Di­chloro­(4,10-di­methyl-1,4,7,10-tetra­azabi­cyclo­[5.5.2]tetra­decane)­iron(III) hexa­fluoro­phosphate

The title compound, [FeCl₂(C₁₂H₂₆N₄)]PF₆, is the first mononuclear Fe³⁺ complex of an ethyl­ene cross-bridged tetra­aza-macrocycle to be structurally characterized. Comparison with the mononuclear Fe²⁺ complex of the same ligand shows that the smaller Fe³⁺ ion is more fully encapsulated by the cavity of the bicyclic ligand. Comparison with the μ-oxo dinuclear complex of an unsubstituted ligand of the same size demonstrates that the methyl groups of 4,10-dimethyl-1,4,7,10-tetra­azabicyclo­[5.5.2]tetra­decane prevent dimerization upon oxidation of the metal centre. N_ax—Fe³⁺—N_ax bond angles (ax is axial), and thus the degree of encapsulation by the ligand, are quite different between the mononuclear and dinuclear μ-oxo species, which is probably the consequence of steric considerations.

Comment

The tendency for iron complexes to form rust limits the utility, especially in aqueous media, of functional catalysts based on common ligands (Ortiz de Montellano, 1986). Even so, iron is one of the predominant metal ions found in biological catalytic systems (Jang et al., 1991; Wallar & Lipscomb, 1996; Boyington et al., 1993). A major feature of numerous synthetic catalysts having familiar nitro­gen donors and vacant coordination sites is their propensity to form dimers in which higher-valent metal ions are present. One of us has produced iron(II) (Hubin et al., 2000) and iron(III) (Hubin et al., 2001) complexes of ethyl­ene cross-bridged tetra­aza-macrocyclic ligands that are remarkably resistant to oxidative hydrolysis while still having available sites for binding of the metal ion to either a terminal oxidant or a substrate. The ability of the complex to remain mononuclear, and thus catalytically useful, appears to hinge on the substitution pattern of the non-bridgehead N atoms of the bicyclic ligands (Hubin et al., 2001). Methyl or benzyl substitution results only in mononuclear complexes, even in the M³⁺ (Hubin et al., 2001, 2003) or M⁴⁺ (Yin et al., 2006) oxidation state, while oxidation of the unsubstituted ligand complexes results in μ-oxo iron(III) dimers (Hubin et al., 2003).

Structural characterization of an Fe³⁺ mononuclear complex has not been achieved prior to the present study, which (i) demonstrates that even upon oxidation the methyl-substituted ligand does not allow dimerization to occur and (ii) provides a structure for comparison to the lower valent analogue and to the unsubstituted analogue's iron(III) μ-oxo dimer. Comparison of the Fe³⁺ 4,10-dimethyl-1,4,7,10-tetra­aza­bicyclo­[5.5.2]tetra­decane dichloride complex, (I) (Fig. 1 and Table 1), with the Fe²⁺ 4,10-dimethyl-1,4,7,10-tetra­aza­bicyclo­[5.5.2]tetra­decane dichloride complex primarily demonstrates the reduction in ionic radius of the iron ion upon oxidation. The N_ax—Fe³⁺—N_ax angle (ax is axial) is 153.20 (9)° in (I), while the N_ax—Fe²⁺—N_ax angle is 146.91 (7)° in the reduced complex (Hubin et al., 2000). The smaller Fe³⁺ ion is pulled further into the ligand cavity as the favored octa­hedral geometry is approached. Inter­estingly, the two methyl substituents are almost exactly eclipsed when viewed down the N_ax—Fe²⁺—N_ax axis, as might be expected from the symmetry of the complex (Fig. 2). However, they are more skewed in the Fe³⁺ structure. Perhaps the ligand must twist to accommodate the Fe³⁺ ion further into the ligand cavity. The Fe—N bond lengths are also affected, having an average of 2.26 Å in the Fe²⁺ complex and 2.17 Å in the Fe³⁺ complex.

Comparison of the Fe³⁺ monomer with the μ-oxo dimer complex is also informative. The secondary amine–Fe³⁺ bond lengths in the dimer are similar to the tertiary amine–Fe³⁺ bond lengths; the Fe—N(secondary) distances average 2.17 Å, with one longer Fe—N(tertiary) bond of 2.258 (5) Å (see Table 2). This may be associated with the asymmetric accommodation of a longer Fe—Cl bond and a shorter Fe—O bond. In the monomer, with all tertiary amines, the average Fe—N bond distance is 2.17 Å, matching the shorter Fe—N bonds in the dimer. The N_ax—Fe—N_ax bond angle averages 147.6 (2)° in the dimer, while this value is 153.20 (9)° in the monomer. Clearly, dimerization and its associated steric consequences push the Fe³⁺ ion further out of the ligand cavity than it is in the Fe³⁺ monomer. In fact, the dimer N_ax—Fe—N_ax bond angle is much closer to that of the Fe²⁺ monomer [146.91 (7)°] than that of the Fe³⁺ monomer [153.20 (9)°; Table 2]. This steric consequence is consistent with the observation that the more sterically demanding methyl-substituted ligand prevents dimerization altogether. This is supported by a comparison of all three structures viewed along the N_ax—Fe—N_ax axis, where a skewing of the methyl groups and a twist in the macrocyclic backbone are observed for the Fe³⁺ monomer relative to the other two structures (Fig. 2).

Figure 1 The structure of (I), with displacement ellipsoids drawn at the 50% probability level.

Figure 2 Comparison of the Fe^3+ monomeric complex (a) from this work with (b) the equivalent Fe^2+ complex and (c) the Fe^3+ dimer formed with the unsubstituted ligand. All views are oriented to look down the Nax—Fe—Nax axis. The methyl groups in the Fe^3+ complex are skewed, whereas they are eclipsed in the Fe^2+ complex. For the sake of clarity, H atoms have been omitted.

Experimental

The title complex was prepared by a procedure slightly modified from those described by Hubin et al. (2000, 2001). In an inert atmosphere glove-box, 4,10-dimethyl-1,4,7,10-tetra­azabicyclo­[5.5.2]tetra­decane (0.226 g, 0.001 mol) [prepared according to the procedure described by Wong et al. (2000)] was dissolved in acetonitrile (20 ml) in a 50 ml Erlenmeyer flask. Anhydrous iron(II) chloride (0.127 g, 0.001 mol) was added to the stirring ligand solution. The reaction was stirred at room temperature overnight. Dimethyl­formamide (12 ml) was added to dissolve a purple solid that had formed, and the reaction was then stirred for an additional 3 h, during which time the solid dissolved to give a light-brown solution. The solution was then filtered through filter paper and the solvent was removed under vacuum to give a brown solid, viz. the iron(II) dichloride complex of 4,10-dimethyl-1,4,7,10-tetra­azabicyclo­[5.5.2]tetra­decane. In the glove-box, the divalent iron complex was dissolved in methanol (20 ml) in a round-bottomed flask. Five equivalents of NH₄PF₆ (0.005 mol, 0.815 g) were dissolved in the solution. The flask was stoppered to protect it from air before being removed from the glove-box. In a fume-hood, a stream of nitro­gen gas was directed over the surface of the solution. Br₂ (4–6 drops) was added and the reaction was stirred for 15 min. A bright-yellow precipitate formed immediately. The nitro­gen gas was allowed to bubble through the solution for 15 min to remove excess Br₂. The flask was then stoppered and placed in a freezer for 30 min to complete the precipitation. The yellow solid product was collected by vacuum filtration on a glass frit and washed successively with methanol and ether. The product was analytically pure as calculated with one-third molar equivalents of water of crystallization. X-ray quality crystals were grown from ether diffusion into an acetonitrile solution.

Crystal data

• [FeCl₂(C₁₂H₂₆N₄)]PF₆

• M_r = 498.09

• Monoclinic, P 2₁ /c

• a = 8.3437 (12) Å

• b = 19.848 (2) Å

• c = 14.028 (2) Å

• β = 120.685 (10)°

• V = 1997.8 (5) ų

• Z = 4

• D_x = 1.656 Mg m⁻³

• Mo Kα radiation

• μ = 1.16 mm⁻¹

• T = 150 (2) K

• Block, orange

• 0.49 × 0.38 × 0.26 mm

Data collection

• Stoe IPDS-II image plate diffractometer

• ω scans

• 13147 measured reflections

• 5655 independent reflections

• 3799 reflections with I > 2σ(I)

• R_int = 0.039

• θ_max = 30°

Refinement

• Refinement on F²

• R[F² > 2σ(F²)] = 0.041

• wR(F²) = 0.117

• S = 0.97

• 5655 reflections

• 236 parameters

• H-atom parameters constrained

• w = 1/[σ²(F_o²) + (0.0692P)²] where P = (F<_o² + 2F_c²²)/3

• (Δ/σ)_max = 0.026

• Δρ_max = 0.75 e Å⁻³

• Δρ_min = −0.73 e Å⁻³

• Extinction correction: SHELXL97

• Extinction coefficient: 0.0022 (5)

Table 1
Selected geometric parameters (Å, °)

Fe1—Cl1	2.2853 (8)
Fe1—Cl2	2.2911 (7)

N4—Fe1—N3	81.26 (9)
N2—Fe1—N1	81.74 (8)
N4—Fe1—N1	77.85 (8)
N3—Fe1—N1	78.62 (8)
N2—Fe1—Cl1	100.39 (7)
N4—Fe1—Cl1	97.62 (6)
N3—Fe1—Cl1	170.88 (6)
N1—Fe1—Cl1	92.29 (6)
N2—Fe1—Cl2	96.51 (6)
N4—Fe1—Cl2	101.50 (6)
N3—Fe1—Cl2	93.99 (6)
N1—Fe1—Cl2	172.60 (6)
Cl1—Fe1—Cl2	95.10 (3)

Table 2
Comparative geometrical parameters (Å, °) for the macrocyclic cavity in Fe²⁺ and Fe³⁺ complexes

Parameter^a	Fe^3+Me2L^b	Fe^2+Me2L^c	Fe^3+H2L dimer^d
Fe—N1	2.179 (2)	2.240 (2)	2.162 (6)
Fe—N2	2.158 (2)	2.270 (2)	2.169 (5)
Fe—N3	2.171 (2)	2.246 (2)	2.186 (5)
Fe—N4	2.163 (2)	2.263 (2)	2.258 (5)
N2ax—Fe—N4ax	153.20 (9)	146.91 (7)	147.6 (2)
N1eq—Fe—N3eq	77.81 (9)	77.15 (7)	77.7 (2)
Notes: (a) where there are two independent molecules in the asymmetric unit, an average value is given; (b) this work; (c) Hubin et al. (2003); (d) Hubin et al. (2000).

H atoms were placed in idealized positions and refined using a riding model, with C—H distances of 0.96 and 0.97 Å for CH₃ and CH₂ H atoms, respectively, and with U_iso(H) values of, respectively, 1.5 and 1.2 times U_eq of the carrier atom.

Data collection: X-AREA (Stoe & Cie, 2002); cell refinement: X-AREA; data reduction: X-RED (Stoe & Cie, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP (Johnson, 1965) and ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97 and WinGX (Farrugia, 1999).

Supporting information

S1. Comment

The tendency for iron complexes to form rust limits the utility, especially in aqueous media, of functional catalysts based on common ligands (Ortiz de Montellano, 1986). Even so, iron is one of the predominant metal ions found in biological catalytic systems (Jang et al., 1991; Wallar & Lipscomb, 1996; Boyington et al., 1993). A major feature of numerous synthetic catalysts having familiar nitrogen donors and vacant coordination sites is their propensity to form dimers in which higher valent metal ions are present. One of us has produced iron(II) (Hubin et al., 2000) and iron(III) (Hubin et al., 2001) complexes of ethylene cross-bridged tetraazamacrocyclic ligands that are remarkably resistant to oxidative hydrolysis while still having available sites for binding of the metal ion to either a terminal oxidant or a substrate. The ability of the complex to remain mononuclear, and thus catalytically useful, appears to hinge on the substitution pattern of the non-bridgehead N atoms of the bicyclic ligands (Hubin et al., 2001). Methyl or benzyl substitution results only in mononuclear complexes, even in the M³⁺ (Hubin et al., 2001, 2003) or M⁴⁺ (Yin et al., 2006) oxidation state, while oxidation of the unsubstituted ligand complexes results in µ-oxo iron(III) dimers (Hubin et al., 2003).

Structural characterization of an Fe³⁺ mononuclear complex has not been achieved prior to the present study, which (1) demonstrates that even upon oxidation the methyl-substituted ligand does not allow dimerization to occur and (2) provides a structure for comparison to the lower valent analogue and to the unsubstituted analogue's iron(III) µ-oxo dimer. Comparison of the Fe³⁺ 4,10-dimethyl-1,4,7,10-tetraazabicyclo[5.5.2]tetradecane dichloride complex, (I) (Fig. 1), to that of the Fe²⁺ 4,10-dimethyl-1,4,7,10-tetraazabicyclo[5.5.2]tetradecane dichloride complex primarily demonstrates the reduction in ionic radius of the iron ion upon oxidation. The N_ax—Fe³⁺—N_ax angle is 153.20 (9)° in our new structure, while the N_ax—Fe²⁺—N_ax angle is 146.91 (7)° in the reduced complex (Hubin et al., 2000). The smaller Fe³⁺ ion is pulled further into the ligand cavity as the favored octahedral geometry is approached. Interestingly, the two methyl substituents are almost exactly eclipsed when viewed down the N_ax—Fe²⁺—N_ax axis, as might be expected from the symmetry of the complex (Fig. 2). However, they are more skewed in the Fe³⁺ structure. Perhaps the ligand must twist to accommodate the Fe³⁺ ion further into the ligand cavity. Fe—N bond lengths are also affected, having an average of 2.26 Å in the Fe²⁺ complex and 2.17 Å in the Fe³⁺ complex.

Comparison of the Fe³⁺ monomer with the µ-oxo dimer complex is also informative. The secondary amine/Fe³⁺ bond lengths in the dimer are similar to the tertiary amine/Fe³⁺ bond lengths: Fe—N(secondary) averages 2.17 Å with one longer Fe—N(tertiary) bond at 2.258 (5) Å (see Table 2). This may be associated with the asymmetric accommodation of a longer Fe—Cl and a shorter Fe—O bond. In the monomer, with all tertiary amines, the average Fe—N bond distance is 2.17 Å, matching the shorter Fe—N bonds in the dimer. The N_ax—Fe—N_ax bond angle averages 147.6 (2)° in the dimer, while this value is 153.20 (9)° in the monomer. Clearly, dimerization, and its associated steric consequences, pushes the Fe³⁺ ion further out of the ligand cavity than it is in the Fe³⁺ monomer. In fact, the dimer N_ax—Fe—N_ax bond angle is much closer to that of the Fe²⁺ monomer (145.78°) than that of the Fe³⁺ monomer (153.30°; Table 2). This steric consequence is consistent with the observation that the more sterically demanding methyl-substituted ligand prevents dimerization altogether. This is supported by a comparison of all three structures viewed along the N_ax—Fe—N_ax skewing of the methyl groups and a twist in the macrocyclic backbone is observed for the Fe³⁺ monomer relative to the other two structures (Fig. 2).

S2. Experimental

The title complex was prepared by a procedure slightly modified from those described by Hubin et al. (2000, 2001). In an inert atmosphere glovebox, 4,10-dimethyl-1,4,7,10-tetraazabicyclo[5.5.2]tetradecane (0.226 g, 0.001 mol)[prepared according to the procedure descrbed by Wong et al. (2000)] was dissolved in acetonitrile (20 ml) in a 50 ml Erlenmeyer flask. Anhydrous iron(II) chloride (0.127 g, 0.001 mol) was added to the stirring ligand solution. The reaction was allowed to stir at room temperature overnight. Dimethylformamide (12 ml) was then added to dissolve a purple solid that had formed, and the reaction was then stirred for an additional 3 h, during which the solid dissolved to give a light-brown solution. The solution was then filtered through filter paper and the solvent was removed under vacuum to give a brown solid, the iron(II) dichloride complex of 4,10-dimethyl-1,4,7,10-tetraazabicyclo[5.5.2]tetradecane. In the glovebox, the divalent iron complex was dissolved in 20 ml of methanol in a round-bottomed flask. Five equivalents (0.005 mol, 0.815 g) of NH₄PF₆ were dissolved in the solution. The flask was stoppered to protect it from air before being removed from the glovebox. In a fume hood, a stream of nitrogen gas was directed over the surface of the solution. Four to six drops of Br₂ were added and the reaction was stirred for 15 minutes. A bright-yellow precipitate formed immediately. The nitrogen gas was then allowed to bubble through the solution for 15 minutes to remove excess Br₂. The flask was then stoppered and placed in a freezer for 30 minutes to complete the precipitation. The yellow solid product was collected by vacuum filtration on a glass frit, and washed with methanol and then ether. The product was analytically pure as calculated with one-third molar equivalents of water of crystallization. X-ray quality crystals were grown from ether diffusion into an acetonitrile solution.

S3. Refinement

H atoms were placed in idealized positions and refined using a riding model with C—H distances of 0.96 and 0.97 Å for CH₃ and CH₂ H atoms, respectively, and with U_iso(H) values of, respectively, 1.2 and 1.5 times U_eq of the carrier atom.

Computing details

Data collection: X-AREA (Stoe & Cie, 2002); cell refinement: X-AREA; data reduction: X-RED (Stoe & Cie, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPIII (Johnson, 1965; Farrugia, 1997); software used to prepare material for publication: SHELXL97 and WinGX (Farrugia, 1999).

Figures

Fig. 1. Structure of (I), with displacement ellipsoids drawn at the 50% probability level. Fig. 2. Comparison of the Fe^3+ monomeric complex (a) from this work with the equivalent Fe^2+ complex (b) and the Fe^3+ dimer formed with the unsubstituted ligand (c). All views are oriented to look down the Nax—Fe—Nax axis. The methyl groups in the Fe^2+ complex are skewed, whereas they are eclipsed in the Fe^3+ complex. For the sake of clarity, H atoms have been omitted.

Dichloro(4,10-dimethyl-1,4,7,10-tetraazabicyclo[5.5.2]tetradecane)iron(III) hexafluorophosphate

Crystal data

[FeCl2(C12H26N4)](F6P)	F(000) = 1020
Mr = 498.09	Dx = 1.656 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 468 reflections
a = 8.3437 (12) Å	θ = 7.6–64.2°
b = 19.848 (2) Å	µ = 1.16 mm^−1
c = 14.028 (2) Å	T = 150 K
β = 120.685 (10)°	Block, orange
V = 1997.8 (5) Å^3	0.49 × 0.38 × 0.26 mm
Z = 4

Data collection

Stoe IPDS-II image plate diffractometer	Rint = 0.039
69 frames at 1° intervals, exposure time 1.5 minutes scans	θmax = 30°, θmin = 2.7°
13147 measured reflections	h = −10→11
5655 independent reflections	k = −23→27
3799 reflections with I > 2σ(I)	l = −19→19

Refinement

Refinement on F^2	H-atom parameters constrained
Least-squares matrix: full	w = 1/[σ^2(Fo^2) + (0.0692P)^2] where P = (Fo^2 + 2Fc^2)/3
R[F^2 > 2σ(F^2)] = 0.041	(Δ/σ)max = 0.026
wR(F^2) = 0.117	Δρmax = 0.75 e Å^−3
S = 0.97	Δρmin = −0.73 e Å^−3
5655 reflections	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
236 parameters	Extinction coefficient: 0.0022 (5)
0 restraints

Special details

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.

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

	x	y	z	Uiso*/Ueq
C1	0.2500 (4)	0.25173 (14)	0.2334 (2)	0.0297 (5)
H1A	0.3112	0.2303	0.3057	0.036*
H1B	0.3347	0.251	0.2053	0.036*
C2	0.0722 (4)	0.21412 (15)	0.1549 (3)	0.0322 (6)
H2A	0.0217	0.2318	0.0805	0.039*
H2B	0.1007	0.1668	0.1538	0.039*
C3	−0.2654 (4)	0.22994 (16)	0.0912 (2)	0.0372 (7)
H3A	−0.3512	0.203	0.1026	0.045*
H3B	−0.2683	0.2131	0.0255	0.045*
C4	−0.3333 (4)	0.30333 (16)	0.0707 (2)	0.0353 (6)
H4A	−0.3997	0.3124	−0.0083	0.042*
H4B	−0.4191	0.31	0.0973	0.042*
C5	−0.2303 (4)	0.41718 (15)	0.1510 (2)	0.0336 (6)
H5A	−0.3077	0.4108	0.1834	0.04*
H5B	−0.3012	0.4423	0.0826	0.04*
C6	−0.0550 (4)	0.45567 (14)	0.2307 (2)	0.0323 (6)
H6A	0.012	0.4679	0.1936	0.039*
H6B	−0.089	0.4969	0.2533	0.039*
C7	0.2734 (4)	0.42108 (15)	0.3671 (2)	0.0303 (5)
H7A	0.3457	0.4271	0.4469	0.036*
H7B	0.2881	0.4614	0.3332	0.036*
C8	0.3529 (3)	0.36058 (14)	0.3357 (2)	0.0287 (5)
H8A	0.4398	0.3765	0.3141	0.034*
H8B	0.42	0.3312	0.3994	0.034*
C9	0.1330 (3)	0.36015 (14)	0.1374 (2)	0.0274 (5)
H9A	0.189	0.3411	0.0975	0.033*
H9B	0.1729	0.4067	0.1544	0.033*
C10	−0.0793 (4)	0.35802 (15)	0.0631 (2)	0.0302 (6)
H10A	−0.1214	0.3991	0.0195	0.036*
H10B	−0.1136	0.3204	0.0121	0.036*
C11	−0.0675 (5)	0.15854 (16)	0.2508 (3)	0.0413 (7)
H11A	−0.1583	0.1623	0.2732	0.062*
H11B	0.0543	0.1534	0.3151	0.062*
H11C	−0.0956	0.12	0.2034	0.062*
C12	0.0426 (4)	0.43620 (16)	0.4241 (2)	0.0365 (6)
H12A	0.1215	0.4103	0.4894	0.055*
H12B	−0.0852	0.4297	0.4032	0.055*
H12C	0.0739	0.4831	0.4391	0.055*
F1	0.4619 (3)	−0.02017 (10)	0.2303 (2)	0.0542 (5)
F2	0.5085 (3)	0.04114 (13)	0.37704 (17)	0.0592 (6)
F3	0.5588 (3)	0.13320 (10)	0.3039 (2)	0.0558 (6)
F4	0.5120 (3)	0.07167 (14)	0.15620 (17)	0.0609 (6)
F5	0.7276 (2)	0.04016 (10)	0.32689 (17)	0.0472 (5)
F6	0.2913 (2)	0.07235 (11)	0.20510 (18)	0.0515 (5)
Fe1	−0.00519 (4)	0.308922 (18)	0.29295 (3)	0.02128 (10)
N1	0.2006 (3)	0.32239 (11)	0.24284 (17)	0.0244 (4)
N2	−0.0719 (3)	0.22085 (12)	0.18921 (19)	0.0294 (5)
N3	−0.1752 (3)	0.35094 (12)	0.12797 (17)	0.0271 (4)
N4	0.0701 (3)	0.41384 (11)	0.33213 (18)	0.0264 (4)
P1	0.50957 (9)	0.05673 (4)	0.26630 (6)	0.02762 (15)
Cl1	0.21124 (8)	0.26485 (4)	0.46060 (5)	0.03195 (16)
Cl2	−0.24930 (8)	0.29978 (3)	0.32333 (5)	0.02870 (14)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0281 (12)	0.0316 (13)	0.0361 (14)	0.0059 (10)	0.0214 (11)	0.0013 (11)
C2	0.0341 (13)	0.0301 (13)	0.0404 (15)	0.0011 (11)	0.0248 (12)	−0.0051 (11)
C3	0.0295 (13)	0.0473 (18)	0.0337 (14)	−0.0145 (12)	0.0153 (12)	−0.0141 (12)
C4	0.0215 (11)	0.0511 (18)	0.0259 (12)	−0.0063 (11)	0.0068 (10)	−0.0016 (12)
C5	0.0292 (12)	0.0358 (15)	0.0331 (13)	0.0119 (11)	0.0139 (11)	0.0084 (11)
C6	0.0382 (14)	0.0266 (13)	0.0354 (14)	0.0066 (11)	0.0212 (12)	0.0036 (11)
C7	0.0284 (12)	0.0360 (14)	0.0280 (12)	−0.0068 (10)	0.0155 (10)	−0.0057 (10)
C8	0.0204 (11)	0.0375 (14)	0.0275 (12)	−0.0020 (9)	0.0117 (10)	0.0002 (10)
C9	0.0295 (12)	0.0330 (13)	0.0251 (11)	−0.0004 (10)	0.0180 (10)	0.0013 (10)
C10	0.0289 (12)	0.0397 (15)	0.0202 (11)	0.0014 (10)	0.0111 (10)	0.0018 (10)
C11	0.0510 (17)	0.0280 (15)	0.0534 (18)	−0.0069 (13)	0.0327 (15)	−0.0002 (13)
C12	0.0393 (15)	0.0407 (17)	0.0345 (14)	−0.0031 (12)	0.0225 (12)	−0.0115 (12)
F1	0.0515 (11)	0.0354 (10)	0.0833 (16)	−0.0113 (8)	0.0399 (11)	−0.0194 (10)
F2	0.0617 (13)	0.0832 (16)	0.0382 (10)	−0.0088 (11)	0.0295 (10)	0.0011 (10)
F3	0.0541 (12)	0.0339 (10)	0.0797 (15)	−0.0052 (9)	0.0342 (11)	−0.0134 (10)
F4	0.0561 (12)	0.0888 (17)	0.0365 (10)	−0.0125 (11)	0.0228 (9)	0.0052 (11)
F5	0.0276 (8)	0.0492 (11)	0.0557 (12)	0.0018 (7)	0.0147 (8)	−0.0068 (9)
F6	0.0293 (9)	0.0560 (12)	0.0599 (12)	0.0058 (8)	0.0160 (8)	−0.0002 (10)
Fe1	0.01848 (15)	0.02585 (18)	0.02013 (16)	0.00082 (12)	0.01030 (12)	0.00073 (13)
N1	0.0209 (9)	0.0290 (11)	0.0233 (10)	0.0013 (7)	0.0114 (8)	0.0007 (8)
N2	0.0292 (10)	0.0298 (11)	0.0327 (11)	−0.0051 (9)	0.0184 (9)	−0.0046 (9)
N3	0.0223 (9)	0.0339 (12)	0.0226 (10)	0.0025 (8)	0.0097 (8)	0.0021 (8)
N4	0.0266 (10)	0.0290 (11)	0.0255 (10)	−0.0010 (8)	0.0148 (9)	−0.0024 (8)
P1	0.0260 (3)	0.0271 (3)	0.0283 (3)	−0.0009 (2)	0.0128 (3)	−0.0019 (3)
Cl1	0.0265 (3)	0.0455 (4)	0.0248 (3)	0.0074 (2)	0.0137 (2)	0.0111 (3)
Cl2	0.0215 (3)	0.0396 (4)	0.0304 (3)	0.0006 (2)	0.0171 (2)	0.0015 (2)

Geometric parameters (Å, º)

C1—N1	1.486 (3)	C9—N1	1.488 (3)
C1—C2	1.518 (4)	C9—C10	1.530 (3)
C1—H1A	0.97	C9—H9A	0.97
C1—H1B	0.97	C9—H9B	0.97
C2—N2	1.513 (4)	C10—N3	1.495 (3)
C2—H2A	0.97	C10—H10A	0.97
C2—H2B	0.97	C10—H10B	0.97
C3—N2	1.504 (4)	C11—N2	1.498 (4)
C3—C4	1.536 (5)	C11—H11A	0.96
C3—H3A	0.97	C11—H11B	0.96
C3—H3B	0.97	C11—H11C	0.96
C4—N3	1.482 (3)	C12—N4	1.489 (3)
C4—H4A	0.97	C12—H12A	0.96
C4—H4B	0.97	C12—H12B	0.96
C5—N3	1.482 (4)	C12—H12C	0.96
C5—C6	1.518 (4)	F1—P1	1.593 (2)
C5—H5A	0.97	F2—P1	1.588 (2)
C5—H5B	0.97	F3—P1	1.590 (2)
C6—N4	1.512 (3)	F4—P1	1.583 (2)
C6—H6A	0.97	F5—P1	1.6008 (18)
C6—H6B	0.97	F6—P1	1.5982 (19)
C7—N4	1.513 (3)	Fe1—N2	2.158 (2)
C7—C8	1.542 (4)	Fe1—N4	2.163 (2)
C7—H7A	0.97	Fe1—N3	2.171 (2)
C7—H7B	0.97	Fe1—N1	2.179 (2)
C8—N1	1.482 (3)	Fe1—Cl1	2.2853 (8)
C8—H8A	0.97	Fe1—Cl2	2.2911 (7)
C8—H8B	0.97
N1—C1—C2	108.4 (2)	N2—C11—H11C	109.5
N1—C1—H1A	110	H11A—C11—H11C	109.5
C2—C1—H1A	110	H11B—C11—H11C	109.5
N1—C1—H1B	110	N4—C12—H12A	109.5
C2—C1—H1B	110	N4—C12—H12B	109.5
H1A—C1—H1B	108.4	H12A—C12—H12B	109.5
N2—C2—C1	111.5 (2)	N4—C12—H12C	109.5
N2—C2—H2A	109.3	H12A—C12—H12C	109.5
C1—C2—H2A	109.3	H12B—C12—H12C	109.5
N2—C2—H2B	109.3	N2—Fe1—N4	153.20 (9)
C1—C2—H2B	109.3	N2—Fe1—N3	77.81 (9)
H2A—C2—H2B	108	N4—Fe1—N3	81.26 (9)
N2—C3—C4	113.9 (2)	N2—Fe1—N1	81.74 (8)
N2—C3—H3A	108.8	N4—Fe1—N1	77.85 (8)
C4—C3—H3A	108.8	N3—Fe1—N1	78.62 (8)
N2—C3—H3B	108.8	N2—Fe1—Cl1	100.39 (7)
C4—C3—H3B	108.8	N4—Fe1—Cl1	97.62 (6)
H3A—C3—H3B	107.7	N3—Fe1—Cl1	170.88 (6)
N3—C4—C3	111.2 (2)	N1—Fe1—Cl1	92.29 (6)
N3—C4—H4A	109.4	N2—Fe1—Cl2	96.51 (6)
C3—C4—H4A	109.4	N4—Fe1—Cl2	101.50 (6)
N3—C4—H4B	109.4	N3—Fe1—Cl2	93.99 (6)
C3—C4—H4B	109.4	N1—Fe1—Cl2	172.60 (6)
H4A—C4—H4B	108	Cl1—Fe1—Cl2	95.10 (3)
N3—C5—C6	108.5 (2)	C8—N1—C1	114.1 (2)
N3—C5—H5A	110	C8—N1—C9	109.6 (2)
C6—C5—H5A	110	C1—N1—C9	111.6 (2)
N3—C5—H5B	110	C8—N1—Fe1	104.05 (16)
C6—C5—H5B	110	C1—N1—Fe1	102.27 (15)
H5A—C5—H5B	108.4	C9—N1—Fe1	114.88 (14)
N4—C6—C5	111.1 (2)	C11—N2—C3	109.0 (2)
N4—C6—H6A	109.4	C11—N2—C2	108.7 (2)
C5—C6—H6A	109.4	C3—N2—C2	112.1 (2)
N4—C6—H6B	109.4	C11—N2—Fe1	110.98 (19)
C5—C6—H6B	109.4	C3—N2—Fe1	107.84 (17)
H6A—C6—H6B	108	C2—N2—Fe1	108.23 (16)
N4—C7—C8	114.1 (2)	C5—N3—C4	113.2 (2)
N4—C7—H7A	108.7	C5—N3—C10	111.8 (2)
C8—C7—H7A	108.7	C4—N3—C10	109.6 (2)
N4—C7—H7B	108.7	C5—N3—Fe1	102.42 (16)
C8—C7—H7B	108.7	C4—N3—Fe1	104.43 (17)
H7A—C7—H7B	107.6	C10—N3—Fe1	115.09 (15)
N1—C8—C7	110.4 (2)	C12—N4—C6	108.3 (2)
N1—C8—H8A	109.6	C12—N4—C7	109.5 (2)
C7—C8—H8A	109.6	C6—N4—C7	112.0 (2)
N1—C8—H8B	109.6	C12—N4—Fe1	110.74 (17)
C7—C8—H8B	109.6	C6—N4—Fe1	108.55 (16)
H8A—C8—H8B	108.1	C7—N4—Fe1	107.82 (16)
N1—C9—C10	112.6 (2)	F4—P1—F2	179.43 (15)
N1—C9—H9A	109.1	F4—P1—F3	90.85 (14)
C10—C9—H9A	109.1	F2—P1—F3	89.49 (13)
N1—C9—H9B	109.1	F4—P1—F1	89.77 (14)
C10—C9—H9B	109.1	F2—P1—F1	89.88 (13)
H9A—C9—H9B	107.8	F3—P1—F1	179.24 (14)
N3—C10—C9	112.4 (2)	F4—P1—F6	91.04 (12)
N3—C10—H10A	109.1	F2—P1—F6	89.40 (12)
C9—C10—H10A	109.1	F3—P1—F6	91.35 (11)
N3—C10—H10B	109.1	F1—P1—F6	89.08 (11)
C9—C10—H10B	109.1	F4—P1—F5	88.82 (12)
H10A—C10—H10B	107.9	F2—P1—F5	90.73 (12)
N2—C11—H11A	109.5	F3—P1—F5	89.36 (11)
N2—C11—H11B	109.5	F1—P1—F5	90.21 (11)
H11A—C11—H11B	109.5	F6—P1—F5	179.28 (12)
N1—C1—C2—N2	−53.2 (3)	Cl1—Fe1—N2—C2	−83.76 (17)
N2—C3—C4—N3	18.3 (4)	Cl2—Fe1—N2—C2	179.82 (17)
N3—C5—C6—N4	−52.5 (3)	C6—C5—N3—C4	167.7 (2)
N4—C7—C8—N1	22.1 (3)	C6—C5—N3—C10	−68.0 (3)
N1—C9—C10—N3	28.7 (3)	C6—C5—N3—Fe1	55.8 (2)
C7—C8—N1—C1	−158.7 (2)	C3—C4—N3—C5	−156.2 (2)
C7—C8—N1—C9	75.2 (3)	C3—C4—N3—C10	78.2 (3)
C7—C8—N1—Fe1	−48.1 (2)	C3—C4—N3—Fe1	−45.6 (3)
C2—C1—N1—C8	166.6 (2)	C9—C10—N3—C5	94.4 (3)
C2—C1—N1—C9	−68.4 (3)	C9—C10—N3—C4	−139.2 (2)
C2—C1—N1—Fe1	55.0 (2)	C9—C10—N3—Fe1	−21.9 (3)
C10—C9—N1—C8	−139.3 (2)	N2—Fe1—N3—C5	162.25 (18)
C10—C9—N1—C1	93.2 (3)	N4—Fe1—N3—C5	−34.59 (16)
C10—C9—N1—Fe1	−22.6 (3)	N1—Fe1—N3—C5	−113.85 (17)
N2—Fe1—N1—C8	−152.59 (16)	Cl2—Fe1—N3—C5	66.44 (16)
N4—Fe1—N1—C8	44.88 (15)	N2—Fe1—N3—C4	43.96 (17)
N3—Fe1—N1—C8	128.26 (16)	N4—Fe1—N3—C4	−152.88 (18)
Cl1—Fe1—N1—C8	−52.42 (15)	N1—Fe1—N3—C4	127.86 (18)
N2—Fe1—N1—C1	−33.56 (16)	Cl2—Fe1—N3—C4	−51.84 (17)
N4—Fe1—N1—C1	163.91 (17)	N2—Fe1—N3—C10	−76.20 (19)
N3—Fe1—N1—C1	−112.70 (16)	N4—Fe1—N3—C10	86.95 (19)
Cl1—Fe1—N1—C1	66.61 (15)	N1—Fe1—N3—C10	7.69 (18)
N2—Fe1—N1—C9	87.56 (18)	Cl2—Fe1—N3—C10	−172.01 (18)
N4—Fe1—N1—C9	−74.97 (17)	C5—C6—N4—C12	−100.4 (3)
N3—Fe1—N1—C9	8.42 (17)	C5—C6—N4—C7	138.8 (2)
Cl1—Fe1—N1—C9	−172.27 (16)	C5—C6—N4—Fe1	19.9 (3)
C4—C3—N2—C11	139.5 (3)	C8—C7—N4—C12	136.4 (2)
C4—C3—N2—C2	−100.1 (3)	C8—C7—N4—C6	−103.4 (3)
C4—C3—N2—Fe1	19.0 (3)	C8—C7—N4—Fe1	15.9 (3)
C1—C2—N2—C11	−99.3 (3)	N2—Fe1—N4—C12	166.01 (19)
C1—C2—N2—C3	140.2 (2)	N3—Fe1—N4—C12	127.09 (18)
C1—C2—N2—Fe1	21.4 (3)	N1—Fe1—N4—C12	−152.76 (18)
N4—Fe1—N2—C11	166.92 (19)	Cl1—Fe1—N4—C12	−62.04 (17)
N3—Fe1—N2—C11	−153.65 (19)	Cl2—Fe1—N4—C12	34.77 (17)
N1—Fe1—N2—C11	126.30 (19)	N2—Fe1—N4—C6	47.2 (3)
Cl1—Fe1—N2—C11	35.47 (18)	N3—Fe1—N4—C6	8.33 (16)
Cl2—Fe1—N2—C11	−60.96 (18)	N1—Fe1—N4—C6	88.47 (17)
N4—Fe1—N2—C3	−73.8 (3)	Cl1—Fe1—N4—C6	179.19 (16)
N3—Fe1—N2—C3	−34.37 (18)	Cl2—Fe1—N4—C6	−83.99 (16)
N1—Fe1—N2—C3	−114.42 (19)	N2—Fe1—N4—C7	−74.3 (2)
Cl1—Fe1—N2—C3	154.75 (17)	N3—Fe1—N4—C7	−113.18 (17)
Cl2—Fe1—N2—C3	58.33 (18)	N1—Fe1—N4—C7	−33.03 (16)
N4—Fe1—N2—C2	47.7 (3)	Cl1—Fe1—N4—C7	57.68 (16)
N3—Fe1—N2—C2	87.13 (18)	Cl2—Fe1—N4—C7	154.50 (15)
N1—Fe1—N2—C2	7.07 (17)