Crystal structure of bis-(4-meth-oxy-pyridine-κN)(meso-5,10,15,20-tetra-phenyl-porphyrinato-κ4 N,N',N'',N''')iron(III) perchlorate.

In the crystal structure of the title compound, [Fe(C44H28N4)(C6H7NO)2]ClO4, the FeIII ions are coordinated in an octa-hedral fashion by four N atoms of the porphyrin moiety and two N atoms of two 4-meth-oxy-pyridine ligands into discrete complexes that are located on inversion centers. Charge-balance is achieved by perchlorate anions that are disordered around twofold rotation axes. In the crystal structure, the discrete cationic complexes and the perchlorate anions are arranged into layers with weak C-H⋯O inter-actions between the cations and the anions. The porphyrin moieties of neighboring layers show a herringbone-like arrangement.

Chemical context

Porphyrins are of great inter­est for a number of different applications in medicine and nature (Peters & Herges, 2018 ▸; Peters et al., 2018 ▸; Shankar et al., 2018 ▸; Dommaschk et al., 2015 ▸). For example, metal porphyrins show spin crossover (SCO), which is the key step in a number of enzymatic reactions, e.g. catalysts in selective CH activation (cytochrome P450) (Konishi et al., 1992 ▸; Momenteau et al., 1983 ▸), hydrogen peroxide decomposition (catalases) (Maté et al., 2001 ▸) and a number of other biologically important processes (Collman et al., 1995 ▸; Gunter et al., 1994 ▸; Morgan & Dolphin, 1987 ▸). The spin state and electronic configuration of ferrous porphyrins are dependent on temperature, pressure, light or axial ligands.

Iron(III) porphyrins can exist in high-spin (S = ), inter­mediate-spin (S = ), admixed-spin (S = , ) and low-spin (S = ) states of iron (Scheidt, 2000 ▸; Ikezaki et al., 2009 ▸; Nakamura, 2006 ▸; Shankar et al., 2018 ▸). Most of the anionic ligands such as chloride, hydroxide and azide lead to the formation of complexes in the high-spin state, whereas weak ligands like ClO4 − and SbF6 − usually give the complexes in an admixed-spin state (Scheidt, 2000 ▸). However, six-coordinate complexes with strong axial ligands tend to be in the low-spin state (Scheidt, 2000 ▸). In our ongoing investigations on SCO compounds based on iron porphyrins, we became inter­ested in the complex bis­(4-meth­oxy­pyridine-κN)(meso-5,10,15,20-tetra­phenyl­porphyrinato-κ4 N,N′,N′′,N′′′iron(III) perchlorate, which was synthesized and characterized by high-resolution mass spectroscopy (Shankar et al., 2018 ▸). Preliminary investigations indicate that the complex is in the low-spin state but unfortunately no single crystals were obtained. In the course of subsequent investigations, we we able to obtain crystals by the layering technique starting from the FeIII tetra­phenyl­porphyrin perchlorate complexes and using 4-meth­oxy­pyridine dissolved in di­chloro­methane as the lower and n-heptane as the upper layer. These crystals were identified by single crystal X-ray diffraction, which confirmed that crystals of the title compound were obtained.

Structural commentary

The crystal structure of the title compound consists of discrete complexes which lie on inversion centers. The FeIII ions are sixfold coordinated by four N atoms of the porphyrin moiety and two N atoms of two 4-meth­oxy­pyridine ligands in an octa­hedral coordination environment (Fig. 1 ▸). The Fe—N bond lengths to the porphyrin atoms of 1.9989 (13) Å and to the pyridine N atoms of 2.0002 (13) Å are nearly identical and the iron cations are located exactly in the plane of the coordinating porphyrin N atoms (Table 1 ▸). The Fe—N bond lengths to the two axial 4-meth­oxy­pyridine ligands at 2.0 Å are typical for low-spin complexes (Geiger et al., 1985 ▸; Scheidt & Geiger, 1979 ▸), whereas high-spin complexes have a significant longer bond length of about 2.2 Å (Geiger et al., 1984 ▸, 1985 ▸; Geiger & Scheidt, 1984 ▸). The N—Fe—N bond angles within the equatorial porphyrin plane range between 88.56 (5) and 91.44 (5)°, whereas that to the axial ligands are 180° because of symmetry, which proves that the octa­hedra are slightly distorted (Table 1 ▸). The six-membered ring planes of the two coordinating 4-meth­oxy­pyridine ligands are eclipsed and rotated relative to the Fe—N bonds of the FeIII-porphyrin moiety (Fig. 2 ▸). Two of the four phenyl rings are nearly perpendicular to the porphyrin ring planes with a dihedral angle of 87.82 (5)°, whereas the other two rings are rotated out of this plane by 63.64 (5)°. The positive charge of the FeIII-porphyrin moiety is compensated by one perchlorate anion that is disordered around a twofold rotation axis.

Figure 1

Mol­ecular structure of the title compound with displacement ellipsoids drawn at the 50% probability level. Atoms with the suffix A are generated by the symmetry operation (1 − x, 1 − y, 1 − z).

Table 1

Selected geometric parameters (Å, °)

Fe1—N1	1.9989 (13)	Fe1—N2	2.0003 (13)
Fe1—N2i	2.0002 (13)	Fe1—N31	2.0177 (14)
N1i—Fe1—N1	180.00 (4)	N1—Fe1—N31	91.13 (5)
N1—Fe1—N2i	91.44 (5)	N2—Fe1—N31	89.64 (6)
N1—Fe1—N2	88.56 (5)	N2—Fe1—N31i	90.36 (6)
N2i—Fe1—N2	180.00 (8)	N31—Fe1—N31i	180.0
N1i—Fe1—N31	88.87 (6)

Symmetry code: (i) .

Figure 2

Mol­ecular structure of the title compound viewed onto the porphyrin plane.

Supra­molecular features

In the crystal structure, the Fe-porphyrin cations and the perchlorate anions are each arranged in layers that are located parallel to the ab plane (Fig. 3 ▸). These layers are connected to the perchlorate anions by weak C—H⋯O contacts (Table 2 ▸). For one of these contacts, the C—H⋯O angle is close to linearity, indicating weak inter­molecular hydrogen bonding (Fig. 3 ▸ and Table 2 ▸). The porphyrin units of neighboring layers exhibit a herringbone-like arrangement (Fig. 4 ▸).

Figure 3

Crystal packing of the title compound viewed along the b axis. Inter­molecular C—H⋯O contacts are shown as dashed lines.

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C35—H35⋯O4ii	0.95	2.55	3.103 (8)	117
C36—H36C⋯O1	0.98	2.64	3.551 (3)	154

Symmetry code: (ii) .

Figure 4

Crystal packing of the title compound viewed along the a axis.

Database survey

According to a search in the Cambridge Structural Database (CSD Version 5.4, update of February 2019; Groom et al., 2016 ▸), 1009 structures of ferrous porphyrins have been reported. However, ferrous porphyrins with axial 4-meth­oxy­pyridine ligands are unknown although ferrous porphyrins with perchlorate as counter-ion and other pyridines as axial ligands have been published, for instance the sterically congested porphyrin (2,3,7,8,12,13,17,18-octa­methyl-5,10,15,20-tetra­phenyl­porph­yrinato)iron(III) perchlorate which has two pyridine mol­ecules as axial ligands (Ohgo et al., 2002 ▸, 2004 ▸). Other iron(III) porphyrin perchlorates are known with 3-chloro­pyridine (Scheidt & Geiger, 1979 ▸), 4-cyano­pyridine (Safo et al., 1994 ▸), 3,5-di­chloro­pyridine (Scheidt et al., 1989 ▸) and 4-cyano­pyridine ligands (Yatsunyk & Walker 2004 ▸; Safo et al. 1994 ▸; Safo et al. 1992 ▸).

Synthesis and crystallization

FeIII tetra­phenyl­porphyrin perchlorate (FeTPPClO4) was synthesized as previously reported (Shankar et al., 2018 ▸). The layering technique was used for crystallization. The lower layer was di­chloro­methane with 50 µL 4-meth­oxy­pyridine and n-heptane was used for the upper anti­solvent.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3 ▸. The C—H hydrogen atoms were positioned with idealized geometries (C—H = 0.95–0.98 Å; methyl H atoms allowed to rotate but not to tip) and were refined isotropically using a riding model with U iso(H) = 1.2U eq(C) or 1.5U eq(C-meth­yl). The perchlorate anion is disordered around a twofold rotation axis that passes through O1 and thus, disordered because of symmetry.

Table 3

Experimental details

Crystal data
Chemical formula	[Fe(C44H28N4)(C6H7NO)2]ClO4
M r	986.25
Crystal system, space group	Orthorhombic, P b c n
Temperature (K)	170
a, b, c (Å)	16.9772 (4), 11.1879 (2), 24.3484 (6)
V (Å3)	4624.72 (18)
Z	4
Radiation type	Mo Kα
μ (mm−1)	0.45
Crystal size (mm)	0.12 × 0.10 × 0.09
Data collection
Diffractometer	Stoe IPDS2
No. of measured, independent and observed [I > 2σ(I)] reflections	36542, 5029, 4454
R int	0.033
(sin θ/λ)max (Å−1)	0.639
Refinement
R[F 2 > 2σ(F 2)], wR(F 2), S	0.040, 0.099, 1.07
No. of reflections	5029
No. of parameters	337
H-atom treatment	H-atom parameters constrained
Δρmax, Δρmin (e Å−3)	0.28, −0.48

Computer programs: X-AREA (Stoe & Cie, 2008 ▸), SHELXS97 (Sheldrick, 2008 ▸), SHELXL2014 (Sheldrick, 2015 ▸), XP (Sheldrick, 2008 ▸), DIAMOND (Brandenburg, 2014 ▸) and publCIF (Westrip, 2010 ▸).

Crystal structure: contains datablock(s) I. DOI: 10.1107/S2056989019006194/lh5899sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989019006194/lh5899Isup2.hkl

CCDC reference: 1913651

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

[Fe(C44H28N4)(C6H7NO)2]ClO4	Dx = 1.416 Mg m−3
Mr = 986.25	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pbcn	Cell parameters from 36542 reflections
a = 16.9772 (4) Å	θ = 1.7–27.0°
b = 11.1879 (2) Å	µ = 0.45 mm−1
c = 24.3484 (6) Å	T = 170 K
V = 4624.72 (18) Å3	Block, colorless
Z = 4	0.12 × 0.10 × 0.09 mm
F(000) = 2044

STOE IPDS-2 diffractometer	Rint = 0.033
ω scans	θmax = 27.0°, θmin = 1.7°
36542 measured reflections	h = −21→21
5029 independent reflections	k = −13→14
4454 reflections with I > 2σ(I)	l = −29→31

Refinement on F2	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.040	H-atom parameters constrained
wR(F2) = 0.099	w = 1/[σ2(Fo2) + (0.0472P)2 + 2.1988P] where P = (Fo2 + 2Fc2)/3
S = 1.07	(Δ/σ)max < 0.001
5029 reflections	Δρmax = 0.28 e Å−3
337 parameters	Δρmin = −0.48 e Å−3

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.

	x	y	z	Uiso*/Ueq	Occ. (<1)
Fe1	0.5000	0.5000	0.5000	0.02670 (10)
N1	0.51998 (8)	0.59036 (13)	0.43056 (5)	0.0287 (3)
N2	0.38550 (8)	0.53845 (13)	0.49210 (5)	0.0285 (3)
C1	0.66431 (9)	0.56717 (15)	0.42585 (6)	0.0303 (3)
C2	0.59265 (9)	0.61091 (16)	0.40705 (7)	0.0312 (3)
C3	0.58436 (10)	0.68660 (18)	0.36008 (7)	0.0386 (4)
H3	0.6257	0.7136	0.3369	0.046*
C4	0.50747 (10)	0.71259 (17)	0.35457 (7)	0.0374 (4)
H4	0.4844	0.7618	0.3271	0.045*
C5	0.46682 (9)	0.65166 (15)	0.39806 (6)	0.0301 (3)
C6	0.38565 (9)	0.65732 (15)	0.40647 (6)	0.0294 (3)
C7	0.34876 (9)	0.60222 (15)	0.45098 (6)	0.0295 (3)
C8	0.26493 (9)	0.60202 (16)	0.45999 (7)	0.0322 (3)
H8	0.2263	0.6386	0.4373	0.039*
C9	0.25149 (10)	0.54030 (17)	0.50662 (7)	0.0332 (3)
H9	0.2016	0.5257	0.5230	0.040*
C10	0.32645 (9)	0.50074 (15)	0.52689 (7)	0.0293 (3)
C11	0.33579 (9)	0.72443 (15)	0.36631 (6)	0.0294 (3)
C12	0.33009 (10)	0.68687 (16)	0.31184 (7)	0.0341 (4)
H12	0.3600	0.6203	0.2996	0.041*
C13	0.28082 (10)	0.74660 (19)	0.27552 (7)	0.0390 (4)
H13	0.2768	0.7199	0.2386	0.047*
C14	0.23762 (10)	0.84445 (19)	0.29253 (8)	0.0415 (4)
H14	0.2040	0.8849	0.2675	0.050*
C15	0.24377 (10)	0.88294 (17)	0.34625 (8)	0.0395 (4)
H15	0.2145	0.9506	0.3581	0.047*
C16	0.29235 (10)	0.82350 (16)	0.38300 (7)	0.0341 (4)
H16	0.2960	0.8506	0.4199	0.041*
C17	0.73642 (9)	0.59461 (16)	0.39261 (7)	0.0312 (3)
C18	0.76060 (12)	0.51717 (19)	0.35181 (8)	0.0437 (4)
H18	0.7316	0.4461	0.3450	0.052*
C19	0.82706 (12)	0.5424 (2)	0.32064 (9)	0.0500 (5)
H19	0.8438	0.4878	0.2931	0.060*
C20	0.86880 (10)	0.6461 (2)	0.32953 (8)	0.0434 (4)
H20	0.9137	0.6640	0.3077	0.052*
C21	0.84516 (11)	0.72356 (19)	0.37005 (9)	0.0460 (5)
H21	0.8740	0.7950	0.3764	0.055*
C22	0.77939 (11)	0.69788 (18)	0.40173 (8)	0.0423 (4)
H22	0.7637	0.7516	0.4299	0.051*
N31	0.48297 (8)	0.34725 (13)	0.45758 (6)	0.0299 (3)
C31	0.50607 (12)	0.23963 (17)	0.47644 (8)	0.0420 (4)
H31	0.5320	0.2360	0.5110	0.050*
C32	0.49415 (13)	0.13525 (18)	0.44838 (8)	0.0457 (5)
H32	0.5116	0.0614	0.4633	0.055*
C33	0.45604 (11)	0.13819 (16)	0.39757 (7)	0.0363 (4)
C34	0.43316 (10)	0.24801 (16)	0.37747 (7)	0.0351 (4)
H34	0.4077	0.2541	0.3429	0.042*
C35	0.44775 (10)	0.34847 (16)	0.40822 (7)	0.0342 (4)
H35	0.4319	0.4235	0.3937	0.041*
O31	0.44631 (9)	0.03299 (12)	0.37175 (6)	0.0467 (3)
C36	0.41268 (13)	0.03669 (19)	0.31772 (8)	0.0461 (5)
H36A	0.3605	0.0738	0.3194	0.069*
H36B	0.4078	−0.0448	0.3034	0.069*
H36C	0.4468	0.0836	0.2934	0.069*
Cl1	0.51249 (9)	0.41187 (7)	0.25605 (9)	0.0354 (3)	0.5
O1	0.5000	0.28459 (18)	0.2500	0.0480 (5)
O2	0.4431 (3)	0.4585 (8)	0.2775 (3)	0.084 (3)	0.5
O3	0.5724 (2)	0.4344 (3)	0.29567 (16)	0.0722 (10)	0.5
O4	0.5362 (5)	0.4650 (9)	0.2069 (3)	0.095 (3)	0.5

	U11	U22	U33	U12	U13	U23
Fe1	0.02464 (16)	0.02978 (17)	0.02567 (16)	0.00148 (12)	0.00190 (11)	0.00273 (12)
N1	0.0254 (6)	0.0324 (7)	0.0282 (6)	0.0014 (5)	0.0020 (5)	0.0033 (5)
N2	0.0259 (6)	0.0325 (7)	0.0272 (6)	0.0018 (5)	0.0017 (5)	0.0032 (5)
C1	0.0285 (7)	0.0334 (9)	0.0292 (8)	0.0003 (6)	0.0032 (6)	0.0012 (6)
C2	0.0294 (8)	0.0347 (9)	0.0296 (8)	0.0003 (6)	0.0044 (6)	0.0042 (7)
C3	0.0323 (8)	0.0479 (11)	0.0357 (9)	0.0010 (7)	0.0057 (7)	0.0118 (8)
C4	0.0324 (8)	0.0431 (10)	0.0367 (9)	0.0022 (7)	0.0018 (7)	0.0116 (8)
C5	0.0296 (8)	0.0327 (9)	0.0281 (7)	0.0023 (6)	0.0002 (6)	0.0047 (6)
C6	0.0294 (7)	0.0302 (8)	0.0288 (7)	0.0025 (6)	0.0003 (6)	0.0005 (6)
C7	0.0276 (7)	0.0322 (8)	0.0286 (8)	0.0023 (6)	−0.0011 (6)	0.0005 (6)
C8	0.0269 (8)	0.0377 (9)	0.0321 (8)	0.0034 (7)	−0.0008 (6)	0.0029 (7)
C9	0.0264 (7)	0.0382 (9)	0.0349 (8)	0.0020 (7)	0.0022 (6)	0.0019 (7)
C10	0.0263 (7)	0.0322 (8)	0.0293 (8)	0.0006 (6)	0.0022 (6)	0.0003 (6)
C11	0.0268 (7)	0.0315 (8)	0.0300 (8)	0.0003 (6)	0.0004 (6)	0.0044 (6)
C12	0.0339 (8)	0.0364 (9)	0.0321 (8)	0.0007 (7)	0.0021 (6)	0.0016 (7)
C13	0.0348 (8)	0.0528 (11)	0.0294 (8)	−0.0045 (8)	−0.0030 (7)	0.0058 (8)
C14	0.0305 (8)	0.0516 (11)	0.0424 (9)	0.0022 (8)	−0.0026 (7)	0.0168 (9)
C15	0.0325 (8)	0.0375 (10)	0.0486 (10)	0.0074 (7)	0.0047 (8)	0.0096 (8)
C16	0.0334 (8)	0.0351 (9)	0.0339 (8)	0.0019 (7)	0.0024 (7)	0.0022 (7)
C17	0.0262 (7)	0.0366 (9)	0.0309 (8)	0.0020 (6)	0.0014 (6)	0.0063 (7)
C18	0.0439 (10)	0.0459 (11)	0.0414 (10)	−0.0082 (8)	0.0113 (8)	−0.0035 (8)
C19	0.0459 (11)	0.0614 (13)	0.0427 (10)	−0.0035 (10)	0.0156 (8)	−0.0055 (10)
C20	0.0288 (8)	0.0622 (13)	0.0394 (9)	−0.0021 (8)	0.0052 (7)	0.0110 (9)
C21	0.0332 (9)	0.0473 (11)	0.0574 (12)	−0.0083 (8)	0.0014 (8)	0.0054 (9)
C22	0.0356 (9)	0.0424 (10)	0.0489 (10)	−0.0017 (8)	0.0081 (8)	−0.0037 (8)
N31	0.0284 (6)	0.0325 (7)	0.0289 (6)	0.0019 (5)	0.0009 (5)	0.0019 (6)
C31	0.0550 (11)	0.0366 (10)	0.0342 (9)	0.0036 (8)	−0.0073 (8)	0.0035 (7)
C32	0.0652 (13)	0.0338 (10)	0.0381 (10)	0.0025 (9)	−0.0075 (9)	0.0052 (8)
C33	0.0404 (9)	0.0330 (9)	0.0355 (9)	−0.0041 (7)	0.0010 (7)	0.0001 (7)
C34	0.0341 (8)	0.0388 (9)	0.0324 (8)	0.0020 (7)	−0.0034 (7)	0.0005 (7)
C35	0.0352 (8)	0.0349 (9)	0.0325 (8)	0.0040 (7)	−0.0017 (6)	0.0021 (7)
O31	0.0652 (9)	0.0333 (7)	0.0416 (7)	−0.0056 (6)	−0.0088 (6)	−0.0011 (6)
C36	0.0558 (12)	0.0411 (10)	0.0413 (10)	−0.0094 (9)	−0.0083 (9)	−0.0030 (8)
Cl1	0.0332 (11)	0.0327 (3)	0.0404 (10)	0.0001 (4)	0.0032 (6)	−0.0014 (4)
O1	0.0637 (13)	0.0331 (10)	0.0472 (11)	0.000	−0.0063 (9)	0.000
O2	0.044 (2)	0.053 (3)	0.154 (8)	0.0169 (19)	0.050 (3)	−0.008 (4)
O3	0.066 (2)	0.067 (2)	0.083 (2)	−0.0006 (18)	−0.0318 (19)	−0.0234 (19)
O4	0.184 (9)	0.051 (3)	0.050 (3)	−0.006 (5)	0.049 (4)	0.006 (2)

Fe1—N1i	1.9988 (13)	C17—C22	1.384 (3)
Fe1—N1	1.9989 (13)	C18—C19	1.389 (3)
Fe1—N2i	2.0002 (13)	C18—H18	0.9500
Fe1—N2	2.0003 (13)	C19—C20	1.377 (3)
Fe1—N31	2.0177 (14)	C19—H19	0.9500
Fe1—N31i	2.0177 (14)	C20—C21	1.373 (3)
N1—C2	1.379 (2)	C20—H20	0.9500
N1—C5	1.382 (2)	C21—C22	1.387 (3)
N2—C10	1.379 (2)	C21—H21	0.9500
N2—C7	1.379 (2)	C22—H22	0.9500
C1—C10i	1.388 (2)	N31—C35	1.342 (2)
C1—C2	1.389 (2)	N31—C31	1.347 (2)
C1—C17	1.499 (2)	C31—C32	1.368 (3)
C2—C3	1.430 (2)	C31—H31	0.9500
C3—C4	1.344 (2)	C32—C33	1.397 (3)
C3—H3	0.9500	C32—H32	0.9500
C4—C5	1.436 (2)	C33—O31	1.344 (2)
C4—H4	0.9500	C33—C34	1.378 (3)
C5—C6	1.395 (2)	C34—C35	1.373 (3)
C6—C7	1.395 (2)	C34—H34	0.9500
C6—C11	1.495 (2)	C35—H35	0.9500
C7—C8	1.440 (2)	O31—C36	1.435 (2)
C8—C9	1.348 (2)	C36—H36A	0.9800
C8—H8	0.9500	C36—H36B	0.9800
C9—C10	1.435 (2)	C36—H36C	0.9800
C9—H9	0.9500	Cl1—Cl1ii	0.5162 (19)
C10—C1i	1.388 (2)	Cl1—O2ii	1.228 (6)
C11—C16	1.392 (2)	Cl1—O4ii	1.361 (8)
C11—C12	1.395 (2)	Cl1—O2	1.391 (5)
C12—C13	1.389 (2)	Cl1—O4	1.396 (8)
C12—H12	0.9500	Cl1—O3	1.425 (3)
C13—C14	1.381 (3)	Cl1—O1	1.447 (2)
C13—H13	0.9500	Cl1—O3ii	1.931 (3)
C14—C15	1.381 (3)	O1—Cl1ii	1.447 (2)
C14—H14	0.9500	O2—O4ii	0.524 (14)
C15—C16	1.387 (2)	O2—Cl1ii	1.228 (6)
C15—H15	0.9500	O3—Cl1ii	1.931 (3)
C16—H16	0.9500	O4—O2ii	0.524 (14)
C17—C18	1.381 (3)	O4—Cl1ii	1.361 (8)
N1i—Fe1—N1	180.00 (4)	C19—C18—H18	119.8
N1i—Fe1—N2i	88.56 (5)	C20—C19—C18	120.21 (19)
N1—Fe1—N2i	91.44 (5)	C20—C19—H19	119.9
N1i—Fe1—N2	91.44 (5)	C18—C19—H19	119.9
N1—Fe1—N2	88.56 (5)	C21—C20—C19	119.64 (17)
N2i—Fe1—N2	180.00 (8)	C21—C20—H20	120.2
N1i—Fe1—N31	88.87 (6)	C19—C20—H20	120.2
N1—Fe1—N31	91.13 (5)	C20—C21—C22	120.27 (19)
N2i—Fe1—N31	90.36 (6)	C20—C21—H21	119.9
N2—Fe1—N31	89.64 (6)	C22—C21—H21	119.9
N1i—Fe1—N31i	91.13 (5)	C17—C22—C21	120.52 (18)
N1—Fe1—N31i	88.87 (6)	C17—C22—H22	119.7
N2i—Fe1—N31i	89.64 (6)	C21—C22—H22	119.7
N2—Fe1—N31i	90.36 (6)	C35—N31—C31	116.36 (15)
N31—Fe1—N31i	180.0	C35—N31—Fe1	120.90 (12)
C2—N1—C5	105.28 (13)	C31—N31—Fe1	122.74 (12)
C2—N1—Fe1	125.95 (11)	N31—C31—C32	123.34 (17)
C5—N1—Fe1	128.63 (11)	N31—C31—H31	118.3
C10—N2—C7	106.01 (13)	C32—C31—H31	118.3
C10—N2—Fe1	125.58 (11)	C31—C32—C33	119.39 (18)
C7—N2—Fe1	128.37 (11)	C31—C32—H32	120.3
C10i—C1—C2	124.42 (15)	C33—C32—H32	120.3
C10i—C1—C17	117.87 (14)	O31—C33—C34	125.44 (16)
C2—C1—C17	117.71 (14)	O31—C33—C32	116.77 (17)
N1—C2—C1	126.01 (15)	C34—C33—C32	117.78 (17)
N1—C2—C3	110.04 (14)	C35—C34—C33	119.04 (16)
C1—C2—C3	123.95 (15)	C35—C34—H34	120.5
C4—C3—C2	107.67 (15)	C33—C34—H34	120.5
C4—C3—H3	126.2	N31—C35—C34	124.07 (16)
C2—C3—H3	126.2	N31—C35—H35	118.0
C3—C4—C5	106.88 (15)	C34—C35—H35	118.0
C3—C4—H4	126.6	C33—O31—C36	116.89 (15)
C5—C4—H4	126.6	O31—C36—H36A	109.5
N1—C5—C6	125.70 (15)	O31—C36—H36B	109.5
N1—C5—C4	110.12 (14)	H36A—C36—H36B	109.5
C6—C5—C4	124.16 (15)	O31—C36—H36C	109.5
C5—C6—C7	122.52 (15)	H36A—C36—H36C	109.5
C5—C6—C11	119.09 (14)	H36B—C36—H36C	109.5
C7—C6—C11	118.39 (14)	Cl1ii—Cl1—O2ii	97.2 (6)
N2—C7—C6	126.14 (14)	Cl1ii—Cl1—O4ii	83.1 (6)
N2—C7—C8	109.61 (14)	O2ii—Cl1—O4ii	128.9 (2)
C6—C7—C8	124.24 (15)	Cl1ii—Cl1—O2	61.2 (6)
C9—C8—C7	107.24 (14)	O2ii—Cl1—O2	127.7 (7)
C9—C8—H8	126.4	O4ii—Cl1—O2	21.9 (6)
C7—C8—H8	126.4	Cl1ii—Cl1—O4	75.4 (6)
C8—C9—C10	107.31 (14)	O2ii—Cl1—O4	21.8 (6)
C8—C9—H9	126.3	O4ii—Cl1—O4	123.9 (7)
C10—C9—H9	126.3	O2—Cl1—O4	114.0 (4)
N2—C10—C1i	126.50 (15)	Cl1ii—Cl1—O3	166.6 (5)
N2—C10—C9	109.82 (14)	O2ii—Cl1—O3	86.4 (4)
C1i—C10—C9	123.66 (15)	O4ii—Cl1—O3	84.7 (4)
C16—C11—C12	118.74 (15)	O2—Cl1—O3	106.5 (4)
C16—C11—C6	120.59 (15)	O4—Cl1—O3	107.4 (4)
C12—C11—C6	120.65 (15)	Cl1ii—Cl1—O1	79.73 (4)
C13—C12—C11	120.16 (17)	O2ii—Cl1—O1	116.1 (5)
C13—C12—H12	119.9	O4ii—Cl1—O1	114.1 (4)
C11—C12—H12	119.9	O2—Cl1—O1	106.5 (4)
C14—C13—C12	120.68 (17)	O4—Cl1—O1	112.0 (4)
C14—C13—H13	119.7	O3—Cl1—O1	110.32 (17)
C12—C13—H13	119.7	Cl1ii—Cl1—O3ii	9.8 (3)
C15—C14—C13	119.41 (16)	O2ii—Cl1—O3ii	88.3 (4)
C15—C14—H14	120.3	O4ii—Cl1—O3ii	85.6 (4)
C13—C14—H14	120.3	O2—Cl1—O3ii	64.1 (4)
C14—C15—C16	120.43 (17)	O4—Cl1—O3ii	66.4 (4)
C14—C15—H15	119.8	O3—Cl1—O3ii	162.2 (3)
C16—C15—H15	119.8	O1—Cl1—O3ii	87.28 (13)
C15—C16—C11	120.57 (16)	Cl1—O1—Cl1ii	20.54 (8)
C15—C16—H16	119.7	O4ii—O2—Cl1ii	97.4 (13)
C11—C16—H16	119.7	O4ii—O2—Cl1	75.8 (13)
C18—C17—C22	118.85 (16)	Cl1ii—O2—Cl1	21.61 (13)
C18—C17—C1	120.18 (16)	Cl1—O3—Cl1ii	3.54 (12)
C22—C17—C1	120.96 (16)	O2ii—O4—Cl1ii	82.2 (13)
C17—C18—C19	120.50 (19)	O2ii—O4—Cl1	60.7 (12)
C17—C18—H18	119.8	Cl1ii—O4—Cl1	21.53 (14)

D—H···A	D—H	H···A	D···A	D—H···A
C35—H35···O4ii	0.95	2.55	3.103 (8)	117
C36—H36C···O1	0.98	2.64	3.551 (3)	154