Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270101003006/gg1037sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270101003006/gg1037Isup2.hkl |
CCDC reference: 164641
For related literature, see: Andersson & Dawson (1991); Benecky et al. (1993); Chung & Van Wart (1992); Egawa et al. (1994); Hoard et al. (1965); Nam, Lim & Oh (2000); Nam, Lim, Moon & Kim (2000); Nam, Lim, Oh, Lee, Woo, Kim & Shin (2000).
To a solution of Fe(TDFPP)Cl (4.0 mg, 0.0042 mmol) in CH2Cl2 (0.5 ml) was added sodium 2-methyl-2-propane thiolate (52 mg, 0.042 mmol) at room temperature. After the reaction mixture was stirred for 3 h and then filtered through a 0.45 filter, methanol (3 ml) was added to the filtered solution. The fitrate was allowed to stand at room temperature for two weeks and crystals of compound (I) were then obtained.
All H atoms except water molecule hydrogen atoms were inserted at calculated positions and treated as riding with isotropic displacement parameters.
Data collection: Kappa-CCD Server Software (Nonius, 1997); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997); data reduction: DENZO-SMN; program(s) used to solve structure: SHELXTL (Sheldrick, 1998); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
[Fe(C44H20F8N4)(CH3O)] | F(000) = 854 |
Mr = 843.3 | Dx = 1.542 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 12.4526 (4) Å | Cell parameters from 11483 reflections |
b = 12.6673 (5) Å | θ = 3.0–25.0° |
c = 12.6426 (5) Å | µ = 0.50 mm−1 |
β = 114.39 (3)° | T = 150 K |
V = 1816.31 (12) Å3 | Plate, dark brown |
Z = 2 | 0.18 × 0.18 × 0.08 mm |
Kappa-CCD diffractometer | 3198 independent reflections |
Radiation source: fine-focus sealed tube | 2188 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.08 |
Detector resolution: 9 pixels mm-1 | θmax = 25.0°, θmin = 3.0° |
ϕ scans ω scans with κ offsets | h = −14→14 |
Absorption correction: multi-scan (DENZO-SMN; Otwinowski & Minor, 1997) | k = −15→15 |
Tmin = 0.915, Tmax = 0.961 | l = −15→13 |
11483 measured reflections |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.079 | H-atom parameters constrained |
wR(F2) = 0.207 | w = 1/[σ2(Fo2) + (0.0657P)2 + 4.6789P] where P = (Fo2 + 2Fc2)/3 |
S = 1.07 | (Δ/σ)max = 0.001 |
3198 reflections | Δρmax = 0.44 e Å−3 |
251 parameters | Δρmin = −0.48 e Å−3 |
16 restraints | Extinction correction: SHELXL97 (Sheldrick, 1998), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.017 (3) |
[Fe(C44H20F8N4)(CH3O)] | V = 1816.31 (12) Å3 |
Mr = 843.3 | Z = 2 |
Monoclinic, P21/n | Mo Kα radiation |
a = 12.4526 (4) Å | µ = 0.50 mm−1 |
b = 12.6673 (5) Å | T = 150 K |
c = 12.6426 (5) Å | 0.18 × 0.18 × 0.08 mm |
β = 114.39 (3)° |
Kappa-CCD diffractometer | 3198 independent reflections |
Absorption correction: multi-scan (DENZO-SMN; Otwinowski & Minor, 1997) | 2188 reflections with I > 2σ(I) |
Tmin = 0.915, Tmax = 0.961 | Rint = 0.08 |
11483 measured reflections |
R[F2 > 2σ(F2)] = 0.079 | 16 restraints |
wR(F2) = 0.207 | H-atom parameters constrained |
S = 1.07 | Δρmax = 0.44 e Å−3 |
3198 reflections | Δρmin = −0.48 e Å−3 |
251 parameters |
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. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Fe1 | 0.01072 (12) | 0.01855 (11) | 0.03678 (11) | 0.0329 (4) | 0.50 |
N1 | −0.0667 (3) | 0.1312 (3) | −0.0954 (3) | 0.0353 (10) | |
N2 | 0.1636 (3) | 0.0414 (3) | 0.0154 (3) | 0.0347 (10) | |
C1 | 0.1154 (4) | 0.2070 (4) | −0.0976 (4) | 0.0363 (11) | |
C2 | −0.2776 (4) | 0.1028 (4) | −0.1423 (4) | 0.0367 (12) | |
C3 | 0.1940 (4) | 0.1285 (4) | −0.0321 (4) | 0.0351 (11) | |
C4 | 0.3189 (4) | 0.1278 (4) | −0.0023 (4) | 0.0383 (12) | |
H4A | 0.3616 | 0.1777 | −0.0260 | 0.046* | |
C5 | 0.3637 (4) | 0.0418 (4) | 0.0663 (4) | 0.0394 (12) | |
H5A | 0.4441 | 0.0208 | 0.1004 | 0.047* | |
C6 | 0.2669 (4) | −0.0115 (4) | 0.0776 (4) | 0.0345 (11) | |
C7 | −0.1840 (4) | 0.1588 (4) | −0.1486 (4) | 0.0374 (12) | |
C8 | −0.1959 (5) | 0.2571 (4) | −0.2114 (4) | 0.0412 (12) | |
H8A | −0.2671 | 0.2937 | −0.2550 | 0.049* | |
C9 | −0.0873 (5) | 0.2862 (4) | −0.1964 (4) | 0.0414 (12) | |
H9A | −0.0674 | 0.3482 | −0.2266 | 0.050* | |
C10 | −0.0064 (4) | 0.2077 (4) | −0.1267 (4) | 0.0369 (11) | |
F1 | 0.0696 (3) | 0.2351 (3) | −0.3330 (3) | 0.0594 (9) | |
F2 | 0.2682 (3) | 0.3636 (3) | 0.0456 (3) | 0.0692 (11) | |
C11 | 0.1632 (4) | 0.2964 (4) | −0.1427 (4) | 0.0404 (12) | |
C12 | 0.1373 (5) | 0.3101 (4) | −0.2590 (5) | 0.0452 (13) | |
C13 | 0.1764 (5) | 0.3938 (5) | −0.3030 (5) | 0.0544 (16) | |
H13A | 0.1550 | 0.4003 | −0.3841 | 0.065* | |
C14 | 0.2469 (6) | 0.4671 (5) | −0.2270 (6) | 0.0609 (17) | |
H14A | 0.2740 | 0.5258 | −0.2560 | 0.073* | |
C15 | 0.2802 (6) | 0.4579 (5) | −0.1079 (6) | 0.0640 (18) | |
H15A | 0.3303 | 0.5085 | −0.0551 | 0.077* | |
C16 | 0.2374 (5) | 0.3723 (4) | −0.0697 (5) | 0.0508 (14) | |
F3 | −0.3936 (5) | 0.0517 (4) | −0.3786 (5) | 0.0524 (16)* | 0.691 (10) |
F4 | −0.4216 (4) | 0.2219 (4) | −0.0602 (3) | 0.0458 (15)* | 0.691 (10) |
C21 | −0.4051 (4) | 0.1360 (4) | −0.2182 (5) | 0.040 (3)* | 0.691 (10) |
C22 | −0.4550 (6) | 0.1090 (3) | −0.3352 (5) | 0.053 (5)* | 0.691 (10) |
C23 | −0.5689 (6) | 0.1415 (4) | −0.4058 (3) | 0.049 (4)* | 0.691 (10) |
H23 | −0.6031 | 0.1230 | −0.4857 | 0.059* | 0.691 (10) |
C24 | −0.6328 (4) | 0.2012 (5) | −0.3594 (4) | 0.045 (2)* | 0.691 (10) |
H24 | −0.7106 | 0.2234 | −0.4077 | 0.054* | 0.691 (10) |
C25 | −0.5828 (4) | 0.2283 (4) | −0.2425 (4) | 0.0392 (19)* | 0.691 (10) |
H25 | −0.6264 | 0.2690 | −0.2108 | 0.047* | 0.691 (10) |
C26 | −0.4689 (4) | 0.1957 (4) | −0.1718 (3) | 0.0350 (17)* | 0.691 (10) |
F3* | −0.4155 (10) | 0.0286 (7) | −0.3637 (10) | 0.043 (3)* | 0.309 (10) |
F4* | −0.3854 (10) | 0.2759 (10) | −0.0730 (8) | 0.061 (4)* | 0.309 (10) |
C21* | −0.3967 (7) | 0.1500 (8) | −0.2172 (9) | 0.032 (7)* | 0.309 (10) |
C22* | −0.4597 (11) | 0.1094 (6) | −0.3279 (10) | 0.019 (6)* | 0.309 (10) |
C23* | −0.5679 (11) | 0.1532 (9) | −0.3994 (7) | 0.044 (9)* | 0.309 (10) |
H23* | −0.6110 | 0.1255 | −0.4750 | 0.053* | 0.309 (10) |
C24* | −0.6129 (10) | 0.2375 (11) | −0.3602 (10) | 0.057 (6)* | 0.309 (10) |
H24* | −0.6868 | 0.2675 | −0.4090 | 0.068* | 0.309 (10) |
C25* | −0.5499 (11) | 0.2781 (10) | −0.2494 (10) | 0.069 (6)* | 0.309 (10) |
H25* | −0.5807 | 0.3358 | −0.2226 | 0.083* | 0.309 (10) |
C26* | −0.4418 (10) | 0.2344 (9) | −0.1780 (7) | 0.045 (5)* | 0.309 (10) |
O1 | 0.0410 (5) | 0.0851 (4) | 0.1708 (4) | 0.0226 (12) | 0.50 |
C27 | 0.0773 (9) | 0.0412 (8) | 0.2826 (8) | 0.037 (2) | 0.50 |
H27A | 0.0668 | 0.0934 | 0.3348 | 0.055* | 0.50 |
H27B | 0.1606 | 0.0212 | 0.3121 | 0.055* | 0.50 |
H27C | 0.0297 | −0.0214 | 0.2788 | 0.055* | 0.50 |
U11 | U22 | U33 | U12 | U13 | U23 | |
Fe1 | 0.0303 (8) | 0.0368 (9) | 0.0290 (8) | 0.0065 (6) | 0.0097 (7) | 0.0035 (6) |
N1 | 0.034 (2) | 0.038 (2) | 0.033 (2) | 0.0074 (18) | 0.0133 (19) | 0.0013 (18) |
N2 | 0.034 (2) | 0.036 (2) | 0.031 (2) | 0.0045 (18) | 0.0101 (19) | 0.0038 (17) |
C1 | 0.042 (3) | 0.037 (3) | 0.029 (3) | 0.003 (2) | 0.014 (2) | −0.001 (2) |
C2 | 0.036 (3) | 0.042 (3) | 0.030 (3) | 0.009 (2) | 0.011 (2) | 0.001 (2) |
C3 | 0.038 (3) | 0.037 (3) | 0.029 (3) | −0.001 (2) | 0.013 (2) | 0.001 (2) |
C4 | 0.040 (3) | 0.037 (3) | 0.037 (3) | 0.000 (2) | 0.015 (2) | −0.001 (2) |
C5 | 0.030 (3) | 0.045 (3) | 0.038 (3) | 0.000 (2) | 0.009 (2) | −0.004 (2) |
C6 | 0.033 (3) | 0.041 (3) | 0.028 (2) | 0.002 (2) | 0.011 (2) | −0.004 (2) |
C7 | 0.040 (3) | 0.042 (3) | 0.030 (3) | 0.010 (2) | 0.013 (2) | 0.003 (2) |
C8 | 0.042 (3) | 0.047 (3) | 0.034 (3) | 0.012 (2) | 0.015 (2) | 0.010 (2) |
C9 | 0.050 (3) | 0.040 (3) | 0.036 (3) | 0.008 (2) | 0.020 (3) | 0.012 (2) |
C10 | 0.042 (3) | 0.040 (3) | 0.032 (3) | 0.006 (2) | 0.018 (2) | 0.006 (2) |
F1 | 0.059 (2) | 0.079 (2) | 0.0378 (18) | −0.0013 (18) | 0.0179 (16) | 0.0048 (17) |
F2 | 0.092 (3) | 0.062 (2) | 0.055 (2) | −0.016 (2) | 0.031 (2) | −0.0059 (17) |
C11 | 0.038 (3) | 0.042 (3) | 0.042 (3) | 0.005 (2) | 0.017 (2) | 0.008 (2) |
C12 | 0.038 (3) | 0.051 (3) | 0.050 (3) | 0.011 (3) | 0.022 (3) | 0.014 (3) |
C13 | 0.049 (3) | 0.065 (4) | 0.056 (4) | 0.018 (3) | 0.028 (3) | 0.029 (3) |
C14 | 0.058 (4) | 0.049 (4) | 0.085 (5) | 0.013 (3) | 0.039 (4) | 0.023 (4) |
C15 | 0.068 (4) | 0.046 (4) | 0.084 (5) | −0.002 (3) | 0.037 (4) | 0.005 (3) |
C16 | 0.057 (4) | 0.046 (3) | 0.055 (4) | 0.003 (3) | 0.028 (3) | 0.003 (3) |
O1 | 0.027 (3) | 0.025 (3) | 0.012 (3) | 0.006 (2) | 0.005 (2) | 0.001 (2) |
C27 | 0.051 (6) | 0.034 (5) | 0.024 (5) | 0.009 (5) | 0.014 (5) | 0.002 (4) |
Fe1—Fe1i | 0.976 (3) | C7—C8 | 1.451 (7) |
Fe1—O1 | 1.788 (5) | C8—C9 | 1.337 (7) |
Fe1—N2 | 2.051 (4) | C9—C10 | 1.431 (7) |
Fe1—N1i | 2.051 (4) | F1—C12 | 1.356 (7) |
Fe1—N1 | 2.104 (4) | F2—C16 | 1.350 (7) |
Fe1—N2i | 2.131 (4) | C11—C12 | 1.381 (7) |
N1—C7 | 1.378 (6) | C11—C16 | 1.387 (8) |
N1—C10 | 1.380 (6) | C12—C13 | 1.376 (8) |
N1—Fe1i | 2.051 (4) | C13—C14 | 1.364 (9) |
N2—C6 | 1.374 (6) | C14—C15 | 1.391 (9) |
N2—C3 | 1.382 (6) | C15—C16 | 1.381 (8) |
N2—Fe1i | 2.131 (4) | F3—C22 | 1.327 (3) |
C1—C3 | 1.401 (7) | F4—C26 | 1.327 (3) |
C1—C10 | 1.405 (7) | C21—C22 | 1.3900 |
C1—C11 | 1.498 (7) | C21—C26 | 1.3900 |
C2—C6i | 1.390 (7) | C22—C23 | 1.3900 |
C2—C7 | 1.395 (7) | C23—C24 | 1.3900 |
C2—C21* | 1.515 (9) | C24—C25 | 1.3900 |
C2—C21 | 1.536 (6) | C25—C26 | 1.3900 |
C3—C4 | 1.441 (7) | F3*—C22* | 1.328 (3) |
C4—C5 | 1.361 (7) | F4*—C26* | 1.327 (3) |
C5—C6 | 1.439 (7) | O1—C27 | 1.409 (10) |
C6—C2i | 1.390 (7) | ||
Fe1i—Fe1—O1 | 176.5 (3) | C5—C4—C3 | 106.6 (4) |
Fe1i—Fe1—N2 | 81.1 (2) | C4—C5—C6 | 107.4 (4) |
O1—Fe1—N2 | 102.4 (2) | N2—C6—C2i | 125.6 (4) |
Fe1i—Fe1—N1i | 79.5 (2) | N2—C6—C5 | 109.8 (4) |
O1—Fe1—N1i | 100.8 (2) | C2i—C6—C5 | 124.6 (4) |
N2—Fe1—N1i | 89.02 (16) | N1—C7—C2 | 125.9 (4) |
Fe1i—Fe1—N1 | 73.42 (19) | N1—C7—C8 | 109.4 (4) |
O1—Fe1—N1 | 106.3 (2) | C2—C7—C8 | 124.7 (4) |
N2—Fe1—N1 | 86.86 (16) | C9—C8—C7 | 106.9 (4) |
N1i—Fe1—N1 | 152.88 (8) | C8—C9—C10 | 108.0 (5) |
Fe1i—Fe1—N2i | 71.96 (19) | N1—C10—C1 | 125.2 (4) |
O1—Fe1—N2i | 104.5 (2) | N1—C10—C9 | 109.7 (4) |
N2—Fe1—N2i | 153.11 (8) | C1—C10—C9 | 125.1 (5) |
N1i—Fe1—N2i | 86.14 (16) | C12—C11—C16 | 114.8 (5) |
N1—Fe1—N2i | 85.53 (16) | C12—C11—C1 | 123.1 (5) |
C7—N1—C10 | 106.0 (4) | C16—C11—C1 | 122.1 (5) |
C7—N1—Fe1i | 123.0 (3) | F1—C12—C13 | 118.9 (5) |
C10—N1—Fe1i | 127.5 (3) | F1—C12—C11 | 116.9 (5) |
C7—N1—Fe1 | 127.3 (3) | C13—C12—C11 | 124.2 (6) |
C10—N1—Fe1 | 125.4 (3) | C14—C13—C12 | 118.1 (6) |
Fe1i—N1—Fe1 | 27.12 (8) | C13—C14—C15 | 121.5 (6) |
C6—N2—C3 | 106.2 (4) | C16—C15—C14 | 117.4 (6) |
C6—N2—Fe1 | 123.8 (3) | F2—C16—C15 | 117.6 (6) |
C3—N2—Fe1 | 127.3 (3) | F2—C16—C11 | 118.5 (5) |
C6—N2—Fe1i | 126.6 (3) | C15—C16—C11 | 123.9 (6) |
C3—N2—Fe1i | 125.2 (3) | C22—C21—C2 | 119.4 (4) |
Fe1—N2—Fe1i | 26.89 (8) | C26—C21—C2 | 120.6 (4) |
C3—C1—C10 | 125.1 (5) | F3—C22—C23 | 120.4 (5) |
C3—C1—C11 | 118.1 (4) | F3—C22—C21 | 119.6 (5) |
C10—C1—C11 | 116.8 (4) | F4—C26—C25 | 119.7 (4) |
C6i—C2—C7 | 125.3 (4) | F4—C26—C21 | 120.3 (4) |
C6i—C2—C21* | 121.8 (5) | C22*—C21*—C2 | 118.9 (8) |
C7—C2—C21* | 112.9 (5) | C26*—C21*—C2 | 121.0 (8) |
C6i—C2—C21 | 114.8 (4) | F3*—C22*—C21* | 119.2 (10) |
C7—C2—C21 | 119.8 (4) | F3*—C22*—C23* | 120.8 (10) |
C21*—C2—C21 | 7.6 (4) | F4*—C26*—C25* | 117.5 (10) |
N2—C3—C1 | 125.0 (4) | F4*—C26*—C21* | 122.5 (10) |
N2—C3—C4 | 110.0 (4) | C27—O1—Fe1 | 128.3 (5) |
C1—C3—C4 | 125.0 (4) | ||
Fe1i—Fe1—N1—C7 | 90.9 (4) | C7—C8—C9—C10 | 0.9 (6) |
O1—Fe1—N1—C7 | −85.5 (4) | C7—N1—C10—C1 | −175.8 (5) |
N2—Fe1—N1—C7 | 172.6 (4) | Fe1i—N1—C10—C1 | −16.8 (7) |
N1i—Fe1—N1—C7 | 90.9 (4) | Fe1—N1—C10—C1 | 17.0 (7) |
N2i—Fe1—N1—C7 | 18.4 (4) | C7—N1—C10—C9 | 2.5 (5) |
Fe1i—Fe1—N1—C10 | −104.6 (4) | Fe1i—N1—C10—C9 | 161.5 (3) |
O1—Fe1—N1—C10 | 79.1 (4) | Fe1—N1—C10—C9 | −164.7 (3) |
N2—Fe1—N1—C10 | −22.9 (4) | C3—C1—C10—N1 | −0.1 (8) |
N1i—Fe1—N1—C10 | −104.6 (4) | C11—C1—C10—N1 | 178.6 (4) |
N2i—Fe1—N1—C10 | −177.1 (4) | C3—C1—C10—C9 | −178.1 (5) |
O1—Fe1—N1—Fe1i | −176.4 (3) | C11—C1—C10—C9 | 0.6 (7) |
N2—Fe1—N1—Fe1i | 81.69 (19) | C8—C9—C10—N1 | −2.2 (6) |
N2i—Fe1—N1—Fe1i | −72.50 (19) | C8—C9—C10—C1 | 176.1 (5) |
Fe1i—Fe1—N2—C6 | −105.4 (4) | C3—C1—C11—C12 | 110.7 (6) |
O1—Fe1—N2—C6 | 74.8 (4) | C10—C1—C11—C12 | −68.1 (6) |
N1i—Fe1—N2—C6 | −26.0 (4) | C3—C1—C11—C16 | −69.5 (7) |
N1—Fe1—N2—C6 | −179.1 (4) | C10—C1—C11—C16 | 111.8 (6) |
N2i—Fe1—N2—C6 | −105.4 (4) | C16—C11—C12—F1 | 177.0 (5) |
Fe1i—Fe1—N2—C3 | 95.8 (4) | C1—C11—C12—F1 | −3.1 (7) |
O1—Fe1—N2—C3 | −83.9 (4) | C16—C11—C12—C13 | −2.4 (8) |
N1i—Fe1—N2—C3 | 175.3 (4) | C1—C11—C12—C13 | 177.4 (5) |
N1—Fe1—N2—C3 | 22.1 (4) | F1—C12—C13—C14 | −178.4 (5) |
N2i—Fe1—N2—C3 | 95.8 (4) | C11—C12—C13—C14 | 1.1 (8) |
O1—Fe1—N2—Fe1i | −179.7 (3) | C12—C13—C14—C15 | 0.8 (9) |
N1i—Fe1—N2—Fe1i | 79.48 (19) | C13—C14—C15—C16 | −1.0 (9) |
N1—Fe1—N2—Fe1i | −73.70 (19) | C14—C15—C16—F2 | −179.2 (5) |
C6—N2—C3—C1 | −176.7 (5) | C14—C15—C16—C11 | −0.5 (9) |
Fe1—N2—C3—C1 | −15.0 (7) | C12—C11—C16—F2 | −179.2 (5) |
Fe1i—N2—C3—C1 | 18.5 (7) | C1—C11—C16—F2 | 1.0 (8) |
C6—N2—C3—C4 | 2.1 (5) | C12—C11—C16—C15 | 2.2 (8) |
Fe1—N2—C3—C4 | 163.8 (3) | C1—C11—C16—C15 | −177.7 (5) |
Fe1i—N2—C3—C4 | −162.7 (3) | C6i—C2—C21—C22 | −97.8 (4) |
C10—C1—C3—N2 | −1.4 (8) | C7—C2—C21—C22 | 77.7 (5) |
C11—C1—C3—N2 | 179.9 (4) | C6i—C2—C21—C26 | 84.3 (5) |
C10—C1—C3—C4 | 180.0 (5) | C7—C2—C21—C26 | −100.1 (5) |
C11—C1—C3—C4 | 1.3 (7) | C21*—C2—C21—C26 | −75 (4) |
N2—C3—C4—C5 | −1.9 (5) | C26—C21—C22—F3 | −179.7 (3) |
C1—C3—C4—C5 | 176.9 (5) | C2—C21—C22—F3 | 2.4 (4) |
C3—C4—C5—C6 | 0.8 (5) | C2—C21—C22—C23 | −177.9 (4) |
C3—N2—C6—C2i | 178.2 (4) | F3—C22—C23—C24 | 179.7 (3) |
Fe1—N2—C6—C2i | 15.7 (7) | C24—C25—C26—F4 | 179.9 (3) |
Fe1i—N2—C6—C2i | −17.2 (7) | C22—C21—C26—F4 | −179.9 (3) |
C3—N2—C6—C5 | −1.6 (5) | C2—C21—C26—F4 | −2.1 (4) |
Fe1—N2—C6—C5 | −164.1 (3) | C2—C21—C26—C25 | 177.8 (4) |
Fe1i—N2—C6—C5 | 163.0 (3) | C6i—C2—C21*—C22* | −82.8 (7) |
C4—C5—C6—N2 | 0.4 (6) | C7—C2—C21*—C22* | 95.7 (6) |
C4—C5—C6—C2i | −179.4 (5) | C21—C2—C21*—C22* | −61 (4) |
C10—N1—C7—C2 | 179.0 (5) | C6i—C2—C21*—C26* | 98.8 (7) |
Fe1i—N1—C7—C2 | 18.9 (7) | C7—C2—C21*—C26* | −82.6 (7) |
Fe1—N1—C7—C2 | −14.0 (7) | C26*—C21*—C22*—F3* | −179.7 (3) |
C10—N1—C7—C8 | −1.9 (5) | C2—C21*—C22*—F3* | 1.9 (7) |
Fe1i—N1—C7—C8 | −162.1 (3) | C2—C21*—C22*—C23* | −178.4 (7) |
Fe1—N1—C7—C8 | 165.0 (3) | F3*—C22*—C23*—C24* | 179.7 (3) |
C6i—C2—C7—N1 | 2.4 (8) | C24*—C25*—C26*—F4* | −179.8 (3) |
C21*—C2—C7—N1 | −176.1 (6) | C22*—C21*—C26*—F4* | 179.8 (3) |
C21—C2—C7—N1 | −172.6 (4) | C2—C21*—C26*—F4* | −1.9 (8) |
C6i—C2—C7—C8 | −176.5 (5) | C2—C21*—C26*—C25* | 178.3 (8) |
C21*—C2—C7—C8 | 5.0 (8) | N2—Fe1—O1—C27 | −99.4 (7) |
C21—C2—C7—C8 | 8.5 (7) | N1i—Fe1—O1—C27 | −8.0 (7) |
N1—C7—C8—C9 | 0.6 (6) | N1—Fe1—O1—C27 | 170.3 (7) |
C2—C7—C8—C9 | 179.7 (5) | N2i—Fe1—O1—C27 | 80.7 (7) |
Symmetry code: (i) −x, −y, −z. |
Experimental details
Crystal data | |
Chemical formula | [Fe(C44H20F8N4)(CH3O)] |
Mr | 843.3 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 150 |
a, b, c (Å) | 12.4526 (4), 12.6673 (5), 12.6426 (5) |
β (°) | 114.39 (3) |
V (Å3) | 1816.31 (12) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.50 |
Crystal size (mm) | 0.18 × 0.18 × 0.08 |
Data collection | |
Diffractometer | Kappa-CCD diffractometer |
Absorption correction | Multi-scan (DENZO-SMN; Otwinowski & Minor, 1997) |
Tmin, Tmax | 0.915, 0.961 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 11483, 3198, 2188 |
Rint | 0.08 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.079, 0.207, 1.07 |
No. of reflections | 3198 |
No. of parameters | 251 |
No. of restraints | 16 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.44, −0.48 |
Computer programs: Kappa-CCD Server Software (Nonius, 1997), DENZO-SMN (Otwinowski & Minor, 1997), DENZO-SMN, SHELXTL (Sheldrick, 1998), SHELXTL.
Fe1—O1 | 1.788 (5) | Fe1—N1 | 2.104 (4) |
Fe1—N2 | 2.051 (4) | Fe1—N2i | 2.131 (4) |
Fe1—N1i | 2.051 (4) | O1—C27 | 1.409 (10) |
O1—Fe1—N2 | 102.4 (2) | O1—Fe1—N2i | 104.5 (2) |
O1—Fe1—N1i | 100.8 (2) | N2—Fe1—N2i | 153.11 (8) |
N2—Fe1—N1i | 89.02 (16) | N1i—Fe1—N2i | 86.14 (16) |
O1—Fe1—N1 | 106.3 (2) | N1—Fe1—N2i | 85.53 (16) |
N2—Fe1—N1 | 86.86 (16) | C27—O1—Fe1 | 128.3 (5) |
N1i—Fe1—N1 | 152.88 (8) | ||
C10—C1—C11—C12 | −68.1 (6) | C7—C2—C21—C22 | 77.7 (5) |
Symmetry code: (i) −x, −y, −z. |
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The active site of heme-dependent enzymes is composed of an iron(III) ion coordinated in the equatorial plane to the four N atoms of protoporphyrin IX and two possible coordination sites of the metal ion in axial positions. The axial sites of electron-transfer enzymes are occupied by two amino acid residues while only one aminoacid is coordinated to the metal for peroxidase, catalase, and P-450 monooxygenase. The latter enzymes can have one labile position for coordination of substrates or oxidants (Andersson & Dawson, 1991). The most important difference among the various heme-dependent enzymes is the nature of their axial ligands. The coordinated atom in peroxidase, catalase and P-450 is the N of histidine (Chung & Van Wart, 1992), O- of tyrosine (Chung & Van Wart, 1992; Benecky et al., 1993), and S- of cysteine (Egawa et al., 1994), respectively. The specific chemical property of each enzyme may be due to its axial ligand. We have elucidated that the cysteinate ligand of P-450 plays an important role in the catalytic cycle of P-450. Also, we recently observed that the reactive oxygenating intermediates of iron(III) porphyrin complexes as model compounds of P-450 are altered by anionic axial ligands (Nam, Lim, Oh et al., 2000; Nam, Lim & Oh et al., 2000; Nam, Lim, Moon & Kim et al., 2000). During the study of the anionic acid ligand effect, we obtained the crystal of an iron(III) porphyrin complex with a methoxy ligand in the axial position. We now report the structure of an electron-deficient iron porphyrin complex, Fe(TDFPP)(OCH3) [TDFPP = meso-tetrakis(2,6-diflorophenyl)porphyrinato dianion], (I). \sch
In space group P21/n with Z = 2, the molecules lie on inversion centers as might be expected for some symmetrically substituted square-planar molecules. In the case of (I) the basic geometry of the molecule is square-pyramidal and the Fe atom lies 0.485 (1) Å out of the plane of the four N atoms to which it is coordinated and from the inversion center at the origin of the unit cell. The Fe atom (and the coordinated –OCH3 ligand) is thus disordered over two sites (50:50) by the inversion symmetry. There is additional conformational disorder in one of the substituted phenyl rings which is disordered over two sites with occupancies in ratio 0.69:0.31. Difluorophenyl rings are tilted from the porphyrinato plane with torsional angles of -68.1 (6) and 77.7 (5)° for C10—C1—C11—C12 and C7—C2—C21—C22, respectively. The Fe—N bond lengths of 2.051 (4) and 2.104 (4) Å are longer than those of low-spin complexes (average 1.986 Å). The –OCH3 group is axially coordinated to the Fe atom with angles of 106.3 (2) and 102.4 (2)° for O1—Fe1—N1 and O1—Fe1—N2, respectively. The Fe1—O1 distance is 1.788 (5) Å which is a little shorter than that of the methoxyiron(III)mesoporphyrin-IX complex (Fe—O 1.842 Å) (Hoard et al., 1965).