Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270101003985/fg1624sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270101003985/fg1624Isup2.hkl |
CCDC reference: 166968
For related literature, see: Adler et al. (1970); Hatano & Scheidt (1979); Maricondi et al. (1969); Neya et al. (1998); Senge (1997); Sessler et al. (2000).
12,17-Bis(ethoxycarbonyl)-2,3,6,7,11,18-hexamethylcorrphycene was synthesized according to the reported method (Neya et al., 1998). Insertion of iron was carried out after Adler (Adler et al., 1970). The chloro iron(III) complex thus obtained was converted to the title complex by cleaving of the µ-oxo-bridged dimers (Maricondi et al., 1969). The solid was recrystallized from chloroform solution.
There is a disorder in one of the two ethoxycarbonyl groups. The site occupation factor for disordered groups (A and B) are A:B = 0.50:0.50. H atoms were refined using a riding model. The positional parameters of H atoms were constrained to have the C—H distances of 0.96 Å for primary, 0.97 Å for secondary, and 0.93 Å for aromatic. Hydrogen U values constrained to 1.2 times the equivalent isotropic U of the atoms to which they are 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: MSC/AFC Diffractometer Control Software and TEXSAN (Molecular Structure Corporation, 1992b); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SV (Nemoto & Ohashi, 1993); software used to prepare material for publication: SHELXL97.
[Fe(C32H32N4O4)I]·CHCl3 | Z = 2 |
Mr = 838.73 | F(000) = 842 |
Triclinic, P1 | Dx = 1.608 Mg m−3 |
a = 8.538 (2) Å | Mo Kα radiation, λ = 0.71069 Å |
b = 14.114 (2) Å | Cell parameters from 25 reflections |
c = 15.648 (4) Å | θ = 15.1–17.0° |
α = 106.040 (14)° | µ = 1.60 mm−1 |
β = 93.59 (2)° | T = 298 K |
γ = 104.964 (16)° | Prismatic, purple |
V = 1732.5 (7) Å3 | 0.5 × 0.4 × 0.1 mm |
RIGAKU AFC7 diffractometer | 5539 reflections with I > 2σ(I) |
Radiation source: rotating anode | Rint = 0.020 |
Graphite monochromator | θmax = 27.5°, θmin = 2.5° |
ω/2θ scans | h = 0→11 |
Absorption correction: ψ scan (North et al., 1968) | k = −18→17 |
Tmin = 0.474, Tmax = 0.852 | l = −20→20 |
8460 measured reflections | 3 standard reflections every 100 reflections |
7927 independent reflections | intensity decay: 0.9% |
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)] = 0.048 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.150 | H-atom parameters constrained |
S = 1.09 | Calculated w = 1/[σ2(Fo2) + (0.0825P)2 + 0.6822P] where P = (Fo2 + 2Fc2)/3 |
7927 reflections | (Δ/σ)max < 0.001 |
432 parameters | Δρmax = 0.88 e Å−3 |
16 restraints | Δρmin = −0.76 e Å−3 |
[Fe(C32H32N4O4)I]·CHCl3 | γ = 104.964 (16)° |
Mr = 838.73 | V = 1732.5 (7) Å3 |
Triclinic, P1 | Z = 2 |
a = 8.538 (2) Å | Mo Kα radiation |
b = 14.114 (2) Å | µ = 1.60 mm−1 |
c = 15.648 (4) Å | T = 298 K |
α = 106.040 (14)° | 0.5 × 0.4 × 0.1 mm |
β = 93.59 (2)° |
RIGAKU AFC7 diffractometer | 5539 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.020 |
Tmin = 0.474, Tmax = 0.852 | 3 standard reflections every 100 reflections |
8460 measured reflections | intensity decay: 0.9% |
7927 independent reflections |
R[F2 > 2σ(F2)] = 0.048 | 16 restraints |
wR(F2) = 0.150 | H-atom parameters constrained |
S = 1.09 | Δρmax = 0.88 e Å−3 |
7927 reflections | Δρmin = −0.76 e Å−3 |
432 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) | |
I1 | 0.81293 (4) | 0.85284 (2) | 0.18885 (2) | 0.05948 (13) | |
Fe1 | 0.56588 (7) | 0.86650 (4) | 0.09197 (4) | 0.03837 (14) | |
Cl1 | 0.3088 (8) | 1.3740 (4) | 0.5315 (4) | 0.289 (3) | |
Cl2 | 0.5752 (7) | 1.3062 (5) | 0.4842 (4) | 0.294 (3) | |
Cl3 | 0.4321 (8) | 1.2793 (4) | 0.6387 (2) | 0.240 (2) | |
O1 | 0.2120 (6) | 0.9080 (4) | 0.4548 (3) | 0.0870 (13) | |
O2 | 0.2729 (9) | 1.0548 (4) | 0.4253 (4) | 0.131 (2) | |
N2 | 0.4342 (4) | 0.7163 (2) | 0.0296 (2) | 0.0438 (7) | |
N3 | 0.3986 (4) | 0.8645 (3) | 0.1829 (2) | 0.0430 (7) | |
N4 | 0.6543 (4) | 1.0193 (2) | 0.0960 (2) | 0.0417 (7) | |
N1 | 0.6237 (4) | 0.8314 (2) | −0.0356 (2) | 0.0429 (7) | |
C5 | 0.4705 (5) | 0.6647 (3) | −0.0507 (3) | 0.0443 (9) | |
C6 | 0.3854 (6) | 0.5566 (3) | −0.0736 (3) | 0.0526 (10) | |
C7 | 0.2961 (5) | 0.5456 (3) | −0.0054 (4) | 0.0536 (11) | |
C8 | 0.3278 (5) | 0.6462 (3) | 0.0591 (3) | 0.0468 (9) | |
C9 | 0.2629 (5) | 0.6763 (3) | 0.1361 (3) | 0.0521 (10) | |
H9 | 0.1900 | 0.6246 | 0.1519 | 0.063* | |
C10 | 0.2945 (5) | 0.7765 (3) | 0.1936 (3) | 0.0495 (10) | |
C11 | 0.2261 (6) | 0.8021 (4) | 0.2751 (3) | 0.0558 (11) | |
C12 | 0.2891 (6) | 0.9037 (4) | 0.3142 (3) | 0.0547 (11) | |
C13 | 0.3976 (5) | 0.9442 (3) | 0.2569 (3) | 0.0464 (9) | |
C14 | 0.4830 (6) | 1.0487 (4) | 0.2793 (3) | 0.0547 (11) | |
H14 | 0.4614 | 1.0848 | 0.3345 | 0.066* | |
C15 | 0.5881 (6) | 1.1128 (3) | 0.2443 (3) | 0.0557 (11) | |
H15 | 0.6190 | 1.1801 | 0.2823 | 0.067* | |
C16 | 0.6627 (5) | 1.1051 (3) | 0.1663 (3) | 0.0461 (9) | |
C17 | 0.7696 (6) | 1.1946 (3) | 0.1492 (3) | 0.0524 (10) | |
C18 | 0.8242 (5) | 1.1629 (3) | 0.0708 (3) | 0.0481 (10) | |
C19 | 0.7517 (5) | 1.0531 (3) | 0.0364 (3) | 0.0419 (8) | |
C20 | 0.7831 (5) | 0.9936 (3) | −0.0440 (3) | 0.0457 (9) | |
H20 | 0.8508 | 1.0281 | −0.0768 | 0.055* | |
C1 | 0.7230 (5) | 0.8885 (3) | −0.0793 (3) | 0.0439 (9) | |
C2 | 0.7439 (6) | 0.8217 (4) | −0.1627 (3) | 0.0507 (10) | |
C3 | 0.6535 (6) | 0.7236 (4) | −0.1691 (3) | 0.0530 (10) | |
C4 | 0.5789 (5) | 0.7316 (3) | −0.0885 (3) | 0.0448 (9) | |
C23 | 0.3882 (7) | 0.4708 (3) | −0.1553 (4) | 0.0680 (14) | |
H23A | 0.3264 | 0.4062 | −0.1495 | 0.102* | |
H23B | 0.4994 | 0.4701 | −0.1606 | 0.102* | |
H23C | 0.3407 | 0.4813 | −0.2080 | 0.102* | |
C24 | 0.1883 (7) | 0.4487 (3) | 0.0045 (4) | 0.0684 (14) | |
H24A | 0.1233 | 0.4075 | −0.0523 | 0.103* | |
H24B | 0.1175 | 0.4652 | 0.0481 | 0.103* | |
H24C | 0.2547 | 0.4110 | 0.0240 | 0.103* | |
C25 | 0.0980 (8) | 0.7238 (5) | 0.3044 (4) | 0.0792 (17) | |
H25A | 0.1509 | 0.7009 | 0.3475 | 0.119* | |
H25B | 0.0440 | 0.6660 | 0.2530 | 0.119* | |
H25C | 0.0187 | 0.7555 | 0.3311 | 0.119* | |
C22 | 0.6363 (9) | 0.6265 (4) | −0.2469 (4) | 0.0818 (18) | |
H22A | 0.6903 | 0.6449 | −0.2944 | 0.123* | |
H22B | 0.5223 | 0.5924 | −0.2687 | 0.123* | |
H22C | 0.6854 | 0.5813 | −0.2263 | 0.123* | |
C21 | 0.8471 (7) | 0.8558 (4) | −0.2296 (3) | 0.0615 (12) | |
H21A | 0.9581 | 0.8567 | −0.2138 | 0.092* | |
H21B | 0.8443 | 0.9236 | −0.2287 | 0.092* | |
H21C | 0.8046 | 0.8087 | −0.2886 | 0.092* | |
C32 | 0.9379 (6) | 1.2245 (3) | 0.0233 (4) | 0.0612 (12) | |
H32A | 0.8866 | 1.2702 | 0.0051 | 0.092* | |
H32B | 0.9621 | 1.1787 | −0.0287 | 0.092* | |
H32C | 1.0377 | 1.2638 | 0.0632 | 0.092* | |
C26 | 0.2616 (8) | 0.9659 (5) | 0.4032 (4) | 0.0712 (15) | |
C27 | 0.1924 (10) | 0.9597 (6) | 0.5467 (4) | 0.093 (2) | |
H27A | 0.1333 | 1.0100 | 0.5472 | 0.111* | |
H27B | 0.2983 | 0.9944 | 0.5836 | 0.111* | |
C28 | 0.0979 (11) | 0.8768 (8) | 0.5805 (5) | 0.115 (3) | |
H28A | −0.0110 | 0.8488 | 0.5478 | 0.173* | |
H28B | 0.0926 | 0.9046 | 0.6432 | 0.173* | |
H28C | 0.1511 | 0.8234 | 0.5723 | 0.173* | |
O3A | 0.9583 (10) | 1.3614 (6) | 0.2133 (7) | 0.099 (2) | 0.502 (5) |
O4A | 0.7218 (11) | 1.3304 (6) | 0.2598 (7) | 0.096 (2) | 0.502 (5) |
C29A | 0.8220 (6) | 1.3025 (3) | 0.2094 (4) | 0.0732 (16) | 0.502 (5) |
C30A | 1.0039 (18) | 1.4641 (7) | 0.2818 (7) | 0.107 (4) | 0.502 (5) |
H30A | 0.9188 | 1.4968 | 0.2755 | 0.128* | 0.502 (5) |
H30B | 1.1044 | 1.5061 | 0.2699 | 0.128* | 0.502 (5) |
C31A | 1.0284 (15) | 1.4618 (8) | 0.3770 (6) | 0.145 (4) | 0.502 (5) |
H31A | 1.0728 | 1.5312 | 0.4169 | 0.217* | 0.502 (5) |
H31B | 1.1067 | 1.4239 | 0.3834 | 0.217* | 0.502 (5) |
H31C | 0.9275 | 1.4297 | 0.3933 | 0.217* | 0.502 (5) |
O3B | 0.8193 (13) | 1.3230 (6) | 0.2927 (5) | 0.099 (2) | 0.498 (5) |
O4B | 0.8818 (14) | 1.3700 (6) | 0.1740 (6) | 0.096 (2) | 0.498 (5) |
C29B | 0.8220 (6) | 1.3025 (3) | 0.2094 (4) | 0.0732 (16) | 0.498 (5) |
C30B | 0.8511 (16) | 1.4321 (7) | 0.3468 (8) | 0.107 (4) | 0.498 (5) |
H30C | 0.8243 | 1.4731 | 0.3106 | 0.128* | 0.498 (5) |
H30D | 0.7899 | 1.4385 | 0.3973 | 0.128* | 0.498 (5) |
C31B | 1.0284 (15) | 1.4618 (8) | 0.3770 (6) | 0.145 (4) | 0.498 (5) |
H31D | 1.0609 | 1.4045 | 0.3861 | 0.217* | 0.498 (5) |
H31E | 1.0581 | 1.5176 | 0.4323 | 0.217* | 0.498 (5) |
H31F | 1.0881 | 1.4843 | 0.3319 | 0.217* | 0.498 (5) |
C33 | 0.4069 (11) | 1.2867 (6) | 0.5335 (6) | 0.108 (3) | |
H33 | 0.3332 | 1.2201 | 0.4968 | 0.129* |
U11 | U22 | U33 | U12 | U13 | U23 | |
I1 | 0.05369 (19) | 0.0609 (2) | 0.0673 (2) | 0.01455 (14) | 0.00409 (14) | 0.02766 (16) |
Fe1 | 0.0407 (3) | 0.0312 (3) | 0.0427 (3) | 0.0046 (2) | 0.0113 (2) | 0.0147 (2) |
Cl1 | 0.351 (7) | 0.207 (4) | 0.326 (7) | 0.156 (5) | −0.063 (6) | 0.065 (4) |
Cl2 | 0.218 (5) | 0.304 (6) | 0.252 (5) | −0.029 (4) | 0.116 (4) | −0.010 (5) |
Cl3 | 0.421 (8) | 0.247 (4) | 0.105 (2) | 0.170 (5) | 0.057 (3) | 0.067 (3) |
O1 | 0.120 (4) | 0.101 (3) | 0.055 (2) | 0.041 (3) | 0.043 (2) | 0.033 (2) |
O2 | 0.214 (7) | 0.091 (4) | 0.105 (4) | 0.054 (4) | 0.101 (5) | 0.030 (3) |
N2 | 0.0459 (18) | 0.0314 (15) | 0.0506 (19) | 0.0025 (13) | 0.0119 (15) | 0.0138 (14) |
N3 | 0.0439 (18) | 0.0436 (17) | 0.0455 (18) | 0.0104 (14) | 0.0143 (14) | 0.0202 (15) |
N4 | 0.0419 (17) | 0.0351 (16) | 0.0479 (19) | 0.0057 (13) | 0.0085 (14) | 0.0170 (14) |
N1 | 0.0469 (18) | 0.0348 (16) | 0.0455 (18) | 0.0045 (13) | 0.0131 (15) | 0.0151 (14) |
C5 | 0.048 (2) | 0.0305 (18) | 0.052 (2) | 0.0068 (16) | 0.0104 (18) | 0.0126 (17) |
C6 | 0.051 (2) | 0.034 (2) | 0.067 (3) | 0.0046 (17) | 0.000 (2) | 0.0146 (19) |
C7 | 0.047 (2) | 0.034 (2) | 0.075 (3) | 0.0004 (17) | 0.003 (2) | 0.020 (2) |
C8 | 0.042 (2) | 0.0371 (19) | 0.060 (3) | 0.0017 (16) | 0.0064 (18) | 0.0222 (18) |
C9 | 0.048 (2) | 0.047 (2) | 0.063 (3) | 0.0032 (18) | 0.014 (2) | 0.027 (2) |
C10 | 0.045 (2) | 0.053 (2) | 0.059 (3) | 0.0109 (18) | 0.0173 (19) | 0.031 (2) |
C11 | 0.051 (2) | 0.073 (3) | 0.053 (3) | 0.016 (2) | 0.018 (2) | 0.033 (2) |
C12 | 0.054 (3) | 0.066 (3) | 0.054 (3) | 0.020 (2) | 0.025 (2) | 0.029 (2) |
C13 | 0.050 (2) | 0.051 (2) | 0.045 (2) | 0.0195 (18) | 0.0161 (18) | 0.0182 (18) |
C14 | 0.062 (3) | 0.053 (2) | 0.052 (2) | 0.021 (2) | 0.021 (2) | 0.012 (2) |
C15 | 0.069 (3) | 0.040 (2) | 0.054 (3) | 0.013 (2) | 0.011 (2) | 0.0083 (19) |
C16 | 0.046 (2) | 0.0365 (19) | 0.053 (2) | 0.0071 (16) | 0.0035 (18) | 0.0148 (17) |
C17 | 0.051 (2) | 0.034 (2) | 0.068 (3) | 0.0072 (17) | 0.003 (2) | 0.0143 (19) |
C18 | 0.042 (2) | 0.0337 (19) | 0.070 (3) | 0.0054 (16) | 0.003 (2) | 0.0241 (19) |
C19 | 0.0412 (19) | 0.0382 (19) | 0.049 (2) | 0.0061 (15) | 0.0082 (17) | 0.0222 (17) |
C20 | 0.043 (2) | 0.046 (2) | 0.052 (2) | 0.0051 (17) | 0.0134 (18) | 0.0258 (18) |
C1 | 0.042 (2) | 0.046 (2) | 0.045 (2) | 0.0090 (16) | 0.0108 (17) | 0.0190 (17) |
C2 | 0.055 (2) | 0.054 (2) | 0.051 (2) | 0.019 (2) | 0.018 (2) | 0.022 (2) |
C3 | 0.057 (3) | 0.054 (2) | 0.051 (2) | 0.019 (2) | 0.015 (2) | 0.017 (2) |
C4 | 0.049 (2) | 0.039 (2) | 0.046 (2) | 0.0105 (17) | 0.0105 (18) | 0.0146 (17) |
C23 | 0.076 (3) | 0.036 (2) | 0.076 (3) | 0.005 (2) | 0.000 (3) | 0.005 (2) |
C24 | 0.062 (3) | 0.036 (2) | 0.103 (4) | 0.001 (2) | 0.015 (3) | 0.027 (3) |
C25 | 0.074 (4) | 0.083 (4) | 0.088 (4) | 0.012 (3) | 0.037 (3) | 0.041 (3) |
C22 | 0.111 (5) | 0.058 (3) | 0.069 (3) | 0.021 (3) | 0.039 (3) | 0.005 (3) |
C21 | 0.068 (3) | 0.070 (3) | 0.056 (3) | 0.024 (2) | 0.028 (2) | 0.026 (2) |
C32 | 0.059 (3) | 0.040 (2) | 0.081 (3) | −0.003 (2) | 0.008 (2) | 0.029 (2) |
C26 | 0.092 (4) | 0.078 (4) | 0.058 (3) | 0.037 (3) | 0.036 (3) | 0.026 (3) |
C27 | 0.105 (5) | 0.124 (6) | 0.053 (3) | 0.033 (4) | 0.032 (3) | 0.028 (4) |
C28 | 0.113 (6) | 0.164 (8) | 0.073 (4) | 0.025 (6) | 0.043 (4) | 0.051 (5) |
O3A | 0.105 (6) | 0.053 (3) | 0.089 (5) | −0.016 (4) | 0.000 (4) | −0.018 (3) |
O4A | 0.120 (6) | 0.042 (3) | 0.091 (5) | −0.011 (4) | −0.009 (4) | 0.004 (3) |
C29A | 0.081 (4) | 0.040 (3) | 0.089 (4) | 0.018 (3) | −0.013 (3) | 0.009 (3) |
C30A | 0.111 (8) | 0.051 (5) | 0.129 (9) | −0.003 (5) | 0.020 (7) | 0.003 (5) |
C31A | 0.179 (11) | 0.128 (8) | 0.097 (6) | 0.035 (7) | −0.006 (7) | 0.001 (6) |
O3B | 0.105 (6) | 0.053 (3) | 0.089 (5) | −0.016 (4) | 0.000 (4) | −0.018 (3) |
O4B | 0.120 (6) | 0.042 (3) | 0.091 (5) | −0.011 (4) | −0.009 (4) | 0.004 (3) |
C29B | 0.081 (4) | 0.040 (3) | 0.089 (4) | 0.018 (3) | −0.013 (3) | 0.009 (3) |
C30B | 0.111 (8) | 0.051 (5) | 0.129 (9) | −0.003 (5) | 0.020 (7) | 0.003 (5) |
C31B | 0.179 (11) | 0.128 (8) | 0.097 (6) | 0.035 (7) | −0.006 (7) | 0.001 (6) |
C33 | 0.133 (7) | 0.085 (5) | 0.101 (6) | 0.029 (5) | 0.035 (5) | 0.020 (4) |
I1—Fe1 | 2.600 (1) | C20—H20 | 0.9300 |
Fe1—N1 | 2.044 (3) | C1—C2 | 1.435 (6) |
Fe1—N2 | 2.049 (3) | C2—C3 | 1.373 (7) |
Fe1—N4 | 2.075 (3) | C2—C21 | 1.509 (6) |
Fe1—N3 | 2.079 (3) | C3—C4 | 1.438 (6) |
Cl1—C33 | 1.665 (9) | C3—C22 | 1.526 (7) |
Cl2—C33 | 1.670 (9) | C23—H23A | 0.9600 |
Cl3—C33 | 1.681 (9) | C23—H23B | 0.9600 |
O1—C26 | 1.314 (7) | C23—H23C | 0.9600 |
O1—C27 | 1.464 (7) | C24—H24A | 0.9600 |
O2—C26 | 1.182 (7) | C24—H24B | 0.9600 |
N2—C8 | 1.362 (5) | C24—H24C | 0.9600 |
N2—C5 | 1.365 (5) | C25—H25A | 0.9600 |
N3—C13 | 1.375 (5) | C25—H25B | 0.9600 |
N3—C10 | 1.388 (5) | C25—H25C | 0.9600 |
N4—C16 | 1.374 (5) | C22—H22A | 0.9600 |
N4—C19 | 1.388 (5) | C22—H22B | 0.9600 |
N1—C4 | 1.361 (5) | C22—H22C | 0.9600 |
N1—C1 | 1.363 (5) | C21—H21A | 0.9600 |
C5—C4 | 1.423 (5) | C21—H21B | 0.9600 |
C5—C6 | 1.441 (5) | C21—H21C | 0.9600 |
C6—C7 | 1.370 (7) | C32—H32A | 0.9600 |
C6—C23 | 1.506 (7) | C32—H32B | 0.9600 |
C7—C8 | 1.444 (6) | C32—H32C | 0.9600 |
C7—C24 | 1.492 (6) | C27—C28 | 1.485 (10) |
C8—C9 | 1.364 (6) | C27—H27A | 0.9700 |
C9—C10 | 1.397 (7) | C27—H27B | 0.9700 |
C9—H9 | 0.9300 | C28—H28A | 0.9600 |
C10—C11 | 1.430 (6) | C28—H28B | 0.9600 |
C11—C12 | 1.341 (7) | C28—H28C | 0.9600 |
C11—C25 | 1.531 (7) | O3A—C29A | 1.230 (7) |
C12—C13 | 1.450 (6) | O3A—C30A | 1.483 (8) |
C12—C26 | 1.496 (7) | O4A—C29A | 1.263 (7) |
C13—C14 | 1.399 (6) | C30A—C31A | 1.502 (9) |
C14—C15 | 1.357 (7) | C30A—H30A | 0.9700 |
C14—H14 | 0.9300 | C30A—H30B | 0.9700 |
C15—C16 | 1.403 (6) | C31A—H31A | 0.9700 |
C15—H15 | 0.9300 | C31A—H31B | 0.9700 |
C16—C17 | 1.457 (6) | C31A—H31D | 0.9600 |
C17—C18 | 1.342 (7) | C31A—H31E | 0.9600 |
C17—C29A | 1.487 (6) | C31A—H31F | 0.9600 |
C18—C19 | 1.441 (5) | O3B—C30B | 1.482 (8) |
C18—C32 | 1.504 (6) | C30B—H30C | 0.9700 |
C19—C20 | 1.390 (6) | C30B—H30D | 0.9700 |
C20—C1 | 1.374 (6) | C33—H33 | 0.9800 |
N1—Fe1—N2 | 74.0 (1) | N1—C4—C5 | 112.6 (4) |
N1—Fe1—N4 | 86.1 (1) | N1—C4—C3 | 109.9 (4) |
N2—Fe1—N4 | 152.6 (1) | C5—C4—C3 | 137.5 (4) |
N1—Fe1—N3 | 152.1 (1) | C6—C23—H23A | 109.5 |
N2—Fe1—N3 | 85.6 (1) | C6—C23—H23B | 109.5 |
N4—Fe1—N3 | 105.6 (1) | H23A—C23—H23B | 109.5 |
N1—Fe1—I1 | 103.92 (10) | C6—C23—H23C | 109.5 |
N2—Fe1—I1 | 103.80 (10) | H23A—C23—H23C | 109.5 |
N4—Fe1—I1 | 99.01 (10) | H23B—C23—H23C | 109.5 |
N3—Fe1—I1 | 99.26 (10) | C7—C24—H24A | 109.5 |
C26—O1—C27 | 117.5 (5) | C7—C24—H24B | 109.5 |
C8—N2—C5 | 107.7 (3) | H24A—C24—H24B | 109.5 |
C8—N2—Fe1 | 131.9 (3) | C7—C24—H24C | 109.5 |
C5—N2—Fe1 | 119.5 (3) | H24A—C24—H24C | 109.5 |
C13—N3—C10 | 106.2 (3) | H24B—C24—H24C | 109.5 |
C13—N3—Fe1 | 126.8 (3) | C11—C25—H25A | 109.5 |
C10—N3—Fe1 | 125.2 (3) | C11—C25—H25B | 109.5 |
C16—N4—C19 | 106.6 (3) | H25A—C25—H25B | 109.5 |
C16—N4—Fe1 | 127.4 (3) | C11—C25—H25C | 109.5 |
C19—N4—Fe1 | 124.4 (3) | H25A—C25—H25C | 109.5 |
C4—N1—C1 | 107.6 (3) | H25B—C25—H25C | 109.5 |
C4—N1—Fe1 | 119.7 (3) | C3—C22—H22A | 109.5 |
C1—N1—Fe1 | 132.0 (3) | C3—C22—H22B | 109.5 |
N2—C5—C4 | 112.2 (3) | H22A—C22—H22B | 109.5 |
N2—C5—C6 | 109.9 (4) | C3—C22—H22C | 109.5 |
C4—C5—C6 | 137.8 (4) | H22A—C22—H22C | 109.5 |
C7—C6—C5 | 106.0 (4) | H22B—C22—H22C | 109.5 |
C7—C6—C23 | 125.3 (4) | C2—C21—H21A | 109.5 |
C5—C6—C23 | 128.7 (4) | C2—C21—H21B | 109.5 |
C6—C7—C8 | 107.5 (4) | H21A—C21—H21B | 109.5 |
C6—C7—C24 | 127.8 (5) | C2—C21—H21C | 109.5 |
C8—C7—C24 | 124.7 (5) | H21A—C21—H21C | 109.5 |
N2—C8—C9 | 121.0 (4) | H21B—C21—H21C | 109.5 |
N2—C8—C7 | 108.9 (4) | C18—C32—H32A | 109.5 |
C9—C8—C7 | 130.0 (4) | C18—C32—H32B | 109.5 |
C8—C9—C10 | 126.8 (4) | H32A—C32—H32B | 109.5 |
C8—C9—H9 | 116.6 | C18—C32—H32C | 109.5 |
C10—C9—H9 | 116.6 | H32A—C32—H32C | 109.5 |
N3—C10—C9 | 126.2 (4) | H32B—C32—H32C | 109.5 |
N3—C10—C11 | 109.9 (4) | O2—C26—O1 | 122.2 (5) |
C9—C10—C11 | 123.9 (4) | O2—C26—C12 | 126.2 (5) |
C12—C11—C10 | 107.1 (4) | O1—C26—C12 | 111.5 (5) |
C12—C11—C25 | 129.4 (5) | O1—C27—C28 | 105.5 (6) |
C10—C11—C25 | 123.5 (5) | O1—C27—H27A | 110.6 |
C11—C12—C13 | 108.0 (4) | C28—C27—H27A | 110.6 |
C11—C12—C26 | 127.2 (4) | O1—C27—H27B | 110.6 |
C13—C12—C26 | 124.8 (5) | C28—C27—H27B | 110.6 |
N3—C13—C14 | 129.2 (4) | H27A—C27—H27B | 108.8 |
N3—C13—C12 | 108.8 (4) | C27—C28—H28A | 109.5 |
C14—C13—C12 | 121.9 (4) | C27—C28—H28B | 109.5 |
C15—C14—C13 | 138.7 (4) | H28A—C28—H28B | 109.5 |
C15—C14—H14 | 110.7 | C27—C28—H28C | 109.5 |
C13—C14—H14 | 110.7 | H28A—C28—H28C | 109.5 |
C14—C15—C16 | 137.3 (4) | H28B—C28—H28C | 109.5 |
C14—C15—H15 | 111.4 | C29A—O3A—C30A | 117.9 (8) |
C16—C15—H15 | 111.4 | O3A—C29A—O4A | 120.9 (6) |
N4—C16—C15 | 129.3 (4) | O3A—C29A—C17 | 122.3 (6) |
N4—C16—C17 | 108.5 (4) | O4A—C29A—C17 | 116.7 (5) |
C15—C16—C17 | 122.1 (4) | O3A—C30A—C31A | 114.4 (9) |
C18—C17—C16 | 108.3 (4) | O3A—C30A—H30A | 108.7 |
C18—C17—C29A | 124.2 (4) | C31A—C30A—H30A | 108.7 |
C16—C17—C29A | 127.4 (4) | O3A—C30A—H30B | 108.7 |
C17—C18—C19 | 106.7 (4) | C31A—C30A—H30B | 108.7 |
C17—C18—C32 | 129.4 (4) | H30A—C30A—H30B | 107.6 |
C19—C18—C32 | 123.8 (4) | C30A—C31A—H31A | 109.7 (10) |
N4—C19—C20 | 127.5 (3) | C30A—C31A—H31B | 109.8 (11) |
N4—C19—C18 | 109.8 (4) | H31A—C31A—H31B | 107.8 (10) |
C20—C19—C18 | 122.7 (4) | C30A—C31A—H31C | 110.4 (10) |
C1—C20—C19 | 125.9 (4) | H31A—C31A—H31C | 109.9 (11) |
C1—C20—H20 | 117.1 | H31B—C31A—H31C | 109.2 (11) |
C19—C20—H20 | 117.1 | O3B—C30B—H31C | 95.5 (10) |
N1—C1—C20 | 121.3 (4) | O3B—C30B—H30C | 111.4 |
N1—C1—C2 | 109.1 (4) | O3B—C30B—H30D | 111.4 |
C20—C1—C2 | 129.6 (4) | H30C—C30B—H30D | 109.3 |
C3—C2—C1 | 107.4 (4) | Cl1—C33—Cl2 | 111.3 (6) |
C3—C2—C21 | 127.5 (4) | Cl1—C33—Cl3 | 109.3 (5) |
C1—C2—C21 | 125.2 (4) | Cl2—C33—Cl3 | 116.4 (7) |
C2—C3—C4 | 106.0 (4) | Cl1—C33—H33 | 106.4 |
C2—C3—C22 | 126.5 (4) | Cl2—C33—H33 | 106.4 |
C4—C3—C22 | 127.5 (4) | Cl3—C33—H33 | 106.4 |
N1—Fe1—N2—C8 | 179.7 (4) | C11—C12—C13—N3 | −0.2 (5) |
N4—Fe1—N2—C8 | −135.5 (4) | C26—C12—C13—N3 | 177.0 (5) |
N3—Fe1—N2—C8 | −19.6 (4) | C11—C12—C13—C14 | −179.9 (4) |
I1—Fe1—N2—C8 | 78.9 (4) | C26—C12—C13—C14 | −2.7 (8) |
N1—Fe1—N2—C5 | 12.5 (3) | N3—C13—C14—C15 | 1.8 (10) |
N4—Fe1—N2—C5 | 57.3 (5) | C12—C13—C14—C15 | −178.6 (6) |
N3—Fe1—N2—C5 | 173.3 (3) | C13—C14—C15—C16 | 0.6 (12) |
I1—Fe1—N2—C5 | −88.3 (3) | C19—N4—C16—C15 | −179.2 (5) |
N1—Fe1—N3—C13 | −138.3 (3) | Fe1—N4—C16—C15 | −13.4 (7) |
N2—Fe1—N3—C13 | 179.1 (4) | C19—N4—C16—C17 | −0.2 (4) |
N4—Fe1—N3—C13 | −26.3 (4) | Fe1—N4—C16—C17 | 165.6 (3) |
I1—Fe1—N3—C13 | 75.8 (3) | C14—C15—C16—N4 | −3.0 (10) |
N1—Fe1—N3—C10 | 59.4 (5) | C14—C15—C16—C17 | 178.1 (6) |
N2—Fe1—N3—C10 | 16.8 (3) | N4—C16—C17—C18 | −0.2 (5) |
N4—Fe1—N3—C10 | 171.4 (3) | C15—C16—C17—C18 | 178.9 (4) |
I1—Fe1—N3—C10 | −86.5 (3) | N4—C16—C17—C29A | −176.2 (4) |
N1—Fe1—N4—C16 | −179.7 (4) | C15—C16—C17—C29A | 2.9 (7) |
N2—Fe1—N4—C16 | 137.5 (4) | C16—C17—C18—C19 | 0.5 (5) |
N3—Fe1—N4—C16 | 26.1 (4) | C29A—C17—C18—C19 | 176.6 (4) |
I1—Fe1—N4—C16 | −76.3 (3) | C16—C17—C18—C32 | −179.6 (4) |
N1—Fe1—N4—C19 | −16.3 (3) | C29A—C17—C18—C32 | −3.5 (8) |
N2—Fe1—N4—C19 | −59.1 (5) | C16—N4—C19—C20 | 178.9 (4) |
N3—Fe1—N4—C19 | −170.5 (3) | Fe1—N4—C19—C20 | 12.6 (6) |
I1—Fe1—N4—C19 | 87.2 (3) | C16—N4—C19—C18 | 0.6 (4) |
N2—Fe1—N1—C4 | −12.0 (3) | Fe1—N4—C19—C18 | −165.8 (3) |
N4—Fe1—N1—C4 | −173.1 (3) | C17—C18—C19—N4 | −0.7 (5) |
N3—Fe1—N1—C4 | −56.6 (5) | C32—C18—C19—N4 | 179.5 (4) |
I1—Fe1—N1—C4 | 88.6 (3) | C17—C18—C19—C20 | −179.1 (4) |
N2—Fe1—N1—C1 | 178.5 (4) | C32—C18—C19—C20 | 1.0 (7) |
N4—Fe1—N1—C1 | 17.5 (4) | N4—C19—C20—C1 | −0.5 (7) |
N3—Fe1—N1—C1 | 133.9 (4) | C18—C19—C20—C1 | 177.7 (4) |
I1—Fe1—N1—C1 | −80.8 (4) | C4—N1—C1—C20 | 177.4 (4) |
C8—N2—C5—C4 | 178.7 (4) | Fe1—N1—C1—C20 | −12.2 (6) |
Fe1—N2—C5—C4 | −11.3 (5) | C4—N1—C1—C2 | −0.9 (5) |
C8—N2—C5—C6 | −0.7 (5) | Fe1—N1—C1—C2 | 169.5 (3) |
Fe1—N2—C5—C6 | 169.3 (3) | C19—C20—C1—N1 | −0.5 (7) |
N2—C5—C6—C7 | 0.8 (5) | C19—C20—C1—C2 | 177.5 (4) |
C4—C5—C6—C7 | −178.4 (5) | N1—C1—C2—C3 | 0.9 (5) |
N2—C5—C6—C23 | 180.0 (5) | C20—C1—C2—C3 | −177.3 (5) |
C4—C5—C6—C23 | 0.8 (9) | N1—C1—C2—C21 | −179.2 (4) |
C5—C6—C7—C8 | −0.5 (5) | C20—C1—C2—C21 | 2.7 (8) |
C23—C6—C7—C8 | −179.8 (4) | C1—C2—C3—C4 | −0.4 (5) |
C5—C6—C7—C24 | −178.9 (5) | C21—C2—C3—C4 | 179.6 (5) |
C23—C6—C7—C24 | 1.8 (8) | C1—C2—C3—C22 | 179.2 (5) |
C5—N2—C8—C9 | −176.6 (4) | C21—C2—C3—C22 | −0.7 (9) |
Fe1—N2—C8—C9 | 15.1 (6) | C1—N1—C4—C5 | −178.3 (4) |
C5—N2—C8—C7 | 0.4 (5) | Fe1—N1—C4—C5 | 9.9 (5) |
Fe1—N2—C8—C7 | −167.9 (3) | C1—N1—C4—C3 | 0.7 (5) |
C6—C7—C8—N2 | 0.1 (5) | Fe1—N1—C4—C3 | −171.1 (3) |
C24—C7—C8—N2 | 178.6 (4) | N2—C5—C4—N1 | 0.9 (5) |
C6—C7—C8—C9 | 176.8 (5) | C6—C5—C4—N1 | −179.9 (5) |
C24—C7—C8—C9 | −4.8 (8) | N2—C5—C4—C3 | −177.7 (5) |
N2—C8—C9—C10 | −0.8 (7) | C6—C5—C4—C3 | 1.5 (10) |
C7—C8—C9—C10 | −177.1 (5) | C2—C3—C4—N1 | −0.1 (5) |
C13—N3—C10—C9 | −177.3 (4) | C22—C3—C4—N1 | −179.8 (5) |
Fe1—N3—C10—C9 | −12.0 (6) | C2—C3—C4—C5 | 178.5 (5) |
C13—N3—C10—C11 | 0.7 (5) | C22—C3—C4—C5 | −1.2 (9) |
Fe1—N3—C10—C11 | 166.1 (3) | C27—O1—C26—O2 | −8.4 (10) |
C8—C9—C10—N3 | 0.0 (8) | C27—O1—C26—C12 | 175.3 (5) |
C8—C9—C10—C11 | −177.8 (5) | C11—C12—C26—O2 | −155.0 (8) |
N3—C10—C11—C12 | −0.9 (5) | C13—C12—C26—O2 | 28.3 (10) |
C9—C10—C11—C12 | 177.2 (5) | C11—C12—C26—O1 | 21.0 (8) |
N3—C10—C11—C25 | 176.1 (5) | C13—C12—C26—O1 | −155.7 (5) |
C9—C10—C11—C25 | −5.7 (8) | C26—O1—C27—C28 | 166.2 (6) |
C10—C11—C12—C13 | 0.7 (5) | C30A—O3A—C29A—O4A | 2.8 (13) |
C25—C11—C12—C13 | −176.1 (5) | C30A—O3A—C29A—C17 | −174.2 (9) |
C10—C11—C12—C26 | −176.5 (5) | C18—C17—C29A—O3A | −29.6 (8) |
C25—C11—C12—C26 | 6.7 (9) | C16—C17—C29A—O3A | 145.8 (8) |
C10—N3—C13—C14 | 179.3 (5) | C18—C17—C29A—O4A | 153.3 (7) |
Fe1—N3—C13—C14 | 14.3 (7) | C16—C17—C29A—O4A | −31.3 (8) |
C10—N3—C13—C12 | −0.3 (5) | C29A—O3A—C30A—C31A | 68.9 (16) |
Fe1—N3—C13—C12 | −165.4 (3) |
Experimental details
Crystal data | |
Chemical formula | [Fe(C32H32N4O4)I]·CHCl3 |
Mr | 838.73 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 298 |
a, b, c (Å) | 8.538 (2), 14.114 (2), 15.648 (4) |
α, β, γ (°) | 106.040 (14), 93.59 (2), 104.964 (16) |
V (Å3) | 1732.5 (7) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 1.60 |
Crystal size (mm) | 0.5 × 0.4 × 0.1 |
Data collection | |
Diffractometer | RIGAKU AFC7 diffractometer |
Absorption correction | ψ scan (North et al., 1968) |
Tmin, Tmax | 0.474, 0.852 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 8460, 7927, 5539 |
Rint | 0.020 |
(sin θ/λ)max (Å−1) | 0.650 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.048, 0.150, 1.09 |
No. of reflections | 7927 |
No. of parameters | 432 |
No. of restraints | 16 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.88, −0.76 |
Computer programs: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1992a), MSC/AFC Diffractometer Control Software and TEXSAN (Molecular Structure Corporation, 1992b), SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 1997), SV (Nemoto & Ohashi, 1993), SHELXL97.
I1—Fe1 | 2.600 (1) | Fe1—N4 | 2.075 (3) |
Fe1—N1 | 2.044 (3) | Fe1—N3 | 2.079 (3) |
Fe1—N2 | 2.049 (3) | ||
N1—Fe1—N2 | 74.0 (1) | N1—Fe1—N3 | 152.1 (1) |
N1—Fe1—N4 | 86.1 (1) | N2—Fe1—N3 | 85.6 (1) |
N2—Fe1—N4 | 152.6 (1) | N4—Fe1—N3 | 105.6 (1) |
Subscribe to Acta Crystallographica Section C: Structural Chemistry
The full text of this article is available to subscribers to the journal.
- Information on subscribing
- Sample issue
- Purchase subscription
- Reduced-price subscriptions
- If you have already subscribed, you may need to register
Corrphycene is one of the porphyrin family and it is transcribed as [18]porphyrin-(2.1.0.1). Although the structure of various metallocorrphycenes has been reported (Sessler et al., 2000), little is known on the structure of iron corrphycene. In this paper, we describe the first example of an X-ray crystallographic analysis of iron(III) corrphycene complex, (I). \sch
The molecular structure of (I) with numbering is shown in Fig. 1. One of the ethoxycarbonyl groups is disordered. On the other hand, another ethoxycarbonyl group takes ordered structure because of the hydrogen bonding with an adjacent chloroform molecule. [C—H.·O hydrogen bonding; C33···O2 3.119 (11) Å] The corrphycene ring exhibits almost planar structure where the shifts of peripheral 24 atoms from the least-squares plane of the C20N4 corrphycenato core are within 0.059 (4) Å. The central N4 cavity shows trapezoidal geometry with N1···N2 2.464 (4), N2···N3 2.805 (5), N3···N4 3.308 (5), and N4···N1 2.811 (5) Å. Thus, the surface area within the N4 coordinating core is 8.015 Å2, which is smaller than the corresponding area of iron porphyrins; 8.123 Å2 in both [Fe(OEP)Cl] and [Fe(TPP)I] (OEP: dianion of 2,3,7,8,12,13,17,18-octaethylporphyrin (Cambridge Structural Database reference code TOYRUU; Senge, 1997; TPP: dianion of meso-tetraphenylporphyrin; Hatano & Scheidt, 1979). The axial Fe—I bond distance is 2.600 (1) Å, which is longer than that reported for [Fe(TPP)I], 2.55 Å. The Fe—N bond distances for direct-linked pyrroles, 2.044 (3) and 2.049 (3) Å, are slightly shorter than those for etheno-bridged pyrroles, 2.080 (3) and 2.075 (3) Å; the average Fe—N bond distance is 2.07 Å in both [Fe(OEP)Cl] and [Fe(TPP)I]. The deviation of the central iron(III) atom from the least-squares plane of the C20N4, 0.416 (1) Å, is significantly smaller than that of [Fe(TPP)I], 0.526 Å. These results clearly demonstrate the difference in cavity geometry between iron(III) corrphycene and iron(III) porphyrin complexes.
One of the two ethoxycarbonyl groups is disordered over two orientations; the other is not diordered and is locked in the conformation found in the crystal by a C—H···O hydrogen bond (see Fig. 1 and Table 2) with the chloroform of solvation.