Owing to increasing interest in the use of N-heterocyclic carbenes (NHCs) based on imidazolidinium ions as ligands in the design of highly efficient transition-metal-based homogeneous catalysts, the characterizations of the 1-ferrocenylmethyl-3-(2,4,6-trimethylbenzyl)imidazolidin-3-ium iodide salt, [Fe(C5H5)(C19H24N2)]I, (I), and the palladium complex trans-bis(3-benzyl-1-ferrocenylmethyl-1H-imidazolidin-2-ylidene)diiodidopalladium(II), [Fe2Pd(C5H5)2(C16H17N2)2I2], (II), are reported. Compound (I) has two iodide anions and two imidazolidinium cations within the asymmetric unit (Z′ = 2). The two cations have distinctly different conformations, with the ferrocene groups orientated exo and endo with respect to the N-heterocyclic carbene. Weak C—H donor hydrogen bonds to both the iodide anions and the π system of the mesitylene group combine to form two-dimensional layers perpendicular to the crystallographic c direction. Only one of the formally charged imidazolidinium rings forms a near-linear hydrogen bond with an iodide anion. Complex (II) shows square-planar coordination around the PdII metal, which is located on an inversion centre (Z′ = 0.5). The ferrocene and benzyl substituents are in a trans–anti arrangement. The Pd—C bond distance between the N-heterocyclic carbene ligands and the metal atom is 2.036 (7) Å. A survey of related structures shows that the lengthening of the N—C bonds and the closure of the N—C—N angle seen here on metal complexation is typical of similar NHCs and their complexes.
Supporting information
CCDC references: 867007; 867008
The syntheses and spectroscopic characterizations of the title compounds have
been detailed in the study by Demirhan et al. (2003). Crystals
of (I)
and (II) were grown from methanol–diethyl ether (Solvent ratio?) and
dichloromethane–diethyl ether (Solvent ratio?), respectively.
All H atoms were placed in geometrically idealized positions and treated as
riding, with C—H = 0.98 (methyl), 0.99 (methylene) or 0.95 Å (aromatic),
and with Uiso(H) = 1.2Ueq(Caromatic, Cmethylene) or
1.5Ueq(Cmethyl).
In molecule A of (I), the C atoms of the unsubstituted Cp ring display
rather elongated displacement ellipsoids, but attempts to model a disordered
system did not improve the quality of the refinement. Moreover, the anistropic
displacement parameters for all the disordered C atoms were unrealistic and
needed to be severely restrained using EADP commands (SHELXL97;
Sheldrick, 2008). Thus, the non-disordered model was preferred.
For both compounds, data collection: CrysAlis CCD (Oxford Diffraction, 2006); cell refinement: CrysAlis RED (Oxford Diffraction, 2006); data reduction: CrysAlis RED (Oxford Diffraction, 2006); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008). Molecular graphics: ORTEPIII (Burnett & Johnson, 1996), ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2009) for (I); ORTEPIII (Burnett & Johnson, 1996) and ORTEP-3 for Windows (Farrugia, 1997) for (II). For both compounds, software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).
(I) 1-ferrocenylmethyl-3-(2,4,6-trimethylbenzyl)imidazolidin-3-ium iodide salt
top
Crystal data top
[Fe(C5H5)(C19H24N2)]I | F(000) = 1064 |
Mr = 528.24 | Dx = 1.574 Mg m−3 |
Monoclinic, P21 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2yb | Cell parameters from 19197 reflections |
a = 10.6277 (12) Å | θ = 2.8–28.2° |
b = 7.4514 (8) Å | µ = 2.07 mm−1 |
c = 28.293 (3) Å | T = 180 K |
β = 95.603 (9)° | Flattened, yellow |
V = 2229.8 (4) Å3 | 0.44 × 0.29 × 0.03 mm |
Z = 4 | |
Data collection top
Oxford Xcalibur diffractometer | 10405 independent reflections |
Radiation source: fine-focus sealed tube | 7372 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.044 |
ω and ϕ scans | θmax = 28.2°, θmin = 2.8° |
Absorption correction: analytical [Analytical numerical absorption correction using a multifaceted crystal model
based on expressions derived by Clark & Reid, implemented in CrysAlis RED
(Oxford Diffraction, 2006)] | h = −13→14 |
Tmin = 0.654, Tmax = 0.964 | k = −9→9 |
19193 measured reflections | l = −35→37 |
Refinement top
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)] = 0.036 | H-atom parameters constrained |
wR(F2) = 0.064 | w = 1/[σ2(Fo2) + (0.0212P)2] where P = (Fo2 + 2Fc2)/3 |
S = 0.84 | (Δ/σ)max = 0.011 |
10405 reflections | Δρmax = 0.67 e Å−3 |
512 parameters | Δρmin = −0.63 e Å−3 |
1 restraint | Absolute structure: Flack (1983), with 4503 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.220 (15) |
Crystal data top
[Fe(C5H5)(C19H24N2)]I | V = 2229.8 (4) Å3 |
Mr = 528.24 | Z = 4 |
Monoclinic, P21 | Mo Kα radiation |
a = 10.6277 (12) Å | µ = 2.07 mm−1 |
b = 7.4514 (8) Å | T = 180 K |
c = 28.293 (3) Å | 0.44 × 0.29 × 0.03 mm |
β = 95.603 (9)° | |
Data collection top
Oxford Xcalibur diffractometer | 10405 independent reflections |
Absorption correction: analytical [Analytical numerical absorption correction using a multifaceted crystal model
based on expressions derived by Clark & Reid, implemented in CrysAlis RED
(Oxford Diffraction, 2006)] | 7372 reflections with I > 2σ(I) |
Tmin = 0.654, Tmax = 0.964 | Rint = 0.044 |
19193 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.036 | H-atom parameters constrained |
wR(F2) = 0.064 | Δρmax = 0.67 e Å−3 |
S = 0.84 | Δρmin = −0.63 e Å−3 |
10405 reflections | Absolute structure: Flack (1983), with 4503 Friedel pairs |
512 parameters | Absolute structure parameter: 0.220 (15) |
1 restraint | |
Special details top
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell esds are taken
into account individually in the estimation of esds in distances, angles
and torsion angles; correlations between esds in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell esds is used for estimating esds involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor
wR and goodness of fit S are based on F2, conventional
R-factors R are based on F, with F set to zero for
negative F2. The threshold expression of F2 >
σ(F2) is used only for calculating R-factors(gt) etc.
and is not relevant to the choice of reflections for refinement.
R-factors based on F2 are statistically about twice as large
as those based on F, and R-factors based on ALL data will be
even larger. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
I1 | 0.95888 (3) | 0.08368 (4) | 0.750410 (13) | 0.04257 (11) | |
Fe1 | 0.62330 (5) | 0.78071 (9) | 0.58868 (2) | 0.01734 (14) | |
C1 | 0.7567 (5) | 0.5055 (7) | 0.75213 (18) | 0.0328 (12) | |
H1 | 0.8003 | 0.3945 | 0.7511 | 0.039* | |
C11 | 0.6942 (4) | 0.5650 (6) | 0.62842 (15) | 0.0207 (10) | |
C12 | 0.6524 (4) | 0.5138 (6) | 0.58061 (15) | 0.0218 (11) | |
H12 | 0.5887 | 0.4278 | 0.5714 | 0.026* | |
C13 | 0.7219 (4) | 0.6129 (6) | 0.54963 (16) | 0.0236 (10) | |
H13 | 0.7135 | 0.6042 | 0.5160 | 0.028* | |
C14 | 0.8062 (4) | 0.7271 (6) | 0.57707 (15) | 0.0221 (11) | |
H14 | 0.8639 | 0.8087 | 0.5650 | 0.026* | |
C15 | 0.7897 (3) | 0.6990 (6) | 0.62607 (14) | 0.0218 (10) | |
H15 | 0.8341 | 0.7586 | 0.6523 | 0.026* | |
C16 | 0.4425 (4) | 0.8404 (7) | 0.5647 (3) | 0.0537 (18) | |
H16 | 0.3822 | 0.7567 | 0.5510 | 0.064* | |
C17 | 0.4634 (6) | 0.8834 (9) | 0.6130 (3) | 0.062 (2) | |
H17 | 0.4200 | 0.8354 | 0.6379 | 0.074* | |
C18 | 0.5604 (6) | 1.0107 (8) | 0.6174 (2) | 0.0584 (19) | |
H18 | 0.5944 | 1.0651 | 0.6463 | 0.070* | |
C19 | 0.5978 (5) | 1.0436 (7) | 0.5740 (3) | 0.0443 (16) | |
H19 | 0.6632 | 1.1238 | 0.5673 | 0.053* | |
C20 | 0.5245 (5) | 0.9405 (8) | 0.54076 (18) | 0.0410 (14) | |
H20 | 0.5302 | 0.9395 | 0.5075 | 0.049* | |
N11 | 0.6882 (3) | 0.5707 (6) | 0.71584 (13) | 0.0291 (10) | |
N12 | 0.7609 (3) | 0.6064 (6) | 0.79084 (13) | 0.0306 (11) | |
C111 | 0.6537 (4) | 0.4739 (6) | 0.67164 (16) | 0.0321 (11) | |
H11A | 0.5607 | 0.4584 | 0.6676 | 0.039* | |
H11B | 0.6922 | 0.3528 | 0.6741 | 0.039* | |
C112 | 0.6271 (5) | 0.7340 (7) | 0.72953 (16) | 0.0385 (14) | |
H11C | 0.5346 | 0.7172 | 0.7290 | 0.046* | |
H11D | 0.6441 | 0.8346 | 0.7082 | 0.046* | |
C113 | 0.6872 (4) | 0.7684 (7) | 0.78016 (15) | 0.0290 (11) | |
H11E | 0.7420 | 0.8760 | 0.7815 | 0.035* | |
H11F | 0.6218 | 0.7839 | 0.8025 | 0.035* | |
C121 | 0.8510 (4) | 0.5853 (8) | 0.83298 (16) | 0.0388 (12) | |
H12A | 0.9237 | 0.6669 | 0.8307 | 0.047* | |
H12B | 0.8834 | 0.4606 | 0.8345 | 0.047* | |
C122 | 0.7890 (4) | 0.6273 (7) | 0.87790 (16) | 0.0285 (13) | |
C123 | 0.7051 (5) | 0.5106 (7) | 0.89601 (17) | 0.0348 (12) | |
C124 | 0.6464 (4) | 0.5586 (8) | 0.93567 (17) | 0.0359 (13) | |
H124 | 0.5886 | 0.4772 | 0.9477 | 0.043* | |
C125 | 0.6692 (4) | 0.7207 (6) | 0.95825 (16) | 0.0311 (13) | |
C126 | 0.7549 (4) | 0.8333 (7) | 0.94080 (16) | 0.0322 (12) | |
H126 | 0.7737 | 0.9440 | 0.9566 | 0.039* | |
C127 | 0.8158 (4) | 0.7916 (8) | 0.90064 (15) | 0.0311 (11) | |
C128 | 0.6757 (5) | 0.3254 (8) | 0.87397 (19) | 0.0551 (16) | |
H12C | 0.6414 | 0.3398 | 0.8408 | 0.083* | |
H12D | 0.6135 | 0.2641 | 0.8916 | 0.083* | |
H12E | 0.7534 | 0.2540 | 0.8754 | 0.083* | |
C129 | 0.6002 (4) | 0.7766 (8) | 1.00007 (16) | 0.0466 (13) | |
H12F | 0.5725 | 0.6695 | 1.0163 | 0.070* | |
H12G | 0.5264 | 0.8492 | 0.9889 | 0.070* | |
H12H | 0.6570 | 0.8474 | 1.0222 | 0.070* | |
C130 | 0.9085 (4) | 0.9263 (7) | 0.88393 (18) | 0.0420 (14) | |
H13A | 0.9215 | 1.0236 | 0.9072 | 0.063* | |
H13B | 0.8748 | 0.9757 | 0.8532 | 0.063* | |
H13C | 0.9894 | 0.8667 | 0.8806 | 0.063* | |
I2 | 0.48223 (3) | 0.17674 (4) | 0.752716 (11) | 0.03052 (8) | |
Fe2 | 0.12131 (5) | 0.25983 (9) | 0.58461 (2) | 0.01750 (14) | |
C21 | 0.1751 (4) | 0.4428 (6) | 0.63545 (16) | 0.0234 (10) | |
C22 | 0.1436 (4) | 0.5301 (6) | 0.59129 (17) | 0.0228 (11) | |
H22 | 0.0804 | 0.6195 | 0.5851 | 0.027* | |
C23 | 0.2223 (4) | 0.4613 (6) | 0.55806 (17) | 0.0253 (11) | |
H23 | 0.2198 | 0.4933 | 0.5255 | 0.030* | |
C24 | 0.3057 (4) | 0.3354 (6) | 0.58232 (16) | 0.0244 (10) | |
H24 | 0.3700 | 0.2700 | 0.5687 | 0.029* | |
C25 | 0.2777 (4) | 0.3234 (6) | 0.62965 (15) | 0.0246 (10) | |
H25 | 0.3195 | 0.2491 | 0.6536 | 0.029* | |
C26 | −0.0382 (4) | 0.1415 (6) | 0.60485 (16) | 0.0342 (13) | |
H26 | −0.0809 | 0.1743 | 0.6315 | 0.041* | |
C27 | −0.0613 (4) | 0.2108 (6) | 0.55810 (16) | 0.0318 (12) | |
H27 | −0.1227 | 0.2988 | 0.5479 | 0.038* | |
C28 | 0.0216 (4) | 0.1276 (6) | 0.52983 (15) | 0.0269 (12) | |
H28 | 0.0260 | 0.1492 | 0.4969 | 0.032* | |
C29 | 0.0974 (4) | 0.0070 (6) | 0.55772 (18) | 0.0319 (12) | |
H29 | 0.1622 | −0.0667 | 0.5473 | 0.038* | |
C30 | 0.0596 (5) | 0.0152 (7) | 0.60425 (18) | 0.0375 (13) | |
H30 | 0.0946 | −0.0532 | 0.6307 | 0.045* | |
N21 | 0.1756 (3) | 0.5537 (6) | 0.71863 (13) | 0.0266 (10) | |
N22 | 0.2803 (3) | 0.5910 (6) | 0.78801 (14) | 0.0274 (9) | |
C2 | 0.2258 (4) | 0.4778 (6) | 0.75701 (17) | 0.0241 (11) | |
H2 | 0.2234 | 0.3520 | 0.7622 | 0.029* | |
C211 | 0.1055 (4) | 0.4608 (6) | 0.67892 (15) | 0.0270 (11) | |
H21A | 0.0255 | 0.5263 | 0.6702 | 0.032* | |
H21B | 0.0832 | 0.3393 | 0.6896 | 0.032* | |
C212 | 0.2036 (5) | 0.7449 (7) | 0.71842 (18) | 0.0326 (13) | |
H21C | 0.1258 | 0.8173 | 0.7116 | 0.039* | |
H21D | 0.2639 | 0.7744 | 0.6950 | 0.039* | |
C213 | 0.2631 (5) | 0.7735 (8) | 0.76974 (17) | 0.0343 (13) | |
H21E | 0.3451 | 0.8370 | 0.7703 | 0.041* | |
H21F | 0.2060 | 0.8430 | 0.7885 | 0.041* | |
C221 | 0.3523 (4) | 0.5484 (6) | 0.83365 (15) | 0.0293 (11) | |
H22A | 0.4362 | 0.6071 | 0.8349 | 0.035* | |
H22B | 0.3663 | 0.4172 | 0.8356 | 0.035* | |
C222 | 0.2868 (4) | 0.6082 (7) | 0.87614 (16) | 0.0251 (11) | |
C223 | 0.1949 (4) | 0.4987 (6) | 0.89363 (17) | 0.0306 (11) | |
C224 | 0.1349 (4) | 0.5571 (8) | 0.93268 (17) | 0.0358 (13) | |
H224 | 0.0733 | 0.4824 | 0.9449 | 0.043* | |
C225 | 0.1631 (4) | 0.7205 (7) | 0.95390 (16) | 0.0298 (13) | |
C226 | 0.2553 (4) | 0.8241 (7) | 0.93705 (16) | 0.0331 (12) | |
H226 | 0.2773 | 0.9346 | 0.9524 | 0.040* | |
C227 | 0.3183 (4) | 0.7732 (7) | 0.89802 (15) | 0.0282 (11) | |
C228 | 0.1598 (5) | 0.3181 (7) | 0.87233 (19) | 0.0485 (15) | |
H22C | 0.0994 | 0.2589 | 0.8913 | 0.073* | |
H22D | 0.2359 | 0.2439 | 0.8722 | 0.073* | |
H22E | 0.1212 | 0.3340 | 0.8397 | 0.073* | |
C229 | 0.0944 (4) | 0.7852 (8) | 0.99512 (16) | 0.0437 (13) | |
H22F | 0.0646 | 0.6816 | 1.0122 | 0.066* | |
H22G | 0.0219 | 0.8590 | 0.9831 | 0.066* | |
H22H | 0.1521 | 0.8568 | 1.0167 | 0.066* | |
C230 | 0.4171 (4) | 0.8988 (6) | 0.88118 (17) | 0.0332 (12) | |
H23A | 0.4355 | 0.9942 | 0.9047 | 0.050* | |
H23B | 0.3850 | 0.9519 | 0.8507 | 0.050* | |
H23C | 0.4946 | 0.8313 | 0.8773 | 0.050* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
I1 | 0.0444 (2) | 0.0393 (2) | 0.0470 (2) | 0.00838 (18) | 0.01985 (17) | 0.01140 (19) |
Fe1 | 0.0177 (3) | 0.0155 (3) | 0.0189 (3) | 0.0013 (3) | 0.0018 (2) | −0.0004 (3) |
C1 | 0.044 (3) | 0.027 (3) | 0.027 (3) | 0.017 (2) | 0.003 (2) | 0.001 (2) |
C11 | 0.026 (2) | 0.014 (2) | 0.022 (2) | 0.0071 (19) | 0.0029 (18) | −0.0013 (19) |
C12 | 0.026 (3) | 0.020 (3) | 0.019 (3) | −0.0035 (19) | −0.001 (2) | −0.007 (2) |
C13 | 0.025 (2) | 0.025 (3) | 0.021 (2) | 0.0045 (19) | 0.0013 (19) | −0.002 (2) |
C14 | 0.015 (2) | 0.026 (3) | 0.024 (2) | 0.0054 (18) | 0.0009 (18) | −0.0026 (19) |
C15 | 0.023 (2) | 0.022 (3) | 0.020 (2) | −0.003 (2) | −0.0017 (17) | −0.006 (2) |
C16 | 0.020 (3) | 0.024 (3) | 0.113 (6) | 0.002 (2) | −0.016 (3) | −0.007 (3) |
C17 | 0.055 (4) | 0.058 (5) | 0.081 (5) | 0.043 (3) | 0.049 (4) | 0.047 (4) |
C18 | 0.074 (5) | 0.051 (4) | 0.046 (4) | 0.049 (4) | −0.017 (3) | −0.025 (3) |
C19 | 0.031 (3) | 0.019 (3) | 0.083 (5) | 0.005 (2) | 0.004 (3) | 0.003 (3) |
C20 | 0.046 (3) | 0.058 (4) | 0.019 (3) | 0.032 (3) | 0.001 (2) | 0.008 (3) |
N11 | 0.042 (2) | 0.029 (2) | 0.016 (2) | 0.007 (2) | 0.0010 (17) | −0.005 (2) |
N12 | 0.032 (2) | 0.042 (3) | 0.017 (2) | 0.017 (2) | 0.0006 (17) | 0.001 (2) |
C111 | 0.052 (3) | 0.021 (3) | 0.023 (3) | −0.001 (2) | 0.002 (2) | 0.000 (2) |
C112 | 0.057 (3) | 0.033 (3) | 0.025 (3) | 0.026 (3) | 0.000 (2) | −0.001 (2) |
C113 | 0.033 (3) | 0.023 (2) | 0.030 (3) | 0.008 (2) | 0.000 (2) | −0.007 (2) |
C121 | 0.038 (3) | 0.054 (3) | 0.022 (3) | 0.019 (3) | −0.005 (2) | −0.001 (3) |
C122 | 0.031 (3) | 0.038 (4) | 0.016 (3) | 0.013 (2) | −0.002 (2) | 0.002 (2) |
C123 | 0.047 (3) | 0.033 (3) | 0.022 (3) | 0.008 (3) | −0.010 (2) | −0.001 (2) |
C124 | 0.035 (3) | 0.047 (4) | 0.025 (3) | −0.005 (3) | −0.003 (2) | 0.011 (3) |
C125 | 0.032 (3) | 0.041 (4) | 0.020 (2) | 0.004 (2) | 0.001 (2) | 0.005 (2) |
C126 | 0.036 (3) | 0.038 (3) | 0.020 (3) | 0.000 (2) | −0.010 (2) | −0.002 (2) |
C127 | 0.025 (3) | 0.047 (3) | 0.020 (3) | 0.000 (2) | −0.005 (2) | 0.006 (3) |
C128 | 0.069 (4) | 0.051 (4) | 0.041 (4) | −0.004 (3) | −0.013 (3) | 0.003 (3) |
C129 | 0.044 (3) | 0.060 (4) | 0.037 (3) | 0.006 (3) | 0.008 (2) | 0.001 (3) |
C130 | 0.038 (3) | 0.060 (4) | 0.027 (3) | −0.009 (3) | 0.001 (2) | 0.008 (3) |
I2 | 0.03428 (17) | 0.02951 (17) | 0.02813 (18) | 0.00323 (16) | 0.00477 (13) | −0.00067 (16) |
Fe2 | 0.0168 (3) | 0.0171 (3) | 0.0180 (3) | −0.0019 (3) | −0.0011 (2) | 0.0004 (3) |
C21 | 0.025 (2) | 0.021 (2) | 0.024 (3) | −0.007 (2) | 0.000 (2) | −0.004 (2) |
C22 | 0.023 (2) | 0.019 (3) | 0.025 (3) | 0.0023 (19) | −0.006 (2) | −0.003 (2) |
C23 | 0.026 (3) | 0.027 (3) | 0.022 (3) | −0.007 (2) | 0.000 (2) | 0.003 (2) |
C24 | 0.015 (2) | 0.026 (3) | 0.032 (3) | −0.0035 (19) | 0.003 (2) | −0.005 (2) |
C25 | 0.020 (2) | 0.025 (3) | 0.026 (3) | −0.0013 (19) | −0.0064 (19) | 0.002 (2) |
C26 | 0.038 (3) | 0.039 (4) | 0.029 (3) | −0.022 (2) | 0.018 (2) | −0.013 (2) |
C27 | 0.017 (2) | 0.032 (3) | 0.044 (3) | 0.002 (2) | −0.010 (2) | −0.005 (2) |
C28 | 0.030 (2) | 0.033 (3) | 0.016 (2) | −0.013 (2) | −0.0034 (19) | −0.0014 (19) |
C29 | 0.026 (3) | 0.024 (3) | 0.046 (3) | −0.001 (2) | 0.004 (2) | −0.017 (2) |
C30 | 0.045 (3) | 0.033 (3) | 0.031 (3) | −0.014 (3) | −0.017 (2) | 0.014 (2) |
N21 | 0.033 (2) | 0.029 (3) | 0.016 (2) | 0.0011 (19) | −0.0007 (17) | −0.0014 (19) |
N22 | 0.030 (2) | 0.030 (2) | 0.022 (2) | 0.005 (2) | −0.0025 (17) | −0.002 (2) |
C2 | 0.030 (3) | 0.019 (2) | 0.025 (3) | 0.001 (2) | 0.008 (2) | −0.002 (2) |
C211 | 0.028 (3) | 0.034 (3) | 0.018 (3) | −0.009 (2) | −0.0020 (19) | −0.003 (2) |
C212 | 0.047 (3) | 0.023 (3) | 0.028 (3) | 0.003 (2) | 0.000 (2) | 0.003 (2) |
C213 | 0.039 (3) | 0.028 (3) | 0.035 (3) | −0.010 (3) | 0.003 (2) | −0.013 (3) |
C221 | 0.028 (3) | 0.035 (3) | 0.024 (3) | 0.008 (2) | −0.0016 (19) | −0.006 (2) |
C222 | 0.021 (2) | 0.032 (3) | 0.021 (3) | 0.009 (2) | −0.0076 (19) | −0.001 (2) |
C223 | 0.040 (3) | 0.025 (3) | 0.025 (3) | 0.001 (2) | −0.004 (2) | −0.004 (2) |
C224 | 0.031 (3) | 0.049 (4) | 0.026 (3) | −0.007 (3) | 0.000 (2) | 0.009 (3) |
C225 | 0.026 (3) | 0.045 (4) | 0.018 (2) | 0.006 (2) | 0.0019 (19) | 0.000 (2) |
C226 | 0.040 (3) | 0.035 (3) | 0.022 (3) | 0.007 (2) | −0.007 (2) | −0.009 (2) |
C227 | 0.025 (3) | 0.036 (3) | 0.023 (3) | 0.002 (2) | −0.001 (2) | 0.001 (3) |
C228 | 0.058 (4) | 0.044 (4) | 0.044 (3) | −0.009 (3) | 0.004 (3) | 0.002 (3) |
C229 | 0.046 (3) | 0.055 (3) | 0.031 (3) | 0.006 (3) | 0.010 (2) | 0.001 (3) |
C230 | 0.041 (3) | 0.037 (3) | 0.022 (3) | −0.008 (2) | 0.001 (2) | −0.001 (2) |
Geometric parameters (Å, º) top
Fe1—C19 | 2.015 (5) | Fe2—C21 | 2.024 (4) |
Fe1—C20 | 2.020 (4) | Fe2—C23 | 2.031 (5) |
Fe1—C16 | 2.024 (5) | Fe2—C30 | 2.033 (5) |
Fe1—C13 | 2.027 (4) | Fe2—C22 | 2.034 (5) |
Fe1—C12 | 2.029 (4) | Fe2—C29 | 2.038 (5) |
Fe1—C18 | 2.038 (5) | Fe2—C26 | 2.042 (4) |
Fe1—C14 | 2.042 (4) | Fe2—C28 | 2.043 (4) |
Fe1—C17 | 2.043 (5) | Fe2—C27 | 2.044 (4) |
Fe1—C11 | 2.061 (4) | Fe2—C24 | 2.046 (4) |
Fe1—C15 | 2.062 (4) | Fe2—C25 | 2.049 (4) |
C1—N11 | 1.294 (5) | C21—C22 | 1.419 (6) |
C1—N12 | 1.325 (6) | C21—C25 | 1.430 (6) |
C1—H1 | 0.9500 | C21—C211 | 1.502 (6) |
C11—C15 | 1.430 (5) | C22—C23 | 1.414 (6) |
C11—C12 | 1.434 (6) | C22—H22 | 0.9500 |
C11—C111 | 1.498 (6) | C23—C24 | 1.421 (6) |
C12—C13 | 1.409 (6) | C23—H23 | 0.9500 |
C12—H12 | 0.9500 | C24—C25 | 1.403 (6) |
C13—C14 | 1.412 (5) | C24—H24 | 0.9500 |
C13—H13 | 0.9500 | C25—H25 | 0.9500 |
C14—C15 | 1.430 (6) | C26—C30 | 1.404 (6) |
C14—H14 | 0.9500 | C26—C27 | 1.419 (6) |
C15—H15 | 0.9500 | C26—H26 | 0.9500 |
C16—C20 | 1.376 (8) | C27—C28 | 1.393 (6) |
C16—C17 | 1.398 (8) | C27—H27 | 0.9500 |
C16—H16 | 0.9500 | C28—C29 | 1.398 (6) |
C17—C18 | 1.398 (8) | C28—H28 | 0.9500 |
C17—H17 | 0.9500 | C29—C30 | 1.414 (7) |
C18—C19 | 1.350 (8) | C29—H29 | 0.9500 |
C18—H18 | 0.9500 | C30—H30 | 0.9500 |
C19—C20 | 1.392 (7) | N21—C2 | 1.292 (5) |
C19—H19 | 0.9500 | N21—C212 | 1.455 (6) |
C20—H20 | 0.9500 | N21—C211 | 1.461 (5) |
N11—C112 | 1.450 (6) | N22—C2 | 1.311 (5) |
N11—C111 | 1.459 (6) | N22—C213 | 1.460 (7) |
N12—C113 | 1.454 (6) | N22—C221 | 1.470 (5) |
N12—C121 | 1.463 (5) | C2—H2 | 0.9500 |
C111—H11A | 0.9900 | C211—H21A | 0.9900 |
C111—H11B | 0.9900 | C211—H21B | 0.9900 |
C112—C113 | 1.532 (6) | C212—C213 | 1.541 (6) |
C112—H11C | 0.9900 | C212—H21C | 0.9900 |
C112—H11D | 0.9900 | C212—H21D | 0.9900 |
C113—H11E | 0.9900 | C213—H21E | 0.9900 |
C113—H11F | 0.9900 | C213—H21F | 0.9900 |
C121—C122 | 1.520 (6) | C221—C222 | 1.514 (6) |
C121—H12A | 0.9900 | C221—H22A | 0.9900 |
C121—H12B | 0.9900 | C221—H22B | 0.9900 |
C122—C123 | 1.379 (7) | C222—C223 | 1.400 (7) |
C122—C127 | 1.400 (7) | C222—C227 | 1.402 (7) |
C123—C124 | 1.383 (7) | C223—C224 | 1.398 (7) |
C123—C128 | 1.534 (7) | C223—C228 | 1.506 (7) |
C124—C125 | 1.377 (7) | C224—C225 | 1.378 (7) |
C124—H124 | 0.9500 | C224—H224 | 0.9500 |
C125—C126 | 1.365 (6) | C225—C226 | 1.369 (7) |
C125—C129 | 1.510 (6) | C225—C229 | 1.514 (6) |
C126—C127 | 1.397 (6) | C226—C227 | 1.399 (6) |
C126—H126 | 0.9500 | C226—H226 | 0.9500 |
C127—C130 | 1.514 (7) | C227—C230 | 1.517 (6) |
C128—H12C | 0.9800 | C228—H22C | 0.9800 |
C128—H12D | 0.9800 | C228—H22D | 0.9800 |
C128—H12E | 0.9800 | C228—H22E | 0.9800 |
C129—H12F | 0.9800 | C229—H22F | 0.9800 |
C129—H12G | 0.9800 | C229—H22G | 0.9800 |
C129—H12H | 0.9800 | C229—H22H | 0.9800 |
C130—H13A | 0.9800 | C230—H23A | 0.9800 |
C130—H13B | 0.9800 | C230—H23B | 0.9800 |
C130—H13C | 0.9800 | C230—H23C | 0.9800 |
| | | |
C19—Fe1—C20 | 40.4 (2) | C21—Fe2—C23 | 69.04 (18) |
C19—Fe1—C16 | 67.2 (2) | C21—Fe2—C30 | 119.1 (2) |
C20—Fe1—C16 | 39.8 (2) | C23—Fe2—C30 | 163.7 (2) |
C19—Fe1—C13 | 123.6 (2) | C21—Fe2—C22 | 40.95 (17) |
C20—Fe1—C13 | 105.09 (19) | C23—Fe2—C22 | 40.70 (18) |
C16—Fe1—C13 | 118.5 (2) | C30—Fe2—C22 | 154.2 (2) |
C19—Fe1—C12 | 161.5 (2) | C21—Fe2—C29 | 154.7 (2) |
C20—Fe1—C12 | 125.3 (2) | C23—Fe2—C29 | 126.6 (2) |
C16—Fe1—C12 | 109.13 (19) | C30—Fe2—C29 | 40.7 (2) |
C13—Fe1—C12 | 40.67 (17) | C22—Fe2—C29 | 163.5 (2) |
C19—Fe1—C18 | 38.9 (2) | C21—Fe2—C26 | 106.04 (18) |
C20—Fe1—C18 | 66.6 (2) | C23—Fe2—C26 | 154.93 (19) |
C16—Fe1—C18 | 67.1 (2) | C30—Fe2—C26 | 40.31 (18) |
C13—Fe1—C18 | 160.7 (3) | C22—Fe2—C26 | 119.59 (19) |
C12—Fe1—C18 | 158.3 (3) | C29—Fe2—C26 | 68.21 (18) |
C19—Fe1—C14 | 105.6 (2) | C21—Fe2—C28 | 162.51 (18) |
C20—Fe1—C14 | 116.6 (2) | C23—Fe2—C28 | 109.23 (18) |
C16—Fe1—C14 | 151.3 (2) | C30—Fe2—C28 | 67.52 (18) |
C13—Fe1—C14 | 40.60 (15) | C22—Fe2—C28 | 126.52 (18) |
C12—Fe1—C14 | 68.44 (17) | C29—Fe2—C28 | 40.05 (17) |
C18—Fe1—C14 | 125.7 (2) | C26—Fe2—C28 | 67.74 (18) |
C19—Fe1—C17 | 66.8 (2) | C21—Fe2—C27 | 124.98 (18) |
C20—Fe1—C17 | 67.0 (2) | C23—Fe2—C27 | 120.87 (19) |
C16—Fe1—C17 | 40.2 (2) | C30—Fe2—C27 | 67.68 (19) |
C13—Fe1—C17 | 154.9 (3) | C22—Fe2—C27 | 107.98 (18) |
C12—Fe1—C17 | 123.1 (2) | C29—Fe2—C27 | 67.58 (18) |
C18—Fe1—C17 | 40.1 (2) | C26—Fe2—C27 | 40.64 (18) |
C14—Fe1—C17 | 164.5 (3) | C28—Fe2—C27 | 39.85 (17) |
C19—Fe1—C11 | 154.8 (2) | C21—Fe2—C24 | 68.42 (17) |
C20—Fe1—C11 | 164.6 (2) | C23—Fe2—C24 | 40.79 (16) |
C16—Fe1—C11 | 129.7 (2) | C30—Fe2—C24 | 126.21 (19) |
C13—Fe1—C11 | 68.62 (17) | C22—Fe2—C24 | 68.12 (18) |
C12—Fe1—C11 | 41.02 (16) | C29—Fe2—C24 | 109.11 (18) |
C18—Fe1—C11 | 123.7 (2) | C26—Fe2—C24 | 162.12 (19) |
C14—Fe1—C11 | 68.43 (16) | C28—Fe2—C24 | 122.41 (18) |
C17—Fe1—C11 | 112.3 (2) | C27—Fe2—C24 | 156.29 (18) |
C19—Fe1—C15 | 118.9 (2) | C21—Fe2—C25 | 41.10 (17) |
C20—Fe1—C15 | 151.9 (2) | C23—Fe2—C25 | 68.50 (17) |
C16—Fe1—C15 | 167.3 (2) | C30—Fe2—C25 | 107.51 (18) |
C13—Fe1—C15 | 68.56 (16) | C22—Fe2—C25 | 68.49 (18) |
C12—Fe1—C15 | 68.66 (17) | C29—Fe2—C25 | 120.65 (18) |
C18—Fe1—C15 | 110.0 (2) | C26—Fe2—C25 | 124.81 (18) |
C14—Fe1—C15 | 40.78 (15) | C28—Fe2—C25 | 155.83 (18) |
C17—Fe1—C15 | 129.6 (2) | C27—Fe2—C25 | 162.38 (18) |
C11—Fe1—C15 | 40.59 (16) | C24—Fe2—C25 | 40.06 (16) |
N11—C1—N12 | 114.5 (4) | C22—C21—C25 | 107.5 (4) |
N11—C1—H1 | 122.8 | C22—C21—C211 | 126.0 (4) |
N12—C1—H1 | 122.8 | C25—C21—C211 | 126.3 (4) |
C15—C11—C12 | 107.3 (4) | C22—C21—Fe2 | 69.9 (2) |
C15—C11—C111 | 128.0 (4) | C25—C21—Fe2 | 70.4 (2) |
C12—C11—C111 | 124.2 (4) | C211—C21—Fe2 | 121.0 (3) |
C15—C11—Fe1 | 69.7 (2) | C23—C22—C21 | 108.4 (4) |
C12—C11—Fe1 | 68.3 (2) | C23—C22—Fe2 | 69.5 (3) |
C111—C11—Fe1 | 132.8 (3) | C21—C22—Fe2 | 69.1 (3) |
C13—C12—C11 | 108.3 (4) | C23—C22—H22 | 125.8 |
C13—C12—Fe1 | 69.6 (2) | C21—C22—H22 | 125.8 |
C11—C12—Fe1 | 70.7 (2) | Fe2—C22—H22 | 127.1 |
C13—C12—H12 | 125.8 | C22—C23—C24 | 107.4 (4) |
C11—C12—H12 | 125.8 | C22—C23—Fe2 | 69.8 (3) |
Fe1—C12—H12 | 125.4 | C24—C23—Fe2 | 70.2 (2) |
C12—C13—C14 | 108.5 (4) | C22—C23—H23 | 126.3 |
C12—C13—Fe1 | 69.7 (2) | C24—C23—H23 | 126.3 |
C14—C13—Fe1 | 70.3 (2) | Fe2—C23—H23 | 125.4 |
C12—C13—H13 | 125.8 | C25—C24—C23 | 108.8 (4) |
C14—C13—H13 | 125.8 | C25—C24—Fe2 | 70.1 (2) |
Fe1—C13—H13 | 125.8 | C23—C24—Fe2 | 69.0 (2) |
C13—C14—C15 | 108.3 (4) | C25—C24—H24 | 125.6 |
C13—C14—Fe1 | 69.1 (2) | C23—C24—H24 | 125.6 |
C15—C14—Fe1 | 70.4 (2) | Fe2—C24—H24 | 126.9 |
C13—C14—H14 | 125.9 | C24—C25—C21 | 107.8 (4) |
C15—C14—H14 | 125.9 | C24—C25—Fe2 | 69.9 (2) |
Fe1—C14—H14 | 126.2 | C21—C25—Fe2 | 68.5 (2) |
C14—C15—C11 | 107.6 (3) | C24—C25—H25 | 126.1 |
C14—C15—Fe1 | 68.9 (2) | C21—C25—H25 | 126.1 |
C11—C15—Fe1 | 69.7 (2) | Fe2—C25—H25 | 127.1 |
C14—C15—H15 | 126.2 | C30—C26—C27 | 107.1 (4) |
C11—C15—H15 | 126.2 | C30—C26—Fe2 | 69.5 (3) |
Fe1—C15—H15 | 126.8 | C27—C26—Fe2 | 69.8 (2) |
C20—C16—C17 | 108.0 (5) | C30—C26—H26 | 126.5 |
C20—C16—Fe1 | 70.0 (3) | C27—C26—H26 | 126.5 |
C17—C16—Fe1 | 70.6 (3) | Fe2—C26—H26 | 125.9 |
C20—C16—H16 | 126.0 | C28—C27—C26 | 108.1 (4) |
C17—C16—H16 | 126.0 | C28—C27—Fe2 | 70.0 (2) |
Fe1—C16—H16 | 125.0 | C26—C27—Fe2 | 69.6 (2) |
C18—C17—C16 | 106.8 (5) | C28—C27—H27 | 125.9 |
C18—C17—Fe1 | 69.8 (3) | C26—C27—H27 | 125.9 |
C16—C17—Fe1 | 69.2 (3) | Fe2—C27—H27 | 126.0 |
C18—C17—H17 | 126.6 | C27—C28—C29 | 108.9 (4) |
C16—C17—H17 | 126.6 | C27—C28—Fe2 | 70.1 (2) |
Fe1—C17—H17 | 126.1 | C29—C28—Fe2 | 69.8 (2) |
C19—C18—C17 | 108.7 (5) | C27—C28—H28 | 125.5 |
C19—C18—Fe1 | 69.7 (3) | C29—C28—H28 | 125.5 |
C17—C18—Fe1 | 70.2 (3) | Fe2—C28—H28 | 126.1 |
C19—C18—H18 | 125.6 | C28—C29—C30 | 107.3 (4) |
C17—C18—H18 | 125.6 | C28—C29—Fe2 | 70.2 (3) |
Fe1—C18—H18 | 126.1 | C30—C29—Fe2 | 69.5 (3) |
C18—C19—C20 | 108.7 (5) | C28—C29—H29 | 126.3 |
C18—C19—Fe1 | 71.4 (3) | C30—C29—H29 | 126.3 |
C20—C19—Fe1 | 70.0 (3) | Fe2—C29—H29 | 125.6 |
C18—C19—H19 | 125.7 | C26—C30—C29 | 108.5 (4) |
C20—C19—H19 | 125.7 | C26—C30—Fe2 | 70.2 (3) |
Fe1—C19—H19 | 124.5 | C29—C30—Fe2 | 69.9 (3) |
C16—C20—C19 | 107.8 (5) | C26—C30—H30 | 125.7 |
C16—C20—Fe1 | 70.2 (3) | C29—C30—H30 | 125.7 |
C19—C20—Fe1 | 69.6 (3) | Fe2—C30—H30 | 125.8 |
C16—C20—H20 | 126.1 | C2—N21—C212 | 111.3 (4) |
C19—C20—H20 | 126.1 | C2—N21—C211 | 125.2 (4) |
Fe1—C20—H20 | 125.6 | C212—N21—C211 | 123.4 (4) |
C1—N11—C112 | 109.6 (4) | C2—N22—C213 | 109.3 (4) |
C1—N11—C111 | 124.7 (4) | C2—N22—C221 | 127.4 (5) |
C112—N11—C111 | 124.2 (4) | C213—N22—C221 | 123.3 (4) |
C1—N12—C113 | 109.0 (4) | N21—C2—N22 | 113.6 (4) |
C1—N12—C121 | 125.4 (4) | N21—C2—H2 | 123.2 |
C113—N12—C121 | 123.7 (4) | N22—C2—H2 | 123.2 |
N11—C111—C11 | 114.0 (4) | N21—C211—C21 | 114.7 (3) |
N11—C111—H11A | 108.7 | N21—C211—H21A | 108.6 |
C11—C111—H11A | 108.7 | C21—C211—H21A | 108.6 |
N11—C111—H11B | 108.7 | N21—C211—H21B | 108.6 |
C11—C111—H11B | 108.7 | C21—C211—H21B | 108.6 |
H11A—C111—H11B | 107.6 | H21A—C211—H21B | 107.6 |
N11—C112—C113 | 103.5 (4) | N21—C212—C213 | 101.3 (4) |
N11—C112—H11C | 111.1 | N21—C212—H21C | 111.5 |
C113—C112—H11C | 111.1 | C213—C212—H21C | 111.5 |
N11—C112—H11D | 111.1 | N21—C212—H21D | 111.5 |
C113—C112—H11D | 111.1 | C213—C212—H21D | 111.5 |
H11C—C112—H11D | 109.0 | H21C—C212—H21D | 109.3 |
N12—C113—C112 | 102.9 (4) | N22—C213—C212 | 103.3 (4) |
N12—C113—H11E | 111.2 | N22—C213—H21E | 111.1 |
C112—C113—H11E | 111.2 | C212—C213—H21E | 111.1 |
N12—C113—H11F | 111.2 | N22—C213—H21F | 111.1 |
C112—C113—H11F | 111.2 | C212—C213—H21F | 111.1 |
H11E—C113—H11F | 109.1 | H21E—C213—H21F | 109.1 |
N12—C121—C122 | 110.9 (4) | N22—C221—C222 | 113.2 (3) |
N12—C121—H12A | 109.5 | N22—C221—H22A | 108.9 |
C122—C121—H12A | 109.5 | C222—C221—H22A | 108.9 |
N12—C121—H12B | 109.5 | N22—C221—H22B | 108.9 |
C122—C121—H12B | 109.5 | C222—C221—H22B | 108.9 |
H12A—C121—H12B | 108.1 | H22A—C221—H22B | 107.8 |
C123—C122—C127 | 119.4 (5) | C223—C222—C227 | 120.0 (4) |
C123—C122—C121 | 122.0 (5) | C223—C222—C221 | 120.0 (4) |
C127—C122—C121 | 118.6 (5) | C227—C222—C221 | 120.0 (4) |
C122—C123—C124 | 119.8 (5) | C224—C223—C222 | 119.1 (4) |
C122—C123—C128 | 122.0 (5) | C224—C223—C228 | 118.7 (5) |
C124—C123—C128 | 118.2 (5) | C222—C223—C228 | 122.2 (5) |
C125—C124—C123 | 122.0 (5) | C225—C224—C223 | 121.5 (5) |
C125—C124—H124 | 119.0 | C225—C224—H224 | 119.2 |
C123—C124—H124 | 119.0 | C223—C224—H224 | 119.2 |
C126—C125—C124 | 117.7 (5) | C226—C225—C224 | 118.6 (4) |
C126—C125—C129 | 120.4 (5) | C226—C225—C229 | 120.3 (5) |
C124—C125—C129 | 121.9 (5) | C224—C225—C229 | 121.1 (5) |
C125—C126—C127 | 122.4 (5) | C225—C226—C227 | 122.4 (5) |
C125—C126—H126 | 118.8 | C225—C226—H226 | 118.8 |
C127—C126—H126 | 118.8 | C227—C226—H226 | 118.8 |
C126—C127—C122 | 118.6 (5) | C226—C227—C222 | 118.3 (5) |
C126—C127—C130 | 118.3 (5) | C226—C227—C230 | 118.7 (5) |
C122—C127—C130 | 123.1 (5) | C222—C227—C230 | 123.0 (4) |
C123—C128—H12C | 109.5 | C223—C228—H22C | 109.5 |
C123—C128—H12D | 109.5 | C223—C228—H22D | 109.5 |
H12C—C128—H12D | 109.5 | H22C—C228—H22D | 109.5 |
C123—C128—H12E | 109.5 | C223—C228—H22E | 109.5 |
H12C—C128—H12E | 109.5 | H22C—C228—H22E | 109.5 |
H12D—C128—H12E | 109.5 | H22D—C228—H22E | 109.5 |
C125—C129—H12F | 109.5 | C225—C229—H22F | 109.5 |
C125—C129—H12G | 109.5 | C225—C229—H22G | 109.5 |
H12F—C129—H12G | 109.5 | H22F—C229—H22G | 109.5 |
C125—C129—H12H | 109.5 | C225—C229—H22H | 109.5 |
H12F—C129—H12H | 109.5 | H22F—C229—H22H | 109.5 |
H12G—C129—H12H | 109.5 | H22G—C229—H22H | 109.5 |
C127—C130—H13A | 109.5 | C227—C230—H23A | 109.5 |
C127—C130—H13B | 109.5 | C227—C230—H23B | 109.5 |
H13A—C130—H13B | 109.5 | H23A—C230—H23B | 109.5 |
C127—C130—H13C | 109.5 | C227—C230—H23C | 109.5 |
H13A—C130—H13C | 109.5 | H23A—C230—H23C | 109.5 |
H13B—C130—H13C | 109.5 | H23B—C230—H23C | 109.5 |
| | | |
C19—Fe1—C11—C15 | −42.8 (6) | C23—Fe2—C21—C22 | 37.1 (2) |
C20—Fe1—C11—C15 | 150.0 (7) | C30—Fe2—C21—C22 | −158.5 (3) |
C16—Fe1—C11—C15 | −168.4 (3) | C29—Fe2—C21—C22 | 170.3 (4) |
C13—Fe1—C11—C15 | 81.6 (2) | C26—Fe2—C21—C22 | −116.9 (3) |
C12—Fe1—C11—C15 | 119.3 (3) | C28—Fe2—C21—C22 | −50.4 (7) |
C18—Fe1—C11—C15 | −81.5 (3) | C27—Fe2—C21—C22 | −76.6 (3) |
C14—Fe1—C11—C15 | 37.8 (2) | C24—Fe2—C21—C22 | 81.0 (3) |
C17—Fe1—C11—C15 | −125.5 (3) | C25—Fe2—C21—C22 | 118.0 (4) |
C19—Fe1—C11—C12 | −162.1 (5) | C23—Fe2—C21—C25 | −80.9 (3) |
C20—Fe1—C11—C12 | 30.7 (8) | C30—Fe2—C21—C25 | 83.5 (3) |
C16—Fe1—C11—C12 | 72.3 (4) | C22—Fe2—C21—C25 | −118.0 (4) |
C13—Fe1—C11—C12 | −37.7 (2) | C29—Fe2—C21—C25 | 52.2 (5) |
C18—Fe1—C11—C12 | 159.1 (3) | C26—Fe2—C21—C25 | 125.0 (3) |
C14—Fe1—C11—C12 | −81.5 (3) | C28—Fe2—C21—C25 | −168.5 (5) |
C17—Fe1—C11—C12 | 115.2 (3) | C27—Fe2—C21—C25 | 165.3 (3) |
C15—Fe1—C11—C12 | −119.3 (3) | C24—Fe2—C21—C25 | −37.0 (3) |
C19—Fe1—C11—C111 | 80.8 (7) | C23—Fe2—C21—C211 | 157.8 (4) |
C20—Fe1—C11—C111 | −86.4 (8) | C30—Fe2—C21—C211 | −37.8 (4) |
C16—Fe1—C11—C111 | −44.8 (5) | C22—Fe2—C21—C211 | 120.7 (5) |
C13—Fe1—C11—C111 | −154.8 (5) | C29—Fe2—C21—C211 | −69.0 (6) |
C12—Fe1—C11—C111 | −117.1 (5) | C26—Fe2—C21—C211 | 3.8 (4) |
C18—Fe1—C11—C111 | 42.0 (5) | C28—Fe2—C21—C211 | 70.2 (8) |
C14—Fe1—C11—C111 | 161.4 (5) | C27—Fe2—C21—C211 | 44.1 (4) |
C17—Fe1—C11—C111 | −1.9 (5) | C24—Fe2—C21—C211 | −158.3 (4) |
C15—Fe1—C11—C111 | 123.6 (5) | C25—Fe2—C21—C211 | −121.3 (5) |
C15—C11—C12—C13 | 0.7 (5) | C25—C21—C22—C23 | 2.1 (5) |
C111—C11—C12—C13 | −172.5 (4) | C211—C21—C22—C23 | −172.9 (4) |
Fe1—C11—C12—C13 | 59.7 (3) | Fe2—C21—C22—C23 | −58.6 (3) |
C15—C11—C12—Fe1 | −59.0 (3) | C25—C21—C22—Fe2 | 60.7 (3) |
C111—C11—C12—Fe1 | 127.9 (4) | C211—C21—C22—Fe2 | −114.3 (4) |
C19—Fe1—C12—C13 | 36.6 (7) | C21—Fe2—C22—C23 | 120.2 (4) |
C20—Fe1—C12—C13 | 70.5 (3) | C30—Fe2—C22—C23 | 167.5 (4) |
C16—Fe1—C12—C13 | 111.9 (3) | C29—Fe2—C22—C23 | −45.1 (7) |
C18—Fe1—C12—C13 | −172.1 (5) | C26—Fe2—C22—C23 | −159.6 (3) |
C14—Fe1—C12—C13 | −37.6 (2) | C28—Fe2—C22—C23 | −76.6 (3) |
C17—Fe1—C12—C13 | 154.2 (3) | C27—Fe2—C22—C23 | −116.7 (3) |
C11—Fe1—C12—C13 | −119.0 (3) | C24—Fe2—C22—C23 | 38.4 (3) |
C15—Fe1—C12—C13 | −81.5 (3) | C25—Fe2—C22—C23 | 81.6 (3) |
C19—Fe1—C12—C11 | 155.6 (6) | C23—Fe2—C22—C21 | −120.2 (4) |
C20—Fe1—C12—C11 | −170.4 (3) | C30—Fe2—C22—C21 | 47.3 (5) |
C16—Fe1—C12—C11 | −129.1 (3) | C29—Fe2—C22—C21 | −165.3 (6) |
C13—Fe1—C12—C11 | 119.0 (3) | C26—Fe2—C22—C21 | 80.2 (3) |
C18—Fe1—C12—C11 | −53.1 (6) | C28—Fe2—C22—C21 | 163.2 (3) |
C14—Fe1—C12—C11 | 81.5 (3) | C27—Fe2—C22—C21 | 123.1 (3) |
C17—Fe1—C12—C11 | −86.7 (3) | C24—Fe2—C22—C21 | −81.8 (3) |
C15—Fe1—C12—C11 | 37.5 (2) | C25—Fe2—C22—C21 | −38.6 (2) |
C11—C12—C13—C14 | −0.6 (5) | C21—C22—C23—C24 | −2.0 (5) |
Fe1—C12—C13—C14 | 59.8 (3) | Fe2—C22—C23—C24 | −60.3 (3) |
C11—C12—C13—Fe1 | −60.4 (3) | C21—C22—C23—Fe2 | 58.3 (3) |
C19—Fe1—C13—C12 | −166.9 (3) | C21—Fe2—C23—C22 | −37.3 (3) |
C20—Fe1—C13—C12 | −127.1 (3) | C30—Fe2—C23—C22 | −160.4 (6) |
C16—Fe1—C13—C12 | −86.5 (3) | C29—Fe2—C23—C22 | 165.5 (3) |
C18—Fe1—C13—C12 | 171.2 (5) | C26—Fe2—C23—C22 | 45.7 (5) |
C14—Fe1—C13—C12 | 119.4 (4) | C28—Fe2—C23—C22 | 124.1 (3) |
C17—Fe1—C13—C12 | −59.2 (6) | C27—Fe2—C23—C22 | 81.8 (3) |
C11—Fe1—C13—C12 | 38.0 (2) | C24—Fe2—C23—C22 | −118.2 (4) |
C15—Fe1—C13—C12 | 81.8 (3) | C25—Fe2—C23—C22 | −81.6 (3) |
C19—Fe1—C13—C14 | 73.7 (3) | C21—Fe2—C23—C24 | 80.9 (3) |
C20—Fe1—C13—C14 | 113.5 (3) | C30—Fe2—C23—C24 | −42.2 (8) |
C16—Fe1—C13—C14 | 154.1 (3) | C22—Fe2—C23—C24 | 118.2 (4) |
C12—Fe1—C13—C14 | −119.4 (4) | C29—Fe2—C23—C24 | −76.3 (3) |
C18—Fe1—C13—C14 | 51.7 (7) | C26—Fe2—C23—C24 | 163.9 (4) |
C17—Fe1—C13—C14 | −178.7 (4) | C28—Fe2—C23—C24 | −117.7 (3) |
C11—Fe1—C13—C14 | −81.4 (3) | C27—Fe2—C23—C24 | −160.1 (3) |
C15—Fe1—C13—C14 | −37.6 (2) | C25—Fe2—C23—C24 | 36.6 (3) |
C12—C13—C14—C15 | 0.2 (5) | C22—C23—C24—C25 | 1.2 (5) |
Fe1—C13—C14—C15 | 59.7 (3) | Fe2—C23—C24—C25 | −58.9 (3) |
C12—C13—C14—Fe1 | −59.5 (3) | C22—C23—C24—Fe2 | 60.1 (3) |
C19—Fe1—C14—C13 | −124.0 (3) | C21—Fe2—C24—C25 | 37.9 (3) |
C20—Fe1—C14—C13 | −82.1 (3) | C23—Fe2—C24—C25 | 120.4 (4) |
C16—Fe1—C14—C13 | −53.1 (5) | C30—Fe2—C24—C25 | −73.1 (3) |
C12—Fe1—C14—C13 | 37.6 (3) | C22—Fe2—C24—C25 | 82.2 (3) |
C18—Fe1—C14—C13 | −161.3 (3) | C29—Fe2—C24—C25 | −115.2 (3) |
C17—Fe1—C14—C13 | 177.9 (7) | C26—Fe2—C24—C25 | −37.1 (7) |
C11—Fe1—C14—C13 | 81.9 (3) | C28—Fe2—C24—C25 | −157.5 (3) |
C15—Fe1—C14—C13 | 119.5 (4) | C27—Fe2—C24—C25 | 167.2 (4) |
C19—Fe1—C14—C15 | 116.5 (3) | C21—Fe2—C24—C23 | −82.5 (3) |
C20—Fe1—C14—C15 | 158.4 (3) | C30—Fe2—C24—C23 | 166.5 (3) |
C16—Fe1—C14—C15 | −172.6 (4) | C22—Fe2—C24—C23 | −38.3 (3) |
C13—Fe1—C14—C15 | −119.5 (4) | C29—Fe2—C24—C23 | 124.3 (3) |
C12—Fe1—C14—C15 | −81.9 (3) | C26—Fe2—C24—C23 | −157.5 (6) |
C18—Fe1—C14—C15 | 79.1 (3) | C28—Fe2—C24—C23 | 82.0 (3) |
C17—Fe1—C14—C15 | 58.4 (8) | C27—Fe2—C24—C23 | 46.7 (6) |
C11—Fe1—C14—C15 | −37.6 (2) | C25—Fe2—C24—C23 | −120.4 (4) |
C13—C14—C15—C11 | 0.2 (5) | C23—C24—C25—C21 | 0.1 (5) |
Fe1—C14—C15—C11 | 59.2 (3) | Fe2—C24—C25—C21 | −58.2 (3) |
C13—C14—C15—Fe1 | −58.9 (3) | C23—C24—C25—Fe2 | 58.3 (3) |
C12—C11—C15—C14 | −0.6 (5) | C22—C21—C25—C24 | −1.4 (5) |
C111—C11—C15—C14 | 172.2 (4) | C211—C21—C25—C24 | 173.6 (4) |
Fe1—C11—C15—C14 | −58.6 (3) | Fe2—C21—C25—C24 | 59.0 (3) |
C12—C11—C15—Fe1 | 58.1 (3) | C22—C21—C25—Fe2 | −60.4 (3) |
C111—C11—C15—Fe1 | −129.1 (4) | C211—C21—C25—Fe2 | 114.6 (4) |
C19—Fe1—C15—C14 | −80.1 (3) | C21—Fe2—C25—C24 | −119.6 (4) |
C20—Fe1—C15—C14 | −44.4 (5) | C23—Fe2—C25—C24 | −37.3 (3) |
C16—Fe1—C15—C14 | 163.7 (8) | C30—Fe2—C25—C24 | 126.0 (3) |
C13—Fe1—C15—C14 | 37.5 (3) | C22—Fe2—C25—C24 | −81.2 (3) |
C12—Fe1—C15—C14 | 81.3 (3) | C29—Fe2—C25—C24 | 83.5 (3) |
C18—Fe1—C15—C14 | −121.9 (3) | C26—Fe2—C25—C24 | 167.0 (3) |
C17—Fe1—C15—C14 | −162.8 (3) | C28—Fe2—C25—C24 | 52.0 (5) |
C11—Fe1—C15—C14 | 119.2 (3) | C27—Fe2—C25—C24 | −162.8 (6) |
C19—Fe1—C15—C11 | 160.7 (3) | C23—Fe2—C25—C21 | 82.3 (3) |
C20—Fe1—C15—C11 | −163.6 (4) | C30—Fe2—C25—C21 | −114.4 (3) |
C16—Fe1—C15—C11 | 44.5 (10) | C22—Fe2—C25—C21 | 38.4 (3) |
C13—Fe1—C15—C11 | −81.7 (3) | C29—Fe2—C25—C21 | −156.9 (3) |
C12—Fe1—C15—C11 | −37.9 (2) | C26—Fe2—C25—C21 | −73.4 (3) |
C18—Fe1—C15—C11 | 118.9 (3) | C28—Fe2—C25—C21 | 171.6 (4) |
C14—Fe1—C15—C11 | −119.2 (3) | C27—Fe2—C25—C21 | −43.2 (7) |
C17—Fe1—C15—C11 | 78.0 (4) | C24—Fe2—C25—C21 | 119.6 (4) |
C19—Fe1—C16—C20 | 38.1 (3) | C21—Fe2—C26—C30 | −116.3 (3) |
C13—Fe1—C16—C20 | −79.0 (4) | C23—Fe2—C26—C30 | 169.0 (4) |
C12—Fe1—C16—C20 | −122.6 (3) | C22—Fe2—C26—C30 | −158.5 (3) |
C18—Fe1—C16—C20 | 80.4 (4) | C29—Fe2—C26—C30 | 37.7 (3) |
C14—Fe1—C16—C20 | −42.7 (6) | C28—Fe2—C26—C30 | 81.0 (3) |
C17—Fe1—C16—C20 | 118.5 (5) | C27—Fe2—C26—C30 | 118.2 (4) |
C11—Fe1—C16—C20 | −164.0 (3) | C24—Fe2—C26—C30 | −47.1 (7) |
C15—Fe1—C16—C20 | 159.7 (8) | C25—Fe2—C26—C30 | −75.3 (3) |
C19—Fe1—C16—C17 | −80.4 (4) | C21—Fe2—C26—C27 | 125.5 (3) |
C20—Fe1—C16—C17 | −118.5 (5) | C23—Fe2—C26—C27 | 50.8 (5) |
C13—Fe1—C16—C17 | 162.5 (3) | C30—Fe2—C26—C27 | −118.2 (4) |
C12—Fe1—C16—C17 | 119.0 (4) | C22—Fe2—C26—C27 | 83.3 (3) |
C18—Fe1—C16—C17 | −38.1 (3) | C29—Fe2—C26—C27 | −80.5 (3) |
C14—Fe1—C16—C17 | −161.2 (4) | C28—Fe2—C26—C27 | −37.2 (3) |
C11—Fe1—C16—C17 | 77.5 (4) | C24—Fe2—C26—C27 | −165.3 (5) |
C15—Fe1—C16—C17 | 41.2 (10) | C25—Fe2—C26—C27 | 166.5 (3) |
C20—C16—C17—C18 | −0.4 (6) | C30—C26—C27—C28 | −0.1 (5) |
Fe1—C16—C17—C18 | 59.9 (4) | Fe2—C26—C27—C28 | 59.7 (3) |
C20—C16—C17—Fe1 | −60.3 (4) | C30—C26—C27—Fe2 | −59.7 (3) |
C19—Fe1—C17—C18 | −36.4 (3) | C21—Fe2—C27—C28 | 168.1 (3) |
C20—Fe1—C17—C18 | −80.4 (4) | C23—Fe2—C27—C28 | 83.3 (3) |
C16—Fe1—C17—C18 | −118.1 (5) | C30—Fe2—C27—C28 | −81.2 (3) |
C13—Fe1—C17—C18 | −156.7 (5) | C22—Fe2—C27—C28 | 126.0 (3) |
C12—Fe1—C17—C18 | 161.4 (3) | C29—Fe2—C27—C28 | −37.1 (3) |
C14—Fe1—C17—C18 | 26.6 (9) | C26—Fe2—C27—C28 | −119.3 (4) |
C11—Fe1—C17—C18 | 116.3 (4) | C24—Fe2—C27—C28 | 49.6 (6) |
C15—Fe1—C17—C18 | 72.8 (4) | C25—Fe2—C27—C28 | −158.6 (5) |
C19—Fe1—C17—C16 | 81.7 (4) | C21—Fe2—C27—C26 | −72.7 (3) |
C20—Fe1—C17—C16 | 37.7 (3) | C23—Fe2—C27—C26 | −157.5 (3) |
C13—Fe1—C17—C16 | −38.6 (6) | C30—Fe2—C27—C26 | 38.1 (3) |
C12—Fe1—C17—C16 | −80.5 (4) | C22—Fe2—C27—C26 | −114.8 (3) |
C18—Fe1—C17—C16 | 118.1 (5) | C29—Fe2—C27—C26 | 82.2 (3) |
C14—Fe1—C17—C16 | 144.7 (7) | C28—Fe2—C27—C26 | 119.3 (4) |
C11—Fe1—C17—C16 | −125.6 (3) | C24—Fe2—C27—C26 | 168.8 (4) |
C15—Fe1—C17—C16 | −169.1 (3) | C25—Fe2—C27—C26 | −39.3 (7) |
C16—C17—C18—C19 | −0.3 (6) | C26—C27—C28—C29 | −0.2 (5) |
Fe1—C17—C18—C19 | 59.2 (4) | Fe2—C27—C28—C29 | 59.2 (3) |
C16—C17—C18—Fe1 | −59.5 (4) | C26—C27—C28—Fe2 | −59.4 (3) |
C20—Fe1—C18—C19 | −38.2 (3) | C21—Fe2—C28—C27 | −34.3 (7) |
C16—Fe1—C18—C19 | −81.6 (4) | C23—Fe2—C28—C27 | −115.5 (3) |
C13—Fe1—C18—C19 | 29.7 (8) | C30—Fe2—C28—C27 | 81.6 (3) |
C12—Fe1—C18—C19 | −166.0 (5) | C22—Fe2—C28—C27 | −73.3 (3) |
C14—Fe1—C18—C19 | 68.7 (4) | C29—Fe2—C28—C27 | 120.0 (4) |
C17—Fe1—C18—C19 | −119.8 (5) | C26—Fe2—C28—C27 | 37.9 (3) |
C11—Fe1—C18—C19 | 154.9 (3) | C24—Fe2—C28—C27 | −158.7 (3) |
C15—Fe1—C18—C19 | 111.7 (3) | C25—Fe2—C28—C27 | 164.3 (4) |
C19—Fe1—C18—C17 | 119.8 (5) | C21—Fe2—C28—C29 | −154.4 (6) |
C20—Fe1—C18—C17 | 81.6 (4) | C23—Fe2—C28—C29 | 124.5 (3) |
C16—Fe1—C18—C17 | 38.2 (3) | C30—Fe2—C28—C29 | −38.4 (3) |
C13—Fe1—C18—C17 | 149.5 (6) | C22—Fe2—C28—C29 | 166.7 (3) |
C12—Fe1—C18—C17 | −46.2 (7) | C26—Fe2—C28—C29 | −82.2 (3) |
C14—Fe1—C18—C17 | −171.5 (3) | C27—Fe2—C28—C29 | −120.0 (4) |
C11—Fe1—C18—C17 | −85.3 (4) | C24—Fe2—C28—C29 | 81.2 (3) |
C15—Fe1—C18—C17 | −128.5 (4) | C25—Fe2—C28—C29 | 44.3 (5) |
C17—C18—C19—C20 | 0.9 (6) | C27—C28—C29—C30 | 0.4 (5) |
Fe1—C18—C19—C20 | 60.4 (4) | Fe2—C28—C29—C30 | 59.8 (3) |
C17—C18—C19—Fe1 | −59.5 (4) | C27—C28—C29—Fe2 | −59.4 (3) |
C20—Fe1—C19—C18 | 118.8 (5) | C21—Fe2—C29—C28 | 162.3 (4) |
C16—Fe1—C19—C18 | 81.3 (4) | C23—Fe2—C29—C28 | −75.8 (3) |
C13—Fe1—C19—C18 | −168.7 (3) | C30—Fe2—C29—C28 | 118.2 (4) |
C12—Fe1—C19—C18 | 163.5 (6) | C22—Fe2—C29—C28 | −40.6 (7) |
C14—Fe1—C19—C18 | −128.2 (4) | C26—Fe2—C29—C28 | 80.9 (3) |
C17—Fe1—C19—C18 | 37.4 (4) | C27—Fe2—C29—C28 | 36.9 (3) |
C11—Fe1—C19—C18 | −56.0 (6) | C24—Fe2—C29—C28 | −118.0 (3) |
C15—Fe1—C19—C18 | −86.3 (4) | C25—Fe2—C29—C28 | −160.6 (3) |
C16—Fe1—C19—C20 | −37.5 (3) | C21—Fe2—C29—C30 | 44.0 (5) |
C13—Fe1—C19—C20 | 72.6 (4) | C23—Fe2—C29—C30 | 166.0 (3) |
C12—Fe1—C19—C20 | 44.8 (7) | C22—Fe2—C29—C30 | −158.9 (6) |
C18—Fe1—C19—C20 | −118.8 (5) | C26—Fe2—C29—C30 | −37.3 (3) |
C14—Fe1—C19—C20 | 113.0 (3) | C28—Fe2—C29—C30 | −118.2 (4) |
C17—Fe1—C19—C20 | −81.4 (4) | C27—Fe2—C29—C30 | −81.4 (3) |
C11—Fe1—C19—C20 | −174.8 (4) | C24—Fe2—C29—C30 | 123.8 (3) |
C15—Fe1—C19—C20 | 154.9 (3) | C25—Fe2—C29—C30 | 81.2 (3) |
C17—C16—C20—C19 | 0.9 (6) | C27—C26—C30—C29 | 0.3 (5) |
Fe1—C16—C20—C19 | −59.8 (3) | Fe2—C26—C30—C29 | −59.6 (3) |
C17—C16—C20—Fe1 | 60.7 (4) | C27—C26—C30—Fe2 | 59.9 (3) |
C18—C19—C20—C16 | −1.1 (6) | C28—C29—C30—C26 | −0.5 (5) |
Fe1—C19—C20—C16 | 60.2 (4) | Fe2—C29—C30—C26 | 59.8 (3) |
C18—C19—C20—Fe1 | −61.3 (4) | C28—C29—C30—Fe2 | −60.2 (3) |
C19—Fe1—C20—C16 | −118.6 (5) | C21—Fe2—C30—C26 | 80.4 (3) |
C13—Fe1—C20—C16 | 116.7 (4) | C23—Fe2—C30—C26 | −163.3 (6) |
C12—Fe1—C20—C16 | 77.2 (4) | C22—Fe2—C30—C26 | 46.9 (5) |
C18—Fe1—C20—C16 | −81.8 (4) | C29—Fe2—C30—C26 | −119.5 (4) |
C14—Fe1—C20—C16 | 158.6 (3) | C28—Fe2—C30—C26 | −81.6 (3) |
C17—Fe1—C20—C16 | −38.0 (3) | C27—Fe2—C30—C26 | −38.4 (3) |
C11—Fe1—C20—C16 | 53.0 (8) | C24—Fe2—C30—C26 | 163.8 (3) |
C15—Fe1—C20—C16 | −170.7 (4) | C25—Fe2—C30—C26 | 123.6 (3) |
C16—Fe1—C20—C19 | 118.6 (5) | C21—Fe2—C30—C29 | −160.2 (3) |
C13—Fe1—C20—C19 | −124.6 (3) | C23—Fe2—C30—C29 | −43.8 (8) |
C12—Fe1—C20—C19 | −164.2 (3) | C22—Fe2—C30—C29 | 166.4 (4) |
C18—Fe1—C20—C19 | 36.8 (3) | C26—Fe2—C30—C29 | 119.5 (4) |
C14—Fe1—C20—C19 | −82.8 (4) | C28—Fe2—C30—C29 | 37.8 (3) |
C17—Fe1—C20—C19 | 80.6 (4) | C27—Fe2—C30—C29 | 81.1 (3) |
C11—Fe1—C20—C19 | 171.6 (6) | C24—Fe2—C30—C29 | −76.7 (3) |
C15—Fe1—C20—C19 | −52.0 (5) | C25—Fe2—C30—C29 | −116.9 (3) |
N12—C1—N11—C112 | −4.1 (6) | C212—N21—C2—N22 | 5.3 (6) |
N12—C1—N11—C111 | −170.5 (4) | C211—N21—C2—N22 | −178.0 (4) |
N11—C1—N12—C113 | −1.5 (6) | C213—N22—C2—N21 | 2.0 (6) |
N11—C1—N12—C121 | −166.0 (5) | C221—N22—C2—N21 | −176.0 (4) |
C1—N11—C111—C11 | −122.4 (5) | C2—N21—C211—C21 | −106.6 (5) |
C112—N11—C111—C11 | 73.1 (6) | C212—N21—C211—C21 | 69.7 (6) |
C15—C11—C111—N11 | 19.8 (6) | C22—C21—C211—N21 | −111.8 (5) |
C12—C11—C111—N11 | −168.5 (4) | C25—C21—C211—N21 | 74.1 (6) |
Fe1—C11—C111—N11 | −77.3 (5) | Fe2—C21—C211—N21 | 161.5 (3) |
C1—N11—C112—C113 | 7.5 (5) | C2—N21—C212—C213 | −9.6 (5) |
C111—N11—C112—C113 | 174.0 (4) | C211—N21—C212—C213 | 173.6 (4) |
C1—N12—C113—C112 | 6.0 (5) | C2—N22—C213—C212 | −7.8 (5) |
C121—N12—C113—C112 | 170.7 (4) | C221—N22—C213—C212 | 170.3 (4) |
N11—C112—C113—N12 | −7.8 (5) | N21—C212—C213—N22 | 9.9 (5) |
C1—N12—C121—C122 | −144.3 (5) | C2—N22—C221—C222 | −112.0 (5) |
C113—N12—C121—C122 | 53.4 (6) | C213—N22—C221—C222 | 70.2 (6) |
N12—C121—C122—C123 | 74.3 (6) | N22—C221—C222—C223 | 84.1 (5) |
N12—C121—C122—C127 | −103.9 (5) | N22—C221—C222—C227 | −96.0 (5) |
C127—C122—C123—C124 | 1.4 (7) | C227—C222—C223—C224 | 0.5 (7) |
C121—C122—C123—C124 | −176.8 (4) | C221—C222—C223—C224 | −179.5 (4) |
C127—C122—C123—C128 | −177.5 (4) | C227—C222—C223—C228 | −178.4 (4) |
C121—C122—C123—C128 | 4.2 (7) | C221—C222—C223—C228 | 1.6 (7) |
C122—C123—C124—C125 | −0.3 (7) | C222—C223—C224—C225 | 0.8 (7) |
C128—C123—C124—C125 | 178.7 (4) | C228—C223—C224—C225 | 179.7 (4) |
C123—C124—C125—C126 | −1.4 (7) | C223—C224—C225—C226 | −2.3 (7) |
C123—C124—C125—C129 | 176.9 (4) | C223—C224—C225—C229 | 177.9 (4) |
C124—C125—C126—C127 | 2.0 (7) | C224—C225—C226—C227 | 2.5 (7) |
C129—C125—C126—C127 | −176.4 (4) | C229—C225—C226—C227 | −177.7 (4) |
C125—C126—C127—C122 | −0.8 (7) | C225—C226—C227—C222 | −1.2 (7) |
C125—C126—C127—C130 | 179.5 (4) | C225—C226—C227—C230 | 178.6 (4) |
C123—C122—C127—C126 | −0.9 (7) | C223—C222—C227—C226 | −0.3 (6) |
C121—C122—C127—C126 | 177.4 (4) | C221—C222—C227—C226 | 179.7 (4) |
C123—C122—C127—C130 | 178.7 (4) | C223—C222—C227—C230 | 179.8 (4) |
C121—C122—C127—C130 | −3.0 (7) | C221—C222—C227—C230 | −0.1 (6) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C1—H1···I1 | 0.95 | 2.87 | 3.811 (5) | 173 |
C113—H11E···I1i | 0.99 | 2.98 | 3.878 (5) | 152 |
C211—H21B···I1ii | 0.99 | 2.96 | 3.877 (5) | 154 |
C212—H21C···I1iii | 0.99 | 2.95 | 3.797 (5) | 145 |
C213—H21E···I2i | 0.99 | 2.99 | 3.860 (6) | 148 |
C24—H24···Cg1iv | 0.95 | 2.90 | 3.688 (5) | 141 |
C230—H23C···Cg2 | 0.98 | 2.90 | 3.781 (5) | 150 |
C14—H14···Cg3v | 0.95 | 2.70 | 3.579 (5) | 154 |
Symmetry codes: (i) x, y+1, z; (ii) x−1, y, z; (iii) x−1, y+1, z; (iv) x, y−1, z; (v) x+1, y+1, z. |
(II)
trans-bis(3-benzyl-1-ferrocenylmethyl-1
H-imidazolidin-
2-ylidene)diiodidopalladium(II)
top
Crystal data top
[Fe2Pd(C5H5)2(C16H17N2)2I2] | F(000) = 1056 |
Mr = 1076.71 | Dx = 1.817 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 1729 reflections |
a = 9.5185 (16) Å | θ = 2.9–32.2° |
b = 11.7851 (17) Å | µ = 2.78 mm−1 |
c = 17.569 (2) Å | T = 180 K |
β = 92.835 (12)° | Needle, yellow |
V = 1968.5 (5) Å3 | 0.17 × 0.07 × 0.06 mm |
Z = 2 | |
Data collection top
Oxford Xcalibur diffractometer | 3890 independent reflections |
Radiation source: fine-focus sealed tube | 2082 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.084 |
ω and ϕ scans | θmax = 26.0°, θmin = 2.9° |
Absorption correction: multi-scan (Blessing, 1997) | h = −11→11 |
Tmin = 0.727, Tmax = 0.797 | k = −14→11 |
14178 measured reflections | l = −21→21 |
Refinement top
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)] = 0.046 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.091 | H-atom parameters constrained |
S = 0.85 | w = 1/[σ2(Fo2) + (0.0293P)2] where P = (Fo2 + 2Fc2)/3 |
3890 reflections | (Δ/σ)max < 0.001 |
232 parameters | Δρmax = 0.94 e Å−3 |
0 restraints | Δρmin = −0.71 e Å−3 |
Crystal data top
[Fe2Pd(C5H5)2(C16H17N2)2I2] | V = 1968.5 (5) Å3 |
Mr = 1076.71 | Z = 2 |
Monoclinic, P21/n | Mo Kα radiation |
a = 9.5185 (16) Å | µ = 2.78 mm−1 |
b = 11.7851 (17) Å | T = 180 K |
c = 17.569 (2) Å | 0.17 × 0.07 × 0.06 mm |
β = 92.835 (12)° | |
Data collection top
Oxford Xcalibur diffractometer | 3890 independent reflections |
Absorption correction: multi-scan (Blessing, 1997) | 2082 reflections with I > 2σ(I) |
Tmin = 0.727, Tmax = 0.797 | Rint = 0.084 |
14178 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.046 | 0 restraints |
wR(F2) = 0.091 | H-atom parameters constrained |
S = 0.85 | Δρmax = 0.94 e Å−3 |
3890 reflections | Δρmin = −0.71 e Å−3 |
232 parameters | |
Special details top
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell esds are taken
into account individually in the estimation of esds in distances, angles
and torsion angles; correlations between esds in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell esds is used for estimating esds involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor
wR and goodness of fit S are based on F2, conventional
R-factors R are based on F, with F set to zero for
negative F2. The threshold expression of F2 >
σ(F2) is used only for calculating R-factors(gt) etc.
and is not relevant to the choice of reflections for refinement.
R-factors based on F2 are statistically about twice as large
as those based on F, and R-factors based on ALL data will be
even larger. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Pd1 | 0.5000 | 0.5000 | 0.5000 | 0.0277 (2) | |
I1 | 0.65918 (6) | 0.66957 (4) | 0.46153 (3) | 0.03860 (17) | |
Fe1 | 0.34269 (11) | 0.58179 (9) | 0.17695 (5) | 0.0308 (3) | |
N1 | 0.2374 (6) | 0.5960 (5) | 0.4199 (3) | 0.0297 (15) | |
N2 | 0.2610 (6) | 0.6553 (4) | 0.5369 (3) | 0.0312 (15) | |
C1 | 0.3204 (7) | 0.5924 (6) | 0.4829 (4) | 0.0278 (17) | |
C2 | 0.1043 (7) | 0.6556 (6) | 0.4286 (4) | 0.0369 (19) | |
H2A | 0.0232 | 0.6030 | 0.4231 | 0.044* | |
H2B | 0.0915 | 0.7178 | 0.3910 | 0.044* | |
C3 | 0.1222 (8) | 0.7014 (6) | 0.5091 (4) | 0.043 (2) | |
H3A | 0.1227 | 0.7854 | 0.5093 | 0.052* | |
H3B | 0.0461 | 0.6741 | 0.5409 | 0.052* | |
C11 | 0.2933 (8) | 0.6239 (5) | 0.2853 (4) | 0.0295 (18) | |
C12 | 0.1887 (7) | 0.6658 (6) | 0.2310 (4) | 0.0312 (17) | |
H12 | 0.0915 | 0.6473 | 0.2289 | 0.037* | |
C13 | 0.2564 (10) | 0.7398 (6) | 0.1811 (4) | 0.049 (2) | |
H13 | 0.2121 | 0.7795 | 0.1394 | 0.059* | |
C14 | 0.3989 (10) | 0.7446 (6) | 0.2032 (4) | 0.045 (2) | |
H14 | 0.4680 | 0.7883 | 0.1792 | 0.054* | |
C15 | 0.4236 (7) | 0.6732 (6) | 0.2678 (4) | 0.0356 (19) | |
H15 | 0.5115 | 0.6609 | 0.2944 | 0.043* | |
C16 | 0.2568 (9) | 0.4904 (7) | 0.0885 (5) | 0.052 (2) | |
H16 | 0.1665 | 0.5026 | 0.0645 | 0.062* | |
C17 | 0.3810 (10) | 0.5393 (7) | 0.0675 (4) | 0.045 (2) | |
H17 | 0.3904 | 0.5911 | 0.0266 | 0.055* | |
C18 | 0.4900 (9) | 0.4998 (8) | 0.1163 (5) | 0.056 (3) | |
H18 | 0.5869 | 0.5183 | 0.1143 | 0.067* | |
C19 | 0.4280 (12) | 0.4258 (7) | 0.1702 (5) | 0.063 (3) | |
H19 | 0.4759 | 0.3878 | 0.2115 | 0.076* | |
C20 | 0.2866 (10) | 0.4201 (7) | 0.1510 (5) | 0.051 (2) | |
H20 | 0.2199 | 0.3755 | 0.1762 | 0.061* | |
C111 | 0.2697 (8) | 0.5408 (5) | 0.3471 (4) | 0.0342 (19) | |
H11A | 0.1907 | 0.4902 | 0.3308 | 0.041* | |
H11B | 0.3549 | 0.4933 | 0.3553 | 0.041* | |
C211 | 0.3105 (8) | 0.6668 (6) | 0.6150 (3) | 0.0379 (19) | |
H21A | 0.4026 | 0.6280 | 0.6219 | 0.045* | |
H21B | 0.2439 | 0.6276 | 0.6476 | 0.045* | |
C212 | 0.3270 (7) | 0.7869 (6) | 0.6418 (4) | 0.0326 (19) | |
C213 | 0.3704 (8) | 0.8732 (6) | 0.5951 (4) | 0.038 (2) | |
H213 | 0.3895 | 0.8561 | 0.5438 | 0.046* | |
C214 | 0.3869 (8) | 0.9843 (7) | 0.6209 (5) | 0.047 (2) | |
H214 | 0.4157 | 1.0421 | 0.5874 | 0.057* | |
C215 | 0.3609 (8) | 1.0097 (7) | 0.6959 (5) | 0.050 (2) | |
H215 | 0.3738 | 1.0846 | 0.7149 | 0.060* | |
C216 | 0.3158 (8) | 0.9242 (7) | 0.7424 (5) | 0.047 (2) | |
H216 | 0.2964 | 0.9416 | 0.7937 | 0.056* | |
C217 | 0.2982 (7) | 0.8155 (6) | 0.7172 (4) | 0.0353 (19) | |
H217 | 0.2664 | 0.7587 | 0.7507 | 0.042* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Pd1 | 0.0364 (5) | 0.0248 (4) | 0.0220 (4) | 0.0042 (4) | 0.0019 (4) | 0.0005 (4) |
I1 | 0.0510 (4) | 0.0356 (3) | 0.0290 (3) | −0.0070 (3) | −0.0011 (2) | 0.0025 (3) |
Fe1 | 0.0400 (7) | 0.0357 (6) | 0.0173 (5) | −0.0025 (6) | 0.0071 (5) | −0.0041 (5) |
N1 | 0.038 (4) | 0.031 (4) | 0.020 (3) | 0.009 (3) | 0.005 (3) | −0.003 (3) |
N2 | 0.055 (4) | 0.021 (3) | 0.019 (3) | 0.014 (3) | 0.005 (3) | −0.005 (3) |
C1 | 0.031 (5) | 0.028 (4) | 0.024 (4) | −0.005 (4) | 0.004 (3) | 0.001 (3) |
C2 | 0.026 (4) | 0.050 (5) | 0.035 (5) | 0.008 (4) | 0.003 (3) | 0.010 (4) |
C3 | 0.047 (6) | 0.051 (6) | 0.032 (5) | 0.001 (4) | 0.013 (4) | 0.000 (4) |
C11 | 0.046 (5) | 0.030 (4) | 0.012 (4) | 0.002 (4) | 0.001 (4) | −0.006 (3) |
C12 | 0.025 (4) | 0.041 (5) | 0.028 (4) | 0.010 (4) | 0.002 (3) | −0.009 (4) |
C13 | 0.091 (8) | 0.031 (5) | 0.023 (5) | 0.015 (5) | −0.009 (5) | 0.000 (4) |
C14 | 0.077 (7) | 0.034 (5) | 0.026 (5) | −0.015 (5) | 0.023 (4) | −0.005 (4) |
C15 | 0.026 (5) | 0.055 (5) | 0.026 (4) | −0.002 (4) | −0.001 (3) | −0.018 (4) |
C16 | 0.053 (6) | 0.062 (6) | 0.041 (5) | −0.013 (5) | 0.003 (5) | −0.030 (5) |
C17 | 0.059 (6) | 0.051 (6) | 0.028 (5) | −0.002 (5) | 0.020 (5) | −0.012 (4) |
C18 | 0.032 (5) | 0.078 (7) | 0.058 (6) | 0.009 (5) | 0.004 (5) | −0.038 (6) |
C19 | 0.111 (9) | 0.042 (6) | 0.035 (5) | 0.027 (6) | −0.007 (6) | −0.004 (5) |
C20 | 0.065 (7) | 0.044 (6) | 0.047 (6) | −0.015 (5) | 0.036 (5) | −0.011 (5) |
C111 | 0.050 (5) | 0.030 (4) | 0.024 (4) | 0.009 (4) | 0.005 (4) | −0.006 (3) |
C211 | 0.063 (6) | 0.038 (5) | 0.012 (4) | 0.003 (4) | 0.000 (3) | −0.005 (4) |
C212 | 0.034 (5) | 0.036 (5) | 0.028 (4) | 0.007 (4) | −0.001 (4) | 0.002 (4) |
C213 | 0.041 (5) | 0.037 (5) | 0.037 (5) | 0.006 (4) | 0.012 (4) | 0.002 (4) |
C214 | 0.048 (6) | 0.045 (6) | 0.048 (6) | 0.006 (5) | −0.003 (4) | 0.010 (5) |
C215 | 0.046 (6) | 0.044 (6) | 0.060 (6) | 0.005 (5) | −0.001 (5) | −0.023 (5) |
C216 | 0.051 (6) | 0.047 (6) | 0.044 (5) | −0.001 (5) | 0.011 (4) | −0.018 (5) |
C217 | 0.045 (5) | 0.045 (5) | 0.017 (4) | 0.002 (4) | 0.011 (3) | −0.006 (4) |
Geometric parameters (Å, º) top
Pd1—C1i | 2.036 (7) | C13—H13 | 0.9500 |
Pd1—C1 | 2.036 (7) | C14—C15 | 1.423 (9) |
Pd1—I1i | 2.6168 (6) | C14—H14 | 0.9500 |
Pd1—I1 | 2.6168 (6) | C15—H15 | 0.9500 |
Fe1—C19 | 2.015 (8) | C16—C17 | 1.382 (10) |
Fe1—C20 | 2.025 (8) | C16—C20 | 1.392 (11) |
Fe1—C16 | 2.029 (7) | C16—H16 | 0.9500 |
Fe1—C17 | 2.038 (7) | C17—C18 | 1.393 (10) |
Fe1—C13 | 2.038 (8) | C17—H17 | 0.9500 |
Fe1—C14 | 2.039 (7) | C18—C19 | 1.435 (11) |
Fe1—C12 | 2.041 (6) | C18—H18 | 0.9500 |
Fe1—C15 | 2.044 (6) | C19—C20 | 1.373 (11) |
Fe1—C11 | 2.044 (6) | C19—H19 | 0.9500 |
Fe1—C18 | 2.045 (7) | C20—H20 | 0.9500 |
N1—C1 | 1.329 (8) | C111—H11A | 0.9900 |
N1—C2 | 1.464 (8) | C111—H11B | 0.9900 |
N1—C111 | 1.481 (7) | C211—C212 | 1.497 (9) |
N2—C1 | 1.350 (8) | C211—H21A | 0.9900 |
N2—C211 | 1.435 (7) | C211—H21B | 0.9900 |
N2—C3 | 1.488 (8) | C212—C213 | 1.382 (9) |
C2—C3 | 1.516 (9) | C212—C217 | 1.408 (9) |
C2—H2A | 0.9900 | C213—C214 | 1.392 (9) |
C2—H2B | 0.9900 | C213—H213 | 0.9500 |
C3—H3A | 0.9900 | C214—C215 | 1.386 (10) |
C3—H3B | 0.9900 | C214—H214 | 0.9500 |
C11—C15 | 1.417 (9) | C215—C216 | 1.379 (10) |
C11—C12 | 1.432 (9) | C215—H215 | 0.9500 |
C11—C111 | 1.487 (9) | C216—C217 | 1.364 (9) |
C12—C13 | 1.414 (10) | C216—H216 | 0.9500 |
C12—H12 | 0.9500 | C217—H217 | 0.9500 |
C13—C14 | 1.394 (10) | | |
| | | |
C1i—Pd1—C1 | 180.0 (4) | C13—C12—H12 | 126.2 |
C1i—Pd1—I1i | 92.64 (18) | C11—C12—H12 | 126.2 |
C1—Pd1—I1i | 87.36 (18) | Fe1—C12—H12 | 126.2 |
C1i—Pd1—I1 | 87.36 (18) | C14—C13—C12 | 108.6 (7) |
C1—Pd1—I1 | 92.64 (18) | C14—C13—Fe1 | 70.1 (5) |
I1i—Pd1—I1 | 180.0 | C12—C13—Fe1 | 69.9 (4) |
C19—Fe1—C20 | 39.7 (3) | C14—C13—H13 | 125.7 |
C19—Fe1—C16 | 67.6 (4) | C12—C13—H13 | 125.7 |
C20—Fe1—C16 | 40.2 (3) | Fe1—C13—H13 | 126.0 |
C19—Fe1—C17 | 68.2 (3) | C13—C14—C15 | 108.5 (7) |
C20—Fe1—C17 | 67.3 (3) | C13—C14—Fe1 | 70.0 (5) |
C16—Fe1—C17 | 39.7 (3) | C15—C14—Fe1 | 69.8 (4) |
C19—Fe1—C13 | 178.6 (3) | C13—C14—H14 | 125.7 |
C20—Fe1—C13 | 139.9 (4) | C15—C14—H14 | 125.7 |
C16—Fe1—C13 | 111.4 (4) | Fe1—C14—H14 | 126.1 |
C17—Fe1—C13 | 110.4 (3) | C11—C15—C14 | 107.7 (6) |
C19—Fe1—C14 | 140.3 (4) | C11—C15—Fe1 | 69.7 (4) |
C20—Fe1—C14 | 179.9 (4) | C14—C15—Fe1 | 69.4 (4) |
C16—Fe1—C14 | 139.8 (4) | C11—C15—H15 | 126.1 |
C17—Fe1—C14 | 112.8 (3) | C14—C15—H15 | 126.1 |
C13—Fe1—C14 | 40.0 (3) | Fe1—C15—H15 | 126.3 |
C19—Fe1—C12 | 140.4 (4) | C17—C16—C20 | 108.4 (8) |
C20—Fe1—C12 | 111.9 (3) | C17—C16—Fe1 | 70.5 (4) |
C16—Fe1—C12 | 110.0 (3) | C20—C16—Fe1 | 69.8 (5) |
C17—Fe1—C12 | 136.4 (3) | C17—C16—H16 | 125.8 |
C13—Fe1—C12 | 40.6 (3) | C20—C16—H16 | 125.8 |
C14—Fe1—C12 | 68.0 (3) | Fe1—C16—H16 | 125.6 |
C19—Fe1—C15 | 112.9 (3) | C16—C17—C18 | 108.4 (8) |
C20—Fe1—C15 | 139.2 (4) | C16—C17—Fe1 | 69.8 (4) |
C16—Fe1—C15 | 178.2 (3) | C18—C17—Fe1 | 70.3 (4) |
C17—Fe1—C15 | 142.0 (3) | C16—C17—H17 | 125.8 |
C13—Fe1—C15 | 68.1 (3) | C18—C17—H17 | 125.8 |
C14—Fe1—C15 | 40.8 (3) | Fe1—C17—H17 | 125.7 |
C12—Fe1—C15 | 68.4 (3) | C17—C18—C19 | 106.9 (8) |
C19—Fe1—C11 | 112.8 (3) | C17—C18—Fe1 | 69.8 (4) |
C20—Fe1—C11 | 111.6 (3) | C19—C18—Fe1 | 68.2 (5) |
C16—Fe1—C11 | 137.7 (3) | C17—C18—H18 | 126.5 |
C17—Fe1—C11 | 177.0 (3) | C19—C18—H18 | 126.5 |
C13—Fe1—C11 | 68.5 (3) | Fe1—C18—H18 | 127.0 |
C14—Fe1—C11 | 68.3 (3) | C20—C19—C18 | 107.3 (8) |
C12—Fe1—C11 | 41.0 (2) | C20—C19—Fe1 | 70.5 (5) |
C15—Fe1—C11 | 40.6 (3) | C18—C19—Fe1 | 70.4 (4) |
C19—Fe1—C18 | 41.4 (3) | C20—C19—H19 | 126.3 |
C20—Fe1—C18 | 67.5 (3) | C18—C19—H19 | 126.3 |
C16—Fe1—C18 | 67.1 (3) | Fe1—C19—H19 | 124.3 |
C17—Fe1—C18 | 39.9 (3) | C19—C20—C16 | 108.9 (8) |
C13—Fe1—C18 | 137.6 (4) | C19—C20—Fe1 | 69.8 (5) |
C14—Fe1—C18 | 112.6 (4) | C16—C20—Fe1 | 70.1 (5) |
C12—Fe1—C18 | 176.3 (3) | C19—C20—H20 | 125.6 |
C15—Fe1—C18 | 114.5 (3) | C16—C20—H20 | 125.6 |
C11—Fe1—C18 | 142.7 (3) | Fe1—C20—H20 | 126.2 |
C1—N1—C2 | 114.3 (5) | N1—C111—C11 | 112.8 (5) |
C1—N1—C111 | 124.4 (6) | N1—C111—H11A | 109.0 |
C2—N1—C111 | 121.2 (6) | C11—C111—H11A | 109.0 |
C1—N2—C211 | 126.5 (6) | N1—C111—H11B | 109.0 |
C1—N2—C3 | 111.5 (6) | C11—C111—H11B | 109.0 |
C211—N2—C3 | 121.5 (5) | H11A—C111—H11B | 107.8 |
N1—C1—N2 | 108.4 (6) | N2—C211—C212 | 114.5 (6) |
N1—C1—Pd1 | 126.9 (5) | N2—C211—H21A | 108.6 |
N2—C1—Pd1 | 124.6 (5) | C212—C211—H21A | 108.6 |
N1—C2—C3 | 102.1 (5) | N2—C211—H21B | 108.6 |
N1—C2—H2A | 111.3 | C212—C211—H21B | 108.6 |
C3—C2—H2A | 111.3 | H21A—C211—H21B | 107.6 |
N1—C2—H2B | 111.3 | C213—C212—C217 | 117.4 (7) |
C3—C2—H2B | 111.3 | C213—C212—C211 | 122.6 (6) |
H2A—C2—H2B | 109.2 | C217—C212—C211 | 120.0 (6) |
N2—C3—C2 | 103.5 (5) | C212—C213—C214 | 122.1 (7) |
N2—C3—H3A | 111.1 | C212—C213—H213 | 119.0 |
C2—C3—H3A | 111.1 | C214—C213—H213 | 119.0 |
N2—C3—H3B | 111.1 | C215—C214—C213 | 119.3 (8) |
C2—C3—H3B | 111.1 | C215—C214—H214 | 120.3 |
H3A—C3—H3B | 109.0 | C213—C214—H214 | 120.3 |
C15—C11—C12 | 107.5 (6) | C216—C215—C214 | 118.8 (8) |
C15—C11—C111 | 126.4 (7) | C216—C215—H215 | 120.6 |
C12—C11—C111 | 126.0 (7) | C214—C215—H215 | 120.6 |
C15—C11—Fe1 | 69.7 (4) | C217—C216—C215 | 122.0 (7) |
C12—C11—Fe1 | 69.4 (4) | C217—C216—H216 | 119.0 |
C111—C11—Fe1 | 124.7 (4) | C215—C216—H216 | 119.0 |
C13—C12—C11 | 107.6 (7) | C216—C217—C212 | 120.3 (7) |
C13—C12—Fe1 | 69.6 (4) | C216—C217—H217 | 119.9 |
C11—C12—Fe1 | 69.6 (4) | C212—C217—H217 | 119.9 |
| | | |
C2—N1—C1—N2 | −5.3 (8) | C20—Fe1—C15—C14 | −179.9 (6) |
C111—N1—C1—N2 | 177.6 (6) | C17—Fe1—C15—C14 | 58.6 (7) |
C2—N1—C1—Pd1 | 170.7 (5) | C13—Fe1—C15—C14 | −37.0 (4) |
C111—N1—C1—Pd1 | −6.5 (10) | C12—Fe1—C15—C14 | −80.8 (5) |
C211—N2—C1—N1 | 174.8 (6) | C11—Fe1—C15—C14 | −119.0 (6) |
C3—N2—C1—N1 | 2.8 (8) | C18—Fe1—C15—C14 | 96.7 (6) |
C211—N2—C1—Pd1 | −1.3 (10) | C19—Fe1—C16—C17 | −82.4 (6) |
C3—N2—C1—Pd1 | −173.3 (5) | C20—Fe1—C16—C17 | −119.2 (8) |
I1i—Pd1—C1—N1 | −85.6 (6) | C13—Fe1—C16—C17 | 96.7 (6) |
I1—Pd1—C1—N1 | 94.4 (6) | C14—Fe1—C16—C17 | 60.9 (8) |
I1i—Pd1—C1—N2 | 89.7 (6) | C12—Fe1—C16—C17 | 140.1 (5) |
I1—Pd1—C1—N2 | −90.3 (6) | C11—Fe1—C16—C17 | 177.8 (5) |
C1—N1—C2—C3 | 5.4 (8) | C18—Fe1—C16—C17 | −37.4 (5) |
C111—N1—C2—C3 | −177.4 (6) | C19—Fe1—C16—C20 | 36.8 (5) |
C1—N2—C3—C2 | 0.5 (8) | C17—Fe1—C16—C20 | 119.2 (8) |
C211—N2—C3—C2 | −172.0 (6) | C13—Fe1—C16—C20 | −144.2 (5) |
N1—C2—C3—N2 | −3.2 (7) | C14—Fe1—C16—C20 | −179.9 (6) |
C19—Fe1—C11—C15 | 99.1 (6) | C12—Fe1—C16—C20 | −100.7 (5) |
C20—Fe1—C11—C15 | 142.2 (5) | C11—Fe1—C16—C20 | −63.1 (7) |
C16—Fe1—C11—C15 | −179.6 (5) | C18—Fe1—C16—C20 | 81.8 (5) |
C13—Fe1—C11—C15 | −81.1 (5) | C20—C16—C17—C18 | 0.3 (9) |
C14—Fe1—C11—C15 | −37.9 (4) | Fe1—C16—C17—C18 | 60.0 (5) |
C12—Fe1—C11—C15 | −118.8 (6) | C20—C16—C17—Fe1 | −59.7 (5) |
C18—Fe1—C11—C15 | 61.3 (7) | C19—Fe1—C17—C16 | 80.7 (6) |
C19—Fe1—C11—C12 | −142.1 (5) | C20—Fe1—C17—C16 | 37.6 (5) |
C20—Fe1—C11—C12 | −99.1 (5) | C13—Fe1—C17—C16 | −99.2 (6) |
C16—Fe1—C11—C12 | −60.9 (6) | C14—Fe1—C17—C16 | −142.3 (6) |
C13—Fe1—C11—C12 | 37.7 (4) | C12—Fe1—C17—C16 | −60.8 (7) |
C14—Fe1—C11—C12 | 80.9 (5) | C15—Fe1—C17—C16 | −179.5 (6) |
C15—Fe1—C11—C12 | 118.8 (6) | C18—Fe1—C17—C16 | 119.3 (8) |
C18—Fe1—C11—C12 | −179.9 (6) | C19—Fe1—C17—C18 | −38.6 (5) |
C19—Fe1—C11—C111 | −21.9 (8) | C20—Fe1—C17—C18 | −81.7 (6) |
C20—Fe1—C11—C111 | 21.2 (8) | C16—Fe1—C17—C18 | −119.3 (8) |
C16—Fe1—C11—C111 | 59.4 (8) | C13—Fe1—C17—C18 | 141.5 (6) |
C13—Fe1—C11—C111 | 158.0 (7) | C14—Fe1—C17—C18 | 98.4 (6) |
C14—Fe1—C11—C111 | −158.9 (7) | C12—Fe1—C17—C18 | 179.8 (5) |
C12—Fe1—C11—C111 | 120.3 (8) | C15—Fe1—C17—C18 | 61.2 (7) |
C15—Fe1—C11—C111 | −121.0 (8) | C16—C17—C18—C19 | −1.4 (9) |
C18—Fe1—C11—C111 | −59.7 (9) | Fe1—C17—C18—C19 | 58.3 (5) |
C15—C11—C12—C13 | 0.1 (8) | C16—C17—C18—Fe1 | −59.6 (5) |
C111—C11—C12—C13 | −178.0 (6) | C19—Fe1—C18—C17 | 118.8 (7) |
Fe1—C11—C12—C13 | −59.4 (5) | C20—Fe1—C18—C17 | 80.9 (5) |
C15—C11—C12—Fe1 | 59.5 (5) | C16—Fe1—C18—C17 | 37.2 (5) |
C111—C11—C12—Fe1 | −118.6 (6) | C13—Fe1—C18—C17 | −59.9 (7) |
C19—Fe1—C12—C13 | −178.5 (6) | C14—Fe1—C18—C17 | −99.1 (5) |
C20—Fe1—C12—C13 | −143.0 (5) | C15—Fe1—C18—C17 | −143.7 (5) |
C16—Fe1—C12—C13 | −99.8 (5) | C11—Fe1—C18—C17 | 177.5 (5) |
C17—Fe1—C12—C13 | −63.4 (6) | C20—Fe1—C18—C19 | −37.9 (5) |
C14—Fe1—C12—C13 | 37.0 (4) | C16—Fe1—C18—C19 | −81.6 (6) |
C15—Fe1—C12—C13 | 81.1 (5) | C17—Fe1—C18—C19 | −118.8 (7) |
C11—Fe1—C12—C13 | 118.9 (6) | C13—Fe1—C18—C19 | −178.7 (6) |
C19—Fe1—C12—C11 | 62.6 (7) | C14—Fe1—C18—C19 | 142.1 (6) |
C20—Fe1—C12—C11 | 98.1 (5) | C15—Fe1—C18—C19 | 97.5 (6) |
C16—Fe1—C12—C11 | 141.2 (5) | C11—Fe1—C18—C19 | 58.7 (8) |
C17—Fe1—C12—C11 | 177.7 (5) | C17—C18—C19—C20 | 1.9 (9) |
C13—Fe1—C12—C11 | −118.9 (6) | Fe1—C18—C19—C20 | 61.2 (6) |
C14—Fe1—C12—C11 | −81.9 (5) | C17—C18—C19—Fe1 | −59.3 (5) |
C15—Fe1—C12—C11 | −37.8 (4) | C16—Fe1—C19—C20 | −37.2 (5) |
C11—C12—C13—C14 | −0.1 (8) | C17—Fe1—C19—C20 | −80.2 (5) |
Fe1—C12—C13—C14 | −59.5 (5) | C14—Fe1—C19—C20 | 179.9 (5) |
C11—C12—C13—Fe1 | 59.4 (5) | C12—Fe1—C19—C20 | 57.6 (7) |
C20—Fe1—C13—C14 | 179.9 (5) | C15—Fe1—C19—C20 | 141.0 (5) |
C16—Fe1—C13—C14 | −144.1 (5) | C11—Fe1—C19—C20 | 96.8 (5) |
C17—Fe1—C13—C14 | −101.5 (5) | C18—Fe1—C19—C20 | −117.5 (7) |
C12—Fe1—C13—C14 | 119.6 (6) | C20—Fe1—C19—C18 | 117.5 (7) |
C15—Fe1—C13—C14 | 37.7 (4) | C16—Fe1—C19—C18 | 80.3 (5) |
C11—Fe1—C13—C14 | 81.5 (5) | C17—Fe1—C19—C18 | 37.3 (5) |
C18—Fe1—C13—C14 | −65.2 (6) | C14—Fe1—C19—C18 | −62.6 (7) |
C20—Fe1—C13—C12 | 60.3 (6) | C12—Fe1—C19—C18 | 175.0 (5) |
C16—Fe1—C13—C12 | 96.2 (5) | C15—Fe1—C19—C18 | −101.6 (5) |
C17—Fe1—C13—C12 | 138.9 (5) | C11—Fe1—C19—C18 | −145.8 (5) |
C14—Fe1—C13—C12 | −119.6 (6) | C18—C19—C20—C16 | −1.8 (9) |
C15—Fe1—C13—C12 | −81.9 (4) | Fe1—C19—C20—C16 | 59.4 (6) |
C11—Fe1—C13—C12 | −38.1 (4) | C18—C19—C20—Fe1 | −61.1 (5) |
C18—Fe1—C13—C12 | 175.2 (5) | C17—C16—C20—C19 | 1.0 (9) |
C12—C13—C14—C15 | 0.1 (8) | Fe1—C16—C20—C19 | −59.2 (6) |
Fe1—C13—C14—C15 | −59.3 (5) | C17—C16—C20—Fe1 | 60.1 (5) |
C12—C13—C14—Fe1 | 59.4 (5) | C16—Fe1—C20—C19 | 120.0 (7) |
C19—Fe1—C14—C13 | 177.9 (5) | C17—Fe1—C20—C19 | 82.8 (5) |
C16—Fe1—C14—C13 | 57.8 (7) | C13—Fe1—C20—C19 | 177.9 (6) |
C17—Fe1—C14—C13 | 95.1 (5) | C12—Fe1—C20—C19 | −144.5 (5) |
C12—Fe1—C14—C13 | −37.6 (4) | C15—Fe1—C20—C19 | −62.6 (7) |
C15—Fe1—C14—C13 | −119.7 (6) | C11—Fe1—C20—C19 | −100.2 (5) |
C11—Fe1—C14—C13 | −81.9 (5) | C18—Fe1—C20—C19 | 39.4 (5) |
C18—Fe1—C14—C13 | 138.5 (5) | C19—Fe1—C20—C16 | −120.0 (7) |
C19—Fe1—C14—C15 | −62.4 (7) | C17—Fe1—C20—C16 | −37.2 (5) |
C16—Fe1—C14—C15 | 177.4 (5) | C13—Fe1—C20—C16 | 57.9 (7) |
C17—Fe1—C14—C15 | −145.3 (5) | C12—Fe1—C20—C16 | 95.4 (5) |
C13—Fe1—C14—C15 | 119.7 (6) | C15—Fe1—C20—C16 | 177.4 (5) |
C12—Fe1—C14—C15 | 82.1 (4) | C11—Fe1—C20—C16 | 139.8 (5) |
C11—Fe1—C14—C15 | 37.7 (4) | C18—Fe1—C20—C16 | −80.6 (5) |
C18—Fe1—C14—C15 | −101.9 (5) | C1—N1—C111—C11 | −113.7 (7) |
C12—C11—C15—C14 | −0.1 (7) | C2—N1—C111—C11 | 69.4 (8) |
C111—C11—C15—C14 | 178.0 (6) | C15—C11—C111—N1 | 89.9 (8) |
Fe1—C11—C15—C14 | 59.2 (5) | C12—C11—C111—N1 | −92.3 (8) |
C12—C11—C15—Fe1 | −59.3 (4) | Fe1—C11—C111—N1 | 179.2 (5) |
C111—C11—C15—Fe1 | 118.8 (6) | C1—N2—C211—C212 | 128.2 (7) |
C13—C14—C15—C11 | 0.0 (8) | C3—N2—C211—C212 | −60.6 (9) |
Fe1—C14—C15—C11 | −59.4 (5) | N2—C211—C212—C213 | −35.1 (10) |
C13—C14—C15—Fe1 | 59.4 (5) | N2—C211—C212—C217 | 145.0 (7) |
C19—Fe1—C15—C11 | −98.9 (5) | C217—C212—C213—C214 | 0.7 (11) |
C20—Fe1—C15—C11 | −60.8 (6) | C211—C212—C213—C214 | −179.2 (7) |
C17—Fe1—C15—C11 | 177.6 (5) | C212—C213—C214—C215 | 0.8 (12) |
C13—Fe1—C15—C11 | 82.0 (5) | C213—C214—C215—C216 | −1.6 (12) |
C14—Fe1—C15—C11 | 119.0 (6) | C214—C215—C216—C217 | 1.0 (12) |
C12—Fe1—C15—C11 | 38.2 (4) | C215—C216—C217—C212 | 0.4 (12) |
C18—Fe1—C15—C11 | −144.2 (5) | C213—C212—C217—C216 | −1.2 (11) |
C19—Fe1—C15—C14 | 142.1 (6) | C211—C212—C217—C216 | 178.7 (7) |
Symmetry code: (i) −x+1, −y+1, −z+1. |
Experimental details
| (I) | (II) |
Crystal data |
Chemical formula | [Fe(C5H5)(C19H24N2)]I | [Fe2Pd(C5H5)2(C16H17N2)2I2] |
Mr | 528.24 | 1076.71 |
Crystal system, space group | Monoclinic, P21 | Monoclinic, P21/n |
Temperature (K) | 180 | 180 |
a, b, c (Å) | 10.6277 (12), 7.4514 (8), 28.293 (3) | 9.5185 (16), 11.7851 (17), 17.569 (2) |
β (°) | 95.603 (9) | 92.835 (12) |
V (Å3) | 2229.8 (4) | 1968.5 (5) |
Z | 4 | 2 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 2.07 | 2.78 |
Crystal size (mm) | 0.44 × 0.29 × 0.03 | 0.17 × 0.07 × 0.06 |
|
Data collection |
Diffractometer | Oxford Xcalibur diffractometer | Oxford Xcalibur diffractometer |
Absorption correction | Analytical [Analytical numerical absorption correction using a multifaceted crystal model
based on expressions derived by Clark & Reid, implemented in CrysAlis RED
(Oxford Diffraction, 2006)] | Multi-scan (Blessing, 1997) |
Tmin, Tmax | 0.654, 0.964 | 0.727, 0.797 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 19193, 10405, 7372 | 14178, 3890, 2082 |
Rint | 0.044 | 0.084 |
(sin θ/λ)max (Å−1) | 0.665 | 0.617 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.036, 0.064, 0.84 | 0.046, 0.091, 0.85 |
No. of reflections | 10405 | 3890 |
No. of parameters | 512 | 232 |
No. of restraints | 1 | 0 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.67, −0.63 | 0.94, −0.71 |
Absolute structure | Flack (1983), with 4503 Friedel pairs | ? |
Absolute structure parameter | 0.220 (15) | ? |
Hydrogen-bond geometry (Å, º) for (I) top
D—H···A | D—H | H···A | D···A | D—H···A |
C1—H1···I1 | 0.95 | 2.87 | 3.811 (5) | 173.3 |
C113—H11E···I1i | 0.99 | 2.98 | 3.878 (5) | 151.5 |
C211—H21B···I1ii | 0.99 | 2.96 | 3.877 (5) | 153.9 |
C212—H21C···I1iii | 0.99 | 2.95 | 3.797 (5) | 144.7 |
C213—H21E···I2i | 0.99 | 2.99 | 3.860 (6) | 147.7 |
C24—H24···Cg1iv | 0.95 | 2.90 | 3.688 (5) | 141 |
C230—H23C···Cg2 | 0.98 | 2.90 | 3.781 (5) | 150 |
C14—H14···Cg3v | 0.95 | 2.70 | 3.579 (5) | 154 |
Symmetry codes: (i) x, y+1, z; (ii) x−1, y, z; (iii) x−1, y+1, z; (iv) x, y−1, z; (v) x+1, y+1, z. |
Comparison of selected C—N distances (Å) and N—C—N angles (°) within
the diaminocarbene moiety for Fc-bearing ligands related to (I) topReferences: (a) Hua et al. (2004);
(b) Bildstein, Malaun, Kopacka, Ongania & Wurst (1999);
(c) Bildstein et al. (1998);
(d) Bildstein, Malaun, Kopacka, Wurst et al. (1999);
(e) Bertoog et al. (2005);
(f) Gischig & Togni (2005);
(g) Coleman et al. (2005);
(h) Varnado et al. (2009);
(i) Labande et al. (2007);
(j) Gülcemal et al. (2009). |
Compound | N—C | C—N | N—C—N | Reference |
(IA) | 1.294 (5) | 1.325 (6) | 114.5 (4) | This study |
(IB) | 1.292 (5) | 1.311 (5) | 113.6 (4) | This study |
C21H21FeIN2 | 1.321 (4) | 1.317 (4) | 109.0 (3) | a |
C18H17BF4FeN2 | 1.332 (5) | 1.312 (5) | 110.9 (3) | b |
C19H19FeIN2.H2O.(CH3OH)1/4 | 1.339 (9) | 1.335 (9) | 109.9 (8) | c |
C25H25Fe2IN2 | 1.317 (5) | 1.329 (5) | 109.0 (3) | c |
C47H41BFe2N2 | 1.334 (5) | 1.325 (5) | 108.4 (4) | d |
C23H23F6Fe2N2P | 1.304 (3) | 1.304 (3) | 113.9 (3) | d |
C25H25Fe2IN2 | 1.327 (3) | 1.332 (3) | 108.6 (2) | e |
C23H21Fe2IN2 | 1.329 (8) | 1.329 (8) | 108.4 (8) | e |
C59H39F24Fe2N2P2.I.CH2Cl2 | 1.336 (8) | 1.325 (7) | 109.3 (5) | f |
C26H36Cl2 FeN4.CH2Cl2 | 1.325 (7) | 1.326 (7) | 108.1 (5) | g |
C28H28B2F8FeN4 | 1.351 (5) | 1.327 (6) | 109.6 (4) | h |
C27H26BF4FeN2PS | 1.324 (5) | 1.313 (5) | 108.6 (3) | i |
C27H26BF4FeN2PS | 1.317 (3) | 1.309 (4) | 109.7 (3) | i |
C40H38BF4FeN2P | 1.321 (3) | 1.331 (3) | 110.5 (2) | j |
(C30H33FeIN2)2 | 1.321 (6) | 1.321 (6) | 110.4 (6) | j |
Comparison of the C—N distances (Å) and N—C—N angles (°) in (II) with
those in related complexes found in the literature topReferences: (a) Bildstein, Malaun, Kopacka, Ongania & Wurst (1999);
(b) Bildstein et al. (1998);
(c) Bildstein, Malaun, Kopacka, Wurst et al. (1999);
(d) Bertoog et al. (2005);
(e) Gischig & Togni (2005);
(f) Coleman et al. (2005);
(g) Varnado et al. (2009);
(h) Labande et al. (2007);
(i) Gülcemal et al. (2009). |
Compound | N—C | C—N | N—C—N | Reference |
(II) | 1.329 (8) | 1.350 (8) | 108.4 (6) | This study |
C23H16FeN2O5W | 1.384 (7) | 1.366 (6) | 104.0 (4) | a |
C40H32Fe2N4O4W.CH2Cl2 | 1.41 (2) | 1.36 (2) | 103.7 (11) | a |
C34H26Fe2N2O5W | 1.350 (2) | 1.357 (14) | 103.3 (11) | b |
C58H52Fe4I2N4Pd.(CH2Cl2)4 | 1.355 (9) | 1.354 (9) | 106.0 (6) | b |
C38H36Fe2Hg2I4N4 | 1.348 (10) | 1.338 (10) | 106.4 (6) | b |
C70H60AgBFe4N4.0.5CHCl3.1.5MeO | 1.364 (5) | 1.354 (5) | 103.8 (3) | c |
| 1.369 (5) | 1.350 (5) | 104.1 (3) | c |
C43H39Fe2I2N2PPd | 1.351 (4) | 1.359 (4) | 104.9 (3) | d |
C59H38F24Fe2IN2P2Pd.PF6.3(CHCl3) | 1.344 (16) | 1.330 (16) | 108.4 (12) | e |
C53H49Fe2N3P2Pd.2(PF6).C2H6O.C4H10O | 1.330 (11) | 1.330 (11) | 106.1 (8) | e |
C26H34Cl2FeN4Pd.2CH2Cl2 | 1.359 (4) | 1.363 (4) | 104.7 (2) | f |
C44H50Cl2FeIr2N4 | 1.371 (5) | 1.355 (5) | 105.8 (3) | g |
C33H27Cl5FeIr2O4N4 | 1.353 (5) | 1.359 (5) | 106.0 (3) | g |
C35H37BF4FeN2PRh | 1.359 (4) | 1.357 (4) | 104.5 (2) | h |
C46H45BF4FeN2PRh | 1.355 (8) | 1.362 (8) | 105.5 (6) | i |
C50H51BF4FeN2PRh | 1.367 (5) | 1.373 (6) | 105.2 (4) | i |
C36H40FeIN2Rh | 1.366 (3) | 1.360 (3) | 106.02 (18) | i |
In recent years, N-heterocyclic carbenes (NHCs) based on imidazolium ions have emerged as useful ligands in the design of highly efficient transition metal-based homogeneous catalysts (Peris & Crabtree, 2004; Cavell & McGuinness, 2004; Glorius, 2007; Sommer & Weck, 2007; Gonzalez et al., 2009; Melaimi et al., 2010). Ferrocenyl-substituted carbenes are interesting compounds because of the influence of the metallocenyl groups with respect to steric protection, electron donation and reversible redox chemistry. Pioneered by Bildstein et al. (1998), this expanding field (Bildstein, 2001) contains a broad range of NHCs (Bildstein, Malaun, Kopacka, Ongania & Wurst, 1999; Bildstein, Malaun, Kopacka, Wurst et al., 1999); Jackstell et al., 2002; Demirhan et al., 2003; Bertoog et al., 2005; Siemeling et al., 2009; Varnado et al., 2009), including derivatives with additional donor groups (Yuan et al., 2005; Gischig & Togni, 2005; Labande et al., 2007; Gülcemal et al., 2009) that can be used as multidentate ligands. Such ferrocenyl-substituted carbene ligands have been shown to be effective in transition metal-catalysed reactions. Some ferrocenyl-substituted NHCs derived from imidazolin-2-ylidene and benzimidazol-2-ylidene have also been structurally characterized by Bildstein and co-workers (Bildstein et al., 1998; Bildstein, Malaun, Kopacka, Ongania & Wurst, 1999; Bildstein, Malaun, Kopacka, Wurst et al., 1999).
Recently, we reported the synthesis and electrochemistry of the title salt, 1-ferrocenylmethyl-3-(2,4,6-trimethylbenzyl)-1H-imidazolium iodide, (I), and the title complex, trans-bis(3-benzyl-1-ferrocenylmethyl-1H-imidazol-2-ylidene)diiodidopalladium(II), (II). The latter is derived from 1-ferrocenylmethyl-3-benzylimidazolium iodide salt (Demirhan et al., 2003). The ferrocene imidazolium salt, (I), can be shown to act as an anion receptor and is used in preparing chiral carbene ligands and their complexes. In complex (II), the ferrocenylmethyl acts as a pendant group on the N atom of imidazol-2-ylidene. It is a new ferrocenyl-substituted carbene and it is hoped that it may prove useful, given its potential applications in homogenous catalysis and electrocatalysis. Initially, the compounds were isolated as microcrystalline solids that were not suitable for structure determination through X-ray diffraction. After several unsuccessful attempts, X-ray quality crystals were obtained and we report here the crystal structures of (I) and (II).
In compound (I), the asymmetric unit contains two 1-ferrocenylmethyl-3-(2,4,6-trimethylbenzyl)-1H-imidazolium cations and two iodide anions (Z' = 2, see Fig. 1). The value of the Flack parameter refined to 0.22 (2), and this is normally taken to indicate the occurrence of a twin by inversion. The two cations have different conformations, as is clearly shown in the molecular overlap representation in Fig. 2. In molecule A, the N-heterocyclic carbene ring is oriented somewhat endo with respect to atom Fe1 and the Cp ring to which it is attached, whereas in molecule B it is exo with respect to atom Fe2 and the related Cp ring. This is clearly shown by the positions of atoms N11 and N21 with respect to the mean planes of the C11–C15 and C21–C25 Cp rings, -0.124 (9) Å out of plane for N11 and 1.045 (9) Å for N21. This difference in conformation is also reflected in the C12—C11—C111—N11 and C22—C21—C211—N21 torsion angles, with values of -168.5 (4) and -111.8 (5)°, respectively. The two imidazolium rings deviate slightly from planarity, with the largest deviations from the least-squares mean planes being 0.047 (3) and -0.060 (3) Å for the methylene atoms C112 and C212. Thus, the two imidazolidinium groups, N11—C1—N12—C112—C113 and N21—C2—N22—C212—C213, display slightly twisted conformations on, respectively, the C112—C113 bond [puckering parameters Q2 = 0.079 (5) Å and ϕ2 = 313 (4)°; Cremer & Pople, 1975; Evans & Boeyens, 1989] for molecule A and the C212—C213 bond [puckering parameters Q2 = 0.102 (5) Å and ϕ2 = 133 (3)°] for molecule B. The conformation of molecule B of (I) is closely related to that of the salt 1-ferrocenylmethyl-3-benzylimidazolium iodide (Hua et al., 2004). The C—C and C—N distances within the imidazolium rings agree with the values observed in this latter salt and with values found in the literature for related Fc-containing compounds (Cambridge Structural Database, Version?; Allen, 2002), as can be seen in Table 2. However, it is interesting to note that the N—C—N angles of 114.5 (4) and 113.6 (4)° in (I) are generally larger than the range found for these related species (108.1–113.9°).
The least-squares planes of the mesitylene rings and imidazolidinium cations of (I) make dihedral angles of 79.94 (14) and 65.52 (14)° in molecules A and B, respectively. The bond lengths and angles within the ferrocene moiety are within expected limits. The Cp rings of the Fc groups are slightly twisted away from the ideal eclipsed conformation [by 8.5 (6) and 6.7 (5)°, respectively; mean value calculated from the five possible C—Cg—Cg—C torsion angles, where Cg are the centroids of the Cp rings] and they are also slightly bent, making dihedral angles between the rings of 5.1 (3)° for molecule A and 1.9 (3)° for molecule B. The displacement parameters for the Cp ring that contains atom C16 indicate some rotational movement, which decreases the accuracy of the geometric parameters associated with this group.
The more pronounced bending for molecule A might be related to the rather short and linear C—H···I interaction between the carbene and the iodide (Table 1). There is no such linear hydrogen-bonding interaction for the B cation. Atom C2 does in fact make a closer contact with the iodide [3.541 (4) Å in molecule B and 3.811 (5) Å in molecule A], but only the linear interaction of molecule A gives a short H···I distance.
The packing within the crystal structure of (I) is governed by weak C—H···I and C—H···π interactions. The latter involve the centroids of the rings C16–C20 (Cg1), C122–C127 (Cg2) and C26–C30 (Cg3) (Table 1) and thus act as a link between cations. All these weak interactions combine to give a layered structure parallel to the (001) plane (Fig. 3).
Compound (II) has a crystallographically imposed centrosymmetric molecular geometry (Z' = 0.5), with the Pd position occupying a centre of symmetry. It shows the expected square-planar coordination with trans-carbene ligands (Fig. 4). Indeed, the ferrocenylmethyl and benzyl substituents in (II) are in a trans–anti arrangement. The imidazoline rings are twisted against the square-planar coordination arrangement by 87.4 (3)°. This is similar to what is observed in other imidazoline-2-ylidene PdII complexes. The Cp rings of the Fc group are much more staggered than in (I), with a rotation angle of 33.3 (6)°. They are also slightly bent, as shown by the dihedral angle between the two Cp ring planes of 1.6 (5)°. The bond lengths and angles within the ferrocene moiety are within expected limits. The Pd1—C1 distance of 2.036 (7) Å and the Pd1—I1 distance of 2.6168 (6) Å are also as observed for related square-planar PdII complexes (Bildstein et al., 1998; Bertoog et al., 2005; Huynh & Wu, 2009).
The carbene-centred N1—C1—N2 ring angle in (II) is 108.4 (6)°. This is within the range of values observed for other NHC–metal complexes, but as with (I) it is at the high end of the range [103.3 (11)–108.4 (12)°; see Table 3]. It is noted that the other large angles are also observed for complexes that contain iodide ligands. The literature survey also shows that coordination of the carbene C atom to metal results, as expected, in a lengthening of the C—N bonds [ranging from 1.329 (8) Å in (II) to 1.41 (2) Å] compared with the free ligands [ranging from 1.292 (5) in (I) to 1.339 (9) Å; Tables 2 and 3]. In both (I) and (II), the C—N carbene bond involving the N atom attached to the ferrocene moiety through the methylene bridge is significantly shorter than the C—N bond involving the N atom attached to the mesitylene or phenyl groups. This slight difference is certainly related to an electronic effect caused by the proximity of the electron-rich ferrocene moiety.