Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270100015833/oa1111sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270100015833/oa1111Isup2.hkl |
CCDC reference: 162538
meso-Tetraisopropylporphyrin was prepared according to the procedure of Ema et al. (1994). Insertion of iron was carried out by refluxing meso-tetraisopropylporphyrin with FeCl2·4H2O in methanol-chloroform (1:3). The resulting chloro-iron(III) complex was converted into the title complex, (I), by treatment with AgClO4 in tetrahydrofuran solution. The solid thus obtained was recrystallized from tetrahydrofuran-heptane (3:1).
There is disorder in one of the two coordinated thf molecules, with site occupancy factors for the disordered atoms, C35A and C35B, of 0.43 and 0.57. H atoms were refined using a riding model, with C—H distances of 0.96 Å for primary H, 0.97 Å for secondary and 0.93 Å for aromatic. H atom U values were constrained to 1.2 times the equivalent isotropic U of the atoms to which they were attached (1.5 for methyl groups).
Data collection: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1992a); cell refinement: MSC/AFC Diffractometer Control Software; data reduction: TEXSAN (Molecular Structure Corporation, 1992b); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SV (Nemoto & Ohashi, 1993); software used to prepare material for publication: SHELXL97.
Fig. 1. The molecular structure (ORTEP; Johnson, 1965) of (I) with the atomic numbering. Displacement ellipsoids are shown at the 30% probability level and H atoms have been omitted for clarity. |
[Fe(C32H36N4)(C4H8O)2]·ClO4 | F(000) = 1644 |
Mr = 776.16 | Dx = 1.274 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71069 Å |
a = 10.56 (10) Å | Cell parameters from 25 reflections |
b = 32.98 (15) Å | θ = 14.4–15.6° |
c = 11.64 (8) Å | µ = 0.49 mm−1 |
β = 92.8 (7)° | T = 298 K |
V = 4048 (51) Å3 | Prismatic, brown |
Z = 4 | 0.5 × 0.4 × 0.2 mm |
Rigaku AFC-5 diffractometer | 4237 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.037 |
Graphite monochromator | θmax = 27.5°, θmin = 2.0° |
ω scans | h = −13→13 |
Absorption correction: ψ-scan (North et al., 1968) | k = 0→42 |
Tmin = 0.819, Tmax = 0.907 | l = 0→15 |
9566 measured reflections | 3 standard reflections every 100 reflections |
9128 independent reflections | intensity decay: −0.7% |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.063 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.215 | H-atom parameters constrained |
S = 0.91 | Calculated w = 1/[σ2(Fo2) + (0.1329P)2] where P = (Fo2 + 2Fc2)/3 |
9128 reflections | (Δ/σ)max < 0.001 |
495 parameters | Δρmax = 0.68 e Å−3 |
6 restraints | Δρmin = −0.41 e Å−3 |
[Fe(C32H36N4)(C4H8O)2]·ClO4 | V = 4048 (51) Å3 |
Mr = 776.16 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 10.56 (10) Å | µ = 0.49 mm−1 |
b = 32.98 (15) Å | T = 298 K |
c = 11.64 (8) Å | 0.5 × 0.4 × 0.2 mm |
β = 92.8 (7)° |
Rigaku AFC-5 diffractometer | 4237 reflections with I > 2σ(I) |
Absorption correction: ψ-scan (North et al., 1968) | Rint = 0.037 |
Tmin = 0.819, Tmax = 0.907 | 3 standard reflections every 100 reflections |
9566 measured reflections | intensity decay: −0.7% |
9128 independent reflections |
R[F2 > 2σ(F2)] = 0.063 | 6 restraints |
wR(F2) = 0.215 | H-atom parameters constrained |
S = 0.91 | Δρmax = 0.68 e Å−3 |
9128 reflections | Δρmin = −0.41 e Å−3 |
495 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 | 0.25256 (5) | 0.122097 (15) | 0.63416 (5) | 0.04879 (18) | |
Cl1 | −0.21760 (18) | 0.14060 (5) | 0.19720 (16) | 0.1082 (5) | |
O1 | 0.4307 (3) | 0.10868 (9) | 0.7364 (2) | 0.0656 (7) | |
O2 | 0.0801 (3) | 0.13103 (9) | 0.5259 (3) | 0.0705 (8) | |
O3 | −0.2323 (7) | 0.17856 (15) | 0.2445 (5) | 0.188 (3) | |
O4 | −0.0944 (7) | 0.1341 (2) | 0.1771 (8) | 0.232 (4) | |
O5 | −0.2488 (5) | 0.10967 (16) | 0.2813 (6) | 0.158 (2) | |
O6 | −0.2833 (15) | 0.1382 (3) | 0.1071 (9) | 0.344 (8) | |
N1 | 0.3525 (3) | 0.14029 (10) | 0.5079 (3) | 0.0562 (8) | |
N2 | 0.2545 (3) | 0.06553 (9) | 0.5753 (3) | 0.0497 (7) | |
N3 | 0.1525 (3) | 0.10439 (10) | 0.7613 (3) | 0.0521 (7) | |
N4 | 0.2513 (3) | 0.17846 (10) | 0.6933 (3) | 0.0568 (8) | |
C1 | 0.4277 (4) | 0.17498 (13) | 0.5060 (4) | 0.0647 (11) | |
C2 | 0.4947 (4) | 0.17452 (17) | 0.4013 (5) | 0.0819 (14) | |
H2 | 0.5544 | 0.1934 | 0.3795 | 0.098* | |
C3 | 0.4554 (5) | 0.14196 (16) | 0.3409 (4) | 0.0763 (13) | |
H3 | 0.4799 | 0.1353 | 0.2675 | 0.092* | |
C4 | 0.3698 (4) | 0.11889 (14) | 0.4067 (3) | 0.0616 (10) | |
C5 | 0.3237 (4) | 0.07968 (14) | 0.3796 (3) | 0.0606 (10) | |
C6 | 0.2782 (4) | 0.05373 (12) | 0.4647 (3) | 0.0543 (9) | |
C7 | 0.2653 (5) | 0.00991 (14) | 0.4567 (4) | 0.0727 (12) | |
H7 | 0.2745 | −0.0055 | 0.3908 | 0.087* | |
C8 | 0.2379 (4) | −0.00453 (13) | 0.5604 (4) | 0.0681 (12) | |
H8 | 0.2278 | −0.0316 | 0.5801 | 0.082* | |
C9 | 0.2272 (3) | 0.02995 (11) | 0.6354 (3) | 0.0515 (9) | |
C10 | 0.1805 (4) | 0.02860 (12) | 0.7450 (3) | 0.0550 (9) | |
C11 | 0.1364 (4) | 0.06421 (12) | 0.7985 (3) | 0.0556 (9) | |
C12 | 0.0571 (4) | 0.06471 (15) | 0.8936 (4) | 0.0716 (12) | |
H12 | 0.0331 | 0.0423 | 0.9359 | 0.086* | |
C13 | 0.0222 (4) | 0.10415 (16) | 0.9116 (4) | 0.0729 (12) | |
H13 | −0.0322 | 0.1131 | 0.9668 | 0.087* | |
C14 | 0.0834 (4) | 0.12910 (13) | 0.8315 (3) | 0.0611 (10) | |
C15 | 0.0829 (4) | 0.17203 (14) | 0.8308 (4) | 0.0674 (11) | |
C16 | 0.1681 (4) | 0.19452 (13) | 0.7699 (4) | 0.0663 (11) | |
C17 | 0.1971 (6) | 0.23750 (14) | 0.7855 (5) | 0.0891 (16) | |
H17 | 0.1526 | 0.2557 | 0.8293 | 0.107* | |
C18 | 0.2987 (6) | 0.24612 (14) | 0.7257 (5) | 0.0866 (16) | |
H18 | 0.3396 | 0.2711 | 0.7236 | 0.104* | |
C19 | 0.3337 (5) | 0.20982 (12) | 0.6650 (4) | 0.0680 (12) | |
C20 | 0.4258 (4) | 0.20738 (13) | 0.5853 (4) | 0.0705 (13) | |
C21 | 0.3302 (5) | 0.06221 (16) | 0.2581 (4) | 0.0776 (13) | |
H21 | 0.2725 | 0.0389 | 0.2560 | 0.093* | |
C22 | 0.2748 (6) | 0.0917 (2) | 0.1650 (4) | 0.112 (2) | |
H22A | 0.1959 | 0.1025 | 0.1890 | 0.168* | |
H22B | 0.2607 | 0.0774 | 0.0937 | 0.168* | |
H22C | 0.3335 | 0.1135 | 0.1547 | 0.168* | |
C23 | 0.4593 (5) | 0.04476 (18) | 0.2321 (5) | 0.1011 (18) | |
H23A | 0.5187 | 0.0665 | 0.2237 | 0.152* | |
H23B | 0.4521 | 0.0294 | 0.1620 | 0.152* | |
H23C | 0.4886 | 0.0274 | 0.2941 | 0.152* | |
C24 | 0.1655 (4) | −0.01377 (13) | 0.7989 (4) | 0.0645 (11) | |
H24 | 0.2150 | −0.0324 | 0.7532 | 0.077* | |
C25 | 0.0280 (5) | −0.02952 (14) | 0.7894 (5) | 0.0856 (15) | |
H25A | −0.0236 | −0.0136 | 0.8378 | 0.128* | |
H25B | 0.0262 | −0.0574 | 0.8133 | 0.128* | |
H25C | −0.0042 | −0.0274 | 0.7110 | 0.128* | |
C26 | 0.2231 (5) | −0.01635 (16) | 0.9228 (4) | 0.0860 (15) | |
H26A | 0.1768 | 0.0011 | 0.9718 | 0.129* | |
H26B | 0.3102 | −0.0080 | 0.9241 | 0.129* | |
H26C | 0.2181 | −0.0438 | 0.9498 | 0.129* | |
C27 | −0.0055 (5) | 0.19439 (17) | 0.9093 (4) | 0.0931 (16) | |
H27 | −0.0566 | 0.1716 | 0.9345 | 0.112* | |
C28 | −0.1074 (7) | 0.2197 (3) | 0.8510 (6) | 0.198 (5) | |
H28A | −0.0932 | 0.2478 | 0.8698 | 0.297* | |
H28B | −0.1885 | 0.2115 | 0.8767 | 0.297* | |
H28C | −0.1058 | 0.2162 | 0.7692 | 0.297* | |
C29 | 0.0546 (6) | 0.20754 (17) | 1.0239 (4) | 0.0984 (18) | |
H29A | 0.1222 | 0.2262 | 1.0113 | 0.148* | |
H29B | 0.0876 | 0.1842 | 1.0647 | 0.148* | |
H29C | −0.0080 | 0.2205 | 1.0683 | 0.148* | |
C30 | 0.5187 (5) | 0.24315 (17) | 0.5793 (6) | 0.110 (2) | |
H30 | 0.4902 | 0.2571 | 0.6478 | 0.132* | |
C31 | 0.4923 (6) | 0.27670 (15) | 0.5000 (5) | 0.1002 (18) | |
H31A | 0.5522 | 0.2981 | 0.5157 | 0.150* | |
H31B | 0.4080 | 0.2866 | 0.5097 | 0.150* | |
H31C | 0.4993 | 0.2674 | 0.4223 | 0.150* | |
C32 | 0.6479 (5) | 0.2327 (2) | 0.6294 (9) | 0.187 (5) | |
H32A | 0.6992 | 0.2227 | 0.5697 | 0.280* | |
H32B | 0.6407 | 0.2123 | 0.6874 | 0.280* | |
H32C | 0.6866 | 0.2565 | 0.6632 | 0.280* | |
C33 | 0.5372 (5) | 0.0885 (2) | 0.6924 (5) | 0.112 (2) | |
H33A | 0.5755 | 0.1051 | 0.6347 | 0.134* | |
H33B | 0.5117 | 0.0629 | 0.6576 | 0.134* | |
C34 | 0.6295 (6) | 0.0816 (3) | 0.7935 (6) | 0.131 (3) | |
H34A | 0.6176 | 0.0551 | 0.8275 | 0.157* | |
H34B | 0.7164 | 0.0841 | 0.7713 | 0.157* | |
C35A | 0.5957 (10) | 0.1147 (9) | 0.874 (3) | 0.228 (19) | 0.43 (2) |
H35A | 0.6373 | 0.1399 | 0.8552 | 0.274* | 0.43 (2) |
H35B | 0.6188 | 0.1075 | 0.9531 | 0.274* | 0.43 (2) |
C35B | 0.5496 (13) | 0.0868 (5) | 0.8959 (8) | 0.113 (7) | 0.57 (2) |
H35C | 0.5082 | 0.0616 | 0.9152 | 0.136* | 0.57 (2) |
H35D | 0.6000 | 0.0963 | 0.9625 | 0.136* | 0.57 (2) |
C36 | 0.4548 (6) | 0.1181 (2) | 0.8550 (5) | 0.117 (2) | |
H36A | 0.4118 | 0.0991 | 0.9034 | 0.140* | |
H36B | 0.4264 | 0.1454 | 0.8718 | 0.140* | |
C37 | 0.0397 (5) | 0.16935 (15) | 0.4739 (5) | 0.0883 (16) | |
H37A | 0.0384 | 0.1675 | 0.3906 | 0.106* | |
H37B | 0.0967 | 0.1910 | 0.4987 | 0.106* | |
C38 | −0.0883 (7) | 0.1769 (2) | 0.5129 (7) | 0.121 (2) | |
H38A | −0.1428 | 0.1880 | 0.4512 | 0.145* | |
H38B | −0.0859 | 0.1956 | 0.5773 | 0.145* | |
C39 | −0.1345 (7) | 0.1351 (3) | 0.5490 (7) | 0.138 (3) | |
H39A | −0.1515 | 0.1350 | 0.6301 | 0.166* | |
H39B | −0.2118 | 0.1280 | 0.5053 | 0.166* | |
C40 | −0.0308 (5) | 0.10559 (16) | 0.5253 (5) | 0.0892 (16) | |
H40A | −0.0228 | 0.0850 | 0.5848 | 0.107* | |
H40B | −0.0460 | 0.0925 | 0.4513 | 0.107* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Fe1 | 0.0517 (3) | 0.0435 (3) | 0.0510 (3) | −0.0051 (2) | 0.0009 (2) | 0.0021 (2) |
Cl1 | 0.1148 (13) | 0.0931 (11) | 0.1175 (13) | 0.0000 (9) | 0.0170 (10) | −0.0177 (10) |
O1 | 0.0624 (18) | 0.0771 (19) | 0.0567 (17) | 0.0065 (15) | −0.0022 (14) | −0.0015 (14) |
O2 | 0.0634 (18) | 0.0611 (18) | 0.085 (2) | −0.0129 (14) | −0.0176 (16) | 0.0168 (15) |
O3 | 0.299 (8) | 0.081 (3) | 0.185 (5) | 0.025 (4) | 0.068 (5) | −0.014 (4) |
O4 | 0.190 (7) | 0.211 (7) | 0.304 (10) | 0.058 (5) | 0.161 (7) | 0.080 (6) |
O5 | 0.143 (4) | 0.109 (4) | 0.230 (6) | 0.007 (3) | 0.068 (4) | 0.034 (4) |
O6 | 0.52 (2) | 0.256 (10) | 0.235 (10) | −0.015 (11) | −0.234 (12) | −0.040 (7) |
N1 | 0.0534 (19) | 0.0572 (19) | 0.058 (2) | −0.0115 (16) | 0.0019 (15) | 0.0124 (16) |
N2 | 0.0531 (18) | 0.0468 (17) | 0.0496 (18) | −0.0040 (14) | 0.0070 (14) | −0.0003 (14) |
N3 | 0.0536 (18) | 0.0530 (18) | 0.0491 (17) | 0.0022 (15) | 0.0072 (14) | −0.0005 (14) |
N4 | 0.062 (2) | 0.0462 (17) | 0.061 (2) | −0.0052 (16) | −0.0088 (16) | 0.0014 (15) |
C1 | 0.057 (2) | 0.063 (3) | 0.072 (3) | −0.015 (2) | −0.008 (2) | 0.020 (2) |
C2 | 0.063 (3) | 0.088 (4) | 0.096 (4) | −0.019 (3) | 0.013 (3) | 0.033 (3) |
C3 | 0.071 (3) | 0.090 (4) | 0.070 (3) | −0.018 (3) | 0.015 (2) | 0.022 (3) |
C4 | 0.058 (2) | 0.077 (3) | 0.051 (2) | −0.010 (2) | 0.0042 (18) | 0.013 (2) |
C5 | 0.056 (2) | 0.077 (3) | 0.049 (2) | −0.007 (2) | 0.0065 (18) | 0.007 (2) |
C6 | 0.056 (2) | 0.059 (2) | 0.050 (2) | −0.0075 (18) | 0.0120 (17) | −0.0068 (18) |
C7 | 0.090 (3) | 0.064 (3) | 0.068 (3) | −0.007 (2) | 0.022 (2) | −0.017 (2) |
C8 | 0.089 (3) | 0.050 (2) | 0.067 (3) | −0.008 (2) | 0.024 (2) | −0.003 (2) |
C9 | 0.051 (2) | 0.047 (2) | 0.057 (2) | −0.0061 (16) | 0.0040 (18) | 0.0016 (17) |
C10 | 0.054 (2) | 0.055 (2) | 0.056 (2) | −0.0014 (18) | 0.0057 (18) | 0.0065 (18) |
C11 | 0.055 (2) | 0.057 (2) | 0.057 (2) | −0.0026 (18) | 0.0110 (18) | 0.0070 (18) |
C12 | 0.077 (3) | 0.072 (3) | 0.065 (3) | −0.005 (2) | 0.022 (2) | 0.005 (2) |
C13 | 0.065 (3) | 0.090 (3) | 0.066 (3) | 0.006 (2) | 0.017 (2) | −0.007 (2) |
C14 | 0.060 (2) | 0.070 (3) | 0.054 (2) | 0.007 (2) | 0.0005 (19) | −0.009 (2) |
C15 | 0.068 (3) | 0.067 (3) | 0.068 (3) | 0.006 (2) | −0.004 (2) | −0.017 (2) |
C16 | 0.080 (3) | 0.051 (2) | 0.063 (3) | 0.009 (2) | −0.016 (2) | −0.008 (2) |
C17 | 0.132 (5) | 0.050 (3) | 0.082 (3) | 0.013 (3) | −0.015 (3) | −0.009 (2) |
C18 | 0.127 (5) | 0.043 (2) | 0.086 (3) | −0.007 (3) | −0.023 (3) | −0.001 (2) |
C19 | 0.082 (3) | 0.050 (2) | 0.069 (3) | −0.011 (2) | −0.028 (2) | 0.011 (2) |
C20 | 0.069 (3) | 0.058 (3) | 0.081 (3) | −0.019 (2) | −0.024 (2) | 0.023 (2) |
C21 | 0.079 (3) | 0.095 (4) | 0.057 (3) | −0.017 (3) | 0.014 (2) | −0.005 (2) |
C22 | 0.120 (5) | 0.164 (7) | 0.053 (3) | −0.020 (4) | −0.001 (3) | 0.011 (3) |
C23 | 0.103 (4) | 0.106 (4) | 0.098 (4) | −0.016 (3) | 0.046 (3) | −0.018 (3) |
C24 | 0.070 (3) | 0.059 (3) | 0.067 (3) | −0.003 (2) | 0.017 (2) | 0.010 (2) |
C25 | 0.085 (3) | 0.069 (3) | 0.104 (4) | −0.020 (3) | 0.016 (3) | 0.015 (3) |
C26 | 0.092 (4) | 0.087 (3) | 0.081 (3) | 0.011 (3) | 0.008 (3) | 0.030 (3) |
C27 | 0.096 (4) | 0.099 (4) | 0.084 (4) | 0.030 (3) | 0.004 (3) | −0.029 (3) |
C28 | 0.140 (7) | 0.314 (14) | 0.145 (7) | 0.125 (8) | −0.038 (6) | −0.099 (8) |
C29 | 0.131 (5) | 0.084 (4) | 0.081 (4) | −0.004 (3) | 0.013 (3) | −0.025 (3) |
C30 | 0.097 (4) | 0.092 (4) | 0.133 (5) | −0.048 (3) | −0.041 (4) | 0.044 (4) |
C31 | 0.123 (5) | 0.067 (3) | 0.111 (4) | −0.030 (3) | −0.013 (3) | 0.031 (3) |
C32 | 0.081 (4) | 0.127 (6) | 0.351 (14) | −0.041 (4) | −0.072 (6) | 0.078 (8) |
C33 | 0.070 (3) | 0.172 (7) | 0.093 (4) | 0.037 (4) | 0.004 (3) | 0.001 (4) |
C34 | 0.090 (4) | 0.170 (7) | 0.132 (6) | 0.036 (4) | −0.033 (4) | −0.006 (5) |
C35A | 0.23 (3) | 0.13 (2) | 0.30 (3) | 0.074 (18) | −0.20 (3) | −0.12 (2) |
C35B | 0.117 (10) | 0.150 (13) | 0.068 (7) | 0.061 (10) | −0.037 (6) | −0.025 (7) |
C36 | 0.125 (5) | 0.127 (5) | 0.087 (4) | 0.024 (4) | −0.037 (4) | −0.029 (4) |
C37 | 0.087 (4) | 0.075 (3) | 0.100 (4) | −0.002 (3) | −0.025 (3) | 0.024 (3) |
C38 | 0.109 (5) | 0.104 (5) | 0.146 (6) | 0.025 (4) | 0.002 (4) | 0.000 (5) |
C39 | 0.080 (4) | 0.189 (8) | 0.150 (7) | 0.003 (5) | 0.026 (4) | 0.010 (6) |
C40 | 0.069 (3) | 0.083 (3) | 0.114 (4) | −0.024 (3) | −0.021 (3) | 0.013 (3) |
Fe1—N1 | 1.946 (14) | C22—H22B | 0.9600 |
Fe1—N3 | 1.950 (14) | C22—H22C | 0.9600 |
Fe1—N4 | 1.982 (9) | C23—H23A | 0.9600 |
Fe1—N2 | 1.988 (9) | C23—H23B | 0.9600 |
Fe1—O2 | 2.183 (19) | C23—H23C | 0.9600 |
Fe1—O1 | 2.221 (19) | C24—C26 | 1.540 (13) |
Cl1—O6 | 1.231 (12) | C24—C25 | 1.541 (14) |
Cl1—O4 | 1.351 (14) | C24—H24 | 0.9800 |
Cl1—O3 | 1.379 (7) | C25—H25A | 0.9600 |
Cl1—O5 | 1.462 (8) | C25—H25B | 0.9600 |
O1—C33 | 1.423 (12) | C25—H25C | 0.9600 |
O1—C36 | 1.426 (11) | C26—H26A | 0.9600 |
O2—C40 | 1.441 (11) | C26—H26B | 0.9600 |
O2—C37 | 1.456 (8) | C26—H26C | 0.9600 |
N1—C1 | 1.393 (8) | C27—C28 | 1.499 (10) |
N1—C4 | 1.393 (9) | C27—C29 | 1.511 (13) |
N2—C6 | 1.380 (10) | C27—H27 | 0.9800 |
N2—C9 | 1.403 (7) | C28—H28A | 0.9600 |
N3—C14 | 1.387 (9) | C28—H28B | 0.9600 |
N3—C11 | 1.407 (8) | C28—H28C | 0.9600 |
N4—C16 | 1.387 (11) | C29—H29A | 0.9600 |
N4—C19 | 1.402 (9) | C29—H29B | 0.9600 |
C1—C20 | 1.413 (9) | C29—H29C | 0.9600 |
C1—C2 | 1.439 (13) | C30—C31 | 1.459 (9) |
C2—C3 | 1.338 (9) | C30—C32 | 1.497 (13) |
C2—H2 | 0.9300 | C30—H30 | 0.9800 |
C3—C4 | 1.432 (10) | C31—H31A | 0.9600 |
C3—H3 | 0.9300 | C31—H31B | 0.9600 |
C4—C5 | 1.412 (8) | C31—H31C | 0.9600 |
C5—C6 | 1.410 (9) | C32—H32A | 0.9600 |
C5—C21 | 1.532 (11) | C32—H32B | 0.9600 |
C6—C7 | 1.454 (9) | C32—H32C | 0.9600 |
C7—C8 | 1.342 (10) | C33—C34 | 1.508 (14) |
C7—H7 | 0.9300 | C33—H33A | 0.9700 |
C8—C9 | 1.441 (8) | C33—H33B | 0.9700 |
C8—H8 | 0.9300 | C34—C35A | 1.493 (8) |
C9—C10 | 1.391 (11) | C34—C35B | 1.504 (12) |
C10—C11 | 1.419 (8) | C34—H34A | 0.9700 |
C10—C24 | 1.543 (8) | C34—H34B | 0.9700 |
C11—C12 | 1.420 (12) | C35A—C36 | 1.498 (15) |
C12—C13 | 1.371 (9) | C35A—H35A | 0.9700 |
C12—H12 | 0.9300 | C35A—H35B | 0.9700 |
C13—C14 | 1.422 (10) | C35B—C36 | 1.501 (9) |
C13—H13 | 0.9300 | C35B—H35C | 0.9700 |
C14—C15 | 1.416 (9) | C35B—H35D | 0.9700 |
C15—C16 | 1.388 (11) | C36—H36A | 0.9700 |
C15—C27 | 1.527 (11) | C36—H36B | 0.9700 |
C16—C17 | 1.459 (9) | C37—C38 | 1.468 (15) |
C17—C18 | 1.337 (13) | C37—H37A | 0.9700 |
C17—H17 | 0.9300 | C37—H37B | 0.9700 |
C18—C19 | 1.447 (9) | C38—C39 | 1.526 (11) |
C18—H18 | 0.9300 | C38—H38A | 0.9700 |
C19—C20 | 1.379 (13) | C38—H38B | 0.9700 |
C20—C30 | 1.538 (9) | C39—C40 | 1.501 (12) |
C21—C23 | 1.524 (14) | C39—H39A | 0.9700 |
C21—C22 | 1.549 (11) | C39—H39B | 0.9700 |
C21—H21 | 0.9800 | C40—H40A | 0.9700 |
C22—H22A | 0.9600 | C40—H40B | 0.9700 |
N1—Fe1—N3 | 179.45 (14) | C26—C24—C25 | 112.1 (7) |
N1—Fe1—N4 | 89.2 (3) | C26—C24—C10 | 112.8 (4) |
N3—Fe1—N4 | 90.2 (3) | C25—C24—C10 | 113.0 (5) |
N1—Fe1—N2 | 90.8 (3) | C26—C24—H24 | 106.1 |
N3—Fe1—N2 | 89.7 (3) | C25—C24—H24 | 106.1 |
N4—Fe1—N2 | 179.75 (14) | C10—C24—H24 | 106.1 |
N1—Fe1—O2 | 89.5 (7) | C24—C25—H25A | 109.5 |
N3—Fe1—O2 | 90.6 (7) | C24—C25—H25B | 109.5 |
N4—Fe1—O2 | 93.1 (3) | H25A—C25—H25B | 109.5 |
N2—Fe1—O2 | 87.1 (3) | C24—C25—H25C | 109.5 |
N1—Fe1—O1 | 89.4 (7) | H25A—C25—H25C | 109.5 |
N3—Fe1—O1 | 90.6 (7) | H25B—C25—H25C | 109.5 |
N4—Fe1—O1 | 91.2 (3) | C24—C26—H26A | 109.5 |
N2—Fe1—O1 | 88.6 (3) | C24—C26—H26B | 109.5 |
O2—Fe1—O1 | 175.53 (12) | H26A—C26—H26B | 109.5 |
O6—Cl1—O4 | 110.5 (10) | C24—C26—H26C | 109.5 |
O6—Cl1—O3 | 109.1 (6) | H26A—C26—H26C | 109.5 |
O4—Cl1—O3 | 110.0 (6) | H26B—C26—H26C | 109.5 |
O6—Cl1—O5 | 112.9 (8) | C28—C27—C29 | 120.0 (7) |
O4—Cl1—O5 | 104.8 (6) | C28—C27—C15 | 116.4 (7) |
O3—Cl1—O5 | 109.4 (6) | C29—C27—C15 | 115.1 (7) |
C33—O1—C36 | 110.2 (7) | C28—C27—H27 | 99.8 |
C33—O1—Fe1 | 124.3 (6) | C29—C27—H27 | 99.8 |
C36—O1—Fe1 | 125.5 (6) | C15—C27—H27 | 99.8 |
C40—O2—C37 | 106.3 (6) | C27—C28—H28A | 109.5 |
C40—O2—Fe1 | 125.4 (5) | C27—C28—H28B | 109.5 |
C37—O2—Fe1 | 125.2 (3) | H28A—C28—H28B | 109.5 |
C1—N1—C4 | 107.7 (6) | C27—C28—H28C | 109.5 |
C1—N1—Fe1 | 126.6 (4) | H28A—C28—H28C | 109.5 |
C4—N1—Fe1 | 125.5 (5) | H28B—C28—H28C | 109.5 |
C6—N2—C9 | 106.3 (5) | C27—C29—H29A | 109.5 |
C6—N2—Fe1 | 126.3 (2) | C27—C29—H29B | 109.5 |
C9—N2—Fe1 | 127.4 (4) | H29A—C29—H29B | 109.5 |
C14—N3—C11 | 107.3 (5) | C27—C29—H29C | 109.5 |
C14—N3—Fe1 | 126.3 (5) | H29A—C29—H29C | 109.5 |
C11—N3—Fe1 | 126.5 (3) | H29B—C29—H29C | 109.5 |
C16—N4—C19 | 106.8 (6) | C31—C30—C32 | 124.2 (6) |
C16—N4—Fe1 | 126.6 (3) | C31—C30—C20 | 120.5 (6) |
C19—N4—Fe1 | 126.6 (5) | C32—C30—C20 | 112.2 (6) |
N1—C1—C20 | 125.7 (6) | C31—C30—H30 | 95.8 |
N1—C1—C2 | 108.0 (5) | C32—C30—H30 | 95.8 |
C20—C1—C2 | 125.8 (5) | C20—C30—H30 | 95.8 |
C3—C2—C1 | 107.5 (5) | C30—C31—H31A | 109.5 |
C3—C2—H2 | 126.3 | C30—C31—H31B | 109.5 |
C1—C2—H2 | 126.3 | H31A—C31—H31B | 109.5 |
C2—C3—C4 | 109.5 (6) | C30—C31—H31C | 109.5 |
C2—C3—H3 | 125.3 | H31A—C31—H31C | 109.5 |
C4—C3—H3 | 125.3 | H31B—C31—H31C | 109.5 |
N1—C4—C5 | 126.5 (5) | C30—C32—H32A | 109.5 |
N1—C4—C3 | 107.2 (6) | C30—C32—H32B | 109.5 |
C5—C4—C3 | 126.0 (5) | H32A—C32—H32B | 109.5 |
C6—C5—C4 | 121.7 (5) | C30—C32—H32C | 109.5 |
C6—C5—C21 | 116.9 (6) | H32A—C32—H32C | 109.5 |
C4—C5—C21 | 121.3 (4) | H32B—C32—H32C | 109.5 |
N2—C6—C5 | 124.6 (5) | O1—C33—C34 | 106.3 (7) |
N2—C6—C7 | 108.6 (4) | O1—C33—H33A | 110.5 |
C5—C6—C7 | 126.3 (4) | C34—C33—H33A | 110.5 |
C8—C7—C6 | 108.6 (4) | O1—C33—H33B | 110.5 |
C8—C7—H7 | 125.7 | C34—C33—H33B | 110.5 |
C6—C7—H7 | 125.7 | H33A—C33—H33B | 108.7 |
C7—C8—C9 | 106.9 (5) | C35A—C34—C35B | 42.2 (12) |
C7—C8—H8 | 126.5 | C35A—C34—C33 | 102.3 (12) |
C9—C8—H8 | 126.5 | C35B—C34—C33 | 103.6 (9) |
C10—C9—N2 | 125.1 (4) | C35A—C34—H34A | 111.3 |
C10—C9—C8 | 124.9 (4) | C35B—C34—H34A | 72.0 |
N2—C9—C8 | 109.5 (6) | C33—C34—H34A | 111.3 |
C9—C10—C11 | 121.0 (4) | C35A—C34—H34B | 111.3 |
C9—C10—C24 | 116.8 (4) | C35B—C34—H34B | 141.0 |
C11—C10—C24 | 121.9 (5) | C33—C34—H34B | 111.3 |
N3—C11—C10 | 126.7 (5) | H34A—C34—H34B | 109.2 |
N3—C11—C12 | 108.3 (4) | C34—C35A—C36 | 103.2 (8) |
C10—C11—C12 | 124.8 (4) | C34—C35A—H35A | 111.1 |
C13—C12—C11 | 107.7 (4) | C36—C35A—H35A | 111.1 |
C13—C12—H12 | 126.2 | C34—C35A—H35B | 111.1 |
C11—C12—H12 | 126.2 | C36—C35A—H35B | 111.1 |
C12—C13—C14 | 108.3 (6) | H35A—C35A—H35B | 109.1 |
C12—C13—H13 | 125.9 | C36—C35B—C34 | 102.6 (8) |
C14—C13—H13 | 125.9 | C36—C35B—H35C | 111.2 |
N3—C14—C15 | 125.9 (5) | C34—C35B—H35C | 111.2 |
N3—C14—C13 | 108.4 (6) | C36—C35B—H35D | 111.2 |
C15—C14—C13 | 125.5 (5) | C34—C35B—H35D | 111.2 |
C16—C15—C14 | 122.3 (5) | H35C—C35B—H35D | 109.2 |
C16—C15—C27 | 118.6 (6) | O1—C36—C35A | 104.8 (12) |
C14—C15—C27 | 118.8 (5) | O1—C36—C35B | 103.9 (7) |
N4—C16—C15 | 124.9 (6) | C35A—C36—C35B | 42.2 (12) |
N4—C16—C17 | 108.4 (5) | O1—C36—H36A | 110.8 |
C15—C16—C17 | 126.3 (5) | C35A—C36—H36A | 110.8 |
C18—C17—C16 | 108.1 (5) | C35B—C36—H36A | 72.2 |
C18—C17—H17 | 126.0 | O1—C36—H36B | 110.8 |
C16—C17—H17 | 126.0 | C35A—C36—H36B | 110.8 |
C17—C18—C19 | 108.0 (6) | C35B—C36—H36B | 141.5 |
C17—C18—H18 | 126.0 | H36A—C36—H36B | 108.9 |
C19—C18—H18 | 126.0 | O2—C37—C38 | 105.9 (6) |
C20—C19—N4 | 125.6 (5) | O2—C37—H37A | 110.6 |
C20—C19—C18 | 125.6 (5) | C38—C37—H37A | 110.6 |
N4—C19—C18 | 108.6 (7) | O2—C37—H37B | 110.6 |
C19—C20—C1 | 121.1 (5) | C38—C37—H37B | 110.6 |
C19—C20—C30 | 117.3 (6) | H37A—C37—H37B | 108.7 |
C1—C20—C30 | 121.4 (7) | C37—C38—C39 | 104.1 (6) |
C23—C21—C5 | 114.0 (7) | C37—C38—H38A | 110.9 |
C23—C21—C22 | 114.1 (6) | C39—C38—H38A | 110.9 |
C5—C21—C22 | 112.1 (6) | C37—C38—H38B | 110.9 |
C23—C21—H21 | 105.1 | C39—C38—H38B | 110.9 |
C5—C21—H21 | 105.1 | H38A—C38—H38B | 108.9 |
C22—C21—H21 | 105.1 | C40—C39—C38 | 106.8 (7) |
C21—C22—H22A | 109.5 | C40—C39—H39A | 110.4 |
C21—C22—H22B | 109.5 | C38—C39—H39A | 110.4 |
H22A—C22—H22B | 109.5 | C40—C39—H39B | 110.4 |
C21—C22—H22C | 109.5 | C38—C39—H39B | 110.4 |
H22A—C22—H22C | 109.5 | H39A—C39—H39B | 108.6 |
H22B—C22—H22C | 109.5 | O2—C40—C39 | 102.8 (7) |
C21—C23—H23A | 109.5 | O2—C40—H40A | 111.2 |
C21—C23—H23B | 109.5 | C39—C40—H40A | 111.2 |
H23A—C23—H23B | 109.5 | O2—C40—H40B | 111.2 |
C21—C23—H23C | 109.5 | C39—C40—H40B | 111.2 |
H23A—C23—H23C | 109.5 | H40A—C40—H40B | 109.1 |
H23B—C23—H23C | 109.5 | ||
N1—Fe1—O1—C33 | −44.5 (6) | N2—C9—C10—C11 | 10.5 (6) |
N3—Fe1—O1—C33 | 136.0 (6) | C8—C9—C10—C11 | −160.2 (5) |
N4—Fe1—O1—C33 | −133.7 (5) | N2—C9—C10—C24 | −176.0 (3) |
N2—Fe1—O1—C33 | 46.3 (5) | C8—C9—C10—C24 | 13.2 (6) |
O2—Fe1—O1—C33 | 30.4 (16) | C14—N3—C11—C10 | 173.8 (4) |
N1—Fe1—O1—C36 | 136.7 (6) | Fe1—N3—C11—C10 | −5.8 (6) |
N3—Fe1—O1—C36 | −42.7 (6) | C14—N3—C11—C12 | −0.6 (4) |
N4—Fe1—O1—C36 | 47.5 (5) | Fe1—N3—C11—C12 | 179.8 (3) |
N2—Fe1—O1—C36 | −132.4 (5) | C9—C10—C11—N3 | −11.5 (6) |
O2—Fe1—O1—C36 | −148.3 (14) | C24—C10—C11—N3 | 175.4 (4) |
N1—Fe1—O2—C40 | 143.2 (4) | C9—C10—C11—C12 | 162.1 (4) |
N3—Fe1—O2—C40 | −37.3 (4) | C24—C10—C11—C12 | −11.1 (6) |
N4—Fe1—O2—C40 | −127.6 (5) | N3—C11—C12—C13 | 1.9 (5) |
N2—Fe1—O2—C40 | 52.4 (5) | C10—C11—C12—C13 | −172.6 (4) |
O1—Fe1—O2—C40 | 68.3 (16) | C11—C12—C13—C14 | −2.5 (5) |
N1—Fe1—O2—C37 | −59.3 (4) | C11—N3—C14—C15 | 173.7 (4) |
N3—Fe1—O2—C37 | 120.1 (4) | Fe1—N3—C14—C15 | −6.7 (6) |
N4—Fe1—O2—C37 | 29.9 (5) | C11—N3—C14—C13 | −0.9 (4) |
N2—Fe1—O2—C37 | −150.2 (5) | Fe1—N3—C14—C13 | 178.7 (3) |
O1—Fe1—O2—C37 | −134.2 (14) | C12—C13—C14—N3 | 2.1 (5) |
N3—Fe1—N1—C1 | 16 (14) | C12—C13—C14—C15 | −172.5 (4) |
N4—Fe1—N1—C1 | 22.3 (4) | N3—C14—C15—C16 | −10.0 (7) |
N2—Fe1—N1—C1 | −157.4 (4) | C13—C14—C15—C16 | 163.8 (5) |
O2—Fe1—N1—C1 | 115.4 (5) | N3—C14—C15—C27 | 176.3 (4) |
O1—Fe1—N1—C1 | −68.9 (5) | C13—C14—C15—C27 | −9.9 (7) |
N3—Fe1—N1—C4 | −170 (23) | C19—N4—C16—C15 | −170.6 (4) |
N4—Fe1—N1—C4 | −163.4 (4) | Fe1—N4—C16—C15 | 9.8 (6) |
N2—Fe1—N1—C4 | 16.9 (4) | C19—N4—C16—C17 | 2.4 (4) |
O2—Fe1—N1—C4 | −70.3 (5) | Fe1—N4—C16—C17 | −177.2 (3) |
O1—Fe1—N1—C4 | 105.4 (5) | C14—C15—C16—N4 | 8.2 (7) |
N1—Fe1—N2—C6 | −20.3 (4) | C27—C15—C16—N4 | −178.1 (4) |
N3—Fe1—N2—C6 | 159.8 (4) | C14—C15—C16—C17 | −163.6 (5) |
N4—Fe1—N2—C6 | −114 (26) | C27—C15—C16—C17 | 10.1 (7) |
O2—Fe1—N2—C6 | 69.1 (7) | N4—C16—C17—C18 | −3.6 (6) |
O1—Fe1—N2—C6 | −109.6 (7) | C15—C16—C17—C18 | 169.3 (5) |
N1—Fe1—N2—C9 | 162.6 (4) | C16—C17—C18—C19 | 3.2 (6) |
N3—Fe1—N2—C9 | −17.3 (4) | C16—N4—C19—C20 | −175.5 (4) |
N4—Fe1—N2—C9 | 68 (26) | Fe1—N4—C19—C20 | 4.1 (6) |
O2—Fe1—N2—C9 | −108.0 (7) | C16—N4—C19—C18 | −0.5 (4) |
O1—Fe1—N2—C9 | 73.3 (7) | Fe1—N4—C19—C18 | 179.1 (3) |
N1—Fe1—N3—C14 | 23 (14) | C17—C18—C19—C20 | 173.2 (4) |
N4—Fe1—N3—C14 | 17.1 (4) | C17—C18—C19—N4 | −1.8 (5) |
N2—Fe1—N3—C14 | −163.2 (4) | N4—C19—C20—C1 | 13.8 (7) |
O2—Fe1—N3—C14 | −76.0 (4) | C18—C19—C20—C1 | −160.4 (4) |
O1—Fe1—N3—C14 | 108.3 (4) | N4—C19—C20—C30 | −171.5 (4) |
N1—Fe1—N3—C11 | −157 (13) | C18—C19—C20—C30 | 14.3 (6) |
N4—Fe1—N3—C11 | −163.4 (4) | N1—C1—C20—C19 | −9.2 (7) |
N2—Fe1—N3—C11 | 16.4 (4) | C2—C1—C20—C19 | 162.0 (4) |
O2—Fe1—N3—C11 | 103.5 (4) | N1—C1—C20—C30 | 176.3 (4) |
O1—Fe1—N3—C11 | −72.2 (4) | C2—C1—C20—C30 | −12.5 (7) |
N1—Fe1—N4—C16 | 161.3 (4) | C6—C5—C21—C23 | −94.6 (6) |
N3—Fe1—N4—C16 | −18.8 (4) | C4—C5—C21—C23 | 80.9 (7) |
N2—Fe1—N4—C16 | −105 (26) | C6—C5—C21—C22 | 133.8 (6) |
O2—Fe1—N4—C16 | 71.9 (7) | C4—C5—C21—C22 | −50.8 (8) |
O1—Fe1—N4—C16 | −109.4 (7) | C9—C10—C24—C26 | 131.4 (6) |
N1—Fe1—N4—C19 | −18.2 (4) | C11—C10—C24—C26 | −55.2 (7) |
N3—Fe1—N4—C19 | 161.7 (4) | C9—C10—C24—C25 | −100.1 (7) |
N2—Fe1—N4—C19 | 76 (26) | C11—C10—C24—C25 | 73.3 (8) |
O2—Fe1—N4—C19 | −107.6 (7) | C16—C15—C27—C28 | 69.7 (9) |
O1—Fe1—N4—C19 | 71.1 (7) | C14—C15—C27—C28 | −116.3 (8) |
C4—N1—C1—C20 | 171.6 (4) | C16—C15—C27—C29 | −78.4 (7) |
Fe1—N1—C1—C20 | −13.3 (6) | C14—C15—C27—C29 | 95.5 (7) |
C4—N1—C1—C2 | −1.0 (5) | C19—C20—C30—C31 | −92.2 (9) |
Fe1—N1—C1—C2 | 174.1 (3) | C1—C20—C30—C31 | 82.5 (9) |
N1—C1—C2—C3 | 3.2 (5) | C19—C20—C30—C32 | 106.8 (9) |
C20—C1—C2—C3 | −169.4 (4) | C1—C20—C30—C32 | −78.5 (9) |
C1—C2—C3—C4 | −4.1 (6) | C36—O1—C33—C34 | 5.3 (8) |
C1—N1—C4—C5 | 171.9 (4) | Fe1—O1—C33—C34 | −173.6 (4) |
Fe1—N1—C4—C5 | −3.3 (6) | O1—C33—C34—C35A | −25.6 (16) |
C1—N1—C4—C3 | −1.4 (5) | O1—C33—C34—C35B | 17.7 (10) |
Fe1—N1—C4—C3 | −176.6 (3) | C35B—C34—C35A—C36 | −61.3 (11) |
C2—C3—C4—N1 | 3.5 (5) | C33—C34—C35A—C36 | 35 (2) |
C2—C3—C4—C5 | −169.8 (5) | C35A—C34—C35B—C36 | 60.8 (10) |
N1—C4—C5—C6 | −14.9 (7) | C33—C34—C35B—C36 | −32.7 (13) |
C3—C4—C5—C6 | 157.2 (5) | C33—O1—C36—C35A | 17.3 (16) |
N1—C4—C5—C21 | 169.8 (4) | Fe1—O1—C36—C35A | −163.7 (15) |
C3—C4—C5—C21 | −18.1 (7) | C33—O1—C36—C35B | −26.2 (9) |
C9—N2—C6—C5 | −172.4 (4) | Fe1—O1—C36—C35B | 152.7 (8) |
Fe1—N2—C6—C5 | 10.0 (6) | C34—C35A—C36—O1 | −33 (3) |
C9—N2—C6—C7 | −0.1 (4) | C34—C35A—C36—C35B | 61.5 (11) |
Fe1—N2—C6—C7 | −177.7 (3) | C34—C35B—C36—O1 | 36.2 (13) |
C4—C5—C6—N2 | 11.1 (7) | C34—C35B—C36—C35A | −60.6 (11) |
C21—C5—C6—N2 | −173.4 (4) | C40—O2—C37—C38 | 36.9 (7) |
C4—C5—C6—C7 | −159.8 (5) | Fe1—O2—C37—C38 | −124.1 (7) |
C21—C5—C6—C7 | 15.6 (7) | O2—C37—C38—C39 | −20.6 (7) |
N2—C6—C7—C8 | −1.6 (5) | C37—C38—C39—C40 | −1.6 (8) |
C5—C6—C7—C8 | 170.5 (4) | C37—O2—C40—C39 | −36.6 (7) |
C6—C7—C8—C9 | 2.5 (5) | Fe1—O2—C40—C39 | 124.4 (6) |
C6—N2—C9—C10 | −170.4 (4) | C38—C39—C40—O2 | 23.1 (8) |
Fe1—N2—C9—C10 | 7.2 (5) | C6—C5—C21—H21 | 20.0 |
C6—N2—C9—C8 | 1.6 (4) | C4—C5—C21—H21 | −164.5 |
Fe1—N2—C9—C8 | 179.2 (3) | C11—C10—C24—H24 | −170.9 |
C7—C8—C9—C10 | 169.4 (4) | C16—C15—C27—H27 | 175.9 |
C7—C8—C9—N2 | −2.6 (5) | C1—C20—C30—H30 | −177.2 |
Experimental details
Crystal data | |
Chemical formula | [Fe(C32H36N4)(C4H8O)2]·ClO4 |
Mr | 776.16 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 298 |
a, b, c (Å) | 10.56 (10), 32.98 (15), 11.64 (8) |
β (°) | 92.8 (7) |
V (Å3) | 4048 (51) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.49 |
Crystal size (mm) | 0.5 × 0.4 × 0.2 |
Data collection | |
Diffractometer | Rigaku AFC-5 diffractometer |
Absorption correction | ψ-scan (North et al., 1968) |
Tmin, Tmax | 0.819, 0.907 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 9566, 9128, 4237 |
Rint | 0.037 |
(sin θ/λ)max (Å−1) | 0.650 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.063, 0.215, 0.91 |
No. of reflections | 9128 |
No. of parameters | 495 |
No. of restraints | 6 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.68, −0.41 |
Computer programs: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1992a), MSC/AFC Diffractometer Control Software, TEXSAN (Molecular Structure Corporation, 1992b), SIR92 (Altomare et al., 1994), SHELXL97 (Sheldrick, 1997), SV (Nemoto & Ohashi, 1993), SHELXL97.
Fe1—N1 | 1.946 (14) | Fe1—N2 | 1.988 (9) |
Fe1—N3 | 1.950 (14) | Fe1—O2 | 2.183 (19) |
Fe1—N4 | 1.982 (9) | Fe1—O1 | 2.221 (19) |
N1—Fe1—N3 | 179.45 (14) | N4—Fe1—N2 | 179.75 (14) |
Fe1—O1—C36—C35A | −163.7 (15) | C11—C10—C24—H24 | −170.9 |
Fe1—O1—C36—C35B | 152.7 (8) | C16—C15—C27—H27 | 175.9 |
Fe1—O2—C37—C38 | −124.1 (7) | C1—C20—C30—H30 | −177.2 |
C4—C5—C21—H21 | −164.5 |
Metalloporphyrins with nonplanar structures are of essential interest in understanding the role and functions of haemoproteins with a deformed porphyrin ring (Finzel et al., 1984; Hobbs & Shelnutt, 1995; Ikeue et al., 2000). In this paper, we describe the molecular structure of the title complex, (I), which shows the presence of a highly deformed porphyrin ring. \sch
The molecular structure of (I) with the atom-numbering scheme is shown in Fig. 1. The porphyrin ring exhibits the S4-ruffled structure, where the shifts of the meso C atoms C5, C10, C15 and C20 from the least-squares plane of the [Fe(C20N4)] porphyrinato core are -0.675 (9), 0.623 (8), -0.579 (8) and 0.640 (8) Å, respectively. The ruffling dihedral angles of the two pairs of diagonal pyrroles, 37.4 (7) and 38.3 (7)°, are much larger than those in [Fe(TEtP)(thf)2]ClO4 [22.3 (1) and 21.2 (1)°; Ohgo et al., 1999; TEtP is the dianion of meso-tetraethylporphyrin and thf is tetrahydrofuran].
Both thf rings in (I) are parallel to the Cmeso—Fe—Cmeso axis and are perpendicular to each other [C5···Fe1—O1—C33 1.4 (4), C10···Fe1—O2—C40 8.5 (4), C40—O2—O1—C33 96.5 (7) and C37—O2—O1—C36 79.5 (7)°]. One of the two coordinated thf molecules shows a bent form, which is well illustrated by the Fe1—O2—C40—C39 and Fe1—O2—C37—C38 dihedral angles of 124.4 (6) and -124.1 (7)°, respectively. In contrast, the other thf molecule shows a planar form: the Fe1—O1—C33—C34 and Fe1—O1–36-C35A dihedral angles are -173.6 (4) and -163.7 (15)°, respectively. This difference in coordination structure of the thf molecules is ascribed to the crystal packing in the direction normal to the porphyrin ring.
The Fe—Np bond distances of (I) [average 1.967 (12) Å] are significantly shorter than those of other bis(thf) complexes, such as [Fe(TEtP)(thf)2]ClO4 [average 2.006 (3) Å; Ohgo et al., 1999], [Fe(TPP)(thf)2]ClO4 [average 2.016 (3) Å; Chen et al., 1998; TPP is the dianion of meso-tetraphenylporphyrin] and [Fe(OEP)(thf)2]ClO4 [1.994 Å; Masuda et al., 1982; OEP is the dianion of 2,3,7,8,12,13,17,18-octaethylporphyrin]. The average deviation of meso C atoms from the least-squares plane of porphyrin ring is well known as an index of the degree of deformation. In the case of (I), it is 0.68 Å, which is much larger than the corresponding values in [Fe(TPP)(thf)2]ClO4 (0.01 Å) and [Fe(OEP)(THF)2]ClO4 (0.03 Å). In addition, there is a tendency that higher deformed complexes have shorter Fe—Np bonds, as in (I). These results suggest that (I) is one of the most highly deformed (porphyrinato)iron(III) complexes known to date.