research communications
Crystal structures of [(N,N-dimethylamino)methyl]ferrocene and (Rp,Rp)-bis{2-[(dimethylamino)methyl]ferrocenyl}dimethylsilane
aTechnische Universität Dortmund, Fakultät Chemie und Chemische Biologie, Otto-Hahn-Strasse 6, 44227 Dortmund, Germany
*Correspondence e-mail: carsten.strohmann@tu-dortmund.de
The title compound [(N,N-dimethylamino)methyl]ferrocene, [Fe(C5H5)(C8H12N)], (1), is an interesting starting material for the synthesis of planar chiral 1,2-disubstituted ferrocenes, as demonstrated by the preparation of (Rp,Rp)-bis{2-[(dimethylamino)methyl]ferrocenyl}dimethylsilane, [Fe2(C5H5)2(C18H18N2Si)], (2), from the lithiated derivative of 1. The configuration of the lithium compound is unchanged after the and the is preserved in P212121. In both compounds, the Cp rings adopt eclipsed conformations. Hirshfeld surface analysis was used to investigate the intermolecular interactions, and showed that H⋯H (van der Waals) interactions dominate in both structures with contact percentages of 83.9 and 88.4% for 1 and 2, respectively.
1. Chemical context
In 1951, ferrocene was synthesized serendipitously (Kealy & Pauson, 1951) and one year later it was examined by X-ray crystallography (Fischer & Pfab, 1952). N,N-Dimethylaminomethylferrocene (C13H17FeN,1) was first synthesized by Hauser & Lindsay (1956) by the reaction of ferrocene with paraformaldehyde and N,N,N′,N′-tetramethyldiaminomethane. The derivatization of ferrocene to planar chiral ferrocene makes it an important ligand for catalytic asymmetric transformations, both for scientific and industrial applications (Schaarschmidt & Lang, 2013). In particular, 1 is appropriate for the formation of 1,2-disubstituted ferrocenes because of the free electron pair at the nitrogen atom: the lithiation of the ortho-position is preferred due to the DoM effect (Directed ortho Metalation) and can be converted by a further step using an (Marr et al., 1967). The ortho-lithiation can be carried out both racemically or with a high degree of enantiomeric control. The best known example for ortho-lithiation with high stereoselectivity is the (R)-N,N-dimethyl-1-ferrocenylethylamine, or Ugi's amine with a chiral directing group (Marquarding et al., 1970).
Many applications based on 1 have been established by our research group: it is an inexpensive non-chiral analogue of Ugi's amine, therefore the must be implemented by the chiral auxiliary (R,R)-tetramethyl-1,2-cyclohexanediamine (TMCDA) with yields in high stereoselectivity (Steffen et al., 2013). One application of the 1,2-disubstituted ferrocenes based on 1 is the formation of racemic and enantiomerically pure siloxides of zinc, whereby disiloxanes can be synthesized while avoiding condensation reactions (Golz et al., 2017). Another application is the kinetically controlled of silicon-stereogenic methoxy using a planar chiral ferrocene backbone based on 1. Here, silicon-stereogenic methoxy could be prepared with excellent stereoinduction (d.r. > 99:1) and the mechanistic course of the reaction can be described by quantum-chemical calculations (Barth et al., 2019). Nayyar et al. (2018) reported 1,2-disubstituted ferrocenes based on 1 and their use as precursors for the diastereoselective synthesis of divalent-element chlorides and an unprecedented organolithium-induced carbon–carbon single-bond cleavage. Furthermore, Gawron et al. (2019) were able to synthesize N,N-dimethylaminomethylferrocene-backboned unsymmetrical pincer-type proligands, which are interesting as ligands for transition-metal complexes as catalysts for a variety of reactions in organic chemistry. The (R,S)-meso-compound of bis[dimethyl(aminomethyl)ferrocenyl]dimethylsilane was characterized by Roewer and co-workers using X-ray and formed during the synthesis of dimethyldichlorosilane with two equivalents of the racemic lithiated N,N-dimethylaminomethylferrocene (Palitzsch et al., 1999).
In this paper, we report the crystal structures of 1 and (Rp,Rp)-bis[dimethyl(aminomethyl)ferrocenyl]dimethylsilane (2) and analyze their intermolecular interactions using Hirshfeld surfaces and two-dimensional fingerprint plots.
2. Structural commentary
Compound 1 crystallizes from n-pentane at 243 K as orange needles with monoclinic (P21/n) symmetry. There are no noticeable irregularities in the bond lengths or bond angles found: the aminomethyl side chain is oriented above its attached cyclopentadienyl ring, and the Cp rings are eclipsed, the dihedral angle between their mean planes being 1.53 (15)°. The molecular structure of 1 is presented in Fig. 1.
Compound 2 is an orange–red crystalline solid and occurs in form in the orthorhombic P212121. The structure is illustrated in Fig. 2. Using Cahn–Ingold–Prelog (CIP) prioritization, compound 2 can be assigned the (Rp,Rp)-configuration; furthermore the cyclopentadienyl rings are also in an eclipsed conformation for both iron atoms [dihedral angles = 4.89 (17) and 1.34 (18)° for the Fe1 and Fe2 rings, respectively]. The Si—C bonds span the range of 1.869 (3) to 1.874 (3) Å, which is consistent with the literature (Allen et al., 1987). The silicon centre of compound 2 adopts a slightly distorted tetrahedral geometry, as shown by the angles of 105.43 (14)° (C14—Si1—C10) as the smallest and 112.17 (13)° (C14—Si1—C16) as the largest. This flexibility is often observed for Si—C bonds (Otte et al., 2017). Compared to compound 1, the aminomethyl side chains are oriented in the direction of the silicon atom, but the N⋯Si contact distances of 3.552 (3) for N2 and 3.584 (3) Å for N1 are too long to be regarded as coordinate bonds to Si from the N lone pairs.
3. Supramolecular features
The crystal packing of compound 1 is shown in Fig. 3. To further investigate close contacts and intermolecular interactions, a Hirshfeld surface analysis was carried out: Fig. 4 illustrates the Hirshfeld surface mapped over dnorm in the range from −0.072 to 1.201 (arbitrary units) and the related fingerprint plots generated by CrystalExplorer (Turner et al., 2017; McKinnon et al., 2007). On the Hirshfeld surface, weak van der Waals H⋯H contacts appear as by far the largest region (83.9%) and show significant red spots on the Hirshfeld surface. C⋯H/H⋯C contacts contribute to 13.2% of the Hirshfeld area and appear as two spikes and also show a slight colouration, which indicates that the cyclopentadienyl ring interacts with adjacent molecules. The N⋯H/H⋯N interactions occupy the smallest region (2.9%) and display no noticeable interactions.
The crystal packing of compound 2 is illustrated in Fig. 5. The Hirshfeld surfaces and contributions of the different types of intermolecular interactions are shown in Fig. 6 in the two-dimensional fingerprint plot. The Hirshfeld surface of compound 2 mapped over dnorm in the range from −0.149 to 1.497 a.u. shows significant intermolecular interactions, indicated by the red spots. Both the van der Waals H⋯H contacts (88.4%) and the C⋯H/H⋯C contacts (11.6%) contribute to the packing arrangement of the crystal. Intermolecular interactions of the cyclopentadienyl rings with neighbouring molecules can also be visualized.
4. Database survey
There are a large number of compounds based on 1. Selected examples found in the Cambridge Structural Database (CSD, version 5.41, update of May 2020; Groom et al., 2016) include (R,S)-meso-bis[dimethyl(aminomethyl)ferrocenyl]dimethylsilane (CSD refcode KENRUQ; Palitzsch et al., 1999), (R,S)-meso-bis[dimethyl(aminomethyl)ferrocenyl]dichlorosilane (KENQUP; Palitzsch et al., 1999), the monoetherate of the homochiral dimer (Sp)-[2-(dimethylaminomethyl)ferrocenyl]lithium (LISBOG; Steffen et al., 2013), bis[μ-{2-[(dimethylammoniumyl)methyl]ferrocenyl}(dimethyl)silanolato]tetrachlorodizinc(II) (FAWPIF; Golz et al., 2017), [dimethyl(aminomethyl)ferrocenyl]methoxymethylphenylsilane (SOKDAA; Barth et al., 2019), 2-(dimethylaminomethyl)-1-{1-[(2,6-di-isopropylphenyl)amino]-2,2-dimethylpropyl}-3-(trimethylsilyl)ferrocene (RIGDOD; Nayyar et al., 2018) and 1-bromo-2-(diphenylphosphino)-5-[(dimethylamino)methyl]ferrocene (MIZMOA; Gawron et al., 2019).
5. Synthesis and crystallization
N,N-Dimethylaminomethylferrocene was purchased from ABCR and used without further purification. A solution of N,N-dimethylaminomethylferrocene (1.00 mmol) in n-pentane (1 ml) was made up and stored at 243 K and compound 1 crystallized in the form of orange needles.
The reaction scheme for the synthesis of compound 2 is illustrated in Fig. 7. To a solution of (Sp)-[2-(dimethylaminomethyl)ferrocenyl]lithium (4.00 mmol) (Steffen et al., 2013) in diethyl ether, dimethyldichlorosilane (2.00 mmol) was added dropwise at 195 K. The reaction was slowly warmed up to room temperature and stirred overnight. Afterwards the reaction was quenched by the addition of water. The aqueous phase was extracted three times with diethyl ether and the combined organic phases were dried with MgSO4. After the volatile components were removed and purified by (n-pentane:diethyl ether + triethylamine; 100:1 + 5 Vol.-%), the product (46%) could be obtained as yellowish plates.
1H NMR (600.3 MHz, C6D6): δ = 0.81 [s, 6H; Si(CH3)2], 2.02 {s, 12H; [N(CH3)2]2}, 2.80, 3.64 [AB-system, 4H, 2JHH = 12.3 Hz; CpCH2N)2], 4.08 [s, 10H; (Cp—CH2)], 4.12 [m, 2H; (Cp—CH2)], 4.19 [m, 2H; (Cp—CH)2], 4.35 [m, 2H; Cp—CH)2] ppm.
{1H}13C NMR (150.9 MHz, C6D6): δ = 0.6 [2C; Si(CH3)2], 45.4 {4C; [CH2N(CH3)2]2}, 60.5 [2C; (CpCH2N)2], 69.7 [10C; (Cp—CH)2], 69.8 [2C; (Cp—CH)2], 72.6 [2C; (Cp—C)2Si)], 74.2 [2C; (Cp—CH)2], 76.6 [2C; (Cp—CH)2], 90.5 [2C; (Cp—CCH2N)2] ppm.
{1H}29Si NMR (119.3 MHz, C6D6): δ = −7.07 [s, 1Si; Si(CH3)2] ppm.
ESI-(+)-MS: m/z (%): 498 (20) [(M–NMe2)+], 409 (100) [(M–NMe2–CH2NMe2–Me2)+], 299 (50) [(M–FcCH2NMe2)+], 199 (50) [(M–SiMe2FcCH2NMe2–NMe2)+].
Rf: (n-pentane: Et2O + Et3N; 100: 1 + 5 Vol.-%) = 0.20.
6. Refinement
Crystal data, data collection and structure . For both compounds, the H atoms were positioned geometrically (C—H = 0.95–1.00 Å) and refined using a riding model, with Uiso(H) = 1.2Ueq(C) for CH2 and CH hydrogen atoms and Uiso(H) = 1.5Ueq(C) for CH3 hydrogen atoms.
details are summarized in Table 1Supporting information
https://doi.org/10.1107/S2056989020010397/hb7933sup1.cif
contains datablocks 1, 2, global. DOI:Structure factors: contains datablock 1. DOI: https://doi.org/10.1107/S2056989020010397/hb79331sup2.hkl
Structure factors: contains datablock 2. DOI: https://doi.org/10.1107/S2056989020010397/hb79332sup3.hkl
For both structures, data collection: APEX2 (Bruker, 2018); cell
SAINT (Bruker, 2016); data reduction: SAINT (Bruker, 2016). Program(s) used to solve structure: SHELXT (Sheldrick, 2015b) for (1); SHELXS (Sheldrick, 2008) for (2). For both structures, program(s) used to refine structure: SHELXL (Sheldrick, 2015a); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009), publCIF (Westrip, 2010), Mercury (Macrae et al., 2020).[Fe(C5H5)(C8H12N)] | F(000) = 512 |
Mr = 243.12 | Dx = 1.413 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 5.6777 (3) Å | Cell parameters from 9923 reflections |
b = 23.0873 (15) Å | θ = 2.5–33.1° |
c = 8.7206 (6) Å | µ = 1.28 mm−1 |
β = 90.590 (2)° | T = 100 K |
V = 1143.06 (12) Å3 | Needle, clear orange |
Z = 4 | 0.55 × 0.22 × 0.19 mm |
Bruker D8 Venture diffractometer | 3960 independent reflections |
Radiation source: Advanced Light Source, station 11.3.1, Incoatec Iµs | 3489 reflections with I > 2σ(I) |
Silicon 111 monochromator | Rint = 0.040 |
Detector resolution: 10.42 pixels mm-1 | θmax = 32.0°, θmin = 2.5° |
φ and ω scans | h = −8→8 |
Absorption correction: multi-scan (SADABS; Bruker, 2016) | k = −34→33 |
Tmin = 0.351, Tmax = 0.435 | l = −13→13 |
19466 measured reflections |
Refinement on F2 | Primary atom site location: dual |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.047 | H-atom parameters constrained |
wR(F2) = 0.118 | w = 1/[σ2(Fo2) + (0.0175P)2 + 3.606P] where P = (Fo2 + 2Fc2)/3 |
S = 1.17 | (Δ/σ)max = 0.001 |
3960 reflections | Δρmax = 1.34 e Å−3 |
138 parameters | Δρmin = −1.47 e Å−3 |
0 restraints |
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 | ||
Fe1 | 0.86749 (6) | 0.35631 (2) | 0.15193 (4) | 0.01111 (9) | |
N1 | 0.4929 (4) | 0.41321 (9) | 0.5681 (2) | 0.0171 (4) | |
C1 | 1.1153 (4) | 0.29284 (11) | 0.1819 (3) | 0.0161 (4) | |
H1 | 1.242570 | 0.293233 | 0.253451 | 0.019* | |
C2 | 0.8841 (5) | 0.27051 (10) | 0.2089 (3) | 0.0184 (5) | |
H2 | 0.830272 | 0.253686 | 0.301558 | 0.022* | |
C3 | 0.7492 (5) | 0.27812 (11) | 0.0714 (3) | 0.0207 (5) | |
H3 | 0.589384 | 0.267101 | 0.056315 | 0.025* | |
C4 | 0.8951 (5) | 0.30501 (11) | −0.0390 (3) | 0.0187 (5) | |
H4 | 0.849873 | 0.315056 | −0.140783 | 0.022* | |
C5 | 1.1209 (4) | 0.31432 (11) | 0.0292 (3) | 0.0160 (4) | |
H5 | 1.252361 | 0.331809 | −0.018966 | 0.019* | |
C6 | 0.9505 (5) | 0.44290 (10) | 0.1543 (3) | 0.0162 (4) | |
H6 | 1.081500 | 0.460538 | 0.106051 | 0.019* | |
C7 | 0.7223 (5) | 0.43439 (11) | 0.0875 (3) | 0.0168 (4) | |
H7 | 0.674308 | 0.445562 | −0.012877 | 0.020* | |
C8 | 0.5801 (4) | 0.40629 (10) | 0.1978 (3) | 0.0151 (4) | |
H8 | 0.420223 | 0.395284 | 0.183084 | 0.018* | |
C9 | 0.7161 (4) | 0.39721 (10) | 0.3345 (3) | 0.0138 (4) | |
C10 | 0.9467 (4) | 0.42004 (10) | 0.3076 (3) | 0.0153 (4) | |
H10 | 1.074704 | 0.420067 | 0.378663 | 0.018* | |
C11 | 0.6260 (5) | 0.37075 (10) | 0.4794 (3) | 0.0156 (4) | |
H11A | 0.523300 | 0.337387 | 0.453899 | 0.019* | |
H11B | 0.760267 | 0.356324 | 0.541817 | 0.019* | |
C12 | 0.6491 (5) | 0.45778 (11) | 0.6315 (3) | 0.0218 (5) | |
H12A | 0.558986 | 0.483504 | 0.698386 | 0.033* | |
H12B | 0.716922 | 0.480354 | 0.547672 | 0.033* | |
H12C | 0.775825 | 0.439342 | 0.690955 | 0.033* | |
C13 | 0.3659 (5) | 0.38483 (12) | 0.6917 (3) | 0.0221 (5) | |
H13A | 0.258109 | 0.355844 | 0.648437 | 0.033* | |
H13B | 0.275809 | 0.413759 | 0.748726 | 0.033* | |
H13C | 0.478642 | 0.365806 | 0.761125 | 0.033* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Fe1 | 0.01275 (15) | 0.00967 (14) | 0.01093 (14) | 0.00032 (12) | 0.00076 (10) | −0.00089 (11) |
N1 | 0.0225 (10) | 0.0131 (9) | 0.0157 (9) | 0.0018 (8) | 0.0041 (8) | −0.0007 (7) |
C1 | 0.0169 (10) | 0.0137 (10) | 0.0176 (11) | 0.0032 (8) | −0.0003 (8) | −0.0004 (8) |
C2 | 0.0235 (12) | 0.0109 (10) | 0.0209 (11) | −0.0015 (9) | 0.0048 (9) | 0.0013 (8) |
C3 | 0.0164 (11) | 0.0162 (11) | 0.0297 (14) | 0.0000 (9) | 0.0004 (10) | −0.0078 (10) |
C4 | 0.0235 (12) | 0.0169 (11) | 0.0157 (11) | 0.0040 (9) | −0.0012 (9) | −0.0065 (8) |
C5 | 0.0175 (10) | 0.0150 (10) | 0.0154 (10) | 0.0024 (8) | 0.0043 (8) | −0.0017 (8) |
C6 | 0.0190 (11) | 0.0124 (10) | 0.0172 (11) | −0.0021 (8) | 0.0022 (8) | 0.0006 (8) |
C7 | 0.0210 (11) | 0.0134 (10) | 0.0160 (10) | 0.0026 (8) | 0.0004 (8) | 0.0011 (8) |
C8 | 0.0159 (10) | 0.0126 (10) | 0.0167 (10) | 0.0021 (8) | 0.0003 (8) | −0.0033 (8) |
C9 | 0.0157 (10) | 0.0123 (9) | 0.0135 (10) | 0.0001 (8) | 0.0009 (8) | −0.0019 (8) |
C10 | 0.0162 (10) | 0.0129 (10) | 0.0166 (10) | −0.0027 (8) | 0.0001 (8) | −0.0023 (8) |
C11 | 0.0205 (11) | 0.0117 (9) | 0.0147 (10) | 0.0009 (8) | 0.0033 (8) | −0.0010 (8) |
C12 | 0.0328 (14) | 0.0144 (11) | 0.0181 (11) | −0.0022 (10) | 0.0022 (10) | −0.0037 (9) |
C13 | 0.0260 (13) | 0.0214 (12) | 0.0190 (12) | 0.0025 (10) | 0.0078 (10) | 0.0027 (9) |
Fe1—C1 | 2.046 (2) | C4—C5 | 1.424 (4) |
Fe1—C2 | 2.044 (2) | C5—H5 | 0.9500 |
Fe1—C3 | 2.048 (3) | C6—H6 | 0.9500 |
Fe1—C4 | 2.051 (2) | C6—C7 | 1.429 (4) |
Fe1—C5 | 2.047 (2) | C6—C10 | 1.437 (3) |
Fe1—C6 | 2.054 (2) | C7—H7 | 0.9500 |
Fe1—C7 | 2.058 (2) | C7—C8 | 1.419 (3) |
Fe1—C8 | 2.041 (2) | C8—H8 | 0.9500 |
Fe1—C9 | 2.048 (2) | C8—C9 | 1.429 (3) |
Fe1—C10 | 2.049 (2) | C9—C10 | 1.433 (3) |
N1—C11 | 1.464 (3) | C9—C11 | 1.498 (3) |
N1—C12 | 1.463 (3) | C10—H10 | 0.9500 |
N1—C13 | 1.459 (3) | C11—H11A | 0.9900 |
C1—H1 | 0.9500 | C11—H11B | 0.9900 |
C1—C2 | 1.432 (4) | C12—H12A | 0.9800 |
C1—C5 | 1.422 (3) | C12—H12B | 0.9800 |
C2—H2 | 0.9500 | C12—H12C | 0.9800 |
C2—C3 | 1.427 (4) | C13—H13A | 0.9800 |
C3—H3 | 0.9500 | C13—H13B | 0.9800 |
C3—C4 | 1.419 (4) | C13—H13C | 0.9800 |
C4—H4 | 0.9500 | ||
C1—Fe1—C3 | 68.61 (11) | C4—C3—Fe1 | 69.85 (15) |
C1—Fe1—C4 | 68.41 (10) | C4—C3—C2 | 108.2 (2) |
C1—Fe1—C5 | 40.65 (10) | C4—C3—H3 | 125.9 |
C1—Fe1—C6 | 122.56 (10) | Fe1—C4—H4 | 126.5 |
C1—Fe1—C7 | 159.23 (10) | C3—C4—Fe1 | 69.63 (15) |
C1—Fe1—C9 | 121.64 (10) | C3—C4—H4 | 125.9 |
C1—Fe1—C10 | 106.48 (10) | C3—C4—C5 | 108.2 (2) |
C2—Fe1—C1 | 40.99 (10) | C5—C4—Fe1 | 69.50 (14) |
C2—Fe1—C3 | 40.83 (11) | C5—C4—H4 | 125.9 |
C2—Fe1—C4 | 68.53 (11) | Fe1—C5—H5 | 126.1 |
C2—Fe1—C5 | 68.73 (10) | C1—C5—Fe1 | 69.66 (14) |
C2—Fe1—C6 | 158.54 (11) | C1—C5—C4 | 108.0 (2) |
C2—Fe1—C7 | 158.83 (11) | C1—C5—H5 | 126.0 |
C2—Fe1—C9 | 106.06 (10) | C4—C5—Fe1 | 69.81 (14) |
C2—Fe1—C10 | 121.71 (10) | C4—C5—H5 | 126.0 |
C3—Fe1—C4 | 40.52 (11) | Fe1—C6—H6 | 126.4 |
C3—Fe1—C6 | 159.37 (11) | C7—C6—Fe1 | 69.81 (14) |
C3—Fe1—C7 | 123.33 (11) | C7—C6—H6 | 126.1 |
C3—Fe1—C10 | 158.34 (11) | C7—C6—C10 | 107.8 (2) |
C4—Fe1—C6 | 123.44 (11) | C10—C6—Fe1 | 69.30 (13) |
C4—Fe1—C7 | 108.54 (10) | C10—C6—H6 | 126.1 |
C5—Fe1—C3 | 68.47 (10) | Fe1—C7—H7 | 126.8 |
C5—Fe1—C4 | 40.69 (10) | C6—C7—Fe1 | 69.52 (14) |
C5—Fe1—C6 | 107.69 (10) | C6—C7—H7 | 126.1 |
C5—Fe1—C7 | 123.64 (10) | C8—C7—Fe1 | 69.13 (14) |
C5—Fe1—C9 | 158.15 (10) | C8—C7—C6 | 107.9 (2) |
C5—Fe1—C10 | 122.41 (10) | C8—C7—H7 | 126.1 |
C6—Fe1—C7 | 40.67 (10) | Fe1—C8—H8 | 125.9 |
C8—Fe1—C1 | 158.39 (10) | C7—C8—Fe1 | 70.38 (14) |
C8—Fe1—C2 | 122.35 (10) | C7—C8—H8 | 125.5 |
C8—Fe1—C3 | 107.78 (10) | C7—C8—C9 | 109.0 (2) |
C8—Fe1—C4 | 123.60 (10) | C9—C8—Fe1 | 69.78 (14) |
C8—Fe1—C5 | 159.71 (10) | C9—C8—H8 | 125.5 |
C8—Fe1—C6 | 68.39 (10) | C8—C9—Fe1 | 69.30 (13) |
C8—Fe1—C7 | 40.50 (10) | C8—C9—C10 | 107.2 (2) |
C8—Fe1—C9 | 40.91 (9) | C8—C9—C11 | 125.3 (2) |
C8—Fe1—C10 | 68.58 (10) | C10—C9—Fe1 | 69.57 (13) |
C9—Fe1—C3 | 122.30 (10) | C10—C9—C11 | 127.5 (2) |
C9—Fe1—C4 | 159.03 (10) | C11—C9—Fe1 | 128.12 (17) |
C9—Fe1—C6 | 68.98 (10) | Fe1—C10—H10 | 126.4 |
C9—Fe1—C7 | 68.78 (10) | C6—C10—Fe1 | 69.69 (14) |
C9—Fe1—C10 | 40.95 (9) | C6—C10—H10 | 126.0 |
C10—Fe1—C4 | 159.18 (11) | C9—C10—Fe1 | 69.48 (13) |
C10—Fe1—C6 | 41.01 (10) | C9—C10—C6 | 108.0 (2) |
C10—Fe1—C7 | 68.67 (10) | C9—C10—H10 | 126.0 |
C12—N1—C11 | 110.9 (2) | N1—C11—C9 | 110.8 (2) |
C13—N1—C11 | 110.6 (2) | N1—C11—H11A | 109.5 |
C13—N1—C12 | 109.8 (2) | N1—C11—H11B | 109.5 |
Fe1—C1—H1 | 126.5 | C9—C11—H11A | 109.5 |
C2—C1—Fe1 | 69.42 (14) | C9—C11—H11B | 109.5 |
C2—C1—H1 | 126.0 | H11A—C11—H11B | 108.1 |
C5—C1—Fe1 | 69.69 (14) | N1—C12—H12A | 109.5 |
C5—C1—H1 | 126.0 | N1—C12—H12B | 109.5 |
C5—C1—C2 | 108.0 (2) | N1—C12—H12C | 109.5 |
Fe1—C2—H2 | 126.1 | H12A—C12—H12B | 109.5 |
C1—C2—Fe1 | 69.59 (14) | H12A—C12—H12C | 109.5 |
C1—C2—H2 | 126.2 | H12B—C12—H12C | 109.5 |
C3—C2—Fe1 | 69.73 (15) | N1—C13—H13A | 109.5 |
C3—C2—C1 | 107.6 (2) | N1—C13—H13B | 109.5 |
C3—C2—H2 | 126.2 | N1—C13—H13C | 109.5 |
Fe1—C3—H3 | 126.4 | H13A—C13—H13B | 109.5 |
C2—C3—Fe1 | 69.44 (14) | H13A—C13—H13C | 109.5 |
C2—C3—H3 | 125.9 | H13B—C13—H13C | 109.5 |
Fe1—C1—C2—C3 | 59.61 (17) | C5—C1—C2—Fe1 | −59.20 (17) |
Fe1—C1—C5—C4 | −59.49 (17) | C5—C1—C2—C3 | 0.4 (3) |
Fe1—C2—C3—C4 | 59.32 (18) | C6—C7—C8—Fe1 | −58.93 (17) |
Fe1—C3—C4—C5 | 58.99 (17) | C6—C7—C8—C9 | 0.3 (3) |
Fe1—C4—C5—C1 | 59.40 (17) | C7—C6—C10—Fe1 | 59.39 (17) |
Fe1—C6—C7—C8 | 58.68 (17) | C7—C6—C10—C9 | 0.3 (3) |
Fe1—C6—C10—C9 | −59.09 (16) | C7—C8—C9—Fe1 | −59.63 (17) |
Fe1—C7—C8—C9 | 59.27 (17) | C7—C8—C9—C10 | −0.2 (3) |
Fe1—C8—C9—C10 | 59.47 (16) | C7—C8—C9—C11 | 177.6 (2) |
Fe1—C8—C9—C11 | −122.8 (2) | C8—C9—C10—Fe1 | −59.31 (16) |
Fe1—C9—C10—C6 | 59.22 (17) | C8—C9—C10—C6 | −0.1 (3) |
Fe1—C9—C11—N1 | −169.70 (17) | C8—C9—C11—N1 | −79.4 (3) |
C1—C2—C3—Fe1 | −59.52 (17) | C10—C6—C7—Fe1 | −59.07 (17) |
C1—C2—C3—C4 | −0.2 (3) | C10—C6—C7—C8 | −0.4 (3) |
C2—C1—C5—Fe1 | 59.04 (17) | C10—C9—C11—N1 | 97.9 (3) |
C2—C1—C5—C4 | −0.5 (3) | C11—C9—C10—Fe1 | 123.0 (2) |
C2—C3—C4—Fe1 | −59.06 (18) | C11—C9—C10—C6 | −177.8 (2) |
C2—C3—C4—C5 | −0.1 (3) | C12—N1—C11—C9 | −69.5 (3) |
C3—C4—C5—Fe1 | −59.07 (18) | C13—N1—C11—C9 | 168.4 (2) |
C3—C4—C5—C1 | 0.3 (3) |
[Fe2(C5H5)2(C18H18N2Si)] | Dx = 1.356 Mg m−3 |
Mr = 542.39 | Cu Kα radiation, λ = 1.54178 Å |
Orthorhombic, P212121 | Cell parameters from 9834 reflections |
a = 12.0132 (7) Å | θ = 4.2–78.6° |
b = 14.0683 (8) Å | µ = 9.32 mm−1 |
c = 15.7169 (11) Å | T = 100 K |
V = 2656.2 (3) Å3 | Plate, clear orangish yellow |
Z = 4 | 0.47 × 0.23 × 0.08 mm |
F(000) = 1144 |
Bruker D8 Venture diffractometer | 5733 independent reflections |
Radiation source: microfocus sealed X-ray tube, Incoatec Iµs | 5518 reflections with I > 2σ(I) |
HELIOS mirror optics monochromator | Rint = 0.060 |
Detector resolution: 10.4167 pixels mm-1 | θmax = 79.9°, θmin = 4.2° |
ω and φ scans | h = −13→15 |
Absorption correction: multi-scan (SADABS; Bruker, 2016) | k = −17→17 |
Tmin = 0.326, Tmax = 0.754 | l = −20→17 |
41156 measured reflections |
Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.028 | w = 1/[σ2(Fo2) + (0.0111P)2 + 2.2762P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.065 | (Δ/σ)max = 0.001 |
S = 1.07 | Δρmax = 0.40 e Å−3 |
5733 reflections | Δρmin = −0.27 e Å−3 |
304 parameters | Absolute structure: Flack x determined using 2287 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013) |
0 restraints | Absolute structure parameter: −0.009 (2) |
Primary atom site location: structure-invariant direct methods |
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 | ||
Fe1 | 0.40210 (4) | 0.41292 (3) | 0.52611 (3) | 0.01371 (10) | |
Fe2 | 0.91114 (4) | 0.56363 (3) | 0.70011 (3) | 0.01381 (10) | |
Si1 | 0.67323 (6) | 0.46262 (5) | 0.60692 (5) | 0.01300 (16) | |
N1 | 0.4872 (2) | 0.5234 (2) | 0.77668 (18) | 0.0250 (6) | |
N2 | 0.7054 (2) | 0.67859 (19) | 0.49626 (19) | 0.0226 (6) | |
C1 | 0.4524 (3) | 0.2732 (2) | 0.5230 (2) | 0.0206 (6) | |
H1 | 0.522465 | 0.249185 | 0.541009 | 0.025* | |
C2 | 0.3558 (3) | 0.2845 (2) | 0.5749 (2) | 0.0230 (7) | |
H2 | 0.350364 | 0.269161 | 0.633668 | 0.028* | |
C3 | 0.2693 (3) | 0.3224 (2) | 0.5237 (3) | 0.0261 (7) | |
H3 | 0.195895 | 0.336837 | 0.542013 | 0.031* | |
C4 | 0.3122 (3) | 0.3350 (2) | 0.4401 (2) | 0.0250 (7) | |
H4 | 0.272369 | 0.359429 | 0.392671 | 0.030* | |
C5 | 0.4250 (3) | 0.3045 (2) | 0.4397 (2) | 0.0221 (7) | |
H5 | 0.473605 | 0.305010 | 0.392052 | 0.027* | |
C6 | 0.4964 (2) | 0.5297 (2) | 0.4952 (2) | 0.0160 (6) | |
H6 | 0.545571 | 0.535356 | 0.448062 | 0.019* | |
C7 | 0.3812 (2) | 0.5528 (2) | 0.4941 (2) | 0.0200 (6) | |
H7 | 0.340403 | 0.576119 | 0.446778 | 0.024* | |
C8 | 0.3381 (3) | 0.5346 (2) | 0.5769 (2) | 0.0209 (7) | |
H8 | 0.263383 | 0.544423 | 0.594646 | 0.025* | |
C9 | 0.4271 (2) | 0.4989 (2) | 0.6289 (2) | 0.0171 (6) | |
C10 | 0.5271 (2) | 0.4965 (2) | 0.5782 (2) | 0.0151 (6) | |
C11 | 0.4148 (3) | 0.4689 (2) | 0.7201 (2) | 0.0218 (6) | |
H11A | 0.336404 | 0.477614 | 0.737880 | 0.026* | |
H11B | 0.432944 | 0.400471 | 0.725163 | 0.026* | |
C12 | 0.4651 (4) | 0.6248 (3) | 0.7704 (3) | 0.0358 (9) | |
H12A | 0.476258 | 0.645725 | 0.711601 | 0.054* | |
H12B | 0.515962 | 0.659448 | 0.808016 | 0.054* | |
H12C | 0.388032 | 0.637477 | 0.787533 | 0.054* | |
C13 | 0.4753 (3) | 0.4906 (3) | 0.8634 (2) | 0.0353 (9) | |
H13A | 0.398706 | 0.501402 | 0.882532 | 0.053* | |
H13B | 0.526785 | 0.525684 | 0.900183 | 0.053* | |
H13C | 0.492332 | 0.422561 | 0.866214 | 0.053* | |
C14 | 0.7422 (2) | 0.4315 (2) | 0.50393 (19) | 0.0188 (6) | |
H14A | 0.699785 | 0.381123 | 0.475523 | 0.028* | |
H14B | 0.818102 | 0.409171 | 0.515008 | 0.028* | |
H14C | 0.744808 | 0.487788 | 0.467287 | 0.028* | |
C15 | 0.6761 (3) | 0.3581 (2) | 0.6803 (2) | 0.0204 (6) | |
H15A | 0.637561 | 0.374313 | 0.733311 | 0.031* | |
H15B | 0.753543 | 0.341244 | 0.692906 | 0.031* | |
H15C | 0.638843 | 0.304102 | 0.653203 | 0.031* | |
C16 | 0.7459 (2) | 0.5622 (2) | 0.66320 (19) | 0.0140 (5) | |
C17 | 0.7559 (2) | 0.5680 (2) | 0.7543 (2) | 0.0174 (6) | |
H17 | 0.726354 | 0.523459 | 0.793791 | 0.021* | |
C18 | 0.8173 (3) | 0.6514 (2) | 0.7758 (2) | 0.0196 (6) | |
H18 | 0.835968 | 0.671817 | 0.831577 | 0.023* | |
C19 | 0.8455 (2) | 0.6984 (2) | 0.6992 (2) | 0.0202 (6) | |
H19 | 0.885821 | 0.756244 | 0.694769 | 0.024* | |
C20 | 0.8032 (2) | 0.6442 (2) | 0.6298 (2) | 0.0157 (6) | |
C21 | 0.8143 (2) | 0.6704 (2) | 0.5375 (2) | 0.0186 (6) | |
H21A | 0.854177 | 0.731777 | 0.532712 | 0.022* | |
H21B | 0.858954 | 0.621447 | 0.507897 | 0.022* | |
C22 | 0.6358 (3) | 0.7504 (2) | 0.5361 (3) | 0.0308 (8) | |
H22A | 0.626762 | 0.735500 | 0.596616 | 0.046* | |
H22B | 0.562731 | 0.751317 | 0.508457 | 0.046* | |
H22C | 0.671115 | 0.812870 | 0.530116 | 0.046* | |
C23 | 0.7193 (4) | 0.6974 (3) | 0.4060 (2) | 0.0333 (8) | |
H23A | 0.761764 | 0.756243 | 0.398401 | 0.050* | |
H23B | 0.646017 | 0.704129 | 0.379302 | 0.050* | |
H23C | 0.759445 | 0.644476 | 0.379535 | 0.050* | |
C24 | 0.9906 (3) | 0.4417 (2) | 0.7387 (2) | 0.0257 (7) | |
H24 | 0.959441 | 0.392924 | 0.773004 | 0.031* | |
C25 | 1.0489 (3) | 0.5225 (2) | 0.7685 (2) | 0.0219 (7) | |
H25 | 1.064181 | 0.537180 | 0.826365 | 0.026* | |
C26 | 1.0806 (2) | 0.5777 (2) | 0.6972 (2) | 0.0242 (6) | |
H26 | 1.120399 | 0.635990 | 0.698549 | 0.029* | |
C27 | 1.0418 (3) | 0.5297 (3) | 0.6227 (2) | 0.0297 (8) | |
H27 | 1.051335 | 0.550430 | 0.565617 | 0.036* | |
C28 | 0.9869 (3) | 0.4461 (3) | 0.6491 (2) | 0.0301 (8) | |
H28 | 0.953179 | 0.400581 | 0.612719 | 0.036* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Fe1 | 0.00972 (19) | 0.01196 (19) | 0.0194 (2) | −0.00185 (16) | −0.00041 (18) | −0.00196 (16) |
Fe2 | 0.00825 (19) | 0.0162 (2) | 0.0170 (2) | −0.00009 (16) | 0.00075 (18) | −0.00221 (17) |
Si1 | 0.0106 (3) | 0.0123 (3) | 0.0160 (4) | −0.0005 (3) | 0.0005 (3) | −0.0018 (3) |
N1 | 0.0189 (13) | 0.0324 (15) | 0.0235 (15) | −0.0047 (11) | 0.0036 (11) | −0.0099 (11) |
N2 | 0.0197 (13) | 0.0177 (12) | 0.0303 (16) | −0.0027 (10) | −0.0049 (11) | 0.0044 (11) |
C1 | 0.0188 (14) | 0.0123 (13) | 0.0307 (18) | −0.0016 (11) | −0.0040 (13) | −0.0030 (13) |
C2 | 0.0243 (16) | 0.0168 (14) | 0.0278 (18) | −0.0088 (12) | −0.0001 (14) | 0.0005 (12) |
C3 | 0.0157 (15) | 0.0211 (15) | 0.042 (2) | −0.0091 (12) | −0.0012 (14) | −0.0060 (15) |
C4 | 0.0232 (16) | 0.0192 (14) | 0.0327 (19) | −0.0065 (12) | −0.0121 (14) | −0.0044 (13) |
C5 | 0.0258 (17) | 0.0167 (13) | 0.0239 (16) | −0.0026 (12) | 0.0014 (13) | −0.0050 (12) |
C6 | 0.0139 (13) | 0.0126 (12) | 0.0215 (16) | −0.0027 (10) | −0.0016 (11) | 0.0014 (11) |
C7 | 0.0167 (14) | 0.0144 (13) | 0.0288 (17) | 0.0009 (11) | −0.0052 (12) | −0.0005 (11) |
C8 | 0.0137 (14) | 0.0158 (13) | 0.0332 (18) | 0.0007 (11) | 0.0016 (12) | −0.0071 (13) |
C9 | 0.0126 (14) | 0.0138 (12) | 0.0248 (16) | −0.0016 (10) | 0.0015 (12) | −0.0067 (11) |
C10 | 0.0131 (13) | 0.0121 (12) | 0.0200 (16) | −0.0022 (10) | 0.0021 (11) | −0.0022 (11) |
C11 | 0.0165 (14) | 0.0264 (14) | 0.0226 (16) | −0.0061 (13) | 0.0039 (13) | −0.0058 (12) |
C12 | 0.039 (2) | 0.0319 (19) | 0.037 (2) | −0.0047 (16) | 0.0037 (17) | −0.0168 (16) |
C13 | 0.031 (2) | 0.055 (2) | 0.0202 (18) | −0.0029 (17) | 0.0012 (15) | −0.0054 (16) |
C14 | 0.0174 (13) | 0.0187 (14) | 0.0203 (15) | 0.0019 (11) | 0.0025 (11) | −0.0044 (12) |
C15 | 0.0212 (15) | 0.0166 (13) | 0.0236 (17) | −0.0005 (12) | −0.0007 (13) | 0.0012 (12) |
C16 | 0.0078 (12) | 0.0164 (13) | 0.0178 (14) | 0.0004 (10) | −0.0002 (10) | −0.0018 (11) |
C17 | 0.0097 (12) | 0.0233 (14) | 0.0191 (15) | −0.0003 (11) | 0.0026 (11) | −0.0056 (12) |
C18 | 0.0132 (14) | 0.0248 (15) | 0.0207 (16) | 0.0006 (12) | 0.0018 (12) | −0.0128 (12) |
C19 | 0.0141 (14) | 0.0156 (13) | 0.0308 (18) | −0.0002 (10) | −0.0003 (13) | −0.0069 (13) |
C20 | 0.0102 (13) | 0.0140 (13) | 0.0229 (16) | 0.0008 (10) | −0.0011 (11) | −0.0014 (11) |
C21 | 0.0142 (14) | 0.0156 (13) | 0.0260 (17) | −0.0019 (11) | −0.0003 (12) | 0.0033 (12) |
C22 | 0.0191 (15) | 0.0251 (16) | 0.048 (2) | 0.0028 (12) | −0.0058 (16) | 0.0012 (16) |
C23 | 0.044 (2) | 0.0260 (17) | 0.030 (2) | −0.0062 (15) | −0.0121 (17) | 0.0113 (15) |
C24 | 0.0162 (14) | 0.0198 (14) | 0.041 (2) | 0.0037 (12) | 0.0011 (14) | 0.0032 (14) |
C25 | 0.0139 (13) | 0.0281 (16) | 0.0237 (17) | 0.0052 (12) | −0.0046 (12) | 0.0007 (13) |
C26 | 0.0083 (12) | 0.0294 (15) | 0.0350 (18) | −0.0011 (12) | 0.0007 (13) | 0.0045 (14) |
C27 | 0.0156 (15) | 0.052 (2) | 0.0215 (18) | 0.0138 (15) | 0.0042 (13) | 0.0007 (16) |
C28 | 0.0178 (15) | 0.0334 (18) | 0.039 (2) | 0.0126 (14) | −0.0078 (14) | −0.0182 (16) |
Fe1—C1 | 2.056 (3) | C8—H8 | 0.9500 |
Fe1—C2 | 2.041 (3) | C8—C9 | 1.437 (4) |
Fe1—C3 | 2.041 (3) | C9—C10 | 1.442 (4) |
Fe1—C4 | 2.049 (3) | C9—C11 | 1.501 (5) |
Fe1—C5 | 2.060 (3) | C11—H11A | 0.9900 |
Fe1—C6 | 2.054 (3) | C11—H11B | 0.9900 |
Fe1—C7 | 2.046 (3) | C12—H12A | 0.9800 |
Fe1—C8 | 2.039 (3) | C12—H12B | 0.9800 |
Fe1—C9 | 2.040 (3) | C12—H12C | 0.9800 |
Fe1—C10 | 2.076 (3) | C13—H13A | 0.9800 |
Fe2—C16 | 2.068 (3) | C13—H13B | 0.9800 |
Fe2—C17 | 2.051 (3) | C13—H13C | 0.9800 |
Fe2—C18 | 2.051 (3) | C14—H14A | 0.9800 |
Fe2—C19 | 2.053 (3) | C14—H14B | 0.9800 |
Fe2—C20 | 2.046 (3) | C14—H14C | 0.9800 |
Fe2—C24 | 2.055 (3) | C15—H15A | 0.9800 |
Fe2—C25 | 2.057 (3) | C15—H15B | 0.9800 |
Fe2—C26 | 2.046 (3) | C15—H15C | 0.9800 |
Fe2—C27 | 2.043 (3) | C16—C17 | 1.440 (4) |
Fe2—C28 | 2.050 (3) | C16—C20 | 1.442 (4) |
Si1—C10 | 1.874 (3) | C17—H17 | 0.9500 |
Si1—C14 | 1.870 (3) | C17—C18 | 1.427 (4) |
Si1—C15 | 1.869 (3) | C18—H18 | 0.9500 |
Si1—C16 | 1.873 (3) | C18—C19 | 1.414 (5) |
N1—C11 | 1.462 (4) | C19—H19 | 0.9500 |
N1—C12 | 1.455 (5) | C19—C20 | 1.424 (4) |
N1—C13 | 1.446 (5) | C20—C21 | 1.502 (5) |
N2—C21 | 1.464 (4) | C21—H21A | 0.9900 |
N2—C22 | 1.453 (5) | C21—H21B | 0.9900 |
N2—C23 | 1.452 (5) | C22—H22A | 0.9800 |
C1—H1 | 0.9500 | C22—H22B | 0.9800 |
C1—C2 | 1.427 (5) | C22—H22C | 0.9800 |
C1—C5 | 1.420 (5) | C23—H23A | 0.9800 |
C2—H2 | 0.9500 | C23—H23B | 0.9800 |
C2—C3 | 1.418 (5) | C23—H23C | 0.9800 |
C3—H3 | 0.9500 | C24—H24 | 0.9500 |
C3—C4 | 1.423 (6) | C24—C25 | 1.415 (5) |
C4—H4 | 0.9500 | C24—C28 | 1.410 (5) |
C4—C5 | 1.421 (5) | C25—H25 | 0.9500 |
C5—H5 | 0.9500 | C25—C26 | 1.416 (5) |
C6—H6 | 0.9500 | C26—H26 | 0.9500 |
C6—C7 | 1.422 (4) | C26—C27 | 1.429 (5) |
C6—C10 | 1.434 (4) | C27—H27 | 0.9500 |
C7—H7 | 0.9500 | C27—C28 | 1.411 (6) |
C7—C8 | 1.423 (5) | C28—H28 | 0.9500 |
C1—Fe1—C5 | 40.36 (14) | C7—C6—C10 | 109.5 (3) |
C1—Fe1—C10 | 109.75 (12) | C10—C6—Fe1 | 70.48 (16) |
C2—Fe1—C1 | 40.77 (14) | C10—C6—H6 | 125.2 |
C2—Fe1—C3 | 40.66 (14) | Fe1—C7—H7 | 126.0 |
C2—Fe1—C4 | 68.32 (14) | C6—C7—Fe1 | 70.02 (16) |
C2—Fe1—C5 | 68.20 (14) | C6—C7—H7 | 126.2 |
C2—Fe1—C6 | 161.37 (13) | C6—C7—C8 | 107.7 (3) |
C2—Fe1—C7 | 155.59 (13) | C8—C7—Fe1 | 69.36 (17) |
C2—Fe1—C10 | 123.40 (13) | C8—C7—H7 | 126.2 |
C3—Fe1—C1 | 68.47 (13) | Fe1—C8—H8 | 126.4 |
C3—Fe1—C4 | 40.73 (16) | C7—C8—Fe1 | 69.87 (17) |
C3—Fe1—C5 | 68.31 (14) | C7—C8—H8 | 125.9 |
C3—Fe1—C6 | 157.77 (13) | C7—C8—C9 | 108.2 (3) |
C3—Fe1—C7 | 119.98 (13) | C9—C8—Fe1 | 69.41 (17) |
C3—Fe1—C10 | 157.81 (14) | C9—C8—H8 | 125.9 |
C4—Fe1—C1 | 68.15 (13) | C8—C9—Fe1 | 69.35 (17) |
C4—Fe1—C5 | 40.45 (14) | C8—C9—C10 | 108.3 (3) |
C4—Fe1—C6 | 124.23 (13) | C8—C9—C11 | 124.6 (3) |
C4—Fe1—C10 | 160.90 (14) | C10—C9—Fe1 | 70.82 (17) |
C5—Fe1—C10 | 125.64 (13) | C10—C9—C11 | 127.1 (3) |
C6—Fe1—C1 | 126.61 (13) | C11—C9—Fe1 | 125.1 (2) |
C6—Fe1—C5 | 111.23 (13) | Si1—C10—Fe1 | 128.94 (15) |
C6—Fe1—C10 | 40.65 (12) | C6—C10—Fe1 | 68.87 (16) |
C7—Fe1—C1 | 161.64 (14) | C6—C10—Si1 | 122.8 (2) |
C7—Fe1—C4 | 106.75 (13) | C6—C10—C9 | 106.3 (3) |
C7—Fe1—C5 | 124.49 (13) | C9—C10—Fe1 | 68.18 (16) |
C7—Fe1—C6 | 40.58 (12) | C9—C10—Si1 | 130.8 (2) |
C7—Fe1—C10 | 68.95 (11) | N1—C11—C9 | 112.0 (3) |
C8—Fe1—C1 | 157.25 (14) | N1—C11—H11A | 109.2 |
C8—Fe1—C2 | 119.58 (14) | N1—C11—H11B | 109.2 |
C8—Fe1—C3 | 103.68 (13) | C9—C11—H11A | 109.2 |
C8—Fe1—C4 | 120.60 (14) | C9—C11—H11B | 109.2 |
C8—Fe1—C5 | 158.37 (14) | H11A—C11—H11B | 107.9 |
C8—Fe1—C6 | 68.25 (12) | N1—C12—H12A | 109.5 |
C8—Fe1—C7 | 40.76 (13) | N1—C12—H12B | 109.5 |
C8—Fe1—C9 | 41.25 (13) | N1—C12—H12C | 109.5 |
C8—Fe1—C10 | 69.08 (12) | H12A—C12—H12B | 109.5 |
C9—Fe1—C1 | 122.80 (13) | H12A—C12—H12C | 109.5 |
C9—Fe1—C2 | 105.50 (13) | H12B—C12—H12C | 109.5 |
C9—Fe1—C3 | 119.96 (14) | N1—C13—H13A | 109.5 |
C9—Fe1—C4 | 156.58 (13) | N1—C13—H13B | 109.5 |
C9—Fe1—C5 | 160.20 (13) | N1—C13—H13C | 109.5 |
C9—Fe1—C6 | 68.43 (12) | H13A—C13—H13B | 109.5 |
C9—Fe1—C7 | 69.06 (12) | H13A—C13—H13C | 109.5 |
C9—Fe1—C10 | 41.00 (12) | H13B—C13—H13C | 109.5 |
C17—Fe2—C16 | 40.91 (12) | Si1—C14—H14A | 109.5 |
C17—Fe2—C18 | 40.70 (12) | Si1—C14—H14B | 109.5 |
C17—Fe2—C19 | 68.06 (13) | Si1—C14—H14C | 109.5 |
C17—Fe2—C24 | 108.96 (13) | H14A—C14—H14B | 109.5 |
C17—Fe2—C25 | 121.53 (13) | H14A—C14—H14C | 109.5 |
C18—Fe2—C16 | 68.97 (12) | H14B—C14—H14C | 109.5 |
C18—Fe2—C19 | 40.30 (14) | Si1—C15—H15A | 109.5 |
C18—Fe2—C24 | 125.95 (15) | Si1—C15—H15B | 109.5 |
C18—Fe2—C25 | 107.97 (13) | Si1—C15—H15C | 109.5 |
C19—Fe2—C16 | 68.80 (12) | H15A—C15—H15B | 109.5 |
C19—Fe2—C24 | 162.07 (14) | H15A—C15—H15C | 109.5 |
C19—Fe2—C25 | 124.93 (13) | H15B—C15—H15C | 109.5 |
C20—Fe2—C16 | 41.04 (11) | Si1—C16—Fe2 | 125.98 (15) |
C20—Fe2—C17 | 68.40 (12) | C17—C16—Fe2 | 68.94 (16) |
C20—Fe2—C18 | 68.38 (13) | C17—C16—Si1 | 123.4 (2) |
C20—Fe2—C19 | 40.66 (12) | C17—C16—C20 | 106.1 (3) |
C20—Fe2—C24 | 156.37 (13) | C20—C16—Fe2 | 68.69 (15) |
C20—Fe2—C25 | 161.45 (13) | C20—C16—Si1 | 130.4 (2) |
C20—Fe2—C28 | 121.11 (14) | Fe2—C17—H17 | 126.2 |
C24—Fe2—C16 | 121.38 (13) | C16—C17—Fe2 | 70.15 (16) |
C24—Fe2—C25 | 40.27 (14) | C16—C17—H17 | 125.5 |
C25—Fe2—C16 | 156.39 (13) | C18—C17—Fe2 | 69.65 (17) |
C26—Fe2—C16 | 161.74 (13) | C18—C17—C16 | 108.9 (3) |
C26—Fe2—C17 | 155.67 (13) | C18—C17—H17 | 125.5 |
C26—Fe2—C18 | 120.12 (13) | Fe2—C18—H18 | 126.0 |
C26—Fe2—C19 | 107.04 (13) | C17—C18—Fe2 | 69.65 (16) |
C26—Fe2—C20 | 124.39 (13) | C17—C18—H18 | 126.0 |
C26—Fe2—C24 | 67.96 (13) | C19—C18—Fe2 | 69.90 (17) |
C26—Fe2—C25 | 40.37 (13) | C19—C18—C17 | 107.9 (3) |
C26—Fe2—C28 | 68.10 (14) | C19—C18—H18 | 126.0 |
C27—Fe2—C16 | 124.63 (14) | Fe2—C19—H19 | 126.6 |
C27—Fe2—C17 | 162.38 (14) | C18—C19—Fe2 | 69.79 (18) |
C27—Fe2—C18 | 155.23 (15) | C18—C19—H19 | 125.8 |
C27—Fe2—C19 | 120.43 (15) | C18—C19—C20 | 108.4 (3) |
C27—Fe2—C20 | 107.13 (14) | C20—C19—Fe2 | 69.42 (16) |
C27—Fe2—C24 | 67.88 (15) | C20—C19—H19 | 125.8 |
C27—Fe2—C25 | 68.11 (14) | C16—C20—Fe2 | 70.27 (16) |
C27—Fe2—C26 | 40.91 (15) | C16—C20—C21 | 126.2 (3) |
C27—Fe2—C28 | 40.32 (16) | C19—C20—Fe2 | 69.92 (17) |
C28—Fe2—C16 | 107.98 (13) | C19—C20—C16 | 108.6 (3) |
C28—Fe2—C17 | 126.17 (14) | C19—C20—C21 | 125.2 (3) |
C28—Fe2—C18 | 162.91 (15) | C21—C20—Fe2 | 127.0 (2) |
C28—Fe2—C19 | 155.80 (16) | N2—C21—C20 | 111.6 (3) |
C28—Fe2—C24 | 40.16 (15) | N2—C21—H21A | 109.3 |
C28—Fe2—C25 | 67.68 (13) | N2—C21—H21B | 109.3 |
C14—Si1—C10 | 105.43 (14) | C20—C21—H21A | 109.3 |
C14—Si1—C16 | 112.17 (13) | C20—C21—H21B | 109.3 |
C15—Si1—C10 | 111.48 (14) | H21A—C21—H21B | 108.0 |
C15—Si1—C14 | 109.98 (15) | N2—C22—H22A | 109.5 |
C15—Si1—C16 | 106.74 (14) | N2—C22—H22B | 109.5 |
C16—Si1—C10 | 111.12 (12) | N2—C22—H22C | 109.5 |
C12—N1—C11 | 111.4 (3) | H22A—C22—H22B | 109.5 |
C13—N1—C11 | 110.3 (3) | H22A—C22—H22C | 109.5 |
C13—N1—C12 | 111.0 (3) | H22B—C22—H22C | 109.5 |
C22—N2—C21 | 112.2 (3) | N2—C23—H23A | 109.5 |
C23—N2—C21 | 110.1 (3) | N2—C23—H23B | 109.5 |
C23—N2—C22 | 111.1 (3) | N2—C23—H23C | 109.5 |
Fe1—C1—H1 | 126.4 | H23A—C23—H23B | 109.5 |
C2—C1—Fe1 | 69.02 (17) | H23A—C23—H23C | 109.5 |
C2—C1—H1 | 126.1 | H23B—C23—H23C | 109.5 |
C5—C1—Fe1 | 69.97 (17) | Fe2—C24—H24 | 125.9 |
C5—C1—H1 | 126.1 | C25—C24—Fe2 | 69.95 (19) |
C5—C1—C2 | 107.7 (3) | C25—C24—H24 | 125.9 |
Fe1—C2—H2 | 125.8 | C28—C24—Fe2 | 69.7 (2) |
C1—C2—Fe1 | 70.21 (17) | C28—C24—H24 | 125.9 |
C1—C2—H2 | 125.9 | C28—C24—C25 | 108.1 (3) |
C3—C2—Fe1 | 69.69 (18) | Fe2—C25—H25 | 126.4 |
C3—C2—C1 | 108.2 (3) | C24—C25—Fe2 | 69.78 (18) |
C3—C2—H2 | 125.9 | C24—C25—H25 | 126.0 |
Fe1—C3—H3 | 125.9 | C24—C25—C26 | 108.1 (3) |
C2—C3—Fe1 | 69.64 (18) | C26—C25—Fe2 | 69.38 (17) |
C2—C3—H3 | 126.1 | C26—C25—H25 | 126.0 |
C2—C3—C4 | 107.8 (3) | Fe2—C26—H26 | 125.7 |
C4—C3—Fe1 | 69.93 (18) | C25—C26—Fe2 | 70.24 (17) |
C4—C3—H3 | 126.1 | C25—C26—H26 | 126.2 |
Fe1—C4—H4 | 126.1 | C25—C26—C27 | 107.6 (3) |
C3—C4—Fe1 | 69.35 (18) | C27—C26—Fe2 | 69.44 (18) |
C3—C4—H4 | 125.9 | C27—C26—H26 | 126.2 |
C5—C4—Fe1 | 70.20 (18) | Fe2—C27—H27 | 125.7 |
C5—C4—C3 | 108.1 (3) | C26—C27—Fe2 | 69.65 (18) |
C5—C4—H4 | 125.9 | C26—C27—H27 | 126.1 |
Fe1—C5—H5 | 126.6 | C28—C27—Fe2 | 70.12 (19) |
C1—C5—Fe1 | 69.67 (17) | C28—C27—C26 | 107.7 (3) |
C1—C5—C4 | 108.1 (3) | C28—C27—H27 | 126.1 |
C1—C5—H5 | 125.9 | Fe2—C28—H28 | 126.1 |
C4—C5—Fe1 | 69.34 (18) | C24—C28—Fe2 | 70.1 (2) |
C4—C5—H5 | 125.9 | C24—C28—C27 | 108.4 (3) |
Fe1—C6—H6 | 126.5 | C24—C28—H28 | 125.8 |
C7—C6—Fe1 | 69.40 (17) | C27—C28—Fe2 | 69.6 (2) |
C7—C6—H6 | 125.2 | C27—C28—H28 | 125.8 |
Fe1—C1—C2—C3 | 59.5 (2) | C8—C9—C11—N1 | −121.0 (3) |
Fe1—C1—C5—C4 | −58.9 (2) | C10—Si1—C16—Fe2 | −175.33 (17) |
Fe1—C2—C3—C4 | 59.7 (2) | C10—Si1—C16—C17 | 97.7 (3) |
Fe1—C3—C4—C5 | 59.7 (2) | C10—Si1—C16—C20 | −83.7 (3) |
Fe1—C4—C5—C1 | 59.1 (2) | C10—C6—C7—Fe1 | −59.2 (2) |
Fe1—C6—C7—C8 | 59.4 (2) | C10—C6—C7—C8 | 0.2 (3) |
Fe1—C6—C10—Si1 | 123.5 (2) | C10—C9—C11—N1 | 59.6 (4) |
Fe1—C6—C10—C9 | −58.09 (19) | C11—C9—C10—Fe1 | 120.0 (3) |
Fe1—C7—C8—C9 | 59.0 (2) | C11—C9—C10—Si1 | −3.3 (4) |
Fe1—C8—C9—C10 | 60.4 (2) | C11—C9—C10—C6 | 178.5 (3) |
Fe1—C8—C9—C11 | −119.1 (3) | C12—N1—C11—C9 | 57.9 (4) |
Fe1—C9—C10—Si1 | −123.3 (2) | C13—N1—C11—C9 | −178.4 (3) |
Fe1—C9—C10—C6 | 58.53 (19) | C14—Si1—C10—Fe1 | 64.7 (2) |
Fe1—C9—C11—N1 | 151.2 (2) | C14—Si1—C10—C6 | −23.6 (3) |
Fe2—C16—C17—C18 | 59.0 (2) | C14—Si1—C10—C9 | 158.4 (3) |
Fe2—C16—C20—C19 | −59.6 (2) | C14—Si1—C16—Fe2 | −57.6 (2) |
Fe2—C16—C20—C21 | 122.0 (3) | C14—Si1—C16—C17 | −144.6 (2) |
Fe2—C17—C18—C19 | 59.7 (2) | C14—Si1—C16—C20 | 34.1 (3) |
Fe2—C18—C19—C20 | 58.8 (2) | C15—Si1—C10—Fe1 | −54.7 (2) |
Fe2—C19—C20—C16 | 59.8 (2) | C15—Si1—C10—C6 | −142.9 (2) |
Fe2—C19—C20—C21 | −121.7 (3) | C15—Si1—C10—C9 | 39.1 (3) |
Fe2—C20—C21—N2 | 147.6 (2) | C15—Si1—C16—Fe2 | 62.9 (2) |
Fe2—C24—C25—C26 | −59.0 (2) | C15—Si1—C16—C17 | −24.0 (3) |
Fe2—C24—C28—C27 | 59.2 (2) | C15—Si1—C16—C20 | 154.6 (3) |
Fe2—C25—C26—C27 | −59.6 (2) | C16—Si1—C10—Fe1 | −173.59 (18) |
Fe2—C26—C27—C28 | −60.0 (2) | C16—Si1—C10—C6 | 98.1 (3) |
Fe2—C27—C28—C24 | −59.5 (2) | C16—Si1—C10—C9 | −79.8 (3) |
Si1—C16—C17—Fe2 | 120.0 (2) | C16—C17—C18—Fe2 | −59.3 (2) |
Si1—C16—C17—C18 | 179.1 (2) | C16—C17—C18—C19 | 0.3 (3) |
Si1—C16—C20—Fe2 | −119.7 (2) | C16—C20—C21—N2 | 56.0 (4) |
Si1—C16—C20—C19 | −179.4 (2) | C17—C16—C20—Fe2 | 59.05 (19) |
Si1—C16—C20—C21 | 2.2 (4) | C17—C16—C20—C19 | −0.6 (3) |
C1—C2—C3—Fe1 | −59.9 (2) | C17—C16—C20—C21 | −179.0 (3) |
C1—C2—C3—C4 | −0.1 (3) | C17—C18—C19—Fe2 | −59.5 (2) |
C2—C1—C5—Fe1 | 58.9 (2) | C17—C18—C19—C20 | −0.7 (3) |
C2—C1—C5—C4 | 0.0 (3) | C18—C19—C20—Fe2 | −59.1 (2) |
C2—C3—C4—Fe1 | −59.6 (2) | C18—C19—C20—C16 | 0.8 (3) |
C2—C3—C4—C5 | 0.2 (3) | C18—C19—C20—C21 | 179.2 (3) |
C3—C4—C5—Fe1 | −59.2 (2) | C19—C20—C21—N2 | −122.1 (3) |
C3—C4—C5—C1 | −0.1 (3) | C20—C16—C17—Fe2 | −58.89 (19) |
C5—C1—C2—Fe1 | −59.5 (2) | C20—C16—C17—C18 | 0.2 (3) |
C5—C1—C2—C3 | 0.1 (3) | C22—N2—C21—C20 | 59.7 (3) |
C6—C7—C8—Fe1 | −59.8 (2) | C23—N2—C21—C20 | −176.0 (3) |
C6—C7—C8—C9 | −0.8 (3) | C24—C25—C26—Fe2 | 59.3 (2) |
C7—C6—C10—Fe1 | 58.5 (2) | C24—C25—C26—C27 | −0.4 (3) |
C7—C6—C10—Si1 | −177.9 (2) | C25—C24—C28—Fe2 | −59.6 (2) |
C7—C6—C10—C9 | 0.5 (3) | C25—C24—C28—C27 | −0.5 (4) |
C7—C8—C9—Fe1 | −59.3 (2) | C25—C26—C27—Fe2 | 60.1 (2) |
C7—C8—C9—C10 | 1.1 (3) | C25—C26—C27—C28 | 0.1 (4) |
C7—C8—C9—C11 | −178.4 (3) | C26—C27—C28—Fe2 | 59.7 (2) |
C8—C9—C10—Fe1 | −59.5 (2) | C26—C27—C28—C24 | 0.2 (4) |
C8—C9—C10—Si1 | 177.3 (2) | C28—C24—C25—Fe2 | 59.5 (2) |
C8—C9—C10—C6 | −0.9 (3) | C28—C24—C25—C26 | 0.5 (4) |
Funding information
Funding for this research was provided by: Mercator Research Center Ruhr. JK thanks the Fonds der Chemischen Industrie for a doctoral fellowship.
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