C1 | 2.140 (2) | Rh1—C5 | 2.176 (3) |
While pyrimidine and pyrimidine derivatives are biologically relevant, only 120 crystal structures with metal–pyrimidine bonds have been reported, none of which contain Cp co-ligands (Barnett et al., 2005; Nedelec & Rochon, 2001; and Sharma et al., 1998). Here we report the crystal structure of [Cp*Rh(NCMe)2(N2C4H4)](PF6)2 as an unique half-sandwich pyrimidine adduct. The Rh—N distance for the two acetonitrile ligands are 2.093 (2) and 2.109 (2) Å. The coordinated pyrimidine has a longer Rh—N distance of 2.148 (2) Å. The N—Rh—N angles are slightly contracted ranging from 86.05 (9) to 88.74 (10)°.