Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807053561/lh2536sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807053561/lh2536Isup2.hkl |
CCDC reference: 672576
Synthesis and chemical characteristion of the title compound N-Ferrocenylmethyl-2-(phenyl)benzimidazole [(C5H5)Fe(C5H4)CH2(C7H4N2)C6H5]
To a mixture of 2-phenylbenzimidazole (2.5 g, 13 mmol) and K2CO3 (2.7 g, 19.5 mmol) in CH3CN (150 ml) was added (trimethylammonium)ferrocenylmethyl iodide ([FcCH2N(CH3)3]+[I]-) (10.0 g, 13 mmol) (Pauson et al., 1966; Ferguson et al., 1994) and the mixture was heated to reflux temperatures for 12 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 an orange gum. The crude product was purified by column chromatography on silica gel using CH2Cl2:CH3OH (97:3) as eluent.
Yield 6.9 g (67%), m.p. 405–409 K (uncorrected). Compound (I) was obtained as a light orange solid. IR (KBr, ν cm-1) (>1500 cm-1): 3016, 1724, 1658.
1H NMR [400 MHz, δH (p.p.m.), CDCl3], 7.83 (m, 2H, Benz-H), 7.73 (m, 1H, aryl-H), 7.65 (m, 4H, aryl-H), 7.25 (m, 2H, Benz-H), 5.20 (s, 2H, Fc—CH2), 4.17 (m, 2H, cpd-H), 4.07 (s, 5H, cpd-H), 4.04 (m, 2H, cpd-H). 13C NMR [δC, CDCl3], 153.21, 138.11, 135.50, 131.27, 130.62, 127.12, 122.41, 122.05, 119.13, 111.28, 82.95, 68.85, 68.79, 68.15, 43.61.
The molecule crystallizes in the orthorhombic system; space group Pc21n (No. 33) or Pcmn (No. 62) from the systematic absences. Space group Pna21 chosen from successful solution and refinement analysis (after transformation from the non-standard setting).
In the refinement, all H atoms were allowed for as riding atoms with C—H distances of 0.93 Å and 0.97 Å for the aromatic and methylene C—H (at 294 K).
The top five peaks in the final difference maps (+0.60 to +0.40 e.Å-3) are within 0.90 Å of the Fe atom.
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: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997) and PREP8 (Ferguson, 1998).
[Fe(C5H5)(C19H15N2)] | Dx = 1.409 Mg m−3 |
Mr = 392.27 | Melting point: 407 K |
Orthorhombic, Pna21 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2c -2n | Cell parameters from 47 reflections |
a = 11.6323 (12) Å | θ = 7.0–35.6° |
b = 13.7738 (10) Å | µ = 0.83 mm−1 |
c = 11.5398 (7) Å | T = 294 K |
V = 1848.9 (3) Å3 | Block, red |
Z = 4 | 0.50 × 0.50 × 0.35 mm |
F(000) = 816 |
Bruker P4 diffractometer | 2435 reflections with I > 2σ(I) |
Radiation source: X-ray tube | Rint = 0.029 |
Graphite monochromator | θmax = 28.0°, θmin = 2.3° |
ω scans | h = 0→15 |
Absorption correction: ψ scan (North et al., 1968) | k = 0→18 |
Tmin = 0.683, Tmax = 0.761 | l = −15→1 |
3270 measured reflections | 3 standard reflections every 197 reflections |
2555 independent reflections | intensity decay: 0.5% |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.037 | H-atom parameters constrained |
wR(F2) = 0.093 | w = 1/[σ2(Fo2) + (0.0673P)2 + 0.0565P] where P = (Fo2 + 2Fc2)/3 |
S = 1.09 | (Δ/σ)max < 0.001 |
2555 reflections | Δρmax = 0.60 e Å−3 |
244 parameters | Δρmin = −0.26 e Å−3 |
1 restraint | Absolute structure: Flack (1983), with 207 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.02 (2) |
[Fe(C5H5)(C19H15N2)] | V = 1848.9 (3) Å3 |
Mr = 392.27 | Z = 4 |
Orthorhombic, Pna21 | Mo Kα radiation |
a = 11.6323 (12) Å | µ = 0.83 mm−1 |
b = 13.7738 (10) Å | T = 294 K |
c = 11.5398 (7) Å | 0.50 × 0.50 × 0.35 mm |
Bruker P4 diffractometer | 2435 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.029 |
Tmin = 0.683, Tmax = 0.761 | 3 standard reflections every 197 reflections |
3270 measured reflections | intensity decay: 0.5% |
2555 independent reflections |
R[F2 > 2σ(F2)] = 0.037 | H-atom parameters constrained |
wR(F2) = 0.093 | Δρmax = 0.60 e Å−3 |
S = 1.09 | Δρmin = −0.26 e Å−3 |
2555 reflections | Absolute structure: Flack (1983), with 207 Friedel pairs |
244 parameters | Absolute structure parameter: 0.02 (2) |
1 restraint |
x | y | z | Uiso*/Ueq | ||
Fe1 | 0.81242 (3) | 0.03598 (2) | 0.24237 (5) | 0.04083 (11) | |
N1 | 0.52595 (19) | −0.17950 (18) | 0.5475 (2) | 0.0498 (5) | |
N2 | 0.71032 (18) | −0.15801 (17) | 0.4965 (2) | 0.0440 (5) | |
C1 | 0.6004 (2) | −0.18169 (18) | 0.4623 (3) | 0.0440 (5) | |
C2 | 0.81119 (19) | −0.1389 (2) | 0.4244 (3) | 0.0455 (6) | |
C3 | 0.7034 (2) | −0.1362 (2) | 0.6134 (3) | 0.0464 (5) | |
C4 | 0.5876 (2) | −0.15079 (19) | 0.6437 (3) | 0.0467 (5) | |
C5 | 0.5527 (3) | −0.1356 (2) | 0.7572 (3) | 0.0566 (7) | |
C6 | 0.6312 (3) | −0.1046 (2) | 0.8361 (3) | 0.0638 (8) | |
C7 | 0.7468 (3) | −0.0896 (3) | 0.8057 (3) | 0.0680 (9) | |
C8 | 0.7846 (3) | −0.1045 (3) | 0.6928 (3) | 0.0606 (8) | |
C11 | 0.8254 (2) | −0.03259 (19) | 0.4000 (3) | 0.0437 (6) | |
C12 | 0.7383 (3) | 0.0407 (2) | 0.4034 (3) | 0.0512 (6) | |
C13 | 0.7909 (4) | 0.1313 (2) | 0.3750 (3) | 0.0649 (8) | |
C14 | 0.9097 (3) | 0.1143 (2) | 0.3543 (3) | 0.0635 (8) | |
C15 | 0.9307 (2) | 0.0137 (3) | 0.3697 (3) | 0.0567 (7) | |
C21 | 0.7798 (3) | −0.0671 (2) | 0.1200 (3) | 0.0588 (7) | |
C22 | 0.6901 (3) | 0.0032 (3) | 0.1212 (3) | 0.0591 (7) | |
C23 | 0.7390 (3) | 0.0943 (2) | 0.0966 (3) | 0.0557 (7) | |
C24 | 0.8585 (3) | 0.0820 (2) | 0.0807 (3) | 0.0542 (7) | |
C25 | 0.8831 (3) | −0.0172 (2) | 0.0952 (3) | 0.0564 (7) | |
C31 | 0.5694 (2) | −0.2044 (2) | 0.3413 (2) | 0.0484 (6) | |
C32 | 0.6256 (3) | −0.2752 (3) | 0.2775 (3) | 0.0641 (8) | |
C33 | 0.5939 (4) | −0.2929 (4) | 0.1637 (4) | 0.0829 (13) | |
C34 | 0.5049 (5) | −0.2420 (4) | 0.1146 (4) | 0.0933 (14) | |
C35 | 0.4467 (4) | −0.1738 (4) | 0.1776 (4) | 0.0842 (13) | |
C36 | 0.4770 (3) | −0.1544 (3) | 0.2923 (3) | 0.0632 (8) | |
H2A | 0.8036 | −0.1737 | 0.3518 | 0.055* | |
H2B | 0.8793 | −0.1629 | 0.4635 | 0.055* | |
H5 | 0.4768 | −0.1464 | 0.7790 | 0.068* | |
H6 | 0.6079 | −0.0930 | 0.9119 | 0.077* | |
H7 | 0.7989 | −0.0695 | 0.8619 | 0.082* | |
H8 | 0.8606 | −0.0936 | 0.6715 | 0.073* | |
H12 | 0.6611 | 0.0311 | 0.4211 | 0.061* | |
H13 | 0.7539 | 0.1910 | 0.3707 | 0.078* | |
H14 | 0.9641 | 0.1609 | 0.3342 | 0.076* | |
H15 | 1.0014 | −0.0169 | 0.3614 | 0.068* | |
H21 | 0.7719 | −0.1334 | 0.1331 | 0.071* | |
H22 | 0.6128 | −0.0090 | 0.1357 | 0.071* | |
H23 | 0.6993 | 0.1527 | 0.0915 | 0.067* | |
H24 | 0.9113 | 0.1307 | 0.0639 | 0.065* | |
H25 | 0.9555 | −0.0454 | 0.0893 | 0.068* | |
H32 | 0.6848 | −0.3108 | 0.3112 | 0.077* | |
H33 | 0.6330 | −0.3394 | 0.1205 | 0.100* | |
H34 | 0.4841 | −0.2540 | 0.0381 | 0.112* | |
H35 | 0.3862 | −0.1400 | 0.1436 | 0.101* | |
H36 | 0.4364 | −0.1088 | 0.3354 | 0.076* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Fe1 | 0.03973 (17) | 0.03969 (17) | 0.04307 (18) | −0.00482 (11) | −0.00106 (18) | 0.00165 (16) |
N1 | 0.0424 (10) | 0.0536 (11) | 0.0533 (11) | −0.0006 (9) | 0.0036 (9) | −0.0052 (10) |
N2 | 0.0394 (9) | 0.0446 (11) | 0.0479 (11) | −0.0005 (8) | 0.0016 (9) | 0.0027 (9) |
C1 | 0.0422 (11) | 0.0374 (11) | 0.0524 (12) | −0.0008 (10) | 0.0007 (11) | 0.0003 (10) |
C2 | 0.0395 (12) | 0.0473 (13) | 0.0496 (13) | 0.0019 (10) | 0.0035 (10) | 0.0042 (11) |
C3 | 0.0469 (13) | 0.0450 (12) | 0.0472 (13) | −0.0029 (10) | −0.0008 (11) | 0.0051 (11) |
C4 | 0.0425 (12) | 0.0437 (12) | 0.0541 (14) | 0.0001 (10) | 0.0037 (11) | −0.0008 (11) |
C5 | 0.0570 (14) | 0.0573 (14) | 0.0556 (18) | 0.0027 (12) | 0.0117 (13) | −0.0037 (13) |
C6 | 0.079 (2) | 0.0670 (18) | 0.0453 (14) | 0.0004 (17) | 0.0054 (15) | −0.0046 (13) |
C7 | 0.071 (2) | 0.082 (2) | 0.0516 (17) | −0.0148 (18) | −0.0088 (17) | −0.0010 (15) |
C8 | 0.0550 (15) | 0.0713 (19) | 0.0554 (15) | −0.0145 (15) | −0.0069 (15) | 0.0059 (15) |
C11 | 0.0456 (13) | 0.0452 (15) | 0.0405 (13) | −0.0041 (10) | −0.0001 (11) | 0.0026 (10) |
C12 | 0.0565 (16) | 0.0510 (16) | 0.0459 (14) | 0.0001 (12) | 0.0054 (13) | −0.0011 (11) |
C13 | 0.096 (2) | 0.0422 (14) | 0.0565 (17) | −0.0031 (15) | 0.0000 (17) | −0.0065 (13) |
C14 | 0.0739 (19) | 0.0588 (16) | 0.0580 (16) | −0.0298 (15) | −0.0114 (15) | −0.0013 (14) |
C15 | 0.0453 (13) | 0.0701 (18) | 0.0545 (15) | −0.0166 (13) | −0.0132 (12) | 0.0096 (14) |
C21 | 0.083 (2) | 0.0484 (14) | 0.0450 (14) | −0.0119 (16) | −0.0039 (15) | −0.0021 (12) |
C22 | 0.0532 (16) | 0.071 (2) | 0.0530 (16) | −0.0131 (14) | −0.0077 (13) | −0.0035 (16) |
C23 | 0.0563 (16) | 0.0576 (16) | 0.0533 (14) | 0.0049 (14) | −0.0067 (13) | 0.0069 (13) |
C24 | 0.0517 (14) | 0.0581 (16) | 0.0527 (15) | −0.0075 (14) | 0.0048 (12) | 0.0105 (13) |
C25 | 0.0615 (18) | 0.0568 (15) | 0.0509 (15) | 0.0149 (15) | 0.0064 (15) | 0.0019 (13) |
C31 | 0.0476 (13) | 0.0488 (12) | 0.0488 (13) | −0.0123 (11) | 0.0005 (11) | −0.0016 (10) |
C32 | 0.0659 (18) | 0.0621 (17) | 0.0642 (18) | −0.0134 (15) | 0.0092 (14) | −0.0154 (15) |
C33 | 0.084 (2) | 0.093 (3) | 0.072 (2) | −0.037 (2) | 0.015 (2) | −0.031 (2) |
C34 | 0.109 (3) | 0.116 (3) | 0.0549 (17) | −0.058 (3) | −0.006 (2) | −0.010 (2) |
C35 | 0.082 (3) | 0.094 (3) | 0.076 (2) | −0.034 (2) | −0.031 (2) | 0.022 (2) |
C36 | 0.0640 (17) | 0.0597 (18) | 0.0658 (18) | −0.0129 (15) | −0.0125 (16) | 0.0054 (15) |
Fe1—C11 | 2.055 (3) | C22—C23 | 1.407 (5) |
Fe1—C12 | 2.050 (3) | C23—C24 | 1.411 (4) |
Fe1—C13 | 2.031 (3) | C24—C25 | 1.407 (5) |
Fe1—C14 | 2.028 (3) | C31—C32 | 1.385 (4) |
Fe1—C15 | 2.036 (3) | C31—C36 | 1.396 (4) |
Fe1—C21 | 2.038 (3) | C32—C33 | 1.386 (6) |
Fe1—C22 | 2.046 (3) | C33—C34 | 1.373 (8) |
Fe1—C23 | 2.050 (3) | C34—C35 | 1.367 (7) |
Fe1—C24 | 2.041 (3) | C35—C36 | 1.397 (5) |
Fe1—C25 | 2.024 (3) | C2—H2A | 0.9700 |
N1—C1 | 1.310 (4) | C2—H2B | 0.9700 |
N1—C4 | 1.379 (4) | C5—H5 | 0.9300 |
N2—C1 | 1.378 (3) | C6—H6 | 0.9300 |
N2—C2 | 1.462 (3) | C7—H7 | 0.9300 |
N2—C3 | 1.384 (4) | C8—H8 | 0.9300 |
C1—C31 | 1.476 (4) | C12—H12 | 0.9300 |
C2—C11 | 1.501 (4) | C13—H13 | 0.9300 |
C3—C4 | 1.406 (4) | C14—H14 | 0.9300 |
C3—C8 | 1.386 (4) | C15—H15 | 0.9300 |
C4—C5 | 1.388 (4) | C21—H21 | 0.9300 |
C5—C6 | 1.358 (5) | C22—H22 | 0.9300 |
C6—C7 | 1.406 (6) | C23—H23 | 0.9300 |
C7—C8 | 1.390 (5) | C24—H24 | 0.9300 |
C11—C12 | 1.431 (4) | C25—H25 | 0.9300 |
C11—C15 | 1.424 (4) | C32—H32 | 0.9300 |
C12—C13 | 1.428 (4) | C33—H33 | 0.9300 |
C13—C14 | 1.422 (5) | C34—H34 | 0.9300 |
C14—C15 | 1.418 (5) | C35—H35 | 0.9300 |
C21—C22 | 1.423 (5) | C36—H36 | 0.9300 |
C21—C25 | 1.414 (5) | ||
C25—Fe1—C14 | 120.02 (16) | C13—C14—Fe1 | 69.63 (18) |
C25—Fe1—C13 | 156.34 (16) | C14—C15—C11 | 108.7 (3) |
C14—Fe1—C13 | 41.00 (15) | C14—C15—Fe1 | 69.29 (17) |
C25—Fe1—C15 | 106.06 (15) | C11—C15—Fe1 | 70.35 (17) |
C14—Fe1—C15 | 40.84 (14) | C25—C21—C22 | 107.1 (3) |
C13—Fe1—C15 | 68.71 (16) | C25—C21—Fe1 | 69.11 (19) |
C25—Fe1—C21 | 40.72 (15) | C22—C21—Fe1 | 69.88 (19) |
C14—Fe1—C21 | 156.31 (17) | C23—C22—C21 | 108.0 (3) |
C13—Fe1—C21 | 161.63 (15) | C23—C22—Fe1 | 70.10 (18) |
C15—Fe1—C21 | 121.40 (15) | C21—C22—Fe1 | 69.34 (18) |
C25—Fe1—C24 | 40.48 (14) | C22—C23—C24 | 108.5 (3) |
C14—Fe1—C24 | 105.66 (14) | C22—C23—Fe1 | 69.72 (19) |
C13—Fe1—C24 | 121.30 (15) | C24—C23—Fe1 | 69.49 (17) |
C15—Fe1—C24 | 121.92 (13) | C25—C24—C23 | 107.5 (3) |
C21—Fe1—C24 | 68.44 (14) | C25—C24—Fe1 | 69.10 (17) |
C25—Fe1—C22 | 68.20 (15) | C23—C24—Fe1 | 70.17 (17) |
C14—Fe1—C22 | 160.24 (16) | C24—C25—C21 | 108.9 (3) |
C13—Fe1—C22 | 124.90 (16) | C24—C25—Fe1 | 70.42 (17) |
C15—Fe1—C22 | 158.44 (16) | C21—C25—Fe1 | 70.17 (18) |
C21—Fe1—C22 | 40.78 (16) | C32—C31—C36 | 119.7 (3) |
C24—Fe1—C22 | 68.07 (14) | C32—C31—C1 | 122.4 (3) |
C25—Fe1—C12 | 160.58 (12) | C36—C31—C1 | 117.8 (3) |
C14—Fe1—C12 | 68.94 (14) | C31—C32—C33 | 120.1 (4) |
C13—Fe1—C12 | 40.96 (13) | C34—C33—C32 | 120.1 (4) |
C15—Fe1—C12 | 68.59 (13) | C35—C34—C33 | 120.3 (4) |
C21—Fe1—C12 | 124.88 (13) | C34—C35—C36 | 120.7 (5) |
C24—Fe1—C12 | 158.24 (13) | C31—C36—C35 | 118.9 (4) |
C22—Fe1—C12 | 109.52 (14) | N2—C2—H2A | 109.3 |
C25—Fe1—C23 | 67.80 (14) | C11—C2—H2A | 109.3 |
C14—Fe1—C23 | 123.13 (15) | N2—C2—H2B | 109.3 |
C13—Fe1—C23 | 108.29 (15) | C11—C2—H2B | 109.3 |
C15—Fe1—C23 | 158.81 (13) | H2A—C2—H2B | 107.9 |
C21—Fe1—C23 | 68.08 (14) | C6—C5—H5 | 120.5 |
C24—Fe1—C23 | 40.35 (13) | C4—C5—H5 | 120.5 |
C22—Fe1—C23 | 40.18 (15) | C5—C6—H6 | 119.3 |
C12—Fe1—C23 | 123.80 (13) | C7—C6—H6 | 119.3 |
C25—Fe1—C11 | 123.12 (12) | C8—C7—H7 | 119.5 |
C14—Fe1—C11 | 68.90 (13) | C6—C7—H7 | 119.5 |
C13—Fe1—C11 | 68.87 (13) | C3—C8—H8 | 121.6 |
C15—Fe1—C11 | 40.76 (11) | C7—C8—H8 | 121.6 |
C21—Fe1—C11 | 107.86 (13) | C13—C12—H12 | 126.1 |
C24—Fe1—C11 | 158.77 (12) | C11—C12—H12 | 126.1 |
C22—Fe1—C11 | 123.68 (14) | Fe1—C12—H12 | 126.9 |
C12—Fe1—C11 | 40.81 (12) | C14—C13—H13 | 125.9 |
C23—Fe1—C11 | 159.53 (12) | C12—C13—H13 | 125.9 |
C1—N1—C4 | 105.5 (2) | Fe1—C13—H13 | 126.1 |
C1—N2—C2 | 128.7 (2) | C15—C14—H14 | 126.1 |
C1—N2—C3 | 106.1 (2) | C13—C14—H14 | 126.1 |
C2—N2—C3 | 124.2 (2) | Fe1—C14—H14 | 126.0 |
N1—C1—N2 | 113.1 (2) | C14—C15—H15 | 125.6 |
N1—C1—C31 | 123.6 (2) | C11—C15—H15 | 125.6 |
N2—C1—C31 | 123.2 (2) | Fe1—C15—H15 | 126.3 |
N2—C2—C11 | 111.8 (2) | C25—C21—H21 | 126.4 |
N2—C3—C4 | 105.5 (3) | C22—C21—H21 | 126.4 |
N2—C3—C8 | 132.3 (3) | Fe1—C21—H21 | 126.1 |
C4—C3—C8 | 122.2 (3) | C23—C22—H22 | 126.0 |
N1—C4—C3 | 109.8 (3) | C21—C22—H22 | 126.0 |
N1—C4—C5 | 130.6 (3) | Fe1—C22—H22 | 126.1 |
C3—C4—C5 | 119.6 (3) | C22—C23—H23 | 125.7 |
C6—C5—C4 | 118.9 (3) | C24—C23—H23 | 125.7 |
C5—C6—C7 | 121.5 (3) | Fe1—C23—H23 | 126.6 |
C6—C7—C8 | 121.0 (3) | C25—C24—H24 | 126.2 |
C3—C8—C7 | 116.8 (3) | C23—C24—H24 | 126.2 |
C12—C11—C15 | 107.4 (3) | Fe1—C24—H24 | 126.1 |
C15—C11—C2 | 125.3 (3) | C24—C25—H25 | 125.6 |
C12—C11—C2 | 127.3 (2) | C21—C25—H25 | 125.6 |
C15—C11—Fe1 | 68.90 (18) | Fe1—C25—H25 | 125.4 |
C12—C11—Fe1 | 69.41 (17) | C31—C32—H32 | 119.9 |
C2—C11—Fe1 | 127.4 (2) | C33—C32—H32 | 119.9 |
C13—C12—C11 | 107.8 (3) | C34—C33—H33 | 120.0 |
C13—C12—Fe1 | 68.8 (2) | C32—C33—H33 | 120.0 |
C11—C12—Fe1 | 69.77 (18) | C35—C34—H34 | 119.8 |
C14—C13—C12 | 108.2 (3) | C33—C34—H34 | 119.8 |
C14—C13—Fe1 | 69.37 (19) | C34—C35—H35 | 119.6 |
C12—C13—Fe1 | 70.22 (18) | C36—C35—H35 | 119.6 |
C15—C14—C13 | 107.9 (3) | C31—C36—H36 | 120.5 |
C15—C14—Fe1 | 69.87 (17) | C35—C36—H36 | 120.5 |
C4—N1—C1—N2 | 1.4 (3) | C4—C5—C6—C7 | −1.3 (5) |
C4—N1—C1—C31 | −176.9 (3) | C5—C6—C7—C8 | 1.2 (6) |
C3—N2—C1—N1 | −1.8 (3) | N2—C3—C8—C7 | 180.0 (3) |
C2—N2—C1—N1 | −170.1 (3) | C4—C3—C8—C7 | 1.5 (5) |
C3—N2—C1—C31 | 176.5 (2) | C6—C7—C8—C3 | −1.2 (6) |
C2—N2—C1—C31 | 8.2 (4) | N2—C2—C11—C15 | 156.6 (3) |
C1—N2—C2—C11 | 93.8 (3) | N2—C2—C11—C12 | −22.7 (4) |
C3—N2—C2—C11 | −72.6 (3) | N2—C2—C11—Fe1 | −114.2 (3) |
C1—N2—C3—C8 | −177.3 (3) | N1—C1—C31—C32 | −127.7 (3) |
C2—N2—C3—C8 | −8.3 (5) | N2—C1—C31—C32 | 54.1 (4) |
C1—N2—C3—C4 | 1.4 (3) | N1—C1—C31—C36 | 49.9 (4) |
C2—N2—C3—C4 | 170.4 (2) | N2—C1—C31—C36 | −128.2 (3) |
C1—N1—C4—C5 | 179.5 (3) | C36—C31—C32—C33 | 3.1 (5) |
C1—N1—C4—C3 | −0.4 (3) | C1—C31—C32—C33 | −179.3 (3) |
N2—C3—C4—N1 | −0.6 (3) | C31—C32—C33—C34 | −1.5 (6) |
C8—C3—C4—N1 | 178.2 (3) | C32—C33—C34—C35 | −0.3 (6) |
N2—C3—C4—C5 | 179.4 (3) | C33—C34—C35—C36 | 0.4 (6) |
C8—C3—C4—C5 | −1.7 (4) | C32—C31—C36—C35 | −2.9 (4) |
N1—C4—C5—C6 | −178.3 (3) | C1—C31—C36—C35 | 179.4 (3) |
C3—C4—C5—C6 | 1.6 (4) | C34—C35—C36—C31 | 1.2 (5) |
D—H···A | D—H | H···A | D···A | D—H···A |
C23—H23···N1i | 0.93 | 2.69 | 3.346 (4) | 128 |
C24—H24···Cgii | 0.93 | 2.90 | 3.556 (3) | 129 |
Symmetry codes: (i) −x+1, −y, z−1/2; (ii) −x+3/2, y+1/2, z−1/2. |
Experimental details
Crystal data | |
Chemical formula | [Fe(C5H5)(C19H15N2)] |
Mr | 392.27 |
Crystal system, space group | Orthorhombic, Pna21 |
Temperature (K) | 294 |
a, b, c (Å) | 11.6323 (12), 13.7738 (10), 11.5398 (7) |
V (Å3) | 1848.9 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.83 |
Crystal size (mm) | 0.50 × 0.50 × 0.35 |
Data collection | |
Diffractometer | Bruker P4 diffractometer |
Absorption correction | ψ scan (North et al., 1968) |
Tmin, Tmax | 0.683, 0.761 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3270, 2555, 2435 |
Rint | 0.029 |
(sin θ/λ)max (Å−1) | 0.661 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.037, 0.093, 1.09 |
No. of reflections | 2555 |
No. of parameters | 244 |
No. of restraints | 1 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.60, −0.26 |
Absolute structure | Flack (1983), with 207 Friedel pairs |
Absolute structure parameter | 0.02 (2) |
Computer programs: XSCANS (Bruker, 1996), SHELXS97 (Sheldrick, 1997), PLATON (Spek, 2003), SHELXL97 (Sheldrick, 1997) and PREP8 (Ferguson, 1998).
D—H···A | D—H | H···A | D···A | D—H···A |
C23—H23···N1i | 0.93 | 2.69 | 3.346 (4) | 128 |
C24—H24···Cgii | 0.93 | 2.90 | 3.556 (3) | 129 |
Symmetry codes: (i) −x+1, −y, z−1/2; (ii) −x+3/2, y+1/2, z−1/2. |
Benzimidazole systems continue to attract much attention in chemical synthesis, structural science and applied biological research (Li et al., 1998; Gallagher, Hanlon & Howarth, 2001; Howarth & Hanlon, 2001; Gallagher, Hanlon, Howarth & Thomas, 2001; Kazak et al., 2006). The title compound, 1-Ferrocenylmethyl-2-(phenyl)-1H-1,3-benzimidazole (Figures 1–3), is obtained from a series of reactions involving the chemical synthesis of 1-Ferrocenylmethyl-2-(phenyl)benzimidazole from 2-(phenyl)benzimidazole and (trimethylammonium)ferrocenylmethyl iodide (Pauson et al., 1966; Ferguson et al., 1994).
Bond lengths in the title compound 1-Ferrocenylmethyl-2-(phenyl)-1H-1,3-benzimidazole are normal and similar to our previously reported ferrocene derivatives (Gallagher, Hanlon & Howarth, 2001, 2007a,b; Gallagher, Hanlon, Howarth & Thomas, 2001).
The major conformation features are the orientation of the benzimidazole group to the ferrocenyl and phenyl rings. The five-membered imidazolyl ring forms dihedral angles of 84.71 (13)° and 52.12 (11)° with the substituted C5H4 and phenyl rings, respectively. These data ressemble the values 84.37 (9)°, 56.21 (8)° for a related 3-Cl substituted benzene ring system (Gallagher, Hanlon, Howarth & Thomas, 2001) and 88.61 (8)°, 42.15 (6)° for a 3,5-dimethyl substituted benzene ring system (Gallagher et al., 2007b). Two related methoxy substituted derivatives differ somewhat from these values with [78.07 (8)°, 40.22 (9)°] and [73.86 (8)°, 70.02 (7)°] for a 4-OMe and a 3,4-(OMe)2 pair (Gallagher, Hanlon & Howarth, 2001).
The angles at N2 differ, with C2—N2—(C1/C3) 128.7 (2)°, 124.2 (2)° (a 4.5° difference) and C1—N2—C3 is 106.1 (2)°. The C2—N2—C1/C3 difference is 4°, 5° in the 3-Cl, 3,5-Me2 derivatives, though extending to 7° in the 4-OMe and closing to 0° in the 3,4-(OMe)2 system (Gallagher, Hanlon & Howarth, 2001), thus displaying a significant variation in the angles at the N2 atom by remote atom site variation on the benzene ring {C31,···,C36}. No clear trend has been established and it is most probably due to the different crystal packing forces at the ferrocenyl–benzimidazole C2 bridge atom that effects subtle differences in the C2—N2—C1/C3 angles. For the C11—C2—N2 angles a small variation of ca 1° is observed for our five previously reported structures and for Fe1—C11—C2 the range is similarly small (127.4 (2)° for the title compound), 127.81 (13)° (3-Cl) and 128.43 (13)° for the 3,5-(Me)2 systems. A greater deviation in the bond angle data values is 126.56 (13)° [for 4-(OMe)] and 125.74 (15)° [for 3,4-(OMe)2], these latter two systems also display the greatest differences at N2 (see above). A wide range of angles is observed between the imidazolyl and C6 aromatic rings in these structures due to a lack of steric hindrance and differing crystal packing forces about the C1—C31 bond.
Of interest is the fact that there are no strong intermolecular interactions in the crystal structure of the title compound and the optimal acceptor N1 only has a closest H23 atom at a distance of 2.69 Å (Table 1). A weak cpC24—H24···π(C═N) is also present with a C24···Cgi distance of 3.556 (3) Å, where Cg is the ring centroid of the C3N2 ring and the symmetry operation i = 3/2 - x, y + 1/2, z - 1/2: the closest C24···(C1,N1) distances are 3.564 (4), 3.572 (4) Å. The corresponding H24···(C1,N1) distances and C24—H24···(C1,N1) angles are 2.72, 2.84 Å and 136°, 152°, respectively. We have noted that in the absence of strong donors and acceptors that the primary interactions in the related derivatives arise from weaker interactions and contacts e.g. C—H···π(arene).
The obvious lack of formation (via C—H···N interactions) of a centrosymmetric R22(8) type hydrogen bonded ring involving molecules of the title compound (about inversion centres) can be explained by the presence of a myriad of weak C—H···π(arene) contacts (the shortest is a C—H···π(C═N) interaction, Table 1) which overall are more energetically favoured in the crystal structure than a series of localized 'hydrogen bonded dimers'. Weak interactions involving the N1 atom is a related 3,5-dimethylbenzene derivative have also been commented upon by us (Gallagher, Hanlon, Howarth, 2007) though the C···N contact distance is long at 3.658 (2) Å.
Examination of the structure with PLATON (Spek, 2003) showed that there were no solvent accessible voids in the crystal lattice.