Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270101009842/ta1328sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270101009842/ta1328Isup2.hkl |
CCDC reference: 173354
3,6,13,16-Tetraethyl-2,7,12,17-tetramethylporphycene was synthesized according to the literature method of Vogel et al. (1993) from ethyl 4-ethyl-3,5-dimethylpyrrole-2-carboxylate as starting material. This porphycene is a positional isomer of etioporphycene reported by Vogel et al. (1993). Insertion of iron was carried out according to Adler et al. (1970) to afford the title chloroiron(III) complex.
There is disorder in the solvent CHCl3 molecule. The site-occupation factors for the disordered groups (A and B) are 0.50 each. H atoms were refined using a riding model. The positional parameters of the H atoms were constrained to have C—H distances of 0.96 Å for primary, 0.97 Å for secondary, and 0.93 Å for aromatic H atoms. H-atom Ueq values were constrained to 1.2 times the Uiso 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: MSC/AFC Diffractometer Control Software. Data Reduction: 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(C32H36N4)Cl]·CHCl3 | F(000) = 1428 |
Mr = 687.32 | Dx = 1.381 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71069 Å |
a = 14.722 (1) Å | Cell parameters from 20513 reflections |
b = 10.225 (1) Å | θ = 0.9–27.5° |
c = 22.319 (2) Å | µ = 0.81 mm−1 |
β = 100.35 (1)° | T = 298 K |
V = 3305.1 (6) Å3 | Prismatic, purple |
Z = 4 | 0.2 × 0.2 × 0.2 mm |
Rigaku R-AXIS RAPID Imaging Plate diffractometer | 7514 independent reflections |
Radiation source: rotating anode | 5436 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.049 |
Detector resolution: 10 pixels mm-1 | θmax = 27.5°, θmin = 1.8° |
ω scans | h = −19→17 |
Absorption correction: multi-scan ABSCOR (Higashi, 1995) | k = −13→10 |
Tmin = 0.849, Tmax = 0.851 | l = −27→28 |
19098 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)] = 0.070 | H-atom parameters constrained |
wR(F2) = 0.205 | w = 1/[σ2(Fo2) + (0.1119P)2 + 1.7054P] where P = (Fo2 + 2Fc2)/3 |
S = 1.08 | (Δ/σ)max < 0.001 |
7514 reflections | Δρmax = 0.77 e Å−3 |
415 parameters | Δρmin = −0.47 e Å−3 |
6 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.025 (2) |
[Fe(C32H36N4)Cl]·CHCl3 | V = 3305.1 (6) Å3 |
Mr = 687.32 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 14.722 (1) Å | µ = 0.81 mm−1 |
b = 10.225 (1) Å | T = 298 K |
c = 22.319 (2) Å | 0.2 × 0.2 × 0.2 mm |
β = 100.35 (1)° |
Rigaku R-AXIS RAPID Imaging Plate diffractometer | 7514 independent reflections |
Absorption correction: multi-scan ABSCOR (Higashi, 1995) | 5436 reflections with I > 2σ(I) |
Tmin = 0.849, Tmax = 0.851 | Rint = 0.049 |
19098 measured reflections |
R[F2 > 2σ(F2)] = 0.070 | 6 restraints |
wR(F2) = 0.205 | H-atom parameters constrained |
S = 1.08 | Δρmax = 0.77 e Å−3 |
7514 reflections | Δρmin = −0.47 e Å−3 |
415 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 | 0.73807 (3) | 0.11207 (4) | 0.08403 (2) | 0.04654 (19) | |
Cl1 | 0.71525 (7) | 0.20457 (10) | −0.00802 (4) | 0.0645 (3) | |
N1 | 0.7147 (2) | −0.0831 (3) | 0.07205 (13) | 0.0526 (7) | |
N2 | 0.8690 (2) | 0.0422 (3) | 0.09608 (12) | 0.0504 (6) | |
N3 | 0.7739 (2) | 0.2654 (3) | 0.14085 (12) | 0.0513 (6) | |
N4 | 0.6195 (2) | 0.1414 (3) | 0.11557 (12) | 0.0519 (6) | |
C1 | 0.6384 (3) | −0.1639 (4) | 0.05794 (16) | 0.0586 (9) | |
C2 | 0.6696 (4) | −0.2917 (4) | 0.04374 (18) | 0.0712 (11) | |
C3 | 0.7638 (3) | −0.2894 (4) | 0.05056 (17) | 0.0663 (10) | |
C4 | 0.7922 (3) | −0.1570 (3) | 0.06731 (15) | 0.0544 (8) | |
C5 | 0.8761 (3) | −0.0869 (4) | 0.07807 (15) | 0.0543 (8) | |
C6 | 0.9713 (3) | −0.1117 (4) | 0.07239 (17) | 0.0646 (10) | |
C7 | 1.0180 (3) | 0.0025 (5) | 0.08583 (18) | 0.0663 (10) | |
C8 | 0.9549 (2) | 0.0978 (4) | 0.10120 (16) | 0.0568 (8) | |
C9 | 0.9820 (3) | 0.2239 (4) | 0.12060 (18) | 0.0661 (10) | |
H9 | 1.0417 | 0.2445 | 0.1155 | 0.079* | |
C10 | 0.9389 (3) | 0.3246 (4) | 0.14575 (18) | 0.0687 (11) | |
H10 | 0.9771 | 0.3965 | 0.1563 | 0.082* | |
C11 | 0.8509 (3) | 0.3418 (4) | 0.15865 (16) | 0.0582 (9) | |
C12 | 0.8266 (4) | 0.4487 (4) | 0.19455 (18) | 0.0732 (12) | |
C13 | 0.7355 (4) | 0.4381 (4) | 0.19787 (17) | 0.0686 (11) | |
C14 | 0.7013 (3) | 0.3236 (3) | 0.16214 (14) | 0.0559 (8) | |
C15 | 0.6159 (3) | 0.2591 (4) | 0.14555 (15) | 0.0541 (8) | |
C16 | 0.5211 (3) | 0.2861 (4) | 0.15004 (17) | 0.0665 (10) | |
C17 | 0.4686 (3) | 0.1852 (5) | 0.12207 (18) | 0.0680 (11) | |
C18 | 0.5306 (3) | 0.0934 (4) | 0.10153 (16) | 0.0585 (9) | |
C19 | 0.5013 (3) | −0.0261 (5) | 0.07452 (18) | 0.0682 (10) | |
H19 | 0.4374 | −0.0355 | 0.0671 | 0.082* | |
C20 | 0.5464 (3) | −0.1332 (4) | 0.05652 (18) | 0.0663 (10) | |
H20 | 0.5064 | −0.1993 | 0.0397 | 0.080* | |
C21 | 0.6063 (5) | −0.4084 (5) | 0.0263 (3) | 0.0993 (18) | |
H21A | 0.6398 | −0.4877 | 0.0377 | 0.149* | |
H21B | 0.5845 | −0.4080 | −0.0169 | 0.149* | |
H21C | 0.5547 | −0.4031 | 0.0471 | 0.149* | |
C22 | 0.8211 (5) | −0.4087 (4) | 0.0430 (3) | 0.0930 (16) | |
H22A | 0.7953 | −0.4839 | 0.0605 | 0.112* | |
H22B | 0.8834 | −0.3957 | 0.0651 | 0.112* | |
C23 | 0.8241 (6) | −0.4361 (7) | −0.0237 (3) | 0.133 (3) | |
H23A | 0.7624 | −0.4391 | −0.0465 | 0.199* | |
H23B | 0.8540 | −0.5185 | −0.0271 | 0.199* | |
H23C | 0.8580 | −0.3679 | −0.0395 | 0.199* | |
C24 | 1.0160 (4) | −0.2360 (5) | 0.0559 (2) | 0.0873 (14) | |
H24A | 1.0624 | −0.2147 | 0.0316 | 0.105* | |
H24B | 0.9698 | −0.2907 | 0.0314 | 0.105* | |
C25 | 1.0609 (5) | −0.3113 (7) | 0.1123 (3) | 0.129 (3) | |
H25A | 1.1080 | −0.2582 | 0.1360 | 0.194* | |
H25B | 1.0881 | −0.3901 | 0.1003 | 0.194* | |
H25C | 1.0150 | −0.3329 | 0.1363 | 0.194* | |
C26 | 1.1197 (3) | 0.0249 (6) | 0.0868 (2) | 0.0908 (15) | |
H26A | 1.1511 | 0.0336 | 0.1282 | 0.136* | |
H26B | 1.1278 | 0.1034 | 0.0648 | 0.136* | |
H26C | 1.1448 | −0.0480 | 0.0681 | 0.136* | |
C27 | 0.8937 (5) | 0.5510 (6) | 0.2254 (3) | 0.112 (2) | |
H27A | 0.8901 | 0.6275 | 0.2001 | 0.169* | |
H27B | 0.9553 | 0.5165 | 0.2314 | 0.169* | |
H27C | 0.8782 | 0.5736 | 0.2640 | 0.169* | |
C28 | 0.6867 (4) | 0.5295 (5) | 0.2346 (2) | 0.0866 (14) | |
H28A | 0.7271 | 0.5481 | 0.2730 | 0.104* | |
H28B | 0.6320 | 0.4863 | 0.2436 | 0.104* | |
C29 | 0.6583 (6) | 0.6575 (5) | 0.2022 (3) | 0.118 (2) | |
H29A | 0.7122 | 0.7017 | 0.1938 | 0.177* | |
H29B | 0.6279 | 0.7117 | 0.2276 | 0.177* | |
H29C | 0.6170 | 0.6400 | 0.1646 | 0.177* | |
C30 | 0.4815 (4) | 0.4020 (5) | 0.1795 (2) | 0.0885 (15) | |
H30A | 0.4220 | 0.4252 | 0.1556 | 0.106* | |
H30B | 0.5222 | 0.4766 | 0.1798 | 0.106* | |
C31 | 0.4698 (5) | 0.3717 (6) | 0.2448 (3) | 0.116 (2) | |
H31A | 0.4259 | 0.3021 | 0.2445 | 0.174* | |
H31B | 0.4481 | 0.4483 | 0.2627 | 0.174* | |
H31C | 0.5282 | 0.3455 | 0.2682 | 0.174* | |
C32 | 0.3652 (3) | 0.1678 (7) | 0.1140 (3) | 0.0968 (16) | |
H32A | 0.3370 | 0.2496 | 0.1212 | 0.145* | |
H32B | 0.3512 | 0.1037 | 0.1424 | 0.145* | |
H32C | 0.3417 | 0.1391 | 0.0732 | 0.145* | |
C33A | 0.3602 (5) | 0.7589 (7) | 0.2314 (3) | 0.177 (4) | 0.50 |
H33A | 0.3985 | 0.7131 | 0.2654 | 0.213* | 0.50 |
Cl2A | 0.3139 (6) | 0.8792 (13) | 0.2666 (5) | 0.295 (8) | 0.50 |
Cl3A | 0.2890 (6) | 0.6337 (8) | 0.1959 (9) | 0.332 (8) | 0.50 |
Cl4A | 0.4327 (5) | 0.7879 (9) | 0.1864 (3) | 0.218 (3) | 0.50 |
C33B | 0.3602 (5) | 0.7589 (7) | 0.2314 (3) | 0.177 (4) | 0.50 |
H33B | 0.4230 | 0.7352 | 0.2509 | 0.213* | 0.50 |
Cl2B | 0.3474 (4) | 0.7544 (8) | 0.1561 (2) | 0.184 (2) | 0.50 |
Cl3B | 0.3412 (15) | 0.9224 (9) | 0.2352 (8) | 0.411 (13) | 0.50 |
Cl4B | 0.2844 (5) | 0.6731 (14) | 0.2564 (4) | 0.262 (7) | 0.50 |
U11 | U22 | U33 | U12 | U13 | U23 | |
Fe1 | 0.0526 (3) | 0.0418 (3) | 0.0457 (3) | −0.00487 (19) | 0.01047 (19) | −0.00421 (18) |
Cl1 | 0.0722 (6) | 0.0712 (6) | 0.0494 (5) | −0.0078 (4) | 0.0087 (4) | 0.0084 (4) |
N1 | 0.0639 (16) | 0.0453 (15) | 0.0497 (14) | −0.0067 (12) | 0.0131 (13) | −0.0017 (12) |
N2 | 0.0559 (15) | 0.0472 (15) | 0.0480 (14) | −0.0014 (12) | 0.0090 (12) | 0.0006 (12) |
N3 | 0.0647 (16) | 0.0452 (14) | 0.0435 (13) | −0.0044 (13) | 0.0087 (12) | −0.0036 (11) |
N4 | 0.0575 (15) | 0.0559 (16) | 0.0438 (13) | −0.0020 (13) | 0.0136 (12) | 0.0005 (12) |
C1 | 0.079 (2) | 0.0483 (18) | 0.0484 (17) | −0.0183 (17) | 0.0098 (16) | −0.0009 (15) |
C2 | 0.108 (3) | 0.049 (2) | 0.056 (2) | −0.022 (2) | 0.011 (2) | −0.0052 (16) |
C3 | 0.103 (3) | 0.0417 (18) | 0.0538 (19) | −0.0020 (19) | 0.014 (2) | −0.0012 (15) |
C4 | 0.075 (2) | 0.0439 (17) | 0.0453 (16) | 0.0022 (16) | 0.0130 (15) | −0.0001 (13) |
C5 | 0.065 (2) | 0.0530 (19) | 0.0456 (16) | 0.0059 (16) | 0.0116 (15) | −0.0010 (14) |
C6 | 0.072 (2) | 0.072 (3) | 0.0522 (19) | 0.017 (2) | 0.0188 (17) | 0.0035 (17) |
C7 | 0.059 (2) | 0.085 (3) | 0.056 (2) | 0.009 (2) | 0.0133 (17) | 0.0027 (19) |
C8 | 0.0558 (19) | 0.066 (2) | 0.0486 (17) | −0.0027 (16) | 0.0099 (15) | 0.0019 (16) |
C9 | 0.060 (2) | 0.077 (3) | 0.062 (2) | −0.0169 (19) | 0.0125 (17) | −0.0008 (19) |
C10 | 0.079 (3) | 0.066 (2) | 0.060 (2) | −0.030 (2) | 0.0083 (19) | −0.0080 (19) |
C11 | 0.079 (2) | 0.0482 (18) | 0.0477 (17) | −0.0160 (17) | 0.0109 (16) | −0.0025 (15) |
C12 | 0.113 (4) | 0.052 (2) | 0.056 (2) | −0.023 (2) | 0.018 (2) | −0.0118 (17) |
C13 | 0.111 (3) | 0.0493 (19) | 0.0480 (18) | −0.004 (2) | 0.020 (2) | −0.0072 (16) |
C14 | 0.079 (2) | 0.0484 (18) | 0.0409 (16) | 0.0017 (17) | 0.0128 (16) | 0.0011 (14) |
C15 | 0.069 (2) | 0.0538 (19) | 0.0411 (15) | 0.0095 (16) | 0.0142 (14) | 0.0058 (14) |
C16 | 0.076 (2) | 0.076 (3) | 0.0527 (19) | 0.020 (2) | 0.0244 (18) | 0.0147 (18) |
C17 | 0.063 (2) | 0.088 (3) | 0.054 (2) | 0.010 (2) | 0.0148 (17) | 0.017 (2) |
C18 | 0.0575 (19) | 0.071 (2) | 0.0485 (18) | −0.0021 (17) | 0.0134 (15) | 0.0106 (16) |
C19 | 0.058 (2) | 0.088 (3) | 0.057 (2) | −0.018 (2) | 0.0090 (17) | 0.007 (2) |
C20 | 0.075 (2) | 0.067 (2) | 0.057 (2) | −0.025 (2) | 0.0107 (18) | −0.0022 (17) |
C21 | 0.151 (5) | 0.060 (3) | 0.086 (3) | −0.044 (3) | 0.017 (3) | −0.014 (2) |
C22 | 0.141 (5) | 0.047 (2) | 0.094 (3) | 0.011 (3) | 0.029 (3) | 0.000 (2) |
C23 | 0.202 (8) | 0.089 (4) | 0.117 (5) | 0.029 (5) | 0.053 (5) | −0.038 (4) |
C24 | 0.107 (4) | 0.086 (3) | 0.078 (3) | 0.031 (3) | 0.040 (3) | −0.003 (2) |
C25 | 0.162 (6) | 0.122 (5) | 0.105 (4) | 0.086 (5) | 0.031 (4) | 0.012 (4) |
C26 | 0.062 (2) | 0.126 (4) | 0.088 (3) | 0.007 (3) | 0.023 (2) | 0.001 (3) |
C27 | 0.150 (5) | 0.091 (4) | 0.100 (4) | −0.054 (4) | 0.034 (4) | −0.052 (3) |
C28 | 0.132 (4) | 0.075 (3) | 0.055 (2) | 0.004 (3) | 0.025 (2) | −0.019 (2) |
C29 | 0.198 (7) | 0.061 (3) | 0.101 (4) | 0.023 (4) | 0.043 (4) | −0.020 (3) |
C30 | 0.101 (4) | 0.086 (3) | 0.084 (3) | 0.038 (3) | 0.030 (3) | 0.010 (3) |
C31 | 0.145 (5) | 0.116 (5) | 0.106 (4) | 0.037 (4) | 0.072 (4) | −0.002 (3) |
C32 | 0.060 (2) | 0.136 (5) | 0.097 (4) | 0.015 (3) | 0.024 (2) | 0.017 (4) |
C33A | 0.137 (7) | 0.210 (11) | 0.178 (9) | 0.013 (8) | 0.012 (7) | 0.028 (8) |
Cl2A | 0.176 (6) | 0.45 (2) | 0.257 (10) | 0.193 (10) | 0.036 (6) | −0.051 (11) |
Cl3A | 0.139 (5) | 0.179 (7) | 0.64 (3) | 0.016 (5) | −0.027 (11) | 0.027 (12) |
Cl4A | 0.174 (5) | 0.314 (10) | 0.176 (5) | −0.047 (6) | 0.059 (4) | 0.059 (6) |
C33B | 0.137 (7) | 0.210 (11) | 0.178 (9) | 0.013 (8) | 0.012 (7) | 0.028 (8) |
Cl2B | 0.164 (4) | 0.279 (8) | 0.107 (3) | 0.009 (5) | 0.020 (3) | 0.044 (4) |
Cl3B | 0.68 (3) | 0.181 (8) | 0.331 (18) | 0.144 (13) | −0.030 (16) | 0.060 (10) |
Cl4B | 0.143 (5) | 0.456 (18) | 0.199 (7) | −0.004 (7) | 0.061 (5) | 0.168 (10) |
Fe1—N4 | 2.019 (3) | C19—H19 | 0.9300 |
Fe1—N3 | 2.026 (3) | C20—H20 | 0.9300 |
Fe1—N2 | 2.028 (3) | C21—H21A | 0.9600 |
Fe1—N1 | 2.034 (3) | C21—H21B | 0.9600 |
Fe1—Cl1 | 2.2316 (10) | C21—H21C | 0.9600 |
N1—C1 | 1.384 (5) | C22—C23 | 1.523 (8) |
N1—C4 | 1.389 (5) | C22—H22A | 0.9700 |
N2—C8 | 1.373 (5) | C22—H22B | 0.9700 |
N2—C5 | 1.389 (4) | C23—H23A | 0.9600 |
N3—C11 | 1.375 (5) | C23—H23B | 0.9600 |
N3—C14 | 1.381 (5) | C23—H23C | 0.9600 |
N4—C18 | 1.380 (5) | C24—C25 | 1.523 (8) |
N4—C15 | 1.382 (5) | C24—H24A | 0.9700 |
C1—C20 | 1.385 (6) | C24—H24B | 0.9700 |
C1—C2 | 1.439 (6) | C25—H25A | 0.9600 |
C2—C3 | 1.368 (7) | C25—H25B | 0.9600 |
C2—C21 | 1.520 (6) | C25—H25C | 0.9600 |
C3—C4 | 1.446 (5) | C26—H26A | 0.9600 |
C3—C22 | 1.510 (6) | C26—H26B | 0.9600 |
C4—C5 | 1.410 (5) | C26—H26C | 0.9600 |
C5—C6 | 1.452 (5) | C27—H27A | 0.9600 |
C6—C7 | 1.362 (6) | C27—H27B | 0.9600 |
C6—C24 | 1.507 (6) | C27—H27C | 0.9600 |
C7—C8 | 1.430 (6) | C28—C29 | 1.517 (8) |
C7—C26 | 1.511 (6) | C28—H28A | 0.9700 |
C8—C9 | 1.395 (6) | C28—H28B | 0.9700 |
C9—C10 | 1.380 (6) | C29—H29A | 0.9600 |
C9—H9 | 0.9300 | C29—H29B | 0.9600 |
C10—C11 | 1.388 (6) | C29—H29C | 0.9600 |
C10—H10 | 0.9300 | C30—C31 | 1.529 (7) |
C11—C12 | 1.438 (6) | C30—H30A | 0.9700 |
C12—C13 | 1.360 (7) | C30—H30B | 0.9700 |
C12—C27 | 1.516 (6) | C31—H31A | 0.9600 |
C13—C14 | 1.454 (5) | C31—H31B | 0.9600 |
C13—C28 | 1.508 (6) | C31—H31C | 0.9600 |
C14—C15 | 1.408 (5) | C32—H32A | 0.9600 |
C15—C16 | 1.444 (5) | C32—H32B | 0.9600 |
C16—C17 | 1.370 (6) | C32—H32C | 0.9600 |
C16—C30 | 1.523 (6) | C33A—Cl4A | 1.618 (7) |
C17—C18 | 1.441 (6) | C33A—Cl2A | 1.670 (8) |
C17—C32 | 1.511 (6) | C33A—Cl3A | 1.751 (8) |
C18—C19 | 1.397 (6) | C33A—H33A | 0.9800 |
C19—C20 | 1.377 (6) | ||
N4—Fe1—N3 | 79.10 (12) | C19—C20—H20 | 113.0 |
N4—Fe1—N2 | 150.13 (11) | C1—C20—H20 | 113.0 |
N3—Fe1—N2 | 93.16 (12) | C2—C21—H21A | 109.5 |
N4—Fe1—N1 | 93.15 (12) | C2—C21—H21B | 109.5 |
N3—Fe1—N1 | 149.33 (12) | H21A—C21—H21B | 109.5 |
N2—Fe1—N1 | 78.83 (12) | C2—C21—H21C | 109.5 |
N4—Fe1—Cl1 | 105.15 (9) | H21A—C21—H21C | 109.5 |
N3—Fe1—Cl1 | 103.16 (8) | H21B—C21—H21C | 109.5 |
N2—Fe1—Cl1 | 104.71 (8) | C3—C22—C23 | 111.9 (5) |
N1—Fe1—Cl1 | 107.50 (9) | C3—C22—H22A | 109.2 |
C1—N1—C4 | 107.6 (3) | C23—C22—H22A | 109.2 |
C1—N1—Fe1 | 136.7 (3) | C3—C22—H22B | 109.2 |
C4—N1—Fe1 | 114.9 (2) | C23—C22—H22B | 109.2 |
C8—N2—C5 | 107.6 (3) | H22A—C22—H22B | 107.9 |
C8—N2—Fe1 | 134.8 (2) | C22—C23—H23A | 109.5 |
C5—N2—Fe1 | 114.5 (2) | C22—C23—H23B | 109.5 |
C11—N3—C14 | 107.7 (3) | H23A—C23—H23B | 109.5 |
C11—N3—Fe1 | 136.8 (3) | C22—C23—H23C | 109.5 |
C14—N3—Fe1 | 114.7 (2) | H23A—C23—H23C | 109.5 |
C18—N4—C15 | 107.6 (3) | H23B—C23—H23C | 109.5 |
C18—N4—Fe1 | 135.4 (2) | C6—C24—C25 | 111.5 (4) |
C15—N4—Fe1 | 114.1 (2) | C6—C24—H24A | 109.3 |
N1—C1—C20 | 128.3 (4) | C25—C24—H24A | 109.3 |
N1—C1—C2 | 108.4 (4) | C6—C24—H24B | 109.3 |
C20—C1—C2 | 123.4 (4) | C25—C24—H24B | 109.3 |
C3—C2—C1 | 108.5 (3) | H24A—C24—H24B | 108.0 |
C3—C2—C21 | 127.2 (5) | C24—C25—H25A | 109.5 |
C1—C2—C21 | 124.3 (5) | C24—C25—H25B | 109.5 |
C2—C3—C4 | 106.6 (4) | H25A—C25—H25B | 109.5 |
C2—C3—C22 | 123.3 (4) | C24—C25—H25C | 109.5 |
C4—C3—C22 | 130.1 (5) | H25A—C25—H25C | 109.5 |
N1—C4—C5 | 114.7 (3) | H25B—C25—H25C | 109.5 |
N1—C4—C3 | 109.0 (3) | C7—C26—H26A | 109.5 |
C5—C4—C3 | 136.3 (4) | C7—C26—H26B | 109.5 |
N2—C5—C4 | 115.0 (3) | H26A—C26—H26B | 109.5 |
N2—C5—C6 | 108.3 (3) | C7—C26—H26C | 109.5 |
C4—C5—C6 | 136.5 (3) | H26A—C26—H26C | 109.5 |
C7—C6—C5 | 106.8 (3) | H26B—C26—H26C | 109.5 |
C7—C6—C24 | 123.5 (4) | C12—C27—H27A | 109.5 |
C5—C6—C24 | 129.8 (4) | C12—C27—H27B | 109.5 |
C6—C7—C8 | 108.3 (3) | H27A—C27—H27B | 109.5 |
C6—C7—C26 | 126.4 (4) | C12—C27—H27C | 109.5 |
C8—C7—C26 | 125.3 (4) | H27A—C27—H27C | 109.5 |
N2—C8—C9 | 128.1 (4) | H27B—C27—H27C | 109.5 |
N2—C8—C7 | 109.0 (3) | C13—C28—C29 | 113.1 (4) |
C9—C8—C7 | 122.8 (4) | C13—C28—H28A | 109.0 |
C10—C9—C8 | 133.5 (4) | C29—C28—H28A | 109.0 |
C10—C9—H9 | 113.2 | C13—C28—H28B | 109.0 |
C8—C9—H9 | 113.2 | C29—C28—H28B | 109.0 |
C9—C10—C11 | 133.9 (4) | H28A—C28—H28B | 107.8 |
C9—C10—H10 | 113.1 | C28—C29—H29A | 109.5 |
C11—C10—H10 | 113.1 | C28—C29—H29B | 109.5 |
N3—C11—C10 | 128.3 (3) | H29A—C29—H29B | 109.5 |
N3—C11—C12 | 108.6 (4) | C28—C29—H29C | 109.5 |
C10—C11—C12 | 123.1 (4) | H29A—C29—H29C | 109.5 |
C13—C12—C11 | 108.4 (3) | H29B—C29—H29C | 109.5 |
C13—C12—C27 | 126.8 (4) | C16—C30—C31 | 111.8 (4) |
C11—C12—C27 | 124.7 (5) | C16—C30—H30A | 109.3 |
C12—C13—C14 | 106.4 (4) | C31—C30—H30A | 109.3 |
C12—C13—C28 | 123.4 (4) | C16—C30—H30B | 109.3 |
C14—C13—C28 | 130.1 (5) | C31—C30—H30B | 109.3 |
N3—C14—C15 | 114.6 (3) | H30A—C30—H30B | 107.9 |
N3—C14—C13 | 108.8 (3) | C30—C31—H31A | 109.5 |
C15—C14—C13 | 136.6 (4) | C30—C31—H31B | 109.5 |
N4—C15—C14 | 115.2 (3) | H31A—C31—H31B | 109.5 |
N4—C15—C16 | 108.7 (3) | C30—C31—H31C | 109.5 |
C14—C15—C16 | 136.0 (4) | H31A—C31—H31C | 109.5 |
C17—C16—C15 | 107.3 (4) | H31B—C31—H31C | 109.5 |
C17—C16—C30 | 123.7 (4) | C17—C32—H32A | 109.5 |
C15—C16—C30 | 129.0 (4) | C17—C32—H32B | 109.5 |
C16—C17—C18 | 107.3 (4) | H32A—C32—H32B | 109.5 |
C16—C17—C32 | 128.1 (4) | C17—C32—H32C | 109.5 |
C18—C17—C32 | 124.6 (5) | H32A—C32—H32C | 109.5 |
N4—C18—C19 | 128.1 (4) | H32B—C32—H32C | 109.5 |
N4—C18—C17 | 109.0 (4) | Cl4A—C33A—Cl2A | 121.8 (8) |
C19—C18—C17 | 122.9 (4) | Cl4A—C33A—Cl3A | 105.2 (7) |
C20—C19—C18 | 133.9 (4) | Cl2A—C33A—Cl3A | 119.3 (7) |
C20—C19—H19 | 113.0 | Cl4A—C33A—H33A | 102.4 |
C18—C19—H19 | 113.0 | Cl2A—C33A—H33A | 102.4 |
C19—C20—C1 | 134.0 (4) | Cl3A—C33A—H33A | 102.4 |
N4—Fe1—N1—C1 | 30.8 (3) | Fe1—N2—C8—C9 | 24.9 (6) |
N3—Fe1—N1—C1 | 104.7 (4) | C5—N2—C8—C7 | 0.3 (4) |
N2—Fe1—N1—C1 | −178.2 (3) | Fe1—N2—C8—C7 | −157.9 (3) |
Cl1—Fe1—N1—C1 | −76.1 (3) | C6—C7—C8—N2 | −1.1 (4) |
N4—Fe1—N1—C4 | −161.5 (2) | C26—C7—C8—N2 | −179.0 (4) |
N3—Fe1—N1—C4 | −87.6 (3) | C6—C7—C8—C9 | 176.4 (4) |
N2—Fe1—N1—C4 | −10.5 (2) | C26—C7—C8—C9 | −1.6 (6) |
Cl1—Fe1—N1—C4 | 91.6 (2) | N2—C8—C9—C10 | 7.8 (7) |
N4—Fe1—N2—C8 | −113.3 (3) | C7—C8—C9—C10 | −169.1 (5) |
N3—Fe1—N2—C8 | −39.8 (3) | C8—C9—C10—C11 | −3.8 (9) |
N1—Fe1—N2—C8 | 170.0 (3) | C14—N3—C11—C10 | −177.4 (4) |
Cl1—Fe1—N2—C8 | 64.7 (3) | Fe1—N3—C11—C10 | −8.2 (6) |
N4—Fe1—N2—C5 | 89.6 (3) | C14—N3—C11—C12 | 2.5 (4) |
N3—Fe1—N2—C5 | 163.1 (2) | Fe1—N3—C11—C12 | 171.7 (3) |
N1—Fe1—N2—C5 | 12.9 (2) | C9—C10—C11—N3 | −10.8 (8) |
Cl1—Fe1—N2—C5 | −92.4 (2) | C9—C10—C11—C12 | 169.3 (5) |
N4—Fe1—N3—C11 | −179.2 (4) | N3—C11—C12—C13 | −0.7 (5) |
N2—Fe1—N3—C11 | 29.9 (4) | C10—C11—C12—C13 | 179.2 (4) |
N1—Fe1—N3—C11 | 103.2 (4) | N3—C11—C12—C27 | 176.7 (4) |
Cl1—Fe1—N3—C11 | −76.0 (3) | C10—C11—C12—C27 | −3.4 (7) |
N4—Fe1—N3—C14 | −10.6 (2) | C11—C12—C13—C14 | −1.3 (5) |
N2—Fe1—N3—C14 | −161.5 (2) | C27—C12—C13—C14 | −178.6 (5) |
N1—Fe1—N3—C14 | −88.1 (3) | C11—C12—C13—C28 | 176.8 (4) |
Cl1—Fe1—N3—C14 | 92.6 (2) | C27—C12—C13—C28 | −0.6 (7) |
N3—Fe1—N4—C18 | 171.5 (4) | C11—N3—C14—C15 | 177.7 (3) |
N2—Fe1—N4—C18 | −111.3 (4) | Fe1—N3—C14—C15 | 5.9 (4) |
N1—Fe1—N4—C18 | −38.4 (3) | C11—N3—C14—C13 | −3.3 (4) |
Cl1—Fe1—N4—C18 | 70.7 (3) | Fe1—N3—C14—C13 | −175.2 (2) |
N3—Fe1—N4—C15 | 13.6 (2) | C12—C13—C14—N3 | 2.9 (4) |
N2—Fe1—N4—C15 | 90.7 (3) | C28—C13—C14—N3 | −175.1 (4) |
N1—Fe1—N4—C15 | 163.7 (2) | C12—C13—C14—C15 | −178.5 (4) |
Cl1—Fe1—N4—C15 | −87.2 (2) | C28—C13—C14—C15 | 3.6 (7) |
C4—N1—C1—C20 | −179.9 (4) | C18—N4—C15—C14 | −178.6 (3) |
Fe1—N1—C1—C20 | −11.6 (6) | Fe1—N4—C15—C14 | −14.7 (4) |
C4—N1—C1—C2 | −0.3 (4) | C18—N4—C15—C16 | −0.4 (4) |
Fe1—N1—C1—C2 | 168.0 (3) | Fe1—N4—C15—C16 | 163.5 (2) |
N1—C1—C2—C3 | 1.4 (4) | N3—C14—C15—N4 | 5.8 (4) |
C20—C1—C2—C3 | −178.9 (4) | C13—C14—C15—N4 | −172.8 (4) |
N1—C1—C2—C21 | 179.6 (4) | N3—C14—C15—C16 | −171.8 (4) |
C20—C1—C2—C21 | −0.8 (6) | C13—C14—C15—C16 | 9.7 (7) |
C1—C2—C3—C4 | −1.9 (4) | N4—C15—C16—C17 | −0.7 (4) |
C21—C2—C3—C4 | 180.0 (4) | C14—C15—C16—C17 | 176.9 (4) |
C1—C2—C3—C22 | 176.3 (4) | N4—C15—C16—C30 | 179.2 (4) |
C21—C2—C3—C22 | −1.8 (7) | C14—C15—C16—C30 | −3.2 (7) |
C1—N1—C4—C5 | 177.6 (3) | C15—C16—C17—C18 | 1.5 (4) |
Fe1—N1—C4—C5 | 6.5 (4) | C30—C16—C17—C18 | −178.4 (4) |
C1—N1—C4—C3 | −0.9 (4) | C15—C16—C17—C32 | −179.4 (4) |
Fe1—N1—C4—C3 | −172.1 (2) | C30—C16—C17—C32 | 0.7 (7) |
C2—C3—C4—N1 | 1.8 (4) | C15—N4—C18—C19 | −175.9 (4) |
C22—C3—C4—N1 | −176.3 (4) | Fe1—N4—C18—C19 | 25.2 (6) |
C2—C3—C4—C5 | −176.3 (4) | C15—N4—C18—C17 | 1.4 (4) |
C22—C3—C4—C5 | 5.6 (7) | Fe1—N4—C18—C17 | −157.5 (3) |
C8—N2—C5—C4 | −176.6 (3) | C16—C17—C18—N4 | −1.8 (4) |
Fe1—N2—C5—C4 | −13.5 (4) | C32—C17—C18—N4 | 179.1 (4) |
C8—N2—C5—C6 | 0.5 (4) | C16—C17—C18—C19 | 175.6 (3) |
Fe1—N2—C5—C6 | 163.7 (2) | C32—C17—C18—C19 | −3.5 (6) |
N1—C4—C5—N2 | 4.6 (4) | N4—C18—C19—C20 | 3.8 (7) |
C3—C4—C5—N2 | −177.4 (4) | C17—C18—C19—C20 | −173.1 (4) |
N1—C4—C5—C6 | −171.5 (4) | C18—C19—C20—C1 | −0.3 (8) |
C3—C4—C5—C6 | 6.5 (7) | N1—C1—C20—C19 | −9.4 (7) |
N2—C5—C6—C7 | −1.1 (4) | C2—C1—C20—C19 | 171.0 (4) |
C4—C5—C6—C7 | 175.1 (4) | C2—C3—C22—C23 | 81.9 (6) |
N2—C5—C6—C24 | 178.2 (4) | C4—C3—C22—C23 | −100.3 (6) |
C4—C5—C6—C24 | −5.5 (7) | C7—C6—C24—C25 | 84.2 (6) |
C5—C6—C7—C8 | 1.3 (4) | C5—C6—C24—C25 | −95.1 (6) |
C24—C6—C7—C8 | −178.1 (4) | C12—C13—C28—C29 | 80.9 (7) |
C5—C6—C7—C26 | 179.2 (4) | C14—C13—C28—C29 | −101.5 (6) |
C24—C6—C7—C26 | −0.2 (7) | C17—C16—C30—C31 | 84.4 (6) |
C5—N2—C8—C9 | −176.9 (4) | C15—C16—C30—C31 | −95.5 (6) |
Experimental details
Crystal data | |
Chemical formula | [Fe(C32H36N4)Cl]·CHCl3 |
Mr | 687.32 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 298 |
a, b, c (Å) | 14.722 (1), 10.225 (1), 22.319 (2) |
β (°) | 100.35 (1) |
V (Å3) | 3305.1 (6) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.81 |
Crystal size (mm) | 0.2 × 0.2 × 0.2 |
Data collection | |
Diffractometer | Rigaku R-AXIS RAPID Imaging Plate diffractometer |
Absorption correction | Multi-scan ABSCOR (Higashi, 1995) |
Tmin, Tmax | 0.849, 0.851 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 19098, 7514, 5436 |
Rint | 0.049 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.070, 0.205, 1.08 |
No. of reflections | 7514 |
No. of parameters | 415 |
No. of restraints | 6 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.77, −0.47 |
Computer programs: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1992a), MSC/AFC Diffractometer Control Software. Data Reduction: TEXSAN (Molecular Structure Corporation, 1992b), SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 1997), SV (Nemoto & Ohashi, 1993), SHELXL97.
Fe1—N4 | 2.019 (3) | Fe1—N1 | 2.034 (3) |
Fe1—N3 | 2.026 (3) | Fe1—Cl1 | 2.2316 (10) |
Fe1—N2 | 2.028 (3) | ||
N4—Fe1—N3 | 79.10 (12) | N4—Fe1—N1 | 93.15 (12) |
N4—Fe1—N2 | 150.13 (11) | N3—Fe1—N1 | 149.33 (12) |
N3—Fe1—N2 | 93.16 (12) | N2—Fe1—N1 | 78.83 (12) |
Porphycene, known as the first porphyrin isomer (Vogel et al., 1986), has attracted much attention because of its possible use as a sensitizer for photodynamic therapy (PDT). Elucidation of the structural features of iron–porphycene complexes is quite important, not only for reconsidering the role of the Fe atom in natural porphyrins from a distinctly structural viewpoint, but for explaining their novel physicochemical properties. Among the complexes containing the porphycenatoiron unit, only a few examples, such as σ-bonded aryliron porphycenes and µ-oxo-iron porphycene dimers have been crystallographically analyzed (Kadish et al., 1998; Lausmann et al., 1994). In this paper, we describe the first example of an X-ray crystallographic analysis of a chloroiron(III) porphycene complex, (I), which is necessary for structural comparison with widely used chloroiron(III) porphyrin complexes.
The porphycene ring (Fig. 1) exhibits a slightly twisted structure where the shifts of the peripheral 24 atoms from the least-squares plane of the C20N4 porphycenato core range from 0.011 to 0.391 (4) Å. The deformation pattern looks like a hybrid of the ruffled and saddled structures frequently observed in porphyrin complexes (Ma et al., 1998). The C atoms showing a large deviation from the C20N4 plane are C3, C9, C13, and C19, the deviations being 0.347 (4), -0.301 (4), 0.391 (4) and 0.234 (4) Å, respectively. The axial Fe—Cl bond distance is 2.232 (1) Å, which is not significantly different to that reported for the similarly β-substituted porphyrin complex [Fe(OEP)Cl] [OEP is the dianion of 2,3,7,8,12,13,17,18-octaethylporphyrin; Senge, M. O. (1997), data taken from the Cambridge Structural Database (Allen & Kennard, 1993)], 2.23 Å. The peripheral ethyl groups take an αβαβ conformation to avoid steric repulsion at the directly linked pyrrole rings. While the average Fe—N bond distance in [Fe(OEP)Cl] is 2.07 Å, those of (I) are much shorter, with values of 2.019 (3), 2.026 (3), 2.028 (3) and 2.034 (3) Å. The central N4 cavity has a rectangular geometry, with a long side of 2.944 (4) Å and a short side of 2.579 (4) Å. Thus, the surface area within the N4-coordination core, 7.593 Å2, is much smaller than the corresponding area of [Fe(OEP)Cl], 8.123 Å2. Because of the smaller surface area in (I), the deviation of the central FeIII atom from the C20N4 plane of 0.594 (1) Å is significantly larger than in [Fe(OEP)Cl] (0.495 Å)·The larger deviation should affect the electronic state of the Fe atom. In fact, complex (I) is determined to be the spin-admixed S = 5/2, 3/2 complex on the basis of the SQUID measurement in our preliminary work; µeff = 5.23 µB at 300 K (Ohgo et al., 2001). This result is in sharp contrast to the case in [Fe(OEP)Cl], which displays a quite pure high-spin S = 5/2 state. In conclusion, the present study has revealed that the unique cavity geometry of porphycene stabilizes the admixed intermediate spin state even in a chloroiron(III) complex.