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
Key indicators
- Single-crystal X-ray study
- T = 294 K
- Mean (C-C) = 0.005 Å
- R factor = 0.037
- wR factor = 0.093
- Data-to-parameter ratio = 10.5
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT062_ALERT_4_C Rescale T(min) & T(max) by ..................... 0.98 PLAT094_ALERT_2_C Ratio of Maximum / Minimum Residual Density .... 2.27 PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for Fe1 PLAT480_ALERT_4_C Long H...A H-Bond Reported H23 .. N1 .. 2.69 Ang.
Alert level G REFLT03_ALERT_4_G WARNING: Large fraction of Friedel related reflns may be needed to determine absolute structure From the CIF: _diffrn_reflns_theta_max 28.00 From the CIF: _reflns_number_total 2555 Count of symmetry unique reflns 2348 Completeness (_total/calc) 108.82% TEST3: Check Friedels for noncentro structure Estimate of Friedel pairs measured 207 Fraction of Friedel pairs measured 0.088 Are heavy atom types Z>Si present yes PLAT794_ALERT_5_G Check Predicted Bond Valency for Fe1 (3) 3.87 PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 1
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 4 ALERT level C = Check and explain 3 ALERT level G = General alerts; check 0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 2 ALERT type 2 Indicator that the structure model may be wrong or deficient 1 ALERT type 3 Indicator that the structure quality may be low 3 ALERT type 4 Improvement, methodology, query or suggestion 1 ALERT type 5 Informative message, check
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.