research communications
rac-1-(4-tert-Butylphenyl)-5-ethyl-4-ferrocenyl-5-hydroxy-1H-pyrrol-2(5H)-one
aUniversity Koblenz, Institute of Integrated Natural Sciences, Universitätsstr. 1, 56070 Koblenz, Germany, and bFriedrich-Schiller-University Jena, Institute of Inorganic and Analytical Chemistry, Humboldtstr. 11, 07743 Jena, Germany
*Correspondence e-mail: imhof@uni-koblenz.de
The title compound, [Fe(C5H5)(C21H24NO2)], which is produced by the oxidation of 1-(4-tert-butylphenyl)-2-ethyl-3-ferrocenylpyrrole, crystallizes as a in the centrosymmetric P21/n. The central heterocyclic pyrrole ring system subtends dihedral angles of 13.7 (2)° with respect to the attached cyclopentadienyl ring and of 43.6 (7)° with the major component of the disordered phenyl group bound to the N atom. The 4-tert-butylphenyl group, as well as the non-substituted Cp ring are disordered with s.o.f. values of 0.589 (16) and 0.411 (16), respectively. In the crystal, molecules with the same are linked into infinite chains along the b-axis direction by O—H⋯O hydrogen bonds between the hydroxy substituent and the carbonyl O atom of the adjacent molecule.
Keywords: crystal structure; pyrrole; pyrrolone; ferrocene.
CCDC reference: 961575
1. Chemical context
In a series of recent publications, we were able to show that the ruthenium-catalysed four-component reaction of an α, β-unsaturated aldehyde with a primary amine (producing an intermediate imine), carbon monoxide and ethylene produces a library of chiral 1,3-dihydropyrrolones and pyrroles, respectively (Biletzki & Imhof, 2011). The ratio of those two products is highly dependent on the of the solvent used, with the yield of the pyrrole increasing with the polarity of the solvent (Gillies et al., 2007). We were also able to show that the oxidation of the resulting pyrroles with oxygen leads to the formation of derivatives of the title compound (Dönnecke & Imhof, 2003). There are some similar reactions reported in the literature where a pyrrole was transformed into a hydroxy-pyrrolone by oxidation with O2, but the reaction mixture had to be irradiated in the presence of a photosensitizer, or radical initiators such as AIBN had to be added in order to induce the reaction (Machida et al. 1982; Dannhardt & Steindl 1985, 1986; Takechi et al. 1988; Boger & Baldino 1991; Procopiou & Highcock 1994; Gonzalez et al. 1999). Therefore, a radical mechanism cannot be ruled out for the formation of the title compound, although no addition of any typical initiator is necessary. So overall, depending on the reaction conditions, either chiral 1,3-dihydropyrrolones, chiral 5-hydroxy-1,5-dihydropyrrolones or 2,3-disubstituted pyrrole derivatives might be the main products of the catalytic synthetic methodology developed in our lab (Biletzki & Imhof, 2011; Gillies et al., 2007; Dönnecke & Imhof, 2003).
2. Structural commentary
The title compound, rac-1-(4-tert-butylphenyl)-5-ethyl-4-ferrocenyl-5-hydroxyl-1H-pyrrol-2(5H)-one, C26H29FeNO2, is derived from 1-(4-tert-butylphenyl)-2-ethyl-3-ferrocenylpyrrole by an oxidation reaction. Therefore, a new is created at C1, which used to be an sp2 carbon atom in the starting compound. Since no chiral reaction conditions were applied, a racemate of the title compound is produced. The title compound also crystallizes as a in the centrosymmetric P21/n. The molecular structure of the S-enantiomer is shown in Fig. 1. The central heterocyclic ring system N1/C1–C4 shows torsional angles of 13.7 (2)° with respect to the attached cyclopentadienyl ring and of 43.6 (7)° with the major component of the disordered phenyl group bound to N1. The 4-tert-butylphenyl group, as well as the non-substituted Cp ring, are disordered with s.o.f. values of 0.589 (16) and 0.411 (16). Bond lengths and angles are of expected values with the C2—C3 bond length of 1.336 (5) Å, clearly indicating a double bond. In addition, the N1—C4 bond [1.366 (5) Å] is shortened with respect to the other nitrogen carbon bonds, as is typical for amides.
3. Supramolecular features
In the crystal, molecules with the same b-axis direction by O—H⋯O hydrogen bonds of the C(6) type (Bernstein et al., 1995) between the hydroxy substituent and the carbonyl oxygen atom of an adjacent molecule (Fig. 2, Table 1). In addition, there are weak contacts between carbon atoms of the phenyl ring and H3A and H23A.
at C1 are linked into infinite chains along the4. Database survey
Some years ago, we published the N-methyl-5-ethyl-5-hydroxy-4-phenyl-1H-pyrrol-2(5H)-one CSD (Groom et al., 2016) refcode ULUJUG; Dönnecke & Imhof, 2003]. The compound shows almost identical structural features concerning the pyrrolone ring system and also crystallizes as a racemate in the Pna21.
of a derivative of the title compound,Compounds with related heterocyclic systems such as ferrocenyl-substituted maleimides or a 1,5-dihydro-2H-pyrrole-2-one with an imino substituent at C5 have also been reported (CATTOI: Mathur et al., 2012; TASNEI, TASNIM: Hildebrandt et al., 2012; ZEPLOY, ZEPLUE, ZEPMAL: Jha et al., 2017; CIVCUI: Raghuvanshi et al., 2017).
5. Synthesis and crystallization
0.5 mmol (200 mg) of 1-(4-tert-butylphenyl)-2-ethyl-3-ferrocenylpyrrole were treated with 5 mol% p-toluene sulfonic acid and were dissolved in 1.0 mL of anhydrous ethanol. The solution was placed in a 10 mL screw-cap vessel closed with parafilm. The process of the oxidation reaction was followed by thin layer and it could be observed that the reaction was finished after approximately 8 days. The reaction mixture was transferred to a Schlenk tube, the solvent was removed in vacuo and the remaining oily residue was purified by (10 × 2 cm, silica) using CH2Cl2 as the Slow evaporation of the solvent at ambient temperature led to the formation of crystalline material of the title compound (yield 183 mg, 83%). 1H NMR (400 MHz, CDCl3, 298 K): (ppm) = 0.55 (t, 3H, JHH = 7.4 Hz, CH3); 1.31 (s, 9H, CH3); 1.92 (q, 2H, JHH = 7.5 Hz, CH2); 2.84 (s, 1H, OH); 4.17 (s, 5H, Cp); 4.44–4.50 (m, 2H, CpR); 4.72–4.73 (m, 2H, CpR); 6.24 (s, 1H, =CH); 7.37–7.43 (m, 2H, CHPh); 7.48–7.52 (m, 2H, CHPh). 13C NMR (100 MHz, CDCl3, 298 K): (ppm) = 7.80 (CH3); 26.37 (CH2); 31.32 (CH3); 34.50 (C); 68.03 (CpR); 68.85 (CpR); 70.03 (Cp); 72.96 (CpR); 95.55 (C); 118.48 (=CH); 125.44 (CHPh); 125.86 (CHPh); 135.19 (CPh); 149.21 (CPh); 160.63 (C); 169.10 (C=O). MS (DEI): m/z (%) = 443 (96) [M+]; 427 (76) [M+ − O]; 426 (40) [M+ − OH]; 425 (75) [M+ − H2O]; 398 (22) [M+ − 3CH3]; 360 (98) [M+ − C5H5 − H2O]; 322 (48) [M+ − C5H5Fe]; 305 (58) [M+ − C5H5Fe − OH]; 294 (64) [M+ − C5H5Fe − CO].
6. Refinement
Crystal data, data collection and structure . The hydrogen atom of the hydroxy substituent (H1O2) was located in a difference-Fourier map and refined freely. All carbon-bound hydrogen atoms were placed in idealized positions and refined using a riding model with isotropic displacement parameters Uiso(H) = 1.2Ueq(C) for methylene and aromatic hydrogen atoms and H3 and Uiso(H) = 1.5Ueq(C) for methyl groups. The p-tBuC6H4 and Cp groups are disordered over two positions and were found to refine well with only one free variable. The proportion of the two positions is 58.94:41.06%. SIMU, RIGU, SAME, SADI and FLAT instructions were used to restrain the geometry and displacement parameters of the disordered moieties.
details are summarized in Table 2Supporting information
CCDC reference: 961575
https://doi.org/10.1107/S2056989023001858/jq2026sup1.cif
contains datablock I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989023001858/jq2026Isup2.hkl
Data collection: COLLECT (Nonius 1998); cell
DENZO (Otwinowski & Minor, 1997); data reduction: DENZO (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2019/1 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: SHELXL2018/3 (Sheldrick, 2015).[Fe(C5H5)(C21H24NO2)] | F(000) = 936 |
Mr = 443.35 | Dx = 1.356 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 15.7256 (5) Å | Cell parameters from 12993 reflections |
b = 7.0155 (2) Å | θ = 2.6–27.5° |
c = 20.0725 (6) Å | µ = 0.72 mm−1 |
β = 101.242 (2)° | T = 133 K |
V = 2171.97 (11) Å3 | Prism, red-brown |
Z = 4 | 0.09 × 0.07 × 0.05 mm |
Nonius KappaCCD diffractometer | 3348 reflections with I > 2σ(I) |
phi + ω – scans | Rint = 0.083 |
Absorption correction: multi-scan (SADABS; Krause et al., 2015) | θmax = 27.5°, θmin = 2.6° |
Tmin = 0.693, Tmax = 0.746 | h = −20→20 |
12993 measured reflections | k = −8→9 |
4945 independent reflections | l = −26→22 |
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)] = 0.073 | Hydrogen site location: mixed |
wR(F2) = 0.144 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.15 | w = 1/[σ2(Fo2) + (0.0092P)2 + 6.8638P] where P = (Fo2 + 2Fc2)/3 |
4945 reflections | (Δ/σ)max = 0.001 |
418 parameters | Δρmax = 0.66 e Å−3 |
950 restraints | Δρmin = −0.46 e Å−3 |
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. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Fe1 | 0.56011 (4) | 1.17446 (9) | 0.36865 (3) | 0.02460 (17) | |
O1 | 0.15960 (18) | 1.0828 (4) | 0.21878 (14) | 0.0262 (7) | |
O2 | 0.32476 (19) | 0.7788 (4) | 0.39389 (14) | 0.0234 (6) | |
H1O2 | 0.327 (3) | 0.705 (7) | 0.364 (2) | 0.025 (13)* | |
N1 | 0.2200 (2) | 0.9892 (5) | 0.32817 (15) | 0.0209 (7) | |
C1 | 0.3081 (3) | 0.9674 (6) | 0.37048 (19) | 0.0211 (8) | |
C2 | 0.3651 (3) | 1.0215 (5) | 0.31929 (19) | 0.0215 (8) | |
C3 | 0.3144 (3) | 1.0722 (5) | 0.2606 (2) | 0.0221 (9) | |
H3A | 0.334929 | 1.115373 | 0.221737 | 0.027* | |
C4 | 0.2233 (3) | 1.0520 (5) | 0.2643 (2) | 0.0222 (8) | |
C5 | 0.3187 (3) | 1.0948 (6) | 0.4330 (2) | 0.0249 (9) | |
H5A | 0.380511 | 1.095715 | 0.455599 | 0.030* | |
H5B | 0.285216 | 1.039071 | 0.465217 | 0.030* | |
C6 | 0.2889 (3) | 1.2999 (6) | 0.4179 (2) | 0.0356 (11) | |
H6A | 0.308703 | 1.378829 | 0.458206 | 0.053* | |
H6B | 0.225458 | 1.303725 | 0.405795 | 0.053* | |
H6C | 0.313400 | 1.348858 | 0.379969 | 0.053* | |
C7 | 0.1414 (9) | 0.960 (4) | 0.3517 (13) | 0.0260 (17) | 0.589 (16) |
C8 | 0.0759 (10) | 1.095 (3) | 0.3342 (10) | 0.030 (2) | 0.589 (16) |
H8A | 0.085728 | 1.206923 | 0.310245 | 0.036* | 0.589 (16) |
C9 | −0.0036 (9) | 1.0638 (19) | 0.3521 (8) | 0.036 (2) | 0.589 (16) |
H9A | −0.048051 | 1.156377 | 0.339971 | 0.043* | 0.589 (16) |
C10 | −0.0208 (7) | 0.9016 (19) | 0.3873 (8) | 0.0370 (19) | 0.589 (16) |
C11 | 0.0469 (9) | 0.776 (2) | 0.4080 (11) | 0.035 (2) | 0.589 (16) |
H11A | 0.038755 | 0.669994 | 0.435654 | 0.042* | 0.589 (16) |
C12 | 0.1271 (9) | 0.801 (4) | 0.3891 (14) | 0.0320 (18) | 0.589 (16) |
H12A | 0.171823 | 0.709245 | 0.401815 | 0.038* | 0.589 (16) |
C13 | −0.1109 (7) | 0.8565 (17) | 0.4023 (6) | 0.046 (2) | 0.589 (16) |
C14 | −0.1043 (8) | 0.753 (2) | 0.4702 (6) | 0.067 (3) | 0.589 (16) |
H14A | −0.162596 | 0.725677 | 0.478082 | 0.101* | 0.589 (16) |
H14B | −0.073419 | 0.833891 | 0.506880 | 0.101* | 0.589 (16) |
H14C | −0.072478 | 0.633291 | 0.469072 | 0.101* | 0.589 (16) |
C15 | −0.1633 (8) | 1.0388 (17) | 0.4038 (8) | 0.060 (3) | 0.589 (16) |
H15A | −0.173123 | 1.099364 | 0.359002 | 0.090* | 0.589 (16) |
H15B | −0.131301 | 1.126349 | 0.437742 | 0.090* | 0.589 (16) |
H15C | −0.219260 | 1.007828 | 0.415800 | 0.090* | 0.589 (16) |
C16 | −0.1578 (13) | 0.726 (3) | 0.3446 (8) | 0.059 (4) | 0.589 (16) |
H16A | −0.155996 | 0.785115 | 0.300598 | 0.089* | 0.589 (16) |
H16B | −0.218311 | 0.709334 | 0.349065 | 0.089* | 0.589 (16) |
H16C | −0.128916 | 0.602035 | 0.347502 | 0.089* | 0.589 (16) |
C7A | 0.1408 (13) | 0.953 (5) | 0.3512 (18) | 0.027 (2) | 0.411 (16) |
C8A | 0.0670 (15) | 1.065 (4) | 0.3316 (14) | 0.031 (2) | 0.411 (16) |
H8B | 0.070014 | 1.175646 | 0.305131 | 0.037* | 0.411 (16) |
C9A | −0.0109 (13) | 1.017 (3) | 0.3500 (11) | 0.035 (2) | 0.411 (16) |
H9B | −0.060483 | 1.094123 | 0.335113 | 0.042* | 0.411 (16) |
C10A | −0.0176 (11) | 0.857 (3) | 0.3901 (12) | 0.037 (2) | 0.411 (16) |
C11A | 0.0559 (12) | 0.745 (4) | 0.4084 (16) | 0.034 (2) | 0.411 (16) |
H11B | 0.051858 | 0.629669 | 0.432550 | 0.041* | 0.411 (16) |
C12A | 0.1357 (13) | 0.795 (5) | 0.393 (2) | 0.030 (2) | 0.411 (16) |
H12B | 0.186103 | 0.722100 | 0.409741 | 0.036* | 0.411 (16) |
C13A | −0.1078 (10) | 0.806 (2) | 0.4038 (8) | 0.047 (2) | 0.411 (16) |
C14A | −0.1049 (11) | 0.639 (3) | 0.4527 (9) | 0.064 (4) | 0.411 (16) |
H14D | −0.089734 | 0.521865 | 0.430827 | 0.096* | 0.411 (16) |
H14E | −0.161791 | 0.622925 | 0.465023 | 0.096* | 0.411 (16) |
H14F | −0.061165 | 0.663229 | 0.493786 | 0.096* | 0.411 (16) |
C15A | −0.1447 (12) | 0.976 (3) | 0.4372 (10) | 0.060 (4) | 0.411 (16) |
H15D | −0.111442 | 0.993369 | 0.483436 | 0.090* | 0.411 (16) |
H15E | −0.205564 | 0.951393 | 0.438885 | 0.090* | 0.411 (16) |
H15F | −0.140515 | 1.091388 | 0.410557 | 0.090* | 0.411 (16) |
C16A | −0.1690 (18) | 0.764 (4) | 0.3356 (10) | 0.054 (4) | 0.411 (16) |
H16D | −0.149443 | 0.649419 | 0.315222 | 0.082* | 0.411 (16) |
H16E | −0.168575 | 0.872598 | 0.304820 | 0.082* | 0.411 (16) |
H16F | −0.228044 | 0.744424 | 0.343292 | 0.082* | 0.411 (16) |
C17 | 0.4581 (3) | 0.9933 (5) | 0.3329 (2) | 0.0223 (8) | |
C18 | 0.5120 (3) | 0.9167 (6) | 0.3926 (2) | 0.0260 (9) | |
H18A | 0.493651 | 0.885965 | 0.433676 | 0.031* | |
C19 | 0.5973 (3) | 0.8941 (6) | 0.3805 (2) | 0.0296 (10) | |
H19A | 0.645737 | 0.845755 | 0.411777 | 0.035* | |
C20 | 0.5972 (3) | 0.9570 (6) | 0.3133 (2) | 0.0285 (10) | |
H20A | 0.645796 | 0.957145 | 0.291622 | 0.034* | |
C21 | 0.5132 (3) | 1.0190 (6) | 0.2841 (2) | 0.0278 (9) | |
H21A | 0.495721 | 1.069417 | 0.239598 | 0.033* | |
C22 | 0.6534 (9) | 1.379 (2) | 0.3699 (7) | 0.032 (3) | 0.589 (16) |
H22A | 0.703759 | 1.368664 | 0.350567 | 0.038* | 0.589 (16) |
C23 | 0.5716 (9) | 1.446 (2) | 0.3365 (6) | 0.032 (3) | 0.589 (16) |
H23A | 0.557045 | 1.488513 | 0.290781 | 0.038* | 0.589 (16) |
C24 | 0.5144 (8) | 1.439 (2) | 0.3840 (7) | 0.030 (3) | 0.589 (16) |
H24A | 0.455170 | 1.476006 | 0.375409 | 0.036* | 0.589 (16) |
C25 | 0.5618 (10) | 1.366 (3) | 0.4457 (7) | 0.033 (3) | 0.589 (16) |
H25A | 0.540087 | 1.346345 | 0.486172 | 0.039* | 0.589 (16) |
C26 | 0.6475 (9) | 1.329 (3) | 0.4369 (7) | 0.030 (3) | 0.589 (16) |
H26A | 0.693122 | 1.278396 | 0.470414 | 0.036* | 0.589 (16) |
C22A | 0.6328 (12) | 1.405 (3) | 0.3552 (10) | 0.032 (4) | 0.411 (16) |
H22B | 0.670190 | 1.410304 | 0.323393 | 0.038* | 0.411 (16) |
C23A | 0.5445 (12) | 1.458 (3) | 0.3431 (9) | 0.028 (4) | 0.411 (16) |
H23B | 0.512555 | 1.507323 | 0.301608 | 0.034* | 0.411 (16) |
C24A | 0.5115 (12) | 1.425 (3) | 0.4027 (10) | 0.028 (4) | 0.411 (16) |
H24B | 0.453618 | 1.446702 | 0.408183 | 0.034* | 0.411 (16) |
C25A | 0.5806 (15) | 1.354 (4) | 0.4528 (10) | 0.030 (4) | 0.411 (16) |
H25B | 0.577286 | 1.320987 | 0.498091 | 0.036* | 0.411 (16) |
C26A | 0.6554 (13) | 1.342 (4) | 0.4233 (11) | 0.034 (5) | 0.411 (16) |
H26B | 0.711089 | 1.299459 | 0.445504 | 0.041* | 0.411 (16) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Fe1 | 0.0254 (3) | 0.0215 (3) | 0.0259 (3) | −0.0029 (3) | 0.0025 (2) | −0.0012 (3) |
O1 | 0.0284 (16) | 0.0264 (16) | 0.0220 (14) | 0.0004 (13) | 0.0004 (12) | 0.0042 (12) |
O2 | 0.0298 (16) | 0.0207 (15) | 0.0187 (14) | 0.0008 (12) | 0.0021 (12) | 0.0002 (12) |
N1 | 0.0201 (17) | 0.0241 (18) | 0.0181 (16) | −0.0013 (14) | 0.0024 (13) | 0.0002 (14) |
C1 | 0.022 (2) | 0.022 (2) | 0.0202 (19) | −0.0008 (16) | 0.0061 (16) | 0.0003 (17) |
C2 | 0.027 (2) | 0.0162 (19) | 0.023 (2) | −0.0048 (16) | 0.0068 (17) | −0.0007 (16) |
C3 | 0.029 (2) | 0.018 (2) | 0.0205 (19) | −0.0003 (17) | 0.0079 (17) | 0.0041 (16) |
C4 | 0.027 (2) | 0.0181 (19) | 0.023 (2) | −0.0002 (16) | 0.0066 (17) | 0.0001 (17) |
C5 | 0.028 (2) | 0.026 (2) | 0.021 (2) | −0.0026 (18) | 0.0048 (17) | −0.0021 (17) |
C6 | 0.043 (3) | 0.028 (2) | 0.037 (3) | −0.004 (2) | 0.010 (2) | −0.008 (2) |
C7 | 0.024 (3) | 0.034 (4) | 0.020 (3) | −0.003 (3) | 0.006 (3) | −0.007 (3) |
C8 | 0.023 (4) | 0.042 (5) | 0.024 (3) | 0.001 (3) | 0.002 (3) | −0.006 (4) |
C9 | 0.027 (3) | 0.048 (5) | 0.033 (3) | 0.002 (3) | 0.006 (3) | −0.008 (4) |
C10 | 0.028 (3) | 0.055 (5) | 0.031 (3) | −0.004 (3) | 0.011 (3) | −0.010 (4) |
C11 | 0.033 (3) | 0.049 (5) | 0.026 (3) | −0.006 (3) | 0.013 (3) | 0.001 (4) |
C12 | 0.032 (3) | 0.039 (3) | 0.027 (4) | −0.004 (3) | 0.008 (3) | −0.003 (3) |
C13 | 0.032 (3) | 0.068 (5) | 0.043 (3) | −0.010 (3) | 0.017 (3) | −0.014 (4) |
C14 | 0.058 (6) | 0.094 (8) | 0.057 (5) | −0.012 (6) | 0.032 (5) | 0.002 (5) |
C15 | 0.033 (5) | 0.075 (6) | 0.078 (7) | −0.011 (4) | 0.026 (6) | −0.019 (6) |
C16 | 0.040 (7) | 0.083 (8) | 0.060 (6) | −0.024 (6) | 0.021 (5) | −0.023 (6) |
C7A | 0.025 (4) | 0.037 (4) | 0.020 (4) | −0.003 (3) | 0.005 (3) | −0.007 (4) |
C8A | 0.027 (4) | 0.042 (5) | 0.025 (4) | 0.000 (4) | 0.004 (4) | −0.006 (4) |
C9A | 0.026 (4) | 0.048 (6) | 0.031 (4) | 0.001 (4) | 0.004 (3) | −0.009 (4) |
C10A | 0.029 (3) | 0.053 (5) | 0.030 (3) | −0.006 (3) | 0.011 (3) | −0.008 (4) |
C11A | 0.031 (4) | 0.046 (5) | 0.028 (4) | −0.006 (4) | 0.011 (4) | −0.005 (4) |
C12A | 0.029 (4) | 0.041 (4) | 0.022 (4) | −0.005 (4) | 0.008 (4) | −0.003 (3) |
C13A | 0.032 (4) | 0.070 (5) | 0.044 (4) | −0.010 (4) | 0.017 (3) | −0.009 (4) |
C14A | 0.043 (7) | 0.089 (9) | 0.066 (8) | −0.019 (7) | 0.023 (6) | 0.010 (7) |
C15A | 0.040 (7) | 0.083 (8) | 0.063 (8) | −0.014 (6) | 0.026 (6) | −0.027 (7) |
C16A | 0.040 (7) | 0.069 (9) | 0.054 (7) | −0.006 (7) | 0.010 (6) | −0.019 (7) |
C17 | 0.025 (2) | 0.0170 (19) | 0.024 (2) | −0.0027 (16) | 0.0038 (17) | −0.0063 (17) |
C18 | 0.028 (2) | 0.022 (2) | 0.029 (2) | −0.0047 (18) | 0.0077 (18) | −0.0020 (18) |
C19 | 0.031 (2) | 0.020 (2) | 0.036 (2) | −0.0020 (18) | 0.003 (2) | −0.0037 (19) |
C20 | 0.025 (2) | 0.031 (2) | 0.030 (2) | −0.0003 (18) | 0.0077 (18) | −0.008 (2) |
C21 | 0.030 (2) | 0.029 (2) | 0.023 (2) | −0.0045 (19) | 0.0033 (18) | −0.0045 (19) |
C22 | 0.030 (5) | 0.030 (6) | 0.033 (6) | −0.006 (4) | 0.000 (4) | −0.001 (4) |
C23 | 0.040 (7) | 0.021 (5) | 0.032 (4) | −0.008 (5) | 0.001 (4) | 0.002 (4) |
C24 | 0.032 (5) | 0.022 (6) | 0.032 (6) | −0.005 (4) | −0.002 (4) | −0.002 (5) |
C25 | 0.031 (6) | 0.033 (7) | 0.033 (5) | −0.006 (5) | 0.001 (4) | −0.010 (5) |
C26 | 0.033 (5) | 0.023 (5) | 0.031 (5) | −0.008 (4) | −0.004 (4) | 0.002 (5) |
C22A | 0.027 (8) | 0.032 (8) | 0.037 (8) | −0.012 (6) | 0.004 (6) | −0.004 (6) |
C23A | 0.033 (8) | 0.014 (6) | 0.038 (7) | −0.004 (6) | 0.005 (5) | 0.007 (5) |
C24A | 0.033 (6) | 0.016 (7) | 0.035 (8) | −0.007 (5) | 0.005 (6) | 0.006 (6) |
C25A | 0.038 (9) | 0.022 (7) | 0.027 (6) | 0.004 (7) | −0.003 (5) | 0.000 (6) |
C26A | 0.030 (6) | 0.035 (10) | 0.034 (8) | −0.004 (6) | −0.002 (5) | −0.013 (7) |
Fe1—C22A | 2.03 (2) | C16—H16C | 0.9800 |
Fe1—C23 | 2.030 (14) | C7A—C8A | 1.392 (12) |
Fe1—C21 | 2.031 (4) | C7A—C12A | 1.395 (12) |
Fe1—C24 | 2.034 (14) | C8A—C9A | 1.388 (12) |
Fe1—C20 | 2.039 (4) | C8A—H8B | 0.9500 |
Fe1—C22 | 2.047 (15) | C9A—C10A | 1.396 (12) |
Fe1—C25 | 2.05 (2) | C9A—H9B | 0.9500 |
Fe1—C26A | 2.05 (3) | C10A—C11A | 1.387 (11) |
Fe1—C26 | 2.050 (19) | C10A—C13A | 1.539 (12) |
Fe1—C19 | 2.052 (4) | C11A—C12A | 1.399 (12) |
Fe1—C18 | 2.053 (4) | C11A—H11B | 0.9500 |
Fe1—C23A | 2.056 (19) | C12A—H12B | 0.9500 |
O1—C4 | 1.236 (5) | C13A—C14A | 1.525 (12) |
O2—C1 | 1.411 (5) | C13A—C15A | 1.536 (13) |
O2—H1O2 | 0.80 (4) | C13A—C16A | 1.541 (13) |
N1—C4 | 1.366 (5) | C14A—H14D | 0.9800 |
N1—C7 | 1.422 (9) | C14A—H14E | 0.9800 |
N1—C7A | 1.433 (12) | C14A—H14F | 0.9800 |
N1—C1 | 1.485 (5) | C15A—H15D | 0.9800 |
C1—C5 | 1.523 (5) | C15A—H15E | 0.9800 |
C1—C2 | 1.537 (5) | C15A—H15F | 0.9800 |
C2—C3 | 1.336 (5) | C16A—H16D | 0.9800 |
C2—C17 | 1.447 (5) | C16A—H16E | 0.9800 |
C3—C4 | 1.455 (6) | C16A—H16F | 0.9800 |
C3—H3A | 0.9500 | C17—C18 | 1.431 (6) |
C5—C6 | 1.525 (6) | C17—C21 | 1.441 (6) |
C5—H5A | 0.9900 | C18—C19 | 1.417 (6) |
C5—H5B | 0.9900 | C18—H18A | 0.9500 |
C6—H6A | 0.9800 | C19—C20 | 1.420 (6) |
C6—H6B | 0.9800 | C19—H19A | 0.9500 |
C6—H6C | 0.9800 | C20—C21 | 1.405 (6) |
C7—C12 | 1.389 (10) | C20—H20A | 0.9500 |
C7—C8 | 1.390 (10) | C21—H21A | 0.9500 |
C8—C9 | 1.385 (10) | C22—C26 | 1.411 (10) |
C8—H8A | 0.9500 | C22—C23 | 1.411 (10) |
C9—C10 | 1.393 (10) | C22—H22A | 0.9500 |
C9—H9A | 0.9500 | C23—C24 | 1.433 (10) |
C10—C11 | 1.384 (9) | C23—H23A | 0.9500 |
C10—C13 | 1.539 (10) | C24—C25 | 1.411 (10) |
C11—C12 | 1.397 (10) | C24—H24A | 0.9500 |
C11—H11A | 0.9500 | C25—C26 | 1.418 (10) |
C12—H12A | 0.9500 | C25—H25A | 0.9500 |
C13—C15 | 1.525 (10) | C26—H26A | 0.9500 |
C13—C14 | 1.530 (11) | C22A—C23A | 1.411 (12) |
C13—C16 | 1.544 (11) | C22A—C26A | 1.414 (12) |
C14—H14A | 0.9800 | C22A—H22B | 0.9500 |
C14—H14B | 0.9800 | C23A—C24A | 1.413 (12) |
C14—H14C | 0.9800 | C23A—H23B | 0.9500 |
C15—H15A | 0.9800 | C24A—C25A | 1.419 (12) |
C15—H15B | 0.9800 | C24A—H24B | 0.9500 |
C15—H15C | 0.9800 | C25A—C26A | 1.419 (12) |
C16—H16A | 0.9800 | C25A—H25B | 0.9500 |
C16—H16B | 0.9800 | C26A—H26B | 0.9500 |
C22A—Fe1—C21 | 116.1 (6) | C9A—C8A—C7A | 121.3 (13) |
C23—Fe1—C21 | 106.2 (4) | C9A—C8A—H8B | 119.4 |
C23—Fe1—C24 | 41.3 (4) | C7A—C8A—H8B | 119.4 |
C21—Fe1—C24 | 122.3 (4) | C8A—C9A—C10A | 121.2 (12) |
C22A—Fe1—C20 | 107.2 (5) | C8A—C9A—H9B | 119.4 |
C23—Fe1—C20 | 118.4 (4) | C10A—C9A—H9B | 119.4 |
C21—Fe1—C20 | 40.40 (17) | C11A—C10A—C9A | 117.1 (11) |
C24—Fe1—C20 | 155.8 (4) | C11A—C10A—C13A | 124.7 (11) |
C23—Fe1—C22 | 40.5 (3) | C9A—C10A—C13A | 117.8 (11) |
C21—Fe1—C22 | 121.9 (4) | C10A—C11A—C12A | 122.3 (13) |
C24—Fe1—C22 | 68.5 (4) | C10A—C11A—H11B | 118.8 |
C20—Fe1—C22 | 104.5 (4) | C12A—C11A—H11B | 118.8 |
C23—Fe1—C25 | 68.6 (5) | C7A—C12A—C11A | 119.6 (13) |
C21—Fe1—C25 | 159.0 (4) | C7A—C12A—H12B | 120.2 |
C24—Fe1—C25 | 40.4 (4) | C11A—C12A—H12B | 120.2 |
C20—Fe1—C25 | 160.3 (4) | C14A—C13A—C15A | 106.5 (12) |
C22—Fe1—C25 | 68.1 (5) | C14A—C13A—C10A | 112.4 (11) |
C22A—Fe1—C26A | 40.6 (5) | C15A—C13A—C10A | 109.7 (11) |
C21—Fe1—C26A | 149.9 (6) | C14A—C13A—C16A | 111.2 (13) |
C20—Fe1—C26A | 117.7 (7) | C15A—C13A—C16A | 108.1 (13) |
C23—Fe1—C26 | 68.1 (5) | C10A—C13A—C16A | 108.9 (14) |
C21—Fe1—C26 | 158.2 (4) | C13A—C14A—H14D | 109.5 |
C24—Fe1—C26 | 68.2 (5) | C13A—C14A—H14E | 109.5 |
C20—Fe1—C26 | 122.2 (5) | H14D—C14A—H14E | 109.5 |
C22—Fe1—C26 | 40.3 (3) | C13A—C14A—H14F | 109.5 |
C25—Fe1—C26 | 40.5 (4) | H14D—C14A—H14F | 109.5 |
C22A—Fe1—C19 | 128.6 (6) | H14E—C14A—H14F | 109.5 |
C23—Fe1—C19 | 153.5 (4) | C13A—C15A—H15D | 109.5 |
C21—Fe1—C19 | 68.37 (18) | C13A—C15A—H15E | 109.5 |
C24—Fe1—C19 | 163.2 (4) | H15D—C15A—H15E | 109.5 |
C20—Fe1—C19 | 40.62 (17) | C13A—C15A—H15F | 109.5 |
C22—Fe1—C19 | 118.8 (4) | H15D—C15A—H15F | 109.5 |
C25—Fe1—C19 | 125.5 (5) | H15E—C15A—H15F | 109.5 |
C26A—Fe1—C19 | 109.0 (7) | C13A—C16A—H16D | 109.5 |
C26—Fe1—C19 | 106.8 (5) | C13A—C16A—H16E | 109.5 |
C22A—Fe1—C18 | 167.5 (6) | H16D—C16A—H16E | 109.5 |
C23—Fe1—C18 | 163.8 (4) | C13A—C16A—H16F | 109.5 |
C21—Fe1—C18 | 68.44 (17) | H16D—C16A—H16F | 109.5 |
C24—Fe1—C18 | 127.6 (4) | H16E—C16A—H16F | 109.5 |
C20—Fe1—C18 | 68.05 (18) | C18—C17—C21 | 106.2 (4) |
C22—Fe1—C18 | 155.4 (4) | C18—C17—C2 | 128.5 (4) |
C25—Fe1—C18 | 110.7 (5) | C21—C17—C2 | 125.0 (4) |
C26A—Fe1—C18 | 130.2 (6) | C18—C17—Fe1 | 69.3 (2) |
C26—Fe1—C18 | 122.5 (4) | C21—C17—Fe1 | 68.2 (2) |
C19—Fe1—C18 | 40.39 (17) | C2—C17—Fe1 | 132.0 (3) |
C22A—Fe1—C23A | 40.4 (4) | C19—C18—C17 | 109.0 (4) |
C21—Fe1—C23A | 107.7 (5) | C19—C18—Fe1 | 69.8 (2) |
C20—Fe1—C23A | 128.3 (6) | C17—C18—Fe1 | 70.0 (2) |
C26A—Fe1—C23A | 67.5 (7) | C19—C18—H18A | 125.5 |
C19—Fe1—C23A | 166.7 (6) | C17—C18—H18A | 125.5 |
C18—Fe1—C23A | 151.5 (5) | Fe1—C18—H18A | 126.3 |
C1—O2—H1O2 | 113 (3) | C18—C19—C20 | 107.6 (4) |
C4—N1—C7 | 123.5 (10) | C18—C19—Fe1 | 69.8 (2) |
C4—N1—C7A | 123.6 (14) | C20—C19—Fe1 | 69.2 (2) |
C4—N1—C1 | 111.6 (3) | C18—C19—H19A | 126.2 |
C7—N1—C1 | 124.8 (10) | C20—C19—H19A | 126.2 |
C7A—N1—C1 | 124.7 (14) | Fe1—C19—H19A | 126.4 |
O2—C1—N1 | 112.2 (3) | C21—C20—C19 | 108.6 (4) |
O2—C1—C5 | 107.0 (3) | C21—C20—Fe1 | 69.5 (2) |
N1—C1—C5 | 110.5 (3) | C19—C20—Fe1 | 70.2 (2) |
O2—C1—C2 | 111.1 (3) | C21—C20—H20A | 125.7 |
N1—C1—C2 | 101.1 (3) | C19—C20—H20A | 125.7 |
C5—C1—C2 | 115.0 (3) | Fe1—C20—H20A | 126.2 |
C3—C2—C17 | 127.6 (4) | C20—C21—C17 | 108.6 (4) |
C3—C2—C1 | 109.3 (4) | C20—C21—Fe1 | 70.1 (2) |
C17—C2—C1 | 122.6 (3) | C17—C21—Fe1 | 70.6 (2) |
C2—C3—C4 | 110.7 (4) | C20—C21—H21A | 125.7 |
C2—C3—H3A | 124.6 | C17—C21—H21A | 125.7 |
C4—C3—H3A | 124.6 | Fe1—C21—H21A | 125.2 |
O1—C4—N1 | 125.2 (4) | C26—C22—C23 | 108.2 (9) |
O1—C4—C3 | 127.5 (4) | C26—C22—Fe1 | 70.0 (9) |
N1—C4—C3 | 107.3 (3) | C23—C22—Fe1 | 69.1 (7) |
C1—C5—C6 | 114.2 (3) | C26—C22—H22A | 125.9 |
C1—C5—H5A | 108.7 | C23—C22—H22A | 125.9 |
C6—C5—H5A | 108.7 | Fe1—C22—H22A | 126.6 |
C1—C5—H5B | 108.7 | C22—C23—C24 | 107.7 (8) |
C6—C5—H5B | 108.7 | C22—C23—Fe1 | 70.4 (7) |
H5A—C5—H5B | 107.6 | C24—C23—Fe1 | 69.5 (6) |
C5—C6—H6A | 109.5 | C22—C23—H23A | 126.1 |
C5—C6—H6B | 109.5 | C24—C23—H23A | 126.1 |
H6A—C6—H6B | 109.5 | Fe1—C23—H23A | 125.6 |
C5—C6—H6C | 109.5 | C25—C24—C23 | 107.7 (9) |
H6A—C6—H6C | 109.5 | C25—C24—Fe1 | 70.3 (10) |
H6B—C6—H6C | 109.5 | C23—C24—Fe1 | 69.2 (7) |
C12—C7—C8 | 119.6 (9) | C25—C24—H24A | 126.1 |
C12—C7—N1 | 122.5 (14) | C23—C24—H24A | 126.1 |
C8—C7—N1 | 117.9 (14) | Fe1—C24—H24A | 125.9 |
C9—C8—C7 | 119.3 (9) | C24—C25—C26 | 108.1 (9) |
C9—C8—H8A | 120.3 | C24—C25—Fe1 | 69.3 (9) |
C7—C8—H8A | 120.3 | C26—C25—Fe1 | 69.9 (10) |
C8—C9—C10 | 122.3 (9) | C24—C25—H25A | 126.0 |
C8—C9—H9A | 118.9 | C26—C25—H25A | 126.0 |
C10—C9—H9A | 118.9 | Fe1—C25—H25A | 126.5 |
C11—C10—C9 | 117.4 (8) | C22—C26—C25 | 108.3 (9) |
C11—C10—C13 | 119.7 (9) | C22—C26—Fe1 | 69.7 (9) |
C9—C10—C13 | 122.9 (8) | C25—C26—Fe1 | 69.6 (10) |
C10—C11—C12 | 121.4 (10) | C22—C26—H26A | 125.9 |
C10—C11—H11A | 119.3 | C25—C26—H26A | 125.9 |
C12—C11—H11A | 119.3 | Fe1—C26—H26A | 126.3 |
C7—C12—C11 | 119.9 (10) | C23A—C22A—C26A | 107.6 (11) |
C7—C12—H12A | 120.1 | C23A—C22A—Fe1 | 70.9 (10) |
C11—C12—H12A | 120.1 | C26A—C22A—Fe1 | 70.5 (14) |
C15—C13—C14 | 108.8 (9) | C23A—C22A—H22B | 126.2 |
C15—C13—C10 | 110.7 (8) | C26A—C22A—H22B | 126.2 |
C14—C13—C10 | 111.4 (8) | Fe1—C22A—H22B | 124.1 |
C15—C13—C16 | 109.3 (10) | C22A—C23A—C24A | 108.8 (11) |
C14—C13—C16 | 109.1 (10) | C22A—C23A—Fe1 | 68.7 (10) |
C10—C13—C16 | 107.4 (9) | C24A—C23A—Fe1 | 71.2 (10) |
C13—C14—H14A | 109.5 | C22A—C23A—H23B | 125.6 |
C13—C14—H14B | 109.5 | C24A—C23A—H23B | 125.6 |
H14A—C14—H14B | 109.5 | Fe1—C23A—H23B | 126.1 |
C13—C14—H14C | 109.5 | C23A—C24A—C25A | 107.5 (11) |
H14A—C14—H14C | 109.5 | C23A—C24A—Fe1 | 68.9 (10) |
H14B—C14—H14C | 109.5 | C25A—C24A—Fe1 | 70.0 (14) |
C13—C15—H15A | 109.5 | C23A—C24A—H24B | 126.3 |
C13—C15—H15B | 109.5 | C25A—C24A—H24B | 126.3 |
H15A—C15—H15B | 109.5 | Fe1—C24A—H24B | 126.4 |
C13—C15—H15C | 109.5 | C24A—C25A—C26A | 107.9 (11) |
H15A—C15—H15C | 109.5 | C24A—C25A—Fe1 | 70.2 (13) |
H15B—C15—H15C | 109.5 | C26A—C25A—Fe1 | 68.6 (15) |
C13—C16—H16A | 109.5 | C24A—C25A—H25B | 126.0 |
C13—C16—H16B | 109.5 | C26A—C25A—H25B | 126.0 |
H16A—C16—H16B | 109.5 | Fe1—C25A—H25B | 126.7 |
C13—C16—H16C | 109.5 | C22A—C26A—C25A | 108.1 (11) |
H16A—C16—H16C | 109.5 | C22A—C26A—Fe1 | 68.9 (13) |
H16B—C16—H16C | 109.5 | C25A—C26A—Fe1 | 71.2 (15) |
C8A—C7A—C12A | 118.2 (12) | C22A—C26A—H26B | 125.9 |
C8A—C7A—N1 | 123 (2) | C25A—C26A—H26B | 125.9 |
C12A—C7A—N1 | 119 (2) | Fe1—C26A—H26B | 125.5 |
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H1O2···O1i | 0.80 (4) | 1.91 (5) | 2.699 (4) | 166 (5) |
Symmetry code: (i) −x+1/2, y−1/2, −z+1/2. |
Funding information
TB gratefully acknowledges a PhD grant from the Deutsche Bundesstiftung Umwelt. The publication was funded by the Open Access Fund of Universität Koblenz.
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