Intermolecular interactions in N-(ferrocenyl­methyl)­anthracene-9-carbox­amide

The title compound, [Fe(C₅H₅)(C₂₁H₁₆NO)], was synthesized from the coupling reaction of anthracene-9-carboxyl­ic acid and ferrocenyl­methyl­amine. The ferrocenyl (Fc) group and the anthracene ring system both lie approximately orthogonal to the amide moiety. An amide–amide interaction (along the a axis) is the principal interaction [N...O = 2.910 (2) Å]. A C—H...π(arene) interaction [C...centroid = 3.573 (2) Å] and a C—H...O interaction [C...O = 3.275 (3) Å] complete the hydrogen bonding; two short (Fc)C...C(anthracene) contacts are also present.

S1. Comment

Applications of novel redox-active ligands in diverse research fields, such as medicinal chemistry and materials science, have recently engaged scientists. Ferrocene continues to attract much interest as an electroactive group, with potential applications ranging from sensors to new optical materials to liquid crystals (Chesney et al., 1998; Zakaria et al., 2002; Gallagher et al., 1999; Kraatz et al., 1999; Hudson et al., 2001a,b; Seo et al., 2001). Our interest in ferrocene stems from its potential use in both novel sensors and biological systems. We have previously reported the crystal structures of three para-(ferrocenyl)benzoyl esters (Savage et al., 2002; Anderson et al., 2003), and the structure of N⁹-(ferrocenylmethyl)-9-anthracenecarboxamide, (I), is reported here. Selected geometric parameters are presented in Table 1, with hydrogen-bond and contact data in Table 2; the molecular and crystal structure are depicted in Figs. 1–3.

In (I), the ferrocenyl (Fc) group [Fc = (C₅H₅)Fe(C₅H₄)] is normal, with Fe1···Cg1/Cg2 distances of 1.6498 (10) and 1.6539 (11) Å, and a Cg1···Fe1···Cg2 angle of 178.51 (6)° (Cg1 and Cg2 are the ring centroids for the substituted and unsubstituted rings, respectively). The Fe1—C bond lengths for the substituted η⁵(C₅H₄) cyclopentadienyl ring are in the range 2.045 (2)–2.047 (2) Å and those in the unsubstituted η⁵(C₅H₅) ring are similar [2.034 (2)–2.060 (2) Å]; the C—C bond-length ranges are tight, viz. 1.414 (3)–1.428 (3) and 1.417 (3)–1.421 (4) Å for the η⁵(C₅H₄) and η⁵(C₅H₅) rings, respectively. The C atoms of the η⁵(C₅) rings are essentially eclipsed, with the five C1n···Cg1···Cg2···C2n angles (n = 1–5) ranging from 0.2 (2)° (for the C14/C24 pair) to 0.57 (19)° (for the C13/C23 pair). The C2—C11—Fe1 angle is 126.92 (15)°, which is similar to the mean value (127.2°) for Fe—C—CH₂ angles in the Cambridge Structural Database (CSD version of July 2003, update 5.24; Allen, 2002) (from 616 'hits' with coordinates and no disorder for Fe—CH₂).

Two torsion angles describe the overall molecular geometry in (I); viz. the N1—C2—C11—C12 and N1—C1—C31—C32 angles are 79.6 (3) and 115.4 (2)°, such that the three major components in (I), i.e. the ferrocenyl, amide and anthracenyl groups, are all approximately orthogonal to one another (Fig. 1). The interplanar angle between the η⁵(C₅H₄) ring and the anthracenyl group is 88.45 (8)° (Fig. 1). The rings in the anthracene group are coplanar with the two external rings, at angles of 1.01 (9) and 1.95 (9)° to the central {C31–C36} ring. In the C₁₄ system, the bond lengths can be arranged in specific groupings, with four from 1.353 (3) to 1.365 (3) Å (a in the scheme), four from 1.390 (3) to 1.412 (3) Å (b) and eight from 1.414 (3) to 1.441 (3) Å [mean 1.428 (3) Å] (c). These bond lengths correspond to the anthracenyl system as depicted in our scheme and are similar to those found in related anthracene-9-carboxamide structures in the CSD [e.g. CSD refcodes CABGAO (Adams et al., 2001) and MEYYOE (Kohmoto et al., 2001)].

The primary intermolecular interaction is the amide···amide interaction along the a axis [N···Oⁱ = 2.910 (2) Å; symmetry code (i) x − 1/2, −y + 1/2, z; Table 2] [graph set C(4); Bernstein et al., 1995]. In tandem with the N—H···O=C hydrogen bond, a C—H···π(arene) interaction [C2—H2A···π(C31–C36)ⁱ, with C2···Cg3ⁱ = 3.573 (2) Å] generates an R²₂(8) ring, with the two donors on one molecule and two acceptors on the other (Figs. 2 and 3). The C15/H15 moiety also forms a C—H···π(arene) contact with the anthracene group [H15···Cg5 = 3.04 Å, some 0.4 Å longer than the C2···π(arene centroid) distance]. However, this contact is directed towards atom C40 atom [H15···C40ⁱ = 2.80 Å and C15—H15···C40ⁱ = 164°]. The C25/H25 group is involved in a similar contact with atom C37 [H25···C37 = 2.87 Å and C25—H25···C37ⁱ = 149°]. A second type of R²₂(8) ring can be considered to form from two C—H···π(arene) interactions involving atoms C2 and C15. A similar arrangement has been observed previously in the crystal structure of 2,4,6-tris(1'-Phenylthio-1-ferrocenyl)boroxin [CSD refcode BOQQAZ; Hua et al., 2001), in which a ferrocenyl group forms two contacts with a neighbouring C₆ aromatic ring, with (cp)H···C₆ distances of 2.78 and 2.87 Å and C—H···C angles of 164 and 160° (the two C₆ atoms are para-related; cp is the cyclopentadienyl ring). In the structure of OBEWOH (Knoesen et al., 2001), the (cp)H···C distances are 2.73 and 2.81 Å, and the C—H···C angles are 161 and 147°; in PALZOR, bis(2-Ferrocenylmethyleneamino)benzenethiolato-S)- mercury(II), the relevant data are 2.84 and 2.71 Å, and 152 and 163° (Kawamoto & Kushi, 1992). Similar C—H···C contacts have been reported in ethynyl steroids (Lutz et al., 1998). A C—H···O hydrogen bond involving atoms C44 and O1ⁱⁱ completes the intermolecular interactions [symmetry code: (ii) −x + 1/2,y − 1/2,-z].

Examination of the structure with PLATON (Spek, 2002) showed that there were four niches, ?each with a volume of 17 ų, but these are too small to contain even a water molecule (40 ų).

The majority of ferrocene derivatives in the CSD that contain an amide group have the ferrocenyl group bonded directly to the amide functionality (usually derived from ferrocene carboxylic acid or acyl chloride reacted with an amino derivative). The combination of Fc and CH₂NHCO moieties is unusual, a nd currently seven examples are available in the CSD. These include FAMFER (Hall & Brown, 1971), PULDUV (Gale et al., 1998), OHEPUM (Denuault et al., 2002), XULRIF (Laurent et al., 2002), XUZSIU and XUZSUG (Coles et al., 2003). By comparison, there are ten 'hits' for the Fc/NH/CO moiety and 79 'hits' for the Fc/CO/NH moiety. This result can be attributed to the difficulty of obtaining aminoferrocene as a starting a material and also the frequency with which ferrocene carboxylic acid or the acyl chloride are used in condensation reactions with amino derivatives.

S2. Experimental

For the synthesis of (I), ferrocenyl methyl amine (0.50 g, 2.3 mmol) was added to a solution of 9-anthracene carboxylic acid (0.56 g, 2.5 mmol), 1-hydroxybenzotriazole (0.38 g, 2.7 mmol) and 1,3-dicyclohexylcarbodiimide (0.55 g, 2.5 mmol) in CH₂Cl₂ (40 ml) at 273 K and stirred for 30 min. The reaction mixture was warmed to room temperature and stirred for a further 48 h. The precipitated N,N'-dicyclohexylcarbourea was removed by filtration and the residue was washed with CH₂Cl₂, with the solvent volume reduced in vacuo. The mixture was purified on a silica-gel column using a mobile phase of hexane:ethyl acetate (2:1). Recrystallization from methanol furnished (I) as orange needles (0.447 g, 48%). The UV–Vis transition is at 435 nm at a concentration of 1.01 mg ml⁻¹ in CHCl₃. IR (KBr, ν_C═O cm⁻¹): 161; ¹H NMR (400 MHz, d₆ DMSO): δ 4.19–4.20, 4.26, 4.36–4.37, 4.43–4.44, 7.54–7.58, 7.94–7.96, 8.12–8.15, 8.66, 9.12; ¹³C NMR (100 MHz, d₆ DMSO): δ 38.75, 67.83, 68.44, 68.82, 86.33, 125.56, 125.93, 126.68, 127.46, 127.63, 128.76, 131.04, 133.61, 168.23. M.p. (uncorrected) 477–479 K.

S3. Refinement

Compound (I) crystallized in the monoclinic system; space group P2₁/a was assigned from the systematic absences and confirmed by the analysis. H atoms attached to C atoms were treated as riding, using SHELXL97 (Sheldrick, 1997) defaults, and the H atom attached to the N atom was refined with isotropic displacement parameters [N—H = 0.82 (3) Å].

Computing details

Data collection: KappaCCD Server Software (Nonius, 1997); cell refinement: DENZO–SMN (Otwinowski & Minor, 1997); data reduction: DENZO–SMN (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP (Johnson, 1976) and PLATON (Spek, 2002); software used to prepare material for publication: SHELXL97 and PREP8 (Ferguson, 1998).

Figures

	Fig. 1. A view of (I), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. A stereoview of the interactions in the crystal structure of (I) (with a labelled unit cell).
	Fig. 3. A stereoview of the interactions between the ferrocenyl moiety and the anthracene ring in (I), with atoms drawn as their van der Waals spheres.

N-(ferrocenylmethyl)anthracene-9-carboxamide

Crystal data

[Fe(C5H5)(C21H16NO)]	F(000) = 872
Mr = 419.29	Dx = 1.417 Mg m^−3
Monoclinic, P21/a	Melting point: 476 K
Hall symbol: -p_2yab	Mo Kα radiation, λ = 0.71073 Å
a = 9.5904 (3) Å	Cell parameters from 7412 reflections
b = 13.4903 (5) Å	θ = 2.6–27.5°
c = 15.8568 (5) Å	µ = 0.78 mm^−1
β = 106.603 (2)°	T = 294 K
V = 1965.98 (11) Å^3	Block, orange
Z = 4	0.24 × 0.20 × 0.20 mm

Data collection

Nonius KappaCCD diffractometer	4481 independent reflections
Radiation source: fine-focus sealed X-ray tube	3287 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.057
ϕ, ω scans with κ offsets	θmax = 27.5°, θmin = 2.7°
Absorption correction: multi-scan (DENZO–SMN; Otwinowski & Minor, 1997)	h = −12→11
Tmin = 0.854, Tmax = 0.907	k = −17→17
13006 measured reflections	l = −20→20

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)] = 0.040	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.097	w = 1/[σ^2(Fo^2) + (0.0383P)^2 + 1.1032P] where P = (Fo^2 + 2Fc^2)/3
S = 1.03	(Δ/σ)max < 0.001
4481 reflections	Δρmax = 0.46 e Å^−3
267 parameters	Δρmin = −0.43 e Å^−3
0 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0024 (6)

Special details

Experimental. ¹H NMR (400 MHz, DMSO -δ₆) 4.20 (2H, s, meta of C5H4) 4.26 (5H, s unsubstituted C5H5 ring) 4.36 (2H, s, ortho on C5H4) 4.43 (2H, d, CH2NH) 7.54–7.57 (4H, m, ArH) 7.93–7.96 (2H, m, ArH) 8.12–8.15 (2H, m, ArH) 8.66 (1H, s, ArH para to C=O) 9.11 (1H, t, NH)

Geometry. Specified hydrogen bonds (with e.s.d.'s except fixed and riding H) ##############################################################

D—H H···A D···A <(DHA)

0.82 (3) 2.10 (3) 2.910 (2) 169 (2) N1—H1···O1_$2 0.99 2.86 3.655 (3) 137.7 C2—H2A···C31_$2 0.99 3.01 3.752 (3) 132.9 C2—H2A···C32_$2 0.99 3.10 3.915 (3) 140.8 C2—H2A···C33_$2 0.99 3.07 3.997 (3) 157.2 C2—H2A···C34_$2 0.99 2.97 3.948 (3) 170.4 C2—H2A···C35_$2 0.99 2.86 3.772 (3) 153.6 C2—H2A···C36_$2 0.95 2.41 3.276 (3) 150.8 C44—H44···O1_$3

Planes data ###########

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

0.1859(0.0111)x + 13.4658(0.0011)y − 0.9552(0.0184)z = 5.2376(0.0072)

* 0.0024 (0.0014) C11 * −0.0006 (0.0014) C12 * −0.0015 (0.0015) C13 * 0.0029 (0.0014) C14 * −0.0033 (0.0014) C15 1.6498 (0.0011) Fe1 − 1.8764 (0.0048) C1 − 0.0130 (0.0039) C2 − 1.3580 (0.0043) N1 − 1.2291 (0.0048) O1

Rms deviation of fitted atoms = 0.0023

−0.0021(0.0117)x + 13.4284(0.0017)y − 1.4533(0.0195)z = 8.3007(0.0080)

Angle to previous plane (with approximate e.s.d.) = 2.49 (3)

* 0.0000 (0.0015) C21 * −0.0009 (0.0015) C22 * 0.0014 (0.0015) C23 * −0.0013 (0.0015) C24 * 0.0008 (0.0015) C25 − 1.6537 (0.0011) Fe1 − 5.0612 (0.0051) C1 − 3.2032 (0.0042) C2 − 4.5282 (0.0047) N1 − 4.4420 (0.0051) O1

Rms deviation of fitted atoms = 0.0010

−9.3807(0.0060)x − 1.9302(0.0330)y + 6.7257(0.0285)z = 0.1784(0.0086)

Angle to previous plane (with approximate e.s.d.) = 80.99 (16)

* 0.0000 (0.0000) C11 * 0.0000 (0.0000) C2 * 0.0000 (0.0000) N1 − 0.2843 (0.0040) Fe1 0.0000 (0.0000) N1 − 2.2319 (0.0028) O1

Rms deviation of fitted atoms = 0.0000

0.0012(0.0275)x − 4.4501(0.0268)y + 14.3446(0.0085)z = 1.1863(0.0104)

Angle to previous plane (with approximate e.s.d.) = 79.07 (20)

* 0.0000 (0.0000) C1 * 0.0000 (0.0000) C2 * 0.0000 (0.0000) N1 − 0.0753 (0.0055) O1 0.1056 (0.0041) C31 1.8478 (0.0079) Fe1 0.3639 (0.0086) C34

Rms deviation of fitted atoms = 0.0000

0.1859(0.0111)x + 13.4658 (0.0011)y − 0.9552(0.0184)z = 5.2376(0.0072)

Angle to previous plane (with approximate e.s.d.) = 67.47 (14)

* 0.0024 (0.0014) C11 * −0.0006 (0.0014) C12 * −0.0015 (0.0015) C13 * 0.0029 (0.0014) C14 * −0.0033 (0.0014) C15 1.6498 (0.0011) Fe1 − 1.8764 (0.0048) C1 − 0.0130 (0.0039) C2 − 1.3580 (0.0043) N1 − 1.2291 (0.0048) O1

Rms deviation of fitted atoms = 0.0023

8.9052(0.0031)x + 0.4084(0.0118)y + 1.4145(0.0137)z = 1.6654(0.0032)

Angle to previous plane (with approximate e.s.d.) = 88.45 (8)

* 0.0108 (0.0015) C35 * −0.0110 (0.0014) C36 * −0.0021 (0.0015) C37 * −0.0065 (0.0016) C38 * 0.0061 (0.0016) C39 * 0.0027 (0.0015) C40

Rms deviation of fitted atoms = 0.0074

8.8757(0.0030)x + 0.6285(0.0116)y + 1.5192(0.0131)z = 1.6897(0.0015)

Angle to previous plane (with approximate e.s.d.) = 1.01 (9)

* 0.0092 (0.0014) C31 * −0.0094 (0.0014) C32 * 0.0023 (0.0015) C33 * 0.0051 (0.0015) C34 * −0.0053 (0.0015) C35 * −0.0019 (0.0014) C36

Rms deviation of fitted atoms = 0.0063

8.9473(0.0031)x + 0.9521(0.0128)y + 1.1376(0.0141)z = 1.7066(0.0017)

Angle to previous plane (with approximate e.s.d.) = 1.95 (9)

* 0.0068 (0.0015) C32 * −0.0056 (0.0015) C33 * −0.0026 (0.0016) C41 * −0.0029 (0.0017) C42 * 0.0043 (0.0017) C43 * 0.0000 (0.0016) C44

Rms deviation of fitted atoms = 0.0043

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

	x	y	z	Uiso*/Ueq
Fe1	0.17185 (3)	0.53590 (2)	0.37775 (2)	0.01869 (11)
O1	0.27952 (15)	0.30605 (11)	0.17238 (9)	0.0198 (3)
N1	0.0453 (2)	0.29996 (14)	0.17575 (12)	0.0179 (4)
C1	0.1644 (2)	0.25890 (16)	0.16301 (13)	0.0167 (4)
C2	0.0470 (2)	0.40206 (16)	0.20743 (14)	0.0190 (4)
C11	0.1156 (2)	0.40919 (16)	0.30518 (14)	0.0178 (4)
C12	0.2680 (2)	0.40997 (16)	0.34898 (14)	0.0212 (5)
C13	0.2863 (3)	0.41618 (17)	0.44108 (15)	0.0245 (5)
C14	0.1472 (3)	0.41942 (17)	0.45502 (15)	0.0245 (5)
C15	0.0415 (2)	0.41447 (16)	0.37116 (14)	0.0217 (5)
C21	0.1123 (3)	0.64962 (17)	0.29068 (16)	0.0291 (5)
C22	0.2640 (3)	0.65415 (17)	0.33291 (16)	0.0276 (5)
C23	0.2835 (3)	0.66425 (18)	0.42467 (16)	0.0271 (5)
C24	0.1445 (3)	0.66560 (18)	0.43924 (17)	0.0294 (6)
C25	0.0385 (3)	0.65678 (18)	0.35639 (18)	0.0306 (6)
C31	0.1572 (2)	0.15172 (16)	0.13712 (14)	0.0176 (4)
C32	0.1712 (2)	0.12709 (16)	0.05334 (14)	0.0182 (4)
C33	0.1834 (2)	0.02484 (16)	0.03196 (14)	0.0198 (5)
C34	0.1784 (2)	−0.04773 (17)	0.09325 (15)	0.0230 (5)
C35	0.1614 (2)	−0.02443 (17)	0.17563 (14)	0.0207 (5)
C36	0.1507 (2)	0.07812 (16)	0.19837 (14)	0.0177 (4)
C37	0.1537 (2)	−0.09947 (18)	0.23722 (15)	0.0253 (5)
C38	0.1393 (2)	−0.07601 (18)	0.31790 (15)	0.0265 (5)
C39	0.1323 (2)	0.02513 (18)	0.34144 (15)	0.0247 (5)
C40	0.1376 (2)	0.09931 (17)	0.28457 (14)	0.0214 (5)
C41	0.1707 (2)	0.19972 (17)	−0.01214 (14)	0.0237 (5)
C42	0.1838 (3)	0.17255 (19)	−0.09246 (15)	0.0273 (5)
C43	0.1979 (3)	0.0716 (2)	−0.11253 (15)	0.0276 (5)
C44	0.1974 (2)	0.00008 (18)	−0.05282 (15)	0.0249 (5)
H1	−0.028 (3)	0.2663 (19)	0.1692 (16)	0.026 (7)*
H2A	−0.0540	0.4273	0.1928	0.023*
H2B	0.1017	0.4443	0.1769	0.023*
H12	0.3438	0.4069	0.3215	0.025*
H13	0.3768	0.4179	0.4857	0.029*
H14	0.1277	0.4241	0.5104	0.029*
H15	−0.0610	0.4147	0.3610	0.026*
H21	0.0678	0.6430	0.2292	0.035*
H22	0.3391	0.6510	0.3048	0.033*
H23	0.3743	0.6692	0.4687	0.033*
H24	0.1257	0.6714	0.4947	0.035*
H25	−0.0640	0.6558	0.3466	0.037*
H34	0.1867	−0.1153	0.0787	0.028*
H37	0.1586	−0.1672	0.2218	0.030*
H38	0.1339	−0.1270	0.3582	0.032*
H39	0.1238	0.0412	0.3981	0.030*
H40	0.1325	0.1663	0.3020	0.026*
H41	0.1612	0.2679	0.0003	0.028*
H42	0.1834	0.2219	−0.1353	0.033*
H43	0.2078	0.0538	−0.1685	0.033*
H44	0.2066	−0.0674	−0.0674	0.030*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Fe1	0.01947 (17)	0.01556 (18)	0.02188 (18)	−0.00051 (13)	0.00728 (13)	−0.00180 (13)
O1	0.0195 (7)	0.0171 (8)	0.0247 (8)	−0.0027 (6)	0.0092 (6)	−0.0010 (6)
N1	0.0166 (9)	0.0149 (10)	0.0227 (9)	−0.0021 (8)	0.0064 (8)	−0.0037 (7)
C1	0.0202 (10)	0.0172 (11)	0.0131 (9)	0.0008 (9)	0.0053 (8)	0.0016 (8)
C2	0.0178 (10)	0.0156 (11)	0.0232 (11)	0.0015 (9)	0.0053 (9)	−0.0006 (9)
C11	0.0202 (10)	0.0133 (11)	0.0205 (10)	0.0000 (8)	0.0066 (9)	−0.0009 (8)
C12	0.0186 (10)	0.0186 (12)	0.0274 (11)	0.0009 (9)	0.0080 (9)	−0.0030 (9)
C13	0.0257 (12)	0.0210 (13)	0.0238 (11)	0.0018 (9)	0.0021 (10)	0.0000 (9)
C14	0.0326 (13)	0.0202 (12)	0.0219 (11)	−0.0021 (10)	0.0097 (10)	0.0015 (9)
C15	0.0223 (11)	0.0177 (12)	0.0272 (11)	−0.0043 (9)	0.0107 (10)	−0.0011 (9)
C21	0.0384 (14)	0.0172 (12)	0.0289 (13)	0.0011 (10)	0.0051 (11)	0.0026 (10)
C22	0.0342 (13)	0.0171 (12)	0.0364 (13)	−0.0042 (10)	0.0178 (11)	0.0002 (10)
C23	0.0269 (12)	0.0185 (13)	0.0342 (13)	−0.0049 (10)	0.0059 (10)	−0.0052 (10)
C24	0.0376 (14)	0.0194 (13)	0.0363 (13)	−0.0007 (10)	0.0185 (12)	−0.0064 (10)
C25	0.0259 (12)	0.0155 (13)	0.0505 (16)	0.0048 (10)	0.0110 (12)	0.0006 (11)
C31	0.0163 (10)	0.0152 (11)	0.0221 (11)	−0.0006 (8)	0.0069 (9)	−0.0004 (8)
C32	0.0179 (10)	0.0162 (11)	0.0206 (10)	−0.0010 (8)	0.0059 (9)	−0.0005 (9)
C33	0.0192 (10)	0.0189 (12)	0.0212 (10)	0.0018 (9)	0.0056 (9)	−0.0025 (9)
C34	0.0230 (11)	0.0159 (12)	0.0299 (12)	0.0009 (9)	0.0071 (10)	−0.0041 (9)
C35	0.0170 (10)	0.0197 (12)	0.0239 (11)	−0.0007 (9)	0.0034 (9)	0.0020 (9)
C36	0.0153 (10)	0.0169 (11)	0.0209 (10)	0.0015 (8)	0.0052 (9)	0.0005 (9)
C37	0.0231 (11)	0.0183 (12)	0.0322 (12)	−0.0006 (9)	0.0042 (10)	0.0027 (10)
C38	0.0243 (12)	0.0271 (13)	0.0271 (12)	−0.0006 (10)	0.0059 (10)	0.0089 (10)
C39	0.0205 (11)	0.0322 (14)	0.0221 (11)	0.0021 (10)	0.0072 (9)	0.0066 (10)
C40	0.0216 (11)	0.0206 (12)	0.0229 (11)	0.0019 (9)	0.0080 (9)	0.0015 (9)
C41	0.0296 (12)	0.0178 (12)	0.0254 (11)	−0.0011 (10)	0.0105 (10)	−0.0007 (9)
C42	0.0335 (13)	0.0290 (14)	0.0210 (11)	−0.0036 (11)	0.0104 (10)	0.0013 (10)
C43	0.0308 (13)	0.0345 (14)	0.0205 (11)	0.0015 (11)	0.0120 (10)	−0.0043 (10)
C44	0.0248 (11)	0.0231 (12)	0.0257 (12)	0.0028 (9)	0.0056 (10)	−0.0078 (10)

Geometric parameters (Å, º)

Fe1—C11	2.045 (2)	C34—C35	1.397 (3)
Fe1—C12	2.046 (2)	C35—C36	1.441 (3)
Fe1—C13	2.047 (2)	C35—C37	1.423 (3)
Fe1—C14	2.047 (2)	C36—C40	1.437 (3)
Fe1—C15	2.045 (2)	C37—C38	1.363 (3)
Fe1—C21	2.034 (2)	C38—C39	1.421 (3)
Fe1—C22	2.047 (2)	C39—C40	1.358 (3)
Fe1—C23	2.060 (2)	C41—C42	1.365 (3)
Fe1—C24	2.056 (2)	C42—C43	1.414 (4)
Fe1—C25	2.040 (2)	C43—C44	1.353 (3)
O1—C1	1.245 (2)	N1—H1	0.82 (3)
N1—C1	1.336 (3)	C2—H2A	0.9900
N1—C2	1.465 (3)	C2—H2B	0.9900
C1—C31	1.499 (3)	C12—H12	0.9500
C2—C11	1.504 (3)	C13—H13	0.9500
C11—C12	1.428 (3)	C14—H14	0.9500
C11—C15	1.424 (3)	C15—H15	0.9500
C12—C13	1.423 (3)	C21—H21	0.9500
C13—C14	1.414 (3)	C22—H22	0.9500
C14—C15	1.425 (3)	C23—H23	0.9500
C21—C22	1.418 (3)	C24—H24	0.9500
C21—C25	1.421 (4)	C25—H25	0.9500
C22—C23	1.419 (3)	C34—H34	0.9500
C23—C24	1.417 (3)	C37—H37	0.9500
C24—C25	1.418 (4)	C38—H38	0.9500
C31—C32	1.412 (3)	C39—H39	0.9500
C31—C36	1.403 (3)	C40—H40	0.9500
C32—C33	1.433 (3)	C41—H41	0.9500
C32—C41	1.427 (3)	C42—H42	0.9500
C33—C34	1.390 (3)	C43—H43	0.9500
C33—C44	1.428 (3)	C44—H44	0.9500
C21—Fe1—C25	40.82 (10)	C24—C25—C21	108.0 (2)
C21—Fe1—C15	121.38 (10)	C24—C25—Fe1	70.34 (14)
C25—Fe1—C15	106.66 (10)	C21—C25—Fe1	69.33 (13)
C21—Fe1—C11	105.71 (9)	C36—C31—C32	121.3 (2)
C25—Fe1—C11	121.50 (10)	C32—C31—C1	118.36 (18)
C15—Fe1—C11	40.76 (8)	C36—C31—C1	120.05 (18)
C21—Fe1—C12	122.15 (9)	C31—C32—C41	122.8 (2)
C25—Fe1—C12	158.11 (10)	C31—C32—C33	119.02 (19)
C15—Fe1—C12	68.35 (9)	C41—C32—C33	118.18 (19)
C11—Fe1—C12	40.85 (8)	C34—C33—C44	121.6 (2)
C21—Fe1—C22	40.68 (10)	C34—C33—C32	119.40 (19)
C25—Fe1—C22	68.41 (10)	C44—C33—C32	118.9 (2)
C15—Fe1—C22	157.63 (9)	C33—C34—C35	122.1 (2)
C11—Fe1—C22	121.78 (9)	C34—C35—C37	121.6 (2)
C12—Fe1—C22	107.63 (9)	C34—C35—C36	119.1 (2)
C21—Fe1—C14	158.01 (10)	C37—C35—C36	119.3 (2)
C25—Fe1—C14	122.59 (10)	C31—C36—C40	123.5 (2)
C15—Fe1—C14	40.75 (9)	C31—C36—C35	119.06 (19)
C11—Fe1—C14	68.79 (9)	C40—C36—C35	117.46 (19)
C12—Fe1—C14	68.44 (9)	C38—C37—C35	121.2 (2)
C22—Fe1—C14	160.23 (10)	C37—C38—C39	119.6 (2)
C21—Fe1—C13	159.27 (10)	C40—C39—C38	121.3 (2)
C25—Fe1—C13	159.19 (10)	C39—C40—C36	121.0 (2)
C15—Fe1—C13	68.13 (9)	C42—C41—C32	120.8 (2)
C11—Fe1—C13	68.59 (9)	C41—C42—C43	120.6 (2)
C12—Fe1—C13	40.68 (9)	C44—C43—C42	120.7 (2)
C22—Fe1—C13	124.11 (10)	C43—C44—C33	120.8 (2)
C14—Fe1—C13	40.40 (9)	C1—N1—H1	119.4 (18)
C21—Fe1—C24	68.33 (10)	C2—N1—H1	119.4 (18)
C25—Fe1—C24	40.51 (10)	N1—C2—H2A	109.2
C15—Fe1—C24	123.17 (9)	C11—C2—H2A	109.2
C11—Fe1—C24	158.33 (9)	N1—C2—H2B	109.2
C12—Fe1—C24	159.92 (10)	C11—C2—H2B	109.2
C22—Fe1—C24	68.14 (10)	H2A—C2—H2B	107.9
C14—Fe1—C24	108.49 (10)	C13—C12—H12	126.0
C13—Fe1—C24	124.19 (10)	C11—C12—H12	126.0
C21—Fe1—C23	68.12 (10)	Fe1—C12—H12	126.3
C25—Fe1—C23	67.97 (10)	C14—C13—H13	125.8
C15—Fe1—C23	159.87 (9)	C12—C13—H13	125.8
C11—Fe1—C23	158.77 (9)	Fe1—C13—H13	126.4
C12—Fe1—C23	123.89 (9)	C13—C14—H14	126.2
C22—Fe1—C23	40.44 (9)	C15—C14—H14	126.2
C14—Fe1—C23	124.47 (10)	Fe1—C14—H14	126.1
C13—Fe1—C23	109.59 (10)	C11—C15—H15	125.8
C24—Fe1—C23	40.27 (9)	C14—C15—H15	125.8
C1—N1—C2	121.03 (18)	Fe1—C15—H15	126.5
O1—C1—N1	122.5 (2)	C22—C21—H21	126.0
O1—C1—C31	119.69 (18)	C25—C21—H21	126.0
N1—C1—C31	117.81 (18)	Fe1—C21—H21	125.6
N1—C2—C11	111.85 (18)	C21—C22—H22	126.1
C2—C11—Fe1	126.92 (15)	C23—C22—H22	126.1
C15—C11—C12	107.35 (19)	Fe1—C22—H22	126.0
C15—C11—C2	126.66 (19)	C24—C23—H23	125.9
C12—C11—C2	125.98 (19)	C22—C23—H23	125.9
C15—C11—Fe1	69.61 (12)	Fe1—C23—H23	126.7
C12—C11—Fe1	69.59 (12)	C23—C24—H24	126.1
C13—C12—C11	108.00 (19)	C25—C24—H24	126.1
C13—C12—Fe1	69.73 (13)	Fe1—C24—H24	126.3
C11—C12—Fe1	69.56 (12)	C24—C25—H25	126.0
C14—C13—C12	108.5 (2)	C21—C25—H25	126.0
C14—C13—Fe1	69.80 (13)	Fe1—C25—H25	125.9
C12—C13—Fe1	69.59 (13)	C33—C34—H34	118.9
C13—C14—C15	107.69 (19)	C35—C34—H34	118.9
C13—C14—Fe1	69.80 (13)	C38—C37—H37	119.4
C15—C14—Fe1	69.53 (13)	C35—C37—H37	119.4
C11—C15—C14	108.48 (19)	C37—C38—H38	120.2
C11—C15—Fe1	69.63 (12)	C39—C38—H38	120.2
C14—C15—Fe1	69.72 (13)	C40—C39—H39	119.3
C22—C21—C25	108.0 (2)	C38—C39—H39	119.3
C22—C21—Fe1	70.17 (14)	C39—C40—H40	119.5
C25—C21—Fe1	69.85 (14)	C36—C40—H40	119.5
C21—C22—C23	107.8 (2)	C42—C41—H41	119.6
C21—C22—Fe1	69.15 (13)	C32—C41—H41	119.6
C23—C22—Fe1	70.27 (13)	C41—C42—H42	119.7
C24—C23—C22	108.3 (2)	C43—C42—H42	119.7
C24—C23—Fe1	69.71 (13)	C44—C43—H43	119.7
C22—C23—Fe1	69.29 (13)	C42—C43—H43	119.7
C23—C24—C25	107.9 (2)	C43—C44—H44	119.6
C23—C24—Fe1	70.02 (13)	C33—C44—H44	119.6
C25—C24—Fe1	69.16 (13)
C2—N1—C1—O1	−4.1 (3)	C12—Fe1—C21—C25	161.61 (14)
C2—N1—C1—C31	175.43 (18)	C22—Fe1—C21—C25	−118.9 (2)
C1—N1—C2—C11	−79.1 (2)	C14—Fe1—C21—C25	48.2 (3)
N1—C2—C11—C15	−99.1 (2)	C13—Fe1—C21—C25	−168.8 (2)
N1—C2—C11—C12	79.6 (3)	C24—Fe1—C21—C25	−37.66 (15)
N1—C2—C11—Fe1	169.99 (14)	C23—Fe1—C21—C25	−81.17 (15)
C21—Fe1—C11—C15	−120.13 (14)	C25—C21—C22—C23	−0.1 (3)
C25—Fe1—C11—C15	−78.69 (15)	Fe1—C21—C22—C23	−59.91 (17)
C12—Fe1—C11—C15	118.54 (18)	C25—C21—C22—Fe1	59.82 (16)
C22—Fe1—C11—C15	−161.34 (13)	C25—Fe1—C22—C21	−37.99 (15)
C14—Fe1—C11—C15	37.39 (13)	C15—Fe1—C22—C21	43.3 (3)
C13—Fe1—C11—C15	80.91 (14)	C11—Fe1—C22—C21	76.59 (16)
C24—Fe1—C11—C15	−49.4 (3)	C12—Fe1—C22—C21	119.13 (14)
C23—Fe1—C11—C15	170.0 (2)	C14—Fe1—C22—C21	−165.7 (2)
C21—Fe1—C11—C12	121.32 (14)	C13—Fe1—C22—C21	160.90 (14)
C25—Fe1—C11—C12	162.76 (13)	C24—Fe1—C22—C21	−81.75 (15)
C15—Fe1—C11—C12	−118.54 (18)	C23—Fe1—C22—C21	−118.9 (2)
C22—Fe1—C11—C12	80.12 (15)	C21—Fe1—C22—C23	118.9 (2)
C14—Fe1—C11—C12	−81.15 (14)	C25—Fe1—C22—C23	80.93 (15)
C13—Fe1—C11—C12	−37.63 (13)	C15—Fe1—C22—C23	162.2 (2)
C24—Fe1—C11—C12	−168.0 (2)	C11—Fe1—C22—C23	−164.49 (13)
C23—Fe1—C11—C12	51.5 (3)	C12—Fe1—C22—C23	−121.94 (14)
C21—Fe1—C11—C2	1.0 (2)	C14—Fe1—C22—C23	−46.8 (3)
C25—Fe1—C11—C2	42.5 (2)	C13—Fe1—C22—C23	−80.18 (16)
C15—Fe1—C11—C2	121.2 (2)	C24—Fe1—C22—C23	37.18 (14)
C12—Fe1—C11—C2	−120.3 (2)	C21—C22—C23—C24	0.2 (3)
C22—Fe1—C11—C2	−40.2 (2)	Fe1—C22—C23—C24	−58.99 (17)
C14—Fe1—C11—C2	158.6 (2)	C21—C22—C23—Fe1	59.20 (16)
C13—Fe1—C11—C2	−157.9 (2)	C21—Fe1—C23—C24	81.87 (16)
C24—Fe1—C11—C2	71.7 (3)	C25—Fe1—C23—C24	37.70 (15)
C23—Fe1—C11—C2	−68.8 (3)	C15—Fe1—C23—C24	−40.4 (3)
C15—C11—C12—C13	−0.3 (3)	C11—Fe1—C23—C24	158.7 (2)
C2—C11—C12—C13	−179.2 (2)	C12—Fe1—C23—C24	−163.23 (14)
Fe1—C11—C12—C13	59.35 (16)	C22—Fe1—C23—C24	119.8 (2)
C15—C11—C12—Fe1	−59.62 (15)	C14—Fe1—C23—C24	−77.58 (17)
C2—C11—C12—Fe1	121.5 (2)	C13—Fe1—C23—C24	−120.17 (15)
C21—Fe1—C12—C13	164.47 (14)	C21—Fe1—C23—C22	−37.94 (14)
C25—Fe1—C12—C13	−162.0 (2)	C25—Fe1—C23—C22	−82.11 (16)
C15—Fe1—C12—C13	−81.19 (14)	C15—Fe1—C23—C22	−160.3 (2)
C11—Fe1—C12—C13	−119.29 (18)	C11—Fe1—C23—C22	38.9 (3)
C22—Fe1—C12—C13	122.21 (14)	C12—Fe1—C23—C22	76.96 (17)
C14—Fe1—C12—C13	−37.21 (13)	C14—Fe1—C23—C22	162.61 (14)
C24—Fe1—C12—C13	47.8 (3)	C13—Fe1—C23—C22	120.02 (15)
C23—Fe1—C12—C13	80.68 (16)	C24—Fe1—C23—C22	−119.8 (2)
C21—Fe1—C12—C11	−76.24 (15)	C22—C23—C24—C25	−0.3 (3)
C25—Fe1—C12—C11	−42.7 (3)	Fe1—C23—C24—C25	−58.98 (17)
C15—Fe1—C12—C11	38.10 (12)	C22—C23—C24—Fe1	58.73 (17)
C22—Fe1—C12—C11	−118.50 (13)	C21—Fe1—C24—C23	−81.29 (16)
C14—Fe1—C12—C11	82.08 (14)	C25—Fe1—C24—C23	−119.2 (2)
C13—Fe1—C12—C11	119.29 (18)	C15—Fe1—C24—C23	164.53 (14)
C24—Fe1—C12—C11	167.1 (2)	C11—Fe1—C24—C23	−159.1 (2)
C23—Fe1—C12—C11	−160.04 (13)	C12—Fe1—C24—C23	44.2 (3)
C11—C12—C13—C14	−0.1 (3)	C22—Fe1—C24—C23	−37.33 (14)
Fe1—C12—C13—C14	59.15 (16)	C14—Fe1—C24—C23	121.90 (15)
C11—C12—C13—Fe1	−59.24 (15)	C13—Fe1—C24—C23	79.93 (17)
C21—Fe1—C13—C14	−159.6 (3)	C21—Fe1—C24—C25	37.94 (14)
C25—Fe1—C13—C14	41.2 (3)	C15—Fe1—C24—C25	−76.24 (17)
C15—Fe1—C13—C14	−38.02 (13)	C11—Fe1—C24—C25	−39.9 (3)
C11—Fe1—C13—C14	−82.02 (14)	C12—Fe1—C24—C25	163.5 (2)
C12—Fe1—C13—C14	−119.81 (19)	C22—Fe1—C24—C25	81.90 (16)
C22—Fe1—C13—C14	163.30 (13)	C14—Fe1—C24—C25	−118.87 (15)
C24—Fe1—C13—C14	78.09 (16)	C13—Fe1—C24—C25	−160.84 (14)
C23—Fe1—C13—C14	120.58 (14)	C23—Fe1—C24—C25	119.2 (2)
C21—Fe1—C13—C12	−39.8 (3)	C23—C24—C25—C21	0.2 (3)
C25—Fe1—C13—C12	161.0 (2)	Fe1—C24—C25—C21	−59.32 (16)
C15—Fe1—C13—C12	81.80 (14)	C23—C24—C25—Fe1	59.52 (17)
C11—Fe1—C13—C12	37.79 (12)	C22—C21—C25—C24	−0.1 (3)
C22—Fe1—C13—C12	−76.89 (16)	Fe1—C21—C25—C24	59.95 (17)
C14—Fe1—C13—C12	119.81 (19)	C22—C21—C25—Fe1	−60.02 (17)
C24—Fe1—C13—C12	−162.10 (13)	C21—Fe1—C25—C24	−119.1 (2)
C23—Fe1—C13—C12	−119.61 (14)	C15—Fe1—C25—C24	121.94 (14)
C12—C13—C14—C15	0.4 (3)	C11—Fe1—C25—C24	163.87 (13)
Fe1—C13—C14—C15	59.44 (16)	C12—Fe1—C25—C24	−164.8 (2)
C12—C13—C14—Fe1	−59.02 (16)	C22—Fe1—C25—C24	−81.19 (15)
C21—Fe1—C14—C13	160.8 (2)	C14—Fe1—C25—C24	80.29 (16)
C25—Fe1—C14—C13	−163.87 (14)	C13—Fe1—C25—C24	49.8 (3)
C15—Fe1—C14—C13	118.88 (19)	C23—Fe1—C25—C24	−37.48 (14)
C11—Fe1—C14—C13	81.47 (14)	C15—Fe1—C25—C21	−119.01 (15)
C12—Fe1—C14—C13	37.45 (13)	C11—Fe1—C25—C21	−77.08 (16)
C22—Fe1—C14—C13	−44.7 (3)	C12—Fe1—C25—C21	−45.7 (3)
C24—Fe1—C14—C13	−121.41 (14)	C22—Fe1—C25—C21	37.87 (14)
C23—Fe1—C14—C13	−79.68 (16)	C14—Fe1—C25—C21	−160.66 (14)
C21—Fe1—C14—C15	41.9 (3)	C13—Fe1—C25—C21	168.9 (2)
C25—Fe1—C14—C15	77.25 (16)	C24—Fe1—C25—C21	119.1 (2)
C11—Fe1—C14—C15	−37.41 (13)	C23—Fe1—C25—C21	81.57 (15)
C12—Fe1—C14—C15	−81.43 (14)	O1—C1—C31—C36	108.9 (2)
C22—Fe1—C14—C15	−163.6 (2)	N1—C1—C31—C36	−70.6 (3)
C13—Fe1—C14—C15	−118.88 (19)	O1—C1—C31—C32	−65.1 (3)
C24—Fe1—C14—C15	119.71 (14)	N1—C1—C31—C32	115.4 (2)
C23—Fe1—C14—C15	161.44 (13)	C36—C31—C32—C41	176.7 (2)
C12—C11—C15—C14	0.5 (2)	C1—C31—C32—C41	−9.3 (3)
C2—C11—C15—C14	179.4 (2)	C36—C31—C32—C33	−1.9 (3)
Fe1—C11—C15—C14	−59.08 (16)	C1—C31—C32—C33	172.02 (18)
C12—C11—C15—Fe1	59.61 (15)	C31—C32—C33—C34	1.3 (3)
C2—C11—C15—Fe1	−121.5 (2)	C41—C32—C33—C34	−177.5 (2)
C13—C14—C15—C11	−0.6 (3)	C31—C32—C33—C44	179.96 (19)
Fe1—C14—C15—C11	59.02 (15)	C41—C32—C33—C44	1.2 (3)
C13—C14—C15—Fe1	−59.61 (16)	C44—C33—C34—C35	−178.6 (2)
C21—Fe1—C15—C11	77.19 (15)	C32—C33—C34—C35	0.1 (3)
C25—Fe1—C15—C11	119.23 (14)	C33—C34—C35—C37	178.8 (2)
C12—Fe1—C15—C11	−38.19 (12)	C33—C34—C35—C36	−0.8 (3)
C22—Fe1—C15—C11	45.6 (3)	C32—C31—C36—C40	179.53 (19)
C14—Fe1—C15—C11	−119.84 (19)	C1—C31—C36—C40	5.7 (3)
C13—Fe1—C15—C11	−82.14 (14)	C32—C31—C36—C35	1.2 (3)
C24—Fe1—C15—C11	160.42 (13)	C1—C31—C36—C35	−172.60 (18)
C23—Fe1—C15—C11	−169.5 (2)	C34—C35—C36—C31	0.1 (3)
C21—Fe1—C15—C14	−162.96 (14)	C37—C35—C36—C31	−179.46 (19)
C25—Fe1—C15—C14	−120.93 (14)	C34—C35—C36—C40	−178.26 (19)
C11—Fe1—C15—C14	119.84 (19)	C37—C35—C36—C40	2.2 (3)
C12—Fe1—C15—C14	81.66 (14)	C34—C35—C37—C38	179.0 (2)
C22—Fe1—C15—C14	165.5 (2)	C36—C35—C37—C38	−1.4 (3)
C13—Fe1—C15—C14	37.71 (13)	C35—C37—C38—C39	−0.2 (3)
C24—Fe1—C15—C14	−79.74 (16)	C37—C38—C39—C40	1.0 (3)
C23—Fe1—C15—C14	−49.7 (3)	C38—C39—C40—C36	−0.1 (3)
C25—Fe1—C21—C22	118.9 (2)	C31—C36—C40—C39	−179.7 (2)
C15—Fe1—C21—C22	−162.20 (13)	C35—C36—C40—C39	−1.4 (3)
C11—Fe1—C21—C22	−120.80 (14)	C31—C32—C41—C42	−179.7 (2)
C12—Fe1—C21—C22	−79.49 (16)	C33—C32—C41—C42	−1.0 (3)
C14—Fe1—C21—C22	167.1 (2)	C32—C41—C42—C43	0.1 (3)
C13—Fe1—C21—C22	−50.0 (3)	C41—C42—C43—C44	0.6 (4)
C24—Fe1—C21—C22	81.23 (15)	C42—C43—C44—C33	−0.3 (4)
C23—Fe1—C21—C22	37.72 (14)	C34—C33—C44—C43	178.1 (2)
C15—Fe1—C21—C25	78.91 (16)	C32—C33—C44—C43	−0.6 (3)
C11—Fe1—C21—C25	120.31 (15)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1^i	0.82 (3)	2.10 (3)	2.910 (2)	169 (2)
C2—H2A···Cg3^i	0.99	2.62	3.573 (2)	161
C15—H15···C40^i	0.95	2.80	3.726 (3)	164
C25—H25···C37^i	0.95	2.87	3.715 (3)	149
C44—H44···O1^ii	0.95	2.41	3.276 (3)	151

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