1-Ferrocenylmethyl-2-phenyl-1H-1,3-benzimidazole

In the title mol­ecule, [Fe(C₅H₅)(C₁₉H₁₅N₂)], the five-membered C₃N₂ imidazole ring forms dihedral angles of 84.71 (13) and 52.12 (11)°, respectively, with the substituted cyclo­penta­dienyl and phenyl rings. In the crystal structure, in addition to a weak C—H...N inter­action, there is a modest C—H...π(ring) inter­action involving a C—H group of the unsubstituted cyclo­penta­dienyl ring and the imidazole ring.

Key indicators

• Single-crystal X-ray study
• T = 294 K
• Mean [sigma](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

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S1. Comment

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.

Related literature

For related ferrocene literature, see: Li et al., (1998); Gallagher, Hanlon & Howarth, (2001); Gallagher, Hanlon, Howarth & Thomas, (2001); Howarth & Hanlon, (2001); Kazak et al., (2006); Gallagher et al. (2007a,b). For the chemical synthesis and crystal structure of [Fe(C₅H₅)₂CH₂N(CH₃)₃]⁺[I]^-, see: Pauson et al., (1966); Ferguson et al. (1994).

S2. Experimental

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.

S3. Refinement

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.

Computing details

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

	Fig. 1. A view of the title compound with the atomic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. A stereoview of the main cpC—H···π-(C═N) interaction in the crystal structure with atoms depicted as their van der Waals spheres.
	Fig. 3. A view of the C—H···N contact in the crystal structure with the N1 atom represented by a '*' and with H24 by a '#' located at symmetry position 1 - x,-y,-1/2 + z, (atoms depicted as for Fig. 2).

1-Ferrocenylmethyl-2-phenyl-1H-1,3-benzimidazole

Crystal data

[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) Å^3	Block, red
Z = 4	0.50 × 0.50 × 0.35 mm
F(000) = 816

Data collection

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

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.037	H-atom parameters constrained
wR(F^2) = 0.093	w = 1/[σ^2(Fo^2) + (0.0673P)^2 + 0.0565P] where P = (Fo^2 + 2Fc^2)/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)

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	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*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

Geometric parameters (Å, º)

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)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C23—H23···N1^i	0.93	2.69	3.346 (4)	128
C24—H24···Cg^ii	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.