Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270103028051/ob1150sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270103028051/ob1150Isup2.hkl |
CCDC reference: 233107
All reactions were carried out in a dry box filled with nitrogen gas. Solvents were purified and reagents were used without purification. The title complex was synthesized from the reduction of (F20TPP)FeCl (23.5 mmol, 0.025 g) with mercury-activated zinc powder in benzene (25 ml) at room temperature for 3 h (Landrum et al., 1980). The resulting red solution was filtered to remove residual Zn(Hg) and ZnCl2, and evaporated to one-third of its volume, at which point heptane (8 ml) was added and the precipitates were filtered off. Crystals of (I) suitable for X-ray analysis were obtained by slow evaporation of the benzene solution. The complex was assigned by NMR in non-coordinating solvent (C6D6), δpyrr, 5.1 p.p.m. (Song & Goff, 1994).
H atoms were postioned geometrically and constrained to ride on their attached atoms [Uiso(H) = 1.2Ueq(parent atom)]. The largest residuals in the final difference map were 0.81 Å from atom F22 (Δρmax) and 0.57 Å from the Fe atom (Δρmin).
Data collection: Collect (Hooft, 1998); cell refinement: HKL SCALEPACK (Otwinowski & Minor, 1997); data reduction: HKL DENZO (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).
[Fe(C44H8F20N4)]·2C6H6 | F(000) = 2360 |
Mr = 1184.61 | Dx = 1.629 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2yc | Cell parameters from 10744 reflections |
a = 34.136 (7) Å | θ = 2.9–27.5° |
b = 6.4633 (13) Å | µ = 0.44 mm−1 |
c = 26.356 (5) Å | T = 190 K |
β = 123.85 (3)° | Block, dark purple |
V = 4829 (2) Å3 | 0.35 × 0.2 × 0.08 mm |
Z = 4 |
Nonius KappaCCD area-detector diffractometer | Rint = 0.025 |
ϕ and ω scans | θmax = 27.5°, θmin = 3.2° |
19916 measured reflections | h = 0→44 |
5520 independent reflections | k = −8→8 |
4550 reflections with I > 2σ(I) | l = −34→28 |
Refinement on F2 | 2 restraints |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.037 | w = 1/[σ2(Fo2) + (0.0586P)2 + 3.8531P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.109 | (Δ/σ)max < 0.001 |
S = 1.03 | Δρmax = 0.33 e Å−3 |
5520 reflections | Δρmin = −0.41 e Å−3 |
366 parameters |
[Fe(C44H8F20N4)]·2C6H6 | V = 4829 (2) Å3 |
Mr = 1184.61 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 34.136 (7) Å | µ = 0.44 mm−1 |
b = 6.4633 (13) Å | T = 190 K |
c = 26.356 (5) Å | 0.35 × 0.2 × 0.08 mm |
β = 123.85 (3)° |
Nonius KappaCCD area-detector diffractometer | 4550 reflections with I > 2σ(I) |
19916 measured reflections | Rint = 0.025 |
5520 independent reflections |
R[F2 > 2σ(F2)] = 0.037 | 2 restraints |
wR(F2) = 0.109 | H-atom parameters constrained |
S = 1.03 | Δρmax = 0.33 e Å−3 |
5520 reflections | Δρmin = −0.41 e Å−3 |
366 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. |
x | y | z | Uiso*/Ueq | ||
Fe | 0 | 0 | 0 | 0.02420 (10) | |
N1 | 0.01937 (4) | −0.01995 (19) | 0.08670 (6) | 0.0273 (3) | |
C2 | −0.00877 (6) | 0.0045 (3) | 0.10843 (7) | 0.0345 (4) | |
C3 | 0.01782 (7) | −0.0311 (4) | 0.17309 (8) | 0.0482 (5) | |
H3 | 0.0063 | −0.0252 | 0.1986 | 0.058* | |
C4 | 0.06238 (6) | −0.0747 (4) | 0.19074 (7) | 0.0449 (4) | |
H4 | 0.0882 | −0.1047 | 0.2311 | 0.054* | |
C5 | 0.06331 (5) | −0.0670 (3) | 0.13704 (7) | 0.0308 (3) | |
C6 | 0.10333 (5) | −0.1020 (3) | 0.13659 (7) | 0.0304 (3) | |
C7 | 0.10385 (5) | −0.1042 (3) | 0.08445 (7) | 0.0319 (3) | |
C8 | 0.14466 (6) | −0.1519 (4) | 0.08387 (8) | 0.0474 (5) | |
H8 | 0.1753 | −0.184 | 0.1183 | 0.057* | |
C9 | 0.13142 (6) | −0.1427 (4) | 0.02539 (8) | 0.0502 (5) | |
H9 | 0.1508 | −0.1682 | 0.0106 | 0.06* | |
C10 | 0.08243 (6) | −0.0868 (3) | −0.01037 (7) | 0.0358 (4) | |
N11 | 0.06568 (4) | −0.0650 (2) | 0.02619 (6) | 0.0282 (3) | |
C12 | 0.05614 (6) | −0.0580 (3) | −0.07317 (7) | 0.0381 (4) | |
C21 | 0.08086 (6) | −0.0885 (4) | −0.10514 (8) | 0.0502 (5) | |
C22 | 0.07466 (9) | −0.2636 (5) | −0.13798 (10) | 0.0678 (7) | |
C23 | 0.09796 (12) | −0.2958 (6) | −0.16696 (12) | 0.0916 (11) | |
C24 | 0.12791 (12) | −0.1474 (7) | −0.16325 (14) | 0.0986 (13) | |
C25 | 0.13455 (9) | 0.0272 (6) | −0.13180 (14) | 0.0894 (12) | |
C26 | 0.11133 (8) | 0.0567 (5) | −0.10243 (11) | 0.0655 (7) | |
F22 | 0.04554 (7) | −0.4116 (3) | −0.14257 (8) | 0.0922 (4) | |
F23 | 0.09057 (10) | −0.4717 (4) | −0.19833 (11) | 0.1415 (10) | |
F24 | 0.15011 (7) | −0.1739 (4) | −0.19120 (9) | 0.1448 (11) | |
F25 | 0.16372 (7) | 0.1740 (4) | −0.12862 (11) | 0.1327 (9) | |
F26 | 0.11927 (6) | 0.2322 (3) | −0.07151 (8) | 0.0875 (5) | |
C31 | 0.14881 (5) | −0.1391 (3) | 0.19671 (7) | 0.0359 (4) | |
C32 | 0.15776 (6) | −0.3213 (3) | 0.22896 (8) | 0.0469 (5) | |
C33 | 0.19938 (8) | −0.3522 (4) | 0.28566 (9) | 0.0579 (6) | |
C34 | 0.23273 (6) | −0.1998 (4) | 0.31075 (8) | 0.0576 (6) | |
C35 | 0.22535 (6) | −0.0197 (4) | 0.27981 (9) | 0.0535 (6) | |
C36 | 0.18352 (6) | 0.0095 (3) | 0.22328 (8) | 0.0434 (4) | |
F32 | 0.12562 (5) | −0.4726 (2) | 0.20595 (6) | 0.0664 (4) | |
F33 | 0.20673 (6) | −0.5296 (3) | 0.31549 (7) | 0.0938 (6) | |
F34 | 0.27256 (4) | −0.2280 (3) | 0.36585 (5) | 0.0855 (5) | |
F35 | 0.25807 (5) | 0.1296 (3) | 0.30396 (6) | 0.0846 (5) | |
F36 | 0.17744 (4) | 0.1900 (2) | 0.19484 (6) | 0.0620 (3) | |
C101 | 0.01181 (16) | 0.4841 (4) | 0.05893 (17) | 0.0962 (12) | |
H101 | 0.02 | 0.4743 | 0.0997 | 0.115* | |
C102 | 0.04348 (14) | 0.4297 (4) | 0.04580 (16) | 0.0960 (12) | |
H102 | 0.0736 | 0.3797 | 0.0774 | 0.115* | |
C103 | 0.03248 (14) | 0.4460 (4) | −0.01328 (19) | 0.0989 (11) | |
H103 | 0.055 | 0.4099 | −0.0222 | 0.119* | |
C111 | 0.26264 (14) | 0.9060 (7) | 0.04029 (15) | 0.1082 (12) | |
H111 | 0.2717 | 1.0167 | 0.0684 | 0.13* | |
C112 | 0.24522 (10) | 0.7307 (7) | 0.04821 (13) | 0.0905 (10) | |
H112 | 0.242 | 0.718 | 0.0816 | 0.109* | |
C113 | 0.23244 (13) | 0.5729 (7) | 0.00806 (16) | 0.1036 (10) | |
H113 | 0.2202 | 0.4485 | 0.0131 | 0.124* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Fe | 0.01988 (15) | 0.02780 (17) | 0.02125 (15) | 0.00103 (11) | 0.00918 (11) | 0.00077 (11) |
N1 | 0.0225 (6) | 0.0325 (7) | 0.0239 (6) | 0.0010 (5) | 0.0110 (5) | 0.0012 (5) |
C2 | 0.0295 (8) | 0.0469 (10) | 0.0263 (7) | 0.0040 (7) | 0.0151 (6) | 0.0027 (6) |
C3 | 0.0349 (9) | 0.0835 (15) | 0.0261 (8) | 0.0098 (9) | 0.0169 (7) | 0.0050 (8) |
C4 | 0.0319 (8) | 0.0732 (13) | 0.0241 (7) | 0.0067 (9) | 0.0121 (7) | 0.0031 (8) |
C5 | 0.0251 (7) | 0.0375 (8) | 0.0238 (7) | −0.0009 (6) | 0.0099 (6) | −0.0010 (6) |
C6 | 0.0230 (7) | 0.0360 (9) | 0.0241 (7) | 0.0005 (6) | 0.0082 (6) | 0.0008 (6) |
C7 | 0.0230 (7) | 0.0392 (9) | 0.0276 (7) | 0.0037 (6) | 0.0104 (6) | 0.0028 (6) |
C8 | 0.0270 (8) | 0.0772 (14) | 0.0333 (8) | 0.0164 (8) | 0.0139 (7) | 0.0106 (9) |
C9 | 0.0307 (8) | 0.0838 (15) | 0.0373 (9) | 0.0207 (9) | 0.0197 (8) | 0.0128 (9) |
C10 | 0.0278 (8) | 0.0485 (10) | 0.0316 (8) | 0.0082 (7) | 0.0168 (7) | 0.0058 (7) |
N11 | 0.0228 (6) | 0.0339 (7) | 0.0248 (6) | 0.0034 (5) | 0.0113 (5) | 0.0023 (5) |
C12 | 0.0306 (8) | 0.0546 (10) | 0.0306 (8) | 0.0083 (7) | 0.0180 (7) | 0.0054 (7) |
C21 | 0.0346 (9) | 0.0862 (15) | 0.0325 (8) | 0.0232 (10) | 0.0203 (8) | 0.0188 (9) |
C22 | 0.0659 (14) | 0.097 (2) | 0.0501 (12) | 0.0260 (14) | 0.0385 (11) | 0.0080 (12) |
C23 | 0.100 (2) | 0.134 (3) | 0.0589 (15) | 0.066 (2) | 0.0553 (16) | 0.0276 (16) |
C24 | 0.088 (2) | 0.170 (4) | 0.0740 (17) | 0.082 (2) | 0.0680 (17) | 0.065 (2) |
C25 | 0.0545 (14) | 0.156 (3) | 0.0792 (18) | 0.0415 (17) | 0.0505 (14) | 0.065 (2) |
C26 | 0.0429 (11) | 0.105 (2) | 0.0578 (13) | 0.0209 (12) | 0.0336 (11) | 0.0303 (14) |
F22 | 0.108 | 0.0985 (12) | 0.0884 (11) | 0.0076 (11) | 0.0663 (8) | −0.0242 (10) |
F23 | 0.189 (3) | 0.171 (2) | 0.1112 (16) | 0.0782 (18) | 0.1127 (18) | 0.0018 (14) |
F24 | 0.1322 (16) | 0.257 (3) | 0.1131 (14) | 0.1233 (19) | 0.1103 (14) | 0.0980 (17) |
F25 | 0.0909 (13) | 0.203 (2) | 0.1528 (18) | 0.0302 (14) | 0.0980 (14) | 0.0807 (17) |
F26 | 0.0714 (10) | 0.1108 (14) | 0.0962 (11) | −0.0105 (9) | 0.0567 (9) | 0.0157 (11) |
C31 | 0.0229 (7) | 0.0541 (11) | 0.0250 (7) | 0.0041 (7) | 0.0098 (6) | 0.0012 (7) |
C32 | 0.0349 (9) | 0.0630 (13) | 0.0328 (8) | 0.0053 (9) | 0.0128 (7) | 0.0083 (8) |
C33 | 0.0464 (11) | 0.0820 (16) | 0.0350 (9) | 0.0206 (11) | 0.0162 (9) | 0.0207 (10) |
C34 | 0.0274 (9) | 0.1087 (19) | 0.0246 (8) | 0.0124 (10) | 0.0070 (7) | 0.0032 (10) |
C35 | 0.0252 (8) | 0.0934 (17) | 0.0333 (9) | −0.0096 (9) | 0.0111 (7) | −0.0128 (10) |
C36 | 0.0288 (8) | 0.0643 (13) | 0.0317 (8) | −0.0029 (8) | 0.0136 (7) | −0.0018 (8) |
F32 | 0.0580 (8) | 0.0587 (8) | 0.0545 (7) | −0.0029 (6) | 0.0140 (6) | 0.0177 (6) |
F33 | 0.0831 (11) | 0.1063 (13) | 0.0570 (9) | 0.0244 (9) | 0.0172 (8) | 0.0462 (8) |
F34 | 0.0377 (6) | 0.1633 (16) | 0.0277 (5) | 0.0202 (8) | 0.0010 (5) | 0.0094 (8) |
F35 | 0.0413 (7) | 0.1313 (14) | 0.0538 (8) | −0.0346 (8) | 0.0095 (6) | −0.0218 (8) |
F36 | 0.0487 (7) | 0.0664 (8) | 0.0532 (7) | −0.0178 (6) | 0.0174 (6) | −0.0014 (6) |
C101 | 0.123 (3) | 0.0354 (14) | 0.083 (2) | −0.0126 (16) | 0.028 (2) | −0.0051 (12) |
C102 | 0.105 (3) | 0.0311 (12) | 0.086 (2) | −0.0102 (15) | 0.0127 (19) | −0.0027 (13) |
C103 | 0.115 (3) | 0.0363 (13) | 0.115 (3) | −0.0139 (15) | 0.045 (2) | −0.0125 (15) |
C111 | 0.114 (3) | 0.131 (3) | 0.0657 (19) | 0.014 (3) | 0.042 (2) | −0.026 (2) |
C112 | 0.0647 (16) | 0.148 (3) | 0.0533 (14) | 0.0243 (19) | 0.0297 (13) | −0.0049 (18) |
C113 | 0.088 (2) | 0.125 (3) | 0.080 (2) | −0.002 (2) | 0.0356 (19) | −0.006 (2) |
Fe—N11i | 1.9891 (13) | C23—F23 | 1.345 (4) |
Fe—N11 | 1.9891 (13) | C23—C24 | 1.365 (5) |
Fe—N1i | 1.9982 (13) | C24—F24 | 1.330 (3) |
Fe—N1 | 1.9982 (13) | C24—C25 | 1.343 (5) |
Fe—C102 | 3.062 (3) | C25—F25 | 1.343 (4) |
Fe—C103 | 3.177 (3) | C25—C26 | 1.396 (3) |
Fe—C101 | 3.416 (3) | C26—F26 | 1.333 (3) |
N1—C5 | 1.373 (2) | C31—C36 | 1.376 (3) |
N1—C2 | 1.374 (2) | C31—C32 | 1.383 (3) |
C2—C12i | 1.387 (2) | C32—F32 | 1.337 (2) |
C2—C3 | 1.435 (2) | C32—C33 | 1.388 (3) |
C3—C4 | 1.349 (3) | C33—F33 | 1.332 (3) |
C3—H3 | 0.95 | C33—C34 | 1.365 (4) |
C4—C5 | 1.434 (2) | C34—F34 | 1.338 (2) |
C4—H4 | 0.95 | C34—C35 | 1.362 (3) |
C5—C6 | 1.391 (2) | C35—F35 | 1.339 (3) |
C6—C7 | 1.384 (2) | C35—C36 | 1.387 (3) |
C6—C31 | 1.496 (2) | C36—F36 | 1.339 (2) |
C7—N11 | 1.375 (2) | C101—C102 | 1.353 (6) |
C7—C8 | 1.435 (2) | C101—C103ii | 1.382 (5) |
C8—C9 | 1.344 (3) | C101—H101 | 0.95 |
C8—H8 | 0.95 | C102—C103 | 1.388 (5) |
C9—C10 | 1.435 (2) | C102—H102 | 0.95 |
C9—H9 | 0.95 | C103—C101ii | 1.382 (5) |
C10—N11 | 1.374 (2) | C103—H103 | 0.95 |
C10—C12 | 1.387 (2) | C111—C112 | 1.348 (5) |
C12—C2i | 1.387 (2) | C111—C113iii | 1.382 (5) |
C12—C21 | 1.501 (2) | C111—H111 | 0.95 |
C21—C22 | 1.368 (4) | C112—C113 | 1.355 (5) |
C21—C26 | 1.373 (4) | C112—H112 | 0.95 |
C22—F22 | 1.336 (3) | C113—C111iii | 1.382 (5) |
C22—C23 | 1.392 (3) | C113—H113 | 0.95 |
N11i—Fe—N11 | 180.00 (10) | F22—C22—C21 | 119.69 (19) |
N11i—Fe—N1i | 89.92 (6) | F22—C22—C23 | 117.9 (3) |
N11—Fe—N1i | 90.08 (6) | C21—C22—C23 | 122.4 (3) |
N11i—Fe—N1 | 90.08 (6) | F23—C23—C24 | 121.0 (3) |
N11—Fe—N1 | 89.92 (6) | F23—C23—C22 | 119.7 (4) |
N1i—Fe—N1 | 180.00 (10) | C24—C23—C22 | 119.3 (3) |
N11i—Fe—C102 | 98.65 (9) | F24—C24—C25 | 119.9 (4) |
N11—Fe—C102 | 81.35 (9) | F24—C24—C23 | 120.3 (4) |
N1i—Fe—C102 | 99.86 (9) | C25—C24—C23 | 119.8 (2) |
N1—Fe—C102 | 80.14 (9) | C24—C25—F25 | 119.8 (3) |
N11i—Fe—C103 | 99.51 (8) | C24—C25—C26 | 120.3 (3) |
N11—Fe—C103 | 80.49 (8) | F25—C25—C26 | 119.9 (4) |
N1i—Fe—C103 | 74.27 (8) | F26—C26—C21 | 120.2 (2) |
N1—Fe—C103 | 105.73 (8) | F26—C26—C25 | 118.1 (3) |
C102—Fe—C103 | 25.61 (10) | C21—C26—C25 | 121.7 (3) |
N11i—Fe—C101 | 77.82 (9) | C36—C31—C32 | 116.67 (16) |
N11—Fe—C101 | 102.18 (9) | C36—C31—C6 | 121.24 (16) |
N1i—Fe—C101 | 109.94 (7) | C32—C31—C6 | 122.08 (16) |
N1—Fe—C101 | 70.06 (7) | F32—C32—C31 | 119.97 (16) |
C102—Fe—C101 | 23.29 (10) | F32—C32—C33 | 118.18 (19) |
C103—Fe—C101 | 42.17 (11) | C31—C32—C33 | 121.8 (2) |
C5—N1—C2 | 105.30 (12) | F33—C33—C34 | 120.18 (19) |
C5—N1—Fe | 127.35 (11) | F33—C33—C32 | 120.2 (2) |
C2—N1—Fe | 127.32 (10) | C34—C33—C32 | 119.7 (2) |
N1—C2—C12i | 125.04 (14) | F34—C34—C35 | 120.2 (2) |
N1—C2—C3 | 110.47 (14) | F34—C34—C33 | 119.8 (2) |
C12i—C2—C3 | 124.49 (16) | C35—C34—C33 | 120.02 (17) |
C4—C3—C2 | 106.80 (15) | F35—C35—C34 | 120.30 (18) |
C4—C3—H3 | 126.6 | F35—C35—C36 | 120.0 (2) |
C2—C3—H3 | 126.6 | C34—C35—C36 | 119.74 (19) |
C3—C4—C5 | 107.03 (15) | F36—C36—C31 | 120.16 (16) |
C3—C4—H4 | 126.5 | F36—C36—C35 | 117.78 (18) |
C5—C4—H4 | 126.5 | C31—C36—C35 | 122.06 (19) |
N1—C5—C6 | 125.25 (14) | C102—C101—C103ii | 120.3 (4) |
N1—C5—C4 | 110.38 (14) | C102—C101—Fe | 63.51 (16) |
C6—C5—C4 | 124.37 (15) | C103ii—C101—Fe | 96.22 (19) |
C7—C6—C5 | 124.45 (14) | C102—C101—H101 | 119.8 |
C7—C6—C31 | 118.06 (14) | C103ii—C101—H101 | 119.8 |
C5—C6—C31 | 117.49 (13) | Fe—C101—H101 | 109.8 |
N11—C7—C6 | 125.37 (14) | C101—C102—C103 | 120.8 (4) |
N11—C7—C8 | 110.43 (14) | C101—C102—Fe | 93.2 (2) |
C6—C7—C8 | 124.19 (14) | C103—C102—Fe | 81.83 (17) |
C9—C8—C7 | 107.10 (15) | C101—C102—H102 | 119.6 |
C9—C8—H8 | 126.4 | C103—C102—H102 | 119.6 |
C7—C8—H8 | 126.4 | Fe—C102—H102 | 95 |
C8—C9—C10 | 106.79 (16) | C101ii—C103—C102 | 118.9 (4) |
C8—C9—H9 | 126.6 | C101ii—C103—Fe | 96.5 (2) |
C10—C9—H9 | 126.6 | C102—C103—Fe | 72.56 (17) |
N11—C10—C12 | 125.28 (14) | C101ii—C103—H103 | 120.6 |
N11—C10—C9 | 110.66 (14) | C102—C103—H103 | 120.6 |
C12—C10—C9 | 124.06 (16) | Fe—C103—H103 | 100.6 |
C10—N11—C7 | 105.01 (12) | C112—C111—C113iii | 121.1 (3) |
C10—N11—Fe | 127.37 (10) | C112—C111—H111 | 119.5 |
C7—N11—Fe | 127.59 (10) | C113iii—C111—H111 | 119.5 |
C2i—C12—C10 | 124.81 (16) | C111—C112—C113 | 119.3 (3) |
C2i—C12—C21 | 117.82 (15) | C111—C112—H112 | 120.4 |
C10—C12—C21 | 117.37 (15) | C113—C112—H112 | 120.4 |
C22—C21—C26 | 116.4 (2) | C112—C113—C111iii | 119.6 (4) |
C22—C21—C12 | 121.8 (2) | C112—C113—H113 | 120.2 |
C26—C21—C12 | 121.8 (2) | C111iii—C113—H113 | 120.2 |
Symmetry codes: (i) −x, −y, −z; (ii) −x, −y+1, −z; (iii) −x+1/2, −y+3/2, −z. |
Experimental details
Crystal data | |
Chemical formula | [Fe(C44H8F20N4)]·2C6H6 |
Mr | 1184.61 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 190 |
a, b, c (Å) | 34.136 (7), 6.4633 (13), 26.356 (5) |
β (°) | 123.85 (3) |
V (Å3) | 4829 (2) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.44 |
Crystal size (mm) | 0.35 × 0.2 × 0.08 |
Data collection | |
Diffractometer | Nonius KappaCCD area-detector diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 19916, 5520, 4550 |
Rint | 0.025 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.037, 0.109, 1.03 |
No. of reflections | 5520 |
No. of parameters | 366 |
No. of restraints | 2 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.33, −0.41 |
Computer programs: Collect (Hooft, 1998), HKL SCALEPACK (Otwinowski & Minor, 1997), HKL DENZO (Otwinowski & Minor, 1997), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).
Fe—N11 | 1.9891 (13) | C5—C6 | 1.391 (2) |
Fe—N1 | 1.9982 (13) | C6—C7 | 1.384 (2) |
Fe—C102 | 3.062 (3) | C6—C31 | 1.496 (2) |
Fe—C103 | 3.177 (3) | C7—N11 | 1.375 (2) |
Fe—C101 | 3.416 (3) | C7—C8 | 1.435 (2) |
N1—C5 | 1.373 (2) | C8—C9 | 1.344 (3) |
N1—C2 | 1.374 (2) | C9—C10 | 1.435 (2) |
C2—C3 | 1.435 (2) | C10—N11 | 1.374 (2) |
C3—C4 | 1.349 (3) | C10—C12 | 1.387 (2) |
C4—C5 | 1.434 (2) | C12—C2i | 1.387 (2) |
N11—Fe—N1 | 89.92 (6) | C7—C6—C5 | 124.45 (14) |
C5—N1—C2 | 105.30 (12) | N11—C7—C6 | 125.37 (14) |
N1—C2—C12i | 125.04 (14) | N11—C7—C8 | 110.43 (14) |
N1—C2—C3 | 110.47 (14) | C9—C8—C7 | 107.10 (15) |
C4—C3—C2 | 106.80 (15) | C8—C9—C10 | 106.79 (16) |
C3—C4—C5 | 107.03 (15) | N11—C10—C12 | 125.28 (14) |
N1—C5—C6 | 125.25 (14) | N11—C10—C9 | 110.66 (14) |
Symmetry code: (i) −x, −y, −z. |
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As iron(II) porphyrin is an active site in heme proteins in biological systems, and its structural features attract chemists and biologists. Structural research on FeII porphyrins has progressed slowly because of their instability in aerobic conditions. Collman et al. (1975) prepared 5,10,15,20-tetraphenylporphinatoiron(II), (TPP)FeII, from the reduction of (TPP)FeCl by Cr(acac)2 in benzene solution and recrystallization from a benzene/ethanol solution. This four-coordinated complex has d6 unusual intermediate FeII.?? Few years later, iron(II) porphyrin in a high spin state was reported? in a biaxially tetrahydrofuran-coordinated iron(II) complex (Reed et al., 1980). We have prepared the title compound, (F20TPP)Fe.2benzene, (I), from the reduction of (F20TPP)FeCl by mercury-activated zinc powder in benzene (Landrum et al., 1980), and the crystal structure of (I) is reported here.
The porphyrin ring is essentially planar and the Fe atom is located on a center of symmetry (Fig. 1). Four pentafluorophenyl rings incline to the porphyrin plane with dihedral angles of 73.0 (1) and 75.8 (1)° (Fig. 2). The Fe—N bond distances depend on the ?ruffled amount of core?, geometry and iron spin state of the porphyrin. The mean Fe—N distance [1.994 (1) Å] in (I) is longer than that in (TPP)Fe [1.972 (4) Å; Collman et al., 1975], in which the core is quite ruffled. Similar results were reported for CoII complexes, with mean Co—N distances of 1.976 (5) Å for (F20TPP)Co and 1.949 (5) Å for the more ruffled (TPP)Co (Kadish et al., 1990). In the β-pyrrolbromonated six-coordinated iron(II) complex, (F20TPPBr8)Fe(py)2 (py = pyridine), the Fe—N distance is 1.963 (7) Å in the more distorted geometry as a result of steric hindrance between the Br and phenyl F atoms (Grinstaff et al., 1995). The average Fe—N distance in the intermediate- or low-spin state is shorter than that in high-spin six-coordinated complexes such as (TPP)FeII(THF)2 [2.057 (2) Å; Reed et al., 1980]. This difference is due to the empty dx2-y2 orbital of the FeII atom in the intermediate-spin state. The Fe—N distances for planar porphyrin complexes can give useful information about porphyrin skeleton contraction (Birnbaum et al., 1995): the more contracted the skeleton, the shorter the metal–N distances and the smaller the C—N—C angles in the pyrrole ring. The average distances between the N atoms and the porphyrin center (or metal) are 2.052, 2.036, 1.996 and 1.994 Å for (F20TPP)H2, (F20TPP)Zn, (F20TPP)Cu and (F20TPP)Fe, respectively (Birnbaum et al., 1995), and the C—N—C angles are 107.4, 106.2, 105.2 and 105.3°, respectively.
As shown in Fig. 1, there is a benzene molecule below the porphyrin ring, and there are substantial interactions [3.062 (3)– 3.416 (3) Å] between the Fe and benzene C atoms, although the benzene ring is not directly coordinated to the Fe atom. It is well known that there are definite π–π interactions between metalloporphyrin molecules and aromatic solvents, with the distances shorter than 3.3 Å (Kadish et al., 1990). In (I), the benzene ring lies sandwiched between two porphyrin rings (Fig. 3). In another sense, two benzene molecules are located at the top and bottom of the porphyrin ring. The spin state of the FeII atom in (I) is intermediate (S=1), as confirmed by NMR studies. The pyrrol H-atom signal was reported at 5.1 p.p.m. in a benzene solution of (TPP)FeII (Goff et al., 1977).