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The low-spin iron(II) ion of bis(4-methyl­piperidine)(5,10,15,20-tetra­phenyl­porphyrinato)­iron(II), [Fe(TPP)(4-MePip)2], where TPP is 5,10,15,20-tetra­phenyl­porphyrinate (C44H28N4) and 4-MePip is 4-methyl­piperidine (C6H13N), is located at a center of inversion, and there is one mol­ecule in the triclinic unit cell. The axial 4-MePip ligands adopt a chair conformation and the α-C atoms are oriented at angles of 21.2 (2) and 32.8 (2)° relative to the closest porphyrin N atoms. The equatorial Fe—NTPP distances are 1.998 (2) and 1.990 (2) Å, while the axial Fe—N distance is 2.107 (2) Å. The relatively short axial coordination distance reflects compression of the mol­ecule along its principal axis by intermolecular non-bonded interactions.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270103008734/fg1690sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270103008734/fg1690Isup2.hkl
Contains datablock I

CCDC reference: 214372

Comment top

We have been investigating the structures, conformations, and electronic properties of bis(alkylamine) derivatives of low-spin iron(II) porphyrinates (Munro et al., 1999) as part of an effort to understand the unusual coordination chemistry displayed by plant cytochrome f, in which one of the axial ligands is the N-terminal amino group of the protein (Martinez et al., 1996). One of the objectives of the present investigation was to synthesize and structurally characterize a non-planar bis(amine) derivative of a ferrous porphyrin for two reasons: (i) the heme group in cytochrome f is non-planar and (ii) it is now widely recognized that non-planar conformations of porphyrins (Shelnutt, 2000) modulate the electronic structure (Barkigia et al., 1999) of the heme iron and thus the reactivity of the metal center in heme proteins.

We previously used molecular mechanics (MM) simulations (Munro et al., 1999) to show that [Fe(TPP)(Pip)2], (II), could adopt three low-energy conformations: (i) a centrosymmetric structure with a planar porphyrin core conformation that matched the X-ray structure reported by Hoard's group in 1971 (Radonovich et al., 1972), (ii) a non-centrosymmetric structure with a planar porphyrin core conformation, and (iii) a non-planar conformation in which a staggered relative orientation of the axial piperidine ligands leads to a marked S4-ruffled porphyrin core conformation. The S4-ruffled conformation of (II) was predicted to be lowest in energy by ~6.7 kJ mol−1. Since there are relatively few crystallographically characterized iron(II) derivatives of tetraphenyl- and octaethylporphyrin that have non-planar porphyrin core conformations (Scheidt, 2000), and our MM simulations suggested that a non-planar conformation for (II) was in fact preferred on steric grounds, our strategy in this study was to build up some additional steric bulk on the axial ligands in the hope that crystal-packing constraints might favor crystallization of (I) in a non-centrosymmetric space group, or indeed at a general position in a centrosymmetric space group. Without crystallographically required inversion symmetry, the structure of (I) would, on conformational energy grounds, likely have an S4-ruffled porphyrin core conformation. Unfortunately, as we show in this paper, a single 4-methyl substituent on the piperidine ring in the case of (I) is not sufficiently bulky to change the centrosymmetric crystal packing that was previously observed for (II). There are, however, crystallographic indicators that suggest an increase in molecular strain attends packing of the more bulky axial ligands of (I) in the triclinic lattice. Compound (I), in fact, experiences significant axial (ax) compression that leads to a rather short unique Fe—Nax distance, a phenomenon that has probably been frequently overlooked as a significant cause of coordination group structural variance in model heme systems.

The reaction of a ferric porphyrin with an excess of a primary or secondary amine in a non-aqueous solvent results in one-electron reduction of the metal to the FeII state by a mechanism which involves initial deprotonation of the metal-bound N—H group by excess ligand in solution (Del Gaudio & La Mar, 1978; Castro et al., 1986). We previously made use of this redox process to synthesize and structurally characterize several [Fe(TPP)L2] derivatives, where L = butylamine, benzylamine, and 2-phenylethylamine (Munro et al., 1999). In the present study, excess 4-MePip was reacted with a labile FeIII complex, namely [Fe(TPP)(OClO3)], to ensure facile substitution of the anion by the secondary amine and thus complete reduction to the ferrous state. Reduction of the complex was confirmed by the dark-red color of the solution after the addition of the amine and the electronic spectrum of (I) under nitrogen, which was consistent with that reported for (II) (Del Gaudio & La Mar, 1978).

The X-ray crystal structure of (I) is shown in Fig. 1. The centrosymmetric structure exhibits an approximately planar porphyrin core conformation. The FeII state is confirmed by the absence of a counter anion (ClO4) in the lattice and the fact that H3 was cleanly located in a difference Fourier map. Importantly, this H atom refined well isotropically and its presence confirms that 4-MePip coordinates as the neutral amine. The axial 4-MePip ligands adopt a chair conformation and the mean planes taken through each 4-MePip ring are exactly eclipsed due to the crystallographically imposed symmetry. This is shown more clearly in Fig. 2, which is a view of the structure perpendicular to the N1—Fe—N2 plane. The Fe—NTPP distances differ by slightly more than 3σ [Fe—N1 = 1.998 (2) Å and Fe—N2 = 1.990 (2) Å]. We surmise that this in-plane coordination group asymmetry reflects the fact that the dihedral angles between each symmetry-unique porphyrin N atom and the closest 4-MePip α-carbon are non-equivalent [N1—Fe—N3—C35 = 21.2 (2)° and N2i—Fe—N3—C31 = 32.8 (2)°; symmetry code: (i) −x, −y, −z]. Evidently, the smaller repulsive steric interaction between N2i and C31 allows for a slightly shorter Fe—NTPP coordination distance than is the case for N1. Interestingly, although not statistically significant, the average Fe—NTPP distance for (I) [1.994 (6) Å] is slightly shorter than that reported by Hoard for the bis(piperidine) analogue (II) [2.004 (4) Å]. Average values for all other chemically unique bonds and angles of (I) are summarized in Fig. 3; these are in good agreement with those reported for (II) (Radonovich et al., 1972) and even better agreement with those of the toluene solvate [Fe(TPP)(Pip)2]·C7H8 (Byrn et al., 1991). The perpendicular displacements of each porphyrin core atom from the 24-atom mean plane of the macrocycle are also shown in Fig. 3. Since none of the displacements exceed 0.06 Å, the porphyrin conformation is essentially flat. Moreover, there is no real pattern or symmetry (e.g. D2 d-saddle or S4-ruffle distortion) evident from the atomic displacements shown in Fig. 3.

The unique axial coordination distance to the 4-MePip ligands, Fe—Nax, measures 2.107 (2) Å in compound (I) and is considerably shorter than that reported for (II) [2.127 (3) Å]. The statistically significant difference between the axial coordination distances (> 6σ) observed for (I) and (II) is noteworthy. AM1 geometry optimizations (Dewar & Thiel, 1977) and calculations of the charge distributions for the free ligands Pip and 4-MePip show that the nitrogen donors are equivalent both geometrically and electronically (charge = −0.298 e) in these two compounds. If the electronic structures of the axial ligand donor atoms are the same, then the shorter axial coordination distance for (I) can only be attributed to crystal-packing constraints, particularly since the metal ions are located at the same (special) positions in the unit cell in both cases (space group P1). In the case of (I), crystal packing (non-bonded contacts with the 4-Me groups of the axial ligands) would have to favor compression of the molecule along its principal axis to bring about the observed ~0.02 Å foreshortening of the Fe—Nax bonds. Interestingly, although the structure of [Fe(TPP)(Pip)2]·C7H8 is also centrosymmetric (space group P1), it displays a somewhat different crystal packing symmetry to both (I) and (II) and, importantly, an even shorter Fe—Nax bond distance of 2.092 Å (Byrn et al., 1991).

The packing symmetry and interactions for (I) are shown more clearly in Fig. 4, which depicts a stereoview of the unit cell. Since the FeII ions are located on special positions, there is a full molecule positioned at each corner of the unit cell that projects into the neighboring unit cells. The crystal symmetry and occupancy of the asymmetric unit requires that the porphyrin rings are tilted equivalently with respect to each of the unit cell axes such that the molecular packing places the molecule at [111] in close van der Waals contact with the molecule at [001] and those at the two flanking positions [101] and [011]. The crystal packing clearly demonstrates that, for example, the upper axial 4-MePip ligand of the molecule located at the cell origin [000] fits into a rather tight pocket created by the molecule at [110] and [001]. This is shown more clearly in the space-filling plot of Fig. 5. Although none of the intermolecular contacts is less than the sum of the van der Waals radii of the interacting atoms, there are several key contacts with the H atoms of the 4-MePip methyl group that are fully consistent with steric interactions being responsible for compression of the axial Fe—N distances in (I). Some of the more noteworthy contacts (Å) to pyrrole ring atoms include the following: C36···H1B(-x + 1, −y + 1, −z) 3.64, H36A···C1B(-x + 1, −y + 1, −z) 3.39, H36A···H1B(-x + 1, −y + 1, −z) 3.31, H36B···C1B(-x + 1, −y + 1, −z) 3.60, H36B···H1B(-x + 1, −y + 1, −z) 3.42 and H36C···H1B(-x + 1, −y + 1, −z) 3.61. There are also several contacts (Å) with neighboring phenyl groups that add to the steric congestion around the 4-MePip methyl group: C36···H22(-x, −y, −z − 1) 3.61, C36···H23(-x, −y, −z − 1) 3.51, H36B···C22(-x, −y, −z − 1) 3.36, H36B···H22(-x, −y, −z − 1) 3.02, H36B···C23(-x, −y, −z − 1) 3.12, H36B···H23(-x, −y, −z − 1) 2.56 and H36C···H22(-x, −y, −z − 1) 3.33.

Finally, inspection of the crystal packing for [Fe(TPP)(Pip)2]·C7H8 (Byrn et al., 1991) shows that the equatorial H atom at the 4-position of the axial Pip ligand points directly between the o- and m-H atoms of one of the phenyl groups of the neighboring porphyrin. Two short H···H contacts of 2.31 and 2.35 Å, respectively, are thus observed which may account for the marked compression of the Fe—Nax bonds in this compound. Collectively, the structural evidence strongly supports the notion that the Fe—Nax bond distances are critically dependent on the nature of the crystal packing in these ferrous porphyrin derivatives.

Experimental top

All manipulations were carried out under nitrogen using a double manifold vacuum line, Schlenkware, and cannula techniques. Tetrahydrofuran (THF) and hexane were distilled over sodium/benzophenone and dichloromethane over CaH2. 4-Methylpiperidine (Aldrich) was freshly distilled over CaH2 under nitrogen prior to use. H2TPP was synthesized using published procedures (Barnett et al., 1975). [Fe(TPP)Cl] was prepared by metallation of H2TPP with anhydrous iron(II) chloride in refluxing dimethylformamide (Adler et al., 1970). Silver perchlorate (Aldrich) was used as received. To [Fe(TPP)Cl] (156.3 mg, 0.222 mmol) and silver perchlorate (99.8 mg, 0.481 mmol) in a 100 ml two-necked round-bottomed flask under nitrogen was added 30 ml of freshly distilled THF. The solution was allowed to stir for ~12 h at room temperature. The solvent was removed in vacuo and the red–brown solid redissolved in dichloromethane (ca 30 ml). The solution was cannula-filtered under nitrogen into a dry 100 ml two-necked round-bottomed flask containing 4-methylpiperidine (2.83 ml, 23.9 mmol). After swirling the solution for 10 min, the color changed from red–brown to deep red, consistent with reduction of the metal to the ferrous state (Castro et al., 1986). The solution was transferred in ~5 ml aliquots into Schlenk tubes and each aliquot layered with hexane; X-ray quality crystals were observed after 6 d. The deep-red crystals of (I) were collected by filtration and washed with 10° ethanol in hexane to remove colorless crystals of 4-methylpiperidine. Isolated yield: 28 mg, 15°. Analysis calculated for C56H54FeN6: C 77.59, H 6.28, N 9.69%; found: C 77.2, H 5.96, N 9.29%. AM1 geometry optimization calculations on Pip and 4-MePip were carried out with the default singlet-state parameters in HYPERCHEM 6.03 (Hypercube, 2000).

Refinement top

Molecule (I) crystallized as deep-red rhombs in the triclinic crystal system (space group P1). A difference Fourier calculation after refinement of all non-H atoms anisotropically located over 80° of the H atoms in the molecule, including the unique H atom appended to amine atom N3. This H atom (H3) was refined isotropically with H—N—C and H—N—Fe angle restraints (SHELXL97 DANG method; Sheldrick, 1997) and a distance restraint of 0.87 (2) Å (SHELXL97 DFIX method) to ensure chemically feasible values for these parameters (Byrn et al., 1991). All other H atoms were refined using the standard riding model of SHELXL97.

Computing details top

Data collection: CAD-4-PC Software (Enraf-Nonius, 1992); cell refinement: CAD-4-PC Software; data reduction: PROFIT (Streltsov & Zavodnik, 1989); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top
[Figure 1] Fig. 1. Selectively labelled ORTEP view of (I) (35% probability displacement ellipsoids). With the exception of the amine atom H3, all H atoms have been omitted for clarity.
[Figure 2] Fig. 2. Selectively labelled ORTEP view of (I) perpendicular to the N1—Fe—N2 plane (35% probability displacement ellipsoids).
[Figure 3] Fig. 3. Formal diagram of (I), showing the perpendicular displacements (in units of 0.01 Å) of each atom from the 24-atom porphyrin mean plane, as well as the average structural parameters for each chemically unique class of bond (in Å) and bond angle (in °) in the porphyrin macrocycle. The FeII ion is located at the center of inversion (perpendicular displacement = 0 Å).
[Figure 4] Fig. 4. Stereoscopic view of the unit-cell contents of (I). H atoms have been omitted for clarity.
[Figure 5] Fig. 5. Space-filling plot (CPK model) of three neighboring molecules of (I) in the crystal lattice at the coordinates [000], [110], and [001]. H36B of the uppermost 4-MePip ligand of the complex at the cell origin is labelled.
(I) top
Crystal data top
[Fe(C6H12N)2(C50H30N4)]Z = 1
Mr = 866.9F(000) = 458
Triclinic, P1Dx = 1.256 Mg m3
a = 10.3189 (14) ÅMo Kα radiation, λ = 0.71073 Å
b = 11.2427 (17) ÅCell parameters from 25 reflections
c = 11.8631 (15) Åθ = 2–12°
α = 93.077 (12)°µ = 0.37 mm1
β = 111.112 (11)°T = 296 K
γ = 113.483 (12)°Rhomb, deep red
V = 1145.8 (3) Å30.54 × 0.31 × 0.23 mm
Data collection top
Enraf-Nonius CAD-4
diffractometer
θmax = 24.0°, θmin = 2.0°
non–profiled ω/2θ scansh = 211
4719 measured reflectionsk = 1212
3593 independent reflectionsl = 1313
3317 reflections with I > 2σ(I)3 standard reflections every 100 reflections
Rint = 0.010 intensity decay: 2%
Refinement top
Refinement on F24 restraints
Least-squares matrix: fullH atoms treated by a mixture of independent and constrained refinement
R[F2 > 2σ(F2)] = 0.038 w = 1/[σ2(Fo2) + (0.0561P)2 + 0.6693P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.107(Δ/σ)max = 0.001
S = 1.06Δρmax = 0.52 e Å3
3593 reflectionsΔρmin = 0.41 e Å3
290 parameters
Crystal data top
[Fe(C6H12N)2(C50H30N4)]γ = 113.483 (12)°
Mr = 866.9V = 1145.8 (3) Å3
Triclinic, P1Z = 1
a = 10.3189 (14) ÅMo Kα radiation
b = 11.2427 (17) ŵ = 0.37 mm1
c = 11.8631 (15) ÅT = 296 K
α = 93.077 (12)°0.54 × 0.31 × 0.23 mm
β = 111.112 (11)°
Data collection top
Enraf-Nonius CAD-4
diffractometer
Rint = 0.010
4719 measured reflectionsθmax = 24.0°
3593 independent reflections3 standard reflections every 100 reflections
3317 reflections with I > 2σ(I) intensity decay: 2%
Refinement top
R[F2 > 2σ(F2)] = 0.0384 restraints
wR(F2) = 0.107H atoms treated by a mixture of independent and constrained refinement
S = 1.06Δρmax = 0.52 e Å3
3593 reflectionsΔρmin = 0.41 e Å3
290 parameters
Special details top

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.

Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane) − 4.9758 (0.0055) x − 5.0976 (0.0044) y + 9.4729 (0.0031) z = 0.0608 (0.0014) * 0.0562 (0.0016) N1 * −0.0263 (0.0016) N2 * −0.0025 (0.0017) C1A * 0.0426 (0.0020) C2A * −0.0219 (0.0020) C3A * 0.0066 (0.0019) C4A * −0.0414 (0.0020) C1B * −0.0085 (0.0020) C2B * −0.0018 (0.0019) C3B * 0.0218 (0.0020) C4B * −0.0058 (0.0019) C1M * −0.0189 (0.0015) C2M −0.0608 (0.0014) Fe

Rms deviation of fitted atoms = 0.0272 − 9.4244 (0.0049) x + 2.5503 (0.0122) y + 0.2042 (0.0133) z = 0.0809 (0.0067)

Angle to previous plane (with approximate e.s.d.) = 69.63 (0.07) * −0.0047 (0.0017) C21 * 0.0013 (0.0018) C22 * 0.0027 (0.0020) C23 * −0.0032 (0.0020) C24 * −0.0003 (0.0021) C25 * 0.0043 (0.0019) C26

Rms deviation of fitted atoms = 0.0031

Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane) − 4.9758 (0.0055) x − 5.0976 (0.0044) y + 9.4729 (0.0031) z = 0.0608 (0.0014) * 0.0562 (0.0016) N1 * −0.0263 (0.0016) N2 * −0.0025 (0.0017) C1A * 0.0426 (0.0020) C2A * −0.0219 (0.0020) C3A * 0.0066 (0.0019) C4A * −0.0414 (0.0020) C1B * −0.0085 (0.0020) C2B * −0.0018 (0.0019) C3B * 0.0218 (0.0020) C4B * −0.0058 (0.0019) C1M * −0.0189 (0.0015) C2M −0.0608 (0.0014) Fe

Rms deviation of fitted atoms = 0.0272 3.4760 (0.0108) x − 9.1050 (0.0079) y − 5.8755 (0.0125) z = 0.0012 (0.0068)

Angle to previous plane (with approximate e.s.d.) = 87.12 (0.06) * −0.0031 (0.0017) C11 * 0.0013 (0.0021) C12 * 0.0014 (0.0022) C13 * −0.0023 (0.0020) C14 * 0.0004 (0.0020) C15 * 0.0023 (0.0018) C16 Rms deviation of fitted atoms = 0.0020

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Fe0000.03121 (15)
N10.17121 (19)0.11410 (17)0.16368 (15)0.0345 (4)
N20.10706 (19)0.11295 (17)0.00090 (16)0.0342 (4)
N30.1210 (2)0.1200 (2)0.09392 (18)0.0449 (5)
C1A0.1888 (2)0.2289 (2)0.22855 (19)0.0371 (5)
C2A0.3067 (2)0.1041 (2)0.22802 (19)0.0367 (5)
C3A0.2505 (2)0.0935 (2)0.0854 (2)0.0370 (5)
C4A0.0540 (2)0.2275 (2)0.08696 (19)0.0366 (5)
C1B0.3362 (3)0.2902 (2)0.3348 (2)0.0462 (6)
H1B0.37470.36840.39290.055*
C2B0.4076 (3)0.2136 (2)0.3346 (2)0.0450 (5)
H2B0.50480.22860.39280.054*
C3B0.2866 (3)0.1965 (2)0.0510 (2)0.0450 (5)
H3B0.37680.20460.09370.054*
C4B0.1662 (3)0.2793 (2)0.0543 (2)0.0455 (5)
H4B0.15720.35560.09770.055*
C1M0.3456 (2)0.0084 (2)0.19183 (19)0.0363 (5)
C2M0.0851 (2)0.2843 (2)0.1932 (2)0.0375 (5)
C110.5046 (2)0.0203 (2)0.2674 (2)0.0371 (5)
C120.6248 (3)0.0872 (3)0.2340 (2)0.0584 (7)
H120.60620.12430.16510.07*
C130.7717 (3)0.1001 (3)0.3010 (3)0.0664 (8)
H130.85110.14560.27690.08*
C140.8015 (3)0.0469 (3)0.4017 (3)0.0588 (7)
H140.90090.05610.4470.071*
C150.6846 (3)0.0201 (3)0.4358 (3)0.0598 (7)
H150.70420.0570.50460.072*
C160.5366 (3)0.0336 (3)0.3688 (2)0.0495 (6)
H160.45760.07990.39310.059*
C210.1257 (2)0.4129 (2)0.2719 (2)0.0413 (5)
C220.1314 (3)0.4222 (3)0.3906 (2)0.0535 (6)
H220.11220.34740.42410.064*
C230.1658 (3)0.5432 (3)0.4599 (3)0.0674 (8)
H230.16960.54890.53960.081*
C240.1941 (3)0.6539 (3)0.4114 (3)0.0708 (9)
H240.21630.73450.45770.085*
C250.1896 (4)0.6455 (3)0.2952 (3)0.0710 (9)
H250.20910.72070.26220.085*
C260.1565 (3)0.5268 (2)0.2261 (3)0.0551 (6)
H260.15480.52310.1470.066*
C310.0462 (3)0.1811 (4)0.1804 (3)0.0796 (10)
H31A0.03210.24570.13470.096*
H31B0.05640.1130.23650.096*
C320.1291 (3)0.2505 (3)0.2575 (3)0.0725 (9)
H32A0.11880.18350.31960.087*
H32B0.07810.30110.30090.087*
C330.2973 (4)0.3420 (4)0.1845 (3)0.0824 (10)
H330.30040.41350.1310.099*
C340.3725 (3)0.2756 (3)0.0991 (3)0.0709 (9)
H34A0.47460.34250.04080.085*
H34B0.38780.21370.14690.085*
C350.2882 (3)0.2012 (3)0.0267 (3)0.0649 (8)
H35A0.33370.14370.00810.078*
H35B0.30650.26530.04230.078*
C360.3830 (4)0.4109 (4)0.2591 (4)0.1014 (14)
H36A0.48870.47040.20430.152*
H36B0.33380.46050.30460.152*
H36C0.38110.34560.31610.152*
H30.106 (2)0.0394 (15)0.1464 (18)0.138 (16)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Fe0.0238 (2)0.0321 (2)0.0309 (2)0.01183 (17)0.00527 (17)0.00501 (17)
N10.0271 (9)0.0346 (9)0.0344 (9)0.0126 (7)0.0067 (7)0.0061 (7)
N20.0265 (9)0.0363 (9)0.0331 (9)0.0132 (7)0.0067 (7)0.0053 (7)
N30.0312 (10)0.0503 (11)0.0459 (11)0.0163 (9)0.0096 (8)0.0172 (9)
C1A0.0316 (11)0.0353 (11)0.0343 (11)0.0118 (9)0.0071 (9)0.0041 (9)
C2A0.0272 (10)0.0385 (11)0.0350 (11)0.0125 (9)0.0056 (9)0.0080 (9)
C3A0.0280 (11)0.0428 (12)0.0373 (11)0.0169 (9)0.0095 (9)0.0095 (9)
C4A0.0335 (11)0.0373 (11)0.0368 (11)0.0162 (9)0.0123 (9)0.0072 (9)
C1B0.0379 (12)0.0393 (12)0.0415 (13)0.0133 (10)0.0017 (10)0.0031 (10)
C2B0.0305 (11)0.0456 (13)0.0407 (12)0.0144 (10)0.0004 (9)0.0026 (10)
C3B0.0352 (12)0.0536 (14)0.0456 (13)0.0266 (11)0.0093 (10)0.0068 (11)
C4B0.0428 (13)0.0466 (13)0.0462 (13)0.0258 (11)0.0123 (11)0.0034 (10)
C1M0.0263 (10)0.0407 (11)0.0364 (11)0.0140 (9)0.0083 (9)0.0108 (9)
C2M0.0348 (11)0.0343 (11)0.0373 (11)0.0133 (9)0.0115 (9)0.0051 (9)
C110.0271 (11)0.0391 (11)0.0378 (11)0.0140 (9)0.0073 (9)0.0049 (9)
C120.0373 (13)0.0772 (18)0.0534 (15)0.0203 (13)0.0158 (12)0.0276 (14)
C130.0321 (13)0.087 (2)0.0690 (18)0.0178 (14)0.0203 (13)0.0150 (16)
C140.0333 (13)0.0716 (17)0.0576 (16)0.0284 (13)0.0009 (12)0.0017 (13)
C150.0512 (16)0.0682 (17)0.0507 (15)0.0319 (14)0.0050 (12)0.0188 (13)
C160.0359 (12)0.0573 (15)0.0471 (14)0.0175 (11)0.0118 (11)0.0167 (11)
C210.0308 (11)0.0395 (12)0.0430 (12)0.0147 (9)0.0066 (9)0.0013 (10)
C220.0489 (14)0.0504 (14)0.0466 (14)0.0165 (12)0.0125 (11)0.0001 (11)
C230.0532 (16)0.078 (2)0.0534 (16)0.0267 (15)0.0108 (13)0.0152 (15)
C240.0530 (16)0.0525 (17)0.081 (2)0.0295 (14)0.0015 (15)0.0184 (15)
C250.0656 (19)0.0426 (15)0.081 (2)0.0244 (14)0.0066 (16)0.0040 (14)
C260.0542 (15)0.0429 (14)0.0568 (15)0.0200 (12)0.0138 (12)0.0078 (11)
C310.0444 (16)0.107 (3)0.086 (2)0.0314 (17)0.0225 (15)0.060 (2)
C320.0524 (17)0.095 (2)0.0716 (19)0.0337 (16)0.0230 (15)0.0476 (18)
C330.0595 (19)0.089 (2)0.093 (2)0.0232 (17)0.0334 (18)0.050 (2)
C340.0386 (14)0.087 (2)0.078 (2)0.0203 (14)0.0203 (14)0.0389 (17)
C350.0360 (14)0.0771 (19)0.0609 (17)0.0128 (13)0.0104 (12)0.0296 (15)
C360.072 (2)0.123 (3)0.108 (3)0.031 (2)0.045 (2)0.073 (3)
Geometric parameters (Å, º) top
Fe—N2i1.9895 (17)C13—H130.93
Fe—N21.9895 (17)C14—C151.359 (4)
Fe—N11.9981 (17)C14—H140.93
Fe—N1i1.9981 (17)C15—C161.384 (4)
Fe—N3i2.1074 (19)C15—H150.93
Fe—N32.1074 (19)C16—H160.93
N1—C1A1.378 (3)C21—C261.383 (3)
N1—C2A1.384 (3)C21—C221.385 (3)
N2—C4A1.377 (3)C22—C231.392 (4)
N2—C3A1.384 (3)C22—H220.93
N3—C311.431 (3)C23—C241.369 (5)
N3—C351.457 (3)C23—H230.93
N3—H30.996 (14)C24—C251.360 (5)
C1A—C2Mi1.395 (3)C24—H240.93
C1A—C1B1.438 (3)C25—C261.373 (4)
C2A—C1M1.386 (3)C25—H250.93
C2A—C2B1.436 (3)C26—H260.93
C3A—C1M1.388 (3)C31—C321.512 (4)
C3A—C3B1.430 (3)C31—H31A0.97
C4A—C2M1.392 (3)C31—H31B0.97
C4A—C4B1.438 (3)C32—C331.490 (4)
C1B—C2B1.339 (3)C32—H32A0.97
C1B—H1B0.93C32—H32B0.97
C2B—H2B0.93C33—C341.472 (4)
C3B—C4B1.344 (3)C33—C361.501 (4)
C3B—H3B0.93C33—H330.98
C4B—H4B0.93C34—C351.494 (4)
C1M—C111.506 (3)C34—H34A0.97
C2M—C1Ai1.395 (3)C34—H34B0.97
C2M—C211.492 (3)C35—H35A0.97
C11—C161.370 (3)C35—H35B0.97
C11—C121.379 (3)C36—H36A0.96
C12—C131.377 (4)C36—H36B0.96
C12—H120.93C36—H36C0.96
C13—C141.356 (4)
N2i—Fe—N2180C12—C13—H13119.7
N2i—Fe—N189.98 (7)C13—C14—C15119.3 (2)
N2—Fe—N190.02 (7)C13—C14—H14120.3
N2i—Fe—N1i90.02 (7)C15—C14—H14120.3
N2—Fe—N1i89.98 (7)C14—C15—C16120.5 (2)
N1—Fe—N1i180C14—C15—H15119.8
N2i—Fe—N3i88.80 (7)C16—C15—H15119.8
N2—Fe—N3i91.20 (7)C11—C16—C15121.0 (2)
N1—Fe—N3i89.41 (7)C11—C16—H16119.5
N1i—Fe—N3i90.59 (7)C15—C16—H16119.5
N2i—Fe—N391.20 (7)C26—C21—C22118.0 (2)
N2—Fe—N388.80 (7)C26—C21—C2M120.1 (2)
N1—Fe—N390.59 (7)C22—C21—C2M121.9 (2)
N1i—Fe—N389.41 (7)C21—C22—C23120.2 (3)
N3i—Fe—N3180C21—C22—H22119.9
C1A—N1—C2A105.22 (16)C23—C22—H22119.9
C1A—N1—Fe127.24 (14)C24—C23—C22120.4 (3)
C2A—N1—Fe127.09 (14)C24—C23—H23119.8
C4A—N2—C3A105.20 (17)C22—C23—H23119.8
C4A—N2—Fe127.46 (14)C25—C24—C23119.6 (3)
C3A—N2—Fe127.34 (14)C25—C24—H24120.2
C31—N3—C35113.6 (2)C23—C24—H24120.2
C31—N3—Fe118.69 (16)C24—C25—C26120.6 (3)
C35—N3—Fe118.09 (15)C24—C25—H25119.7
C31—N3—H3104.5 (12)C26—C25—H25119.7
C35—N3—H3106.4 (12)C25—C26—C21121.2 (3)
Fe—N3—H390.6 (11)C25—C26—H26119.4
N1—C1A—C2Mi125.64 (19)C21—C26—H26119.4
N1—C1A—C1B110.21 (19)N3—C31—C32116.3 (2)
C2Mi—C1A—C1B124.0 (2)N3—C31—H31A108.2
N1—C2A—C1M125.68 (19)C32—C31—H31A108.2
N1—C2A—C2B109.93 (19)N3—C31—H31B108.2
C1M—C2A—C2B124.25 (19)C32—C31—H31B108.2
N2—C3A—C1M125.68 (19)H31A—C31—H31B107.4
N2—C3A—C3B110.11 (19)C33—C32—C31114.2 (3)
C1M—C3A—C3B124.2 (2)C33—C32—H32A108.7
N2—C4A—C2M125.77 (19)C31—C32—H32A108.7
N2—C4A—C4B110.23 (18)C33—C32—H32B108.7
C2M—C4A—C4B124.0 (2)C31—C32—H32B108.7
C2B—C1B—C1A107.2 (2)H32A—C32—H32B107.6
C2B—C1B—H1B126.4C34—C33—C32110.2 (3)
C1A—C1B—H1B126.4C34—C33—C36114.6 (3)
C1B—C2B—C2A107.45 (19)C32—C33—C36115.3 (3)
C1B—C2B—H2B126.3C34—C33—H33105.2
C2A—C2B—H2B126.3C32—C33—H33105.2
C4B—C3B—C3A107.46 (19)C36—C33—H33105.2
C4B—C3B—H3B126.3C33—C34—C35116.4 (3)
C3A—C3B—H3B126.3C33—C34—H34A108.2
C3B—C4B—C4A107.0 (2)C35—C34—H34A108.2
C3B—C4B—H4B126.5C33—C34—H34B108.2
C4A—C4B—H4B126.5C35—C34—H34B108.2
C2A—C1M—C3A124.01 (19)H34A—C34—H34B107.3
C2A—C1M—C11118.34 (19)N3—C35—C34116.7 (2)
C3A—C1M—C11117.52 (19)N3—C35—H35A108.1
C4A—C2M—C1Ai123.7 (2)C34—C35—H35A108.1
C4A—C2M—C21117.66 (19)N3—C35—H35B108.1
C1Ai—C2M—C21118.63 (19)C34—C35—H35B108.1
C16—C11—C12117.6 (2)H35A—C35—H35B107.3
C16—C11—C1M122.9 (2)C33—C36—H36A109.5
C12—C11—C1M119.5 (2)C33—C36—H36B109.5
C13—C12—C11121.1 (2)H36A—C36—H36B109.5
C13—C12—H12119.4C33—C36—H36C109.5
C11—C12—H12119.4H36A—C36—H36C109.5
C14—C13—C12120.5 (2)H36B—C36—H36C109.5
C14—C13—H13119.7
N2i—Fe—N1—C1A4.63 (18)N2—C4A—C4B—C3B0.0 (3)
N2—Fe—N1—C1A175.37 (18)C2M—C4A—C4B—C3B177.9 (2)
N3i—Fe—N1—C1A93.43 (18)N1—C2A—C1M—C3A1.3 (4)
N3—Fe—N1—C1A86.57 (18)C2B—C2A—C1M—C3A176.7 (2)
N2i—Fe—N1—C2A175.76 (17)N1—C2A—C1M—C11174.40 (19)
N2—Fe—N1—C2A4.24 (17)C2B—C2A—C1M—C111.0 (3)
N3i—Fe—N1—C2A95.44 (17)N2—C3A—C1M—C2A1.7 (4)
N3—Fe—N1—C2A84.56 (17)C3B—C3A—C1M—C2A176.6 (2)
N1—Fe—N2—C4A175.68 (18)N2—C3A—C1M—C11174.03 (19)
N1i—Fe—N2—C4A4.32 (18)C3B—C3A—C1M—C117.7 (3)
N3i—Fe—N2—C4A86.27 (18)N2—C4A—C2M—C1Ai1.8 (4)
N3—Fe—N2—C4A93.73 (18)C4B—C4A—C2M—C1Ai175.8 (2)
N1—Fe—N2—C3A3.90 (17)N2—C4A—C2M—C21177.0 (2)
N1i—Fe—N2—C3A176.10 (17)C4B—C4A—C2M—C215.4 (3)
N3i—Fe—N2—C3A93.31 (18)C2A—C1M—C11—C1687.9 (3)
N3—Fe—N2—C3A86.69 (18)C3A—C1M—C11—C1696.1 (3)
N2i—Fe—N3—C3132.8 (2)C2A—C1M—C11—C1292.6 (3)
N2—Fe—N3—C31147.2 (2)C3A—C1M—C11—C1283.4 (3)
N1—Fe—N3—C31122.8 (2)C16—C11—C12—C130.5 (4)
N1i—Fe—N3—C3157.2 (2)C1M—C11—C12—C13180.0 (3)
N2i—Fe—N3—C35111.2 (2)C11—C12—C13—C140.0 (5)
N2—Fe—N3—C3568.8 (2)C12—C13—C14—C150.3 (5)
N1—Fe—N3—C3521.2 (2)C13—C14—C15—C160.2 (4)
N1i—Fe—N3—C35158.8 (2)C12—C11—C16—C150.6 (4)
C2A—N1—C1A—C2Mi175.4 (2)C1M—C11—C16—C15179.9 (2)
Fe—N1—C1A—C2Mi2.8 (3)C14—C15—C16—C110.2 (4)
C2A—N1—C1A—C1B0.5 (2)C4A—C2M—C21—C2665.8 (3)
Fe—N1—C1A—C1B173.16 (15)C1Ai—C2M—C21—C26113.1 (3)
C1A—N1—C2A—C1M175.3 (2)C4A—C2M—C21—C22113.1 (3)
Fe—N1—C2A—C1M2.6 (3)C1Ai—C2M—C21—C2268.0 (3)
C1A—N1—C2A—C2B0.7 (2)C26—C21—C22—C230.6 (4)
Fe—N1—C2A—C2B173.39 (15)C2M—C21—C22—C23178.3 (2)
C4A—N2—C3A—C1M177.8 (2)C21—C22—C23—C240.1 (4)
Fe—N2—C3A—C1M1.8 (3)C22—C23—C24—C250.5 (4)
C4A—N2—C3A—C3B0.7 (2)C23—C24—C25—C260.2 (5)
Fe—N2—C3A—C3B179.68 (15)C24—C25—C26—C210.5 (4)
C3A—N2—C4A—C2M178.3 (2)C22—C21—C26—C250.9 (4)
Fe—N2—C4A—C2M2.1 (3)C2M—C21—C26—C25178.0 (2)
C3A—N2—C4A—C4B0.4 (2)C35—N3—C31—C3242.4 (4)
Fe—N2—C4A—C4B179.94 (15)Fe—N3—C31—C32172.0 (2)
N1—C1A—C1B—C2B0.1 (3)N3—C31—C32—C3348.2 (5)
C2Mi—C1A—C1B—C2B175.9 (2)C31—C32—C33—C3447.6 (5)
C1A—C1B—C2B—C2A0.4 (3)C31—C32—C33—C36179.2 (3)
N1—C2A—C2B—C1B0.7 (3)C32—C33—C34—C3545.6 (5)
C1M—C2A—C2B—C1B175.3 (2)C36—C33—C34—C35177.7 (3)
N2—C3A—C3B—C4B0.7 (3)C31—N3—C35—C3439.6 (4)
C1M—C3A—C3B—C4B177.8 (2)Fe—N3—C35—C34174.6 (2)
C3A—C3B—C4B—C4A0.4 (3)C33—C34—C35—N343.0 (5)
Symmetry code: (i) x, y, z.

Experimental details

Crystal data
Chemical formula[Fe(C6H12N)2(C50H30N4)]
Mr866.9
Crystal system, space groupTriclinic, P1
Temperature (K)296
a, b, c (Å)10.3189 (14), 11.2427 (17), 11.8631 (15)
α, β, γ (°)93.077 (12), 111.112 (11), 113.483 (12)
V3)1145.8 (3)
Z1
Radiation typeMo Kα
µ (mm1)0.37
Crystal size (mm)0.54 × 0.31 × 0.23
Data collection
DiffractometerEnraf-Nonius CAD-4
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
4719, 3593, 3317
Rint0.010
θmax (°)24.0
(sin θ/λ)max1)0.572
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.038, 0.107, 1.06
No. of reflections3593
No. of parameters290
No. of restraints4
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.52, 0.41

Computer programs: CAD-4-PC Software (Enraf-Nonius, 1992), CAD-4-PC Software, PROFIT (Streltsov & Zavodnik, 1989), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).

Selected geometric parameters (Å, º) top
Fe—N21.9895 (17)N3—C311.431 (3)
Fe—N11.9981 (17)N3—C351.457 (3)
Fe—N32.1074 (19)
N2—Fe—N190.02 (7)C31—N3—C35113.6 (2)
N2—Fe—N3i91.20 (7)C31—N3—Fe118.69 (16)
N1—Fe—N3i89.41 (7)C35—N3—Fe118.09 (15)
N3—Fe—N1—C1A86.57 (18)N1—Fe—N3—C31122.8 (2)
N3—Fe—N1—C2A84.56 (17)N2—Fe—N3—C3568.8 (2)
N3—Fe—N2—C4A93.73 (18)N1—Fe—N3—C3521.2 (2)
N3—Fe—N2—C3A86.69 (18)Fe—N3—C31—C32172.0 (2)
N2—Fe—N3—C31147.2 (2)Fe—N3—C35—C34174.6 (2)
Symmetry code: (i) x, y, z.
 

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