Magnetism and crystal structure of an N₃O₃-coordinated iron(II) complex

The reaction of [FeL(MeOH)₂] {where L is the tetra­dentate N₂O₂-coordinating Schiff base-like ligand (E,E)-diethyl 2,2'-[1,2-phenyl­enebis(nitrilo­methyl­idyne)]bis­(3-oxo­butanoate)(2-) and MeOH is methanol} with 3-amino­pyridine (3-apy) in methanol results in the formation of the octa­hedral complex (3-amino­pyridine-[kappa]N¹){(E,E)-diethyl 2,2'-[1,2-phen­yl­ene­bis­(nitrilo­methyl­idyne)]bis­(3-oxobutanoato)(2-)-[kappa]⁴O³,N,N',O^3'}(methanol-[kappa]O)iron(II), [Fe(C₂₀H₂₂N₂O₆)(C₅H₆N₂)(CH₄O)] or [FeL(3-apy)(MeOH)], in which the Fe^II ion is centered in an N₃O₃ coordination environment with two different axial ligands. This is the first example of an octa­hedral complex of this multidentate ligand type with two different axial ligands, and the title compound can be considered as a precursor for a new class of complexes with potential spin-crossover behavior. An infinite two-dimensional hydrogen-bond network is formed, involving the amine NH group, the methanol OH group and the carbonyl O atoms of the equatorial ligand. T-dependent susceptibility measurements revealed that the complex remains in the high-spin state over the entire temperature range investigated.

S1. Comment

Octahedral iron(II) complexes are an interesting class of complexes because of the possible occurrence of the spin crossover phenomenon. The ability to switch between two or more electronic states on the molecular level under changes in temperature, pressure or light is of potential interest for future applications in molecular switches or memory devices. Although spin crossover could be observed for any octahedral complex with dⁿ (n = 4–7) electronic configuration, the spin transition in octahedral iron(II) complexes with the diamagnetic low-spin (LS) and the paramagnetic high-spin (HS) state are by far the most thoroughly investigated. Of those iron(II) complexes that have been studied, about 90% exhibit N₆ coordination, while the others have N₄O₂, N₄C₂, N₃C₂O₂ or N₄S₂ coordination environments (Gütlich et al., 1994; Goodwin, 1976; König, 1991; Kahn & Martinez, 1998). So far, no examples with an N₃O₃ coordination environment are known.

In this paper we present the strucural and magnetic properties of the octahedral iron(II) complex (3-aminopyridine-κN¹){(E,E)-diethyl 2,2'-[1,2-phenylenebis(nitrilomethylidyne)]bis(3-oxobutanate)(2-)-κ²O³,N,N',O^3'}(methanol-κO)iron(II), (I), in which the iron ion is centered in an N₃O₃ coordination environment. The complex was obtained in a one-pot reaction under argon by conversion of [FeL(MeOH)₂] and 3-aminopyridine (3-apy) in methanol as solvent and heating to reflux for one hour. A 30 molar excess of 3-apy was used in order to obtain a partial substitution of the axial methanol ligands and therefore an unsymmetric complex with two different axial ligands (Fig. 1).

The coordination around the iron(II) ion is almost ideal octahedral, with a displacement of the Fe²⁺ ion from the N₂O₂ coordination plane towards the axial 3-apy ligand of about 0.08 Å. This is surprising, because with methanol as a relatively weak ligand in the axial position one could expect some larger distortion towards the stronger 3-apy. Accordingly, the average bond lengths and angles within the first coordination sphere of the iron centre (Table 1) are within the range reported for similar octahedral iron(II) complexes with N₄O₂ coordination and the iron centre in the high-spin state (Fe–N_eq = 2.09 Å and Fe–O_eq = 2.04 Å; Leibeling, 2003; Weber et al., 2008). The equatorial O2—Fe1—O1 angle is a characteristic tool for the determination of the spin state of this type of iron(II) complex, because the angle changes from about 110° in the HS state to about 90° in the LS state. At 110.64 (6)° in (I), this angle is in the region observed for N₄O₂-coordinated iron(II) complexes in the HS state (Leibeling, 2003; Weber et al., 2008). The heteroatoms of the axial ligands face one another almost linearly. A possible explanation for the minor distortion is the hydrogen-bond network that the amine group of 3-apy is involved in.

Intermolecular interactions such as hydrogen bonding, π-stacking and van der Waals interactions are thought to play a central role for transmitting cooperative interactions during a spin transition in mononuclear complexes. In complex (I), three different hydrogen bonds (see Table 2) form an infinite two-dimensional network along the (101) plane. The base vectors are [010] and [101]. Amine atom N4 acts as a double hydrogen-bond donor, firstly via atom H4A to carboxylate atom O1ⁱ [symmetry code: (i) -x, -y, -z + 1], so that complexes facing each other with the axial methanol ligand are linked, and secondly via atom H4B to carboxylate atom O5ⁱⁱ [symmetry code: (ii) x, y - 1, z], linking the asymmetric units into chains along [010] (Fig. 2). The molecules are further linked along [100] by methanol atom O3, acting as a hydrogen-bond donor via atom H31 to carboxylate atom O7ⁱⁱⁱ [symmetry code: (iii) -x + 1, -y, -z] of the equatorial ligand of the neighboring complex (Fig. 3).

At room temperature, the magnetic moment, expressed as the product χ_MT, is equal to 3.2 cm³ mol^-1 K, which is a typical value for iron(II) in the HS state. The moment remains almost constant down to 25 K (χ_MT = 3.01 cm³ mol^-1 K), indicating that no spin crossover occurs. The decrease of χ_MT below 25 K is due to zero-field splitting. Obviously, the methanol ligand is too weak to put the overall ligand field in the spin crossover region.

Related literature

For related literature, see: Gütlich et al. (1994); Goodwin (1976); Jäger et al. (1985); König (1991); Kahn & Martinez (1998); Leibeling (2003); Weber et al. (2008).

S2. Experimental

The synthesis of (I) was carried out under argon using Schlenk tube techniques. [FeL(MeOH)₂] (Jäger et al., 1985) and 30 equivalents of 3-aminopyridine (Fluka) were dissolved in 40 ml of absolute methanol and heated to reflux for 1 h. 24 h later, the product was filtered off and washed two times with ice-cold methanol. Pure crystals of (I) were obtained, with a yield of 70%. Analysis found: C 54.8, H 5.5, N 10.1%; C₂₆H₃₂FeN₄O₇ requires: C 54.9, H 5.7, N 9.9%. IR (PE): ν% 3344 (w, NH), 1676 (m, COO), 1569 (m, CO) cm^-1. MS (DEI⁺,70 eV): m/z (%) 442 (100) [M⁺].

S3. Refinement

With the exception of the methanol hydroxy atom H31, all H atoms were located in difference maps and treated as riding on their parent atoms (N—H = 0.88 Å and C—H = 0.95-0.98 Å). One common U_iso(H) parameter for these H atoms was refined to 0.0649 (15). Atom H31 was refined isotropically.

Computing details

Data collection: CrysAlis CCD (Oxford Diffraction, 2005); cell refinement: CrysAlis RED (Oxford Diffraction, 2005); data reduction: CrysAlis RED (Oxford Diffraction, 2005); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPIII (Burnett & Johnson, 1996) and SCHAKAL99 (Keller, 1999); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures

	Fig. 1. The molecular structure of (I), with atom labels and anisotropic displacement ellipsoids (drawn at the 50% probability level) for non-H atoms. H atoms have been omitted for clarity.
	Fig. 2. The molecular packing of (I), showing N—H···O hydrogen bonds forming chains along [010]. C-bonded H atoms have been omitted for clarity.
	Fig. 3. The molecular packing of (I), showing paired O—H···O hydrogen bonds linking opposite asymmetric units. C-bonded H atoms have been omitted for clarity.
	Fig. 4. The thermal dependence of χMT for (I).

(3-aminopyridine-κN¹){(E,E)-diethyl 2,2'-[1,2-phenylenebis(nitrilomethylidyne)]bis(3-oxobutanate)(2-)- κ²O³,N,N',O^3'}(methanol-κO)iron(II)

Crystal data

[Fe(C20H22N2O6)(C5H6N2)(CH4O)]	Z = 2
Mr = 568.40	F(000) = 596
Triclinic, P1	Dx = 1.394 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 11.234 (4) Å	Cell parameters from 8635 reflections
b = 11.5760 (11) Å	θ = 3.7–26.2°
c = 11.834 (3) Å	µ = 0.61 mm^−1
α = 72.740 (17)°	T = 200 K
β = 75.67 (3)°	Block, brown
γ = 68.91 (2)°	0.32 × 0.12 × 0.08 mm
V = 1354.0 (6) Å^3

Data collection

Oxford XCalibur diffractometer	2998 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.037
Graphite monochromator	θmax = 25.2°, θmin = 3.7°
ω scans	h = −13→13
23067 measured reflections	k = −14→14
4708 independent reflections	l = −14→14

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)] = 0.033	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.081	H atoms treated by a mixture of independent and constrained refinement
S = 0.94	w = 1/[σ^2(Fo^2) + (0.045P)^2] where P = (Fo^2 + 2Fc^2)/3
4708 reflections	(Δ/σ)max < 0.001
353 parameters	Δρmax = 0.34 e Å^−3
0 restraints	Δρmin = −0.21 e Å^−3

Special details

Experimental. Susceptibility measurements were performed using a Quantum Design MPMSR-XL SQUID magnetometer in the temperature range from 295 to 20 K at 500 G.

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. C-bonded H: H-atom parameters constrained, N-bonded H: H-atom parameters constrained, anisotrop refinement of all none-hydrogen atoms.

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

	x	y	z	Uiso*/Ueq
Fe1	0.26975 (3)	0.13889 (3)	0.24612 (3)	0.03288 (13)
O1	0.23706 (14)	0.24756 (14)	0.36599 (13)	0.0376 (4)
O2	0.34759 (14)	−0.04822 (14)	0.32078 (13)	0.0353 (4)
O3	0.47277 (17)	0.1377 (2)	0.21418 (17)	0.0525 (5)
O4	0.16546 (15)	0.66097 (14)	0.12468 (14)	0.0439 (4)
O5	0.12752 (18)	0.64697 (16)	0.32171 (16)	0.0582 (5)
O6	0.49180 (16)	−0.37323 (15)	0.19183 (14)	0.0502 (5)
O7	0.45911 (15)	−0.26432 (14)	0.00782 (14)	0.0438 (4)
N1	0.21335 (16)	0.31245 (16)	0.12293 (15)	0.0297 (4)
N2	0.29832 (17)	0.07854 (17)	0.08867 (16)	0.0300 (4)
N3	0.07251 (17)	0.12383 (17)	0.30644 (15)	0.0320 (5)
N4	−0.09005 (18)	−0.11921 (18)	0.38595 (16)	0.0440 (5)
H4A	−0.1655	−0.1300	0.4201	0.0649 (15)*
H4B	−0.0272	−0.1811	0.3589	0.0649 (15)*
C1	0.2158 (2)	0.3659 (2)	0.3551 (2)	0.0352 (6)
C2	0.1918 (2)	0.4573 (2)	0.24656 (19)	0.0326 (6)
C3	0.1927 (2)	0.4259 (2)	0.1386 (2)	0.0328 (6)
H3	0.1766	0.4947	0.0706	0.0649 (15)*
C4	0.2048 (2)	0.3014 (2)	0.00887 (18)	0.0283 (5)
C5	0.1529 (2)	0.4018 (2)	−0.0823 (2)	0.0367 (6)
H5	0.1208	0.4860	−0.0703	0.0649 (15)*
C6	0.1470 (2)	0.3818 (2)	−0.1900 (2)	0.0389 (6)
H6	0.1125	0.4517	−0.2518	0.0649 (15)*
C7	0.1918 (2)	0.2591 (2)	−0.2071 (2)	0.0394 (6)
H7	0.1879	0.2444	−0.2808	0.0649 (15)*
C8	0.2415 (2)	0.1592 (2)	−0.1179 (2)	0.0367 (6)
H8	0.2707	0.0754	−0.1302	0.0649 (15)*
C9	0.2506 (2)	0.1769 (2)	−0.00948 (18)	0.0273 (5)
C10	0.3581 (2)	−0.0371 (2)	0.0728 (2)	0.0314 (6)
H10	0.3704	−0.0472	−0.0065	0.0649 (15)*
C11	0.4067 (2)	−0.1494 (2)	0.16015 (19)	0.0305 (6)
C12	0.4023 (2)	−0.1482 (2)	0.2806 (2)	0.0324 (6)
C13	0.2200 (3)	0.4007 (2)	0.4664 (2)	0.0532 (7)
H13A	0.1323	0.4271	0.5104	0.0649 (15)*
H13B	0.2568	0.4709	0.4441	0.0649 (15)*
H13C	0.2738	0.3269	0.5172	0.0649 (15)*
C14	0.1603 (2)	0.5939 (2)	0.2401 (2)	0.0360 (6)
C15	0.1199 (2)	0.7980 (2)	0.1010 (2)	0.0423 (6)
H15A	0.1766	0.8299	0.1276	0.0649 (15)*
H15B	0.0309	0.8279	0.1438	0.0649 (15)*
C16	0.1227 (3)	0.8440 (2)	−0.0316 (2)	0.0603 (8)
H16A	0.2097	0.8076	−0.0727	0.0649 (15)*
H16B	0.0994	0.9370	−0.0533	0.0649 (15)*
H16C	0.0608	0.8176	−0.0556	0.0649 (15)*
C17	0.4627 (2)	−0.2647 (2)	0.3719 (2)	0.0486 (7)
H17A	0.4620	−0.2395	0.4443	0.0649 (15)*
H17B	0.5520	−0.3055	0.3383	0.0649 (15)*
H17C	0.4133	−0.3247	0.3924	0.0649 (15)*
C18	0.4546 (2)	−0.2631 (2)	0.1122 (2)	0.0354 (6)
C19	0.5383 (3)	−0.4887 (2)	0.1480 (2)	0.0542 (7)
H19A	0.6054	−0.4819	0.0763	0.0649 (15)*
H19B	0.4664	−0.5035	0.1259	0.0649 (15)*
C20	0.5923 (3)	−0.5928 (3)	0.2445 (3)	0.0927 (11)
H20A	0.6610	−0.5753	0.2676	0.0649 (15)*
H20B	0.6281	−0.6723	0.2171	0.0649 (15)*
H20C	0.5242	−0.6008	0.3137	0.0649 (15)*
C21	−0.0230 (2)	0.2191 (2)	0.3454 (2)	0.0396 (6)
H21	−0.0079	0.2977	0.3344	0.0649 (15)*
C22	−0.1425 (2)	0.2073 (2)	0.4010 (2)	0.0438 (6)
H22	−0.2080	0.2765	0.4287	0.0649 (15)*
C23	−0.1667 (2)	0.0945 (2)	0.4163 (2)	0.0378 (6)
H23	−0.2487	0.0853	0.4550	0.0649 (15)*
C24	−0.0702 (2)	−0.0052 (2)	0.37487 (19)	0.0329 (6)
C25	0.0479 (2)	0.0151 (2)	0.32063 (18)	0.0327 (6)
H25	0.1151	−0.0524	0.2919	0.0649 (15)*
C26	0.5549 (2)	0.0917 (2)	0.3009 (2)	0.0527 (7)
H26A	0.5189	0.1415	0.3623	0.0649 (15)*
H26B	0.6405	0.0993	0.2626	0.0649 (15)*
H26C	0.5624	0.0021	0.3381	0.0649 (15)*
H31	0.493 (3)	0.182 (3)	0.155 (3)	0.070 (11)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Fe1	0.0385 (2)	0.0325 (2)	0.0263 (2)	−0.01143 (16)	−0.00592 (16)	−0.00364 (16)
O1	0.0485 (11)	0.0363 (10)	0.0286 (9)	−0.0144 (8)	−0.0084 (8)	−0.0048 (8)
O2	0.0389 (10)	0.0342 (10)	0.0287 (9)	−0.0090 (8)	−0.0065 (8)	−0.0033 (8)
O3	0.0451 (12)	0.0788 (15)	0.0318 (11)	−0.0307 (11)	−0.0119 (10)	0.0088 (11)
O4	0.0639 (12)	0.0289 (10)	0.0365 (11)	−0.0142 (8)	−0.0047 (9)	−0.0069 (8)
O5	0.0903 (15)	0.0422 (11)	0.0403 (11)	−0.0089 (10)	−0.0151 (10)	−0.0175 (10)
O6	0.0732 (13)	0.0309 (10)	0.0360 (10)	−0.0040 (9)	−0.0144 (9)	−0.0026 (9)
O7	0.0583 (12)	0.0381 (10)	0.0296 (10)	−0.0116 (8)	−0.0034 (9)	−0.0069 (8)
N1	0.0329 (11)	0.0318 (12)	0.0253 (11)	−0.0106 (9)	−0.0066 (9)	−0.0058 (9)
N2	0.0302 (11)	0.0312 (12)	0.0282 (11)	−0.0109 (9)	−0.0063 (9)	−0.0033 (9)
N3	0.0360 (12)	0.0305 (11)	0.0286 (11)	−0.0078 (10)	−0.0068 (9)	−0.0069 (9)
N4	0.0453 (13)	0.0529 (14)	0.0445 (13)	−0.0261 (11)	0.0005 (10)	−0.0193 (11)
C1	0.0360 (15)	0.0419 (16)	0.0303 (15)	−0.0153 (12)	−0.0015 (11)	−0.0112 (13)
C2	0.0385 (15)	0.0339 (14)	0.0260 (14)	−0.0105 (11)	−0.0068 (12)	−0.0073 (12)
C3	0.0335 (14)	0.0345 (15)	0.0272 (13)	−0.0094 (11)	−0.0065 (11)	−0.0026 (11)
C4	0.0284 (13)	0.0331 (14)	0.0214 (13)	−0.0111 (11)	−0.0051 (10)	−0.0008 (11)
C5	0.0432 (15)	0.0320 (14)	0.0344 (15)	−0.0103 (12)	−0.0116 (12)	−0.0043 (12)
C6	0.0470 (16)	0.0399 (16)	0.0265 (14)	−0.0118 (13)	−0.0154 (12)	0.0028 (12)
C7	0.0489 (16)	0.0431 (16)	0.0286 (14)	−0.0161 (13)	−0.0114 (12)	−0.0049 (13)
C8	0.0456 (16)	0.0332 (14)	0.0307 (14)	−0.0115 (12)	−0.0077 (12)	−0.0060 (12)
C9	0.0322 (14)	0.0312 (14)	0.0199 (13)	−0.0133 (11)	−0.0065 (11)	−0.0016 (11)
C10	0.0336 (14)	0.0366 (15)	0.0263 (13)	−0.0155 (12)	−0.0036 (11)	−0.0055 (12)
C11	0.0310 (14)	0.0295 (14)	0.0257 (14)	−0.0071 (11)	−0.0043 (11)	−0.0018 (11)
C12	0.0271 (14)	0.0349 (15)	0.0299 (15)	−0.0095 (12)	−0.0021 (11)	−0.0021 (12)
C13	0.079 (2)	0.0505 (17)	0.0349 (15)	−0.0196 (15)	−0.0171 (14)	−0.0098 (13)
C14	0.0368 (15)	0.0366 (15)	0.0330 (15)	−0.0093 (12)	−0.0063 (12)	−0.0074 (14)
C15	0.0435 (16)	0.0303 (14)	0.0509 (17)	−0.0112 (12)	−0.0078 (13)	−0.0059 (13)
C16	0.074 (2)	0.0382 (16)	0.0526 (19)	−0.0118 (14)	−0.0043 (16)	0.0005 (14)
C17	0.0599 (18)	0.0439 (16)	0.0290 (15)	−0.0026 (13)	−0.0112 (13)	−0.0027 (13)
C18	0.0307 (14)	0.0319 (15)	0.0369 (16)	−0.0085 (11)	−0.0022 (12)	−0.0021 (13)
C19	0.072 (2)	0.0308 (15)	0.0528 (18)	−0.0052 (14)	−0.0141 (15)	−0.0101 (14)
C20	0.138 (3)	0.0406 (19)	0.084 (3)	−0.0024 (19)	−0.033 (2)	−0.0105 (18)
C21	0.0396 (16)	0.0336 (15)	0.0420 (16)	−0.0080 (13)	−0.0071 (13)	−0.0070 (13)
C22	0.0365 (16)	0.0452 (17)	0.0450 (16)	−0.0034 (13)	−0.0067 (13)	−0.0149 (13)
C23	0.0314 (15)	0.0550 (17)	0.0281 (14)	−0.0131 (13)	−0.0058 (11)	−0.0104 (13)
C24	0.0402 (16)	0.0416 (15)	0.0206 (13)	−0.0164 (13)	−0.0083 (12)	−0.0053 (11)
C25	0.0369 (15)	0.0373 (15)	0.0232 (13)	−0.0086 (12)	−0.0061 (11)	−0.0082 (11)
C26	0.0496 (17)	0.0648 (19)	0.0470 (17)	−0.0185 (14)	−0.0160 (14)	−0.0099 (15)

Geometric parameters (Å, º)

Fe1—O2	2.0298 (16)	C7—H7	0.9500
Fe1—O1	2.0489 (16)	C8—C9	1.390 (3)
Fe1—N1	2.0896 (18)	C8—H8	0.9500
Fe1—N2	2.0924 (18)	C10—C11	1.424 (3)
Fe1—N3	2.2071 (19)	C10—H10	0.9500
Fe1—O3	2.2132 (19)	C11—C12	1.418 (3)
O1—C1	1.275 (2)	C11—C18	1.458 (3)
O2—C12	1.271 (2)	C12—C17	1.512 (3)
O3—C26	1.406 (3)	C13—H13A	0.9800
O3—H31	0.77 (3)	C13—H13B	0.9800
O4—C14	1.355 (3)	C13—H13C	0.9800
O4—C15	1.442 (2)	C15—C16	1.496 (3)
O5—C14	1.208 (3)	C15—H15A	0.9900
O6—C18	1.337 (3)	C15—H15B	0.9900
O6—C19	1.451 (3)	C16—H16A	0.9800
O7—C18	1.228 (3)	C16—H16B	0.9800
N1—C3	1.310 (3)	C16—H16C	0.9800
N1—C4	1.422 (3)	C17—H17A	0.9800
N2—C10	1.311 (3)	C17—H17B	0.9800
N2—C9	1.420 (3)	C17—H17C	0.9800
N3—C21	1.336 (3)	C19—C20	1.458 (4)
N3—C25	1.338 (3)	C19—H19A	0.9900
N4—C24	1.379 (3)	C19—H19B	0.9900
N4—H4A	0.8800	C20—H20A	0.9800
N4—H4B	0.8800	C20—H20B	0.9800
C1—C2	1.415 (3)	C20—H20C	0.9800
C1—C13	1.502 (3)	C21—C22	1.377 (3)
C2—C3	1.425 (3)	C21—H21	0.9500
C2—C14	1.473 (3)	C22—C23	1.379 (3)
C3—H3	0.9500	C22—H22	0.9500
C4—C5	1.391 (3)	C23—C24	1.386 (3)
C4—C9	1.409 (3)	C23—H23	0.9500
C5—C6	1.383 (3)	C24—C25	1.393 (3)
C5—H5	0.9500	C25—H25	0.9500
C6—C7	1.385 (3)	C26—H26A	0.9800
C6—H6	0.9500	C26—H26B	0.9800
C7—C8	1.367 (3)	C26—H26C	0.9800
O2—Fe1—O1	110.64 (6)	O2—C12—C11	122.6 (2)
O2—Fe1—N1	163.09 (6)	O2—C12—C17	114.2 (2)
O1—Fe1—N1	85.29 (7)	C11—C12—C17	123.3 (2)
O2—Fe1—N2	85.15 (7)	C1—C13—H13A	109.5
O1—Fe1—N2	163.46 (6)	C1—C13—H13B	109.5
N1—Fe1—N2	78.54 (7)	H13A—C13—H13B	109.5
O2—Fe1—N3	91.17 (7)	C1—C13—H13C	109.5
O1—Fe1—N3	90.29 (7)	H13A—C13—H13C	109.5
N1—Fe1—N3	94.49 (7)	H13B—C13—H13C	109.5
N2—Fe1—N3	94.42 (7)	O5—C14—O4	120.9 (2)
O2—Fe1—O3	82.78 (7)	O5—C14—C2	128.2 (2)
O1—Fe1—O3	85.81 (7)	O4—C14—C2	110.7 (2)
N1—Fe1—O3	93.13 (7)	O4—C15—C16	106.23 (19)
N2—Fe1—O3	91.54 (7)	O4—C15—H15A	110.5
N3—Fe1—O3	171.13 (7)	C16—C15—H15A	110.5
C1—O1—Fe1	133.45 (14)	O4—C15—H15B	110.5
C12—O2—Fe1	134.73 (14)	C16—C15—H15B	110.5
C26—O3—Fe1	126.01 (16)	H15A—C15—H15B	108.7
C26—O3—H31	117 (2)	C15—C16—H16A	109.5
Fe1—O3—H31	115 (2)	C15—C16—H16B	109.5
C14—O4—C15	118.66 (18)	H16A—C16—H16B	109.5
C18—O6—C19	117.13 (19)	C15—C16—H16C	109.5
C3—N1—C4	118.54 (19)	H16A—C16—H16C	109.5
C3—N1—Fe1	126.93 (15)	H16B—C16—H16C	109.5
C4—N1—Fe1	114.42 (13)	C12—C17—H17A	109.5
C10—N2—C9	119.02 (19)	C12—C17—H17B	109.5
C10—N2—Fe1	126.51 (16)	H17A—C17—H17B	109.5
C9—N2—Fe1	114.43 (14)	C12—C17—H17C	109.5
C21—N3—C25	117.7 (2)	H17A—C17—H17C	109.5
C21—N3—Fe1	119.87 (15)	H17B—C17—H17C	109.5
C25—N3—Fe1	121.81 (15)	O7—C18—O6	119.3 (2)
C24—N4—H4A	120.0	O7—C18—C11	125.3 (2)
C24—N4—H4B	120.0	O6—C18—C11	115.4 (2)
H4A—N4—H4B	120.0	O6—C19—C20	107.0 (2)
O1—C1—C2	122.8 (2)	O6—C19—H19A	110.3
O1—C1—C13	114.7 (2)	C20—C19—H19A	110.3
C2—C1—C13	122.5 (2)	O6—C19—H19B	110.3
C1—C2—C3	123.5 (2)	C20—C19—H19B	110.3
C1—C2—C14	120.9 (2)	H19A—C19—H19B	108.6
C3—C2—C14	115.6 (2)	C19—C20—H20A	109.5
N1—C3—C2	127.1 (2)	C19—C20—H20B	109.5
N1—C3—H3	116.5	H20A—C20—H20B	109.5
C2—C3—H3	116.5	C19—C20—H20C	109.5
C5—C4—C9	118.8 (2)	H20A—C20—H20C	109.5
C5—C4—N1	125.4 (2)	H20B—C20—H20C	109.5
C9—C4—N1	115.80 (18)	N3—C21—C22	122.2 (2)
C6—C5—C4	121.4 (2)	N3—C21—H21	118.9
C6—C5—H5	119.3	C22—C21—H21	118.9
C4—C5—H5	119.3	C21—C22—C23	119.7 (2)
C5—C6—C7	119.5 (2)	C21—C22—H22	120.2
C5—C6—H6	120.3	C23—C22—H22	120.2
C7—C6—H6	120.3	C22—C23—C24	119.4 (2)
C8—C7—C6	119.8 (2)	C22—C23—H23	120.3
C8—C7—H7	120.1	C24—C23—H23	120.3
C6—C7—H7	120.1	N4—C24—C23	121.7 (2)
C7—C8—C9	121.9 (2)	N4—C24—C25	121.4 (2)
C7—C8—H8	119.1	C23—C24—C25	116.9 (2)
C9—C8—H8	119.1	N3—C25—C24	124.1 (2)
C8—C9—C4	118.7 (2)	N3—C25—H25	118.0
C8—C9—N2	125.5 (2)	C24—C25—H25	118.0
C4—C9—N2	115.83 (18)	O3—C26—H26A	109.5
N2—C10—C11	127.8 (2)	O3—C26—H26B	109.5
N2—C10—H10	116.1	H26A—C26—H26B	109.5
C11—C10—H10	116.1	O3—C26—H26C	109.5
C12—C11—C10	122.6 (2)	H26A—C26—H26C	109.5
C12—C11—C18	125.1 (2)	H26B—C26—H26C	109.5
C10—C11—C18	112.2 (2)
O2—Fe1—O1—C1	163.20 (18)	Fe1—N1—C4—C5	170.70 (16)
N1—Fe1—O1—C1	−10.96 (19)	C3—N1—C4—C9	168.82 (18)
N2—Fe1—O1—C1	1.3 (3)	Fe1—N1—C4—C9	−7.7 (2)
N3—Fe1—O1—C1	−105.4 (2)	C9—C4—C5—C6	−0.8 (3)
O3—Fe1—O1—C1	82.5 (2)	N1—C4—C5—C6	−179.1 (2)
O1—Fe1—O2—C12	−166.91 (18)	C4—C5—C6—C7	1.0 (3)
N1—Fe1—O2—C12	−7.3 (3)	C5—C6—C7—C8	−0.2 (3)
N2—Fe1—O2—C12	8.01 (19)	C6—C7—C8—C9	−1.0 (3)
N3—Fe1—O2—C12	102.3 (2)	C7—C8—C9—C4	1.2 (3)
O3—Fe1—O2—C12	−84.2 (2)	C7—C8—C9—N2	178.56 (19)
O2—Fe1—O3—C26	−52.5 (2)	C5—C4—C9—C8	−0.3 (3)
O1—Fe1—O3—C26	58.9 (2)	N1—C4—C9—C8	178.15 (18)
N1—Fe1—O3—C26	144.0 (2)	C5—C4—C9—N2	−177.94 (18)
N2—Fe1—O3—C26	−137.4 (2)	N1—C4—C9—N2	0.5 (3)
O2—Fe1—N1—C3	−152.0 (2)	C10—N2—C9—C8	11.6 (3)
O1—Fe1—N1—C3	8.92 (18)	Fe1—N2—C9—C8	−170.60 (17)
N2—Fe1—N1—C3	−167.56 (18)	C10—N2—C9—C4	−170.96 (18)
N3—Fe1—N1—C3	98.83 (18)	Fe1—N2—C9—C4	6.8 (2)
O3—Fe1—N1—C3	−76.62 (18)	C9—N2—C10—C11	−176.44 (19)
O2—Fe1—N1—C4	24.2 (3)	Fe1—N2—C10—C11	6.1 (3)
O1—Fe1—N1—C4	−174.95 (14)	N2—C10—C11—C12	−3.8 (3)
N2—Fe1—N1—C4	8.58 (13)	N2—C10—C11—C18	173.6 (2)
N3—Fe1—N1—C4	−85.03 (14)	Fe1—O2—C12—C11	−8.4 (3)
O3—Fe1—N1—C4	99.52 (14)	Fe1—O2—C12—C17	171.10 (14)
O2—Fe1—N2—C10	−6.20 (17)	C10—C11—C12—O2	4.4 (3)
O1—Fe1—N2—C10	156.87 (19)	C18—C11—C12—O2	−172.6 (2)
N1—Fe1—N2—C10	169.30 (18)	C10—C11—C12—C17	−175.1 (2)
N3—Fe1—N2—C10	−97.00 (17)	C18—C11—C12—C17	7.9 (3)
O3—Fe1—N2—C10	76.42 (18)	C15—O4—C14—O5	−5.6 (3)
O2—Fe1—N2—C9	176.20 (14)	C15—O4—C14—C2	171.33 (17)
O1—Fe1—N2—C9	−20.7 (3)	C1—C2—C14—O5	−15.0 (4)
N1—Fe1—N2—C9	−8.30 (13)	C3—C2—C14—O5	163.4 (2)
N3—Fe1—N2—C9	85.40 (14)	C1—C2—C14—O4	168.31 (19)
O3—Fe1—N2—C9	−101.18 (14)	C3—C2—C14—O4	−13.3 (3)
O2—Fe1—N3—C21	141.91 (17)	C14—O4—C15—C16	−173.29 (19)
O1—Fe1—N3—C21	31.27 (17)	C19—O6—C18—O7	1.2 (3)
N1—Fe1—N3—C21	−54.04 (17)	C19—O6—C18—C11	179.14 (19)
N2—Fe1—N3—C21	−132.86 (17)	C12—C11—C18—O7	−179.6 (2)
O2—Fe1—N3—C25	−28.95 (16)	C10—C11—C18—O7	3.1 (3)
O1—Fe1—N3—C25	−139.60 (16)	C12—C11—C18—O6	2.6 (3)
N1—Fe1—N3—C25	135.10 (16)	C10—C11—C18—O6	−174.66 (18)
N2—Fe1—N3—C25	56.28 (16)	C18—O6—C19—C20	170.9 (2)
Fe1—O1—C1—C2	9.4 (3)	C25—N3—C21—C22	1.5 (3)
Fe1—O1—C1—C13	−169.77 (15)	Fe1—N3—C21—C22	−169.77 (17)
O1—C1—C2—C3	−1.9 (4)	N3—C21—C22—C23	−0.9 (4)
C13—C1—C2—C3	177.3 (2)	C21—C22—C23—C24	−0.3 (3)
O1—C1—C2—C14	176.42 (19)	C22—C23—C24—N4	−178.8 (2)
C13—C1—C2—C14	−4.4 (3)	C22—C23—C24—C25	0.8 (3)
C4—N1—C3—C2	177.4 (2)	C21—N3—C25—C24	−0.9 (3)
Fe1—N1—C3—C2	−6.6 (3)	Fe1—N3—C25—C24	170.12 (15)
C1—C2—C3—N1	0.9 (4)	N4—C24—C25—N3	179.42 (19)
C14—C2—C3—N1	−177.4 (2)	C23—C24—C25—N3	−0.2 (3)
C3—N1—C4—C5	−12.8 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4A···O1^i	0.88	2.58	3.215 (3)	130
N4—H4B···O5^ii	0.88	2.20	3.068 (3)	171
O3—H31···O7^iii	0.77 (3)	1.92 (3)	2.676 (3)	167 (4)

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