Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807047769/lh2519sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807047769/lh2519Isup2.hkl |
CCDC reference: 667107
Synthesis of the neutral starting material N-Ferrocenylmethyl-2-(3-methylstyryl)benzimidazole [(C5H5)Fe(C5H4)CH2(C7H4N2)CH=CHC6H4CH3]
To a mixture of 2-(3-methylstyryl)benzimidazole (1.9 g, 8 mmol) and K2CO3 (1.66 g, 12 mmol) in CH3CN (100 ml) was added (trimethylammonium)ferrocenylmethyl iodide ([FcCH2N(CH3)3]+[I]-) (3.09 g, 8 mmol) (Pauson et al., 1966; Ferguson et al., 1994) and the mixture was heated to reflux temperatures for 10 h. The reaction was cooled to room temperature, water was added and the suspension extracted into CHCl3. The organic layer was washed with water, dried MgSO4 and evaporated under vacuum to leave a brown semi-solid. The crude product was purified by column chromatography on silica gel using CH2Cl2:CH3OH (97:3) as eluent.
Yield 2.6 g (74%), m.p. 429–433 K (uncorrected). Compound (I) was obtained as a light orange solid. IR (KBr, ν cm-1) (>1500 cm-1): 3062, 2982, 2925, 2685, 2308, 1713, 1632 1604, 1581. 1H NMR [400 MHz, δH (p.p.m.), CDCl3], 7.90 (d, 1H, CH=CH, J=15.6 Hz), 7.69 (m, 1H, benz-H), 7.33 (m, 3H, benz-H + aryl-H), 7.19 (m, 3H, aryl-H + benz H), 7.10 (m, 2H, CH=CH + aryl-H), 5.06 (s, 2H, Fc—CH2), 4.16 (m, 2H, cpd-H), 4.07 (m, 7H, cpd-H), 2.32 (s, 3H, CH3). 13C NMR [δC, CDCl3], 150.93, 143.48, 138.94, 137.71, 136.47, 135.63, 130.35, 129.23, 128.43, 124.74, 123.0, 122.91, 119.78, 113.56, 109.96, 83.96, 69.24, 68.89, 68.84, 43.32, 21.92.
Synthesis of the N-Ferrocenylmethyl-2-(3-methylstyryl)-N'-methylbenzimidazolium iodide and hexafluorophosphate salts, [(C5H5)Fe(C5H4)CH2(C7H4N2CH3)CH=CHC6H4CH3]+ [I]- and [PF6]- salts.
N-Ferrocenylmethyl-2-(3-methylstyryl)benzimidazole (1.3 g, 3 mmol) was heated to reflux in excess methyl iodide (7 ml) for 2 h. The resultant orange precipitate was filtered and washed several times with ether to provide the iodo salt.
Yield 1.46 g (85 mmol) (74%), m.p. 492–495 K (uncorrected). IR (KBr, ν cm-1) (>1500 cm-1): 3062, 2994, 1649, 1637.
1H NMR [400 MHz, δH (p.p.m.), CDCl3], 8.24 (m, 1H, benz-H), 8.06 (m, 1H, benz-H), 7.82 (m, 2H, Aryl-H), 7.78 (m, 2H, CH=CH), 7.72 (m, 2H, Benz-H), 7.50 (t, 1H, aryl-H, J=7.6 Hz), 7.39 (d, 1H, Aryl-H, J=7.6 Hz), 5.74 (s, 2H, Fc—CH2), 4.36 (m, 2H, cpd-H), 4.28 (s, 5H, cpd-H), 4.12 (s, 5H, cpd-H + N—CH3), 2.32 (s, 3H, CH3). 13C NMR [δC, CDCl3], 150.93, 143.48, 138.94, 137.71, 136.47, 135.63, 130.35, 129.23, 128.43, 124.74, 123.0, 122.91, 119.78, 113.56, 109.96, 83.96, 69.24, 68.89, 68.84, 43.32, 21.92.
The [PF6]- salt was obtained by stirring the iodide derivative (from above) (0.4 g, 0.7 mmol) and ammonium hexafluorophosphate (0.12 g, 0.7 mmol) in methanol (50 ml) at room temperature for 24 h. The resultant orange-red precipitate was filtered and washed several times with methanol.
Yield 0.35 g (85%), m.p. 442–445 K (uncorrected). IR (KBr, ν cm-1) (>1500 cm-1): 3062, 2994, 1648, 1639.
1H NMR [400 MHz, δH (p.p.m.), CDCl3], 8.22 (m, 1H, benz-H), 8.06 (m, 1H, benz-H), 7.80 (m, 2H, Aryl-H), 7.76–7.73 (m, 2H, CH=CH), 7.71 (m, 2H, Benz-H), 7.49 (t, 1H, aryl-H, J=7.6 Hz), 7.39 (d, 1H, Aryl-H, J=7.6 Hz), 5.71 (s, 2H, Fc—CH2), 4.35 (m, 2H, cpd-H), 4.28 (s, 5H, cpd-H), 4.14 (s, 5H, cpd-H + N—CH3), 2.43 (s, 3H, CH3). 13C NMR [δC, CDCl3], 148.09, 147.07, 138.89, 134.61, 132.62, 132.28, 130.78, 129.45, 126.96, 125.99, 113.65, 113.57, 108.39, 81.27, 69.32, 68.93, 44.95, 33.81, 21.30.
Analysis for C28H27N2FePF6: Calc. C: 56.78, H: 4.59, 4.73; Found C: 56.78, H 4.55, N 4.80.
In the refinement all H atoms were allowed for as riding atoms with C—H distances of 0.93, 0.97 & 0.96 Å for the aromatic, methylene and methyl C—H [using the SHELXL97 (Sheldrick, 1997) defaults at 294 K].
There is considerable disorder in the hexafluorophosphate anion The commonly observed disorder over two sites of the [PF6]- moiety was further complicated by the presence of significant peaks of electron density between the modelled F atom site positions. The F atom sites were fixed using soft DFIX restraints [in SHELXL97 (Sheldrick, 1997)] for distance (P—F 1.579 Å) and angle (cis-F at 2.233 and trans-F at 3.158 Å) with soft parameters used for the DELU/ISOR restraints [in SHELXL97 (Sheldrick, 1997)]. The P atom is not disordered.
A satisfactory model was developed and the results are as follows: Two orientations of the [PF6]- moiety were discernible and input with 25% site occupancy per F atom for site positions labelled as A/C where A and C are related by a 30° rotation about one of the F—P—F axes (two A/C F atom sites are almost coincident whilst the other four are separated by the 30° rotation). Two remaining [PF6]- orientations (each with 25% F site occupancy) were subsequently included in a reasonable manner in the disorder model. The residual electron density in the final difference maps is +0.26/-0.28 e.Å-3 and therefore the disorder treatment can be said to have achieved a satisfactory conclusion. One PLATON (Spek, 2003) Alert B for a short intermolecular F4A···F4A contact can be disregarded as all F atom sites are modelled with 25% site occupancy.
Overall, the extensive disorder in the [PF6]- counterion is not surprising given that the [PF6]- anion occupies a void in the lattice of volume 215 Å3 or ca 30.7 Å3 per P/F atom: this is almost twice the average value expected for non-H atoms. Two voids of 64 Å3 per unit cell remain after the final refinement and analysis but these voids are featureless and are devoid of electron density.
Benzimidazole systems have attracted considerable attention in synthetic and structural as well as in applied biological research (Gallagher, Hanlon & Howarth, 2001; Howarth & Hanlon, 2001; Gallagher, Hanlon, Howarth & Thomas, 2001). The title compound (Figures 1–3) was obtained from a series of reactions involving synthesis of the parent N-Ferrocenylmethyl-2-(3-methylstyryl)benzimidazole from 2-(3-methylstyryl)benzimidazole and (trimethylammonium)ferrocenylmethyl iodide: subsequent treatment of the product with methyl iodide and replacement of the iodo salt with the hexafluorophosphate anion yields the [PF6]- salt.
Bond lengths and angles are normal and similar to those reported in the literature (Gallagher, Hanlon & Howarth, 2001; Gallagher, Hanlon, Howarth & Thomas, 2001). There is no disorder in the cation although the unsubstituted C5H5 ring displays large displacement parameters as could be expected given the geometry and the low energy barrier to rotation for Fe···η5-C5H5 π-bonding. The [PF6]- anion is disordered and a discussion of the treatment of this disorder is detailed below. The C3N2 5-membered imidazolium ring is almost orthogonal to the substituted C5H4 ring at 71.48 (10)° and deviates from co-planarity with the aromatic styryl C6 ring by 19.83 (10)°: the latter C6 ring is oriented at an angle of 85.52 (9)° to the C5H4 ring.
In the crystal structure there is only one intermolecular interaction of note (as detailed in Table 1) and involving C34—H34···Cg1i (where Cg1 is the ring centroid of C5H4 and the symmetry operation i = x - 3/2,3/2 - y,z). Several C—H···F contacts involving the disordered [PF6]- are present but are not important as they are relatively weak and involve the partial occupancy F atom sites.
Related structures include N-ferrocenylmethyl-2-ferrocenylbenzimidazole (Benito et al., 1995) and the salt N-ferrocenylmethyl-2-ferrocenyl-benzimidazolium tetrafluoroborate (Li et al., 1998) which differ from the title compound by having a ferrocenyl moiety at the 2-position of the benzimidazolium ring instead of the 3-methylstyryl group.
For related ferrocene literature, see: Benito et al. (1995); Li et al. (1998); Gallagher, Hanlon & Howarth (2001); Gallagher, Hanlon, Howarth & Thomas (2001); Howarth & Hanlon, (2001). For the chemical synthesis and crystal structure of [FcCH2N(CH3)3]+[I]-, see: Pauson et al. (1966); Ferguson et al. (1994).
Data collection: XSCANS (Bruker, 1996); cell refinement: XSCANS (Bruker, 1996); data reduction: XSCANS (Bruker, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEX (McArdle, 1995) and PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997) and PREP8 (Ferguson, 1998).
[Fe(C5H5)(C23H22N2)]PF6 | F(000) = 1216 |
Mr = 592.34 | Dx = 1.483 Mg m−3 |
Monoclinic, P21/a | Melting point: 483 K |
Hall symbol: -P 2yab | Mo Kα radiation, λ = 0.71073 Å |
a = 13.515 (1) Å | Cell parameters from 85 reflections |
b = 12.8743 (10) Å | θ = 8.9–30.4° |
c = 15.2839 (9) Å | µ = 0.69 mm−1 |
β = 94.037 (5)° | T = 294 K |
V = 2652.7 (3) Å3 | Block, red |
Z = 4 | 0.29 × 0.25 × 0.17 mm |
Bruker P4 diffractometer | 3922 reflections with I > 2σ(I) |
Radiation source: X-ray tube | Rint = 0.025 |
Graphite monochromator | θmax = 28.0°, θmin = 2.1° |
ω scans | h = −17→1 |
Absorption correction: ψ scan (North et al., 1968) | k = −1→17 |
Tmin = 0.826, Tmax = 0.889 | l = −20→20 |
8107 measured reflections | 3 standard reflections every 197 reflections |
6387 independent reflections | intensity decay: 0.5% |
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)] = 0.047 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.113 | H-atom parameters constrained |
S = 1.01 | w = 1/[σ2(Fo2) + (0.0435P)2 + 0.5898P] where P = (Fo2 + 2Fc2)/3 |
6387 reflections | (Δ/σ)max = 0.001 |
507 parameters | Δρmax = 0.26 e Å−3 |
228 restraints | Δρmin = −0.28 e Å−3 |
[Fe(C5H5)(C23H22N2)]PF6 | V = 2652.7 (3) Å3 |
Mr = 592.34 | Z = 4 |
Monoclinic, P21/a | Mo Kα radiation |
a = 13.515 (1) Å | µ = 0.69 mm−1 |
b = 12.8743 (10) Å | T = 294 K |
c = 15.2839 (9) Å | 0.29 × 0.25 × 0.17 mm |
β = 94.037 (5)° |
Bruker P4 diffractometer | 3922 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.025 |
Tmin = 0.826, Tmax = 0.889 | 3 standard reflections every 197 reflections |
8107 measured reflections | intensity decay: 0.5% |
6387 independent reflections |
R[F2 > 2σ(F2)] = 0.047 | 228 restraints |
wR(F2) = 0.113 | H-atom parameters constrained |
S = 1.01 | Δρmax = 0.26 e Å−3 |
6387 reflections | Δρmin = −0.28 e Å−3 |
507 parameters |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Fe1 | 0.82902 (3) | 0.82379 (3) | 0.11263 (2) | 0.04913 (13) | |
P1 | 0.54550 (6) | 0.93397 (6) | 0.33825 (5) | 0.0581 (2) | |
F1A | 0.6347 (14) | 0.8544 (17) | 0.360 (2) | 0.106 (11) | 0.25 |
F2A | 0.559 (3) | 0.919 (2) | 0.2396 (11) | 0.143 (11) | 0.25 |
F3A | 0.4607 (14) | 1.0136 (15) | 0.321 (2) | 0.105 (10) | 0.25 |
F4A | 0.533 (2) | 0.947 (2) | 0.4403 (8) | 0.119 (9) | 0.25 |
F5A | 0.4701 (12) | 0.8394 (9) | 0.3395 (19) | 0.083 (10) | 0.25 |
F6A | 0.6243 (14) | 1.0236 (17) | 0.345 (2) | 0.120 (13) | 0.25 |
F1C | 0.6291 (19) | 0.8609 (17) | 0.312 (2) | 0.145 (12) | 0.25 |
F2C | 0.522 (3) | 0.9619 (16) | 0.2384 (9) | 0.115 (9) | 0.25 |
F3C | 0.4564 (14) | 1.0103 (15) | 0.362 (2) | 0.123 (9) | 0.25 |
F4C | 0.5611 (19) | 0.9047 (17) | 0.4371 (11) | 0.106 (9) | 0.25 |
F5C | 0.4652 (18) | 0.8425 (15) | 0.3265 (18) | 0.129 (15) | 0.25 |
F6C | 0.6175 (16) | 1.0283 (12) | 0.3520 (15) | 0.085 (10) | 0.25 |
F1B | 0.4510 (13) | 0.876 (2) | 0.3717 (18) | 0.105 (8) | 0.25 |
F2B | 0.556 (2) | 0.8398 (15) | 0.2719 (13) | 0.100 (7) | 0.25 |
F3B | 0.6385 (12) | 0.9846 (19) | 0.303 (2) | 0.110 (9) | 0.25 |
F4B | 0.531 (3) | 1.0242 (15) | 0.4024 (15) | 0.164 (10) | 0.25 |
F5B | 0.6096 (15) | 0.8745 (16) | 0.4128 (13) | 0.087 (8) | 0.25 |
F6B | 0.4771 (17) | 0.989 (2) | 0.2649 (17) | 0.085 (8) | 0.25 |
F1D | 0.487 (2) | 0.9106 (15) | 0.4142 (14) | 0.107 (6) | 0.25 |
F2D | 0.5115 (15) | 0.8346 (10) | 0.2877 (12) | 0.071 (4) | 0.25 |
F3D | 0.6158 (18) | 0.9605 (14) | 0.2560 (13) | 0.102 (7) | 0.25 |
F4D | 0.5959 (16) | 1.0353 (11) | 0.3844 (13) | 0.077 (7) | 0.25 |
F5D | 0.6401 (15) | 0.8699 (16) | 0.3792 (19) | 0.085 (10) | 0.25 |
F6D | 0.4659 (15) | 1.008 (2) | 0.2932 (19) | 0.087 (10) | 0.25 |
N1 | 1.00823 (15) | 1.13875 (16) | 0.40497 (12) | 0.0454 (5) | |
N2 | 0.94783 (14) | 0.99330 (14) | 0.35027 (12) | 0.0387 (4) | |
C1 | 0.92886 (17) | 1.09458 (18) | 0.36126 (14) | 0.0409 (5) | |
C2 | 0.88229 (18) | 0.91633 (18) | 0.30194 (15) | 0.0425 (6) | |
C3 | 1.04403 (17) | 0.97278 (19) | 0.38485 (14) | 0.0405 (5) | |
C4 | 1.08141 (18) | 1.06479 (19) | 0.41968 (15) | 0.0433 (6) | |
C5 | 1.1776 (2) | 1.0705 (2) | 0.45951 (17) | 0.0583 (7) | |
C6 | 1.2326 (2) | 0.9824 (3) | 0.46061 (19) | 0.0695 (9) | |
C7 | 1.1952 (2) | 0.8897 (3) | 0.42499 (19) | 0.0686 (8) | |
C8 | 1.0999 (2) | 0.8825 (2) | 0.38654 (17) | 0.0552 (7) | |
C10 | 1.0168 (2) | 1.2464 (2) | 0.4364 (2) | 0.0673 (8) | |
C11 | 0.89295 (17) | 0.91959 (18) | 0.20553 (15) | 0.0394 (5) | |
C12 | 0.83444 (19) | 0.9779 (2) | 0.14174 (17) | 0.0519 (6) | |
C13 | 0.8722 (2) | 0.9597 (2) | 0.05876 (17) | 0.0613 (8) | |
C14 | 0.9536 (2) | 0.8921 (2) | 0.07054 (17) | 0.0562 (7) | |
C15 | 0.96684 (18) | 0.8670 (2) | 0.16044 (17) | 0.0479 (6) | |
C21 | 0.7325 (4) | 0.7294 (4) | 0.1683 (3) | 0.0947 (13) | |
C22 | 0.6852 (3) | 0.7801 (4) | 0.0999 (4) | 0.1069 (14) | |
C23 | 0.7315 (4) | 0.7541 (5) | 0.0254 (3) | 0.1191 (19) | |
C24 | 0.8057 (4) | 0.6891 (4) | 0.0457 (4) | 0.1104 (17) | |
C25 | 0.8105 (4) | 0.6704 (3) | 0.1362 (4) | 0.1108 (16) | |
C1E | 0.83780 (19) | 1.1431 (2) | 0.32685 (16) | 0.0471 (6) | |
C2E | 0.8272 (2) | 1.2409 (2) | 0.30173 (17) | 0.0511 (6) | |
C31 | 0.73912 (19) | 1.28689 (19) | 0.25643 (16) | 0.0477 (6) | |
C32 | 0.7369 (2) | 1.3941 (2) | 0.24249 (18) | 0.0571 (7) | |
C33 | 0.6559 (2) | 1.4394 (2) | 0.19980 (19) | 0.0632 (8) | |
C34 | 0.5766 (2) | 1.3800 (2) | 0.16931 (17) | 0.0599 (8) | |
C35 | 0.57701 (19) | 1.2725 (2) | 0.17876 (17) | 0.0536 (7) | |
C36 | 0.65917 (19) | 1.2276 (2) | 0.22400 (16) | 0.0503 (6) | |
C37 | 0.4940 (2) | 1.2062 (3) | 0.1393 (2) | 0.0773 (9) | |
H2A | 0.8138 | 0.9305 | 0.3131 | 0.051* | |
H2B | 0.8985 | 0.8472 | 0.3237 | 0.051* | |
H5 | 1.2027 | 1.1320 | 0.4841 | 0.070* | |
H6 | 1.2973 | 0.9839 | 0.4859 | 0.083* | |
H7 | 1.2354 | 0.8310 | 0.4272 | 0.082* | |
H8 | 1.0746 | 0.8205 | 0.3631 | 0.066* | |
H10A | 1.0431 | 1.2891 | 0.3920 | 0.101* | |
H10B | 1.0605 | 1.2489 | 0.4887 | 0.101* | |
H10C | 0.9525 | 1.2717 | 0.4490 | 0.101* | |
H12 | 0.7810 | 1.0204 | 0.1526 | 0.062* | |
H13 | 0.8473 | 0.9877 | 0.0056 | 0.074* | |
H14 | 0.9921 | 0.8680 | 0.0267 | 0.067* | |
H15 | 1.0156 | 0.8235 | 0.1860 | 0.057* | |
H21 | 0.7164 | 0.7327 | 0.2265 | 0.114* | |
H22 | 0.6312 | 0.8244 | 0.1027 | 0.128* | |
H23 | 0.7134 | 0.7785 | −0.0308 | 0.143* | |
H24 | 0.8476 | 0.6605 | 0.0064 | 0.132* | |
H25 | 0.8555 | 0.6282 | 0.1683 | 0.133* | |
H1E | 0.7814 | 1.1016 | 0.3219 | 0.057* | |
H2E | 0.8811 | 1.2847 | 0.3141 | 0.061* | |
H32 | 0.7908 | 1.4347 | 0.2623 | 0.069* | |
H33 | 0.6545 | 1.5110 | 0.1914 | 0.076* | |
H34 | 0.5213 | 1.4122 | 0.1417 | 0.072* | |
H36 | 0.6605 | 1.1561 | 0.2327 | 0.060* | |
H37A | 0.4331 | 1.2448 | 0.1373 | 0.116* | |
H37B | 0.4878 | 1.1451 | 0.1744 | 0.116* | |
H37C | 0.5081 | 1.1864 | 0.0809 | 0.116* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Fe1 | 0.0420 (2) | 0.0572 (2) | 0.0479 (2) | −0.01612 (18) | 0.00050 (15) | −0.01005 (18) |
P1 | 0.0602 (5) | 0.0412 (4) | 0.0721 (5) | −0.0013 (4) | −0.0008 (4) | 0.0038 (4) |
F1A | 0.106 (15) | 0.056 (11) | 0.16 (2) | 0.005 (8) | 0.015 (16) | 0.015 (14) |
F2A | 0.20 (3) | 0.15 (3) | 0.073 (10) | 0.05 (2) | 0.011 (13) | −0.037 (14) |
F3A | 0.081 (13) | 0.090 (13) | 0.15 (2) | 0.066 (10) | 0.021 (13) | 0.049 (15) |
F4A | 0.170 (18) | 0.14 (2) | 0.042 (7) | −0.016 (17) | −0.016 (8) | −0.014 (9) |
F5A | 0.065 (10) | 0.035 (8) | 0.15 (3) | −0.009 (7) | −0.007 (14) | 0.021 (10) |
F6A | 0.055 (11) | 0.11 (2) | 0.20 (3) | −0.015 (11) | 0.030 (14) | 0.014 (17) |
F1C | 0.108 (17) | 0.14 (2) | 0.19 (2) | 0.003 (14) | 0.075 (17) | −0.020 (19) |
F2C | 0.20 (3) | 0.085 (13) | 0.063 (8) | 0.021 (15) | 0.014 (13) | −0.004 (7) |
F3C | 0.078 (10) | 0.099 (12) | 0.20 (2) | 0.006 (8) | 0.036 (12) | −0.033 (16) |
F4C | 0.119 (17) | 0.086 (14) | 0.111 (14) | −0.037 (12) | −0.016 (12) | 0.059 (11) |
F5C | 0.14 (3) | 0.125 (19) | 0.12 (2) | −0.083 (16) | −0.011 (18) | −0.022 (14) |
F6C | 0.13 (2) | 0.039 (9) | 0.078 (13) | −0.046 (11) | −0.006 (12) | 0.027 (9) |
F1B | 0.079 (11) | 0.15 (2) | 0.091 (15) | −0.010 (12) | 0.031 (11) | 0.018 (13) |
F2B | 0.130 (18) | 0.072 (9) | 0.106 (10) | −0.011 (12) | 0.053 (12) | −0.029 (8) |
F3B | 0.060 (8) | 0.105 (18) | 0.17 (2) | −0.019 (11) | 0.017 (14) | 0.029 (17) |
F4B | 0.18 (2) | 0.099 (13) | 0.21 (2) | 0.051 (18) | 0.00 (2) | −0.065 (13) |
F5B | 0.082 (16) | 0.084 (12) | 0.090 (12) | −0.001 (10) | −0.032 (10) | 0.002 (10) |
F6B | 0.087 (12) | 0.078 (14) | 0.090 (18) | 0.019 (9) | 0.002 (9) | 0.019 (14) |
F1D | 0.15 (2) | 0.113 (14) | 0.059 (11) | −0.002 (13) | 0.033 (10) | 0.020 (10) |
F2D | 0.069 (10) | 0.066 (7) | 0.078 (11) | −0.029 (8) | −0.001 (7) | −0.002 (8) |
F3D | 0.128 (19) | 0.089 (10) | 0.093 (13) | −0.016 (11) | 0.043 (11) | −0.019 (10) |
F4D | 0.078 (12) | 0.050 (7) | 0.095 (14) | 0.016 (9) | −0.036 (10) | −0.021 (8) |
F5D | 0.058 (10) | 0.039 (7) | 0.15 (2) | 0.027 (6) | −0.047 (13) | −0.021 (11) |
F6D | 0.069 (13) | 0.096 (16) | 0.094 (18) | 0.016 (10) | −0.017 (12) | 0.004 (13) |
N1 | 0.0533 (12) | 0.0407 (11) | 0.0415 (11) | −0.0010 (10) | −0.0019 (9) | −0.0064 (9) |
N2 | 0.0409 (10) | 0.0370 (11) | 0.0376 (10) | 0.0020 (9) | −0.0025 (8) | −0.0021 (8) |
C1 | 0.0445 (13) | 0.0398 (13) | 0.0381 (12) | 0.0008 (11) | 0.0018 (10) | −0.0018 (10) |
C2 | 0.0423 (13) | 0.0371 (13) | 0.0472 (13) | −0.0030 (11) | −0.0023 (11) | −0.0001 (11) |
C3 | 0.0391 (12) | 0.0449 (14) | 0.0369 (12) | 0.0034 (11) | −0.0026 (10) | −0.0003 (11) |
C4 | 0.0445 (13) | 0.0479 (14) | 0.0369 (12) | 0.0011 (12) | −0.0017 (10) | −0.0016 (11) |
C5 | 0.0535 (16) | 0.0706 (19) | 0.0491 (15) | −0.0076 (15) | −0.0088 (13) | −0.0081 (14) |
C6 | 0.0470 (16) | 0.098 (3) | 0.0608 (18) | 0.0082 (17) | −0.0147 (13) | −0.0026 (18) |
C7 | 0.0584 (17) | 0.077 (2) | 0.0682 (19) | 0.0236 (16) | −0.0116 (15) | 0.0043 (17) |
C8 | 0.0582 (16) | 0.0515 (16) | 0.0544 (15) | 0.0113 (14) | −0.0064 (13) | 0.0007 (13) |
C10 | 0.085 (2) | 0.0451 (16) | 0.0694 (19) | −0.0046 (15) | −0.0150 (16) | −0.0169 (14) |
C11 | 0.0372 (12) | 0.0361 (12) | 0.0442 (13) | −0.0058 (10) | −0.0018 (10) | −0.0029 (10) |
C12 | 0.0503 (15) | 0.0499 (15) | 0.0545 (15) | 0.0042 (13) | −0.0042 (12) | −0.0005 (13) |
C13 | 0.0752 (19) | 0.0642 (18) | 0.0436 (14) | −0.0138 (16) | −0.0023 (14) | 0.0049 (13) |
C14 | 0.0522 (16) | 0.0639 (18) | 0.0539 (16) | −0.0187 (14) | 0.0126 (13) | −0.0122 (14) |
C15 | 0.0374 (13) | 0.0475 (14) | 0.0586 (15) | −0.0063 (11) | 0.0018 (11) | −0.0084 (12) |
C21 | 0.109 (3) | 0.098 (3) | 0.080 (3) | −0.068 (3) | 0.025 (2) | −0.021 (2) |
C22 | 0.050 (2) | 0.119 (3) | 0.149 (4) | −0.037 (2) | −0.006 (3) | −0.009 (3) |
C23 | 0.106 (3) | 0.168 (5) | 0.079 (3) | −0.083 (4) | −0.022 (3) | −0.015 (3) |
C24 | 0.094 (3) | 0.103 (3) | 0.137 (4) | −0.052 (3) | 0.031 (3) | −0.065 (3) |
C25 | 0.099 (3) | 0.055 (2) | 0.172 (5) | −0.039 (2) | −0.034 (3) | 0.012 (3) |
C1E | 0.0447 (14) | 0.0464 (14) | 0.0500 (14) | 0.0048 (11) | 0.0009 (11) | −0.0019 (12) |
C2E | 0.0507 (15) | 0.0495 (16) | 0.0525 (15) | 0.0016 (12) | −0.0004 (12) | 0.0014 (12) |
C31 | 0.0504 (15) | 0.0443 (14) | 0.0488 (14) | 0.0087 (12) | 0.0060 (12) | 0.0060 (12) |
C32 | 0.0613 (17) | 0.0476 (15) | 0.0625 (17) | 0.0062 (14) | 0.0058 (14) | 0.0023 (13) |
C33 | 0.074 (2) | 0.0455 (16) | 0.0698 (18) | 0.0131 (15) | 0.0060 (16) | 0.0083 (14) |
C34 | 0.0616 (18) | 0.0650 (19) | 0.0538 (16) | 0.0264 (16) | 0.0079 (14) | 0.0135 (14) |
C35 | 0.0481 (15) | 0.0679 (18) | 0.0454 (14) | 0.0065 (14) | 0.0074 (12) | 0.0093 (13) |
C36 | 0.0506 (15) | 0.0484 (15) | 0.0522 (15) | 0.0078 (13) | 0.0057 (12) | 0.0113 (12) |
C37 | 0.0588 (18) | 0.100 (3) | 0.071 (2) | 0.0011 (18) | −0.0060 (16) | 0.0133 (18) |
Fe1—C11 | 2.028 (2) | C2E—C31 | 1.460 (4) |
Fe1—C12 | 2.034 (3) | C31—C36 | 1.386 (4) |
Fe1—C13 | 2.036 (3) | C31—C32 | 1.396 (4) |
Fe1—C14 | 2.043 (3) | C32—C33 | 1.366 (4) |
Fe1—C15 | 2.030 (2) | C33—C34 | 1.372 (4) |
Fe1—C21 | 2.016 (3) | C34—C35 | 1.391 (4) |
Fe1—C22 | 2.020 (3) | C35—C36 | 1.392 (3) |
Fe1—C23 | 2.018 (3) | C35—C37 | 1.502 (4) |
Fe1—C25 | 2.025 (4) | C2—H2A | 0.9700 |
Fe1—C24 | 2.027 (4) | C2—H2B | 0.9700 |
N1—C1 | 1.349 (3) | C5—H5 | 0.9300 |
N1—C4 | 1.380 (3) | C6—H6 | 0.9300 |
N1—C10 | 1.469 (3) | C7—H7 | 0.9300 |
N2—C1 | 1.342 (3) | C8—H8 | 0.9300 |
N2—C2 | 1.490 (3) | C1E—H1E | 0.9300 |
N2—C3 | 1.394 (3) | C2E—H2E | 0.9300 |
C1—C1E | 1.446 (3) | C12—H12 | 0.9300 |
C2—C11 | 1.491 (3) | C13—H13 | 0.9300 |
C3—C4 | 1.380 (3) | C14—H14 | 0.9300 |
C3—C8 | 1.385 (3) | C15—H15 | 0.9300 |
C4—C5 | 1.398 (3) | C21—H21 | 0.9300 |
C5—C6 | 1.356 (4) | C22—H22 | 0.9300 |
C6—C7 | 1.392 (4) | C23—H23 | 0.9300 |
C7—C8 | 1.380 (4) | C24—H24 | 0.9300 |
C11—C15 | 1.424 (3) | C25—H25 | 0.9300 |
C11—C12 | 1.425 (3) | C32—H32 | 0.9300 |
C12—C13 | 1.420 (4) | C33—H33 | 0.9300 |
C13—C14 | 1.404 (4) | C34—H34 | 0.9300 |
C14—C15 | 1.410 (4) | C36—H36 | 0.9300 |
C21—C22 | 1.355 (6) | C10—H10A | 0.9600 |
C21—C25 | 1.415 (6) | C10—H10B | 0.9600 |
C22—C23 | 1.379 (6) | C10—H10C | 0.9600 |
C23—C24 | 1.326 (6) | C37—H37A | 0.9600 |
C24—C25 | 1.400 (6) | C37—H37B | 0.9600 |
C1E—C2E | 1.321 (3) | C37—H37C | 0.9600 |
C21—Fe1—C23 | 66.35 (17) | C15—C11—Fe1 | 69.55 (13) |
C21—Fe1—C22 | 39.22 (17) | C12—C11—Fe1 | 69.70 (14) |
C23—Fe1—C22 | 39.94 (18) | C2—C11—Fe1 | 127.50 (16) |
C21—Fe1—C25 | 41.00 (17) | C13—C12—C11 | 107.9 (2) |
C23—Fe1—C25 | 66.5 (2) | C13—C12—Fe1 | 69.67 (16) |
C22—Fe1—C25 | 67.38 (19) | C11—C12—Fe1 | 69.21 (14) |
C21—Fe1—C24 | 67.33 (17) | C13—C12—H12 | 126.1 |
C23—Fe1—C24 | 38.27 (19) | C11—C12—H12 | 126.1 |
C22—Fe1—C24 | 66.32 (18) | Fe1—C12—H12 | 126.6 |
C25—Fe1—C24 | 40.43 (19) | C14—C13—C12 | 108.4 (2) |
C21—Fe1—C11 | 109.13 (12) | C14—C13—Fe1 | 70.12 (16) |
C23—Fe1—C11 | 163.6 (2) | C12—C13—Fe1 | 69.50 (16) |
C22—Fe1—C11 | 126.64 (17) | C14—C13—H13 | 125.8 |
C25—Fe1—C11 | 121.36 (17) | C12—C13—H13 | 125.8 |
C24—Fe1—C11 | 156.6 (2) | Fe1—C13—H13 | 126.2 |
C21—Fe1—C15 | 128.19 (16) | C13—C14—C15 | 108.1 (2) |
C23—Fe1—C15 | 154.1 (2) | C13—C14—Fe1 | 69.62 (16) |
C22—Fe1—C15 | 164.46 (19) | C15—C14—Fe1 | 69.25 (14) |
C25—Fe1—C15 | 108.97 (15) | C13—C14—H14 | 125.9 |
C24—Fe1—C15 | 121.50 (18) | C15—C14—H14 | 125.9 |
C11—Fe1—C15 | 41.08 (9) | Fe1—C14—H14 | 126.8 |
C21—Fe1—C12 | 120.70 (16) | C14—C15—C11 | 108.5 (2) |
C23—Fe1—C12 | 126.2 (2) | C14—C15—Fe1 | 70.22 (14) |
C22—Fe1—C12 | 108.21 (16) | C11—C15—Fe1 | 69.36 (13) |
C25—Fe1—C12 | 156.2 (2) | C14—C15—H15 | 125.7 |
C24—Fe1—C12 | 161.3 (2) | C11—C15—H15 | 125.7 |
C11—Fe1—C12 | 41.09 (9) | Fe1—C15—H15 | 126.2 |
C15—Fe1—C12 | 68.64 (10) | C22—C21—C25 | 108.2 (4) |
C21—Fe1—C13 | 154.4 (2) | C22—C21—Fe1 | 70.6 (2) |
C23—Fe1—C13 | 107.88 (16) | C25—C21—Fe1 | 69.9 (2) |
C22—Fe1—C13 | 120.11 (18) | C22—C21—H21 | 125.9 |
C25—Fe1—C13 | 162.1 (2) | C25—C21—H21 | 125.9 |
C24—Fe1—C13 | 124.74 (19) | Fe1—C21—H21 | 125.2 |
C11—Fe1—C13 | 68.93 (10) | C21—C22—C23 | 107.7 (4) |
C15—Fe1—C13 | 68.17 (11) | C21—C22—Fe1 | 70.2 (2) |
C12—Fe1—C13 | 40.83 (11) | C23—C22—Fe1 | 70.0 (2) |
C21—Fe1—C14 | 164.81 (19) | C21—C22—H22 | 126.1 |
C23—Fe1—C14 | 119.83 (17) | C23—C22—H22 | 126.1 |
C22—Fe1—C14 | 153.94 (19) | Fe1—C22—H22 | 125.3 |
C25—Fe1—C14 | 126.19 (19) | C24—C23—C22 | 109.8 (5) |
C24—Fe1—C14 | 108.17 (15) | C24—C23—Fe1 | 71.2 (2) |
C11—Fe1—C14 | 68.82 (10) | C22—C23—Fe1 | 70.1 (2) |
C15—Fe1—C14 | 40.52 (10) | C24—C23—H23 | 125.1 |
C12—Fe1—C14 | 68.35 (11) | C22—C23—H23 | 125.1 |
C13—Fe1—C14 | 40.26 (11) | Fe1—C23—H23 | 125.2 |
C1—N1—C4 | 109.00 (19) | C23—C24—C25 | 108.8 (4) |
C1—N1—C10 | 127.0 (2) | C23—C24—Fe1 | 70.5 (2) |
C4—N1—C10 | 124.0 (2) | C25—C24—Fe1 | 69.7 (2) |
C1—N2—C3 | 108.54 (19) | C23—C24—H24 | 125.6 |
C1—N2—C2 | 126.60 (19) | C25—C24—H24 | 125.6 |
C3—N2—C2 | 124.62 (19) | Fe1—C24—H24 | 125.7 |
N2—C1—N1 | 108.6 (2) | C24—C25—C21 | 105.5 (4) |
N2—C1—C1E | 122.7 (2) | C24—C25—Fe1 | 69.8 (2) |
N1—C1—C1E | 128.7 (2) | C21—C25—Fe1 | 69.1 (2) |
N2—C2—C11 | 112.06 (18) | C24—C25—H25 | 127.3 |
N2—C2—H2A | 109.2 | C21—C25—H25 | 127.3 |
C11—C2—H2A | 109.2 | Fe1—C25—H25 | 125.4 |
N2—C2—H2B | 109.2 | C2E—C1E—C1 | 126.1 (3) |
C11—C2—H2B | 109.2 | C2E—C1E—H1E | 116.9 |
H2A—C2—H2B | 107.9 | C1—C1E—H1E | 116.9 |
C4—C3—C8 | 121.9 (2) | C1E—C2E—C31 | 126.3 (3) |
C4—C3—N2 | 106.9 (2) | C1E—C2E—H2E | 116.8 |
C8—C3—N2 | 131.2 (2) | C31—C2E—H2E | 116.8 |
C3—C4—N1 | 106.9 (2) | C36—C31—C32 | 118.8 (2) |
C3—C4—C5 | 121.1 (2) | C36—C31—C2E | 122.4 (2) |
N1—C4—C5 | 131.9 (2) | C32—C31—C2E | 118.8 (3) |
C6—C5—C4 | 117.0 (3) | C33—C32—C31 | 120.2 (3) |
C6—C5—H5 | 121.5 | C33—C32—H32 | 119.9 |
C4—C5—H5 | 121.5 | C31—C32—H32 | 119.9 |
C5—C6—C7 | 121.9 (3) | C32—C33—C34 | 120.3 (3) |
C5—C6—H6 | 119.1 | C32—C33—H33 | 119.8 |
C7—C6—H6 | 119.1 | C34—C33—H33 | 119.8 |
C8—C7—C6 | 121.8 (3) | C33—C34—C35 | 121.5 (3) |
C8—C7—H7 | 119.1 | C33—C34—H34 | 119.3 |
C6—C7—H7 | 119.1 | C35—C34—H34 | 119.3 |
C7—C8—C3 | 116.3 (3) | C34—C35—C36 | 117.5 (3) |
C7—C8—H8 | 121.9 | C34—C35—C37 | 121.7 (3) |
C3—C8—H8 | 121.9 | C36—C35—C37 | 120.7 (3) |
N1—C10—H10A | 109.5 | C31—C36—C35 | 121.6 (3) |
N1—C10—H10B | 109.5 | C31—C36—H36 | 119.2 |
H10A—C10—H10B | 109.5 | C35—C36—H36 | 119.2 |
N1—C10—H10C | 109.5 | C35—C37—H37A | 109.5 |
H10A—C10—H10C | 109.5 | C35—C37—H37B | 109.5 |
H10B—C10—H10C | 109.5 | H37A—C37—H37B | 109.5 |
C15—C11—C12 | 107.1 (2) | C35—C37—H37C | 109.5 |
C15—C11—C2 | 125.8 (2) | H37A—C37—H37C | 109.5 |
C12—C11—C2 | 127.1 (2) | H37B—C37—H37C | 109.5 |
C3—N2—C1—N1 | −2.5 (3) | C23—Fe1—C15—C14 | 48.9 (5) |
C2—N2—C1—N1 | −177.06 (19) | C22—Fe1—C15—C14 | −162.4 (6) |
C3—N2—C1—C1E | 175.4 (2) | C25—Fe1—C15—C14 | 124.0 (3) |
C2—N2—C1—C1E | 0.8 (4) | C24—Fe1—C15—C14 | 81.1 (3) |
C4—N1—C1—N2 | 2.2 (3) | C11—Fe1—C15—C14 | −119.7 (2) |
C10—N1—C1—N2 | −175.3 (2) | C12—Fe1—C15—C14 | −81.25 (17) |
C4—N1—C1—C1E | −175.6 (2) | C13—Fe1—C15—C14 | −37.19 (16) |
C10—N1—C1—C1E | 7.0 (4) | C21—Fe1—C15—C11 | −74.5 (2) |
C1—N2—C2—C11 | 82.7 (3) | C23—Fe1—C15—C11 | 168.7 (4) |
C3—N2—C2—C11 | −91.1 (3) | C22—Fe1—C15—C11 | −42.7 (6) |
C1—N2—C3—C4 | 1.9 (3) | C25—Fe1—C15—C11 | −116.3 (3) |
C2—N2—C3—C4 | 176.57 (19) | C24—Fe1—C15—C11 | −159.1 (2) |
C1—N2—C3—C8 | −176.9 (3) | C12—Fe1—C15—C11 | 38.47 (14) |
C2—N2—C3—C8 | −2.2 (4) | C13—Fe1—C15—C11 | 82.53 (16) |
C8—C3—C4—N1 | 178.4 (2) | C14—Fe1—C15—C11 | 119.7 (2) |
N2—C3—C4—N1 | −0.5 (3) | C23—Fe1—C21—C22 | −38.1 (3) |
C8—C3—C4—C5 | −0.9 (4) | C25—Fe1—C21—C22 | −118.8 (4) |
N2—C3—C4—C5 | −179.8 (2) | C24—Fe1—C21—C22 | −79.8 (3) |
C1—N1—C4—C3 | −1.0 (3) | C11—Fe1—C21—C22 | 125.0 (3) |
C10—N1—C4—C3 | 176.6 (2) | C15—Fe1—C21—C22 | 167.1 (3) |
C1—N1—C4—C5 | 178.1 (3) | C12—Fe1—C21—C22 | 81.2 (3) |
C10—N1—C4—C5 | −4.3 (4) | C13—Fe1—C21—C22 | 44.0 (4) |
C3—C4—C5—C6 | 1.3 (4) | C14—Fe1—C21—C22 | −155.4 (5) |
N1—C4—C5—C6 | −177.7 (3) | C23—Fe1—C21—C25 | 80.8 (3) |
C4—C5—C6—C7 | −0.9 (4) | C22—Fe1—C21—C25 | 118.8 (4) |
C5—C6—C7—C8 | 0.1 (5) | C24—Fe1—C21—C25 | 39.0 (3) |
C6—C7—C8—C3 | 0.4 (4) | C11—Fe1—C21—C25 | −116.1 (3) |
C4—C3—C8—C7 | 0.0 (4) | C15—Fe1—C21—C25 | −74.1 (3) |
N2—C3—C8—C7 | 178.6 (3) | C12—Fe1—C21—C25 | −159.9 (3) |
N2—C2—C11—C15 | 84.2 (3) | C13—Fe1—C21—C25 | 162.9 (3) |
N2—C2—C11—C12 | −93.4 (3) | C14—Fe1—C21—C25 | −36.6 (6) |
N2—C2—C11—Fe1 | 174.77 (15) | C25—C21—C22—C23 | 0.2 (4) |
C21—Fe1—C11—C15 | 126.7 (2) | Fe1—C21—C22—C23 | 60.2 (3) |
C23—Fe1—C11—C15 | −162.3 (5) | C25—C21—C22—Fe1 | −60.0 (2) |
C22—Fe1—C11—C15 | 166.9 (2) | C23—Fe1—C22—C21 | 118.4 (4) |
C25—Fe1—C11—C15 | 83.1 (3) | C25—Fe1—C22—C21 | 38.5 (3) |
C24—Fe1—C11—C15 | 49.7 (4) | C24—Fe1—C22—C21 | 82.6 (3) |
C12—Fe1—C11—C15 | −118.2 (2) | C11—Fe1—C22—C21 | −74.6 (3) |
C13—Fe1—C11—C15 | −80.54 (17) | C15—Fe1—C22—C21 | −40.9 (7) |
C14—Fe1—C11—C15 | −37.24 (15) | C12—Fe1—C22—C21 | −116.5 (3) |
C21—Fe1—C11—C12 | −115.1 (2) | C13—Fe1—C22—C21 | −159.7 (3) |
C23—Fe1—C11—C12 | −44.1 (6) | C14—Fe1—C22—C21 | 165.6 (3) |
C22—Fe1—C11—C12 | −74.9 (3) | C21—Fe1—C22—C23 | −118.4 (4) |
C25—Fe1—C11—C12 | −158.7 (2) | C25—Fe1—C22—C23 | −79.9 (4) |
C24—Fe1—C11—C12 | 167.9 (4) | C24—Fe1—C22—C23 | −35.7 (3) |
C15—Fe1—C11—C12 | 118.2 (2) | C11—Fe1—C22—C23 | 167.0 (3) |
C13—Fe1—C11—C12 | 37.63 (16) | C15—Fe1—C22—C23 | −159.3 (5) |
C14—Fe1—C11—C12 | 80.93 (16) | C12—Fe1—C22—C23 | 125.1 (3) |
C21—Fe1—C11—C2 | 6.7 (3) | C13—Fe1—C22—C23 | 82.0 (4) |
C23—Fe1—C11—C2 | 77.7 (6) | C14—Fe1—C22—C23 | 47.3 (5) |
C22—Fe1—C11—C2 | 46.9 (3) | C21—C22—C23—C24 | 0.0 (5) |
C25—Fe1—C11—C2 | −36.9 (3) | Fe1—C22—C23—C24 | 60.4 (3) |
C24—Fe1—C11—C2 | −70.3 (4) | C21—C22—C23—Fe1 | −60.3 (3) |
C15—Fe1—C11—C2 | −120.0 (3) | C21—Fe1—C23—C24 | −82.9 (3) |
C12—Fe1—C11—C2 | 121.8 (3) | C22—Fe1—C23—C24 | −120.3 (5) |
C13—Fe1—C11—C2 | 159.4 (2) | C25—Fe1—C23—C24 | −37.9 (3) |
C14—Fe1—C11—C2 | −157.3 (2) | C11—Fe1—C23—C24 | −160.1 (5) |
C15—C11—C12—C13 | 0.6 (3) | C15—Fe1—C23—C24 | 47.2 (5) |
C2—C11—C12—C13 | 178.6 (2) | C12—Fe1—C23—C24 | 165.4 (3) |
Fe1—C11—C12—C13 | −59.15 (19) | C13—Fe1—C23—C24 | 123.9 (3) |
C15—C11—C12—Fe1 | 59.78 (16) | C14—Fe1—C23—C24 | 81.6 (3) |
C2—C11—C12—Fe1 | −122.3 (2) | C21—Fe1—C23—C22 | 37.4 (3) |
C21—Fe1—C12—C13 | −156.4 (2) | C25—Fe1—C23—C22 | 82.3 (3) |
C23—Fe1—C12—C13 | −74.7 (3) | C24—Fe1—C23—C22 | 120.3 (5) |
C22—Fe1—C12—C13 | −115.3 (2) | C11—Fe1—C23—C22 | −39.8 (7) |
C25—Fe1—C12—C13 | 169.7 (4) | C15—Fe1—C23—C22 | 167.5 (3) |
C24—Fe1—C12—C13 | −45.6 (5) | C12—Fe1—C23—C22 | −74.3 (4) |
C11—Fe1—C12—C13 | 119.4 (2) | C13—Fe1—C23—C22 | −115.8 (3) |
C15—Fe1—C12—C13 | 80.91 (18) | C14—Fe1—C23—C22 | −158.2 (3) |
C14—Fe1—C12—C13 | 37.20 (16) | C22—C23—C24—C25 | −0.3 (5) |
C21—Fe1—C12—C11 | 84.2 (2) | Fe1—C23—C24—C25 | 59.4 (3) |
C23—Fe1—C12—C11 | 165.9 (2) | C22—C23—C24—Fe1 | −59.7 (3) |
C22—Fe1—C12—C11 | 125.3 (2) | C21—Fe1—C24—C23 | 80.1 (3) |
C25—Fe1—C12—C11 | 50.3 (4) | C22—Fe1—C24—C23 | 37.3 (3) |
C24—Fe1—C12—C11 | −164.9 (4) | C25—Fe1—C24—C23 | 119.6 (4) |
C15—Fe1—C12—C11 | −38.47 (14) | C11—Fe1—C24—C23 | 166.0 (3) |
C13—Fe1—C12—C11 | −119.4 (2) | C15—Fe1—C24—C23 | −157.9 (3) |
C14—Fe1—C12—C11 | −82.17 (16) | C12—Fe1—C24—C23 | −39.4 (6) |
C11—C12—C13—C14 | −0.7 (3) | C13—Fe1—C24—C23 | −74.0 (3) |
Fe1—C12—C13—C14 | −59.54 (19) | C14—Fe1—C24—C23 | −115.4 (3) |
C11—C12—C13—Fe1 | 58.87 (17) | C21—Fe1—C24—C25 | −39.6 (3) |
C21—Fe1—C13—C14 | 172.2 (3) | C23—Fe1—C24—C25 | −119.6 (4) |
C23—Fe1—C13—C14 | −115.3 (3) | C22—Fe1—C24—C25 | −82.4 (3) |
C22—Fe1—C13—C14 | −157.2 (2) | C11—Fe1—C24—C25 | 46.4 (5) |
C25—Fe1—C13—C14 | −46.8 (5) | C15—Fe1—C24—C25 | 82.4 (3) |
C24—Fe1—C13—C14 | −76.6 (3) | C12—Fe1—C24—C25 | −159.0 (4) |
C11—Fe1—C13—C14 | 81.72 (16) | C13—Fe1—C24—C25 | 166.4 (3) |
C15—Fe1—C13—C14 | 37.43 (15) | C14—Fe1—C24—C25 | 125.0 (3) |
C12—Fe1—C13—C14 | 119.6 (2) | C23—C24—C25—C21 | 0.4 (4) |
C21—Fe1—C13—C12 | 52.6 (4) | Fe1—C24—C25—C21 | 60.3 (2) |
C23—Fe1—C13—C12 | 125.1 (3) | C23—C24—C25—Fe1 | −59.9 (3) |
C22—Fe1—C13—C12 | 83.2 (2) | C22—C21—C25—C24 | −0.3 (4) |
C25—Fe1—C13—C12 | −166.4 (5) | Fe1—C21—C25—C24 | −60.8 (2) |
C24—Fe1—C13—C12 | 163.8 (2) | C22—C21—C25—Fe1 | 60.4 (3) |
C11—Fe1—C13—C12 | −37.87 (15) | C21—Fe1—C25—C24 | 116.4 (4) |
C15—Fe1—C13—C12 | −82.16 (17) | C23—Fe1—C25—C24 | 36.0 (3) |
C14—Fe1—C13—C12 | −119.6 (2) | C22—Fe1—C25—C24 | 79.5 (3) |
C12—C13—C14—C15 | 0.4 (3) | C11—Fe1—C25—C24 | −160.3 (3) |
Fe1—C13—C14—C15 | −58.71 (18) | C15—Fe1—C25—C24 | −116.7 (3) |
C12—C13—C14—Fe1 | 59.15 (19) | C12—Fe1—C25—C24 | 163.4 (3) |
C21—Fe1—C14—C13 | −167.1 (5) | C13—Fe1—C25—C24 | −39.1 (6) |
C23—Fe1—C14—C13 | 82.6 (3) | C14—Fe1—C25—C24 | −74.8 (3) |
C22—Fe1—C14—C13 | 49.6 (4) | C23—Fe1—C25—C21 | −80.4 (3) |
C25—Fe1—C14—C13 | 163.9 (2) | C22—Fe1—C25—C21 | −36.9 (2) |
C24—Fe1—C14—C13 | 122.7 (3) | C24—Fe1—C25—C21 | −116.4 (4) |
C11—Fe1—C14—C13 | −82.00 (16) | C11—Fe1—C25—C21 | 83.3 (3) |
C15—Fe1—C14—C13 | −119.7 (2) | C15—Fe1—C25—C21 | 127.0 (3) |
C12—Fe1—C14—C13 | −37.71 (16) | C12—Fe1—C25—C21 | 47.0 (5) |
C21—Fe1—C14—C15 | −47.4 (5) | C13—Fe1—C25—C21 | −155.5 (4) |
C23—Fe1—C14—C15 | −157.7 (3) | C14—Fe1—C25—C21 | 168.8 (2) |
C22—Fe1—C14—C15 | 169.4 (3) | N2—C1—C1E—C2E | −150.1 (3) |
C25—Fe1—C14—C15 | −76.4 (3) | N1—C1—C1E—C2E | 27.4 (4) |
C24—Fe1—C14—C15 | −117.5 (3) | C1—C1E—C2E—C31 | 171.4 (2) |
C11—Fe1—C14—C15 | 37.74 (15) | C1E—C2E—C31—C36 | −8.8 (4) |
C12—Fe1—C14—C15 | 82.03 (16) | C1E—C2E—C31—C32 | 173.6 (3) |
C13—Fe1—C14—C15 | 119.7 (2) | C36—C31—C32—C33 | 1.9 (4) |
C13—C14—C15—C11 | −0.1 (3) | C2E—C31—C32—C33 | 179.6 (3) |
Fe1—C14—C15—C11 | −58.98 (16) | C31—C32—C33—C34 | −0.8 (4) |
C13—C14—C15—Fe1 | 58.93 (19) | C32—C33—C34—C35 | −1.6 (4) |
C12—C11—C15—C14 | −0.4 (3) | C33—C34—C35—C36 | 2.9 (4) |
C2—C11—C15—C14 | −178.3 (2) | C33—C34—C35—C37 | −175.0 (3) |
Fe1—C11—C15—C14 | 59.52 (17) | C32—C31—C36—C35 | −0.5 (4) |
C12—C11—C15—Fe1 | −59.87 (16) | C2E—C31—C36—C35 | −178.1 (2) |
C2—C11—C15—Fe1 | 122.2 (2) | C34—C35—C36—C31 | −1.8 (4) |
C21—Fe1—C15—C14 | 165.8 (2) | C37—C35—C36—C31 | 176.1 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
C34—H34···Cg1i | 0.93 | 2.65 | 3.472 (3) | 149 |
Symmetry code: (i) x−3/2, −y+3/2, z. |
Experimental details
Crystal data | |
Chemical formula | [Fe(C5H5)(C23H22N2)]PF6 |
Mr | 592.34 |
Crystal system, space group | Monoclinic, P21/a |
Temperature (K) | 294 |
a, b, c (Å) | 13.515 (1), 12.8743 (10), 15.2839 (9) |
β (°) | 94.037 (5) |
V (Å3) | 2652.7 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.69 |
Crystal size (mm) | 0.29 × 0.25 × 0.17 |
Data collection | |
Diffractometer | Bruker P4 |
Absorption correction | ψ scan (North et al., 1968) |
Tmin, Tmax | 0.826, 0.889 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 8107, 6387, 3922 |
Rint | 0.025 |
(sin θ/λ)max (Å−1) | 0.661 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.047, 0.113, 1.01 |
No. of reflections | 6387 |
No. of parameters | 507 |
No. of restraints | 228 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.26, −0.28 |
Computer programs: XSCANS (Bruker, 1996), SHELXS97 (Sheldrick, 1997), ORTEX (McArdle, 1995) and PLATON (Spek, 2003), SHELXL97 (Sheldrick, 1997) and PREP8 (Ferguson, 1998).
D—H···A | D—H | H···A | D···A | D—H···A |
C34—H34···Cg1i | 0.93 | 2.65 | 3.472 (3) | 149 |
Symmetry code: (i) x−3/2, −y+3/2, z. |
Benzimidazole systems have attracted considerable attention in synthetic and structural as well as in applied biological research (Gallagher, Hanlon & Howarth, 2001; Howarth & Hanlon, 2001; Gallagher, Hanlon, Howarth & Thomas, 2001). The title compound (Figures 1–3) was obtained from a series of reactions involving synthesis of the parent N-Ferrocenylmethyl-2-(3-methylstyryl)benzimidazole from 2-(3-methylstyryl)benzimidazole and (trimethylammonium)ferrocenylmethyl iodide: subsequent treatment of the product with methyl iodide and replacement of the iodo salt with the hexafluorophosphate anion yields the [PF6]- salt.
Bond lengths and angles are normal and similar to those reported in the literature (Gallagher, Hanlon & Howarth, 2001; Gallagher, Hanlon, Howarth & Thomas, 2001). There is no disorder in the cation although the unsubstituted C5H5 ring displays large displacement parameters as could be expected given the geometry and the low energy barrier to rotation for Fe···η5-C5H5 π-bonding. The [PF6]- anion is disordered and a discussion of the treatment of this disorder is detailed below. The C3N2 5-membered imidazolium ring is almost orthogonal to the substituted C5H4 ring at 71.48 (10)° and deviates from co-planarity with the aromatic styryl C6 ring by 19.83 (10)°: the latter C6 ring is oriented at an angle of 85.52 (9)° to the C5H4 ring.
In the crystal structure there is only one intermolecular interaction of note (as detailed in Table 1) and involving C34—H34···Cg1i (where Cg1 is the ring centroid of C5H4 and the symmetry operation i = x - 3/2,3/2 - y,z). Several C—H···F contacts involving the disordered [PF6]- are present but are not important as they are relatively weak and involve the partial occupancy F atom sites.
Related structures include N-ferrocenylmethyl-2-ferrocenylbenzimidazole (Benito et al., 1995) and the salt N-ferrocenylmethyl-2-ferrocenyl-benzimidazolium tetrafluoroborate (Li et al., 1998) which differ from the title compound by having a ferrocenyl moiety at the 2-position of the benzimidazolium ring instead of the 3-methylstyryl group.