2-(3,5-Dimethyl­benzene)-1-ferrocenylmethyl-1H-1,3-benzimidazole

Gallagher, J.F.; Hanlon, K.; Howarth, J.

doi:10.1107/S1600536807049549

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2-(3,5-Dimethylbenzene)-1-ferrocenylmethyl-1H-1,3-benzimidazole

J. F. Gallagher, K. Hanlon and J. Howarth

In the title molecule, [Fe(C₅H₅)(C₂₁H₁₉N₂)], the five-membered imidazole ring forms dihedral angles of 88.61 (8) and 42.15 (6)° with the substituted cyclopentadienyl and dimethyl-substituted benzene rings, respectively. In the crystal structure, there is an Nsp²

H contact and a modest C—H

π(arene) interaction involving the benzene ring of the benzimidizole system.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807049549/lh2528sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536807049549/lh2528Isup2.hkl Contains datablock I

CCDC reference: 667173

checkCIF report

Key indicators

Single-crystal X-ray study
T = 294 K
Mean (C-C) = 0.003 Å
R factor = 0.037
wR factor = 0.099
Data-to-parameter ratio = 18.9

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT230_ALERT_2_B Hirshfeld Test Diff for    C21    -   C22     ..       9.44 su
PLAT230_ALERT_2_B Hirshfeld Test Diff for    C22    -   C23     ..      10.01 su

Alert level C
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for        C22
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        Fe1
PLAT480_ALERT_4_C Long H...A H-Bond Reported H2B    ..  N1      ..       2.75 Ang.
PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd.  #          1
              C26 H24 Fe N2

Alert level G
PLAT794_ALERT_5_G Check Predicted Bond Valency for Fe1         (3)       3.93

   0 ALERT level A = In general: serious problem
   2 ALERT level B = Potentially serious problem
   4 ALERT level C = Check and explain
   1 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   4 ALERT type 2 Indicator that the structure model may be wrong or deficient
   0 ALERT type 3 Indicator that the structure quality may be low
   2 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check

Comment top

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 (I) (Figs. 1–2) is obtained from a series of reactions involving synthesis of N-Ferrocenylmethyl-2-(3,5-dimethylbenzene)benzimidazole from 2-(3,5-dimethylbenzene)benzimidazole and (trimethylammonium)ferrocenylmethyl iodide.

Bond lengths and angles in the title compound 1-Ferrocenylmethyl-2-(3,5-dimethylbenzene)-1H-1,3-benzimidazole are normal and similar to previously reported ferrocene systems. Of note is the fact that the five-membered imidazole ring forms dihedral angles of 88.61 (8)° and 42.15 (6)° with the substituted C₅H₄ and 3,4-dimethyl substituted benzene rings, respectively. The former is similar to the 71.48 (10)° observed in a related cationic derivative (Gallagher et al., 2007) and 84.37 (9)° in the neutral 3-chlorophenyl derivative (Gallagher, Hanlon, Howarth & Thomas, 2001). Similar data of 78.07 (8)° and 73.86 (8)° are observed in both a methoxy and dimethoxy derivative (Gallagher, Hanlon & Howarth, 2001). These data highlight that the most important dihedral angle in these systems is defined by the imidazole/C₅H₄ angle which is remarkably invariant in a series of closely related systems. This is due to steric constraints at the hinge atom C2, between the 5-membered imidazole ring and the substituted C₅H₄ ring which does not facilitate for opening or closing of the rings attached at C2. A wide range of angles between the imidazole and C₆ aromatic rings in these structures is due to a lack of steric hindrance and crystal packing forces about the C—C bond.

Of interest is the fact that there are no strong intermolecular interactions in the crystal structure and the optimal acceptor N1 only has a closest H2B atom at a distance of 2.75 Å. A weak C22—H22···Cgⁱ is also present with a C···Cgⁱ of 3.764 (3) Å, where Cg is the ring centroid of the C3–C8 ring and the symmetry operation i = 1 - x, y + 1/2, -z + 1/2.

Examination of the structure with PLATON (Spek, 2003) showed that there were no solvent accessible voids in the crystal lattice unlike the cationic 3-methylstyryl derivative where the hexafluorophosphate anion is located in a void and adopts four orientations each with equal 0.25 site occupancy (Gallagher et al., 2007).

Related literature top

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); Kazak et al. (2006); Gallagher et al. (2007). For the chemical synthesis and crystal structure of [FcCH₂N(CH₃)₃]⁺[I]^- see: Pauson et al. (1966); Ferguson et al. (1994).

Experimental top

Synthesis of the neutral starting material N-Ferrocenylmethyl-2-(3,5-dimethylbenzene)benzimidazole [(C₅H₅)Fe(C₅H₄)CH₂(C₇H₄N₂)C₆H₄(CH₃)₂]

To a mixture of 2-(3,5-dimethylbenzene)benzimidazole (4.0 g, 18 mmol) and K₂CO₃ (3.73 g, 27 mmol) in CH₃CN (150 ml) was added (trimethylammonium)ferrocenylmethyl iodide ([FcCH₂N(CH₃)₃]⁺[I]^-) (7.29 g, 18 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 a brown gum. The crude product was purified by column chromatography on silica gel using CH₂Cl₂:CH₃OH (97:3) as eluent.

Yield 5.3 g (70%), m.p. 407–411 K (uncorrected). Compound (I) was obtained as a light orange solid. IR (KBr, ν cm^-1) (>1500 cm^-1): 3017, 2399, 1709, 1641.

¹H NMR [400 MHz, δH (p.p.m.), CDCl₃], 7.65 (m, 2H, benz-H), 7.43 (m, 2H, aryl-H), 7.27–7.22 (m, 3H, benz-H + aryl-H), 5.32 (s, 2H, Fc—CH₂), 4.09 (s, 5H, cpd-H), 4.03 (m, 2H, cpd-H), 4.01 (m, 2H, cpd-H), 2.42 (s, 6H, 2 x CH₃). ¹³C NMR [δC, CDCl₃], 153.36, 142.82, 138.26, 135.77, 131.45, 130.79, 127.41, 122.66, 122.27, 119.35, 111.48, 83.74, 68.97, 68.87, 68.12, 43.84, 21.26.

Structure description top

Computing details top

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).

Figures top

	Fig. 1. The molecular structure with the atomic numbering scheme: displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. A stereoview of the primary C22—H22···π(C₆H₄) interaction in the crystal structure with atoms drawn as their van der Waals spheres. The H···N contact can be discerned in the middle of the diagram.

2-(3,5-Dimethylbenzene)-1-ferrocenylmethyl-1H-1,3-benzimidazole top

Crystal data top

[Fe(C₅H₅)(C₂₁H₁₉N₂)]	F(000) = 880
M_r = 420.32	D_x = 1.342 Mg m⁻³
Monoclinic, P2₁/c	Melting point: 410 K
Hall symbol: -p 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 9.6613 (11) Å	Cell parameters from 67 reflections
b = 10.9314 (8) Å	θ = 2.1–17.5°
c = 19.7129 (15) Å	µ = 0.74 mm⁻¹
β = 92.194 (8)°	T = 294 K
V = 2080.4 (3) Å³	Block, red
Z = 4	0.45 × 0.35 × 0.16 mm

Data collection top

Bruker P4 diffractometer	4092 reflections with I > 2σ(I)
Radiation source: X-ray tube	R_int = 0.024
Graphite monochromator	θ_max = 28.0°, θ_min = 2.1°
ω scans	h = −1→12
Absorption correction: ψ scan (North et al., 1968)	k = −14→1
T_min = 0.732, T_max = 0.891	l = −26→26
6769 measured reflections	3 standard reflections every 197 reflections
5011 independent reflections	intensity decay: 0.5%

Refinement top

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) = 0.099	w = 1/[σ²(F_o²) + (0.0462P)² + 0.6685P] where P = (F_o² + 2F_c²)/3
S = 1.04	(Δ/σ)_max < 0.001
5011 reflections	Δρ_max = 0.39 e Å⁻³
265 parameters	Δρ_min = −0.30 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0028 (5)

Crystal data top

[Fe(C₅H₅)(C₂₁H₁₉N₂)]	V = 2080.4 (3) Å³
M_r = 420.32	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 9.6613 (11) Å	µ = 0.74 mm⁻¹
b = 10.9314 (8) Å	T = 294 K
c = 19.7129 (15) Å	0.45 × 0.35 × 0.16 mm
β = 92.194 (8)°

Data collection top

Bruker P4 diffractometer	4092 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.024
T_min = 0.732, T_max = 0.891	3 standard reflections every 197 reflections
6769 measured reflections	intensity decay: 0.5%
5011 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.037	0 restraints
wR(F²) = 0.099	H-atom parameters constrained
S = 1.04	Δρ_max = 0.39 e Å⁻³
5011 reflections	Δρ_min = −0.30 e Å⁻³
265 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Fe1	0.16527 (3)	0.02092 (2)	0.203406 (12)	0.03664 (9)
N1	0.31594 (17)	−0.54213 (14)	0.24456 (8)	0.0414 (3)
N2	0.33107 (15)	−0.33696 (13)	0.24774 (7)	0.0358 (3)
C1	0.31443 (18)	−0.44048 (16)	0.20884 (8)	0.0360 (3)
C2	0.36082 (19)	−0.21155 (16)	0.22604 (9)	0.0390 (4)
C3	0.34290 (17)	−0.37604 (17)	0.31466 (8)	0.0360 (4)
C4	0.33363 (19)	−0.50394 (17)	0.31142 (9)	0.0399 (4)
C5	0.3399 (2)	−0.5723 (2)	0.37127 (10)	0.0517 (5)
C6	0.3543 (3)	−0.5101 (2)	0.43183 (10)	0.0564 (5)
C7	0.3624 (2)	−0.3834 (2)	0.43415 (10)	0.0526 (5)
C8	0.3573 (2)	−0.31273 (19)	0.37569 (9)	0.0441 (4)
C11	0.26040 (19)	−0.12095 (17)	0.25347 (9)	0.0394 (4)
C12	0.2969 (2)	−0.00784 (19)	0.28531 (10)	0.0505 (5)
C13	0.1730 (3)	0.0495 (2)	0.30552 (11)	0.0604 (6)
C14	0.0614 (3)	−0.0275 (2)	0.28735 (11)	0.0588 (6)
C15	0.1143 (2)	−0.13241 (19)	0.25545 (10)	0.0485 (5)
C21	0.2002 (3)	0.0058 (3)	0.10306 (11)	0.0700 (8)
C22	0.2672 (3)	0.1103 (3)	0.13086 (14)	0.0790 (9)
C23	0.1620 (3)	0.1873 (2)	0.15712 (12)	0.0642 (6)
C24	0.0383 (3)	0.1286 (2)	0.14448 (11)	0.0613 (6)
C25	0.0600 (3)	0.0194 (3)	0.11158 (12)	0.0682 (7)
C31	0.28576 (19)	−0.44061 (17)	0.13477 (8)	0.0393 (4)
C32	0.3423 (2)	−0.53307 (18)	0.09602 (10)	0.0462 (4)
C33	0.3087 (3)	−0.5439 (2)	0.02729 (10)	0.0547 (5)
C34	0.2157 (3)	−0.4606 (2)	−0.00208 (10)	0.0588 (6)
C35	0.1558 (2)	−0.36883 (19)	0.03505 (10)	0.0515 (5)
C36	0.1925 (2)	−0.35852 (18)	0.10382 (9)	0.0448 (4)
C37	0.3691 (4)	−0.6461 (3)	−0.01382 (13)	0.0796 (8)
C38	0.0499 (3)	−0.2837 (2)	0.00229 (13)	0.0761 (8)
H2A	0.3565	−0.2078	0.1768	0.047*
H2B	0.4541	−0.1896	0.2415	0.047*
H5	0.3346	−0.6573	0.3703	0.062*
H6	0.3587	−0.5540	0.4722	0.068*
H7	0.3715	−0.3448	0.4761	0.063*
H8	0.3633	−0.2279	0.3772	0.053*
H12	0.3861	0.0230	0.2917	0.061*
H13	0.1669	0.1250	0.3270	0.072*
H14	−0.0314	−0.0122	0.2950	0.071*
H15	0.0622	−0.1979	0.2386	0.058*
H21	0.2429	−0.0602	0.0827	0.084*
H22	0.3618	0.1260	0.1319	0.095*
H23	0.1751	0.2625	0.1786	0.077*
H24	−0.0477	0.1582	0.1564	0.074*
H25	−0.0084	−0.0359	0.0975	0.082*
H32	0.4037	−0.5885	0.1166	0.055*
H34	0.1931	−0.4669	−0.0482	0.071*
H36	0.1545	−0.2963	0.1294	0.054*
H37A	0.4677	−0.6484	−0.0058	0.119*
H37B	0.3484	−0.6321	−0.0612	0.119*
H37C	0.3297	−0.7226	−0.0006	0.119*
H38A	0.0932	−0.2072	−0.0080	0.114*
H38B	−0.0235	−0.2699	0.0329	0.114*
H38C	0.0126	−0.3199	−0.0388	0.114*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Fe1	0.03931 (15)	0.03539 (14)	0.03527 (14)	0.00490 (10)	0.00200 (10)	0.00486 (10)
N1	0.0516 (9)	0.0367 (8)	0.0355 (7)	0.0032 (7)	−0.0013 (6)	0.0051 (6)
N2	0.0406 (7)	0.0346 (7)	0.0321 (7)	0.0015 (6)	−0.0010 (6)	0.0063 (6)
C1	0.0371 (8)	0.0359 (8)	0.0348 (8)	0.0029 (7)	−0.0007 (7)	0.0043 (7)
C2	0.0404 (9)	0.0358 (9)	0.0407 (9)	0.0012 (7)	0.0017 (7)	0.0078 (7)
C3	0.0349 (8)	0.0407 (9)	0.0323 (8)	0.0036 (7)	−0.0005 (6)	0.0050 (7)
C4	0.0434 (9)	0.0417 (10)	0.0345 (8)	0.0053 (7)	0.0004 (7)	0.0070 (7)
C5	0.0676 (13)	0.0446 (11)	0.0428 (10)	0.0051 (10)	0.0004 (9)	0.0139 (9)
C6	0.0712 (14)	0.0629 (14)	0.0349 (10)	0.0064 (11)	0.0002 (9)	0.0147 (9)
C7	0.0579 (12)	0.0667 (14)	0.0331 (9)	0.0043 (10)	0.0000 (8)	−0.0001 (9)
C8	0.0470 (10)	0.0465 (10)	0.0386 (9)	0.0018 (8)	−0.0004 (8)	0.0000 (8)
C11	0.0456 (10)	0.0374 (9)	0.0350 (8)	0.0032 (7)	−0.0008 (7)	0.0069 (7)
C12	0.0589 (12)	0.0472 (11)	0.0442 (10)	0.0063 (9)	−0.0137 (9)	−0.0034 (8)
C13	0.0853 (17)	0.0573 (13)	0.0382 (10)	0.0212 (12)	−0.0019 (10)	−0.0075 (9)
C14	0.0618 (13)	0.0673 (14)	0.0489 (11)	0.0192 (12)	0.0218 (10)	0.0127 (10)
C15	0.0487 (11)	0.0478 (11)	0.0497 (11)	−0.0006 (9)	0.0133 (8)	0.0125 (9)
C21	0.105 (2)	0.0660 (15)	0.0402 (11)	0.0265 (15)	0.0213 (12)	0.0122 (10)
C22	0.0519 (13)	0.111 (2)	0.0743 (16)	−0.0059 (14)	0.0102 (12)	0.0523 (17)
C23	0.0906 (18)	0.0418 (11)	0.0599 (13)	0.0011 (12)	−0.0008 (12)	0.0163 (10)
C24	0.0628 (14)	0.0664 (15)	0.0543 (12)	0.0223 (12)	−0.0043 (10)	0.0140 (11)
C25	0.0851 (18)	0.0727 (16)	0.0456 (12)	0.0002 (14)	−0.0147 (12)	0.0041 (11)
C31	0.0462 (9)	0.0385 (9)	0.0328 (8)	−0.0047 (8)	−0.0024 (7)	0.0051 (7)
C32	0.0564 (11)	0.0425 (10)	0.0396 (9)	−0.0001 (9)	−0.0015 (8)	0.0030 (8)
C33	0.0766 (15)	0.0470 (12)	0.0404 (10)	−0.0073 (10)	0.0019 (10)	−0.0057 (8)
C34	0.0840 (16)	0.0551 (13)	0.0361 (10)	−0.0136 (11)	−0.0124 (10)	0.0033 (9)
C35	0.0633 (13)	0.0463 (11)	0.0435 (10)	−0.0087 (9)	−0.0147 (9)	0.0114 (9)
C36	0.0523 (11)	0.0426 (10)	0.0390 (9)	−0.0006 (8)	−0.0054 (8)	0.0059 (8)
C37	0.116 (2)	0.0701 (17)	0.0529 (13)	0.0058 (16)	0.0039 (14)	−0.0183 (12)
C38	0.0933 (18)	0.0667 (16)	0.0653 (15)	−0.0021 (14)	−0.0363 (14)	0.0185 (13)

Geometric parameters (Å, º) top

Fe1—C11	2.0383 (17)	C31—C32	1.391 (3)
Fe1—C12	2.041 (2)	C31—C36	1.395 (3)
Fe1—C13	2.036 (2)	C32—C33	1.386 (3)
Fe1—C14	2.038 (2)	C33—C34	1.389 (3)
Fe1—C15	2.0353 (19)	C33—C37	1.511 (3)
Fe1—C21	2.026 (2)	C34—C35	1.382 (3)
Fe1—C22	2.019 (2)	C35—C36	1.393 (3)
Fe1—C23	2.035 (2)	C35—C38	1.509 (3)
Fe1—C24	2.032 (2)	C2—H2A	0.9700
Fe1—C25	2.042 (2)	C2—H2B	0.9700
N1—C1	1.315 (2)	C5—H5	0.9300
N1—C4	1.387 (2)	C6—H6	0.9300
N2—C1	1.373 (2)	C7—H7	0.9300
N2—C2	1.468 (2)	C8—H8	0.9300
N2—C3	1.387 (2)	C12—H12	0.9300
C1—C31	1.476 (2)	C13—H13	0.9300
C2—C11	1.502 (3)	C14—H14	0.9300
C3—C8	1.390 (3)	C15—H15	0.9300
C3—C4	1.402 (3)	C21—H21	0.9300
C4—C5	1.396 (2)	C22—H22	0.9300
C5—C6	1.377 (3)	C23—H23	0.9300
C6—C7	1.387 (3)	C24—H24	0.9300
C7—C8	1.387 (3)	C25—H25	0.9300
C11—C15	1.419 (3)	C32—H32	0.9300
C11—C12	1.425 (3)	C34—H34	0.9300
C12—C13	1.422 (3)	C36—H36	0.9300
C13—C14	1.404 (4)	C37—H37A	0.9600
C14—C15	1.413 (3)	C37—H37B	0.9600
C21—C25	1.379 (4)	C37—H37C	0.9600
C21—C22	1.413 (4)	C38—H38A	0.9600
C22—C23	1.432 (4)	C38—H38B	0.9600
C23—C24	1.371 (4)	C38—H38C	0.9600
C24—C25	1.379 (4)

C22—Fe1—C21	40.88 (12)	C22—C21—Fe1	69.29 (14)
C22—Fe1—C24	67.35 (10)	C21—C22—C23	107.2 (2)
C21—Fe1—C24	66.96 (10)	C21—C22—Fe1	69.83 (13)
C22—Fe1—C23	41.36 (11)	C23—C22—Fe1	69.91 (13)
C21—Fe1—C23	68.61 (11)	C24—C23—C22	106.5 (2)
C24—Fe1—C23	39.40 (10)	C24—C23—Fe1	70.21 (13)
C22—Fe1—C15	152.78 (12)	C22—C23—Fe1	68.73 (13)
C21—Fe1—C15	118.53 (10)	C23—C24—C25	110.1 (2)
C24—Fe1—C15	127.80 (10)	C23—C24—Fe1	70.39 (13)
C23—Fe1—C15	164.23 (10)	C25—C24—Fe1	70.59 (13)
C22—Fe1—C13	128.73 (13)	C24—C25—C21	108.6 (3)
C21—Fe1—C13	167.62 (12)	C24—C25—Fe1	69.85 (13)
C24—Fe1—C13	118.34 (10)	C21—C25—Fe1	69.57 (14)
C23—Fe1—C13	107.78 (10)	C32—C31—C36	119.19 (17)
C15—Fe1—C13	68.19 (10)	C32—C31—C1	118.76 (16)
C22—Fe1—C14	165.82 (13)	C36—C31—C1	121.71 (17)
C21—Fe1—C14	151.31 (13)	C33—C32—C31	121.07 (19)
C24—Fe1—C14	108.04 (10)	C32—C33—C34	118.4 (2)
C23—Fe1—C14	126.65 (10)	C32—C33—C37	120.4 (2)
C15—Fe1—C14	40.58 (9)	C34—C33—C37	121.2 (2)
C13—Fe1—C14	40.31 (11)	C35—C34—C33	122.16 (18)
C22—Fe1—C11	119.21 (10)	C34—C35—C36	118.55 (19)
C21—Fe1—C11	108.78 (9)	C34—C35—C38	120.8 (2)
C24—Fe1—C11	165.60 (9)	C36—C35—C38	120.6 (2)
C23—Fe1—C11	153.67 (10)	C35—C36—C31	120.64 (19)
C15—Fe1—C11	40.77 (8)	N2—C2—H2A	109.2
C13—Fe1—C11	68.86 (8)	C11—C2—H2A	109.2
C14—Fe1—C11	68.65 (8)	N2—C2—H2B	109.2
C22—Fe1—C12	109.20 (10)	C11—C2—H2B	109.2
C21—Fe1—C12	129.62 (11)	H2A—C2—H2B	107.9
C24—Fe1—C12	152.31 (10)	C6—C5—H5	121.1
C23—Fe1—C12	119.40 (10)	C4—C5—H5	121.1
C15—Fe1—C12	68.27 (9)	C5—C6—H6	119.1
C13—Fe1—C12	40.82 (9)	C7—C6—H6	119.1
C14—Fe1—C12	68.21 (10)	C8—C7—H7	119.1
C11—Fe1—C12	40.88 (8)	C6—C7—H7	119.1
C22—Fe1—C25	67.41 (12)	C7—C8—H8	121.9
C21—Fe1—C25	39.63 (12)	C3—C8—H8	121.9
C24—Fe1—C25	39.56 (10)	C13—C12—H12	126.0
C23—Fe1—C25	67.13 (11)	C11—C12—H12	126.0
C15—Fe1—C25	108.55 (10)	Fe1—C12—H12	126.7
C13—Fe1—C25	151.16 (11)	C14—C13—H13	126.0
C14—Fe1—C25	118.28 (12)	C12—C13—H13	126.0
C11—Fe1—C25	128.53 (10)	Fe1—C13—H13	125.9
C12—Fe1—C25	166.90 (10)	C13—C14—H14	125.9
C1—N1—C4	104.65 (15)	C15—C14—H14	125.9
C1—N2—C3	106.31 (14)	Fe1—C14—H14	126.3
C1—N2—C2	128.85 (14)	C14—C15—H15	125.7
C3—N2—C2	123.70 (15)	C11—C15—H15	125.7
N1—C1—N2	113.50 (14)	Fe1—C15—H15	126.3
N1—C1—C31	121.78 (16)	C25—C21—H21	126.2
N2—C1—C31	124.53 (15)	C22—C21—H21	126.2
N2—C2—C11	112.01 (14)	Fe1—C21—H21	125.3
N2—C3—C8	132.19 (18)	C21—C22—H22	126.4
N2—C3—C4	105.12 (15)	C23—C22—H22	126.4
C8—C3—C4	122.67 (17)	Fe1—C22—H22	125.4
N1—C4—C5	129.92 (19)	C24—C23—H23	126.7
N1—C4—C3	110.41 (15)	C22—C23—H23	126.7
C5—C4—C3	119.66 (18)	Fe1—C23—H23	125.9
C6—C5—C4	117.9 (2)	C23—C24—H24	125.0
C5—C6—C7	121.72 (19)	C25—C24—H24	125.0
C8—C7—C6	121.90 (19)	Fe1—C24—H24	125.7
C7—C8—C3	116.17 (19)	C24—C25—H25	125.7
C15—C11—C12	107.10 (18)	C21—C25—H25	125.7
C15—C11—C2	127.50 (18)	Fe1—C25—H25	126.4
C12—C11—C2	125.36 (18)	C33—C32—H32	119.5
C15—C11—Fe1	69.50 (11)	C31—C32—H32	119.5
C12—C11—Fe1	69.66 (11)	C35—C34—H34	118.9
C2—C11—Fe1	127.81 (12)	C33—C34—H34	118.9
C13—C12—C11	108.0 (2)	C35—C36—H36	119.7
C13—C12—Fe1	69.39 (12)	C31—C36—H36	119.7
C11—C12—Fe1	69.46 (11)	C33—C37—H37A	109.5
C14—C13—C12	108.1 (2)	C33—C37—H37B	109.5
C14—C13—Fe1	69.93 (12)	H37A—C37—H37B	109.5
C12—C13—Fe1	69.79 (12)	C33—C37—H37C	109.5
C13—C14—C15	108.3 (2)	H37A—C37—H37C	109.5
C13—C14—Fe1	69.76 (13)	H37B—C37—H37C	109.5
C15—C14—Fe1	69.61 (11)	C35—C38—H38A	109.5
C14—C15—C11	108.5 (2)	C35—C38—H38B	109.5
C14—C15—Fe1	69.80 (12)	H38A—C38—H38B	109.5
C11—C15—Fe1	69.73 (11)	C35—C38—H38C	109.5
C25—C21—C22	107.7 (2)	H38A—C38—H38C	109.5
C25—C21—Fe1	70.80 (14)	H38B—C38—H38C	109.5

C4—N1—C1—N2	0.5 (2)	C13—Fe1—C15—C14	37.31 (15)
C4—N1—C1—C31	−174.80 (16)	C11—Fe1—C15—C14	119.79 (19)
C3—N2—C1—N1	−0.7 (2)	C12—Fe1—C15—C14	81.43 (15)
C2—N2—C1—N1	167.27 (17)	C25—Fe1—C15—C14	−112.11 (16)
C3—N2—C1—C31	174.46 (16)	C22—Fe1—C15—C11	51.6 (3)
C2—N2—C1—C31	−17.6 (3)	C21—Fe1—C15—C11	86.02 (16)
C1—N2—C2—C11	128.17 (18)	C24—Fe1—C15—C11	167.85 (12)
C3—N2—C2—C11	−65.8 (2)	C23—Fe1—C15—C11	−160.6 (3)
C1—N2—C3—C8	−177.85 (19)	C13—Fe1—C15—C11	−82.48 (13)
C2—N2—C3—C8	13.4 (3)	C14—Fe1—C15—C11	−119.79 (19)
C1—N2—C3—C4	0.55 (19)	C12—Fe1—C15—C11	−38.36 (12)
C2—N2—C3—C4	−168.17 (16)	C25—Fe1—C15—C11	128.09 (14)
C1—N1—C4—C5	178.5 (2)	C22—Fe1—C21—C25	−118.4 (2)
C1—N1—C4—C3	−0.1 (2)	C24—Fe1—C21—C25	−36.87 (16)
N2—C3—C4—N1	−0.3 (2)	C23—Fe1—C21—C25	−79.54 (17)
C8—C3—C4—N1	178.30 (16)	C15—Fe1—C21—C25	84.92 (17)
N2—C3—C4—C5	−179.07 (17)	C13—Fe1—C21—C25	−154.8 (4)
C8—C3—C4—C5	−0.5 (3)	C14—Fe1—C21—C25	48.8 (3)
N1—C4—C5—C6	−178.1 (2)	C11—Fe1—C21—C25	128.39 (16)
C3—C4—C5—C6	0.4 (3)	C12—Fe1—C21—C25	169.35 (15)
C4—C5—C6—C7	0.0 (4)	C24—Fe1—C21—C22	81.48 (17)
C5—C6—C7—C8	−0.4 (4)	C23—Fe1—C21—C22	38.81 (16)
C6—C7—C8—C3	0.4 (3)	C15—Fe1—C21—C22	−156.73 (15)
N2—C3—C8—C7	178.26 (19)	C13—Fe1—C21—C22	−36.4 (5)
C4—C3—C8—C7	0.1 (3)	C14—Fe1—C21—C22	167.11 (19)
N2—C2—C11—C15	−44.5 (2)	C11—Fe1—C21—C22	−113.25 (16)
N2—C2—C11—C12	132.75 (18)	C12—Fe1—C21—C22	−72.30 (18)
N2—C2—C11—Fe1	−136.62 (14)	C25—Fe1—C21—C22	118.4 (2)
C22—Fe1—C11—C15	−155.76 (15)	C25—C21—C22—C23	0.5 (3)
C21—Fe1—C11—C15	−112.22 (15)	Fe1—C21—C22—C23	−60.24 (16)
C24—Fe1—C11—C15	−42.0 (4)	C25—C21—C22—Fe1	60.71 (17)
C23—Fe1—C11—C15	168.2 (2)	C24—Fe1—C22—C21	−80.45 (17)
C13—Fe1—C11—C15	80.71 (14)	C23—Fe1—C22—C21	−118.0 (2)
C14—Fe1—C11—C15	37.32 (13)	C15—Fe1—C22—C21	49.4 (3)
C12—Fe1—C11—C15	118.26 (18)	C13—Fe1—C22—C21	170.61 (15)
C25—Fe1—C11—C15	−72.50 (17)	C14—Fe1—C22—C21	−154.1 (4)
C22—Fe1—C11—C12	85.98 (17)	C11—Fe1—C22—C21	85.27 (17)
C21—Fe1—C11—C12	129.52 (15)	C12—Fe1—C22—C21	129.01 (15)
C24—Fe1—C11—C12	−160.2 (3)	C25—Fe1—C22—C21	−37.44 (16)
C23—Fe1—C11—C12	50.0 (2)	C21—Fe1—C22—C23	118.0 (2)
C15—Fe1—C11—C12	−118.26 (18)	C24—Fe1—C22—C23	37.52 (15)
C13—Fe1—C11—C12	−37.55 (14)	C15—Fe1—C22—C23	167.35 (19)
C14—Fe1—C11—C12	−80.94 (15)	C13—Fe1—C22—C23	−71.42 (19)
C25—Fe1—C11—C12	169.24 (15)	C14—Fe1—C22—C23	−36.1 (5)
C22—Fe1—C11—C2	−33.6 (2)	C11—Fe1—C22—C23	−156.76 (14)
C21—Fe1—C11—C2	10.0 (2)	C12—Fe1—C22—C23	−113.02 (16)
C24—Fe1—C11—C2	80.2 (4)	C25—Fe1—C22—C23	80.53 (17)
C23—Fe1—C11—C2	−69.6 (3)	C21—C22—C23—C24	−0.2 (3)
C15—Fe1—C11—C2	122.2 (2)	Fe1—C22—C23—C24	−60.35 (16)
C13—Fe1—C11—C2	−157.1 (2)	C21—C22—C23—Fe1	60.19 (16)
C14—Fe1—C11—C2	159.5 (2)	C22—Fe1—C23—C24	117.7 (2)
C12—Fe1—C11—C2	−119.6 (2)	C21—Fe1—C23—C24	79.32 (17)
C25—Fe1—C11—C2	49.7 (2)	C15—Fe1—C23—C24	−40.7 (4)
C15—C11—C12—C13	−0.8 (2)	C13—Fe1—C23—C24	−113.25 (16)
C2—C11—C12—C13	−178.56 (17)	C14—Fe1—C23—C24	−72.68 (19)
Fe1—C11—C12—C13	58.85 (14)	C11—Fe1—C23—C24	168.63 (17)
C15—C11—C12—Fe1	−59.68 (13)	C12—Fe1—C23—C24	−156.25 (14)
C2—C11—C12—Fe1	122.59 (17)	C25—Fe1—C23—C24	36.42 (15)
C22—Fe1—C12—C13	127.61 (17)	C21—Fe1—C23—C22	−38.37 (17)
C21—Fe1—C12—C13	168.93 (16)	C24—Fe1—C23—C22	−117.7 (2)
C24—Fe1—C12—C13	50.0 (3)	C15—Fe1—C23—C22	−158.4 (3)
C23—Fe1—C12—C13	83.34 (17)	C13—Fe1—C23—C22	129.06 (17)
C15—Fe1—C12—C13	−81.35 (15)	C14—Fe1—C23—C22	169.64 (17)
C14—Fe1—C12—C13	−37.50 (15)	C11—Fe1—C23—C22	50.9 (3)
C11—Fe1—C12—C13	−119.6 (2)	C12—Fe1—C23—C22	86.06 (18)
C25—Fe1—C12—C13	−159.7 (4)	C25—Fe1—C23—C22	−81.27 (18)
C22—Fe1—C12—C11	−112.78 (16)	C22—C23—C24—C25	−0.2 (3)
C21—Fe1—C12—C11	−71.46 (18)	Fe1—C23—C24—C25	−59.60 (17)
C24—Fe1—C12—C11	169.57 (18)	C22—C23—C24—Fe1	59.40 (15)
C23—Fe1—C12—C11	−157.05 (13)	C22—Fe1—C24—C23	−39.35 (17)
C15—Fe1—C12—C11	38.26 (12)	C21—Fe1—C24—C23	−83.88 (18)
C13—Fe1—C12—C11	119.6 (2)	C15—Fe1—C24—C23	167.04 (15)
C14—Fe1—C12—C11	82.11 (14)	C13—Fe1—C24—C23	83.70 (18)
C25—Fe1—C12—C11	−40.1 (5)	C14—Fe1—C24—C23	126.34 (16)
C11—C12—C13—C14	0.8 (2)	C11—Fe1—C24—C23	−159.4 (3)
Fe1—C12—C13—C14	59.68 (15)	C12—Fe1—C24—C23	49.0 (3)
C11—C12—C13—Fe1	−58.89 (14)	C25—Fe1—C24—C23	−120.8 (2)
C22—Fe1—C13—C14	167.36 (15)	C22—Fe1—C24—C25	81.46 (19)
C21—Fe1—C13—C14	−162.8 (4)	C21—Fe1—C24—C25	36.93 (18)
C24—Fe1—C13—C14	84.73 (16)	C23—Fe1—C24—C25	120.8 (2)
C23—Fe1—C13—C14	126.22 (15)	C15—Fe1—C24—C25	−72.15 (19)
C15—Fe1—C13—C14	−37.56 (13)	C13—Fe1—C24—C25	−155.49 (17)
C11—Fe1—C13—C14	−81.51 (14)	C14—Fe1—C24—C25	−112.84 (18)
C12—Fe1—C13—C14	−119.1 (2)	C11—Fe1—C24—C25	−38.6 (4)
C25—Fe1—C13—C14	51.5 (3)	C12—Fe1—C24—C25	169.9 (2)
C22—Fe1—C13—C12	−73.53 (18)	C23—C24—C25—C21	0.5 (3)
C21—Fe1—C13—C12	−43.6 (5)	Fe1—C24—C25—C21	−58.98 (17)
C24—Fe1—C13—C12	−156.16 (14)	C23—C24—C25—Fe1	59.49 (16)
C23—Fe1—C13—C12	−114.66 (15)	C22—C21—C25—C24	−0.6 (3)
C15—Fe1—C13—C12	81.56 (14)	Fe1—C21—C25—C24	59.15 (16)
C14—Fe1—C13—C12	119.1 (2)	C22—C21—C25—Fe1	−59.75 (16)
C11—Fe1—C13—C12	37.60 (13)	C22—Fe1—C25—C24	−81.30 (19)
C25—Fe1—C13—C12	170.6 (2)	C21—Fe1—C25—C24	−119.9 (2)
C12—C13—C14—C15	−0.4 (2)	C23—Fe1—C25—C24	−36.27 (16)
Fe1—C13—C14—C15	59.16 (15)	C15—Fe1—C25—C24	127.50 (16)
C12—C13—C14—Fe1	−59.59 (15)	C13—Fe1—C25—C24	49.2 (3)
C22—Fe1—C14—C13	−44.2 (5)	C14—Fe1—C25—C24	84.31 (18)
C21—Fe1—C14—C13	172.39 (19)	C11—Fe1—C25—C24	168.56 (14)
C24—Fe1—C14—C13	−112.82 (15)	C12—Fe1—C25—C24	−158.8 (4)
C23—Fe1—C14—C13	−73.23 (17)	C22—Fe1—C25—C21	38.59 (17)
C15—Fe1—C14—C13	119.6 (2)	C24—Fe1—C25—C21	119.9 (2)
C11—Fe1—C14—C13	82.08 (14)	C23—Fe1—C25—C21	83.62 (18)
C12—Fe1—C14—C13	37.96 (13)	C15—Fe1—C25—C21	−112.61 (17)
C25—Fe1—C14—C13	−154.62 (14)	C13—Fe1—C25—C21	169.1 (2)
C22—Fe1—C14—C15	−163.7 (4)	C14—Fe1—C25—C21	−155.80 (16)
C21—Fe1—C14—C15	52.8 (3)	C11—Fe1—C25—C21	−71.6 (2)
C24—Fe1—C14—C15	127.63 (14)	C12—Fe1—C25—C21	−38.9 (5)
C23—Fe1—C14—C15	167.22 (14)	N1—C1—C31—C32	−40.1 (3)
C13—Fe1—C14—C15	−119.6 (2)	N2—C1—C31—C32	145.14 (19)
C11—Fe1—C14—C15	−37.48 (13)	N1—C1—C31—C36	133.1 (2)
C12—Fe1—C14—C15	−81.59 (14)	N2—C1—C31—C36	−41.6 (3)
C25—Fe1—C14—C15	85.83 (16)	C36—C31—C32—C33	0.7 (3)
C13—C14—C15—C11	−0.1 (2)	C1—C31—C32—C33	174.14 (19)
Fe1—C14—C15—C11	59.16 (13)	C31—C32—C33—C34	−0.6 (3)
C13—C14—C15—Fe1	−59.25 (15)	C31—C32—C33—C37	−179.0 (2)
C12—C11—C15—C14	0.6 (2)	C32—C33—C34—C35	−0.5 (4)
C2—C11—C15—C14	178.24 (17)	C37—C33—C34—C35	177.9 (2)
Fe1—C11—C15—C14	−59.21 (14)	C33—C34—C35—C36	1.4 (3)
C12—C11—C15—Fe1	59.78 (13)	C33—C34—C35—C38	−177.0 (2)
C2—C11—C15—Fe1	−122.55 (18)	C34—C35—C36—C31	−1.2 (3)
C22—Fe1—C15—C14	171.4 (2)	C38—C35—C36—C31	177.1 (2)
C21—Fe1—C15—C14	−154.19 (16)	C32—C31—C36—C35	0.2 (3)
C24—Fe1—C15—C14	−72.36 (18)	C1—C31—C36—C35	−173.01 (18)
C23—Fe1—C15—C14	−40.8 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2B···N1ⁱ	0.97	2.75	3.658 (2)	156
C22—H22···Cgⁱ	0.93	2.91	3.764 (3)	154

Symmetry code: (i) −x+1, y+1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	[Fe(C₅H₅)(C₂₁H₁₉N₂)]
M_r	420.32
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	294
a, b, c (Å)	9.6613 (11), 10.9314 (8), 19.7129 (15)
β (°)	92.194 (8)
V (Å³)	2080.4 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.74
Crystal size (mm)	0.45 × 0.35 × 0.16

Data collection
Diffractometer	Bruker P4
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.732, 0.891
No. of measured, independent and observed [I > 2σ(I)] reflections	6769, 5011, 4092
R_int	0.024
(sin θ/λ)_max (Å⁻¹)	0.661

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.037, 0.099, 1.04
No. of reflections	5011
No. of parameters	265
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.39, −0.30

Computer programs: XSCANS (Bruker, 1996), SHELXS97 (Sheldrick, 1997), PLATON (Spek, 2003), SHELXL97 (Sheldrick, 1997) and PREP8 (Ferguson, 1998).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2B···N1ⁱ	0.97	2.75	3.658 (2)	156
C22—H22···Cgⁱ	0.93	2.91	3.764 (3)	154

Symmetry code: (i) −x+1, y+1/2, −z+1/2.

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