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The precise structure of the title compound, [Fe2O(C44H24Br4N4)2]·2CH2Cl2, is reported. The Fe—N distances are non-equivalent in pairs because of the asymmetric peripheral substitution; the values are 2.098 Å to the brominated rings and 2.041 Å to the other two rings. The Fe—O bond distance is 1.7583 (4) Å. The mol­ecule has required twofold symmetry so that there is one unique porphyrin macrocycle and one Fe—O bond length in contrast to a previous report on the same species.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270100010222/bk1532sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270100010222/bk1532Isup2.hkl
Contains datablock I

CCDC reference: 152598

Comment top

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.

Experimental top

Crystals of the title compound were obtained during an investigation of the oxidation reaction of [Fe(TPPBr4)(1-MeIm)2].

Computing details top

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).

Figures top
[Figure 1] 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.
[(TPPBr4)Fe]2O·2CH2Cl2 top
Crystal data top
[Fe2O(C44H24Br4N4)2]·2CH2Cl2F(000) = 4224
Mr = 2154.18Dx = 1.796 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
a = 35.161 (6) ÅCell parameters from 250 reflections
b = 13.763 (6) Åθ = 0–0°
c = 18.845 (3) ŵ = 4.57 mm1
β = 119.104 (12)°T = 130 K
V = 7968.4 Å3Needle, red–brown
Z = 40.32 × 0.12 × 0.08 mm
Data collection top
Enraf-Nonius FAST area-detector
diffractometer
9134 independent reflections
Radiation source: rotating anode7483 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.049
Detector resolution: 8.2/10.9 pixels mm-1θmax = 28.3°, θmin = 2.2°
Ellipsoid–mask fitting scansh = 3546
Absorption correction: part of the refinement model (ΔF)
empirical (using intensity measurements) (Blessing, 1997)
k = 1217
Tmin = 0.492, Tmax = 0.694l = 2322
25463 measured reflections
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.040Idealized 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 reflectionsΔρmax = 1.16 e Å3
511 parametersΔρmin = 0.63 e Å3
0 restraintsExtinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.00097 (5)
Crystal data top
[Fe2O(C44H24Br4N4)2]·2CH2Cl2V = 7968.4 Å3
Mr = 2154.18Z = 4
Monoclinic, C2/cMo Kα radiation
a = 35.161 (6) ŵ = 4.57 mm1
b = 13.763 (6) ÅT = 130 K
c = 18.845 (3) Å0.32 × 0.12 × 0.08 mm
β = 119.104 (12)°
Data collection top
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 = 0.694Rint = 0.049
25463 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0400 restraints
wR(F2) = 0.099Idealized with riding models
S = 1.04 w = 1/[σ2(Fo2) + (0.0581P)2 + 11.1319P]
where P = (Fo2 + 2Fc2)/3
9134 reflectionsΔρmax = 1.16 e Å3
511 parametersΔρmin = 0.63 e Å3
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Fe0.487947 (13)0.69720 (3)0.14786 (3)0.01267 (10)
O10.50000.6958 (2)0.25000.0178 (6)
N10.42279 (8)0.74098 (17)0.08012 (15)0.0137 (5)
N20.46602 (8)0.56018 (18)0.10749 (16)0.0150 (5)
N30.54712 (8)0.65504 (18)0.15505 (16)0.0152 (5)
N40.50419 (8)0.83546 (18)0.13328 (16)0.0156 (5)
C1A0.40744 (10)0.8320 (2)0.04829 (18)0.0151 (6)
C2A0.38753 (10)0.6801 (2)0.05339 (18)0.0147 (6)
C3A0.42765 (10)0.5268 (2)0.10136 (18)0.0155 (6)
C4A0.49213 (10)0.4809 (2)0.12281 (19)0.0165 (6)
C5A0.55880 (10)0.5639 (2)0.14255 (18)0.0153 (6)
C6A0.58264 (9)0.7145 (2)0.17938 (18)0.0156 (6)
C7A0.54628 (10)0.8677 (2)0.17874 (19)0.0174 (6)
C8A0.47804 (10)0.9152 (2)0.1187 (2)0.0173 (6)
C1B0.36169 (10)0.8242 (2)0.00646 (18)0.0153 (6)
C2B0.34946 (9)0.7324 (2)0.00159 (18)0.0161 (6)
C3B0.43113 (11)0.4245 (2)0.1173 (2)0.0210 (7)
H3B0.40980.38440.11970.025*
C4B0.47001 (11)0.3957 (2)0.1282 (2)0.0206 (7)
H4B0.48090.33110.13770.025*
C5B0.60190 (10)0.5695 (2)0.15218 (19)0.0169 (6)
C6B0.61689 (10)0.6599 (2)0.17706 (19)0.0171 (6)
C7B0.54586 (10)0.9687 (2)0.1954 (2)0.0207 (7)
H7B0.57061.00790.22750.025*
C8B0.50446 (10)0.9985 (2)0.1577 (2)0.0197 (6)
H8B0.49441.06280.15700.024*
C1M0.39020 (10)0.5822 (2)0.07570 (19)0.0156 (6)
C2M0.53417 (10)0.4803 (2)0.13254 (18)0.0164 (6)
C3M0.58345 (10)0.8125 (2)0.20009 (19)0.0154 (6)
C4M0.43311 (10)0.9158 (2)0.07344 (19)0.0166 (6)
Br10.324966 (10)0.91518 (2)0.08185 (2)0.02274 (9)
Br20.293345 (10)0.68506 (2)0.06584 (2)0.02356 (9)
Br30.631044 (11)0.47720 (2)0.12386 (2)0.02222 (9)
Br40.671164 (10)0.70352 (2)0.19521 (2)0.02223 (9)
C110.35097 (9)0.5346 (2)0.07157 (18)0.0154 (6)
C120.33162 (10)0.4534 (2)0.02368 (19)0.0191 (6)
H120.34350.42610.00760.023*
C130.29513 (11)0.4122 (2)0.0213 (2)0.0224 (7)
H130.28210.35660.01160.027*
C140.27744 (11)0.4511 (3)0.0662 (2)0.0266 (7)
H140.25210.42300.06370.032*
C150.29667 (12)0.5310 (3)0.1149 (2)0.0279 (8)
H150.28460.55820.14590.033*
C160.33362 (11)0.5717 (2)0.1183 (2)0.0216 (7)
H160.34720.62550.15310.026*
C210.55404 (10)0.3827 (2)0.1409 (2)0.0183 (6)
C220.58789 (11)0.3529 (3)0.2150 (2)0.0238 (7)
H220.59940.39580.26010.029*
C230.60485 (13)0.2604 (3)0.2228 (3)0.0368 (10)
H230.62800.23960.27370.044*
C240.58827 (14)0.1983 (3)0.1570 (3)0.0391 (10)
H240.60040.13530.16240.047*
C250.55456 (14)0.2268 (3)0.0843 (3)0.0366 (9)
H250.54300.18350.03940.044*
C260.53722 (12)0.3189 (2)0.0760 (2)0.0242 (7)
H260.51360.33840.02530.029*
C310.62572 (10)0.8623 (2)0.24996 (19)0.0165 (6)
C320.65079 (10)0.8360 (2)0.33087 (19)0.0189 (6)
H320.64160.78380.35200.023*
C330.68879 (10)0.8846 (3)0.3810 (2)0.0231 (7)
H330.70580.86590.43630.028*
C340.70209 (10)0.9605 (2)0.3505 (2)0.0224 (7)
H340.72830.99410.38490.027*
C350.67734 (11)0.9880 (2)0.2700 (2)0.0218 (7)
H350.68641.04070.24930.026*
C360.63950 (10)0.9387 (2)0.2198 (2)0.0186 (6)
H360.62280.95710.16440.022*
C410.41201 (10)1.0126 (2)0.0556 (2)0.0192 (6)
C420.38299 (11)1.0371 (2)0.0835 (2)0.0238 (7)
H420.37670.99140.11420.029*
C430.36343 (12)1.1273 (3)0.0666 (2)0.0315 (8)
H430.34371.14390.08570.038*
C440.37264 (14)1.1929 (3)0.0221 (3)0.0385 (10)
H440.35861.25440.00930.046*
C450.40174 (13)1.1711 (3)0.0042 (2)0.0339 (9)
H450.40831.21790.03360.041*
C460.42146 (11)1.0813 (2)0.0120 (2)0.0239 (7)
H460.44151.06610.00640.029*
C500.79005 (12)0.8189 (3)0.2309 (2)0.0299 (8)
H50A0.80640.79420.28730.036*
H50B0.81020.85840.22010.036*
Cl10.74721 (3)0.89210 (8)0.22152 (6)0.0367 (2)
Cl20.77117 (4)0.72066 (8)0.16346 (7)0.0518 (3)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Fe0.0133 (2)0.0114 (2)0.0127 (2)0.00033 (14)0.00582 (17)0.00016 (15)
O10.0179 (15)0.0188 (15)0.0166 (15)0.0000.0085 (13)0.000
N10.0158 (12)0.0122 (11)0.0128 (12)0.0009 (9)0.0068 (10)0.0006 (9)
N20.0170 (13)0.0120 (11)0.0164 (13)0.0003 (9)0.0084 (10)0.0004 (10)
N30.0160 (12)0.0138 (12)0.0162 (12)0.0011 (9)0.0082 (10)0.0001 (10)
N40.0134 (12)0.0149 (12)0.0156 (13)0.0002 (9)0.0047 (10)0.0014 (10)
C1A0.0175 (15)0.0151 (14)0.0123 (14)0.0005 (11)0.0069 (12)0.0004 (11)
C2A0.0174 (15)0.0154 (14)0.0121 (14)0.0011 (11)0.0078 (12)0.0009 (11)
C3A0.0185 (15)0.0163 (14)0.0130 (14)0.0029 (11)0.0086 (12)0.0026 (11)
C4A0.0177 (15)0.0160 (14)0.0154 (15)0.0007 (11)0.0079 (12)0.0001 (12)
C5A0.0184 (15)0.0156 (14)0.0127 (14)0.0006 (11)0.0081 (12)0.0010 (11)
C6A0.0153 (14)0.0164 (14)0.0158 (15)0.0017 (11)0.0080 (12)0.0012 (12)
C7A0.0163 (15)0.0173 (15)0.0165 (15)0.0034 (11)0.0063 (12)0.0006 (12)
C8A0.0215 (16)0.0134 (14)0.0195 (16)0.0005 (11)0.0118 (13)0.0024 (12)
C1B0.0168 (14)0.0154 (14)0.0137 (14)0.0023 (11)0.0074 (12)0.0011 (11)
C2B0.0138 (14)0.0202 (15)0.0133 (14)0.0001 (11)0.0057 (12)0.0024 (12)
C3B0.0246 (17)0.0160 (15)0.0233 (17)0.0027 (12)0.0124 (14)0.0004 (13)
C4B0.0238 (17)0.0117 (14)0.0261 (17)0.0008 (12)0.0119 (14)0.0026 (12)
C5B0.0211 (16)0.0170 (14)0.0159 (15)0.0038 (11)0.0115 (13)0.0035 (12)
C6B0.0170 (15)0.0190 (15)0.0161 (15)0.0001 (11)0.0086 (12)0.0031 (12)
C7B0.0195 (16)0.0166 (15)0.0243 (17)0.0033 (12)0.0094 (13)0.0011 (13)
C8B0.0210 (16)0.0139 (14)0.0224 (16)0.0009 (11)0.0091 (13)0.0008 (12)
C1M0.0192 (15)0.0158 (14)0.0142 (14)0.0035 (11)0.0100 (12)0.0034 (11)
C2M0.0215 (15)0.0152 (14)0.0140 (14)0.0019 (11)0.0099 (12)0.0002 (11)
C3M0.0165 (14)0.0141 (14)0.0149 (14)0.0018 (11)0.0072 (12)0.0011 (11)
C4M0.0199 (15)0.0126 (14)0.0165 (15)0.0009 (11)0.0080 (13)0.0009 (11)
Br10.01905 (17)0.02196 (17)0.02016 (17)0.00285 (11)0.00400 (13)0.00655 (12)
Br20.01585 (16)0.02399 (17)0.02136 (17)0.00390 (11)0.00161 (13)0.00073 (13)
Br30.02725 (18)0.02044 (17)0.02754 (18)0.00402 (12)0.02005 (15)0.00098 (13)
Br40.01643 (16)0.02316 (17)0.02954 (18)0.00028 (11)0.01309 (14)0.00170 (13)
C110.0144 (14)0.0165 (14)0.0142 (14)0.0010 (11)0.0060 (12)0.0027 (11)
C120.0216 (16)0.0190 (15)0.0181 (16)0.0022 (12)0.0108 (13)0.0023 (12)
C130.0204 (16)0.0203 (16)0.0205 (16)0.0060 (12)0.0052 (13)0.0027 (13)
C140.0210 (17)0.0321 (18)0.0267 (18)0.0084 (14)0.0117 (15)0.0017 (15)
C150.0270 (18)0.0345 (19)0.0304 (19)0.0033 (15)0.0205 (16)0.0035 (15)
C160.0234 (16)0.0225 (16)0.0206 (16)0.0029 (13)0.0121 (14)0.0044 (13)
C210.0198 (15)0.0161 (14)0.0237 (16)0.0019 (11)0.0143 (13)0.0031 (12)
C220.0239 (17)0.0257 (17)0.0257 (17)0.0038 (13)0.0152 (14)0.0067 (14)
C230.032 (2)0.033 (2)0.051 (3)0.0109 (16)0.0246 (19)0.0226 (19)
C240.052 (3)0.0170 (17)0.070 (3)0.0127 (16)0.046 (2)0.0128 (18)
C250.054 (3)0.0213 (18)0.054 (3)0.0027 (17)0.041 (2)0.0069 (18)
C260.0311 (18)0.0203 (16)0.0269 (18)0.0004 (13)0.0187 (15)0.0035 (14)
C310.0143 (14)0.0155 (14)0.0195 (15)0.0002 (11)0.0081 (12)0.0023 (12)
C320.0179 (15)0.0191 (15)0.0183 (15)0.0017 (11)0.0078 (13)0.0012 (12)
C330.0203 (16)0.0294 (18)0.0177 (16)0.0032 (13)0.0078 (13)0.0014 (13)
C340.0167 (15)0.0234 (16)0.0246 (17)0.0042 (12)0.0080 (13)0.0057 (13)
C350.0239 (17)0.0177 (15)0.0248 (17)0.0063 (12)0.0126 (14)0.0010 (13)
C360.0210 (16)0.0162 (14)0.0180 (15)0.0011 (11)0.0092 (13)0.0016 (12)
C410.0195 (15)0.0149 (14)0.0184 (15)0.0008 (11)0.0054 (13)0.0001 (12)
C420.0231 (17)0.0242 (17)0.0201 (16)0.0030 (13)0.0073 (14)0.0015 (13)
C430.0295 (19)0.0252 (18)0.034 (2)0.0077 (14)0.0106 (16)0.0075 (16)
C440.040 (2)0.0179 (18)0.042 (2)0.0118 (15)0.0078 (19)0.0005 (16)
C450.041 (2)0.0181 (17)0.029 (2)0.0012 (15)0.0062 (17)0.0104 (15)
C460.0241 (17)0.0193 (16)0.0240 (17)0.0011 (12)0.0083 (14)0.0025 (13)
C500.0246 (18)0.0298 (19)0.0304 (19)0.0004 (14)0.0095 (15)0.0026 (15)
Cl10.0323 (5)0.0439 (5)0.0402 (5)0.0070 (4)0.0225 (4)0.0082 (4)
Cl20.0544 (7)0.0300 (5)0.0472 (6)0.0014 (4)0.0060 (5)0.0108 (5)
Geometric parameters (Å, º) top
Fe—O11.7583 (4)C11—C161.390 (4)
Fe—N22.039 (2)C12—C131.383 (4)
Fe—N42.043 (2)C12—H120.9500
Fe—N12.097 (2)C13—C141.380 (5)
Fe—N32.100 (3)C13—H130.9500
O1—Fei1.7583 (4)C14—C151.380 (5)
N1—C2A1.373 (4)C14—H140.9500
N1—C1A1.380 (4)C15—C161.386 (5)
N2—C4A1.364 (4)C15—H150.9500
N2—C3A1.376 (4)C16—H160.9500
N3—C6A1.372 (4)C21—C261.384 (5)
N3—C5A1.376 (4)C21—C221.384 (5)
N4—C8A1.371 (4)C22—C231.383 (5)
N4—C7A1.374 (4)C22—H220.9500
C1A—C4M1.398 (4)C23—C241.381 (6)
C1A—C1B1.432 (4)C23—H230.9500
C2A—C1M1.402 (4)C24—C251.363 (6)
C2A—C2B1.426 (4)C24—H240.9500
C3A—C1M1.389 (4)C25—C261.381 (5)
C3A—C3B1.433 (4)C25—H250.9500
C4A—C2M1.398 (4)C26—H260.9500
C4A—C4B1.438 (4)C31—C321.388 (4)
C5A—C2M1.397 (4)C31—C361.389 (4)
C5A—C5B1.438 (4)C32—C331.377 (5)
C6A—C3M1.401 (4)C32—H320.9500
C6A—C6B1.438 (4)C33—C341.379 (5)
C7A—C3M1.391 (4)C33—H330.9500
C7A—C7B1.427 (4)C34—C351.386 (5)
C8A—C4M1.383 (4)C34—H340.9500
C8A—C8B1.433 (4)C35—C361.378 (4)
C1B—C2B1.352 (4)C35—H350.9500
C1B—Br11.862 (3)C36—H360.9500
C2B—Br21.860 (3)C41—C461.394 (5)
C3B—C4B1.340 (5)C41—C421.397 (5)
C3B—H3B0.9500C42—C431.380 (5)
C4B—H4B0.9500C42—H420.9500
C5B—C6B1.343 (4)C43—C441.375 (6)
C5B—Br31.866 (3)C43—H430.9500
C6B—Br41.867 (3)C44—C451.369 (6)
C7B—C8B1.336 (5)C44—H440.9500
C7B—H7B0.9500C45—C461.376 (5)
C8B—H8B0.9500C45—H450.9500
C1M—C111.494 (4)C46—H460.9500
C2M—C211.486 (4)C50—Cl11.748 (4)
C3M—C311.485 (4)C50—Cl21.751 (4)
C4M—C411.482 (4)C50—H50A0.9900
C11—C121.389 (4)C50—H50B0.9900
O1—Fe—N2104.12 (12)C8A—C4M—C41116.2 (3)
O1—Fe—N4102.91 (12)C1A—C4M—C41119.7 (3)
N2—Fe—N4152.96 (11)C12—C11—C16118.7 (3)
O1—Fe—N1106.26 (8)C12—C11—C1M122.3 (3)
N2—Fe—N186.32 (10)C16—C11—C1M119.0 (3)
N4—Fe—N186.82 (10)C13—C12—C11120.3 (3)
O1—Fe—N3102.86 (8)C13—C12—H12119.9
N2—Fe—N387.21 (10)C11—C12—H12119.9
N4—Fe—N386.16 (10)C14—C13—C12120.6 (3)
N1—Fe—N3150.88 (10)C14—C13—H13119.7
Fe—O1—Fei178.7 (2)C12—C13—H13119.7
C2A—N1—C1A107.6 (2)C15—C14—C13119.7 (3)
C2A—N1—Fe124.91 (19)C15—C14—H14120.2
C1A—N1—Fe127.28 (19)C13—C14—H14120.2
C4A—N2—C3A106.4 (2)C14—C15—C16119.9 (3)
C4A—N2—Fe124.6 (2)C14—C15—H15120.0
C3A—N2—Fe121.1 (2)C16—C15—H15120.0
C6A—N3—C5A107.6 (2)C15—C16—C11120.8 (3)
C6A—N3—Fe124.7 (2)C15—C16—H16119.6
C5A—N3—Fe127.6 (2)C11—C16—H16119.6
C8A—N4—C7A106.3 (2)C26—C21—C22119.4 (3)
C8A—N4—Fe124.6 (2)C26—C21—C2M120.2 (3)
C7A—N4—Fe120.2 (2)C22—C21—C2M120.2 (3)
N1—C1A—C4M123.4 (3)C23—C22—C21119.7 (4)
N1—C1A—C1B108.1 (2)C23—C22—H22120.2
C4M—C1A—C1B128.3 (3)C21—C22—H22120.2
N1—C2A—C1M124.1 (3)C24—C23—C22120.1 (4)
N1—C2A—C2B108.6 (3)C24—C23—H23119.9
C1M—C2A—C2B127.3 (3)C22—C23—H23119.9
N2—C3A—C1M124.9 (3)C25—C24—C23120.4 (3)
N2—C3A—C3B109.3 (3)C25—C24—H24119.8
C1M—C3A—C3B125.6 (3)C23—C24—H24119.8
N2—C4A—C2M126.3 (3)C24—C25—C26119.9 (4)
N2—C4A—C4B109.6 (3)C24—C25—H25120.1
C2M—C4A—C4B124.0 (3)C26—C25—H25120.1
N3—C5A—C2M123.9 (3)C25—C26—C21120.5 (4)
N3—C5A—C5B108.3 (3)C25—C26—H26119.8
C2M—C5A—C5B127.4 (3)C21—C26—H26119.8
N3—C6A—C3M124.0 (3)C32—C31—C36119.0 (3)
N3—C6A—C6B108.6 (3)C32—C31—C3M118.7 (3)
C3M—C6A—C6B127.4 (3)C36—C31—C3M122.1 (3)
N4—C7A—C3M125.4 (3)C33—C32—C31120.8 (3)
N4—C7A—C7B109.2 (3)C33—C32—H32119.6
C3M—C7A—C7B125.3 (3)C31—C32—H32119.6
N4—C8A—C4M125.6 (3)C32—C33—C34119.7 (3)
N4—C8A—C8B109.5 (3)C32—C33—H33120.2
C4M—C8A—C8B125.0 (3)C34—C33—H33120.2
C2B—C1B—C1A107.7 (3)C33—C34—C35120.2 (3)
C2B—C1B—Br1123.7 (2)C33—C34—H34119.9
C1A—C1B—Br1128.2 (2)C35—C34—H34119.9
C1B—C2B—C2A107.7 (3)C36—C35—C34120.0 (3)
C1B—C2B—Br2123.7 (2)C36—C35—H35120.0
C2A—C2B—Br2128.3 (2)C34—C35—H35120.0
C4B—C3B—C3A107.4 (3)C35—C36—C31120.3 (3)
C4B—C3B—H3B126.3C35—C36—H36119.9
C3A—C3B—H3B126.3C31—C36—H36119.9
C3B—C4B—C4A107.2 (3)C46—C41—C42119.0 (3)
C3B—C4B—H4B126.4C46—C41—C4M120.5 (3)
C4A—C4B—H4B126.4C42—C41—C4M120.5 (3)
C6B—C5B—C5A107.7 (3)C43—C42—C41120.2 (3)
C6B—C5B—Br3123.6 (2)C43—C42—H42119.9
C5A—C5B—Br3128.2 (2)C41—C42—H42119.9
C5B—C6B—C6A107.6 (3)C44—C43—C42119.5 (4)
C5B—C6B—Br4123.7 (2)C44—C43—H43120.2
C6A—C6B—Br4128.5 (2)C42—C43—H43120.2
C8B—C7B—C7A107.9 (3)C45—C44—C43121.0 (3)
C8B—C7B—H7B126.0C45—C44—H44119.5
C7A—C7B—H7B126.0C43—C44—H44119.5
C7B—C8B—C8A107.1 (3)C44—C45—C46120.1 (4)
C7B—C8B—H8B126.4C44—C45—H45120.0
C8A—C8B—H8B126.4C46—C45—H45120.0
C3A—C1M—C2A123.1 (3)C45—C46—C41120.1 (3)
C3A—C1M—C11118.3 (3)C45—C46—H46120.0
C2A—C1M—C11118.7 (3)C41—C46—H46120.0
C5A—C2M—C4A124.0 (3)Cl1—C50—Cl2111.6 (2)
C5A—C2M—C21120.1 (3)Cl1—C50—H50A109.3
C4A—C2M—C21115.6 (3)Cl2—C50—H50A109.3
C7A—C3M—C6A123.8 (3)Cl1—C50—H50B109.3
C7A—C3M—C31116.2 (3)Cl2—C50—H50B109.3
C6A—C3M—C31120.0 (3)H50A—C50—H50B108.0
C8A—C4M—C1A124.0 (3)
Symmetry code: (i) x+1, y, z+1/2.

Experimental details

Crystal data
Chemical formula[Fe2O(C44H24Br4N4)2]·2CH2Cl2
Mr2154.18
Crystal system, space groupMonoclinic, C2/c
Temperature (K)130
a, b, c (Å)35.161 (6), 13.763 (6), 18.845 (3)
β (°) 119.104 (12)
V3)7968.4
Z4
Radiation typeMo Kα
µ (mm1)4.57
Crystal size (mm)0.32 × 0.12 × 0.08
Data collection
DiffractometerEnraf-Nonius FAST area-detector
diffractometer
Absorption correctionPart of the refinement model (ΔF)
empirical (using intensity measurements) (Blessing, 1997)
Tmin, Tmax0.492, 0.694
No. of measured, independent and
observed [I > 2σ(I)] reflections
25463, 9134, 7483
Rint0.049
(sin θ/λ)max1)0.668
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.040, 0.099, 1.04
No. of reflections9134
No. of parameters511
H-atom treatmentIdealized with riding models
w = 1/[σ2(Fo2) + (0.0581P)2 + 11.1319P]
where P = (Fo2 + 2Fc2)/3
Δρmax, Δρmin (e Å3)1.16, 0.63

Computer programs: MADNES (Messerschmitt & Pflugrath, 1987), MADNES, SHELXS86 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), ORTEP-3 (Farrugia, 1997), SHELXTL (Siemens, 1994).

Selected geometric parameters (Å, º) top
Fe—O11.7583 (4)Fe—N12.097 (2)
Fe—N22.039 (2)Fe—N32.100 (3)
Fe—N42.043 (2)O1—Fei1.7583 (4)
O1—Fe—N2104.12 (12)Fe—O1—Fei178.7 (2)
O1—Fe—N4102.91 (12)C3A—C1M—C11118.3 (3)
N2—Fe—N4152.96 (11)C2A—C1M—C11118.7 (3)
O1—Fe—N1106.26 (8)C5A—C2M—C21120.1 (3)
N2—Fe—N186.32 (10)C4A—C2M—C21115.6 (3)
N4—Fe—N186.82 (10)C7A—C3M—C31116.2 (3)
O1—Fe—N3102.86 (8)C6A—C3M—C31120.0 (3)
N2—Fe—N387.21 (10)C8A—C4M—C41116.2 (3)
N4—Fe—N386.16 (10)C1A—C4M—C41119.7 (3)
N1—Fe—N3150.88 (10)
Symmetry code: (i) x+1, y, z+1/2.
 

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