supplementary materials


ng5339 scheme

Acta Cryst. (2013). E69, m530-m531    [ doi:10.1107/S1600536813021880 ]

(2,3,5,6-Tetrafluorophenolato)[5,10,15,20-tetrakis(4-methoxyphenyl)porphyrinato]iron(III) cyclohexane monosolvate

N. Xu, D. R. Powell and G. B. Richter-Addo

Abstract top

The title compound, [Fe(C6HF4O)(C48H36N4O4)]·C6H12, represents a five-coordinate iron(III) porphyrin complex in a square-pyramidal geometry with a tetrafluorophenolate anion as the axial ligand. The FeIII atom is displaced by 0.364 (2) Å from the 24-atom mean plane of the porphyrinate ring towards the tetrafluoro phenolate anion. The average Fe-N distance is 2.053 (2) Å and the Fe-O distance is 1.883 (2) Å. A porphyrin aryl H atom points in the general direction of the phenoxide ring. The mean plane separation between the 24-atom porphyrin planes of two adjacent porphyrin rings is ~3.7 Å, and the lateral shift is ~3.5 Å resu, ting in an Fe...Fe separation of 5.6167 (14) Å.

Comment top

Synthetic metalloporphyrins have been studied intensively due to their potential to act as models for heme enzymes in biological systems. Catalase is a heme enzyme that catalyzes the decomposition of hydrogen peroxide to water and oxygen (Nicholls et al., 2001). Heme catalase contains an active-site tyrosine, a phenolato type ligand, that binds to the heme iron center (Nicholls et al., 2001). A number of iron phenolate porphyrin complexes has been prepared and structurally characterized (Chaudhary et al., 2010, Ueyama et al., 1998, Kanamori et al., 2005). In this paper, we report the structure of (5,10,15,20-tetrakis(4-methoxyphenyl)porphyrinato)(tetrafluorophenolato)iron(III) with a cyclohexane monosolvate.

The molecular structure of (5,10,15,20-tetrakis(4-methoxyphenyl)porphyrinato)(2,3,5,6-tetrafluorophenolato)iron(III) is shown in Fig. 1. The porphyrin core of is saddle shaped. The iron atom is displaced by 0.364 (2) Å from the 24-atom mean porphyrin plane toward the tetrafluorophenolate anion. In addition, the Fe—Np distances range from 2.048 (2) Å to 2.056 (2) Å, suggesting a high-spin ferric center (Scheidt & Reid, 1981). The Fe—O distance is 1.883 (2) Å which is typical of Fe—O bond distances in the iron phenolato porphyrin complexes reported previously. The Fe—O—C linkage shows a bent geometry with a bond angle of 130.46 (17)°.

Related literature top

For the function and structure of catalase, see: Nicholls et al. (2001). For the structures of other related ferric pheno porphyrin derivatives, see: Chaudhary et al. (2010); Ueyama et al. (1998); Kanamori et al. (2005). For the typical geometry parameters for high-spin ferric porphyrin complexes, see: Scheidt & Reed (1981). For the synthesis of [(T(p-OMe)PP)Fe]2O, see: Helms et al. (1986).

Experimental top

To a CH2Cl2 solution (20 ml) of [(T(p-OMe)PP)Fe]2O (Helms et al., 1986) (0.030 g, 0.019 mmol) was added 2,3,5,6-tetrafluorophenol (0.051 g, 0.307 mmol) (purchased from Aldrich Chemical Company and used as received) under N2. After stirring for 1 h, the color of the solution changed from green to red. The solution was reduced to 2 ml under reduced pressure, and 10 ml hexane was added. The resulting black precipitation was collected by filtration and dried under vacuum. A suitable prism-shaped crystal was grown by slow evaporation of a CH2Cl2-cyclohexane (1:1) solution of the complex at room temperature under N2.

Refinement top

The positions of H atoms bonded to carbons were initially determined by geometry and were refined using a riding model. H atoms bonded to N atoms and O atoms were located on a difference map, and their positions were refined independently. Non-hydrogen atoms were refined with anisotropic displacement parameters. Hydrogen atom displacement parameters were set to 1.2 (1.5 for methyl) times the isotropic equivalent displacement parameters of the bonded atoms. Carbon-bound H atoms were placed in calculated positions (aromatic 0.95, ethyl 0.99, and methyl 0.95 Angstroms) and were refined using a riding model. The C—C bond distances in the cyclohexane were restrained to 1.52 Angstroms and the 1–3 C···C distances were restrained to be equal. Rigid-bond restraints were also applied to the anisotropic displacement parameters of the solvent carbons.

Computing details top

Data collection: SMART (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXL2013 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL2013 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The molecular structure of (T(p-OMe)PP)Fe(OC6HF4).(C6H12) with displacement ellipsoids drawn at the 35% probability level. H atoms are omitted for clarity.
(2,3,5,6-Tetrafluorophenolato)[5,10,15,20-tetrakis(4-methoxyphenyl)porphyrinato]iron(III) cyclohexane monosolvate top
Crystal data top
[Fe(C6HF4O)(C48H36N4O4)]·C6H12Z = 2
Mr = 1037.88F(000) = 1078
Triclinic, P1Dx = 1.413 Mg m3
a = 10.294 (3) ÅMo Kα radiation, λ = 0.71073 Å
b = 15.617 (5) ÅCell parameters from 9754 reflections
c = 16.082 (5) Åθ = 2.3–28.1°
α = 90.984 (7)°µ = 0.38 mm1
β = 103.010 (8)°T = 100 K
γ = 103.869 (8)°Prism, black
V = 2438.6 (13) Å30.47 × 0.22 × 0.21 mm
Data collection top
Bruker APEX
diffractometer
8303 reflections with I > 2σ(I)
φ and ω scansRint = 0.057
Absorption correction: multi-scan
(SADABS; Bruker, 2002)
θmax = 28.3°, θmin = 1.9°
Tmin = 0.841, Tmax = 0.924h = 1213
33926 measured reflectionsk = 2020
12007 independent reflectionsl = 2121
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.060Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.159H-atom parameters constrained
S = 1.04 w = 1/[σ2(Fo2) + (0.070P)2 + 1.4P]
where P = (Fo2 + 2Fc2)/3
12007 reflections(Δ/σ)max = 0.001
671 parametersΔρmax = 0.87 e Å3
69 restraintsΔρmin = 0.66 e Å3
Crystal data top
[Fe(C6HF4O)(C48H36N4O4)]·C6H12γ = 103.869 (8)°
Mr = 1037.88V = 2438.6 (13) Å3
Triclinic, P1Z = 2
a = 10.294 (3) ÅMo Kα radiation
b = 15.617 (5) ŵ = 0.38 mm1
c = 16.082 (5) ÅT = 100 K
α = 90.984 (7)°0.47 × 0.22 × 0.21 mm
β = 103.010 (8)°
Data collection top
Bruker APEX
diffractometer
8303 reflections with I > 2σ(I)
Absorption correction: multi-scan
(SADABS; Bruker, 2002)
Rint = 0.057
Tmin = 0.841, Tmax = 0.924θmax = 28.3°
33926 measured reflectionsStandard reflections: ?
12007 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.060H-atom parameters constrained
wR(F2) = 0.159Δρmax = 0.87 e Å3
S = 1.04Δρmin = 0.66 e Å3
12007 reflectionsAbsolute structure: ?
671 parametersAbsolute structure parameter: ?
69 restraintsRogers parameter: ?
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Fe10.54850 (4)0.40039 (2)0.36835 (2)0.01450 (11)
F10.4734 (2)0.37222 (14)0.12137 (12)0.0413 (5)
F20.4990 (3)0.25191 (16)0.00941 (13)0.0649 (7)
F30.8499 (2)0.18073 (15)0.21702 (16)0.0589 (7)
F40.83646 (19)0.30860 (14)0.32666 (12)0.0424 (5)
O10.2238 (2)0.41310 (13)0.03430 (12)0.0243 (5)
O20.8053 (2)1.00037 (13)0.41908 (16)0.0351 (6)
O31.1901 (2)0.33946 (13)0.84395 (12)0.0243 (5)
O40.3294 (2)0.18471 (12)0.21551 (12)0.0255 (5)
O50.6454 (2)0.40630 (12)0.28145 (12)0.0255 (5)
N10.3719 (2)0.30765 (14)0.30928 (14)0.0173 (5)
N20.4441 (2)0.49621 (14)0.33532 (13)0.0156 (5)
N30.6809 (2)0.48904 (14)0.46420 (13)0.0144 (5)
N40.6120 (2)0.30102 (14)0.43442 (14)0.0160 (5)
C10.3555 (3)0.21711 (18)0.30401 (17)0.0187 (6)
C20.2245 (3)0.17497 (19)0.24803 (18)0.0242 (6)
H20.18820.11320.23390.029*
C30.1630 (3)0.23938 (18)0.21940 (18)0.0237 (6)
H30.07430.23120.18230.028*
C40.2557 (3)0.32252 (18)0.25498 (17)0.0181 (6)
C50.2365 (3)0.40538 (18)0.23235 (16)0.0175 (6)
C60.3294 (3)0.48624 (18)0.26853 (16)0.0171 (6)
C70.3195 (3)0.57118 (17)0.23963 (17)0.0180 (6)
H70.25000.58250.19440.022*
C80.4270 (3)0.63249 (18)0.28848 (16)0.0170 (6)
H80.44710.69460.28380.020*
C90.5046 (3)0.58593 (17)0.34871 (16)0.0157 (5)
C100.6233 (3)0.62673 (16)0.41159 (16)0.0155 (5)
C110.6990 (3)0.57991 (17)0.46875 (16)0.0154 (5)
C120.8083 (3)0.62018 (17)0.54139 (16)0.0176 (6)
H120.84070.68160.55860.021*
C130.8561 (3)0.55420 (17)0.58059 (16)0.0178 (6)
H130.92750.56070.63110.021*
C140.7794 (3)0.47207 (17)0.53198 (16)0.0157 (5)
C150.8038 (3)0.38896 (17)0.54911 (16)0.0145 (5)
C160.7302 (3)0.31050 (17)0.49889 (16)0.0161 (5)
C170.7663 (3)0.22693 (18)0.50638 (17)0.0196 (6)
H170.84360.21570.54540.024*
C180.6708 (3)0.16726 (18)0.44797 (17)0.0191 (6)
H180.66900.10680.43800.023*
C190.5731 (3)0.21268 (17)0.40407 (17)0.0174 (6)
C200.4528 (3)0.17299 (17)0.34366 (16)0.0174 (6)
C210.1133 (3)0.40780 (17)0.16372 (17)0.0181 (6)
C220.0897 (3)0.36430 (18)0.08309 (17)0.0205 (6)
H220.15280.33240.07240.025*
C230.0231 (3)0.36665 (18)0.01868 (17)0.0222 (6)
H230.03680.33670.03570.027*
C240.1169 (3)0.41300 (18)0.03331 (17)0.0193 (6)
C250.0956 (3)0.45660 (18)0.11327 (17)0.0188 (6)
H250.15910.48810.12400.023*
C260.0186 (3)0.45390 (17)0.17720 (17)0.0186 (6)
H260.03250.48420.23150.022*
C270.3165 (3)0.4657 (2)0.02335 (19)0.0256 (7)
H27A0.37230.43810.01560.038*
H27B0.37700.46960.07890.038*
H27C0.26350.52520.00080.038*
C280.6737 (3)0.72541 (17)0.41580 (16)0.0160 (6)
C290.8035 (3)0.76400 (18)0.40272 (17)0.0202 (6)
H290.86130.72720.39410.024*
C300.8507 (3)0.85510 (19)0.40196 (19)0.0242 (6)
H300.93870.87980.39140.029*
C310.7689 (3)0.90978 (18)0.41667 (18)0.0226 (6)
C320.6398 (3)0.87256 (19)0.43091 (19)0.0251 (7)
H320.58330.90970.44090.030*
C330.5928 (3)0.78155 (18)0.43067 (17)0.0196 (6)
H330.50440.75710.44080.024*
C340.9249 (4)1.0414 (2)0.3893 (2)0.0401 (9)
H34A1.00681.02980.42720.060*
H34B0.93441.10540.38940.060*
H34C0.91541.01710.33100.060*
C350.9110 (3)0.38021 (17)0.62544 (16)0.0159 (5)
C361.0483 (3)0.42617 (17)0.64082 (16)0.0172 (6)
H361.07710.46690.60140.021*
C371.1450 (3)0.41403 (18)0.71251 (17)0.0181 (6)
H371.23850.44620.72170.022*
C381.1040 (3)0.35481 (18)0.77047 (17)0.0183 (6)
C390.9663 (3)0.30805 (17)0.75673 (17)0.0175 (6)
H390.93760.26790.79660.021*
C400.8725 (3)0.32036 (17)0.68520 (16)0.0161 (5)
H400.77930.28760.67590.019*
C411.3346 (3)0.3732 (2)0.8523 (2)0.0316 (7)
H41A1.36060.35150.80250.047*
H41B1.38520.35320.90440.047*
H41C1.35720.43790.85590.047*
C420.4271 (3)0.07705 (17)0.31487 (17)0.0180 (6)
C430.4813 (4)0.0550 (2)0.2500 (2)0.0452 (11)
H430.54050.10030.22770.054*
C440.4528 (4)0.0317 (2)0.2153 (2)0.0432 (10)
H440.49260.04500.17030.052*
C450.3675 (3)0.09726 (17)0.24639 (17)0.0187 (6)
C460.3129 (4)0.07695 (19)0.3128 (2)0.0338 (8)
H460.25410.12240.33530.041*
C470.3439 (4)0.00976 (19)0.3468 (2)0.0322 (8)
H470.30680.02290.39310.039*
C480.3723 (4)0.2052 (2)0.1411 (2)0.0355 (8)
H48A0.34000.16940.09520.053*
H48B0.33340.26810.12260.053*
H48C0.47300.19220.15410.053*
C490.6532 (3)0.34337 (18)0.22824 (17)0.0195 (6)
C500.5682 (3)0.3249 (2)0.14612 (19)0.0265 (7)
C510.5817 (4)0.2627 (2)0.0895 (2)0.0373 (8)
C520.6752 (4)0.2133 (2)0.1113 (2)0.0397 (9)
H520.68260.16960.07190.048*
C530.7571 (4)0.2293 (2)0.1916 (2)0.0350 (8)
C540.7490 (3)0.2932 (2)0.24924 (19)0.0268 (7)
C1S0.9771 (6)0.8891 (5)0.0965 (4)0.127 (2)
H1S11.02260.84030.11060.152*
H1S21.04810.94160.08880.152*
C2S0.9200 (8)0.9095 (5)0.1691 (4)0.145 (3)
H2S10.99720.94010.21680.174*
H2S20.87390.85320.18900.174*
C3S0.8180 (9)0.9665 (6)0.1485 (4)0.173 (3)
H3S10.76690.96220.19410.208*
H3S20.87081.02880.15070.208*
C4S0.7174 (6)0.9457 (5)0.0658 (4)0.132 (2)
H4S10.67910.99750.05190.159*
H4S20.64060.89600.07180.159*
C5S0.7717 (8)0.9213 (6)0.0085 (4)0.150 (3)
H5S10.69300.89070.05530.180*
H5S20.81960.97620.02990.180*
C6S0.8694 (9)0.8628 (6)0.0135 (4)0.186 (4)
H6S10.91690.86180.03350.223*
H6S20.81490.80180.01600.223*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Fe10.0163 (2)0.01043 (19)0.01492 (19)0.00252 (15)0.00085 (15)0.00100 (14)
F10.0424 (12)0.0535 (13)0.0327 (10)0.0241 (10)0.0049 (9)0.0109 (9)
F20.0936 (19)0.0673 (16)0.0233 (10)0.0151 (14)0.0010 (11)0.0129 (10)
F30.0588 (15)0.0543 (15)0.0928 (18)0.0405 (12)0.0473 (14)0.0322 (13)
F40.0237 (10)0.0589 (14)0.0405 (11)0.0075 (10)0.0015 (9)0.0105 (10)
O10.0211 (11)0.0280 (11)0.0200 (10)0.0091 (9)0.0056 (8)0.0050 (8)
O20.0315 (13)0.0111 (10)0.0604 (15)0.0033 (9)0.0087 (11)0.0018 (10)
O30.0172 (10)0.0304 (12)0.0213 (10)0.0053 (9)0.0031 (8)0.0024 (8)
O40.0387 (13)0.0097 (9)0.0264 (11)0.0017 (9)0.0094 (9)0.0043 (8)
O50.0352 (12)0.0143 (10)0.0266 (11)0.0006 (9)0.0142 (9)0.0026 (8)
N10.0175 (12)0.0130 (11)0.0200 (11)0.0039 (9)0.0014 (9)0.0000 (9)
N20.0151 (12)0.0142 (11)0.0160 (10)0.0039 (9)0.0002 (9)0.0014 (8)
N30.0169 (12)0.0098 (11)0.0152 (10)0.0030 (9)0.0019 (9)0.0005 (8)
N40.0185 (12)0.0107 (11)0.0177 (11)0.0038 (9)0.0021 (9)0.0009 (8)
C10.0188 (15)0.0134 (13)0.0217 (13)0.0027 (11)0.0017 (11)0.0004 (10)
C20.0228 (16)0.0148 (14)0.0274 (15)0.0002 (12)0.0044 (12)0.0013 (11)
C30.0191 (15)0.0176 (15)0.0280 (15)0.0023 (12)0.0046 (12)0.0019 (12)
C40.0159 (14)0.0150 (13)0.0216 (13)0.0032 (11)0.0016 (11)0.0000 (10)
C50.0175 (14)0.0174 (14)0.0170 (13)0.0046 (11)0.0025 (11)0.0019 (10)
C60.0180 (14)0.0172 (14)0.0159 (12)0.0050 (11)0.0033 (11)0.0018 (10)
C70.0218 (15)0.0164 (14)0.0164 (12)0.0081 (12)0.0021 (11)0.0005 (10)
C80.0203 (15)0.0138 (13)0.0174 (13)0.0057 (11)0.0037 (11)0.0002 (10)
C90.0178 (14)0.0148 (13)0.0151 (12)0.0056 (11)0.0039 (11)0.0009 (10)
C100.0199 (14)0.0100 (12)0.0169 (12)0.0040 (11)0.0048 (11)0.0018 (10)
C110.0176 (14)0.0129 (13)0.0157 (12)0.0032 (11)0.0044 (11)0.0010 (10)
C120.0205 (15)0.0122 (13)0.0173 (13)0.0016 (11)0.0018 (11)0.0028 (10)
C130.0201 (15)0.0164 (14)0.0149 (12)0.0040 (11)0.0010 (11)0.0003 (10)
C140.0151 (13)0.0136 (13)0.0175 (12)0.0023 (11)0.0037 (11)0.0025 (10)
C150.0161 (13)0.0128 (13)0.0148 (12)0.0038 (11)0.0039 (10)0.0011 (10)
C160.0172 (14)0.0147 (13)0.0153 (12)0.0043 (11)0.0015 (11)0.0013 (10)
C170.0217 (15)0.0166 (14)0.0199 (13)0.0066 (12)0.0018 (12)0.0003 (11)
C180.0216 (15)0.0127 (13)0.0218 (13)0.0052 (11)0.0015 (12)0.0011 (10)
C190.0220 (15)0.0111 (13)0.0188 (13)0.0041 (11)0.0045 (11)0.0006 (10)
C200.0224 (15)0.0120 (13)0.0166 (12)0.0023 (11)0.0042 (11)0.0007 (10)
C210.0187 (14)0.0144 (13)0.0177 (13)0.0020 (11)0.0004 (11)0.0001 (10)
C220.0215 (15)0.0165 (14)0.0229 (14)0.0066 (12)0.0024 (12)0.0024 (11)
C230.0264 (16)0.0183 (14)0.0183 (13)0.0045 (12)0.0004 (12)0.0069 (11)
C240.0183 (15)0.0174 (14)0.0182 (13)0.0022 (11)0.0011 (11)0.0010 (10)
C250.0180 (14)0.0167 (14)0.0217 (13)0.0063 (11)0.0029 (11)0.0012 (11)
C260.0220 (15)0.0160 (14)0.0163 (13)0.0048 (11)0.0018 (11)0.0010 (10)
C270.0198 (16)0.0319 (17)0.0238 (15)0.0092 (13)0.0004 (12)0.0018 (12)
C280.0220 (15)0.0121 (13)0.0137 (12)0.0057 (11)0.0023 (11)0.0004 (10)
C290.0208 (15)0.0149 (14)0.0241 (14)0.0056 (11)0.0029 (12)0.0015 (11)
C300.0205 (15)0.0175 (15)0.0326 (16)0.0014 (12)0.0055 (13)0.0013 (12)
C310.0267 (16)0.0093 (13)0.0287 (15)0.0041 (12)0.0008 (13)0.0002 (11)
C320.0243 (16)0.0166 (14)0.0345 (16)0.0089 (12)0.0036 (13)0.0038 (12)
C330.0191 (15)0.0173 (14)0.0218 (13)0.0027 (12)0.0057 (11)0.0010 (11)
C340.043 (2)0.0154 (16)0.055 (2)0.0035 (15)0.0107 (18)0.0054 (15)
C350.0180 (14)0.0115 (13)0.0166 (12)0.0034 (11)0.0016 (11)0.0019 (10)
C360.0211 (15)0.0130 (13)0.0175 (13)0.0036 (11)0.0053 (11)0.0003 (10)
C370.0143 (14)0.0150 (13)0.0240 (14)0.0032 (11)0.0033 (11)0.0030 (11)
C380.0179 (14)0.0183 (14)0.0173 (13)0.0076 (11)0.0014 (11)0.0024 (10)
C390.0190 (14)0.0133 (13)0.0200 (13)0.0034 (11)0.0048 (11)0.0018 (10)
C400.0143 (13)0.0127 (13)0.0193 (13)0.0016 (11)0.0018 (11)0.0010 (10)
C410.0176 (16)0.043 (2)0.0298 (16)0.0080 (14)0.0043 (13)0.0031 (14)
C420.0191 (14)0.0117 (13)0.0196 (13)0.0025 (11)0.0014 (11)0.0015 (10)
C430.068 (3)0.0129 (15)0.061 (2)0.0072 (16)0.047 (2)0.0058 (15)
C440.069 (3)0.0175 (16)0.051 (2)0.0002 (17)0.044 (2)0.0074 (15)
C450.0209 (15)0.0115 (13)0.0206 (13)0.0039 (11)0.0010 (11)0.0021 (10)
C460.052 (2)0.0112 (14)0.0396 (18)0.0016 (14)0.0232 (17)0.0018 (13)
C470.051 (2)0.0161 (15)0.0321 (17)0.0023 (15)0.0231 (16)0.0020 (12)
C480.064 (2)0.0159 (15)0.0278 (16)0.0072 (16)0.0163 (16)0.0042 (12)
C490.0224 (15)0.0132 (13)0.0236 (14)0.0003 (11)0.0114 (12)0.0009 (11)
C500.0304 (17)0.0265 (16)0.0240 (15)0.0086 (14)0.0077 (13)0.0042 (12)
C510.053 (2)0.0341 (19)0.0209 (15)0.0047 (17)0.0081 (15)0.0039 (13)
C520.063 (3)0.0246 (17)0.042 (2)0.0129 (17)0.0312 (19)0.0009 (15)
C530.039 (2)0.0263 (18)0.054 (2)0.0192 (15)0.0277 (18)0.0165 (15)
C540.0227 (16)0.0279 (17)0.0304 (16)0.0032 (13)0.0104 (13)0.0052 (13)
C1S0.130 (5)0.112 (5)0.166 (5)0.043 (4)0.069 (4)0.076 (4)
C2S0.204 (6)0.117 (5)0.126 (5)0.071 (5)0.032 (4)0.010 (4)
C3S0.199 (7)0.182 (7)0.157 (5)0.093 (5)0.031 (5)0.007 (5)
C4S0.118 (5)0.122 (5)0.165 (5)0.028 (4)0.052 (4)0.010 (4)
C5S0.134 (5)0.176 (6)0.132 (5)0.029 (5)0.026 (4)0.011 (5)
C6S0.249 (7)0.186 (7)0.151 (5)0.095 (5)0.063 (5)0.027 (5)
Geometric parameters (Å, º) top
Fe1—O51.883 (2)C27—H27A0.9800
Fe1—N42.048 (2)C27—H27B0.9800
Fe1—N22.054 (2)C27—H27C0.9800
Fe1—N12.054 (2)C28—C291.392 (4)
Fe1—N32.056 (2)C28—C331.397 (4)
F1—C501.356 (4)C29—C301.390 (4)
F2—C511.358 (4)C29—H290.9500
F3—C531.355 (4)C30—C311.386 (4)
F4—C541.342 (4)C30—H300.9500
O1—C241.362 (3)C31—C321.388 (4)
O1—C271.436 (3)C32—C331.387 (4)
O2—C311.372 (3)C32—H320.9500
O2—C341.433 (4)C33—H330.9500
O3—C381.371 (3)C34—H34A0.9800
O3—C411.428 (4)C34—H34B0.9800
O4—C451.378 (3)C34—H34C0.9800
O4—C481.422 (3)C35—C361.387 (4)
O5—C491.321 (3)C35—C401.407 (4)
N1—C11.382 (3)C36—C371.392 (4)
N1—C41.384 (4)C36—H360.9500
N2—C61.381 (3)C37—C381.386 (4)
N2—C91.382 (3)C37—H370.9500
N3—C111.385 (3)C38—C391.396 (4)
N3—C141.388 (3)C39—C401.375 (4)
N4—C161.384 (3)C39—H390.9500
N4—C191.388 (3)C40—H400.9500
C1—C201.394 (4)C41—H41A0.9800
C1—C21.438 (4)C41—H41B0.9800
C2—C31.347 (4)C41—H41C0.9800
C2—H20.9500C42—C431.364 (4)
C3—C41.435 (4)C42—C471.374 (4)
C3—H30.9500C43—C441.393 (4)
C4—C51.397 (4)C43—H430.9500
C5—C61.412 (4)C44—C451.361 (4)
C5—C211.490 (4)C44—H440.9500
C6—C71.432 (4)C45—C461.379 (4)
C7—C81.354 (4)C46—C471.387 (4)
C7—H70.9500C46—H460.9500
C8—C91.435 (4)C47—H470.9500
C8—H80.9500C48—H48A0.9800
C9—C101.404 (4)C48—H48B0.9800
C10—C111.400 (4)C48—H48C0.9800
C10—C281.499 (4)C49—C541.389 (4)
C11—C121.439 (4)C49—C501.392 (4)
C12—C131.352 (4)C50—C511.371 (4)
C12—H120.9500C51—C521.364 (5)
C13—C141.443 (3)C52—C531.356 (5)
C13—H130.9500C52—H520.9500
C14—C151.400 (4)C53—C541.380 (4)
C15—C161.405 (3)C1S—C2S1.481 (5)
C15—C351.487 (4)C1S—C6S1.509 (5)
C16—C171.440 (4)C1S—H1S10.9900
C17—C181.354 (4)C1S—H1S20.9900
C17—H170.9500C2S—C3S1.519 (5)
C18—C191.433 (4)C2S—H2S10.9900
C18—H180.9500C2S—H2S20.9900
C19—C201.389 (4)C3S—C4S1.467 (5)
C20—C421.503 (4)C3S—H3S10.9900
C21—C261.394 (4)C3S—H3S20.9900
C21—C221.397 (4)C4S—C5S1.507 (5)
C22—C231.379 (4)C4S—H4S10.9900
C22—H220.9500C4S—H4S20.9900
C23—C241.394 (4)C5S—C6S1.504 (5)
C23—H230.9500C5S—H5S10.9900
C24—C251.392 (4)C5S—H5S20.9900
C25—C261.386 (4)C6S—H6S10.9900
C25—H250.9500C6S—H6S20.9900
C26—H260.9500
O5—Fe1—N4100.32 (9)C29—C30—H30120.1
O5—Fe1—N2100.55 (9)O2—C31—C30125.0 (3)
N4—Fe1—N2159.11 (9)O2—C31—C32115.6 (3)
O5—Fe1—N199.31 (9)C30—C31—C32119.4 (3)
N4—Fe1—N187.60 (9)C33—C32—C31120.5 (3)
N2—Fe1—N188.17 (9)C33—C32—H32119.7
O5—Fe1—N3103.67 (9)C31—C32—H32119.7
N4—Fe1—N388.18 (9)C32—C33—C28120.9 (3)
N2—Fe1—N387.76 (9)C32—C33—H33119.6
N1—Fe1—N3157.02 (9)C28—C33—H33119.6
C24—O1—C27117.5 (2)O2—C34—H34A109.5
C31—O2—C34117.8 (2)O2—C34—H34B109.5
C38—O3—C41117.1 (2)H34A—C34—H34B109.5
C45—O4—C48116.8 (2)O2—C34—H34C109.5
C49—O5—Fe1130.46 (17)H34A—C34—H34C109.5
C1—N1—C4106.0 (2)H34B—C34—H34C109.5
C1—N1—Fe1125.89 (19)C36—C35—C40117.5 (2)
C4—N1—Fe1127.28 (18)C36—C35—C15124.1 (2)
C6—N2—C9106.2 (2)C40—C35—C15118.5 (2)
C6—N2—Fe1124.70 (17)C35—C36—C37121.6 (3)
C9—N2—Fe1123.93 (18)C35—C36—H36119.2
C11—N3—C14106.0 (2)C37—C36—H36119.2
C11—N3—Fe1126.15 (17)C38—C37—C36119.6 (3)
C14—N3—Fe1127.56 (17)C38—C37—H37120.2
C16—N4—C19106.0 (2)C36—C37—H37120.2
C16—N4—Fe1126.28 (17)O3—C38—C37124.3 (3)
C19—N4—Fe1124.43 (18)O3—C38—C39115.8 (2)
N1—C1—C20125.6 (2)C37—C38—C39119.9 (3)
N1—C1—C2109.6 (2)C40—C39—C38119.7 (3)
C20—C1—C2124.7 (2)C40—C39—H39120.2
C3—C2—C1107.2 (2)C38—C39—H39120.2
C3—C2—H2126.4C39—C40—C35121.7 (3)
C1—C2—H2126.4C39—C40—H40119.2
C2—C3—C4107.7 (3)C35—C40—H40119.2
C2—C3—H3126.2O3—C41—H41A109.5
C4—C3—H3126.2O3—C41—H41B109.5
N1—C4—C5125.4 (2)H41A—C41—H41B109.5
N1—C4—C3109.4 (2)O3—C41—H41C109.5
C5—C4—C3124.9 (3)H41A—C41—H41C109.5
C4—C5—C6123.7 (3)H41B—C41—H41C109.5
C4—C5—C21117.7 (2)C43—C42—C47117.4 (3)
C6—C5—C21118.5 (2)C43—C42—C20119.1 (3)
N2—C6—C5126.1 (3)C47—C42—C20123.4 (2)
N2—C6—C7109.5 (2)C42—C43—C44122.3 (3)
C5—C6—C7124.4 (3)C42—C43—H43118.8
C8—C7—C6107.6 (2)C44—C43—H43118.8
C8—C7—H7126.2C45—C44—C43119.5 (3)
C6—C7—H7126.2C45—C44—H44120.3
C7—C8—C9107.1 (2)C43—C44—H44120.3
C7—C8—H8126.5C44—C45—O4124.4 (3)
C9—C8—H8126.5C44—C45—C46119.4 (3)
N2—C9—C10126.0 (2)O4—C45—C46116.2 (2)
N2—C9—C8109.7 (2)C45—C46—C47120.1 (3)
C10—C9—C8124.4 (2)C45—C46—H46120.0
C11—C10—C9123.4 (2)C47—C46—H46120.0
C11—C10—C28118.5 (2)C42—C47—C46121.3 (3)
C9—C10—C28118.1 (2)C42—C47—H47119.4
N3—C11—C10125.7 (2)C46—C47—H47119.4
N3—C11—C12110.0 (2)O4—C48—H48A109.5
C10—C11—C12124.4 (2)O4—C48—H48B109.5
C13—C12—C11107.1 (2)H48A—C48—H48B109.5
C13—C12—H12126.5O4—C48—H48C109.5
C11—C12—H12126.5H48A—C48—H48C109.5
C12—C13—C14107.8 (2)H48B—C48—H48C109.5
C12—C13—H13126.1O5—C49—C54122.5 (3)
C14—C13—H13126.1O5—C49—C50121.9 (3)
N3—C14—C15125.6 (2)C54—C49—C50115.6 (3)
N3—C14—C13109.2 (2)F1—C50—C51119.8 (3)
C15—C14—C13125.2 (2)F1—C50—C49118.5 (3)
C14—C15—C16123.9 (2)C51—C50—C49121.7 (3)
C14—C15—C35119.8 (2)F2—C51—C52120.1 (3)
C16—C15—C35116.3 (2)F2—C51—C50117.8 (3)
N4—C16—C15125.7 (2)C52—C51—C50122.1 (3)
N4—C16—C17109.2 (2)C53—C52—C51116.9 (3)
C15—C16—C17125.1 (2)C53—C52—H52121.5
C18—C17—C16107.9 (3)C51—C52—H52121.5
C18—C17—H17126.1F3—C53—C52119.3 (3)
C16—C17—H17126.1F3—C53—C54118.3 (3)
C17—C18—C19106.9 (2)C52—C53—C54122.4 (3)
C17—C18—H18126.5F4—C54—C53119.8 (3)
C19—C18—H18126.5F4—C54—C49119.0 (3)
N4—C19—C20125.0 (3)C53—C54—C49121.3 (3)
N4—C19—C18110.0 (2)C2S—C1S—C6S113.2 (5)
C20—C19—C18124.9 (2)C2S—C1S—H1S1108.9
C19—C20—C1124.5 (2)C6S—C1S—H1S1108.9
C19—C20—C42118.8 (2)C2S—C1S—H1S2108.9
C1—C20—C42116.7 (2)C6S—C1S—H1S2108.9
C26—C21—C22117.7 (2)H1S1—C1S—H1S2107.8
C26—C21—C5121.5 (2)C1S—C2S—C3S114.6 (4)
C22—C21—C5120.8 (2)C1S—C2S—H2S1108.6
C23—C22—C21121.5 (3)C3S—C2S—H2S1108.6
C23—C22—H22119.3C1S—C2S—H2S2108.6
C21—C22—H22119.3C3S—C2S—H2S2108.6
C22—C23—C24120.1 (2)H2S1—C2S—H2S2107.6
C22—C23—H23120.0C4S—C3S—C2S116.8 (5)
C24—C23—H23120.0C4S—C3S—H3S1108.1
O1—C24—C25124.5 (3)C2S—C3S—H3S1108.1
O1—C24—C23116.1 (2)C4S—C3S—H3S2108.1
C25—C24—C23119.4 (3)C2S—C3S—H3S2108.1
C26—C25—C24119.8 (3)H3S1—C3S—H3S2107.3
C26—C25—H25120.1C3S—C4S—C5S115.6 (4)
C24—C25—H25120.1C3S—C4S—H4S1108.4
C25—C26—C21121.5 (2)C5S—C4S—H4S1108.4
C25—C26—H26119.2C3S—C4S—H4S2108.4
C21—C26—H26119.2C5S—C4S—H4S2108.4
O1—C27—H27A109.5H4S1—C4S—H4S2107.4
O1—C27—H27B109.5C6S—C5S—C4S113.7 (5)
H27A—C27—H27B109.5C6S—C5S—H5S1108.8
O1—C27—H27C109.5C4S—C5S—H5S1108.8
H27A—C27—H27C109.5C6S—C5S—H5S2108.8
H27B—C27—H27C109.5C4S—C5S—H5S2108.8
C29—C28—C33117.8 (2)H5S1—C5S—H5S2107.7
C29—C28—C10120.2 (2)C5S—C6S—C1S115.7 (5)
C33—C28—C10122.1 (2)C5S—C6S—H6S1108.4
C30—C29—C28121.7 (3)C1S—C6S—H6S1108.4
C30—C29—H29119.2C5S—C6S—H6S2108.4
C28—C29—H29119.2C1S—C6S—H6S2108.4
C31—C30—C29119.8 (3)H6S1—C6S—H6S2107.4
C31—C30—H30120.1
N4—Fe1—O5—C4951.2 (3)C4—C5—C21—C2255.8 (4)
N2—Fe1—O5—C49127.9 (3)C6—C5—C21—C22121.9 (3)
N1—Fe1—O5—C4938.0 (3)C26—C21—C22—C230.1 (4)
N3—Fe1—O5—C49141.8 (3)C5—C21—C22—C23179.4 (3)
C4—N1—C1—C20175.2 (3)C21—C22—C23—C240.2 (4)
Fe1—N1—C1—C205.3 (4)C27—O1—C24—C253.4 (4)
C4—N1—C1—C22.2 (3)C27—O1—C24—C23175.4 (3)
Fe1—N1—C1—C2172.12 (18)C22—C23—C24—O1178.9 (3)
N1—C1—C2—C30.4 (3)C22—C23—C24—C250.1 (4)
C20—C1—C2—C3177.1 (3)O1—C24—C25—C26178.5 (3)
C1—C2—C3—C41.6 (3)C23—C24—C25—C260.3 (4)
C1—N1—C4—C5171.7 (3)C24—C25—C26—C210.4 (4)
Fe1—N1—C4—C52.0 (4)C22—C21—C26—C250.2 (4)
C1—N1—C4—C33.2 (3)C5—C21—C26—C25179.6 (3)
Fe1—N1—C4—C3172.89 (18)C11—C10—C28—C2959.9 (3)
C2—C3—C4—N13.0 (3)C9—C10—C28—C29118.3 (3)
C2—C3—C4—C5171.9 (3)C11—C10—C28—C33121.7 (3)
N1—C4—C5—C66.0 (4)C9—C10—C28—C3360.1 (3)
C3—C4—C5—C6179.9 (3)C33—C28—C29—C301.8 (4)
N1—C4—C5—C21171.6 (2)C10—C28—C29—C30176.8 (2)
C3—C4—C5—C212.5 (4)C28—C29—C30—C311.7 (4)
C9—N2—C6—C5179.4 (3)C34—O2—C31—C3011.9 (4)
Fe1—N2—C6—C524.3 (4)C34—O2—C31—C32168.6 (3)
C9—N2—C6—C70.5 (3)C29—C30—C31—O2178.7 (3)
Fe1—N2—C6—C7154.71 (18)C29—C30—C31—C320.8 (4)
C4—C5—C6—N26.0 (4)O2—C31—C32—C33179.4 (3)
C21—C5—C6—N2176.4 (2)C30—C31—C32—C330.1 (4)
C4—C5—C6—C7172.8 (3)C31—C32—C33—C280.3 (4)
C21—C5—C6—C74.8 (4)C29—C28—C33—C321.1 (4)
N2—C6—C7—C80.1 (3)C10—C28—C33—C32177.4 (3)
C5—C6—C7—C8179.1 (2)C14—C15—C35—C3657.4 (4)
C6—C7—C8—C90.3 (3)C16—C15—C35—C36123.9 (3)
C6—N2—C9—C10178.9 (2)C14—C15—C35—C40124.0 (3)
Fe1—N2—C9—C1025.6 (4)C16—C15—C35—C4054.7 (3)
C6—N2—C9—C80.6 (3)C40—C35—C36—C370.1 (4)
Fe1—N2—C9—C8154.79 (17)C15—C35—C36—C37178.6 (2)
C7—C8—C9—N20.6 (3)C35—C36—C37—C380.1 (4)
C7—C8—C9—C10179.0 (2)C41—O3—C38—C3712.9 (4)
N2—C9—C10—C111.7 (4)C41—O3—C38—C39168.8 (2)
C8—C9—C10—C11178.8 (2)C36—C37—C38—O3178.4 (2)
N2—C9—C10—C28179.8 (2)C36—C37—C38—C390.2 (4)
C8—C9—C10—C280.7 (4)O3—C38—C39—C40179.1 (2)
C14—N3—C11—C10178.6 (2)C37—C38—C39—C400.7 (4)
Fe1—N3—C11—C104.6 (4)C38—C39—C40—C350.9 (4)
C14—N3—C11—C121.2 (3)C36—C35—C40—C390.6 (4)
Fe1—N3—C11—C12175.27 (17)C15—C35—C40—C39179.3 (2)
C9—C10—C11—N39.8 (4)C19—C20—C42—C4385.6 (4)
C28—C10—C11—N3168.3 (2)C1—C20—C42—C4391.5 (4)
C9—C10—C11—C12170.4 (2)C19—C20—C42—C4798.7 (4)
C28—C10—C11—C1211.5 (4)C1—C20—C42—C4784.2 (4)
N3—C11—C12—C130.0 (3)C47—C42—C43—C441.2 (6)
C10—C11—C12—C13179.8 (3)C20—C42—C43—C44174.8 (4)
C11—C12—C13—C141.2 (3)C42—C43—C44—C450.3 (7)
C11—N3—C14—C15176.1 (2)C43—C44—C45—O4178.2 (3)
Fe1—N3—C14—C152.2 (4)C43—C44—C45—C461.2 (6)
C11—N3—C14—C132.0 (3)C48—O4—C45—C446.2 (5)
Fe1—N3—C14—C13175.89 (17)C48—O4—C45—C46173.2 (3)
C12—C13—C14—N32.0 (3)C44—C45—C46—C470.6 (5)
C12—C13—C14—C15176.1 (3)O4—C45—C46—C47178.8 (3)
N3—C14—C15—C160.0 (4)C43—C42—C47—C461.8 (5)
C13—C14—C15—C16177.8 (3)C20—C42—C47—C46174.0 (3)
N3—C14—C15—C35178.6 (2)C45—C46—C47—C420.9 (5)
C13—C14—C15—C353.6 (4)Fe1—O5—C49—C5486.9 (3)
C19—N4—C16—C15178.5 (3)Fe1—O5—C49—C5095.1 (3)
Fe1—N4—C16—C1521.6 (4)O5—C49—C50—F11.2 (4)
C19—N4—C16—C171.7 (3)C54—C49—C50—F1179.4 (3)
Fe1—N4—C16—C17158.28 (18)O5—C49—C50—C51176.4 (3)
C14—C15—C16—N410.2 (4)C54—C49—C50—C511.7 (4)
C35—C15—C16—N4168.4 (2)F1—C50—C51—F20.8 (5)
C14—C15—C16—C17169.6 (3)C49—C50—C51—F2176.9 (3)
C35—C15—C16—C1711.8 (4)F1—C50—C51—C52179.9 (3)
N4—C16—C17—C180.6 (3)C49—C50—C51—C522.5 (5)
C15—C16—C17—C18179.5 (3)F2—C51—C52—C53178.2 (3)
C16—C17—C18—C190.7 (3)C50—C51—C52—C531.2 (5)
C16—N4—C19—C20174.4 (3)C51—C52—C53—F3178.6 (3)
Fe1—N4—C19—C2025.2 (4)C51—C52—C53—C540.8 (5)
C16—N4—C19—C182.1 (3)F3—C53—C54—F43.3 (4)
Fe1—N4—C19—C18158.31 (18)C52—C53—C54—F4177.3 (3)
C17—C18—C19—N41.8 (3)F3—C53—C54—C49177.9 (3)
C17—C18—C19—C20174.7 (3)C52—C53—C54—C491.5 (5)
N4—C19—C20—C11.1 (4)O5—C49—C54—F40.5 (4)
C18—C19—C20—C1177.1 (3)C50—C49—C54—F4178.6 (3)
N4—C19—C20—C42178.0 (2)O5—C49—C54—C53178.4 (3)
C18—C19—C20—C426.1 (4)C50—C49—C54—C530.3 (4)
N1—C1—C20—C199.5 (4)C6S—C1S—C2S—C3S44.3 (10)
C2—C1—C20—C19173.4 (3)C1S—C2S—C3S—C4S41.9 (12)
N1—C1—C20—C42167.3 (2)C2S—C3S—C4S—C5S39.7 (12)
C2—C1—C20—C429.7 (4)C3S—C4S—C5S—C6S40.7 (11)
C4—C5—C21—C26124.8 (3)C4S—C5S—C6S—C1S44.7 (11)
C6—C5—C21—C2657.5 (4)C2S—C1S—C6S—C5S47.1 (11)
Selected bond lengths (Å) top
Fe1—O51.883 (2)Fe1—N12.054 (2)
Fe1—N42.048 (2)Fe1—N32.056 (2)
Fe1—N22.054 (2)
Acknowledgements top

The authors wish to thank the National Science Foundation (grant CHE-1213674) and the University of Oklahoma for funds to support this research and to acquire the diffractometer and computers used in this work.

references
References top

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