Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270100010222/bk1532sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270100010222/bk1532Isup2.hkl |
CCDC reference: 152598
Crystals of the title compound were obtained during an investigation of the oxidation reaction of [Fe(TPPBr4)(1-MeIm)2].
Data collection: MADNES (Messerschmitt & Pflugrath, 1987); cell refinement: MADNES; data reduction: MADNES; program(s) used to solve structure: SHELXS86 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXTL (Siemens, 1994).
Fig. 1. Top view of [Fe(TPPBr4)]2O. Thermal ellipsoids are drawn at the 50% probability level. Porphyrin H atoms have been omitted for clarity. |
[Fe2O(C44H24Br4N4)2]·2CH2Cl2 | F(000) = 4224 |
Mr = 2154.18 | Dx = 1.796 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
a = 35.161 (6) Å | Cell parameters from 250 reflections |
b = 13.763 (6) Å | θ = 0–0° |
c = 18.845 (3) Å | µ = 4.57 mm−1 |
β = 119.104 (12)° | T = 130 K |
V = 7968.4 Å3 | Needle, red–brown |
Z = 4 | 0.32 × 0.12 × 0.08 mm |
Enraf-Nonius FAST area-detector diffractometer | 9134 independent reflections |
Radiation source: rotating anode | 7483 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.049 |
Detector resolution: 8.2/10.9 pixels mm-1 | θmax = 28.3°, θmin = 2.2° |
Ellipsoid–mask fitting scans | h = −35→46 |
Absorption correction: part of the refinement model (ΔF) empirical (using intensity measurements) (Blessing, 1997) | k = −12→17 |
Tmin = 0.492, Tmax = 0.694 | l = −23→22 |
25463 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)] = 0.040 | Idealized with riding models |
wR(F2) = 0.099 | w = 1/[σ2(Fo2) + (0.0581P)2 + 11.1319P] where P = (Fo2 + 2Fc2)/3 |
S = 1.04 | (Δ/σ)max = 0.003 |
9134 reflections | Δρmax = 1.16 e Å−3 |
511 parameters | Δρmin = −0.63 e Å−3 |
0 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.00097 (5) |
[Fe2O(C44H24Br4N4)2]·2CH2Cl2 | V = 7968.4 Å3 |
Mr = 2154.18 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 35.161 (6) Å | µ = 4.57 mm−1 |
b = 13.763 (6) Å | T = 130 K |
c = 18.845 (3) Å | 0.32 × 0.12 × 0.08 mm |
β = 119.104 (12)° |
Enraf-Nonius FAST area-detector diffractometer | 9134 independent reflections |
Absorption correction: part of the refinement model (ΔF) empirical (using intensity measurements) (Blessing, 1997) | 7483 reflections with I > 2σ(I) |
Tmin = 0.492, Tmax = 0.694 | Rint = 0.049 |
25463 measured reflections |
R[F2 > 2σ(F2)] = 0.040 | 0 restraints |
wR(F2) = 0.099 | Idealized with riding models |
S = 1.04 | w = 1/[σ2(Fo2) + (0.0581P)2 + 11.1319P] where P = (Fo2 + 2Fc2)/3 |
9134 reflections | Δρmax = 1.16 e Å−3 |
511 parameters | Δρmin = −0.63 e Å−3 |
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 | ||
Fe | 0.487947 (13) | 0.69720 (3) | 0.14786 (3) | 0.01267 (10) | |
O1 | 0.5000 | 0.6958 (2) | 0.2500 | 0.0178 (6) | |
N1 | 0.42279 (8) | 0.74098 (17) | 0.08012 (15) | 0.0137 (5) | |
N2 | 0.46602 (8) | 0.56018 (18) | 0.10749 (16) | 0.0150 (5) | |
N3 | 0.54712 (8) | 0.65504 (18) | 0.15505 (16) | 0.0152 (5) | |
N4 | 0.50419 (8) | 0.83546 (18) | 0.13328 (16) | 0.0156 (5) | |
C1A | 0.40744 (10) | 0.8320 (2) | 0.04829 (18) | 0.0151 (6) | |
C2A | 0.38753 (10) | 0.6801 (2) | 0.05339 (18) | 0.0147 (6) | |
C3A | 0.42765 (10) | 0.5268 (2) | 0.10136 (18) | 0.0155 (6) | |
C4A | 0.49213 (10) | 0.4809 (2) | 0.12281 (19) | 0.0165 (6) | |
C5A | 0.55880 (10) | 0.5639 (2) | 0.14255 (18) | 0.0153 (6) | |
C6A | 0.58264 (9) | 0.7145 (2) | 0.17938 (18) | 0.0156 (6) | |
C7A | 0.54628 (10) | 0.8677 (2) | 0.17874 (19) | 0.0174 (6) | |
C8A | 0.47804 (10) | 0.9152 (2) | 0.1187 (2) | 0.0173 (6) | |
C1B | 0.36169 (10) | 0.8242 (2) | −0.00646 (18) | 0.0153 (6) | |
C2B | 0.34946 (9) | 0.7324 (2) | −0.00159 (18) | 0.0161 (6) | |
C3B | 0.43113 (11) | 0.4245 (2) | 0.1173 (2) | 0.0210 (7) | |
H3B | 0.4098 | 0.3844 | 0.1197 | 0.025* | |
C4B | 0.47001 (11) | 0.3957 (2) | 0.1282 (2) | 0.0206 (7) | |
H4B | 0.4809 | 0.3311 | 0.1377 | 0.025* | |
C5B | 0.60190 (10) | 0.5695 (2) | 0.15218 (19) | 0.0169 (6) | |
C6B | 0.61689 (10) | 0.6599 (2) | 0.17706 (19) | 0.0171 (6) | |
C7B | 0.54586 (10) | 0.9687 (2) | 0.1954 (2) | 0.0207 (7) | |
H7B | 0.5706 | 1.0079 | 0.2275 | 0.025* | |
C8B | 0.50446 (10) | 0.9985 (2) | 0.1577 (2) | 0.0197 (6) | |
H8B | 0.4944 | 1.0628 | 0.1570 | 0.024* | |
C1M | 0.39020 (10) | 0.5822 (2) | 0.07570 (19) | 0.0156 (6) | |
C2M | 0.53417 (10) | 0.4803 (2) | 0.13254 (18) | 0.0164 (6) | |
C3M | 0.58345 (10) | 0.8125 (2) | 0.20009 (19) | 0.0154 (6) | |
C4M | 0.43311 (10) | 0.9158 (2) | 0.07344 (19) | 0.0166 (6) | |
Br1 | 0.324966 (10) | 0.91518 (2) | −0.08185 (2) | 0.02274 (9) | |
Br2 | 0.293345 (10) | 0.68506 (2) | −0.06584 (2) | 0.02356 (9) | |
Br3 | 0.631044 (11) | 0.47720 (2) | 0.12386 (2) | 0.02222 (9) | |
Br4 | 0.671164 (10) | 0.70352 (2) | 0.19521 (2) | 0.02223 (9) | |
C11 | 0.35097 (9) | 0.5346 (2) | 0.07157 (18) | 0.0154 (6) | |
C12 | 0.33162 (10) | 0.4534 (2) | 0.02368 (19) | 0.0191 (6) | |
H12 | 0.3435 | 0.4261 | −0.0076 | 0.023* | |
C13 | 0.29513 (11) | 0.4122 (2) | 0.0213 (2) | 0.0224 (7) | |
H13 | 0.2821 | 0.3566 | −0.0116 | 0.027* | |
C14 | 0.27744 (11) | 0.4511 (3) | 0.0662 (2) | 0.0266 (7) | |
H14 | 0.2521 | 0.4230 | 0.0637 | 0.032* | |
C15 | 0.29667 (12) | 0.5310 (3) | 0.1149 (2) | 0.0279 (8) | |
H15 | 0.2846 | 0.5582 | 0.1459 | 0.033* | |
C16 | 0.33362 (11) | 0.5717 (2) | 0.1183 (2) | 0.0216 (7) | |
H16 | 0.3472 | 0.6255 | 0.1531 | 0.026* | |
C21 | 0.55404 (10) | 0.3827 (2) | 0.1409 (2) | 0.0183 (6) | |
C22 | 0.58789 (11) | 0.3529 (3) | 0.2150 (2) | 0.0238 (7) | |
H22 | 0.5994 | 0.3958 | 0.2601 | 0.029* | |
C23 | 0.60485 (13) | 0.2604 (3) | 0.2228 (3) | 0.0368 (10) | |
H23 | 0.6280 | 0.2396 | 0.2737 | 0.044* | |
C24 | 0.58827 (14) | 0.1983 (3) | 0.1570 (3) | 0.0391 (10) | |
H24 | 0.6004 | 0.1353 | 0.1624 | 0.047* | |
C25 | 0.55456 (14) | 0.2268 (3) | 0.0843 (3) | 0.0366 (9) | |
H25 | 0.5430 | 0.1835 | 0.0394 | 0.044* | |
C26 | 0.53722 (12) | 0.3189 (2) | 0.0760 (2) | 0.0242 (7) | |
H26 | 0.5136 | 0.3384 | 0.0253 | 0.029* | |
C31 | 0.62572 (10) | 0.8623 (2) | 0.24996 (19) | 0.0165 (6) | |
C32 | 0.65079 (10) | 0.8360 (2) | 0.33087 (19) | 0.0189 (6) | |
H32 | 0.6416 | 0.7838 | 0.3520 | 0.023* | |
C33 | 0.68879 (10) | 0.8846 (3) | 0.3810 (2) | 0.0231 (7) | |
H33 | 0.7058 | 0.8659 | 0.4363 | 0.028* | |
C34 | 0.70209 (10) | 0.9605 (2) | 0.3505 (2) | 0.0224 (7) | |
H34 | 0.7283 | 0.9941 | 0.3849 | 0.027* | |
C35 | 0.67734 (11) | 0.9880 (2) | 0.2700 (2) | 0.0218 (7) | |
H35 | 0.6864 | 1.0407 | 0.2493 | 0.026* | |
C36 | 0.63950 (10) | 0.9387 (2) | 0.2198 (2) | 0.0186 (6) | |
H36 | 0.6228 | 0.9571 | 0.1644 | 0.022* | |
C41 | 0.41201 (10) | 1.0126 (2) | 0.0556 (2) | 0.0192 (6) | |
C42 | 0.38299 (11) | 1.0371 (2) | 0.0835 (2) | 0.0238 (7) | |
H42 | 0.3767 | 0.9914 | 0.1142 | 0.029* | |
C43 | 0.36343 (12) | 1.1273 (3) | 0.0666 (2) | 0.0315 (8) | |
H43 | 0.3437 | 1.1439 | 0.0857 | 0.038* | |
C44 | 0.37264 (14) | 1.1929 (3) | 0.0221 (3) | 0.0385 (10) | |
H44 | 0.3586 | 1.2544 | 0.0093 | 0.046* | |
C45 | 0.40174 (13) | 1.1711 (3) | −0.0042 (2) | 0.0339 (9) | |
H45 | 0.4083 | 1.2179 | −0.0336 | 0.041* | |
C46 | 0.42146 (11) | 1.0813 (2) | 0.0120 (2) | 0.0239 (7) | |
H46 | 0.4415 | 1.0661 | −0.0064 | 0.029* | |
C50 | 0.79005 (12) | 0.8189 (3) | 0.2309 (2) | 0.0299 (8) | |
H50A | 0.8064 | 0.7942 | 0.2873 | 0.036* | |
H50B | 0.8102 | 0.8584 | 0.2201 | 0.036* | |
Cl1 | 0.74721 (3) | 0.89210 (8) | 0.22152 (6) | 0.0367 (2) | |
Cl2 | 0.77117 (4) | 0.72066 (8) | 0.16346 (7) | 0.0518 (3) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Fe | 0.0133 (2) | 0.0114 (2) | 0.0127 (2) | −0.00033 (14) | 0.00582 (17) | −0.00016 (15) |
O1 | 0.0179 (15) | 0.0188 (15) | 0.0166 (15) | 0.000 | 0.0085 (13) | 0.000 |
N1 | 0.0158 (12) | 0.0122 (11) | 0.0128 (12) | −0.0009 (9) | 0.0068 (10) | 0.0006 (9) |
N2 | 0.0170 (13) | 0.0120 (11) | 0.0164 (13) | −0.0003 (9) | 0.0084 (10) | 0.0004 (10) |
N3 | 0.0160 (12) | 0.0138 (12) | 0.0162 (12) | −0.0011 (9) | 0.0082 (10) | 0.0001 (10) |
N4 | 0.0134 (12) | 0.0149 (12) | 0.0156 (13) | −0.0002 (9) | 0.0047 (10) | 0.0014 (10) |
C1A | 0.0175 (15) | 0.0151 (14) | 0.0123 (14) | 0.0005 (11) | 0.0069 (12) | 0.0004 (11) |
C2A | 0.0174 (15) | 0.0154 (14) | 0.0121 (14) | 0.0011 (11) | 0.0078 (12) | −0.0009 (11) |
C3A | 0.0185 (15) | 0.0163 (14) | 0.0130 (14) | −0.0029 (11) | 0.0086 (12) | −0.0026 (11) |
C4A | 0.0177 (15) | 0.0160 (14) | 0.0154 (15) | 0.0007 (11) | 0.0079 (12) | 0.0001 (12) |
C5A | 0.0184 (15) | 0.0156 (14) | 0.0127 (14) | 0.0006 (11) | 0.0081 (12) | 0.0010 (11) |
C6A | 0.0153 (14) | 0.0164 (14) | 0.0158 (15) | −0.0017 (11) | 0.0080 (12) | −0.0012 (12) |
C7A | 0.0163 (15) | 0.0173 (15) | 0.0165 (15) | −0.0034 (11) | 0.0063 (12) | −0.0006 (12) |
C8A | 0.0215 (16) | 0.0134 (14) | 0.0195 (16) | −0.0005 (11) | 0.0118 (13) | 0.0024 (12) |
C1B | 0.0168 (14) | 0.0154 (14) | 0.0137 (14) | 0.0023 (11) | 0.0074 (12) | 0.0011 (11) |
C2B | 0.0138 (14) | 0.0202 (15) | 0.0133 (14) | −0.0001 (11) | 0.0057 (12) | −0.0024 (12) |
C3B | 0.0246 (17) | 0.0160 (15) | 0.0233 (17) | −0.0027 (12) | 0.0124 (14) | 0.0004 (13) |
C4B | 0.0238 (17) | 0.0117 (14) | 0.0261 (17) | 0.0008 (12) | 0.0119 (14) | 0.0026 (12) |
C5B | 0.0211 (16) | 0.0170 (14) | 0.0159 (15) | 0.0038 (11) | 0.0115 (13) | 0.0035 (12) |
C6B | 0.0170 (15) | 0.0190 (15) | 0.0161 (15) | 0.0001 (11) | 0.0086 (12) | 0.0031 (12) |
C7B | 0.0195 (16) | 0.0166 (15) | 0.0243 (17) | −0.0033 (12) | 0.0094 (13) | −0.0011 (13) |
C8B | 0.0210 (16) | 0.0139 (14) | 0.0224 (16) | −0.0009 (11) | 0.0091 (13) | −0.0008 (12) |
C1M | 0.0192 (15) | 0.0158 (14) | 0.0142 (14) | −0.0035 (11) | 0.0100 (12) | −0.0034 (11) |
C2M | 0.0215 (15) | 0.0152 (14) | 0.0140 (14) | 0.0019 (11) | 0.0099 (12) | 0.0002 (11) |
C3M | 0.0165 (14) | 0.0141 (14) | 0.0149 (14) | −0.0018 (11) | 0.0072 (12) | 0.0011 (11) |
C4M | 0.0199 (15) | 0.0126 (14) | 0.0165 (15) | 0.0009 (11) | 0.0080 (13) | 0.0009 (11) |
Br1 | 0.01905 (17) | 0.02196 (17) | 0.02016 (17) | 0.00285 (11) | 0.00400 (13) | 0.00655 (12) |
Br2 | 0.01585 (16) | 0.02399 (17) | 0.02136 (17) | −0.00390 (11) | 0.00161 (13) | 0.00073 (13) |
Br3 | 0.02725 (18) | 0.02044 (17) | 0.02754 (18) | 0.00402 (12) | 0.02005 (15) | 0.00098 (13) |
Br4 | 0.01643 (16) | 0.02316 (17) | 0.02954 (18) | −0.00028 (11) | 0.01309 (14) | 0.00170 (13) |
C11 | 0.0144 (14) | 0.0165 (14) | 0.0142 (14) | −0.0010 (11) | 0.0060 (12) | 0.0027 (11) |
C12 | 0.0216 (16) | 0.0190 (15) | 0.0181 (16) | −0.0022 (12) | 0.0108 (13) | −0.0023 (12) |
C13 | 0.0204 (16) | 0.0203 (16) | 0.0205 (16) | −0.0060 (12) | 0.0052 (13) | −0.0027 (13) |
C14 | 0.0210 (17) | 0.0321 (18) | 0.0267 (18) | −0.0084 (14) | 0.0117 (15) | 0.0017 (15) |
C15 | 0.0270 (18) | 0.0345 (19) | 0.0304 (19) | −0.0033 (15) | 0.0205 (16) | −0.0035 (15) |
C16 | 0.0234 (16) | 0.0225 (16) | 0.0206 (16) | −0.0029 (13) | 0.0121 (14) | −0.0044 (13) |
C21 | 0.0198 (15) | 0.0161 (14) | 0.0237 (16) | 0.0019 (11) | 0.0143 (13) | 0.0031 (12) |
C22 | 0.0239 (17) | 0.0257 (17) | 0.0257 (17) | 0.0038 (13) | 0.0152 (14) | 0.0067 (14) |
C23 | 0.032 (2) | 0.033 (2) | 0.051 (3) | 0.0109 (16) | 0.0246 (19) | 0.0226 (19) |
C24 | 0.052 (3) | 0.0170 (17) | 0.070 (3) | 0.0127 (16) | 0.046 (2) | 0.0128 (18) |
C25 | 0.054 (3) | 0.0213 (18) | 0.054 (3) | −0.0027 (17) | 0.041 (2) | −0.0069 (18) |
C26 | 0.0311 (18) | 0.0203 (16) | 0.0269 (18) | −0.0004 (13) | 0.0187 (15) | −0.0035 (14) |
C31 | 0.0143 (14) | 0.0155 (14) | 0.0195 (15) | −0.0002 (11) | 0.0081 (12) | −0.0023 (12) |
C32 | 0.0179 (15) | 0.0191 (15) | 0.0183 (15) | 0.0017 (11) | 0.0078 (13) | 0.0012 (12) |
C33 | 0.0203 (16) | 0.0294 (18) | 0.0177 (16) | 0.0032 (13) | 0.0078 (13) | −0.0014 (13) |
C34 | 0.0167 (15) | 0.0234 (16) | 0.0246 (17) | −0.0042 (12) | 0.0080 (13) | −0.0057 (13) |
C35 | 0.0239 (17) | 0.0177 (15) | 0.0248 (17) | −0.0063 (12) | 0.0126 (14) | −0.0010 (13) |
C36 | 0.0210 (16) | 0.0162 (14) | 0.0180 (15) | 0.0011 (11) | 0.0092 (13) | 0.0016 (12) |
C41 | 0.0195 (15) | 0.0149 (14) | 0.0184 (15) | 0.0008 (11) | 0.0054 (13) | −0.0001 (12) |
C42 | 0.0231 (17) | 0.0242 (17) | 0.0201 (16) | 0.0030 (13) | 0.0073 (14) | −0.0015 (13) |
C43 | 0.0295 (19) | 0.0252 (18) | 0.034 (2) | 0.0077 (14) | 0.0106 (16) | −0.0075 (16) |
C44 | 0.040 (2) | 0.0179 (18) | 0.042 (2) | 0.0118 (15) | 0.0078 (19) | −0.0005 (16) |
C45 | 0.041 (2) | 0.0181 (17) | 0.029 (2) | 0.0012 (15) | 0.0062 (17) | 0.0104 (15) |
C46 | 0.0241 (17) | 0.0193 (16) | 0.0240 (17) | −0.0011 (12) | 0.0083 (14) | 0.0025 (13) |
C50 | 0.0246 (18) | 0.0298 (19) | 0.0304 (19) | 0.0004 (14) | 0.0095 (15) | −0.0026 (15) |
Cl1 | 0.0323 (5) | 0.0439 (5) | 0.0402 (5) | 0.0070 (4) | 0.0225 (4) | 0.0082 (4) |
Cl2 | 0.0544 (7) | 0.0300 (5) | 0.0472 (6) | −0.0014 (4) | 0.0060 (5) | −0.0108 (5) |
Fe—O1 | 1.7583 (4) | C11—C16 | 1.390 (4) |
Fe—N2 | 2.039 (2) | C12—C13 | 1.383 (4) |
Fe—N4 | 2.043 (2) | C12—H12 | 0.9500 |
Fe—N1 | 2.097 (2) | C13—C14 | 1.380 (5) |
Fe—N3 | 2.100 (3) | C13—H13 | 0.9500 |
O1—Fei | 1.7583 (4) | C14—C15 | 1.380 (5) |
N1—C2A | 1.373 (4) | C14—H14 | 0.9500 |
N1—C1A | 1.380 (4) | C15—C16 | 1.386 (5) |
N2—C4A | 1.364 (4) | C15—H15 | 0.9500 |
N2—C3A | 1.376 (4) | C16—H16 | 0.9500 |
N3—C6A | 1.372 (4) | C21—C26 | 1.384 (5) |
N3—C5A | 1.376 (4) | C21—C22 | 1.384 (5) |
N4—C8A | 1.371 (4) | C22—C23 | 1.383 (5) |
N4—C7A | 1.374 (4) | C22—H22 | 0.9500 |
C1A—C4M | 1.398 (4) | C23—C24 | 1.381 (6) |
C1A—C1B | 1.432 (4) | C23—H23 | 0.9500 |
C2A—C1M | 1.402 (4) | C24—C25 | 1.363 (6) |
C2A—C2B | 1.426 (4) | C24—H24 | 0.9500 |
C3A—C1M | 1.389 (4) | C25—C26 | 1.381 (5) |
C3A—C3B | 1.433 (4) | C25—H25 | 0.9500 |
C4A—C2M | 1.398 (4) | C26—H26 | 0.9500 |
C4A—C4B | 1.438 (4) | C31—C32 | 1.388 (4) |
C5A—C2M | 1.397 (4) | C31—C36 | 1.389 (4) |
C5A—C5B | 1.438 (4) | C32—C33 | 1.377 (5) |
C6A—C3M | 1.401 (4) | C32—H32 | 0.9500 |
C6A—C6B | 1.438 (4) | C33—C34 | 1.379 (5) |
C7A—C3M | 1.391 (4) | C33—H33 | 0.9500 |
C7A—C7B | 1.427 (4) | C34—C35 | 1.386 (5) |
C8A—C4M | 1.383 (4) | C34—H34 | 0.9500 |
C8A—C8B | 1.433 (4) | C35—C36 | 1.378 (4) |
C1B—C2B | 1.352 (4) | C35—H35 | 0.9500 |
C1B—Br1 | 1.862 (3) | C36—H36 | 0.9500 |
C2B—Br2 | 1.860 (3) | C41—C46 | 1.394 (5) |
C3B—C4B | 1.340 (5) | C41—C42 | 1.397 (5) |
C3B—H3B | 0.9500 | C42—C43 | 1.380 (5) |
C4B—H4B | 0.9500 | C42—H42 | 0.9500 |
C5B—C6B | 1.343 (4) | C43—C44 | 1.375 (6) |
C5B—Br3 | 1.866 (3) | C43—H43 | 0.9500 |
C6B—Br4 | 1.867 (3) | C44—C45 | 1.369 (6) |
C7B—C8B | 1.336 (5) | C44—H44 | 0.9500 |
C7B—H7B | 0.9500 | C45—C46 | 1.376 (5) |
C8B—H8B | 0.9500 | C45—H45 | 0.9500 |
C1M—C11 | 1.494 (4) | C46—H46 | 0.9500 |
C2M—C21 | 1.486 (4) | C50—Cl1 | 1.748 (4) |
C3M—C31 | 1.485 (4) | C50—Cl2 | 1.751 (4) |
C4M—C41 | 1.482 (4) | C50—H50A | 0.9900 |
C11—C12 | 1.389 (4) | C50—H50B | 0.9900 |
O1—Fe—N2 | 104.12 (12) | C8A—C4M—C41 | 116.2 (3) |
O1—Fe—N4 | 102.91 (12) | C1A—C4M—C41 | 119.7 (3) |
N2—Fe—N4 | 152.96 (11) | C12—C11—C16 | 118.7 (3) |
O1—Fe—N1 | 106.26 (8) | C12—C11—C1M | 122.3 (3) |
N2—Fe—N1 | 86.32 (10) | C16—C11—C1M | 119.0 (3) |
N4—Fe—N1 | 86.82 (10) | C13—C12—C11 | 120.3 (3) |
O1—Fe—N3 | 102.86 (8) | C13—C12—H12 | 119.9 |
N2—Fe—N3 | 87.21 (10) | C11—C12—H12 | 119.9 |
N4—Fe—N3 | 86.16 (10) | C14—C13—C12 | 120.6 (3) |
N1—Fe—N3 | 150.88 (10) | C14—C13—H13 | 119.7 |
Fe—O1—Fei | 178.7 (2) | C12—C13—H13 | 119.7 |
C2A—N1—C1A | 107.6 (2) | C15—C14—C13 | 119.7 (3) |
C2A—N1—Fe | 124.91 (19) | C15—C14—H14 | 120.2 |
C1A—N1—Fe | 127.28 (19) | C13—C14—H14 | 120.2 |
C4A—N2—C3A | 106.4 (2) | C14—C15—C16 | 119.9 (3) |
C4A—N2—Fe | 124.6 (2) | C14—C15—H15 | 120.0 |
C3A—N2—Fe | 121.1 (2) | C16—C15—H15 | 120.0 |
C6A—N3—C5A | 107.6 (2) | C15—C16—C11 | 120.8 (3) |
C6A—N3—Fe | 124.7 (2) | C15—C16—H16 | 119.6 |
C5A—N3—Fe | 127.6 (2) | C11—C16—H16 | 119.6 |
C8A—N4—C7A | 106.3 (2) | C26—C21—C22 | 119.4 (3) |
C8A—N4—Fe | 124.6 (2) | C26—C21—C2M | 120.2 (3) |
C7A—N4—Fe | 120.2 (2) | C22—C21—C2M | 120.2 (3) |
N1—C1A—C4M | 123.4 (3) | C23—C22—C21 | 119.7 (4) |
N1—C1A—C1B | 108.1 (2) | C23—C22—H22 | 120.2 |
C4M—C1A—C1B | 128.3 (3) | C21—C22—H22 | 120.2 |
N1—C2A—C1M | 124.1 (3) | C24—C23—C22 | 120.1 (4) |
N1—C2A—C2B | 108.6 (3) | C24—C23—H23 | 119.9 |
C1M—C2A—C2B | 127.3 (3) | C22—C23—H23 | 119.9 |
N2—C3A—C1M | 124.9 (3) | C25—C24—C23 | 120.4 (3) |
N2—C3A—C3B | 109.3 (3) | C25—C24—H24 | 119.8 |
C1M—C3A—C3B | 125.6 (3) | C23—C24—H24 | 119.8 |
N2—C4A—C2M | 126.3 (3) | C24—C25—C26 | 119.9 (4) |
N2—C4A—C4B | 109.6 (3) | C24—C25—H25 | 120.1 |
C2M—C4A—C4B | 124.0 (3) | C26—C25—H25 | 120.1 |
N3—C5A—C2M | 123.9 (3) | C25—C26—C21 | 120.5 (4) |
N3—C5A—C5B | 108.3 (3) | C25—C26—H26 | 119.8 |
C2M—C5A—C5B | 127.4 (3) | C21—C26—H26 | 119.8 |
N3—C6A—C3M | 124.0 (3) | C32—C31—C36 | 119.0 (3) |
N3—C6A—C6B | 108.6 (3) | C32—C31—C3M | 118.7 (3) |
C3M—C6A—C6B | 127.4 (3) | C36—C31—C3M | 122.1 (3) |
N4—C7A—C3M | 125.4 (3) | C33—C32—C31 | 120.8 (3) |
N4—C7A—C7B | 109.2 (3) | C33—C32—H32 | 119.6 |
C3M—C7A—C7B | 125.3 (3) | C31—C32—H32 | 119.6 |
N4—C8A—C4M | 125.6 (3) | C32—C33—C34 | 119.7 (3) |
N4—C8A—C8B | 109.5 (3) | C32—C33—H33 | 120.2 |
C4M—C8A—C8B | 125.0 (3) | C34—C33—H33 | 120.2 |
C2B—C1B—C1A | 107.7 (3) | C33—C34—C35 | 120.2 (3) |
C2B—C1B—Br1 | 123.7 (2) | C33—C34—H34 | 119.9 |
C1A—C1B—Br1 | 128.2 (2) | C35—C34—H34 | 119.9 |
C1B—C2B—C2A | 107.7 (3) | C36—C35—C34 | 120.0 (3) |
C1B—C2B—Br2 | 123.7 (2) | C36—C35—H35 | 120.0 |
C2A—C2B—Br2 | 128.3 (2) | C34—C35—H35 | 120.0 |
C4B—C3B—C3A | 107.4 (3) | C35—C36—C31 | 120.3 (3) |
C4B—C3B—H3B | 126.3 | C35—C36—H36 | 119.9 |
C3A—C3B—H3B | 126.3 | C31—C36—H36 | 119.9 |
C3B—C4B—C4A | 107.2 (3) | C46—C41—C42 | 119.0 (3) |
C3B—C4B—H4B | 126.4 | C46—C41—C4M | 120.5 (3) |
C4A—C4B—H4B | 126.4 | C42—C41—C4M | 120.5 (3) |
C6B—C5B—C5A | 107.7 (3) | C43—C42—C41 | 120.2 (3) |
C6B—C5B—Br3 | 123.6 (2) | C43—C42—H42 | 119.9 |
C5A—C5B—Br3 | 128.2 (2) | C41—C42—H42 | 119.9 |
C5B—C6B—C6A | 107.6 (3) | C44—C43—C42 | 119.5 (4) |
C5B—C6B—Br4 | 123.7 (2) | C44—C43—H43 | 120.2 |
C6A—C6B—Br4 | 128.5 (2) | C42—C43—H43 | 120.2 |
C8B—C7B—C7A | 107.9 (3) | C45—C44—C43 | 121.0 (3) |
C8B—C7B—H7B | 126.0 | C45—C44—H44 | 119.5 |
C7A—C7B—H7B | 126.0 | C43—C44—H44 | 119.5 |
C7B—C8B—C8A | 107.1 (3) | C44—C45—C46 | 120.1 (4) |
C7B—C8B—H8B | 126.4 | C44—C45—H45 | 120.0 |
C8A—C8B—H8B | 126.4 | C46—C45—H45 | 120.0 |
C3A—C1M—C2A | 123.1 (3) | C45—C46—C41 | 120.1 (3) |
C3A—C1M—C11 | 118.3 (3) | C45—C46—H46 | 120.0 |
C2A—C1M—C11 | 118.7 (3) | C41—C46—H46 | 120.0 |
C5A—C2M—C4A | 124.0 (3) | Cl1—C50—Cl2 | 111.6 (2) |
C5A—C2M—C21 | 120.1 (3) | Cl1—C50—H50A | 109.3 |
C4A—C2M—C21 | 115.6 (3) | Cl2—C50—H50A | 109.3 |
C7A—C3M—C6A | 123.8 (3) | Cl1—C50—H50B | 109.3 |
C7A—C3M—C31 | 116.2 (3) | Cl2—C50—H50B | 109.3 |
C6A—C3M—C31 | 120.0 (3) | H50A—C50—H50B | 108.0 |
C8A—C4M—C1A | 124.0 (3) |
Symmetry code: (i) −x+1, y, −z+1/2. |
Experimental details
Crystal data | |
Chemical formula | [Fe2O(C44H24Br4N4)2]·2CH2Cl2 |
Mr | 2154.18 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 130 |
a, b, c (Å) | 35.161 (6), 13.763 (6), 18.845 (3) |
β (°) | 119.104 (12) |
V (Å3) | 7968.4 |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 4.57 |
Crystal size (mm) | 0.32 × 0.12 × 0.08 |
Data collection | |
Diffractometer | Enraf-Nonius FAST area-detector diffractometer |
Absorption correction | Part of the refinement model (ΔF) empirical (using intensity measurements) (Blessing, 1997) |
Tmin, Tmax | 0.492, 0.694 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 25463, 9134, 7483 |
Rint | 0.049 |
(sin θ/λ)max (Å−1) | 0.668 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.040, 0.099, 1.04 |
No. of reflections | 9134 |
No. of parameters | 511 |
H-atom treatment | Idealized with riding models |
w = 1/[σ2(Fo2) + (0.0581P)2 + 11.1319P] where P = (Fo2 + 2Fc2)/3 | |
Δρmax, Δρmin (e Å−3) | 1.16, −0.63 |
Computer programs: MADNES (Messerschmitt & Pflugrath, 1987), MADNES, SHELXS86 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), ORTEP-3 (Farrugia, 1997), SHELXTL (Siemens, 1994).
Fe—O1 | 1.7583 (4) | Fe—N1 | 2.097 (2) |
Fe—N2 | 2.039 (2) | Fe—N3 | 2.100 (3) |
Fe—N4 | 2.043 (2) | O1—Fei | 1.7583 (4) |
O1—Fe—N2 | 104.12 (12) | Fe—O1—Fei | 178.7 (2) |
O1—Fe—N4 | 102.91 (12) | C3A—C1M—C11 | 118.3 (3) |
N2—Fe—N4 | 152.96 (11) | C2A—C1M—C11 | 118.7 (3) |
O1—Fe—N1 | 106.26 (8) | C5A—C2M—C21 | 120.1 (3) |
N2—Fe—N1 | 86.32 (10) | C4A—C2M—C21 | 115.6 (3) |
N4—Fe—N1 | 86.82 (10) | C7A—C3M—C31 | 116.2 (3) |
O1—Fe—N3 | 102.86 (8) | C6A—C3M—C31 | 120.0 (3) |
N2—Fe—N3 | 87.21 (10) | C8A—C4M—C41 | 116.2 (3) |
N4—Fe—N3 | 86.16 (10) | C1A—C4M—C41 | 119.7 (3) |
N1—Fe—N3 | 150.88 (10) |
Symmetry code: (i) −x+1, y, −z+1/2. |
Kadish et al. (1997) previously described the molecular structure of the title compound, (I), in which there are highly disordered alcohol molecules of solvation. In this paper, we report the precise structure of the species. There is an obvious difference between the current and previous crystal structures. Owing to the different solvents used for crystallization, two different space groups are found for the same species, i.e. P21/n and C2/c. Consequently, there are two non-equivalent porphyrin macrocycles and Fe—O distances [1.775 (8) and 1.741 (8) Å] in the previous structure. But the present molecule has a twofold axis which passes through the bridging O atom and is perpendicular to a line joining the two Fe atoms, leading to the rigorous requirement that the two porphyrin macrocycles bee equivalent. Fig. 1 shows a topview of the title compound. The two Fe—O bond lengths are the same at 1.7583 (4) Å, a distance which is comparable to those found in the analogous non-brominated [Fe(TPP)]2O [1.763 (1) Å; Hoffmann et al., 1972] and [Fe(TPFP)]2O [1.775 (1) Å; Gold et al., 1988]. However, the conformation of the porphyrin cores and the Fe—N distances in the two crystalline species are not significantly different.
As pointed out by Scheidt (2000), the introduction of Br atoms on the two opposite pyrrole rings contributes to an interaction between the meso- and β-substituents, resulting in an increase in the N···N distance for the two β-substituted pyrrole rings, unequal angles subtended at the methine C atom for the exo substituent and non-planar cores. The transannular distance N···N of 4.062 Å between the two brominated pyrrole rings is longer than the distance of 3.970 Å in the other direction. Also, the Fe—N bond lengths to the brominated pyrrole N atoms are longer that the bond lengths to the unsubstituted pyrrole rings [2.098 (2) versus 2.041 (3) Å; Table 1]. However, the average of the four Fe—N distances of 2.070 (33) Å in the present structure is shorter than the average Fe—N distance of 2.087 (5) Å in [Fe(TPP)]2O and of 2.088 (11) Å in [Fe(TPFP)]2O, owing to the saddled and ruffled porphyrin cores in the title compound. On the other hand, the same peripheral substituent effect induces two distinct saddled core conformations to minimize unfavorable contact between the Br atoms and the phenyl rings in [Fe(TPPBr4)(NO)] (Scheidt, 1999), while [Zn(TppBr4)] (Zou, 1997) is planar and [Ni(TPPBr4)] (Zou, 1994) is ruffled. In all cases, The M—N bonds to the brominated pyrrole ring are longer.