Chlorido­(2,3,7,8,12,13,17,18-octa­ethyl­porphyrinato)iron(III): a new triclinic polymorph of Fe(OEP)Cl

The previous structure determination of the title compound, [Fe(C₃₆H₄₄N₄)Cl], was of a monoclinic polymorph [Senge (2005). Acta Cryst. E61, m399–m400]. The crystal structure of a new triclinic polymorph has been determined based on single-crystal X-ray diffraction data collected at 100 K. The asymmetric unit contains one mol­ecule of the high-spin square-pyramidal iron(III) porphyrinate. The structure exhibits distinct nonstatistical alternative positions for most atoms and was consequently modeled as a whole-mol­ecule disorder. The compound is characterized by an average Fe—N bond length of 2.065 (2) Å, an Fe—Cl bond length of 2.225 (4) Å, and the iron(III) cation displaced by 0.494 (4) Å from the plane of the 24-atom porphyrinate core, essentially the same as in the previously determined polymorph. Common features of the porphyrin plane–plane stacking involve two types of synthons, each of which can be further stabilized with additional H...Cl inter­actions to the axial chloride ligand, exhibiting concerted inter­actions of H atoms from the ethyl groups with the π-cloud electron density of adjacent mol­ecules; the shortest methyl­ene H-atom contacts are in the range 2.75–2.91 Å, resulting in plane–plane separations of 3.407 (4) and 3.416 (4) Å, and the shortest methyl H-atom contacts are 2.56–2.95 Å, resulting in plane–plane separations of 4.900 (5) and 4.909 (5) Å in the monoclinic polymorph. The plane-to-plane stacking synthons in the triclinic polymorph are similar, but at greater distances; the shortest methyl­ene H-atom contacts are 2.86–2.94 Å, resulting in plane–plane separations of 3.45 (2) and 3.45 (3) Å, and the shortest methyl H-atom contacts are 2.89–3.20 Å, resulting in plane–plane separations of 5.081 (13) and 5.134 (13) Å, consistent with the density of the triclinic polymorph being 1.5% lower, suggesting lesser packing efficiency and lower stability in the triclinic polymorph. The major mol­ecular differences found in the polymorphs is in three different orientations of the ethyl-group side chains on the periphery of the porphyrin core.

S1. Introduction

Fe(OEP)Cl, (I), is a convenient starting material to form derivatives of the iron–2,3,7,8,12,13,17,18-o­cta­ethyl­porphyrin macrocycle (OEP) to be used as biomimetic models for heme function (Wyllie & Scheidt, 2002), and also for other studies of iron porphyrin complexes (Senge, 2000), including the recent use, along with other chlorido and oxido derivatives, as models for malaria pigment (Puntharod et al., 2010, 2012, 2014) or as a reference compound (Kalish et al., 2002) as an archetypal high-spin five-coordinate iron(III) porphyrin (Scheidt, 2000). Although (I) was reported in a crystalline form in 1977 (Ernst et al., 1977), the first occurance of Fe(OEP)Cl in the Cambridge Structural Database (CSD, Version 5.32, May 2011; Allen, 2002) was in combination with C₆₀ and chloro­form (CSD refcode CELYOH; Olmstead et al., 1999), followed by the report of the monoclinic polymorph (refcode TOYRUU; Senge, 2005) and another multicomponent (methyl­ene chloride solvate) report (refcode QUXFIZ; Safo et al., 2010). We present here the structure of a new triclinic polymorph of Fe(OEP)Cl which appeared serendipitously as a by-product of the frustrated synthesis of an OEP heme complex with a 2,6-di­nitro­phen­oxy axial ligand (see Experimental), and a comparison of the plane-to-plane packing efficiency of the two polymorphs.

S2. Experimental

S2.1. Synthesis and crystallization

Beautiful dark-purple block-shaped crystals were obtained from the remains from a frustrated attempt to obtain an OEP heme complex with a 2,6-di­nitro­phen­oxy axial ligand. A solution of chlorido(o­cta­ethyl­porphyrinato)iron(III) (1.58 mg, 2.53 mmol; Sigma) and 2,6-di­nitro­phenol (1.86 mg, 10.1 mmol; Sigma) in di­methyl formamide (10 ml) and chloro­form (90 ml) were refluxed 6 h and allowed to cool and stand at room temperature for 30 d and filtered. The data crystal was selected from the fine crystalline product obtained.

S2.2. Refinement

Intensity data measurements were carried out on a visually well-formed single dark-purple block-shaped crystal of (I)-triclinic at 100 K on a Bruker SMART APEXII CCD diffractometer with a graphite monochromatized Mo Kα (λ = 0.71073 Å) X-radiation source. The positions for all non-H atoms were located by direct methods and H atoms were added in geometrically sensible positions using the SHELX program system through the shelXle inter­face tool (Hübschle et al., 2011). Preliminary refinement including anisotropic atomic displacement parameters for the non-H atoms revealed discrepencies in the model. Many bond distances and angles were not reasonable, most of the core atoms exhibited atomic displacement parameters oriented out of the porphyrinate plane, and the highest positions on the difference electron density Fourier map were in the region near atoms C7, C8, and C27 indicating disorder. The major peaks were at rational separations for disorder of the pyrrole C atoms and the attached ethyl groups of the pyrrole ring containing atom N2. The disorder was incorporated into the model with identical distance and angle geometry imposed on the overlapping planar parts of the porphyrinate ligand and including occupancy variables for the two parts constrained to sum to unity (atom labels of the major occupancy atoms were used for the corresponding minor occupancy atoms with a letter m appended to the end of the label). A series of least-squares refinement/difference electron-density Fourier-map calculations indicated more disordered positions of lesser magnitude suggesting alternative positions in all areas of the porphyrinate ligand and for the axial Cl ligand. The minor positions were modeled as a second set of atomic positions for the entire molecule with corresponding distances and angles restrained to be similar between the overlapping planes of the two partial molecules. Positional parameters were further controlled by additional restraints introduced to keep the C_β—C_methyl­ene and C_methyl­ene—C_methyl distances similar, to impose planarity at C12, and to control the coplanarity of the individual pyrrole rings. H atoms were included in geometrically idealized riding positions for the methine (C—H = 0.95 Å) and methyl­ene (C—H = 0.99 Å) positions, and as idealized rigid rotating groups (C3v; C—H = 0.98 Å), each with tetra­hedral angles for the methyl H-atom positions. This highly constrained refinement of the whole molecule disorder had 703 parameters (compared to 459 parameters for the corresponding ordered single-molecule model) and 1185 restraints. The structure was refined against all data using SHELXL97 (Sheldrick, 2008). The methyl H atoms for both major- and minor-occupancy partial molecules were relocated by difference electron-density ring Fourier calculations before the final cycles of refinement demonstrating that the appropriate maxima for both major and minor partial H atoms were present. Anisotropic atomic displacement parameters for the non-H atoms as described above and isotropic parameters for the H atoms maintained at U_iso(H) = 1.5U_eq(C) for methyl H atoms or 1.2U_eq(C) otherwise, were utilized in the final cycles of least-squares refinement.

S3. Results and discussion

The structure of the new triclinic polymorph of Fe(OEP)Cl is characterized by five-coordinate iron, with an average Fe—N bond length of 2.065 (2) Å, an Fe—Cl bond length of 2.225 (4) Å, and an iron(III) cation displaced by 0.494 (4) Å from the 24-atom porphyrinate core, essentially the same as in the previously determined structures of (I) summarized in key characteristics of (I) (see table in Supporting information). The relative positioning of the major- and minor-occupancy molecules within the asymmetric unit can be seen in Fig. 2, a perspective drawing of the total content of the asymmetric unit. The inter­section of the porphyrin cores, visible in Fig. 2, allows them to occupy the same approximate space in the lattice. The larger apparent core separation can be seen on the left side of the illustration [inter­planar angle between the least-squares planes through the 24-atom cores = 3.9 (3)°] with a maximum apparent separation of the core-plane atoms at C27—C27m of 0.83 Å. The absolute maximum apparent separation of major–minor atoms occurs at C28—C28m = 1.77 Å, where the methyl group occupies opposite sides of the porphyrin plane.

The striking molecular difference between the two partial molecules in the lattice is a difference in the orientations of the ethyl side chains on the periphery of the porphyrin core. With the axial chloride ligand as a reference, the major occupancy molecule, (I)-triclinic-major, has four adjacent ethyl groups up and four down, while the minor occupancy molecule, (I)-triclinic-minor, has five adjacent ethyl groups up and three down as shown in the stick diagrams for the known structurally determined forms of (I) illustrated in Fig. 3. The monoclinic polymorph, (I)-monoclinic, has three ethyl groups up and five down, while both multicomponent crystals (Figs. 3d and 3e) have all eight ethyl groups down, and a closely related complex, the analogous Fe^III(OEP-π-cation radical)Cl cationic complex (refcode JOVRIV; Scheidt et al., 1992) forms a tight face-to-face dimer with all eight ethyl groups up (Fig. 3f).

The cell parameters of the (I)-monoclinic polymorph were redetermined at 100 (2) K [a = 15.0003 (8), b = 22.1238 (12), c = 9.9552 (6) Å, β = 106.198 (3)°, V = 3172.6 (3) ų and d_calc = 1.307 Mg m^-3] for comparison with the (I)-triclinic polymorph. The normalized molecular volumes of the two polymorphic forms at 100 K [793.2 ų for the (I)-monoclinic form compared to 805.2 ų for the (I)-triclinic form] shows the packing of the new triclinic form to be less favorable; the volume is 1.52% greater for the same composition implying greater stability for the (I)-monoclinic polymorph. The normalized molecular volume of 798.5 ų for (I)-monoclinic at the previous structure determination temperature (Senge, 2005) demonstrates a volume increase of 0.67% for the 26 K higher temperature (thus, less than 1% relative volume change for the structures discussed herein).

A partial packing diagram for (I)-monoclinic showing the adjacent molecules that directly contact the porphyrin core is given in Fig. 4. The packing is dominated by four modified π–π stacking motifs, each exhibiting concerted weak supra­molecular inter­actions. Previous discussion of π–π contacts by the authors has long involved contacts between π-cloud electron density on adjacent delocalized fragments where the non-H atoms being considered are sp²-hybridized (Haller & Enemark, 1978). Senge's report (Senge, 2005) that (I)-monoclinic has very weak π–π aggregates of the aromatic systems with a mean plane separation of 4.02 (1) Å, more akin to methyl–methyl contacts (Pauling, 1960) than aromatic–aromatic contacts, piqued our curiosity to examine these contacts more closely. We cannot find the reported 4.02 Å porphyrin plane-to-plane contact distance reported. In fact, the planar systems in OEP consist of the 24-atom porphyrin core plus the eight methyl­ene C atoms of the ethyl groups. In the polymorphic structures under consideration here, methyl­ene H atoms can be seen to be between the planes of the inter­acting rings [as in Fig. 4a for (I)-monoclinic]. This leads to π–π contact distances of 3.407 (4) Å on the chloride side of the porphyrin core (Fig. 4a, upper-left quadrant) and 3.416 (4) Å on the opposite side (Fig. 4a, lower-right quadrant) for (I)-monoclinic similar to Pauling's aromatic π–π contact estimate of 1.7 Å half-thickness of an aromatic ring (Pauling, 1960; Haller et al., 1979). The corresponding methyl­ene H···π inter­actions (perpendicular distance from the H atom to the best porphyrin 24-atom least-squares plane) range between 2.75 (3) and 2.89 (4) Å. Furthermore, the remaining plane–plane inter­actions show a second type of aliphatic H atom to porphyrin plane inter­action at similar H···π distances involving methyl H atoms (vide infra). The lower-left quadrant of Fig. 4(c) shows an ideal stacking/packing inter­action opposite the chloride ligand, across the inversion center at (1/2, 0, 0), involving eight ethyl groups in an inter­locking arrangement between two adjacent molecules. The shortest methyl H···π inter­actions from the central four ethyl groups in contact with the inversion-related planes are in the range 2.90–2.96 Å and the plane–plane distance is 4.909 (5) Å. The upper-right quadrant contains a similar methyl-to-porphyrin plane stacking/packing inter­action, across the inversion center at (1, 0, 1/2), involving only six ethyl groups (a consequence of only three ethyl groups on the chloride side of the molecule) and placing a single methyl group in contact with the face of the corresponding pyrrole ring, but also including C—H···Cl support with shortest methyl H···π inter­actions of 2.82 Å and a plane–plane distance of 4.900 (5) Å. Much of the additional plane–plane separation of these contacts results from the distances of the methyl C atoms to the porphyrin plane.

The packings of the two polymorphic forms have a common edge-to-edge contact feature between adjacent parallel porphyrin cores as illustrated by the left halfs of the perpendicular views in Figs. 4(b) and 5(b). This compact region contains the complete plane-to-plane edge contact extending from one methyl­ene group to the fourth methyl­ene group around the porphyrin core (nine C atoms). The second and third methyl­ene group H atoms contact the adjacent porphyrin core plane in an efficient plane-to-plane stacking motif mediated by extensive π–π and H···π contacts, further supported by four C—H···Cl contacts in two R₂¹(10) motifs (Etter et al., 1990), combined to make the arguably most stable supra­molecular inter­action represented within the lattice; the closest methyl­ene C—H···π inter­actions range from 2.86 to 2.94 Å and the methyl­ene C—H···Cl inter­actions are at 2.85 and 3.10 Å. The resulting perpendicular distance between the porphyrin cores is 3.45 (2) Å in (I)-triclinic-major, and similar but somewhat shorter in (I)-monoclinic at 3.407 (4) Å where the methyl­ene C—H···Cl inter­actions are at 2.86 and 2.97 Å. A weaker methyl­ene–plane contact extending approximately six C atoms along the opposite edge also occurs in each of the polymorphs on the bottom side of the porphyrin plane (Figs. 4b and 5b), with closest methyl­ene C—H···π inter­actions ranging from 2.89 to 3.20 Å and the perpendicular distance between the porphyrin cores at 3.45 (3) Å in (I)-triclinic-major, and again, similar but slightly shorter in (I)-monoclinic at 3.416 (4) Å. Thus, the monoclinic polymorph has on average 0.036 Å or 1.05% tighter methyl­ene plane–plane contacts than the triclinic polymorph.

A second common feature in the packings of the two polymorphs is similar corner-to-corner inter­actions involving methyl H···π contacts. (I)-monoclinic contains two of these inter­actions, one nearly ideal involving four concerted methyl–plane contacts and the other involving two concerted methyl–plane contacts as discussed above. (I)-triclinic-major does not exhibit the ideal highly concerted inter­action, but instead contains four of the two concerted methyl–plane contacts (Fig. 5c), all of which occur across inversion centers and provide porphyrin plane–plane contact distances of 5.081 (13) and 5.134 (14) Å on both the top and bottom sides of the porphyrin plane, compared with the shorter contacts at 4.900 (5) and 4.910 (5) Å in (I)-monoclinic. The average ruffling of the porphyrin cores is the same [Δ = 0.045 Å for (I)-monoclinic (Senge, 2005) and Δ = 0.043 Å for (I)-triclinic]. Thus, the core conformation is unlikely to contribute to the observed density differences. The plane-to-plane contacts are all shorter for the (I)-monoclinic polymorph; 1.05% (2–3σ) for the methyl­ene C—H···π, and 0.202 Å or 4.05% (10–20σ) for the methyl C—H···π contacts. The average difference in the spacings, at 2.55% in favor of the previously reported monoclinic form, is significantly greater than the 1.52% change in density, but none the less supports greater stability for the monoclinic polymorph.

The other existing Fe(OEP)Cl structures both exhibit all eight ethyl groups on the opposite side of the porphyrin plane relative to the Fe and Cl atoms. The more highly concerted R₂¹(10) supra­molecular motifs observed in (I)-monoclinic and (I)-triclinic also occur in these structures. The compact complete 9-C edge-edge methyl­ene-plane synthon, including the four C—H···Cl inter­actions, occurs once in the structure of the methyene chloride solvate (Safo et al., 2010) as shown in the projection diagram viewed perpendicular to the porphyrin core in Fig. 6(a), and twice in the methyl­ene chloride solvated (I).C₆₀ cocrystal structure (Olmstead et al., 1999), as shown in the projection diagram viewed perpendicular to the porphyrin core in Fig. 7. These are the only porphyrin plane–plane inter­actions in the (I).C₆₀ cocrystal structure since the eight ethyl groups embrace the C₆₀ molecule completely filling the space opposite the chloride ligand, and giving shortest π–π fullerene to the N₄ plane contacts of 2.748 Å (Olmstead et al., 1999).

The nearly perfect concerted four methyl–plane type inter­action found in (I)-monoclinic occurs twice in (I).CH₂Cl₂, completely covering the aliphatic side of the porphyrin plane as shown in Fig. 6(b. The remainder of the porphyrin plane–plane contacts in (I).CH₂Cl₂ are a third type of methyl­ene–plane contact, i.e. corner–corner type contacts involving only one methyl­ene group per molecule in contact with the face of pyrrole rings as can be seen on the right-hand side of Fig. 7. The common nature of the supra­molecular contacts in all occurances of (I) to date is reflected in the shortest Fe···Fe contact distance [see table of key characteristics of (I) in the Supporting information], which range from 7.896 Å in (I)-monoclinic to 8.079 Å in (I).CH₂Cl₂. The pronounced lateral shifts place all of these (I) in Group W (Scheidt, 2000).

The closely related analogous Fe^III(OEP-π-cation radical)Cl cationic complex (Scheidt et al., 1992) forms a tight face-to-face dimer (plane–plane distance of 3.24 Å; lower portion of Fig. 8a) with all eight ethyl groups required to be on the chloride side of the porphyrin plane. The aliphatic side of the complex exhibits two of the two concerted methyl–plane contacts found in both polymorphs (right-hand side, Fig. 8b) and a new full edge-edge contact (left-hand side, Fig. 8) analogous to the methyl­ene π–π contact.

Related literature

For related literature, see: Allen (2002); Burnett & Johnson (1996); Ernst et al. (1977); Etter et al. (1990); Farrugia (2012); Hübschle et al. (2011); Haller & Enemark (1978); Haller et al. (1979); Kalish et al. (2002); Olmstead et al. (1999); Pauling (1960); Puntharod et al. (2010, 2012, 2014); Safo et al. (2010); Scheidt (2000); Scheidt et al. (1992); Senge (2000, 2005); Wyllie & Scheidt (2002).

Computing details

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT (Bruker, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPIII (Burnett & Johnson, 1996) and ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and publCIF (Westrip, 2010).

Figures

	Fig. 1. Perspective drawing of the major-occupancy molecule of (I)-triclinic, showing the atomic labeling scheme. The corresponding atoms of the minor-occupancy molecule are labeled with a small letter m appended to the respective label. Atomic displacement parameters for the non-H atoms are drawn as 50% probability ellipsoids.
	Fig. 2. Perspective drawing showing the overlap of the major- [0.684 (5)] and minor-occupancy [0.316 (5)] molecules of the whole-molecule disorder model. The major difference between the two partial molecules is the positioning of the C27/C28 ethyl group of the major-occupancy molecule to the opposite side of the porphyrinate plane as the axial chloride ligand, while the C27m/C28m ethyl group of the minor-occupancy molecule is to the same side of the porphyrinate plane as the axial chloride ligand. The bonds of the major-occupancy molecule are represented as solid lines and the bonds of the minor-occupancy molecule are represented as open lines. The atoms of the major-occupancy molecule are represented as eighth-cutout spheres and the atoms of the minor-occupancy molecule are represented as open spheres, both of arbitrary radius, for clarity.
	Fig. 3. Comparison of the various Fe(OEP)Cl side-group orientations found to date: (a) (I)-monoclinic, (b) (I)-triclinic-major, (c) (I)-triclinic-minor, (d) (I).CH2Cl2, (e) (I).C60.CHCl3, (f) Fe(OEP-π-cation radical)Cl.
	Fig. 4. Projection drawings showing the π–π stackings in the (I)-monoclinic lattice: (a) viewed parallel to the porphyrin planes of (I) showing the four packing/stacking interactions to the porphyrin planes; (b) viewed perpendicular to the porphyrin plane of (I), showing adjacent parallel molecules with CH2···plane contacts; (c) viewed perpendicular to the porphyrin plane of (I), showing adjacent parallel molecules with Me···plane contacts. Ellipsoids are of arbitrary radii.
	Fig. 5. Projection drawings showing the π–π stackings in the (I)-triclinic lattice: (a) viewed parallel to the porphyrin planes of (I), showing the six packing/stacking interactions to the porphyrin planes; (b) viewed perpendicular to the porphyrin plane of (I), showing adjacent parallel molecules with CH2···plane contacts; (c) viewed perpendicular to the porphyrin plane of (I), showing adjacent parallel molecules with Me···plane contacts. Ellipsoids are of arbitrary radii.
	Fig. 6. Projection drawings showing the π–π stackings in the (I).CH2Cl2 lattice: (a) viewed parallel to the porphyrin planes of (I), showing the five packing/stacking interactions to the porphyrin planes; (b) viewed perpendicular to the porphyrin plane of (I), showing adjacent parallel molecules with CH2···plane contacts; (c) viewed perpendicular to the porphyrin plane of (I), showing adjacent parallel molecules with Me···plane contacts. Ellipsoids are of arbitrary radii.
	Fig. 7. Projection drawings showing the two equivalent CH2···plane π–π stacking/packing contacts on the chloride side of the porphyrin plane in the C60.(I).CH2Cl2 lattice: (a) viewed parallel to the porphyrin planes of (I); (b) viewed perpendicular to the porphyrin planes of (I). Ellipsoids are of arbitrary radii.
	Fig. 8. Projection drawings showing the π–π stackings in the Fe(OEP-π-cation radical)Cl lattice: (a) viewed parallel to the porphyrin planes, showing the four packing/stacking interactions to the porphyrin planes (the lower interaction is the tight face-to-face dimer interaction; Scheidt et al., 1992); (b) viewed perpendicular to the porphyrin plane, showing adjacent parallel molecules with Me···plane contacts. Ellipsoids are of arbitrary radii.

Chlorido(2,3,7,8,12,13,17,18-octaethylporphyrinato)iron(III)

Crystal data

[Fe(C36H44N4)Cl]	Z = 2
Mr = 624.05	F(000) = 662
Triclinic, P1	Dx = 1.287 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 10.4495 (3) Å	Cell parameters from 9866 reflections
b = 10.7805 (4) Å	θ = 2.8–30.6°
c = 15.7360 (5) Å	µ = 0.58 mm^−1
α = 71.949 (1)°	T = 100 K
β = 73.034 (1)°	Block, dark purple
γ = 82.440 (1)°	0.47 × 0.35 × 0.22 mm
V = 1610.42 (9) Å^3

Data collection

Bruker APEXII CCD area-detector diffractometer	9534 independent reflections
Radiation source: fine-focus sealed tube	7545 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.021
ϕ and ω scans	θmax = 30.6°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −14→14
Tmin = 0.772, Tmax = 0.880	k = −15→15
34934 measured reflections	l = −22→22

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.051	H-atom parameters constrained
wR(F^2) = 0.148	w = 1/[σ^2(Fo^2) + (0.0746P)^2 + 0.9291P] where P = (Fo^2 + 2Fc^2)/3
S = 1.05	(Δ/σ)max = 0.072
9534 reflections	Δρmax = 1.03 e Å^−3
727 parameters	Δρmin = −0.46 e Å^−3
1185 restraints

Special details

Experimental. 1 reflection (0 0 1) was omitted from the data set due to beamstop interference. The default recommendation for scan sets was used. The _diffrn_measured_fraction_theta_full = 96.0% is relatively constant over the entire angular range suggesting the recommendation was not optimal. Probable reasons for the missing data thus include: beamstop interference, nonoptimal data collection strategy, and data truncation losses at resolutions higher than 0.70 Å. The data yield near the limiting 2θ value of 61.26 ° is about 54%. The data/variable ratio is 13.6 and the observed data/variable ratio is 10.7 for 2θ_max = 61.26 °.

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two least squares 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 least squares planes.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Fe1	0.5886 (3)	0.9903 (4)	0.7352 (3)	0.0287 (2)	0.689 (5)
Cl1	0.7286 (3)	1.1120 (3)	0.61042 (19)	0.0477 (4)	0.689 (5)
N1	0.4024 (5)	1.0494 (8)	0.7119 (5)	0.0306 (11)	0.689 (5)
N2	0.5814 (8)	0.8304 (6)	0.6913 (6)	0.0304 (10)	0.689 (5)
N3	0.7168 (6)	0.8774 (6)	0.8100 (4)	0.0297 (10)	0.689 (5)
N4	0.5377 (6)	1.0954 (7)	0.8310 (5)	0.0301 (10)	0.689 (5)
C1	0.3241 (7)	1.1570 (8)	0.7296 (5)	0.0361 (12)	0.689 (5)
C2	0.2198 (6)	1.1859 (7)	0.6823 (4)	0.0414 (13)	0.689 (5)
C21	0.1158 (9)	1.2977 (10)	0.6845 (7)	0.0554 (18)	0.689 (5)
H21A	0.1560	1.3730	0.6887	0.067*	0.689 (5)
H21B	0.0889	1.3250	0.6257	0.067*	0.689 (5)
C3	0.2349 (7)	1.0964 (8)	0.6345 (5)	0.0370 (12)	0.689 (5)
C23	0.1507 (10)	1.0778 (10)	0.5765 (6)	0.0406 (14)	0.689 (5)
H23A	0.2110	1.0642	0.5183	0.049*	0.689 (5)
H23B	0.0956	1.1590	0.5597	0.049*	0.689 (5)
C4	0.3501 (7)	1.0131 (7)	0.6530 (5)	0.0313 (13)	0.689 (5)
C5	0.4015 (10)	0.9107 (9)	0.6155 (6)	0.0297 (14)	0.689 (5)
H5	0.3580	0.8965	0.5743	0.036*	0.689 (5)
C6	0.5095 (8)	0.8268 (7)	0.6318 (6)	0.0307 (11)	0.689 (5)
C7	0.5639 (7)	0.7256 (6)	0.5867 (5)	0.0321 (11)	0.689 (5)
C25	0.5033 (8)	0.6893 (9)	0.5220 (5)	0.0373 (12)	0.689 (5)
H25A	0.5718	0.6392	0.4858	0.045*	0.689 (5)
H25B	0.4793	0.7704	0.4778	0.045*	0.689 (5)
C8	0.6688 (4)	0.6674 (4)	0.6205 (4)	0.0358 (10)	0.689 (5)
C27	0.7569 (4)	0.5525 (3)	0.5996 (3)	0.0485 (9)	0.689 (5)
H27A	0.8486	0.5633	0.6012	0.058*	0.689 (5)
H27B	0.7614	0.5523	0.5359	0.058*	0.689 (5)
C9	0.6809 (8)	0.7329 (7)	0.6851 (6)	0.0389 (13)	0.689 (5)
C10	0.7759 (7)	0.7027 (9)	0.7350 (6)	0.047 (2)	0.689 (5)
H10	0.8382	0.6322	0.7261	0.057*	0.689 (5)
C11	0.7888 (6)	0.7656 (6)	0.7969 (4)	0.0398 (12)	0.689 (5)
C12	0.8862 (5)	0.7311 (5)	0.8494 (4)	0.0517 (13)	0.689 (5)
C29	0.9754 (5)	0.6068 (7)	0.8614 (4)	0.0651 (16)	0.689 (5)
H29A	1.0120	0.5945	0.9150	0.078*	0.689 (5)
H29B	0.9217	0.5308	0.8743	0.078*	0.689 (5)
C13	0.8742 (6)	0.8224 (6)	0.8941 (5)	0.0422 (13)	0.689 (5)
C31	0.9562 (7)	0.8298 (11)	0.9565 (5)	0.0543 (16)	0.689 (5)
H31A	0.9859	0.7406	0.9877	0.065*	0.689 (5)
H31B	0.9004	0.8696	1.0049	0.065*	0.689 (5)
C14	0.7659 (7)	0.9114 (7)	0.8718 (5)	0.0331 (11)	0.689 (5)
C15	0.7146 (9)	1.0134 (9)	0.9103 (8)	0.0336 (12)	0.689 (5)
H15	0.7565	1.0262	0.9528	0.040*	0.689 (5)
C16	0.6081 (7)	1.0978 (8)	0.8921 (6)	0.0312 (11)	0.689 (5)
C17	0.5510 (7)	1.1994 (7)	0.9371 (5)	0.0342 (10)	0.689 (5)
C33	0.6026 (9)	1.2315 (10)	1.0073 (6)	0.0451 (15)	0.689 (5)
H33A	0.6402	1.1507	1.0442	0.054*	0.689 (5)
H33B	0.5273	1.2659	1.0502	0.054*	0.689 (5)
C18	0.4495 (9)	1.2598 (8)	0.9010 (7)	0.0385 (13)	0.689 (5)
C35	0.3624 (11)	1.3773 (8)	0.9193 (8)	0.0506 (17)	0.689 (5)
H35A	0.3599	1.3815	0.9817	0.061*	0.689 (5)
H35B	0.2699	1.3655	0.9195	0.061*	0.689 (5)
C19	0.4397 (8)	1.1946 (9)	0.8355 (6)	0.0348 (11)	0.689 (5)
C20	0.3425 (12)	1.2229 (11)	0.7877 (8)	0.0410 (15)	0.689 (5)
H20	0.2821	1.2950	0.7956	0.049*	0.689 (5)
C22	−0.0070 (8)	1.2618 (12)	0.7647 (8)	0.097 (3)	0.689 (5)
H22A	−0.0512	1.1917	0.7583	0.146*	0.689 (5)
H22B	−0.0690	1.3384	0.7650	0.146*	0.689 (5)
H22C	0.0192	1.2320	0.8230	0.146*	0.689 (5)
C24	0.0586 (9)	0.9643 (11)	0.6235 (9)	0.0647 (19)	0.689 (5)
H24A	0.1122	0.8819	0.6291	0.097*	0.689 (5)
H24B	−0.0033	0.9680	0.5864	0.097*	0.689 (5)
H24C	0.0075	0.9698	0.6853	0.097*	0.689 (5)
C26	0.3801 (6)	0.6095 (6)	0.5700 (5)	0.0501 (11)	0.689 (5)
H26A	0.4034	0.5272	0.6123	0.075*	0.689 (5)
H26B	0.3465	0.5907	0.5235	0.075*	0.689 (5)
H26C	0.3108	0.6587	0.6052	0.075*	0.689 (5)
C28	0.7098 (5)	0.4221 (4)	0.6658 (4)	0.0799 (15)	0.689 (5)
H28A	0.7089	0.4196	0.7287	0.120*	0.689 (5)
H28B	0.7706	0.3522	0.6473	0.120*	0.689 (5)
H28C	0.6192	0.4100	0.6643	0.120*	0.689 (5)
C30	1.0894 (5)	0.6144 (5)	0.7750 (4)	0.0801 (16)	0.689 (5)
H30A	1.0535	0.6383	0.7208	0.120*	0.689 (5)
H30B	1.1378	0.5293	0.7803	0.120*	0.689 (5)
H30C	1.1506	0.6806	0.7680	0.120*	0.689 (5)
C32	1.0770 (7)	0.9102 (8)	0.9018 (6)	0.0760 (18)	0.689 (5)
H32A	1.1349	0.8680	0.8563	0.114*	0.689 (5)
H32B	1.1268	0.9171	0.9440	0.114*	0.689 (5)
H32C	1.0477	0.9978	0.8694	0.114*	0.689 (5)
C34	0.7088 (9)	1.3308 (10)	0.9616 (7)	0.0602 (19)	0.689 (5)
H34A	0.7815	1.2988	0.9170	0.090*	0.689 (5)
H34B	0.7442	1.3451	1.0089	0.090*	0.689 (5)
H34C	0.6698	1.4133	0.9293	0.090*	0.689 (5)
C36	0.4096 (13)	1.5056 (9)	0.8491 (9)	0.078 (3)	0.689 (5)
H36A	0.4967	1.5232	0.8534	0.116*	0.689 (5)
H36B	0.3444	1.5761	0.8617	0.116*	0.689 (5)
H36C	0.4181	1.5004	0.7865	0.116*	0.689 (5)
Fe1M	0.5775 (8)	0.9964 (8)	0.7316 (6)	0.0287 (2)	0.311 (5)
Cl1M	0.7214 (7)	1.1349 (6)	0.6218 (5)	0.0477 (4)	0.311 (5)
N1M	0.3996 (11)	1.0577 (16)	0.6958 (11)	0.0265 (16)	0.311 (5)
N2M	0.5782 (18)	0.8420 (13)	0.6799 (14)	0.0300 (18)	0.311 (5)
N3M	0.6922 (13)	0.8773 (12)	0.8147 (9)	0.0268 (15)	0.311 (5)
N4M	0.5132 (14)	1.0970 (17)	0.8300 (10)	0.0284 (17)	0.311 (5)
C1M	0.3192 (14)	1.1645 (16)	0.7137 (11)	0.0318 (19)	0.311 (5)
C2M	0.2178 (12)	1.1930 (15)	0.6650 (9)	0.0300 (17)	0.311 (5)
C21M	0.113 (2)	1.304 (2)	0.6682 (15)	0.047 (3)	0.311 (5)
H21C	0.1585	1.3858	0.6548	0.056*	0.311 (5)
H21D	0.0677	1.3150	0.6192	0.056*	0.311 (5)
C3M	0.2353 (13)	1.1047 (16)	0.6166 (10)	0.0296 (18)	0.311 (5)
C23M	0.152 (2)	1.093 (2)	0.5563 (14)	0.041 (3)	0.311 (5)
H23C	0.2097	1.0777	0.4979	0.049*	0.311 (5)
H23D	0.0950	1.1732	0.5411	0.049*	0.311 (5)
C4M	0.3499 (15)	1.0208 (15)	0.6356 (11)	0.0246 (17)	0.311 (5)
C5M	0.404 (2)	0.9203 (19)	0.5957 (13)	0.024 (2)	0.311 (5)
H5M	0.3710	0.9116	0.5479	0.029*	0.311 (5)
C6M	0.5055 (16)	0.8319 (15)	0.6223 (13)	0.029 (2)	0.311 (5)
C7M	0.5395 (13)	0.7082 (13)	0.6006 (10)	0.031 (2)	0.311 (5)
C25M	0.4831 (19)	0.666 (2)	0.5365 (11)	0.043 (3)	0.311 (5)
H25C	0.5454	0.6004	0.5115	0.052*	0.311 (5)
H25D	0.4730	0.7421	0.4837	0.052*	0.311 (5)
C8M	0.6335 (9)	0.6423 (7)	0.6448 (8)	0.035 (2)	0.311 (5)
C27M	0.7000 (8)	0.5095 (8)	0.6441 (6)	0.0478 (18)	0.311 (5)
H27C	0.6414	0.4593	0.6288	0.057*	0.311 (5)
H27D	0.7088	0.4623	0.7071	0.057*	0.311 (5)
C9M	0.6556 (16)	0.7268 (14)	0.6939 (12)	0.037 (2)	0.311 (5)
C10M	0.7425 (14)	0.6927 (17)	0.7500 (12)	0.035 (2)	0.311 (5)
H10M	0.7945	0.6133	0.7509	0.042*	0.311 (5)
C11M	0.7601 (12)	0.7639 (12)	0.8046 (8)	0.0344 (19)	0.311 (5)
C12M	0.8549 (9)	0.7231 (10)	0.8609 (7)	0.0323 (15)	0.311 (5)
C29M	0.9409 (10)	0.5955 (13)	0.8658 (9)	0.050 (2)	0.311 (5)
H29C	0.9548	0.5540	0.9282	0.060*	0.311 (5)
H29D	0.9032	0.5324	0.8465	0.060*	0.311 (5)
C13M	0.8424 (11)	0.8152 (13)	0.9056 (9)	0.0338 (18)	0.311 (5)
C31M	0.9194 (15)	0.820 (2)	0.9716 (11)	0.051 (3)	0.311 (5)
H31C	0.9466	0.7299	1.0023	0.061*	0.311 (5)
H31D	0.8585	0.8565	1.0204	0.061*	0.311 (5)
C14M	0.7411 (14)	0.9099 (14)	0.8776 (10)	0.0293 (18)	0.311 (5)
C15M	0.688 (2)	1.017 (2)	0.9094 (18)	0.033 (2)	0.311 (5)
H15M	0.7300	1.0346	0.9502	0.039*	0.311 (5)
C16M	0.5838 (15)	1.1014 (16)	0.8904 (12)	0.0292 (19)	0.311 (5)
C17M	0.5324 (18)	1.2133 (16)	0.9263 (12)	0.038 (2)	0.311 (5)
C33M	0.580 (2)	1.241 (2)	1.0001 (13)	0.043 (3)	0.311 (5)
H33C	0.5974	1.1568	1.0446	0.052*	0.311 (5)
H33D	0.5080	1.2904	1.0345	0.052*	0.311 (5)
C18M	0.4348 (19)	1.2730 (17)	0.8882 (13)	0.032 (2)	0.311 (5)
C35M	0.353 (2)	1.3944 (17)	0.9029 (16)	0.048 (3)	0.311 (5)
H35C	0.3414	1.3961	0.9672	0.058*	0.311 (5)
H35D	0.2625	1.3906	0.8954	0.058*	0.311 (5)
C19M	0.4200 (17)	1.2017 (18)	0.8269 (13)	0.032 (2)	0.311 (5)
C20M	0.334 (2)	1.231 (2)	0.7726 (18)	0.035 (2)	0.311 (5)
H20M	0.2758	1.3057	0.7755	0.042*	0.311 (5)
C22M	0.010 (2)	1.282 (2)	0.7608 (14)	0.058 (3)*	0.311 (5)
H22D	−0.0455	1.2100	0.7695	0.087*	0.311 (5)
H22E	−0.0461	1.3613	0.7626	0.087*	0.311 (5)
H22F	0.0557	1.2587	0.8104	0.087*	0.311 (5)
C24M	0.066 (3)	0.977 (3)	0.613 (2)	0.078 (6)*	0.311 (5)
H24D	0.1185	0.9089	0.6476	0.116*	0.311 (5)
H24E	0.0365	0.9427	0.5711	0.116*	0.311 (5)
H24F	−0.0124	1.0047	0.6561	0.116*	0.311 (5)
C26M	0.3487 (16)	0.6079 (19)	0.5884 (13)	0.062 (4)*	0.311 (5)
H26D	0.3594	0.5308	0.6393	0.093*	0.311 (5)
H26E	0.3117	0.5826	0.5460	0.093*	0.311 (5)
H26F	0.2875	0.6728	0.6136	0.093*	0.311 (5)
C28M	0.8369 (9)	0.5134 (11)	0.5761 (7)	0.071 (3)*	0.311 (5)
H28D	0.8284	0.5531	0.5128	0.106*	0.311 (5)
H28E	0.8760	0.4244	0.5822	0.106*	0.311 (5)
H28F	0.8951	0.5654	0.5892	0.106*	0.311 (5)
C30M	1.0673 (13)	0.6527 (16)	0.7954 (11)	0.094 (4)*	0.311 (5)
H30D	1.0480	0.6961	0.7355	0.142*	0.311 (5)
H30E	1.1361	0.5826	0.7886	0.142*	0.311 (5)
H30F	1.0996	0.7163	0.8164	0.142*	0.311 (5)
C32M	1.0428 (17)	0.900 (2)	0.9291 (13)	0.077 (5)*	0.311 (5)
H32D	1.0993	0.8726	0.8757	0.116*	0.311 (5)
H32E	1.0931	0.8863	0.9752	0.116*	0.311 (5)
H32F	1.0162	0.9927	0.9087	0.116*	0.311 (5)
C34M	0.705 (2)	1.317 (3)	0.960 (2)	0.079 (6)*	0.311 (5)
H34D	0.7808	1.2609	0.9372	0.118*	0.311 (5)
H34E	0.7228	1.3474	1.0076	0.118*	0.311 (5)
H34F	0.6929	1.3923	0.9080	0.118*	0.311 (5)
C36M	0.415 (3)	1.519 (2)	0.836 (2)	0.062 (4)*	0.311 (5)
H36D	0.5107	1.5147	0.8335	0.093*	0.311 (5)
H36E	0.3705	1.5937	0.8575	0.093*	0.311 (5)
H36F	0.4057	1.5286	0.7743	0.093*	0.311 (5)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Fe1	0.0266 (6)	0.0296 (4)	0.0370 (3)	0.0064 (3)	−0.0152 (3)	−0.0164 (3)
Cl1	0.0471 (5)	0.0478 (10)	0.0482 (8)	−0.0009 (6)	−0.0089 (5)	−0.0178 (5)
N1	0.0279 (13)	0.037 (2)	0.037 (3)	0.0075 (11)	−0.0165 (13)	−0.022 (2)
N2	0.0339 (18)	0.0296 (16)	0.038 (2)	0.0076 (13)	−0.0227 (15)	−0.0151 (16)
N3	0.023 (2)	0.0329 (14)	0.0422 (18)	0.0070 (13)	−0.0185 (17)	−0.0174 (12)
N4	0.023 (2)	0.0346 (15)	0.0425 (15)	0.0053 (15)	−0.0145 (15)	−0.0213 (12)
C1	0.0310 (18)	0.042 (2)	0.045 (3)	0.0124 (15)	−0.0203 (17)	−0.022 (2)
C2	0.038 (2)	0.047 (2)	0.050 (3)	0.0159 (16)	−0.0220 (19)	−0.026 (2)
C21	0.052 (2)	0.064 (3)	0.063 (5)	0.028 (2)	−0.034 (2)	−0.031 (3)
C3	0.0343 (19)	0.044 (2)	0.041 (3)	0.0078 (15)	−0.0214 (19)	−0.018 (2)
C23	0.042 (2)	0.046 (3)	0.042 (4)	0.0130 (17)	−0.029 (3)	−0.013 (3)
C4	0.0297 (16)	0.0354 (19)	0.036 (3)	0.0078 (14)	−0.0176 (19)	−0.015 (2)
C5	0.0363 (18)	0.035 (2)	0.026 (4)	0.0025 (15)	−0.019 (2)	−0.012 (2)
C6	0.035 (2)	0.0300 (19)	0.036 (2)	0.0070 (15)	−0.0182 (17)	−0.0161 (17)
C7	0.035 (2)	0.029 (2)	0.038 (2)	−0.0007 (16)	−0.0137 (19)	−0.0147 (17)
C25	0.046 (2)	0.035 (3)	0.042 (2)	0.0012 (16)	−0.0194 (18)	−0.020 (2)
C8	0.035 (2)	0.0350 (18)	0.047 (3)	0.0057 (15)	−0.0158 (18)	−0.0229 (18)
C27	0.046 (2)	0.050 (2)	0.067 (2)	0.0191 (15)	−0.0251 (18)	−0.0398 (19)
C9	0.036 (3)	0.0387 (19)	0.058 (2)	0.0136 (18)	−0.025 (2)	−0.0308 (18)
C10	0.038 (4)	0.053 (3)	0.076 (4)	0.024 (3)	−0.036 (4)	−0.044 (3)
C11	0.029 (2)	0.0434 (19)	0.065 (3)	0.0164 (16)	−0.0282 (19)	−0.0328 (18)
C12	0.042 (3)	0.059 (2)	0.080 (3)	0.022 (2)	−0.043 (2)	−0.041 (2)
C29	0.053 (3)	0.069 (3)	0.104 (3)	0.020 (3)	−0.056 (3)	−0.045 (3)
C13	0.035 (3)	0.046 (2)	0.060 (3)	0.0083 (19)	−0.031 (2)	−0.023 (2)
C31	0.051 (4)	0.062 (3)	0.074 (3)	0.011 (3)	−0.046 (3)	−0.031 (3)
C14	0.030 (3)	0.0383 (18)	0.040 (2)	0.0015 (16)	−0.017 (2)	−0.0180 (16)
C15	0.032 (3)	0.0400 (18)	0.041 (2)	0.0029 (18)	−0.022 (2)	−0.0181 (14)
C16	0.027 (3)	0.0385 (18)	0.0366 (18)	−0.0008 (16)	−0.0123 (17)	−0.0198 (15)
C17	0.036 (2)	0.0359 (19)	0.038 (2)	0.0009 (14)	−0.0130 (15)	−0.0182 (17)
C33	0.045 (3)	0.057 (3)	0.049 (3)	0.002 (2)	−0.0178 (19)	−0.034 (2)
C18	0.043 (3)	0.042 (2)	0.040 (3)	0.0077 (16)	−0.0160 (17)	−0.026 (2)
C35	0.054 (3)	0.056 (3)	0.056 (4)	0.017 (2)	−0.023 (2)	−0.036 (3)
C19	0.029 (2)	0.039 (2)	0.045 (2)	0.0074 (15)	−0.0165 (16)	−0.0227 (18)
C20	0.041 (2)	0.043 (3)	0.055 (4)	0.0165 (17)	−0.023 (2)	−0.033 (3)
C22	0.054 (4)	0.127 (7)	0.092 (4)	0.049 (4)	−0.006 (3)	−0.039 (4)
C24	0.039 (2)	0.088 (4)	0.078 (4)	−0.013 (2)	−0.033 (3)	−0.020 (3)
C26	0.056 (3)	0.055 (2)	0.056 (3)	−0.013 (2)	−0.020 (3)	−0.030 (2)
C28	0.096 (4)	0.043 (2)	0.108 (4)	0.022 (2)	−0.038 (3)	−0.033 (2)
C30	0.059 (2)	0.067 (3)	0.127 (4)	0.029 (2)	−0.032 (3)	−0.050 (3)
C32	0.069 (4)	0.088 (4)	0.096 (5)	−0.012 (3)	−0.052 (4)	−0.030 (4)
C34	0.065 (3)	0.070 (3)	0.066 (3)	−0.023 (2)	−0.0174 (19)	−0.039 (3)
C36	0.114 (5)	0.046 (3)	0.074 (6)	0.028 (3)	−0.027 (4)	−0.032 (3)
Fe1M	0.0266 (6)	0.0296 (4)	0.0370 (3)	0.0064 (3)	−0.0152 (3)	−0.0164 (3)
Cl1M	0.0471 (5)	0.0478 (10)	0.0482 (8)	−0.0009 (6)	−0.0089 (5)	−0.0178 (5)
N1M	0.030 (3)	0.029 (3)	0.025 (4)	0.011 (2)	−0.016 (2)	−0.011 (3)
N2M	0.035 (4)	0.028 (3)	0.035 (5)	0.013 (2)	−0.021 (3)	−0.015 (3)
N3M	0.019 (4)	0.034 (3)	0.033 (3)	0.001 (2)	−0.009 (2)	−0.017 (2)
N4M	0.016 (4)	0.039 (3)	0.041 (3)	0.003 (2)	−0.014 (2)	−0.022 (3)
C1M	0.033 (4)	0.033 (4)	0.037 (5)	0.009 (3)	−0.014 (3)	−0.020 (3)
C2M	0.025 (3)	0.043 (4)	0.022 (3)	0.007 (2)	−0.011 (2)	−0.007 (3)
C21M	0.047 (5)	0.057 (5)	0.044 (6)	0.024 (4)	−0.020 (4)	−0.026 (4)
C3M	0.026 (3)	0.039 (4)	0.024 (4)	0.011 (3)	−0.010 (3)	−0.011 (3)
C23M	0.041 (4)	0.055 (6)	0.033 (6)	0.006 (4)	−0.024 (4)	−0.012 (5)
C4M	0.029 (3)	0.032 (3)	0.016 (4)	−0.002 (2)	−0.010 (2)	−0.007 (3)
C5M	0.031 (3)	0.029 (3)	0.017 (6)	0.005 (2)	−0.013 (4)	−0.010 (4)
C6M	0.032 (4)	0.031 (4)	0.033 (5)	−0.001 (3)	−0.019 (3)	−0.012 (3)
C7M	0.029 (5)	0.027 (4)	0.044 (5)	−0.001 (3)	−0.014 (4)	−0.016 (4)
C25M	0.061 (7)	0.036 (7)	0.047 (5)	0.008 (4)	−0.030 (5)	−0.023 (5)
C8M	0.035 (5)	0.032 (3)	0.048 (5)	0.003 (3)	−0.017 (4)	−0.021 (3)
C27M	0.059 (5)	0.038 (4)	0.062 (5)	0.015 (3)	−0.032 (4)	−0.027 (4)
C9M	0.032 (5)	0.034 (3)	0.060 (5)	0.012 (3)	−0.030 (4)	−0.024 (3)
C10M	0.024 (6)	0.034 (3)	0.057 (5)	0.013 (4)	−0.020 (4)	−0.024 (3)
C11M	0.029 (5)	0.038 (3)	0.041 (4)	0.005 (3)	−0.023 (3)	−0.009 (3)
C12M	0.025 (4)	0.034 (3)	0.033 (3)	−0.005 (2)	−0.009 (2)	−0.001 (2)
C29M	0.044 (5)	0.054 (4)	0.071 (4)	0.008 (3)	−0.050 (4)	−0.017 (3)
C13M	0.023 (4)	0.051 (3)	0.031 (3)	−0.005 (3)	−0.012 (3)	−0.011 (3)
C31M	0.042 (7)	0.060 (5)	0.067 (5)	0.006 (5)	−0.036 (5)	−0.025 (4)
C14M	0.019 (4)	0.037 (3)	0.033 (4)	−0.003 (3)	−0.011 (3)	−0.008 (3)
C15M	0.030 (6)	0.047 (4)	0.035 (4)	−0.002 (3)	−0.019 (4)	−0.021 (3)
C16M	0.020 (5)	0.037 (3)	0.036 (4)	−0.001 (3)	−0.010 (3)	−0.015 (3)
C17M	0.045 (5)	0.047 (4)	0.035 (4)	0.004 (3)	−0.018 (3)	−0.024 (4)
C33M	0.041 (6)	0.060 (5)	0.038 (4)	0.002 (4)	−0.017 (4)	−0.024 (4)
C18M	0.031 (4)	0.037 (4)	0.033 (5)	0.004 (3)	−0.014 (3)	−0.016 (4)
C35M	0.058 (5)	0.053 (5)	0.049 (7)	0.020 (4)	−0.021 (5)	−0.039 (5)
C19M	0.029 (5)	0.034 (4)	0.042 (5)	0.009 (3)	−0.014 (3)	−0.025 (3)
C20M	0.030 (4)	0.045 (4)	0.040 (6)	0.015 (3)	−0.021 (3)	−0.022 (4)

Geometric parameters (Å, º)

Fe1—N2	2.0639 (17)	Fe1M—N2M	2.065 (2)
Fe1—N3	2.0654 (18)	Fe1M—N3M	2.065 (2)
Fe1—N1	2.0664 (18)	Fe1M—N1M	2.066 (2)
Fe1—N4	2.0666 (17)	Fe1M—N4M	2.066 (2)
Fe1—Cl1	2.225 (4)	Fe1M—Cl1M	2.225 (10)
N1—C4	1.375 (5)	N1M—C4M	1.378 (10)
N1—C1	1.382 (6)	N1M—C1M	1.385 (11)
N2—C6	1.372 (5)	N2M—C6M	1.376 (11)
N2—C9	1.382 (6)	N2M—C9M	1.384 (11)
N3—C11	1.373 (5)	N3M—C11M	1.359 (11)
N3—C14	1.380 (5)	N3M—C14M	1.387 (11)
N4—C16	1.378 (5)	N4M—C16M	1.377 (11)
N4—C19	1.383 (5)	N4M—C19M	1.389 (11)
C1—C20	1.386 (5)	C1M—C20M	1.381 (10)
C1—C2	1.441 (5)	C1M—C2M	1.430 (11)
C2—C3	1.365 (6)	C2M—C3M	1.357 (11)
C2—C21	1.515 (4)	C2M—C21M	1.511 (5)
C21—C22	1.508 (5)	C21M—C22M	1.509 (5)
C21—H21A	0.99	C21M—H21C	0.99
C21—H21B	0.99	C21M—H21D	0.99
C3—C4	1.448 (6)	C3M—C4M	1.448 (11)
C3—C23	1.509 (4)	C3M—C23M	1.506 (5)
C23—C24	1.517 (4)	C23M—C24M	1.514 (5)
C23—H23A	0.99	C23M—H23C	0.99
C23—H23B	0.99	C23M—H23D	0.99
C4—C5	1.385 (6)	C4M—C5M	1.393 (11)
C5—C6	1.384 (6)	C5M—C6M	1.395 (11)
C5—H5	0.95	C5M—H5M	0.95
C6—C7	1.448 (6)	C6M—C7M	1.451 (12)
C7—C8	1.353 (6)	C7M—C8M	1.365 (11)
C7—C25	1.509 (4)	C7M—C25M	1.509 (5)
C25—C26	1.513 (4)	C25M—C26M	1.509 (5)
C25—H25A	0.99	C25M—H25C	0.99
C25—H25B	0.99	C25M—H25D	0.99
C8—C9	1.445 (6)	C8M—C9M	1.441 (11)
C8—C27	1.506 (4)	C8M—C27M	1.509 (5)
C27—C28	1.509 (4)	C27M—C28M	1.512 (5)
C27—H27A	0.99	C27M—H27C	0.99
C27—H27B	0.99	C27M—H27D	0.99
C9—C10	1.386 (6)	C9M—C10M	1.384 (11)
C10—C11	1.392 (6)	C10M—C11M	1.378 (12)
C10—H10	0.95	C10M—H10M	0.95
C11—C12	1.433 (5)	C11M—C12M	1.455 (10)
C12—C13	1.351 (6)	C12M—C13M	1.357 (11)
C12—C29	1.522 (6)	C12M—C29M	1.534 (11)
C29—C30	1.5117 (10)	C29M—C30M	1.5130 (10)
C29—H29A	0.99	C29M—H29C	0.99
C29—H29B	0.99	C29M—H29D	0.99
C13—C14	1.437 (5)	C13M—C14M	1.438 (11)
C13—C31	1.504 (4)	C13M—C31M	1.505 (5)
C31—C32	1.509 (5)	C31M—C32M	1.510 (5)
C31—H31A	0.99	C31M—H31C	0.99
C31—H31B	0.99	C31M—H31D	0.99
C14—C15	1.390 (6)	C14M—C15M	1.388 (12)
C15—C16	1.381 (5)	C15M—C16M	1.362 (11)
C15—H15	0.95	C15M—H15M	0.95
C16—C17	1.456 (5)	C16M—C17M	1.462 (11)
C17—C18	1.346 (5)	C17M—C18M	1.326 (11)
C17—C33	1.504 (4)	C17M—C33M	1.505 (5)
C33—C34	1.505 (4)	C33M—C34M	1.507 (5)
C33—H33A	0.99	C33M—H33C	0.99
C33—H33B	0.99	C33M—H33D	0.99
C18—C19	1.448 (6)	C18M—C19M	1.457 (11)
C18—C35	1.512 (4)	C18M—C35M	1.510 (5)
C35—C36	1.514 (5)	C35M—C36M	1.513 (5)
C35—H35A	0.99	C35M—H35C	0.99
C35—H35B	0.99	C35M—H35D	0.99
C19—C20	1.382 (6)	C19M—C20M	1.363 (11)
C20—H20	0.95	C20M—H20M	0.95
C22—H22A	0.98	C22M—H22D	0.98
C22—H22B	0.98	C22M—H22E	0.98
C22—H22C	0.98	C22M—H22F	0.98
C24—H24A	0.98	C24M—H24D	0.98
C24—H24B	0.98	C24M—H24E	0.98
C24—H24C	0.98	C24M—H24F	0.98
C26—H26A	0.98	C26M—H26D	0.98
C26—H26B	0.98	C26M—H26E	0.98
C26—H26C	0.98	C26M—H26F	0.98
C28—H28A	0.98	C28M—H28D	0.98
C28—H28B	0.98	C28M—H28E	0.98
C28—H28C	0.98	C28M—H28F	0.98
C30—H30A	0.98	C30M—H30D	0.98
C30—H30B	0.98	C30M—H30E	0.98
C30—H30C	0.98	C30M—H30F	0.98
C32—H32A	0.98	C32M—H32D	0.98
C32—H32B	0.98	C32M—H32E	0.98
C32—H32C	0.98	C32M—H32F	0.98
C34—H34A	0.98	C34M—H34D	0.98
C34—H34B	0.98	C34M—H34E	0.98
C34—H34C	0.98	C34M—H34F	0.98
C36—H36A	0.98	C36M—H36D	0.98
C36—H36B	0.98	C36M—H36E	0.98
C36—H36C	0.98	C36M—H36F	0.98
N2—Fe1—N3	86.9 (2)	N1M—C1M—C2M	110.8 (8)
N2—Fe1—N1	87.3 (3)	C3M—C2M—C1M	106.7 (9)
N3—Fe1—N1	153.8 (4)	C3M—C2M—C21M	128.7 (13)
N2—Fe1—N4	153.7 (4)	C1M—C2M—C21M	124.6 (13)
N3—Fe1—N4	87.2 (2)	C2M—C21M—C22M	114.1 (8)
N1—Fe1—N4	86.8 (2)	C2M—C21M—H21C	108.7
N2—Fe1—Cl1	100.6 (3)	C22M—C21M—H21C	108.7
N3—Fe1—Cl1	102.6 (3)	C2M—C21M—H21D	108.7
N1—Fe1—Cl1	103.6 (3)	C22M—C21M—H21D	108.7
N4—Fe1—Cl1	105.8 (3)	H21C—C21M—H21D	107.6
C4—N1—C1	105.1 (3)	C2M—C3M—C4M	107.3 (9)
C4—N1—Fe1	125.7 (4)	C2M—C3M—C23M	126.8 (12)
C1—N1—Fe1	126.9 (3)	C4M—C3M—C23M	125.9 (12)
C6—N2—C9	105.5 (4)	C3M—C23M—C24M	105.3 (7)
C6—N2—Fe1	124.9 (4)	C3M—C23M—H23C	110.7
C9—N2—Fe1	125.2 (4)	C24M—C23M—H23C	110.7
C11—N3—C14	105.3 (4)	C3M—C23M—H23D	110.7
C11—N3—Fe1	127.4 (4)	C24M—C23M—H23D	110.7
C14—N3—Fe1	126.3 (4)	H23C—C23M—H23D	108.8
C16—N4—C19	105.7 (4)	N1M—C4M—C5M	125.1 (11)
C16—N4—Fe1	127.1 (3)	N1M—C4M—C3M	109.8 (9)
C19—N4—Fe1	126.4 (4)	C5M—C4M—C3M	125.1 (10)
N1—C1—C20	123.8 (4)	C6M—C5M—C4M	123.8 (12)
N1—C1—C2	110.2 (4)	C6M—C5M—H5M	118.1
C20—C1—C2	125.8 (5)	C4M—C5M—H5M	118.1
C3—C2—C1	107.7 (4)	N2M—C6M—C5M	125.3 (11)
C3—C2—C21	126.8 (7)	N2M—C6M—C7M	109.8 (9)
C1—C2—C21	125.4 (6)	C5M—C6M—C7M	124.7 (11)
C22—C21—C2	112.1 (5)	C8M—C7M—C6M	108.3 (9)
C22—C21—H21A	109.2	C8M—C7M—C25M	126.3 (13)
C2—C21—H21A	109.2	C6M—C7M—C25M	125.3 (12)
C22—C21—H21B	109.2	C26M—C25M—C7M	109.2 (9)
C2—C21—H21B	109.2	C26M—C25M—H25C	109.8
H21A—C21—H21B	107.9	C7M—C25M—H25C	109.8
C2—C3—C4	105.4 (4)	C26M—C25M—H25D	109.8
C2—C3—C23	130.1 (6)	C7M—C25M—H25D	109.8
C4—C3—C23	124.4 (5)	H25C—C25M—H25D	108.3
C3—C23—C24	114.6 (4)	C7M—C8M—C9M	104.8 (8)
C3—C23—H23A	108.6	C7M—C8M—C27M	128.2 (9)
C24—C23—H23A	108.6	C9M—C8M—C27M	127.1 (9)
C3—C23—H23B	108.6	C8M—C27M—C28M	113.7 (7)
C24—C23—H23B	108.6	C8M—C27M—H27C	108.8
H23A—C23—H23B	107.6	C28M—C27M—H27C	108.8
N1—C4—C5	124.4 (5)	C8M—C27M—H27D	108.8
N1—C4—C3	111.5 (4)	C28M—C27M—H27D	108.8
C5—C4—C3	124.1 (5)	H27C—C27M—H27D	107.7
C6—C5—C4	126.7 (6)	C10M—C9M—N2M	125.0 (11)
C6—C5—H5	116.6	C10M—C9M—C8M	122.7 (11)
C4—C5—H5	116.6	N2M—C9M—C8M	112.4 (8)
N2—C6—C5	124.6 (5)	C11M—C10M—C9M	125.5 (11)
N2—C6—C7	110.9 (4)	C11M—C10M—H10M	117.2
C5—C6—C7	124.5 (5)	C9M—C10M—H10M	117.2
C8—C7—C6	106.1 (4)	N3M—C11M—C10M	126.2 (10)
C8—C7—C25	129.4 (6)	N3M—C11M—C12M	111.0 (8)
C6—C7—C25	124.3 (6)	C10M—C11M—C12M	122.8 (10)
C7—C25—C26	114.6 (5)	C13M—C12M—C11M	106.3 (8)
C7—C25—H25A	108.6	C13M—C12M—C29M	130.2 (10)
C26—C25—H25A	108.6	C11M—C12M—C29M	123.4 (9)
C7—C25—H25B	108.6	C30M—C29M—C12M	102.3 (6)
C26—C25—H25B	108.6	C30M—C29M—H29C	111.3
H25A—C25—H25B	107.6	C12M—C29M—H29C	111.3
C7—C8—C9	107.8 (4)	C30M—C29M—H29D	111.3
C7—C8—C27	128.0 (4)	C12M—C29M—H29D	111.3
C9—C8—C27	124.2 (4)	H29C—C29M—H29D	109.2
C8—C27—C28	114.1 (4)	C12M—C13M—C14M	106.9 (8)
C8—C27—H27A	108.7	C12M—C13M—C31M	126.6 (12)
C28—C27—H27A	108.7	C14M—C13M—C31M	126.5 (12)
C8—C27—H27B	108.7	C13M—C31M—C32M	114.9 (8)
C28—C27—H27B	108.7	C13M—C31M—H31C	108.5
H27A—C27—H27B	107.6	C32M—C31M—H31C	108.5
N2—C9—C10	124.3 (5)	C13M—C31M—H31D	108.5
N2—C9—C8	109.7 (4)	C32M—C31M—H31D	108.5
C10—C9—C8	126.0 (5)	H31C—C31M—H31D	107.5
C9—C10—C11	126.4 (6)	C15M—C14M—N3M	121.3 (11)
C9—C10—H10	116.8	C15M—C14M—C13M	128.0 (11)
C11—C10—H10	116.8	N3M—C14M—C13M	110.7 (9)
N3—C11—C10	123.8 (5)	C16M—C15M—C14M	128.9 (12)
N3—C11—C12	110.5 (4)	C16M—C15M—H15M	115.6
C10—C11—C12	125.5 (5)	C14M—C15M—H15M	115.6
C13—C12—C11	107.1 (4)	C15M—C16M—N4M	124.6 (11)
C13—C12—C29	126.5 (5)	C15M—C16M—C17M	125.9 (11)
C11—C12—C29	126.2 (5)	N4M—C16M—C17M	109.4 (8)
C30—C29—C12	110.5 (4)	C18M—C17M—C16M	107.1 (9)
C30—C29—H29A	109.6	C18M—C17M—C33M	130.6 (13)
C12—C29—H29A	109.6	C16M—C17M—C33M	122.2 (14)
C30—C29—H29B	109.6	C17M—C33M—C34M	116.2 (11)
C12—C29—H29B	109.6	C17M—C33M—H33C	108.2
H29A—C29—H29B	108.1	C34M—C33M—H33C	108.2
C12—C13—C14	106.9 (4)	C17M—C33M—H33D	108.2
C12—C13—C31	127.6 (6)	C34M—C33M—H33D	108.2
C14—C13—C31	125.5 (5)	H33C—C33M—H33D	107.4
C13—C31—C32	110.9 (4)	C17M—C18M—C19M	108.3 (9)
C13—C31—H31A	109.5	C17M—C18M—C35M	127.6 (12)
C32—C31—H31A	109.5	C19M—C18M—C35M	124.1 (12)
C13—C31—H31B	109.5	C18M—C35M—C36M	111.8 (11)
C32—C31—H31B	109.5	C18M—C35M—H35C	109.3
H31A—C31—H31B	108.0	C36M—C35M—H35C	109.3
N3—C14—C15	125.0 (5)	C18M—C35M—H35D	109.3
N3—C14—C13	110.2 (4)	C36M—C35M—H35D	109.3
C15—C14—C13	124.7 (5)	H35C—C35M—H35D	107.9
C16—C15—C14	125.9 (6)	C20M—C19M—N4M	123.1 (9)
C16—C15—H15	117.0	C20M—C19M—C18M	128.2 (10)
C14—C15—H15	117.0	N4M—C19M—C18M	108.6 (8)
N4—C16—C15	124.9 (5)	C19M—C20M—C1M	129.2 (9)
N4—C16—C17	110.0 (4)	C19M—C20M—H20M	115.4
C15—C16—C17	125.1 (5)	C1M—C20M—H20M	115.4
C18—C17—C16	107.0 (4)	C21M—C22M—H22D	109.5
C18—C17—C33	127.3 (6)	C21M—C22M—H22E	109.5
C16—C17—C33	125.7 (6)	H22D—C22M—H22E	109.5
C17—C33—C34	110.3 (5)	C21M—C22M—H22F	109.5
C17—C33—H33A	109.6	H22D—C22M—H22F	109.5
C34—C33—H33A	109.6	H22E—C22M—H22F	109.5
C17—C33—H33B	109.6	C23M—C24M—H24D	109.5
C34—C33—H33B	109.6	C23M—C24M—H24E	109.5
H33A—C33—H33B	108.1	H24D—C24M—H24E	109.5
C17—C18—C19	107.2 (4)	C23M—C24M—H24F	109.5
C17—C18—C35	128.4 (6)	H24D—C24M—H24F	109.5
C19—C18—C35	124.3 (6)	H24E—C24M—H24F	109.5
C18—C35—C36	114.4 (6)	C25M—C26M—H26D	109.5
C18—C35—H35A	108.7	C25M—C26M—H26E	109.5
C36—C35—H35A	108.7	H26D—C26M—H26E	109.5
C18—C35—H35B	108.7	C25M—C26M—H26F	109.5
C36—C35—H35B	108.7	H26D—C26M—H26F	109.5
H35A—C35—H35B	107.6	H26E—C26M—H26F	109.5
N4—C19—C20	125.0 (5)	C27M—C28M—H28D	109.5
N4—C19—C18	110.2 (4)	C27M—C28M—H28E	109.5
C20—C19—C18	124.7 (5)	H28D—C28M—H28E	109.5
C19—C20—C1	126.3 (4)	C27M—C28M—H28F	109.5
C19—C20—H20	116.8	H28D—C28M—H28F	109.5
C1—C20—H20	116.8	H28E—C28M—H28F	109.5
N2M—Fe1M—N3M	87.6 (5)	C29M—C30M—H30D	109.5
N2M—Fe1M—N1M	85.9 (5)	C29M—C30M—H30E	109.5
N3M—Fe1M—N1M	153.4 (8)	H30D—C30M—H30E	109.5
N2M—Fe1M—N4M	153.7 (9)	C29M—C30M—H30F	109.5
N3M—Fe1M—N4M	86.7 (5)	H30D—C30M—H30F	109.5
N1M—Fe1M—N4M	87.9 (5)	H30E—C30M—H30F	109.5
N2M—Fe1M—Cl1M	105.6 (7)	C31M—C32M—H32D	109.5
N3M—Fe1M—Cl1M	104.0 (5)	C31M—C32M—H32E	109.5
N1M—Fe1M—Cl1M	102.6 (6)	H32D—C32M—H32E	109.5
N4M—Fe1M—Cl1M	100.7 (6)	C31M—C32M—H32F	109.5
C4M—N1M—C1M	105.4 (7)	H32D—C32M—H32F	109.5
C4M—N1M—Fe1M	128.0 (8)	H32E—C32M—H32F	109.5
C1M—N1M—Fe1M	125.4 (8)	C33M—C34M—H34D	109.5
C6M—N2M—C9M	104.8 (8)	C33M—C34M—H34E	109.5
C6M—N2M—Fe1M	128.0 (8)	H34D—C34M—H34E	109.5
C9M—N2M—Fe1M	127.2 (8)	C33M—C34M—H34F	109.5
C11M—N3M—C14M	105.1 (7)	H34D—C34M—H34F	109.5
C11M—N3M—Fe1M	126.5 (7)	H34E—C34M—H34F	109.5
C14M—N3M—Fe1M	127.0 (8)	C35M—C36M—H36D	109.5
C16M—N4M—C19M	106.6 (8)	C35M—C36M—H36E	109.5
C16M—N4M—Fe1M	124.7 (7)	H36D—C36M—H36E	109.5
C19M—N4M—Fe1M	125.3 (8)	C35M—C36M—H36F	109.5
C20M—C1M—N1M	123.6 (10)	H36D—C36M—H36F	109.5
C20M—C1M—C2M	125.6 (10)	H36E—C36M—H36F	109.5

Key characteristics of (I) (Å)

Form	Fe—Nave	Fe—Cl (typical HS Cl)	Fe–porp^a	Fe—4N^a	Cl–porp^a	Δ^a	Shortest Fe···Fe^a	Reference
C60.(I).CHCl3	2.073 (8)	2.235 (9)	-	-	-	-	8.079	Olmstead et al. (1999)
(I).CH2Cl2 modest saddle	2.065 (3)	2.243 (1)	0.518 (1)	0.468 (1)	-	0.049	9.711 (3)	Safo et al. (2010)
(I)-monoclinic	2.071 (2)	2.231 (1)	0.494 (1)	0.465 (1)	2.723 (2)	0.045	7.876 (5)	Senge (2005)
(I)-triclinic-major	2.065 (2)	2.225 (4)	0.494 (4)	0.469 (5)	2.712 (3)	0.043	8.056 (8)	This work
(I)-triclinic-minor	2.065 (3)	2.225 (10)	0.545 (10)	0.473 (12)	2.759 (8)	0.063	7.890 (16)	This work
π-cation radical	2.058 (5)	2.186 (1)	0.43	-	-	0.031	4.112 (1)	Scheidt et al. (1992)

Note: (a) value or e.s.d. not available when not reported in the original work.