Crystal structure of bis­(benzyl­amine-κN)[5,10,15,20-tetra­kis­(4-chloro­phen­yl)porphyrinato-κ4N]iron(II) n-hexane monosolvate

Dhifaoui, S.; Harhouri, W.; Bujacz, A.; Nasri, H.

doi:10.1107/S2056989015024135

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Volume 72| Part 1| January 2016| Pages 102-105

doi:10.1107/S2056989015024135

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Crystal structure of bis(benzylamine-κN)[5,10,15,20-tetrakis(4-chlorophenyl)porphyrinato-κ⁴N]iron(II) n-hexane monosolvate

Selma Dhifaoui,^a Wafa Harhouri,^a Anna Bujacz ^b and Habib Nasri ^a ^*

^aLaboratoire de Physico-chimie des Matériaux, Faculté des Sciences de Monastir, Avenue de l'environnement, 5019 Monastir, University of Monastir, Tunisia, and ^bX-Ray Analysis Laboratory, Institute of Technical Biochemistry, Lodz University of Technology, Stefanowskiego 4/10, 90-924 Lodz, Poland
^*Correspondence e-mail: hnasri1@gmail.com

Edited by M. Weil, Vienna University of Technology, Austria (Received 9 December 2015; accepted 15 December 2015; online 1 January 2016)

In the title compound, [Fe^II(C₄₄H₂₄Cl₄N₄)(C₆H₅CH₂NH₂)₂]·C₆H₁₄ or [Fe^II(TPP-Cl)(BzNH₂)₂]·n-hexane [where TPP-Cl and BzNH₂ are 5,10,15,20-tetrakis(4-chlorophenyl)porphyrinate and benzylamine ligands, respectively], the Fe^II cation lies on an inversion centre and is octahedrally coordinated by the four pyrrole N atoms of the porphyrin ligand in the equatorial plane and by two amine N atoms of the benzylamine ligand in the axial sites. The crystal structure also contains one inversion-symmetric n-hexane solvent molecule per complex molecule. The average Fe—N_pyrrole bond length [1.994 (3) Å] indicates a low-spin complex. The crystal packing is sustained by N—H⋯Cl and C—H⋯Cl hydrogen-bonding interactions and by C—H⋯π intermolecular interactions, leading to a three-dimensional network structure.

Keywords: crystal structure; hydrogen bonding; UV–vis spectra; iron(II)–porphyrin; benzylamine.

CCDC reference: 1442707

1. Chemical context

The structure of turnip cytochrome f has been determined on the basis of X-ray measurements (Martinez et al., 1996 ), showing that the α-amino group of the Tyr-1 entity coordinates trans to the His-25 entity in the c-type heme protein. Thus, bis-amine Fe^II metalloporphyrins appear to be functionally significant as models for cytochrome f. On the other hand, it has been shown that the reaction of primary and secondary amines with iron(III) metalloporphyrins results in a base-catalysed one-electron reduction process and concomitant dissociation of the deprotonated amine radical (Del Gaudio & La Mar, 1978 ). It is also known that the addition of an excess of sterically unhindered alkylamines to an Fe(III) porphyrin derivative leads to bis(amine)–iron(II) porphyrins with the central metal cation in a six-coordination (Morice et al., 1998 ). Notably, the number of published structures of these type of iron(II) metalloporphyrins is small. In the Cambridge Structural Database (CSD, Version 5.35; Groom & Allen, 2014 ), only six amine porphyrin structures are reported, including [Fe^II(TPP)(BzNH₂)₂] (TPP is the 5,10,15,20-tetraphenylporphyrinato ligand; Bz is benzyl) (Munro et al., 1999 ).

We report herein the synthesis, the molecular and crystal structures as well as UV-spectroscopic properties of bis(benzylamine)[5,10,15,20-tetra(para-chlorophenyl)porphyrinato]iron(II) n-hexane monosolvate, [Fe^II(TPP-Cl)(BzNH₂)₂])·n-hexane, (I).

2. Structural commentary

The molecular structure of (I) is illustrated in Fig. 1. The Fe^II cation is located on an inversion centre and shows an octahedral coordination environment. The equatorial plane is formed by the four nitrogen atoms of the porphyrin moiety whereas the axial positions are occupied by the N atoms of the two benzylamine ligands.

Figure 1
The structures of the molecular entities in the title compound. Displacement ellipsoids are drawn at the 60% probability level. H atoms have been omitted for clarity. [Symmetry code: (i) −x + 1, −y + 1, −z + 1.]

The Fe—N_benzylamine bond length of 2.036 (2) Å is in the range of other iron(II)–bis(amine) porphyrin complexes [1.799-2.285 Å] reported in the literature (CSD refcodes FAVGUE: Godbout et al., 1999 ; IMELIV: Wyllie et al., 2003 ) and is slightly smaller than in the related structure of [Fe^II(TPP)(BzNH₂)₂] [2.043 (3) Å; Munro et al., 1999]. The porphyrin core of (I) is represented in Fig. 2. The porphyrin macrocycle presents a nearly planar conformation with maximum and minimum deviations from the C₂₀N₄ least-squares plane of 0.044 (2) and −0.051 (2) Å for atoms C3 and N1, respectively, while the Fe^II cation is co-planar with this plane with a minute deviation of 0.003 (1) Å. The α-CH₂ group of the benzylamine ligand is inclined at 24.8 (1)° relative to the shortest Fe—N_pyrrole bond (Fe—N1). This value is close to those of the related [Fe^II(TPP)(BzNH₂)₂] derivative [18.2 (4), 30.1 (4)°; Munro et al., 1999].

Figure 2
Schematic representation of the porphyrin core illustrating the displacements of each atom from the 24-atom plane in units of 0.01 Å.

For iron(II) porphyrins, the relationship between the spin-state of the Fe^II cation and the value of the average equatorial Fe—N_pyrrole bond length has been discussed (Scheidt & Reed, 1981 ). For high-spin (S = 2) complexes, the Fe—N_pyrrole bond lengths are the longest, e.g. for the [Fe(TpivPP)(NO₃)]⁻ complex (TpivPP = picket-fence porphyrin), Fe—N_pyrrole amounts to 2.070 (16) Å (Nasri et al., 2006 ). For low-spin (S = 0) complexes, the average Fe—N_pyrrole bond length is shorter, e.g. for the [Fe(TPP)(4-MePip)₂] complex (4-MePip is 4-methyl piperidine), the Fe—N_pyrrole bond length is 1.994 (4) Å (Munro & Ntshangase, 2003 ) and 1.990 (15) Å for the [Fe^II(TpivPP)(NO₂)(pyridine)]⁻ species (Nasri et al., 2000 ). The intermediate spin state (S = 1) of Fe^II porphyrin complexes is represented by the shortest Fe—N_pyrrole distances, e.g. Fe(TTP) exhibits an Fe—N_pyrrole bond length of 1.979 (6) Å (Hu et al., 2007 ). The averaged Fe—N_pyrrole bond length of 1.994 (3) Å for (I) is an indication that this species has a low-spin state (S = 0). This value is virtually the same as in the related [Fe^II(TPP)(BzNH₂)₂] derivative [Fe—N_pyrrole = 1.992 (4) Å; Munro et al., 1999].

3. Supramolecular features

The complex molecules are packed in such a way that channels are formed parallel to [010] in which the n-hexane molecules are situated. The linkage of the molecular components in the crystal structure of (I) is accomplished by C—H⋯Cl, N—H⋯Cl hydrogen-bonding interactions as well as C—H⋯π interactions (Figs. 3 and 4; Table 1). Each [Fe^II(TPP-Cl)(BzNH₂)₂] complex is linked to neighbouring complexes through N—H⋯Cl hydrogen bonds between the N3 atom of the benzylamine ligand and the Cl2 atom of a TPP-Cl moiety and by C—H⋯Cl interactions between the pyrrole C7 atom and the Cl2 atom. In addition, the phenyl C19 atom of the [Fe^II(TClPP)(BzNH₂)₂] complex interacts with the centroid Cg1 of the (N1/C1–C4) pyrrole ring through C—H⋯π interactions. The three-dimensional supramolecular network is consolidated by another C—H⋯π intramolecular interaction involving the C31 atom of the n-hexane solvent molecule and the centroid Cg7 of the (C11–C16) phenyl ring.

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 and Cg7 are the centroids of the N1/C1–C4 and C11–C16 rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C19—H19⋯Cg1ⁱ	0.93	2.66	3.586 (3)	133
C31—H31A⋯Cg7ⁱ	0.97	2.63	3.701 (5)	160
N3—H3B⋯Cl2ⁱⁱ	0.89	2.68	3.651 (2)	133
C7—H7⋯Cl2ⁱⁱⁱ	0.93	3.00	3.926 (2)	175
Symmetry codes: (i) x-1, y, z; (ii) -x, -y+1, -z+1; (iii) -x, -y+1, -z+2.

Figure 3
A partial view of the crystal packing of (I)

, showing the linkage between the [Fe^II(TPP-Cl)(BzNH₂)₂] complexes through C—H⋯Cl and N—H⋯Cl hydrogen bonds. The n-hexane solvent molecules have been omitted for clarity.

Figure 4
The crystal structure of the title compound plotted in a projection along [010]. Contacts between the entities are given as dashed lines.

4. Synthesis

4.1. Synthesis of 5,10,15,20-tetra(para-chlorophenyl)porphyrin

In a 100 ml two-necked flask, 4-chlorobenzaldehyde (6 g, 42 mmol) was dissolved in 50 ml of propionic acid. The solution was heated under reflex at 413 K. Freshly distilled pyrrole (3.36 ml, 42 mmol) was added dropwise and the mixture stirred for another 40 min. The mixture was then cooled overnight to 277 K and filtered in vacuo. The crude product was purified using column chromatography (chloroform/hexane = 4/1 v/v as an eluent). A purple solid was obtained that was dried in vacuo (1.5 g, yield 25%). UV–vis spectrum in CHCl₃: λ_max (10⁻³·∊) 420 (512.7), 516 (16.7), 552 (7.4), 591 (4.7), 646 (4.0).

4.2. Metallation of the porphyrin and synthesis of (triflato)[5,10,15,20-tetra(para-chlorophenyl)porphyrinato]iron(III)

The metallation of the porphyrin was performed using the literature method to yield the chlorido–iron(III) derivative [Fe^III(TPP-Cl)Cl] (Collman et al., 1975 ). We used the triflato–iron(III) TPP-Cl derivative [Fe^III(TPP-Cl)(SO₃CF₃)] as starting material because the triflato ligand (SO₃CF₃⁻) is much easier to substitute than the chlorido ligand. This complex was prepared according to a literature protocol (Gismelseed et al., 1990 ).

4.3. Synthesis and crystallization of bis(benzylamine-κN)[5,10,15,20-tetrakis(4-chlorophenyl)porphyrinato-κ⁴N]iron(II) n-hexane monosolvate complex, (I)

To a solution of [Fe^III(TPP-Cl)(SO₃CF₃)] (Gismelseed et al., 1990) (15 mg, 0.0156 mmol) in dichloromethane (15 ml) was added an excess of benzylamine (50 mg, 0.48 mmol). The reaction mixture was stirred at room temperature for 2 h. Crystals of the title complex were obtained by diffusion of n-hexane through the dichloromethane solution.

5. UV–vis spectra

The UV–visible spectra with absorption bands at λ_max 425/426, 532/527, 562/566 nm (CHCl₃ solution/solid state) were recorded on a WinASPECT PLUS (validation for SPECORD PLUS version 4.2) scanning spectrophotometer. In Fig. 5 are illustrated the electronic spectra of the solid [Fe^III(TPP-Cl)(SO₃CF₃)] complex, used as starting material, and complex (I) which shows that the Soret band of the latter species is red-shifted compared to the one of the starting material. The λ_max values of the Soret and Q bands of (I) in the solid state and in chloroform solution are very close. These values also compare well with those of the related [Fe^II(TPP)(L)₂] (L = 1-BuNH₂, BzNH₂, PhCH₂CH₂NH₂) species (Munro et al., 1999).

Figure 5
UV–vis spectra of the solid [Fe^III(TClPP)(SO₃CF₃)] starting material (black) and solid (I)

(blue).

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. H atoms were positioned geometrically and refined using a riding model with C—H = 0.93 Å (aromatic), 0.97 Å (methylene), 0.96 Å (methyl) and N—H = 0.89 Å for the axial ligand, with U_iso(H_phenyl, H_methylene, H_amine) = 1.2U_eq(C/N) and U_iso(H_methyl) = 1.5U_eq(C).

Table 2
Experimental details

Crystal data
Chemical formula	[Fe(C₄₄H₂₄Cl₄N₄)(C₇H₉N)₂]·C₆H₁₄
M_r	1106.79
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	100
a, b, c (Å)	10.7986 (6), 11.0555 (6), 11.4118 (4)
α, β, γ (°)	87.918 (4), 82.785 (4), 79.815 (5)
V (Å³)	1330.16 (12)
Z	1
Radiation type	Cu Kα
μ (mm⁻¹)	4.50
Crystal size (mm)	0.4 × 0.3 × 0.1

Data collection
Diffractometer	Agilent SuperNova Dual Source diffractometer with a TitanS2 detector
Absorption correction	Multi-scan (CrysAlis PRO; Agilent, 2014 )
T_min, T_max	0.416, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	12765, 5355, 4825
R_int	0.028
(sin θ/λ)_max (Å⁻¹)	0.627

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.048, 0.133, 1.06
No. of reflections	5355
No. of parameters	340
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.09, −0.54
Computer programs: CrysAlis PRO (Agilent, 2014), SIR2004 (Burla et al., 2005 ), SHELXL2014 (Sheldrick, 2015 ), ORTEPIII (Burnett & Johnson, 1996 ) and ORTEP-3 for Windows and WinGX (Farrugia, 2012 ).

Supporting information

CCDC reference: 1442707

Crystal structure: contains datablock I. DOI: 10.1107/S2056989015024135/wm5253sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S2056989015024135/wm5253Isup2.hkl

checkCIF report

Computing details top

Data collection: CrysAlis PRO (Agilent, 2014); cell refinement: CrysAlis PRO (Agilent, 2014); data reduction: CrysAlis PRO (Agilent, 2014); program(s) used to solve structure: SIR2004 (Burla et al., 2005); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: ORTEPIII (Burnett & Johnson, 1996) and ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: WinGX (Farrugia, 2012).

Bis(benzylamine-κN)[5,10,15,20-tetrakis(4-chlorophenyl)porphyrinato-κ⁴N]iron(II) n-hexane monosolvate top

Crystal data top

[Fe(C₄₄H₂₄Cl₄N₄)(C₇H₉N)₂]·C₆H₁₄	Z = 1
M_r = 1106.79	F(000) = 576
Triclinic, P1	D_x = 1.382 Mg m⁻³
a = 10.7986 (6) Å	Cu Kα radiation, λ = 1.54184 Å
b = 11.0555 (6) Å	Cell parameters from 10827 reflections
c = 11.4118 (4) Å	θ = 4.1–74.9°
α = 87.918 (4)°	µ = 4.50 mm⁻¹
β = 82.785 (4)°	T = 100 K
γ = 79.815 (5)°	Prism, dark red
V = 1330.16 (12) Å³	0.4 × 0.3 × 0.1 mm

Data collection top

Agilent SuperNova Dual Source diffractometer with a TitanS2 detector	5355 independent reflections
Radiation source: sealed X-ray tube	4825 reflections with I > 2σ(I)
Detector resolution: 4.1685 pixels mm^-1	R_int = 0.028
ω scans	θ_max = 75.3°, θ_min = 3.9°
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2014)	h = −13→13
T_min = 0.416, T_max = 1.000	k = −13→10
12765 measured reflections	l = −14→12

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.048	H-atom parameters constrained
wR(F²) = 0.133	w = 1/[σ²(F_o²) + (0.0771P)² + 0.8782P] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max = 0.001
5355 reflections	Δρ_max = 1.09 e Å⁻³
340 parameters	Δρ_min = −0.54 e Å⁻³

Special details top

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

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Fe	0.5000	0.5000	0.5000	0.01855 (14)
N1	0.65294 (17)	0.39615 (18)	0.55478 (16)	0.0209 (4)
N2	0.40204 (17)	0.47595 (18)	0.65683 (16)	0.0210 (4)
N3	0.43283 (18)	0.35548 (18)	0.44078 (17)	0.0238 (4)
H3A	0.3486	0.3738	0.4512	0.029*
H3B	0.4563	0.3509	0.3632	0.029*
C1	0.7729 (2)	0.3693 (2)	0.4932 (2)	0.0224 (4)
C2	0.8596 (2)	0.2991 (2)	0.5658 (2)	0.0242 (5)
H2	0.9452	0.2700	0.5437	0.029*
C3	0.7939 (2)	0.2831 (2)	0.6725 (2)	0.0242 (5)
H3	0.8255	0.2414	0.7377	0.029*
C4	0.6649 (2)	0.3434 (2)	0.6655 (2)	0.0221 (4)
C5	0.5680 (2)	0.3471 (2)	0.75867 (19)	0.0219 (4)
C6	0.4447 (2)	0.4080 (2)	0.75297 (19)	0.0226 (5)
C7	0.3420 (2)	0.4066 (2)	0.8463 (2)	0.0250 (5)
H7	0.3468	0.3666	0.9191	0.030*
C8	0.2375 (2)	0.4742 (2)	0.8080 (2)	0.0254 (5)
H8	0.1568	0.4897	0.8497	0.030*
C9	0.2745 (2)	0.5176 (2)	0.6907 (2)	0.0225 (4)
C10	0.1926 (2)	0.5909 (2)	0.6214 (2)	0.0232 (5)
C11	0.59738 (19)	0.2788 (2)	0.87045 (19)	0.0220 (5)
C12	0.6263 (2)	0.3395 (2)	0.9655 (2)	0.0269 (5)
H12	0.6267	0.4236	0.9597	0.032*
C13	0.6548 (2)	0.2760 (3)	1.0695 (2)	0.0295 (5)
H13	0.6735	0.3172	1.1329	0.035*
C14	0.6547 (2)	0.1513 (3)	1.0766 (2)	0.0281 (5)
C15	0.6267 (2)	0.0882 (2)	0.9836 (2)	0.0302 (5)
H15	0.6276	0.0039	0.9895	0.036*
C16	0.5972 (2)	0.1531 (2)	0.8810 (2)	0.0289 (5)
H16	0.5770	0.1117	0.8185	0.035*
C17	0.0571 (2)	0.6294 (2)	0.6735 (2)	0.0252 (5)
C18	−0.0257 (2)	0.5459 (3)	0.6854 (2)	0.0306 (5)
H18	0.0029	0.4657	0.6600	0.037*
C19	−0.1513 (2)	0.5807 (3)	0.7349 (2)	0.0329 (6)
H19	−0.2063	0.5242	0.7431	0.039*
C20	−0.1927 (2)	0.6994 (3)	0.7714 (2)	0.0296 (5)
C21	−0.1134 (3)	0.7858 (3)	0.7565 (3)	0.0384 (6)
H21	−0.1433	0.8668	0.7788	0.046*
C22	0.0120 (2)	0.7492 (3)	0.7077 (3)	0.0352 (6)
H22	0.0662	0.8065	0.6980	0.042*
C23	0.4696 (2)	0.2302 (2)	0.4923 (2)	0.0276 (5)
H23A	0.4913	0.2379	0.5713	0.033*
H23B	0.5444	0.1877	0.4449	0.033*
C24	0.3655 (2)	0.1546 (2)	0.4982 (2)	0.0258 (5)
C25	0.3711 (2)	0.0611 (2)	0.4198 (2)	0.0304 (5)
H25	0.4395	0.0450	0.3611	0.036*
C26	0.2759 (3)	−0.0093 (3)	0.4274 (3)	0.0397 (6)
H26	0.2810	−0.0722	0.3741	0.048*
C27	0.1738 (3)	0.0136 (3)	0.5138 (3)	0.0423 (7)
H27	0.1102	−0.0339	0.5191	0.051*
C28	0.1663 (3)	0.1070 (3)	0.5921 (3)	0.0428 (7)
H28	0.0971	0.1230	0.6500	0.051*
C29	0.2623 (3)	0.1784 (3)	0.5854 (2)	0.0347 (6)
H29	0.2570	0.2412	0.6389	0.042*
Cl1	0.69094 (6)	0.07092 (7)	1.20562 (5)	0.03984 (18)
Cl2	−0.34861 (5)	0.74242 (7)	0.83650 (5)	0.03639 (17)
C30	−0.0017 (4)	0.2924 (5)	0.9519 (4)	0.0738 (12)
H30A	−0.0290	0.3479	0.8900	0.111*
H30B	−0.0494	0.3193	1.0259	0.111*
H30C	0.0868	0.2909	0.9562	0.111*
C31	−0.0232 (4)	0.1616 (5)	0.9258 (4)	0.0739 (13)
H31A	−0.1125	0.1668	0.9185	0.089*
H31B	0.0230	0.1384	0.8492	0.089*
C32	0.0130 (3)	0.0575 (4)	1.0118 (3)	0.0581 (9)
H32A	0.1032	0.0489	1.0161	0.070*
H32B	−0.0301	0.0817	1.0893	0.070*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Fe	0.0152 (2)	0.0252 (3)	0.0155 (2)	−0.00339 (18)	−0.00488 (17)	0.00556 (18)
N1	0.0167 (8)	0.0284 (10)	0.0176 (9)	−0.0040 (7)	−0.0038 (7)	0.0055 (7)
N2	0.0171 (8)	0.0276 (10)	0.0181 (9)	−0.0025 (7)	−0.0056 (7)	0.0058 (7)
N3	0.0236 (9)	0.0278 (10)	0.0217 (9)	−0.0068 (8)	−0.0083 (7)	0.0063 (7)
C1	0.0178 (10)	0.0269 (11)	0.0231 (11)	−0.0038 (8)	−0.0067 (8)	0.0056 (9)
C2	0.0174 (10)	0.0299 (12)	0.0252 (11)	−0.0028 (8)	−0.0062 (8)	0.0058 (9)
C3	0.0208 (11)	0.0291 (12)	0.0239 (11)	−0.0046 (9)	−0.0095 (8)	0.0080 (9)
C4	0.0208 (10)	0.0268 (11)	0.0198 (10)	−0.0046 (8)	−0.0075 (8)	0.0053 (8)
C5	0.0221 (10)	0.0269 (11)	0.0179 (10)	−0.0055 (8)	−0.0073 (8)	0.0055 (8)
C6	0.0228 (11)	0.0281 (12)	0.0172 (10)	−0.0046 (9)	−0.0046 (8)	0.0049 (8)
C7	0.0242 (11)	0.0316 (12)	0.0185 (10)	−0.0035 (9)	−0.0040 (8)	0.0073 (9)
C8	0.0210 (10)	0.0336 (13)	0.0200 (11)	−0.0027 (9)	−0.0010 (8)	0.0051 (9)
C9	0.0199 (10)	0.0277 (11)	0.0198 (10)	−0.0041 (8)	−0.0033 (8)	0.0041 (8)
C10	0.0178 (10)	0.0290 (12)	0.0224 (11)	−0.0029 (8)	−0.0038 (8)	0.0035 (9)
C11	0.0160 (10)	0.0312 (12)	0.0183 (10)	−0.0021 (8)	−0.0044 (8)	0.0068 (9)
C12	0.0244 (11)	0.0342 (13)	0.0220 (11)	−0.0047 (9)	−0.0051 (9)	0.0052 (9)
C13	0.0262 (11)	0.0444 (15)	0.0184 (11)	−0.0054 (10)	−0.0068 (9)	0.0037 (10)
C14	0.0177 (10)	0.0451 (14)	0.0197 (11)	−0.0021 (9)	−0.0038 (8)	0.0121 (10)
C15	0.0294 (12)	0.0327 (13)	0.0277 (12)	−0.0039 (10)	−0.0050 (10)	0.0100 (10)
C16	0.0305 (12)	0.0348 (13)	0.0224 (11)	−0.0069 (10)	−0.0072 (9)	0.0064 (10)
C17	0.0201 (11)	0.0347 (13)	0.0201 (11)	−0.0028 (9)	−0.0049 (8)	0.0087 (9)
C18	0.0225 (11)	0.0369 (14)	0.0318 (13)	−0.0038 (10)	−0.0030 (9)	0.0001 (10)
C19	0.0214 (11)	0.0459 (15)	0.0322 (13)	−0.0093 (10)	−0.0038 (10)	0.0050 (11)
C20	0.0166 (10)	0.0465 (15)	0.0229 (11)	0.0009 (10)	−0.0026 (8)	0.0079 (10)
C21	0.0279 (13)	0.0364 (15)	0.0464 (16)	0.0011 (11)	0.0021 (11)	0.0017 (12)
C22	0.0232 (12)	0.0342 (14)	0.0474 (16)	−0.0051 (10)	−0.0024 (11)	0.0060 (11)
C23	0.0253 (11)	0.0303 (12)	0.0285 (12)	−0.0045 (9)	−0.0104 (9)	0.0049 (9)
C24	0.0231 (11)	0.0284 (12)	0.0262 (11)	−0.0027 (9)	−0.0095 (9)	0.0102 (9)
C25	0.0273 (12)	0.0308 (13)	0.0336 (13)	−0.0052 (10)	−0.0072 (10)	0.0050 (10)
C26	0.0365 (14)	0.0335 (14)	0.0526 (17)	−0.0088 (11)	−0.0167 (13)	0.0054 (12)
C27	0.0281 (13)	0.0420 (16)	0.0606 (19)	−0.0124 (11)	−0.0183 (13)	0.0248 (14)
C28	0.0233 (12)	0.0570 (19)	0.0416 (15)	0.0028 (11)	−0.0005 (11)	0.0270 (14)
C29	0.0326 (13)	0.0393 (14)	0.0289 (13)	0.0012 (11)	−0.0035 (10)	0.0085 (11)
Cl1	0.0326 (3)	0.0590 (4)	0.0244 (3)	−0.0004 (3)	−0.0064 (2)	0.0208 (3)
Cl2	0.0187 (3)	0.0606 (4)	0.0256 (3)	0.0012 (2)	0.0002 (2)	0.0068 (3)
C30	0.070 (3)	0.086 (3)	0.074 (3)	−0.035 (2)	−0.018 (2)	0.021 (2)
C31	0.053 (2)	0.105 (4)	0.060 (2)	−0.003 (2)	−0.0111 (18)	0.014 (2)
C32	0.0321 (15)	0.088 (3)	0.0495 (19)	0.0010 (16)	−0.0071 (14)	0.0095 (19)

Geometric parameters (Å, º) top

Fe—N1	1.9932 (18)	C15—C16	1.393 (3)
Fe—N1ⁱ	1.9932 (18)	C15—H15	0.9300
Fe—N2	1.9955 (18)	C16—H16	0.9300
Fe—N2ⁱ	1.9956 (18)	C17—C22	1.381 (4)
Fe—N3ⁱ	2.036 (2)	C17—C18	1.386 (4)
Fe—N3	2.036 (2)	C18—C19	1.396 (3)
N1—C1	1.382 (3)	C18—H18	0.9300
N1—C4	1.384 (3)	C19—C20	1.371 (4)
N2—C9	1.383 (3)	C19—H19	0.9300
N2—C6	1.387 (3)	C20—C21	1.384 (4)
N3—C23	1.492 (3)	C20—Cl2	1.744 (2)
N3—H3A	0.8900	C21—C22	1.393 (4)
N3—H3B	0.8900	C21—H21	0.9300
C1—C10ⁱ	1.391 (3)	C22—H22	0.9300
C1—C2	1.435 (3)	C23—C24	1.509 (3)
C2—C3	1.353 (3)	C23—H23A	0.9700
C2—H2	0.9300	C23—H23B	0.9700
C3—C4	1.444 (3)	C24—C25	1.380 (4)
C3—H3	0.9300	C24—C29	1.392 (4)
C4—C5	1.391 (3)	C25—C26	1.388 (4)
C5—C6	1.390 (3)	C25—H25	0.9300
C5—C11	1.498 (3)	C26—C27	1.377 (5)
C6—C7	1.439 (3)	C26—H26	0.9300
C7—C8	1.351 (3)	C27—C28	1.375 (5)
C7—H7	0.9300	C27—H27	0.9300
C8—C9	1.438 (3)	C28—C29	1.403 (4)
C8—H8	0.9300	C28—H28	0.9300
C9—C10	1.393 (3)	C29—H29	0.9300
C10—C1ⁱ	1.391 (3)	C30—C31	1.550 (7)
C10—C17	1.502 (3)	C30—H30A	0.9600
C11—C16	1.391 (4)	C30—H30B	0.9600
C11—C12	1.392 (3)	C30—H30C	0.9600
C12—C13	1.396 (3)	C31—C32	1.514 (6)
C12—H12	0.9300	C31—H31A	0.9700
C13—C14	1.378 (4)	C31—H31B	0.9700
C13—H13	0.9300	C32—C32ⁱⁱ	1.392 (9)
C14—C15	1.384 (4)	C32—H32A	0.9700
C14—Cl1	1.742 (2)	C32—H32B	0.9700

N1—Fe—N1ⁱ	180.0	C15—C14—Cl1	119.1 (2)
N1—Fe—N2	89.69 (8)	C14—C15—C16	118.8 (2)
N1ⁱ—Fe—N2	90.31 (8)	C14—C15—H15	120.6
N1—Fe—N2ⁱ	90.31 (8)	C16—C15—H15	120.6
N1ⁱ—Fe—N2ⁱ	89.69 (8)	C11—C16—C15	121.2 (2)
N2—Fe—N2ⁱ	180.0	C11—C16—H16	119.4
N1—Fe—N3ⁱ	85.61 (8)	C15—C16—H16	119.4
N1ⁱ—Fe—N3ⁱ	94.39 (8)	C22—C17—C18	118.9 (2)
N2—Fe—N3ⁱ	92.04 (8)	C22—C17—C10	120.6 (2)
N2ⁱ—Fe—N3ⁱ	87.96 (8)	C18—C17—C10	120.5 (2)
N1—Fe—N3	94.39 (8)	C17—C18—C19	120.8 (3)
N1ⁱ—Fe—N3	85.61 (8)	C17—C18—H18	119.6
N2—Fe—N3	87.96 (8)	C19—C18—H18	119.6
N2ⁱ—Fe—N3	92.04 (8)	C20—C19—C18	119.1 (2)
N3ⁱ—Fe—N3	180.0	C20—C19—H19	120.4
C1—N1—C4	104.92 (18)	C18—C19—H19	120.4
C1—N1—Fe	127.30 (15)	C19—C20—C21	121.2 (2)
C4—N1—Fe	127.61 (15)	C19—C20—Cl2	119.3 (2)
C9—N2—C6	104.94 (18)	C21—C20—Cl2	119.5 (2)
C9—N2—Fe	127.24 (15)	C20—C21—C22	118.8 (3)
C6—N2—Fe	127.72 (15)	C20—C21—H21	120.6
C23—N3—Fe	119.69 (15)	C22—C21—H21	120.6
C23—N3—H3A	107.4	C17—C22—C21	121.1 (3)
Fe—N3—H3A	107.4	C17—C22—H22	119.5
C23—N3—H3B	107.4	C21—C22—H22	119.5
Fe—N3—H3B	107.4	N3—C23—C24	112.64 (19)
H3A—N3—H3B	106.9	N3—C23—H23A	109.1
N1—C1—C10ⁱ	125.2 (2)	C24—C23—H23A	109.1
N1—C1—C2	110.57 (19)	N3—C23—H23B	109.1
C10ⁱ—C1—C2	124.1 (2)	C24—C23—H23B	109.1
C3—C2—C1	107.4 (2)	H23A—C23—H23B	107.8
C3—C2—H2	126.3	C25—C24—C29	119.2 (2)
C1—C2—H2	126.3	C25—C24—C23	121.4 (2)
C2—C3—C4	106.6 (2)	C29—C24—C23	119.4 (2)
C2—C3—H3	126.7	C24—C25—C26	120.9 (3)
C4—C3—H3	126.7	C24—C25—H25	119.6
N1—C4—C5	125.7 (2)	C26—C25—H25	119.6
N1—C4—C3	110.55 (19)	C27—C26—C25	120.2 (3)
C5—C4—C3	123.7 (2)	C27—C26—H26	119.9
C6—C5—C4	123.7 (2)	C25—C26—H26	119.9
C6—C5—C11	118.1 (2)	C28—C27—C26	119.6 (3)
C4—C5—C11	118.13 (19)	C28—C27—H27	120.2
N2—C6—C5	125.4 (2)	C26—C27—H27	120.2
N2—C6—C7	110.37 (19)	C27—C28—C29	120.6 (3)
C5—C6—C7	124.2 (2)	C27—C28—H28	119.7
C8—C7—C6	107.1 (2)	C29—C28—H28	119.7
C8—C7—H7	126.5	C24—C29—C28	119.5 (3)
C6—C7—H7	126.5	C24—C29—H29	120.3
C7—C8—C9	107.2 (2)	C28—C29—H29	120.3
C7—C8—H8	126.4	C31—C30—H30A	109.5
C9—C8—H8	126.4	C31—C30—H30B	109.5
N2—C9—C10	125.1 (2)	H30A—C30—H30B	109.5
N2—C9—C8	110.46 (19)	C31—C30—H30C	109.5
C10—C9—C8	124.4 (2)	H30A—C30—H30C	109.5
C1ⁱ—C10—C9	124.7 (2)	H30B—C30—H30C	109.5
C1ⁱ—C10—C17	117.5 (2)	C32—C31—C30	119.2 (4)
C9—C10—C17	117.8 (2)	C32—C31—H31A	107.5
C16—C11—C12	118.6 (2)	C30—C31—H31A	107.5
C16—C11—C5	120.6 (2)	C32—C31—H31B	107.5
C12—C11—C5	120.8 (2)	C30—C31—H31B	107.5
C11—C12—C13	120.9 (2)	H31A—C31—H31B	107.0
C11—C12—H12	119.5	C32ⁱⁱ—C32—C31	117.6 (4)
C13—C12—H12	119.5	C32ⁱⁱ—C32—H32A	107.9
C14—C13—C12	119.0 (2)	C31—C32—H32A	107.9
C14—C13—H13	120.5	C32ⁱⁱ—C32—H32B	107.9
C12—C13—H13	120.5	C31—C32—H32B	107.9
C13—C14—C15	121.5 (2)	H32A—C32—H32B	107.2
C13—C14—Cl1	119.4 (2)

C4—N1—C1—C10ⁱ	−176.9 (2)	C4—C5—C11—C16	−82.1 (3)
Fe—N1—C1—C10ⁱ	−1.4 (3)	C6—C5—C11—C12	−84.1 (3)
C4—N1—C1—C2	0.2 (3)	C4—C5—C11—C12	97.5 (3)
Fe—N1—C1—C2	175.67 (16)	C16—C11—C12—C13	0.1 (3)
N1—C1—C2—C3	−0.3 (3)	C5—C11—C12—C13	−179.5 (2)
C10ⁱ—C1—C2—C3	176.8 (2)	C11—C12—C13—C14	0.4 (4)
C1—C2—C3—C4	0.3 (3)	C12—C13—C14—C15	−0.3 (4)
C1—N1—C4—C5	179.8 (2)	C12—C13—C14—Cl1	179.66 (18)
Fe—N1—C4—C5	4.3 (3)	C13—C14—C15—C16	−0.4 (4)
C1—N1—C4—C3	0.0 (3)	Cl1—C14—C15—C16	179.65 (19)
Fe—N1—C4—C3	−175.45 (16)	C12—C11—C16—C15	−0.8 (4)
C2—C3—C4—N1	−0.2 (3)	C5—C11—C16—C15	178.7 (2)
C2—C3—C4—C5	−180.0 (2)	C14—C15—C16—C11	1.0 (4)
N1—C4—C5—C6	−1.6 (4)	C1ⁱ—C10—C17—C22	−72.8 (3)
C3—C4—C5—C6	178.2 (2)	C9—C10—C17—C22	107.5 (3)
N1—C4—C5—C11	176.8 (2)	C1ⁱ—C10—C17—C18	105.6 (3)
C3—C4—C5—C11	−3.4 (3)	C9—C10—C17—C18	−74.1 (3)
C9—N2—C6—C5	179.4 (2)	C22—C17—C18—C19	−2.3 (4)
Fe—N2—C6—C5	2.9 (3)	C10—C17—C18—C19	179.3 (2)
C9—N2—C6—C7	0.7 (3)	C17—C18—C19—C20	0.4 (4)
Fe—N2—C6—C7	−175.80 (16)	C18—C19—C20—C21	2.0 (4)
C4—C5—C6—N2	−2.2 (4)	C18—C19—C20—Cl2	−178.5 (2)
C11—C5—C6—N2	179.4 (2)	C19—C20—C21—C22	−2.5 (4)
C4—C5—C6—C7	176.3 (2)	Cl2—C20—C21—C22	178.0 (2)
C11—C5—C6—C7	−2.1 (4)	C18—C17—C22—C21	1.8 (4)
N2—C6—C7—C8	−0.6 (3)	C10—C17—C22—C21	−179.8 (2)
C5—C6—C7—C8	−179.3 (2)	C20—C21—C22—C17	0.5 (4)
C6—C7—C8—C9	0.2 (3)	Fe—N3—C23—C24	146.34 (17)
C6—N2—C9—C10	179.6 (2)	N3—C23—C24—C25	104.7 (3)
Fe—N2—C9—C10	−3.9 (4)	N3—C23—C24—C29	−76.1 (3)
C6—N2—C9—C8	−0.6 (3)	C29—C24—C25—C26	−0.4 (4)
Fe—N2—C9—C8	175.94 (16)	C23—C24—C25—C26	178.8 (2)
C7—C8—C9—N2	0.2 (3)	C24—C25—C26—C27	0.2 (4)
C7—C8—C9—C10	−179.9 (2)	C25—C26—C27—C28	0.3 (4)
N2—C9—C10—C1ⁱ	1.4 (4)	C26—C27—C28—C29	−0.5 (4)
C8—C9—C10—C1ⁱ	−178.4 (2)	C25—C24—C29—C28	0.1 (4)
N2—C9—C10—C17	−178.9 (2)	C23—C24—C29—C28	−179.1 (2)
C8—C9—C10—C17	1.3 (4)	C27—C28—C29—C24	0.3 (4)
C6—C5—C11—C16	96.4 (3)	C30—C31—C32—C32ⁱⁱ	177.2 (4)

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

Hydrogen-bond geometry (Å, º) top

Cg1 and Cg7 are the centroids of the N1/C1–C4 and C11–C16 rings, respectively.

D—H···A	D—H	H···A	D···A	D—H···A
C19—H19···Cg1ⁱⁱⁱ	0.93	2.66	3.586 (3)	133
C31—H31A···Cg7ⁱⁱⁱ	0.97	2.63	3.701 (5)	160
N3—H3B···Cl2^iv	0.89	2.68	3.651 (2)	133
C7—H7···Cl2^v	0.93	3.00	3.926 (2)	175

Symmetry codes: (iii) x−1, y, z; (iv) −x, −y+1, −z+1; (v) −x, −y+1, −z+2.

Acknowledgements

The authors gratefully acknowledge financial support from the Ministry of Higher Education and Scientific Research of Tunisia.

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