2-(3-Chloro­phenyl)-1-ferrocenyl­methyl-1H-1,3-benz­imidazole: an electroactive agent for anion sensor and malarial parasite studies

The title compound, [Fe(C₅H₅)(C₁₉H₁₄ClN₂)], a model electroactive agent for anion sensor and malarial parasite studies, has Fe—C bond lengths in the range 2.020 (3)–2.0543 (18) Å. The Fe...Cg distances (Cg indicates a ring centroid) are essentially similar, with values of 1.6467 (10) and 1.6487 (11) Å for the substituted and unsubstituted cyclo­penta­dienyl rings, respectively, with a linear Cg...Fe...Cg angle of 179.12 (7)°. The Fe—C_Cp—Csp³ angle is 128.43 (13)° and the Fe1—C_Cp—Csp³—N_Bz torsion angle 110.27 (17)° (Cp is cyclo­penta­dienyl and Bz is benz­imidazole). Weak C—H...Cl contacts form the only intermolecular interactions of significance.

Key indicators

• Single-crystal X-ray study
• T = 297 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.041
• wR factor = 0.105
• Data-to-parameter ratio = 18.5

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry

General Notes



ABSTM_02  When printed, the submitted absorption T values will be replaced
          by the scaled T values. Since the ratio of scaled T's is
          identical to the ratio of reported T values, the scaling does
          not imply a change to the absorption corrections used in the
          study.
          Ratio of Tmax expected/reported      1.104
          Tmax scaled      0.823 Tmin scaled      0.753

---

S1. Comment

The synthesis of anion receptors is currently an area of intense research activity due primarily to the ubiquitous roles which anions play in both chemical and biological processes, for example, as substrates or co-factors for enzymes and as nucleophiles, redox agents and phase transfer catalysts. In the past decade, combinations of an organometallic moiety with an amide N—H group have been demonstrated to be essential components in many anion-recognition receptors (Beer, 1998; Kingston et al., 1999). 1,3-Disubstituted imidazolium cations have been utilized as such recently (Sato et al., 1999; Thomas et al., 2000) and their synthetic intermediates (imidazolin-2-ylidenes) are also of interest as carbenes and the subject of several synthetic and structural investigations (Benito et al., 1995; Bildstein et al., 1998, 1999).

Recently, benzimidazole systems have attracted our considerable attention in synthetic and applied biological research (Howarth et al., 2000; Thomas et al., 2000; Howarth & Hanlon, 2001). Compound (I), depicted in Fig. 1, is obtained from 2-(3-chlorophenyl)benzimidazole and (trimethyl)ammoniumferrocenylmethyl iodide (Pauson et al., 1966; Ferguson et al., 1994a) and is an important electroactive model compound for application in anion sensor studies (Thomas et al., 2000), as well as in malarial parasite research (Howarth & Hanlon, 2001).

In (I), selected bond lengths and angles are listed in Table 1. The Fe—C bond lengths are in the range 2.020 (3)–2.0543 (18) Å; the Fe1···Cg(1,2) distances (Cg1 and Cg2 are centroids of the cyclopentadienyl rings) are comparable, 1.6467 (10) and 1.6487 (11) Å for the substituted and unsubstituted rings, respectively, with a linear Cg1···Fe1···Cg2 angle of 179.12 (7)°. The cyclopentadienyl rings are essentially eclipsed, with a C21—Fe1—C11—C2 torsion angle of -2.8 (2)° and there is no evidence for disorder in the unsubstituted C₅H₅ ring. The Fe—C_Cp—Csp³ angle is 128.43 (13)° and similar to 128.3 (3)° in N-ferrocenylmethyl-2-ferrocenylbenzimidazole, (II) (Benito et al., 1995), or 127.86 (12) and 126.80 (12)° in the two independent molecules of racemic ferrocenyl(phenyl)methanol (Ferguson et al., 1994b). The benzimidazole is twisted with respect to the ferrocenyl moiety, with Fe1—-C_Cp–Csp³—N2 = 110.27 (17)° and C_Cp—Csp³—N2—C3 = 71.7 (2)° [the N1—C1—C31—C32 angle is 126.9 (2)°], and due to the bulky ferrocenyl and benzimidazole groups avoiding possible sterically hindered H···H contacts. In the crystal structure, the shortest H···Cl1 contacts and involving C25—H25 and C36—H36 [C···Cl 3.802 (5) and 3.670 (2) Å] are listed in Table 2.

A search of the October 2000 version of the Cambridge Structural Database using CONQUEST Version 1.1 (Allen & Kennard, 1993) for molecules similar to (I) shows that such compounds are relatively rare and include N-ferrocenylmethyl-2-ferrocenylbenzimidazole (ZIJPIR; Benito et al., 1995) and N-ferrocenylmethyl-2-ferrocenyl-benzimidazolium tetrafluoroborate (GIFLUC; Li et al., 1998), which differ from (I) primarily through replacement of the chlorophenyl group by a ferrocenyl group.

S2. Experimental

To a mixture of 2-(chlorophenyl)benzimidazole (2.5 g, 10 mmol) and K₂CO₃ (2.07 g, 15 mmol) in CH₃CN (100 ml) was added (trimethyl)ammoniumferrocenylmethyl iodide (4.05 g, 10.5 mmol) (Pauson et al., 1966; Ferguson et al., 1994a), and the mixture was refluxed for 12 h. The reaction was cooled to room temperature, water added and the suspension extracted into CHCl₃. The organic layer was washed with water, dried (MgSO₄) and evaporated under vacuum to leave a brown solid. The crude product was purified by column chromatography on silica gel using CH₂Cl₂–CH₃OH (97:3) as eluent. The title compound was obtained as a light-brown powder. Yield 2.8 g (64%), m.p. 435–438 K (uncorrected). Analysis for C₂₄H₁₉ClFeN₂, calculated: C 67.57, H 4.45, N 6.56%; found: C 67.47, H 4.51, N 6.52%. IR (KBr, ν cm^-1), 3051, 2971, 2308, 1708, 1639, 1456, 1422, 1364, 1330, 1261, 1153, 1101, 1027, 1008, 895, 741, 706, 695. ¹H NMR [400 MHz, δH (p.p.m.), CDCl₃], 7.82 (m, 2H, aryl-H), 7.69 (m, 1H, C₆H₄), 7.56–7.48 (m, 3H, aryl-H and C₆H₄), 7.34 (m, 2H, C₆H₄), 5.22 (s, 2H, Fc—CH₂), 4.13–4.07 (M, 9H, Fc—H). ¹³C NMR (δC, CDCl₃), 152.27, 143.27, 136.04, 135.08, 132.79, 130.4, 130.35, 130.08, 128.21, 123.49, 123.05, 120.48, 110.86, 83.36, 69.25, 69.14, 68.71, 44.95.

S3. Refinement

All H atoms bound to C atoms were treated as riding, with SHELXL97 (Sheldrick, 1997) defaults for C—H distances and with U_iso(H) = 1.5U_eq(C) for methyl H atoms and 1.2U_eq(C) for the remainder. Examination of the structure with PLATON (Spek, 1998) showed that there were no solvent-accessible voids in the crystal lattice.

Computing details

Data collection: XSCANS (Siemens, 1994); cell refinement: XSCANS; data reduction: XSCANS; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPIII (Burnett & Johnson, 1996) and PLATON (Spek, 1998); software used to prepare material for publication: SHELXL97 and PREP8 (Ferguson, 1998).

Figures

Fig. 1. A view of (I) with the atomic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.

2-(3-Chlorophenyl)-1-ferrocenylmethyl-1H-1,3-benzimidazole

Crystal data

[Fe(C5H5)(C19H14ClN2)]	Dx = 1.46 Mg m^−3
Mr = 426.71	Melting point: 437 K
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 11.6838 (9) Å	Cell parameters from 27 reflections
b = 9.9220 (6) Å	θ = 4.5–16.1°
c = 16.7493 (14) Å	µ = 0.93 mm^−1
β = 90.542 (6)°	T = 297 K
V = 1941.6 (2) Å^3	Block, orange
Z = 4	0.37 × 0.24 × 0.21 mm
F(000) = 880

Data collection

Bruker P4 diffractometer	3646 reflections with I > 2σ(I)
Radiation source: X-ray tube	Rint = 0.033
Graphite monochromator	θmax = 28.0°, θmin = 2.1°
ω–2θ scans	h = −15→1
Absorption correction: ψ scan (North et al., 1968)	k = −13→1
Tmin = 0.682, Tmax = 0.746	l = −22→22
5483 measured reflections	3 standard reflections every 197 reflections
4669 independent reflections	intensity decay: 2%

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.105	H-atom parameters constrained
S = 1.03	w = 1/[σ^2(Fo^2) + (0.0495P)^2 + 0.6062P] where P = (Fo^2 + 2Fc^2)/3
4669 reflections	(Δ/σ)max < 0.001
253 parameters	Δρmax = 0.70 e Å^−3
0 restraints	Δρmin = −0.55 e Å^−3

Special details

Geometry. Mean plane data ex-SHELXL97 for compound (I) #################################################################

Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane)

2.8856(0.0125)x + 8.7907(0.0034)y + 6.5342(0.0116)z = 8.2081(0.0140)

* 0.0410 (0.0012) C1 * -0.0613 (0.0011) N1 * 0.0862 (0.0014) N2 * -0.0656 (0.0008) C2 * -0.0003 (0.0006) C3 - 0.0682 (0.0026) C4 - 2.8098 (0.0030) Fe1 - 2.0934 (0.0061) Cl1

Rms deviation of fitted atoms = 0.0586

11.1300(0.0039)x - 0.2023(0.0106)y - 5.2347(0.0169)z = 11.9425(0.0065)

Angle to previous plane (with approximate e.s.d.) = 84.37 (9)

* 0.0010 (0.0013) C11 * -0.0009 (0.0013) C12 * 0.0005 (0.0014) C13 * 0.0002 (0.0014) C14 * -0.0007 (0.0013) C15 - 1.6466 (0.0010) Fe1 - 4.8199 (0.0055) Cl1 0.5014 (0.0057) N1 0.5217 (0.0040) N2

Rms deviation of fitted atoms = 0.0007

11.1763(0.0044)x - 0.1369(0.0130)y - 5.0289(0.0198)z = 8.7321(0.0072)

Angle to previous plane (with approximate e.s.d.) = 0.83 (9)

* -0.0003 (0.0016) C21 * 0.0019 (0.0016) C22 * -0.0027 (0.0016) C23 * 0.0024 (0.0015) C24 * -0.0013 (0.0016) C25 1.6480 (0.0011) Fe1 - 1.4702 (0.0065) Cl1 3.8641 (0.0067) N1 3.8669 (0.0047) N2

Rms deviation of fitted atoms = 0.0019

4.6333(0.0105)x + 1.1270(0.0100)y + 15.1943(0.0071)z = 11.1411(0.0082)

Angle to previous plane (with approximate e.s.d.) = 83.54 (8)

* -0.0048 (0.0016) C31 * -0.0008 (0.0018) C32 * 0.0027 (0.0019) C33 * 0.0012 (0.0018) C34 * -0.0068 (0.0018) C35 * 0.0086 (0.0016) C36 - 4.4427 (0.0021) Fe1 - 0.0685 (0.0034) Cl1 0.8866 (0.0039) N1 - 0.8935 (0.0040) N2

Rms deviation of fitted atoms = 0.0050

11.1300(0.0039)x - 0.2023(0.0106)y - 5.2347(0.0169)z = 11.9425(0.0065)

Angle to previous plane (with approximate e.s.d.) = 84.32 (7)

* 0.0010 (0.0013) C11 * -0.0009 (0.0013) C12 * 0.0005 (0.0014) C13 * 0.0002 (0.0014) C14 * -0.0007 (0.0013) C15 - 1.6466 (0.0010) Fe1

Rms deviation of fitted atoms = 0.0007

4.6333(0.0105)x + 1.1270(0.0100)y + 15.1943(0.0071)z = 11.1411(0.0082)

Angle to previous plane (with approximate e.s.d.) = 84.32 (7)

* -0.0048 (0.0016) C31 * -0.0008 (0.0018) C32 * 0.0027 (0.0019) C33 * 0.0012 (0.0018) C34 * -0.0068 (0.0018) C35 * 0.0086 (0.0016) C36 - 4.4427 (0.0021) Fe1 - 0.0685 (0.0034) Cl1 0.8866 (0.0039) N1 - 0.8935 (0.0040) N2

Rms deviation of fitted atoms = 0.0050

2.8856(0.0125)x + 8.7907(0.0034)y + 6.5342(0.0116)z = 8.2081(0.0140)

Angle to previous plane (with approximate e.s.d.) = 56.21 (8)

* 0.0410 (0.0012) C1 * -0.0613 (0.0011) N1 * 0.0862 (0.0014) N2 * -0.0656 (0.0008) C2 * -0.0003 (0.0006) C3 - 0.0682 (0.0026) C4 - 2.8098 (0.0030) Fe1 - 2.0934 (0.0061) Cl1

Rms deviation of fitted atoms = 0.0586

11.1300(0.0039)x - 0.2023(0.0106)y - 5.2347(0.0169)z = 11.9425(0.0065)

Angle to previous plane (with approximate e.s.d.) = 84.37 (9)

* 0.0010 (0.0013) C11 * -0.0009 (0.0013) C12 * 0.0005 (0.0014) C13 * 0.0002 (0.0014) C14 * -0.0007 (0.0013) C15 - 1.6466 (0.0010) Fe1 - 4.8199 (0.0055) Cl1 0.5014 (0.0057) N1 0.5217 (0.0040) N2

Rms deviation of fitted atoms = 0.0007

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

	x	y	z	Uiso*/Ueq
Fe1	0.98748 (2)	0.19694 (3)	0.125118 (17)	0.04373 (10)
Cl1	0.85839 (6)	0.07059 (8)	0.46174 (5)	0.0889 (2)
N1	1.30022 (14)	0.21830 (17)	0.37891 (10)	0.0485 (4)
N2	1.25195 (13)	0.33341 (16)	0.26794 (10)	0.0416 (3)
C1	1.21910 (16)	0.28455 (18)	0.34126 (12)	0.0421 (4)
C2	1.18019 (17)	0.38725 (19)	0.20396 (12)	0.0454 (4)
C3	1.36474 (15)	0.29349 (19)	0.25859 (12)	0.0439 (4)
C4	1.39374 (17)	0.2243 (2)	0.32843 (13)	0.0475 (5)
C5	1.50397 (19)	0.1720 (3)	0.33798 (17)	0.0622 (6)
C6	1.5807 (2)	0.1918 (3)	0.2781 (2)	0.0744 (8)
C7	1.5508 (2)	0.2614 (3)	0.2087 (2)	0.0748 (8)
C8	1.4415 (2)	0.3124 (2)	0.19671 (16)	0.0601 (6)
C11	1.14627 (15)	0.28015 (19)	0.14477 (12)	0.0418 (4)
C12	1.14919 (17)	0.1385 (2)	0.15682 (14)	0.0492 (5)
C13	1.11425 (18)	0.0742 (2)	0.08476 (15)	0.0585 (6)
C14	1.08948 (19)	0.1749 (3)	0.02825 (14)	0.0581 (6)
C15	1.10874 (18)	0.3024 (2)	0.06444 (13)	0.0513 (5)
C21	0.8768 (2)	0.2774 (4)	0.2048 (2)	0.0798 (9)
C22	0.8794 (2)	0.1419 (4)	0.21387 (16)	0.0776 (8)
C23	0.8466 (2)	0.0813 (3)	0.14345 (19)	0.0749 (8)
C24	0.82292 (19)	0.1806 (4)	0.08709 (17)	0.0833 (10)
C25	0.8419 (2)	0.3069 (3)	0.1267 (3)	0.0937 (12)
C31	1.10316 (17)	0.3059 (2)	0.37384 (12)	0.0454 (4)
C32	1.0548 (2)	0.4329 (2)	0.37944 (14)	0.0580 (5)
C33	0.9467 (2)	0.4477 (3)	0.41151 (16)	0.0688 (7)
C34	0.8862 (2)	0.3376 (3)	0.43803 (15)	0.0659 (6)
C35	0.93509 (19)	0.2121 (2)	0.43191 (14)	0.0568 (5)
C36	1.04353 (18)	0.1948 (2)	0.40115 (13)	0.0506 (5)
H2A	1.2214	0.4582	0.1766	0.055*
H2B	1.1118	0.4266	0.2267	0.055*
H5	1.5246	0.1249	0.3839	0.075*
H6	1.6546	0.1581	0.2838	0.089*
H7	1.6056	0.2740	0.1695	0.090*
H8	1.4207	0.3568	0.1499	0.072*
H12	1.1704	0.0951	0.2039	0.059*
H13	1.1088	−0.0183	0.0765	0.070*
H14	1.0647	0.1606	−0.0240	0.070*
H15	1.0987	0.3859	0.0401	0.062*
H21	0.8952	0.3404	0.2440	0.096*
H22	0.9002	0.0967	0.2605	0.093*
H23	0.8411	−0.0111	0.1349	0.090*
H24	0.7995	0.1677	0.0344	0.100*
H25	0.8328	0.3922	0.1045	0.112*
H32	1.0947	0.5080	0.3617	0.070*
H33	0.9146	0.5332	0.4152	0.083*
H34	0.8137	0.3479	0.4597	0.079*
H36	1.0760	0.1093	0.3988	0.061*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Fe1	0.03316 (15)	0.04911 (17)	0.04894 (17)	−0.00090 (11)	0.00201 (11)	−0.00238 (13)
Cl1	0.0661 (4)	0.0896 (5)	0.1116 (6)	−0.0184 (4)	0.0282 (4)	0.0133 (4)
N1	0.0443 (9)	0.0493 (10)	0.0520 (9)	0.0046 (7)	−0.0030 (7)	−0.0052 (8)
N2	0.0342 (7)	0.0401 (8)	0.0505 (9)	−0.0016 (6)	0.0016 (6)	−0.0032 (7)
C1	0.0381 (9)	0.0387 (9)	0.0493 (10)	−0.0019 (7)	0.0024 (8)	−0.0085 (8)
C2	0.0429 (10)	0.0381 (9)	0.0553 (11)	0.0002 (8)	−0.0001 (8)	0.0028 (8)
C3	0.0327 (8)	0.0386 (9)	0.0603 (12)	−0.0037 (7)	0.0028 (8)	−0.0110 (9)
C4	0.0377 (9)	0.0429 (10)	0.0618 (12)	0.0001 (8)	−0.0040 (8)	−0.0133 (9)
C5	0.0425 (11)	0.0595 (14)	0.0843 (17)	0.0058 (10)	−0.0119 (11)	−0.0129 (12)
C6	0.0371 (11)	0.0716 (17)	0.115 (2)	0.0059 (11)	0.0012 (13)	−0.0200 (16)
C7	0.0457 (12)	0.0714 (16)	0.108 (2)	−0.0093 (12)	0.0293 (14)	−0.0203 (16)
C8	0.0494 (12)	0.0554 (13)	0.0757 (15)	−0.0064 (10)	0.0159 (11)	−0.0065 (11)
C11	0.0325 (8)	0.0439 (10)	0.0490 (10)	0.0012 (7)	0.0037 (7)	0.0019 (8)
C12	0.0431 (10)	0.0413 (10)	0.0631 (12)	0.0062 (8)	−0.0076 (9)	−0.0006 (9)
C13	0.0471 (11)	0.0510 (12)	0.0773 (15)	0.0058 (9)	−0.0005 (10)	−0.0187 (11)
C14	0.0454 (11)	0.0792 (16)	0.0498 (11)	−0.0018 (11)	0.0055 (9)	−0.0130 (11)
C15	0.0429 (10)	0.0619 (13)	0.0493 (11)	−0.0005 (9)	0.0045 (8)	0.0084 (10)
C21	0.0426 (12)	0.103 (2)	0.094 (2)	−0.0047 (13)	0.0126 (13)	−0.0402 (18)
C22	0.0538 (14)	0.117 (3)	0.0624 (15)	−0.0143 (15)	0.0130 (11)	0.0053 (16)
C23	0.0511 (13)	0.0758 (17)	0.098 (2)	−0.0219 (12)	0.0153 (13)	−0.0169 (16)
C24	0.0338 (11)	0.154 (3)	0.0622 (15)	−0.0081 (15)	−0.0020 (10)	−0.0121 (18)
C25	0.0369 (12)	0.084 (2)	0.160 (4)	0.0166 (13)	0.0215 (17)	0.032 (2)
C31	0.0407 (10)	0.0503 (11)	0.0453 (10)	0.0006 (8)	0.0039 (8)	−0.0067 (8)
C32	0.0557 (12)	0.0498 (12)	0.0688 (14)	0.0031 (10)	0.0131 (10)	−0.0067 (10)
C33	0.0628 (14)	0.0638 (15)	0.0800 (16)	0.0185 (12)	0.0178 (12)	−0.0093 (13)
C34	0.0468 (12)	0.0842 (17)	0.0669 (15)	0.0100 (12)	0.0164 (11)	−0.0063 (13)
C35	0.0464 (11)	0.0691 (14)	0.0552 (12)	−0.0054 (10)	0.0106 (9)	0.0015 (11)
C36	0.0471 (11)	0.0508 (11)	0.0539 (11)	0.0004 (9)	0.0074 (9)	−0.0003 (9)

Geometric parameters (Å, º)

Fe1—C11	2.0543 (18)	C21—C25	1.398 (5)
Fe1—C12	2.0419 (19)	C22—C23	1.375 (4)
Fe1—C13	2.038 (2)	C23—C24	1.390 (4)
Fe1—C14	2.034 (2)	C24—C25	1.434 (5)
Fe1—C15	2.040 (2)	C31—C32	1.385 (3)
Fe1—C21	2.031 (3)	C31—C36	1.384 (3)
Fe1—C22	2.034 (3)	C32—C33	1.384 (3)
Fe1—C23	2.032 (2)	C33—C34	1.378 (4)
Fe1—C24	2.026 (2)	C34—C35	1.374 (4)
Fe1—C25	2.020 (3)	C35—C36	1.383 (3)
Cl1—C35	1.742 (2)	C2—H2A	0.9700
N1—C1	1.310 (3)	C2—H2B	0.9700
N1—C4	1.389 (3)	C5—H5	0.9300
N2—C1	1.378 (3)	C6—H6	0.9300
N2—C2	1.456 (2)	C7—H7	0.9300
N2—C3	1.386 (2)	C8—H8	0.9300
C1—C31	1.480 (3)	C12—H12	0.9300
C2—C11	1.504 (3)	C13—H13	0.9300
C3—C4	1.395 (3)	C14—H14	0.9300
C3—C8	1.390 (3)	C15—H15	0.9300
C4—C5	1.396 (3)	C21—H21	0.9300
C5—C6	1.365 (4)	C22—H22	0.9300
C6—C7	1.394 (4)	C23—H23	0.9300
C7—C8	1.387 (4)	C24—H24	0.9300
C11—C12	1.420 (3)	C25—H25	0.9300
C11—C15	1.428 (3)	C32—H32	0.9300
C12—C13	1.422 (3)	C33—H33	0.9300
C13—C14	1.405 (3)	C34—H34	0.9300
C14—C15	1.419 (3)	C36—H36	0.9300
C21—C22	1.354 (5)
C11—Fe1—C12	40.58 (8)	C22—C23—Fe1	70.31 (14)
C11—Fe1—C13	68.61 (8)	C24—C23—Fe1	69.74 (15)
C11—Fe1—C14	68.64 (9)	C23—C24—Fe1	70.19 (14)
C11—Fe1—C15	40.83 (8)	C25—C24—Fe1	69.04 (14)
C11—Fe1—C21	108.43 (10)	C21—C25—Fe1	70.20 (15)
C11—Fe1—C22	123.82 (10)	C24—C25—Fe1	69.46 (15)
C11—Fe1—C23	159.10 (11)	C32—C31—C1	122.05 (19)
C11—Fe1—C24	159.29 (13)	C36—C31—C1	118.23 (18)
C11—Fe1—C25	122.67 (12)	C32—C31—C36	119.69 (19)
C1—N1—C4	104.77 (17)	C31—C32—C33	119.8 (2)
C1—N2—C2	128.44 (16)	C32—C33—C34	120.9 (2)
C1—N2—C3	105.85 (16)	C33—C34—C35	118.7 (2)
C2—N2—C3	124.26 (17)	C34—C35—C36	121.6 (2)
N1—C1—N2	113.52 (17)	C34—C35—Cl1	119.60 (18)
N1—C1—C31	123.68 (19)	C36—C35—Cl1	118.82 (19)
N2—C1—C31	122.80 (18)	C31—C36—C35	119.3 (2)
N2—C2—C11	111.86 (15)	N2—C2—H2A	109.2
N2—C3—C4	105.63 (17)	N2—C2—H2B	109.2
N2—C3—C8	131.8 (2)	C11—C2—H2A	109.2
C4—C3—C8	122.6 (2)	C11—C2—H2B	109.2
N1—C4—C3	110.20 (17)	C4—C5—H5	120.9
N1—C4—C5	130.1 (2)	C6—C5—H5	120.9
C3—C4—C5	119.7 (2)	C5—C6—H6	119.2
C4—C5—C6	118.2 (3)	C7—C6—H6	119.2
C5—C6—C7	121.6 (2)	C6—C7—H7	119.2
C6—C7—C8	121.6 (2)	C8—C7—H7	119.2
C3—C8—C7	116.3 (3)	C3—C8—H8	121.9
C12—C11—C2	126.85 (18)	C7—C8—H8	121.9
C15—C11—C2	126.04 (18)	C11—C12—H12	125.8
C12—C11—C15	107.08 (18)	C13—C12—H12	125.8
C11—C12—C13	108.48 (19)	C12—C13—H13	126.0
C12—C13—C14	107.95 (19)	C14—C13—H13	126.0
C13—C14—C15	108.4 (2)	C13—C14—H14	125.8
C11—C15—C14	108.09 (19)	C15—C14—H14	125.8
C2—C11—Fe1	128.43 (13)	C11—C15—H15	126.0
C12—C11—Fe1	69.24 (11)	C14—C15—H15	126.0
C15—C11—Fe1	69.05 (11)	C22—C21—H21	125.7
C11—C12—Fe1	70.18 (11)	C25—C21—H21	125.7
C13—C12—Fe1	69.46 (12)	C21—C22—H22	125.3
C12—C13—Fe1	69.76 (12)	C23—C22—H22	125.3
C14—C13—Fe1	69.66 (12)	C22—C23—H23	125.5
C13—C14—Fe1	69.97 (13)	C24—C23—H23	125.5
C15—C14—Fe1	69.85 (12)	C23—C24—H24	127.0
C11—C15—Fe1	70.12 (11)	C25—C24—H24	127.0
C14—C15—Fe1	69.37 (13)	C21—C25—H25	126.5
C22—C21—C25	108.6 (3)	C24—C25—H25	126.5
C21—C22—C23	109.4 (3)	C31—C32—H32	120.1
C22—C23—C24	109.0 (3)	C33—C32—H32	120.1
C23—C24—C25	106.0 (3)	C32—C33—H33	119.5
C21—C25—C24	107.0 (3)	C34—C33—H33	119.5
C22—C21—Fe1	70.68 (16)	C33—C34—H34	120.7
C25—C21—Fe1	69.42 (16)	C35—C34—H34	120.7
C21—C22—Fe1	70.41 (17)	C31—C36—H36	120.3
C23—C22—Fe1	70.16 (15)	C35—C36—H36	120.3
C4—N1—C1—N2	0.8 (2)	N2—C2—C11—Fe1	110.27 (17)
C4—N1—C1—C31	−179.03 (17)	C12—Fe1—C11—C2	−121.2 (2)
C3—N2—C1—N1	0.2 (2)	C13—Fe1—C11—C2	−158.8 (2)
C2—N2—C1—N1	166.77 (17)	C14—Fe1—C11—C2	157.7 (2)
C3—N2—C1—C31	180.00 (16)	C15—Fe1—C11—C2	120.0 (2)
C2—N2—C1—C31	−13.4 (3)	C21—Fe1—C11—C2	−2.8 (2)
C1—N2—C2—C11	−92.6 (2)	C22—Fe1—C11—C2	−43.0 (2)
C3—N2—C2—C11	71.7 (2)	C23—Fe1—C11—C2	−75.0 (3)
C1—N2—C3—C8	179.3 (2)	C24—Fe1—C11—C2	74.5 (3)
C2—N2—C3—C8	12.0 (3)	C25—Fe1—C11—C2	39.5 (2)
C1—N2—C3—C4	−1.1 (2)	C15—C11—C12—C13	0.2 (2)
C2—N2—C3—C4	−168.37 (16)	C2—C11—C12—C13	−177.78 (18)
C1—N1—C4—C3	−1.5 (2)	N1—C1—C31—C36	−51.4 (3)
C1—N1—C4—C5	179.5 (2)	N2—C1—C31—C36	128.8 (2)
N2—C3—C4—N1	1.6 (2)	N1—C1—C31—C32	126.9 (2)
C8—C3—C4—N1	−178.74 (18)	N2—C1—C31—C32	−52.9 (3)
N2—C3—C4—C5	−179.24 (18)	C36—C31—C32—C33	−0.7 (4)
C8—C3—C4—C5	0.4 (3)	C1—C31—C32—C33	−179.0 (2)
N1—C4—C5—C6	179.6 (2)	C31—C32—C33—C34	0.0 (4)
C3—C4—C5—C6	0.6 (3)	C32—C33—C34—C35	−0.1 (4)
C4—C5—C6—C7	−0.4 (4)	C33—C34—C35—C36	1.1 (4)
C5—C6—C7—C8	−0.8 (4)	C33—C34—C35—Cl1	−177.7 (2)
C6—C7—C8—C3	1.8 (4)	C34—C35—C36—C31	−1.8 (4)
N2—C3—C8—C7	178.0 (2)	Cl1—C35—C36—C31	177.04 (17)
C4—C3—C8—C7	−1.6 (3)	C32—C31—C36—C35	1.5 (3)
N2—C2—C11—C12	18.6 (3)	C1—C31—C36—C35	180.0 (2)
N2—C2—C11—C15	−158.99 (18)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C25—H25···Cl1^i	0.93	3.05	3.802 (5)	139
C36—H36···Cl1^ii	0.93	3.03	3.670 (2)	127

Symmetry codes: (i) −x+3/2, y+1/2, −z+1/2; (ii) −x+2, −y, −z+1.