Crystal structure of bis-(benzyl-amine-κN)[5,10,15,20-tetra-kis-(4-chloro-phen-yl)porphyrinato-κ(4) N]iron(II) n-hexane monosolvate.

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-tetra-kis-(4-chloro-phen-yl)porphyrinate and benzyl-amine ligands, respectively], the Fe(II) cation lies on an inversion centre and is octa-hedrally coordinated by the four pyrrole N atoms of the porphyrin ligand in the equatorial plane and by two amine N atoms of the benzyl-amine ligand in the axial sites. The crystal structure also contains one inversion-symmetric n-hexane solvent mol-ecule per complex mol-ecule. The average Fe-Npyrrole 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 inter-actions and by C-H⋯π inter-molecular inter-actions, leading to a three-dimensional network structure.

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 FeII 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 [FeII(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, [FeII(TPP-Cl)(BzNH2)2])·n-hexane, (I).

Structural commentary

The mol­ecular structure of (I) is illustrated in Fig. 1 ▸. The FeII 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—Nbenzyl­amine 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 [FeII(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 FeII 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—Npyrrole bond (Fe—N1). This value is close to those of the related [FeII(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 FeII cation and the value of the average equatorial Fe—Npyrrole bond length has been discussed (Scheidt & Reed, 1981 ▸). For high-spin (S = 2) complexes, the Fe—Npyrrole bond lengths are the longest, e.g. for the [Fe(TpivPP)(NO3)]− complex (TpivPP = picket-fence porphyrin), Fe—Npyrrole amounts to 2.070 (16) Å (Nasri et al., 2006 ▸). For low-spin (S = 0) complexes, the average Fe—Npyrrole bond length is shorter, e.g. for the [Fe(TPP)(4-MePip)2] complex (4-MePip is 4-methyl piperidine), the Fe—Npyrrole bond length is 1.994 (4) Å (Munro & Ntshangase, 2003 ▸) and 1.990 (15) Å for the [FeII(TpivPP)(NO2)(pyridine)]− species (Nasri et al., 2000 ▸). The inter­mediate spin state (S = 1) of FeII porphyrin complexes is represented by the shortest Fe—Npyrrole distances, e.g. Fe(TTP) exhibits an Fe—Npyrrole bond length of 1.979 (6) Å (Hu et al., 2007 ▸). The averaged Fe—Npyrrole 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 [FeII(TPP)(BzNH2)2] derivative [Fe—Npyrrole = 1.992 (4) Å; Munro et al., 1999 ▸].

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 [FeII(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 [FeII(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.

Figure 3

A partial view of the crystal packing of (I), showing the linkage between the [FeII(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.

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) ; (ii) ; (iii) .

Synthesis

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: λmax (10−3·∊) 420 (512.7), 516 (16.7), 552 (7.4), 591 (4.7), 646 (4.0).

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 [FeIII(TPP-Cl)Cl] (Collman et al., 1975 ▸). We used the triflato–iron(III) TPP-Cl derivative [FeIII(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 ▸).

Synthesis and crystallization of bis­(benzyl­amine-κN)[5,10,15,20-tetra­kis­(4-chloro­phen­yl)porphyrinato-κ4 N]iron(II) n-hexane monosolvate complex, (I)

To a solution of [FeIII(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.

UV–vis spectra

The UV–visible spectra with absorption bands at λmax 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 [FeIII(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 λmax 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 [FeII(TPP)(L)2] (L = 1-BuNH2, BzNH2, PhCH2CH2NH2) species (Munro et al., 1999 ▸).

Figure 5

UV–vis spectra of the solid [FeIII(TClPP)(SO3CF3)] starting material (black) and solid (I) (blue).

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(Hphen­yl, Hmethyl­ene, Hamine) = 1.2U eq(C/N) and U iso(Hmeth­yl) = 1.5U(C).

Table 2

Experimental details

Crystal data
Chemical formula	[Fe(C44H24Cl4N4)(C7H9N)2]·C6H14
M r	1106.79
Crystal system, space group	Triclinic, P
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[F 2 > 2σ(F 2)], wR(F 2), S	0.048, 0.133, 1.06
No. of reflections	5355
No. of parameters	340
H-atom treatment	H-atom parameters constrained
Δρmax, Δρmin (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 ▸).

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

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

CCDC reference: 1442707

Additional supporting information: crystallographic information; 3D view; checkCIF report

[Fe(C44H24Cl4N4)(C7H9N)2]·C6H14	Z = 1
Mr = 1106.79	F(000) = 576
Triclinic, P1	Dx = 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

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	Rint = 0.028
ω scans	θmax = 75.3°, θmin = 3.9°
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2014)	h = −13→13
Tmin = 0.416, Tmax = 1.000	k = −13→10
12765 measured reflections	l = −14→12

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(Fo2) + (0.0771P)2 + 0.8782P] where P = (Fo2 + 2Fc2)/3
S = 1.06	(Δ/σ)max = 0.001
5355 reflections	Δρmax = 1.09 e Å−3
340 parameters	Δρmin = −0.53 e Å−3

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.

	x	y	z	Uiso*/Ueq
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*

	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)

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)

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···Cl2iv	0.89	2.68	3.651 (2)	133
C7—H7···Cl2v	0.93	3.00	3.926 (2)	175