Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270102009435/fg1649sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270102009435/fg1649Isup2.hkl |
CCDC reference: 192946
For the synthesis of [Fe(phox)3], FeCl3·6H2O (0.27 g, 1.0 mmol) dissolved in water (10 ml) was added to a stirred solution of Hphox (0.49 g, 3.0 mmol) and triethylamine (0.30 g, 3.0 mmol) in methanol (10 ml). A dark-red product precipitated within a number of days and was collected by filtration. The complex was recrystallized from acetonitrile to yield 0.40 g (0.74 mmol, 74%) of [Fe(phox)3]. X-ray quality crystals were obtained after recrystallization from MeOH/MeCN (3:1). IR (cm-1): 1617 (s), 1589 (w), 1545 (m), 1470 (s), 1441 (m), 1390 (m), 1336 (m), 1260 (m), 1239 (m), 1154 (m), 1071 (m), 947 (w), 928 (w), 856 (m), 759 (m), 688 (m), 660 (w), 601 (w). Analysis calculated for C27H24FeN3O6: C 59.80, H 4.46, N 7,75%; found: C 59.38, H 4.63, N 7.75%. ES—MS: m/z: 543 ([Fe(phox)3]+H+), 380 ([Fe(phox)2]+), 164 (Hphox+H+). Electronic absorption spectrum in MeOH, λmax/nm (ε/M-1 × cm-1) 461 (4.1 × 103), 307 (1.4 × 104), 222 (5.1 × 104). µeff = 5.70µB (at 290.6 K).
The phox ligand was found to be disordered over two positions, related by a non-crystallographic twofold rotation axis. The smallest angle of the disorder axis to a translation axis is approximately 9°. The coordinates of both components and their occupation ratio were refined. Corresponding distances and 1–3 distances of the disorder components were restrained to be equal within an s.u. of 0.02 Å. H atoms were included in the model on calculated positions, riding on their carrier atoms. The minor component non-H atoms were refined with an isotropic displacement parameter. The isotropic displacement parameters of H atoms bonded to C atoms were coupled to the equivalent isotropic displacement parameter of their carrier atoms by a fixed factor of 1.2.
Data collection: locally modified CAD-4 Software (Enraf-Nonius, 1989); cell refinement: SET4 (de Boer & Duisenberg, 1984); data reduction: HELENA (Spek, 1997); program(s) used to solve structure: SHELXS86 (Sheldrick, 1985); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2002); software used to prepare material for publication: PLATON.
[Fe(C9H8NO2)3] | Least Squares Treatment of 25 SET4 setting angles. |
Mr = 542.34 | Dx = 1.466 Mg m−3 |
Trigonal, P3 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 3 | Cell parameters from 25 reflections |
a = 14.882 (2) Å | θ = 10.2–15.3° |
c = 6.4052 (11) Å | µ = 0.66 mm−1 |
V = 1228.5 (3) Å3 | T = 150 K |
Z = 2 | Block, dark red |
F(000) = 562 | 0.30 × 0.15 × 0.05 mm |
Enraf-Nonius CAD-4 Turbo diffractometer | Rint = 0.057 |
Radiation source: Rotating Anode | θmax = 25.0°, θmin = 1.6° |
Graphite monochromator | h = −19→17 |
ω scans with Δω = 1.26+0.35 tan θ | k = −17→19 |
1686 measured reflections | l = −8→0 |
1448 independent reflections | 3 standard reflections every 60 min |
970 reflections with I > 2σ(I) | intensity decay: 3% |
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)] = 0.074 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.168 | H-atom parameters not refined |
S = 1.19 | w = 1/[σ2(Fo2) + (0.0615P)2 + 1.78P] where P = (Fo2 + 2Fc2)/3 |
1448 reflections | (Δ/σ)max < 0.001 |
161 parameters | Δρmax = 0.51 e Å−3 |
31 restraints | Δρmin = −0.53 e Å−3 |
[Fe(C9H8NO2)3] | Z = 2 |
Mr = 542.34 | Mo Kα radiation |
Trigonal, P3 | µ = 0.66 mm−1 |
a = 14.882 (2) Å | T = 150 K |
c = 6.4052 (11) Å | 0.30 × 0.15 × 0.05 mm |
V = 1228.5 (3) Å3 |
Enraf-Nonius CAD-4 Turbo diffractometer | Rint = 0.057 |
1686 measured reflections | 3 standard reflections every 60 min |
1448 independent reflections | intensity decay: 3% |
970 reflections with I > 2σ(I) |
R[F2 > 2σ(F2)] = 0.074 | 31 restraints |
wR(F2) = 0.168 | H-atom parameters not refined |
S = 1.19 | Δρmax = 0.51 e Å−3 |
1448 reflections | Δρmin = −0.53 e Å−3 |
161 parameters |
Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All e.s.d.'s are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles |
Refinement. Refinement on F2 for ALL reflections except those flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The observed criterion of F2 > σ(F2) is used only for calculating -R-factor-obs 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 | 0.66667 | 0.33333 | 0.6262 (2) | 0.0197 (3) | |
O11 | 0.5362 (4) | 0.2853 (5) | 0.7719 (9) | 0.038 (2) | 0.758 (5) |
O12 | 0.4886 (4) | 0.4313 (5) | 0.2576 (8) | 0.0422 (19) | 0.758 (5) |
N11 | 0.6037 (5) | 0.3974 (5) | 0.4131 (10) | 0.026 (2) | 0.758 (5) |
C11 | 0.4433 (6) | 0.2738 (6) | 0.7262 (13) | 0.029 (3) | 0.758 (5) |
C12 | 0.3603 (6) | 0.2190 (7) | 0.8634 (14) | 0.046 (3) | 0.758 (5) |
C13 | 0.2650 (6) | 0.2047 (7) | 0.8198 (15) | 0.052 (3) | 0.758 (5) |
C14 | 0.2473 (6) | 0.2461 (7) | 0.6441 (15) | 0.049 (3) | 0.758 (5) |
C15 | 0.3269 (7) | 0.3022 (7) | 0.5106 (13) | 0.043 (3) | 0.758 (5) |
C16 | 0.4262 (5) | 0.3181 (6) | 0.5502 (11) | 0.027 (3) | 0.758 (5) |
C17 | 0.5089 (6) | 0.3822 (6) | 0.4104 (11) | 0.029 (3) | 0.758 (5) |
C18 | 0.6614 (6) | 0.4711 (7) | 0.2434 (12) | 0.039 (3) | 0.758 (5) |
C19 | 0.5807 (6) | 0.4849 (6) | 0.1292 (11) | 0.038 (3) | 0.758 (5) |
C25 | 0.3080 (15) | 0.2456 (17) | 0.640 (3) | 0.032 (6)* | 0.242 (5) |
C26 | 0.4148 (15) | 0.278 (2) | 0.648 (4) | 0.039 (9)* | 0.242 (5) |
C27 | 0.4501 (14) | 0.2350 (17) | 0.808 (3) | 0.029 (6)* | 0.242 (5) |
C28 | 0.5430 (13) | 0.1883 (16) | 1.012 (3) | 0.027 (5)* | 0.242 (5) |
C29 | 0.4328 (14) | 0.1337 (16) | 1.082 (3) | 0.027 (5)* | 0.242 (5) |
C22 | 0.4453 (16) | 0.3961 (18) | 0.370 (4) | 0.035 (6)* | 0.242 (5) |
C23 | 0.3417 (16) | 0.3622 (19) | 0.361 (3) | 0.044 (7)* | 0.242 (5) |
C24 | 0.2745 (18) | 0.287 (2) | 0.491 (4) | 0.051 (9)* | 0.242 (5) |
O21 | 0.5853 (11) | 0.3846 (13) | 0.513 (3) | 0.027 (5)* | 0.242 (5) |
O22 | 0.3783 (11) | 0.1634 (12) | 0.938 (2) | 0.035 (4)* | 0.242 (5) |
N21 | 0.5443 (14) | 0.2542 (16) | 0.839 (3) | 0.037 (7)* | 0.242 (5) |
C21 | 0.4833 (14) | 0.3543 (16) | 0.515 (3) | 0.017 (5)* | 0.242 (5) |
H18B | 0.71630 | 0.53800 | 0.30060 | 0.0470* | 0.758 (5) |
H19A | 0.60260 | 0.55940 | 0.11590 | 0.0460* | 0.758 (5) |
H19B | 0.56820 | 0.45380 | −0.01200 | 0.0460* | 0.758 (5) |
H12 | 0.37100 | 0.19140 | 0.98870 | 0.0560* | 0.758 (5) |
H13 | 0.20920 | 0.16520 | 0.91300 | 0.0630* | 0.758 (5) |
H14 | 0.18000 | 0.23560 | 0.61590 | 0.0580* | 0.758 (5) |
H15 | 0.31500 | 0.33100 | 0.38860 | 0.0520* | 0.758 (5) |
H18A | 0.69370 | 0.44250 | 0.14940 | 0.0470* | 0.758 (5) |
H22 | 0.49160 | 0.44840 | 0.27660 | 0.0420* | 0.242 (5) |
H23 | 0.31640 | 0.39160 | 0.26150 | 0.0530* | 0.242 (5) |
H24 | 0.20240 | 0.26320 | 0.47890 | 0.0610* | 0.242 (5) |
H25 | 0.26060 | 0.19600 | 0.73620 | 0.0380* | 0.242 (5) |
H28A | 0.59010 | 0.23070 | 1.12560 | 0.0330* | 0.242 (5) |
H28B | 0.56380 | 0.13820 | 0.96270 | 0.0330* | 0.242 (5) |
H29A | 0.40370 | 0.05760 | 1.07990 | 0.0330* | 0.242 (5) |
H29B | 0.42730 | 0.15500 | 1.22580 | 0.0330* | 0.242 (5) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Fe1 | 0.0173 (5) | 0.0173 (5) | 0.0244 (7) | 0.0086 (2) | 0.0000 | 0.0000 |
O11 | 0.026 (3) | 0.060 (4) | 0.043 (4) | 0.032 (3) | 0.009 (2) | 0.021 (3) |
O12 | 0.044 (3) | 0.061 (4) | 0.040 (3) | 0.040 (3) | 0.001 (3) | 0.017 (3) |
N11 | 0.025 (4) | 0.032 (4) | 0.024 (4) | 0.017 (3) | 0.004 (3) | 0.009 (3) |
C11 | 0.025 (4) | 0.032 (5) | 0.032 (5) | 0.015 (4) | 0.006 (4) | 0.007 (4) |
C12 | 0.032 (5) | 0.058 (6) | 0.058 (6) | 0.029 (4) | 0.009 (4) | 0.021 (5) |
C13 | 0.025 (5) | 0.045 (6) | 0.081 (7) | 0.014 (4) | 0.005 (4) | 0.014 (5) |
C14 | 0.013 (4) | 0.057 (6) | 0.082 (7) | 0.022 (4) | −0.002 (4) | 0.003 (5) |
C15 | 0.036 (6) | 0.058 (6) | 0.043 (5) | 0.029 (5) | −0.010 (4) | −0.001 (4) |
C16 | 0.015 (4) | 0.034 (5) | 0.030 (4) | 0.010 (4) | −0.001 (3) | 0.004 (4) |
C17 | 0.037 (5) | 0.040 (5) | 0.024 (4) | 0.029 (4) | −0.001 (4) | 0.004 (4) |
C18 | 0.042 (5) | 0.048 (5) | 0.038 (5) | 0.031 (4) | 0.018 (4) | 0.023 (4) |
C19 | 0.052 (5) | 0.044 (5) | 0.030 (4) | 0.032 (4) | 0.007 (4) | 0.010 (4) |
Fe1—O11 | 1.940 (7) | C21—C26 | 1.38 (3) |
Fe1—N11 | 2.132 (7) | C22—C23 | 1.36 (4) |
Fe1—O21 | 1.870 (19) | C23—C24 | 1.35 (3) |
Fe1—N21 | 2.10 (2) | C24—C25 | 1.36 (4) |
O11—C11 | 1.338 (12) | C25—C26 | 1.41 (4) |
O12—C17 | 1.343 (10) | C26—C27 | 1.44 (3) |
O12—C19 | 1.448 (11) | C28—C29 | 1.49 (3) |
O21—C21 | 1.35 (3) | C12—H12 | 0.9506 |
O22—C27 | 1.35 (3) | C13—H13 | 0.9505 |
O22—C29 | 1.44 (3) | C14—H14 | 0.9506 |
N11—C17 | 1.313 (13) | C15—H15 | 0.9495 |
N11—C18 | 1.476 (11) | C18—H18A | 0.9896 |
N21—C27 | 1.30 (3) | C18—H18B | 0.9897 |
N21—C28 | 1.47 (3) | C19—H19A | 0.9906 |
C11—C12 | 1.398 (13) | C19—H19B | 0.9903 |
C11—C16 | 1.392 (11) | C22—H22 | 0.9498 |
C12—C13 | 1.354 (15) | C23—H23 | 0.9508 |
C13—C14 | 1.370 (14) | C24—H24 | 0.9501 |
C14—C15 | 1.357 (14) | C25—H25 | 0.9494 |
C15—C16 | 1.398 (14) | C28—H28A | 0.9882 |
C16—C17 | 1.433 (11) | C28—H28B | 0.9911 |
C18—C19 | 1.505 (14) | C29—H29A | 0.9899 |
C21—C22 | 1.39 (3) | C29—H29B | 0.9907 |
Fe1···C26i | 3.41 (2) | C17···H18Aix | 2.9204 |
Fe1···C27i | 3.028 (18) | C18···H18Aix | 2.8988 |
Fe1···C17i | 3.108 (10) | C18···H12iv | 2.8674 |
Fe1···C18i | 3.222 (11) | C19···H19Avi | 2.9227 |
Fe1···C21i | 2.98 (2) | C19···H19Bvi | 2.8858 |
Fe1···C28i | 3.19 (2) | C21···H22x | 3.0734 |
Fe1···H18Ai | 3.3874 | C22···H22x | 3.0312 |
Fe1···H18Bi | 3.4529 | C23···H29Axi | 2.8845 |
Fe1···H28Aii | 3.4889 | C24···H29Bxii | 2.7784 |
Fe1···H28Aiii | 3.4889 | C25···H24vii | 2.5989 |
Fe1···H28Aiv | 3.4889 | C25···H29Axii | 2.7825 |
Fe1···H28Ai | 3.4818 | C26···H24vii | 2.9843 |
Fe1···H28Bi | 3.3131 | C26···H29Axii | 3.0814 |
O11···C18v | 3.313 (10) | C26···H23vii | 2.9192 |
O12···C19vi | 3.169 (10) | C27···H28Bi | 2.7983 |
O21···C28iv | 3.36 (3) | C27···H23vii | 2.1310 |
O22···C24vii | 3.37 (3) | C28···H22v | 2.7979 |
O22···C23vii | 2.78 (3) | C28···H28Ai | 2.9538 |
O11···H19Bviii | 2.6901 | C28···H23vii | 2.6807 |
O11···H18Av | 2.5230 | C29···H22v | 2.9790 |
O12···H19Bvi | 2.7493 | C29···H23vii | 2.3326 |
O12···H15 | 2.3980 | H12···H18Bv | 2.4753 |
O12···H19Avi | 2.7879 | H12···C18v | 2.8674 |
O21···H28Aiv | 2.5819 | H15···O12 | 2.3980 |
O22···H25 | 2.4133 | H18A···N11i | 2.5619 |
O22···H23vii | 1.9117 | H18A···C17i | 2.9204 |
N21···C23vii | 3.41 (4) | H18A···C18i | 2.8988 |
N11···H18Aix | 2.5619 | H18A···H18Ai | 2.5383 |
N21···H28Ai | 2.7335 | H18A···O11iv | 2.5230 |
N21···H23vii | 2.5732 | H18A···H18Aix | 2.5383 |
N21···H28Bi | 2.6365 | H18B···C17i | 2.8411 |
C15···C19x | 3.591 (12) | H18B···C16i | 2.8769 |
C16···C18ix | 3.567 (14) | H18B···C14x | 3.0003 |
C17···C18ix | 3.200 (14) | H18B···C15x | 3.0100 |
C18···C16i | 3.567 (14) | H18B···H12iv | 2.4753 |
C18···O11iv | 3.313 (11) | H19A···O12vi | 2.7879 |
C18···C17i | 3.200 (16) | H19A···C12x | 3.0623 |
C19···O12vi | 3.169 (10) | H19A···C13x | 3.0756 |
C19···C19vi | 3.129 (13) | H19A···C11x | 3.0573 |
C19···C15x | 3.591 (12) | H19A···H19Bvi | 2.5383 |
C21···C22x | 3.39 (3) | H19A···C19vi | 2.9227 |
C22···C21x | 3.39 (3) | H19A···C16x | 2.9770 |
C22···C22x | 3.15 (3) | H19A···C14x | 3.0439 |
C22···C28iv | 3.50 (4) | H19A···C15x | 2.9842 |
C23···C29xi | 3.20 (3) | H19B···C11ii | 2.9092 |
C23···N21xi | 3.41 (4) | H19B···O12vi | 2.7493 |
C23···C28xi | 3.53 (3) | H19B···C19vi | 2.8858 |
C23···O22xi | 2.78 (3) | H19B···H19Avi | 2.5383 |
C23···C27xi | 2.98 (4) | H19B···O11ii | 2.6901 |
C23···C26xi | 3.51 (5) | H22···C28iv | 2.7979 |
C24···C29xii | 3.40 (3) | H22···C29iv | 2.9790 |
C24···C26xi | 3.54 (5) | H22···H28Biv | 2.4120 |
C24···O22xi | 3.37 (3) | H22···C21x | 3.0734 |
C24···C25xi | 3.43 (5) | H22···C22x | 3.0312 |
C24···C27xi | 3.53 (4) | H23···O22xi | 1.9117 |
C25···C24vii | 3.43 (4) | H23···N21xi | 2.5732 |
C25···C29xii | 3.36 (3) | H23···C26xi | 2.9192 |
C26···C23vii | 3.51 (4) | H23···C27xi | 2.1310 |
C26···C24vii | 3.54 (4) | H23···C28xi | 2.6807 |
C27···C23vii | 2.98 (4) | H23···C29xi | 2.3326 |
C27···C28i | 3.38 (3) | H23···H29Axi | 2.2204 |
C27···C24vii | 3.53 (4) | H24···C25xi | 2.5989 |
C28···C22v | 3.50 (4) | H24···C26xi | 2.9843 |
C28···C27ix | 3.39 (4) | H24···H25xi | 2.4548 |
C28···O21v | 3.36 (3) | H25···O22 | 2.4133 |
C28···C28ix | 3.50 (4) | H25···H24vii | 2.4548 |
C28···C23vii | 3.53 (3) | H28A···Fe1viii | 3.4889 |
C28···C28i | 3.50 (3) | H28A···Fe1v | 3.4889 |
C29···C23vii | 3.20 (3) | H28A···O21v | 2.5819 |
C29···C25xiii | 3.36 (3) | H28A···N21ix | 2.7337 |
C29···C24xiii | 3.40 (4) | H28A···C28ix | 2.9541 |
C11···H19Ax | 3.0573 | H28A···H28Aix | 2.3817 |
C11···H19Bviii | 2.9092 | H28A···Fe1xiv | 3.4889 |
C12···H19Ax | 3.0623 | H28A···H28Ai | 2.3817 |
C13···H19Ax | 3.0756 | H28B···N21ix | 2.6360 |
C14···H19Ax | 3.0439 | H28B···C27ix | 2.7985 |
C14···H18Bx | 3.0003 | H28B···H22v | 2.4120 |
C15···H19Ax | 2.9842 | H29A···C23vii | 2.8845 |
C15···H18Bx | 3.0100 | H29A···C25xiii | 2.7825 |
C16···H19Ax | 2.9770 | H29A···C26xiii | 3.0814 |
C16···H18Bix | 2.8769 | H29A···H23vii | 2.2204 |
C17···H18Bix | 2.8411 | H29B···C24xiii | 2.7784 |
O11—Fe1—N11 | 83.7 (3) | C22—C23—C24 | 121 (2) |
O11—Fe1—O11ix | 98.8 (3) | C23—C24—C25 | 121 (3) |
O11—Fe1—N11ix | 93.4 (3) | C24—C25—C26 | 118 (2) |
O11—Fe1—O11i | 98.8 (3) | C21—C26—C25 | 120 (2) |
O11—Fe1—N11i | 167.0 (3) | C21—C26—C27 | 122 (2) |
O11ix—Fe1—N11 | 167.0 (3) | C25—C26—C27 | 118 (2) |
N11—Fe1—N11ix | 83.4 (3) | O22—C27—N21 | 114.8 (19) |
O11i—Fe1—N11 | 93.4 (3) | O22—C27—C26 | 118 (2) |
N11—Fe1—N11i | 83.4 (3) | N21—C27—C26 | 127 (2) |
O21—Fe1—N21 | 85.6 (8) | N21—C28—C29 | 103.5 (18) |
O21—Fe1—O21ix | 105.9 (9) | O22—C29—C28 | 106.0 (16) |
O21—Fe1—N21ix | 162.3 (9) | C11—C12—H12 | 119.51 |
O21—Fe1—O21i | 105.9 (9) | C13—C12—H12 | 119.66 |
O21—Fe1—N21i | 83.0 (10) | C12—C13—H13 | 119.36 |
O21ix—Fe1—N21 | 83.0 (9) | C14—C13—H13 | 119.27 |
N21—Fe1—N21ix | 82.5 (9) | C13—C14—H14 | 120.38 |
O21i—Fe1—N21 | 162.3 (9) | C15—C14—H14 | 120.34 |
N21—Fe1—N21i | 82.5 (8) | C14—C15—H15 | 119.58 |
Fe1—O11—C11 | 136.2 (5) | C16—C15—H15 | 119.53 |
C17—O12—C19 | 107.8 (7) | N11—C18—H18A | 110.83 |
Fe1—O21—C21 | 135.2 (15) | N11—C18—H18B | 110.84 |
C27—O22—C29 | 107.0 (18) | C19—C18—H18A | 110.81 |
C17—N11—C18 | 107.1 (7) | C19—C18—H18B | 110.87 |
Fe1—N11—C17 | 127.3 (5) | H18A—C18—H18B | 108.89 |
Fe1—N11—C18 | 125.5 (6) | O12—C19—H19A | 110.88 |
Fe1—N21—C27 | 124.2 (15) | O12—C19—H19B | 110.87 |
Fe1—N21—C28 | 125.5 (17) | C18—C19—H19A | 110.85 |
C27—N21—C28 | 108.4 (19) | C18—C19—H19B | 110.87 |
O11—C11—C12 | 119.5 (8) | H19A—C19—H19B | 108.93 |
O11—C11—C16 | 122.6 (8) | C21—C22—H22 | 119.88 |
C12—C11—C16 | 117.9 (9) | C23—C22—H22 | 119.98 |
C11—C12—C13 | 120.8 (9) | C22—C23—H23 | 119.54 |
C12—C13—C14 | 121.4 (9) | C24—C23—H23 | 119.65 |
C13—C14—C15 | 119.3 (10) | C23—C24—H24 | 119.25 |
C14—C15—C16 | 120.9 (8) | C25—C24—H24 | 119.36 |
C11—C16—C15 | 119.7 (8) | C24—C25—H25 | 120.66 |
C15—C16—C17 | 118.9 (7) | C26—C25—H25 | 120.91 |
C11—C16—C17 | 121.5 (8) | N21—C28—H28A | 111.08 |
O12—C17—N11 | 115.5 (7) | N21—C28—H28B | 110.86 |
N11—C17—C16 | 126.7 (7) | C29—C28—H28A | 111.26 |
O12—C17—C16 | 117.8 (8) | C29—C28—H28B | 111.00 |
N11—C18—C19 | 104.6 (8) | H28A—C28—H28B | 109.05 |
O12—C19—C18 | 104.4 (6) | O22—C29—H29A | 110.61 |
O21—C21—C22 | 119 (2) | O22—C29—H29B | 110.42 |
O21—C21—C26 | 122 (2) | C28—C29—H29A | 110.65 |
C22—C21—C26 | 119 (2) | C28—C29—H29B | 110.48 |
C21—C22—C23 | 120 (2) | H29A—C29—H29B | 108.65 |
N11—Fe1—O11—C11 | 16.1 (8) | C17—N11—C18—C19 | −6.5 (8) |
O11ix—Fe1—O11—C11 | −150.9 (8) | Fe1—N11—C17—O12 | −179.4 (5) |
N11ix—Fe1—O11—C11 | −66.8 (8) | Fe1—N11—C17—C16 | −0.5 (11) |
O11i—Fe1—O11—C11 | 108.7 (8) | O11—C11—C12—C13 | −179.0 (8) |
O11—Fe1—N11—C17 | −8.4 (7) | O11—C11—C16—C15 | 179.4 (8) |
O11—Fe1—N11—C18 | 169.4 (6) | O11—C11—C16—C17 | −2.2 (12) |
N11ix—Fe1—N11—C17 | 85.9 (7) | C16—C11—C12—C13 | 3.7 (13) |
N11ix—Fe1—N11—C18 | −96.4 (6) | C12—C11—C16—C17 | 175.1 (8) |
O11i—Fe1—N11—C17 | −106.8 (7) | C12—C11—C16—C15 | −3.3 (12) |
O11i—Fe1—N11—C18 | 70.9 (6) | C11—C12—C13—C14 | −2.2 (14) |
N11i—Fe1—N11—C17 | 169.9 (7) | C12—C13—C14—C15 | 0.3 (14) |
N11i—Fe1—N11—C18 | −12.3 (6) | C13—C14—C15—C16 | 0.0 (14) |
Fe1—O11—C11—C12 | 169.0 (6) | C14—C15—C16—C11 | 1.6 (13) |
Fe1—O11—C11—C16 | −13.8 (13) | C14—C15—C16—C17 | −176.9 (8) |
C19—O12—C17—N11 | 2.9 (9) | C11—C16—C17—O12 | −172.7 (7) |
C19—O12—C17—C16 | −176.1 (6) | C15—C16—C17—N11 | −173.2 (8) |
C17—O12—C19—C18 | −6.7 (8) | C11—C16—C17—N11 | 8.4 (12) |
C18—N11—C17—O12 | 2.5 (9) | C15—C16—C17—O12 | 5.7 (11) |
C18—N11—C17—C16 | −178.6 (7) | N11—C18—C19—O12 | 7.9 (8) |
Fe1—N11—C18—C19 | 175.4 (5) |
Symmetry codes: (i) −x+y+1, −x+1, z; (ii) x, y, z−1; (iii) −y+1, x−y, z−1; (iv) −x+y+1, −x+1, z−1; (v) −y+1, x−y, z+1; (vi) −x+1, −y+1, −z; (vii) y, −x+y, −z+1; (viii) x, y, z+1; (ix) −y+1, x−y, z; (x) −x+1, −y+1, −z+1; (xi) x−y, x, −z+1; (xii) x−y, x, −z+2; (xiii) y, −x+y, −z+2; (xiv) −x+y+1, −x+1, z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
C15—H15···O12 | 0.95 | 2.40 | 2.736 (11) | 101 |
C18—H18A···O11iv | 0.99 | 2.52 | 3.313 (11) | 137 |
C18—H18A···N11i | 0.99 | 2.56 | 2.914 (14) | 101 |
C28—H28A···O21v | 0.99 | 2.58 | 3.36 (3) | 136 |
Symmetry codes: (i) −x+y+1, −x+1, z; (iv) −x+y+1, −x+1, z−1; (v) −y+1, x−y, z+1. |
Experimental details
Crystal data | |
Chemical formula | [Fe(C9H8NO2)3] |
Mr | 542.34 |
Crystal system, space group | Trigonal, P3 |
Temperature (K) | 150 |
a, c (Å) | 14.882 (2), 6.4052 (11) |
V (Å3) | 1228.5 (3) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.66 |
Crystal size (mm) | 0.30 × 0.15 × 0.05 |
Data collection | |
Diffractometer | Enraf-Nonius CAD-4 Turbo diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 1686, 1448, 970 |
Rint | 0.057 |
(sin θ/λ)max (Å−1) | 0.594 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.074, 0.168, 1.19 |
No. of reflections | 1448 |
No. of parameters | 161 |
No. of restraints | 31 |
H-atom treatment | H-atom parameters not refined |
Δρmax, Δρmin (e Å−3) | 0.51, −0.53 |
Computer programs: locally modified CAD-4 Software (Enraf-Nonius, 1989), SET4 (de Boer & Duisenberg, 1984), HELENA (Spek, 1997), SHELXS86 (Sheldrick, 1985), SHELXL97 (Sheldrick, 1997), PLATON (Spek, 2002), PLATON.
Fe1—O11 | 1.940 (7) | O22—C27 | 1.35 (3) |
Fe1—N11 | 2.132 (7) | O22—C29 | 1.44 (3) |
Fe1—O21 | 1.870 (19) | N11—C17 | 1.313 (13) |
Fe1—N21 | 2.10 (2) | N11—C18 | 1.476 (11) |
O11—C11 | 1.338 (12) | N21—C27 | 1.30 (3) |
O12—C17 | 1.343 (10) | N21—C28 | 1.47 (3) |
O12—C19 | 1.448 (11) | C18—C19 | 1.505 (14) |
O21—C21 | 1.35 (3) | C28—C29 | 1.49 (3) |
O11—Fe1—N11 | 83.7 (3) | O21—Fe1—N21 | 85.6 (8) |
O11—Fe1—O11i | 98.8 (3) | O21—Fe1—O21i | 105.9 (9) |
O11—Fe1—N11i | 93.4 (3) | O21—Fe1—N21i | 162.3 (9) |
O11—Fe1—N11ii | 167.0 (3) | O21—Fe1—N21ii | 83.0 (10) |
N11—Fe1—N11i | 83.4 (3) | N21—Fe1—N21i | 82.5 (9) |
Symmetry codes: (i) −y+1, x−y, z; (ii) −x+y+1, −x+1, z. |
D—H···A | D—H | H···A | D···A | D—H···A |
C18—H18A···O11iii | 0.99 | 2.52 | 3.313 (11) | 137 |
C28—H28A···O21iv | 0.99 | 2.58 | 3.36 (3) | 136 |
Symmetry codes: (iii) −x+y+1, −x+1, z−1; (iv) −y+1, x−y, z+1. |
The title compound, (I), was prepared in the course of our investigation aimed at producing new epoxidation catalysts (Hoogenraad et al., 2002). The crystal structure, abbreviated as [Fe(phox)3], shows the FeIII ion located on a crystallographic threefold rotation axis. The distribution of the FeIII ions over the unit cell follows space group P3m1, which is a supergroup of P3, the actual space group of (I). The higher symmetry only holds for the iron substructure.
The phox ligand is found to be disordered over two orientations, hereafter indicated by A [occupancy factor refined to 0.758 (5)] and B [occupancy factor 0.242 (5)]. Orientations A and B are related by a non-crystallographic twofold rotation axis perpendicular to the crystallographic threefold rotation axis. In Fig. 1, a displacement ellipsoid plot of the major component is given. Fig. 2 shows both orientations of the ligand in ball-and-stick model.
The crystal packing can accommodate both orientations of the ligand in the ratio found during refinement. Only when the contact ligands of two neighbouring complexes are in the minor disorder component orientations (B), interatomic distances that are shorter than the Van der Waals radii are found.
Exact analysis of the configuration of the coordinating phox ligands to the central cation is very difficult due to the presence of disorder in the crystal structure. We expected Fe(phox)3 to assume the meridional configuration, as all other previous reported FeIIIN3O3 species [Cambridge Structural Database (CSD), February 2002 update; Allen & Kennard, 1993; the only exception to found is the mixed valence FeII/FeIII complex reported by Mashuta et al., 1992) and as the related manganese(III) complex Mn(phox)3 (Hoogenraad et al., 1998). A complex in the meridional configuration would have its three phox ligands in an AAB orientation. The threefold crystallographic symmetry would generate the permutations ABA and BAA, resulting in an occupancy of 2/3 for the major component. However, the Fe(phox)3 complex as a whole can also be rotated by the local twofold axis that causes the disorder, resulting in the BBA orientation of the ligands (and permutations thereof). The observed occupation factor of component A could therefore lie between the values 2/3 and 1/3, depending on the amount of disorder of the complete molecule over the local twofold rotation axis.
The observed value of 0.758 (5) for the occupancy of A clearly lies outside of the expected range. If this is not an artifact caused by effects unaccounted for in the present model [FOOTNOTE: There is no indication of twinning over one of the symmetry elements of the supergroup of the iron substructure, as is illustrated by the averaging index Rint, which amounts to 0.359 for P3m1 as opposed to 0.057 for P3. Systematic deviations of Fcalc from Fobs, another indicator of twinning, were not found.], the high value found for the occupancy of the major component would suggest that at least a fraction of 0.25 of the molecules has its three ligands in the AAA (or BBB) configuration. AAA represents a structure with facial configuration of the ligands. The disorder model can also be interpreted as consisting of 75.8% AAA configuration and 24.2% BBB configuration, i.e. 100% facial configuration distributed over two orientations which are related by the disorder operation. It should be noted that according to the CSD, the facial configuration only occurs if the ligands are forced by covalent or coordinating bonds to adopt this orientation. Since the facial configuration has not been corroborated with other techniques, further study is necessary to unequivocally assign this configuration to a part of the complex molecules present in the crystal.
The Cremer & Pople (1975) total puckering amplitude amounts to 0.077 (9) Å for the oxazolinyl ring and to 0.020 (10) Å for the phenyl ring of the major disorder component, indicating that the former ring deviates slightly more from planarity than the latter. For the minor disorder component, the puckering parameters are 0.05 (2) and 0.03 (3) for the oxazolinyl and phenyl rings, respectively, showing a less pronounced difference. The acute angle between the least-squares planes through the oxazolinyl and phenyl rings amounts to 6.1 (4) and 3.0 (12)° for the major and the minor disorder components, respectively. The six-membered chelate rings deviate significantly from planarity, as is indicated by a total puckering amplitude of 0.167 (6) Å for the major disorder component and 0.263 (18) Å for the minor disorder component.
The crystal structure displays a close C—H···O contact for each disorder component. Geometry details are given in Table 2. These interactions link the molecules into infinite chains parallel to c. An illustration is given in Fig. 3.
In the IR spectrum of [Fe(phox)3] the effect of complexation on the C═N bond is demonstrated by the shift from 1644 cm-1 in the free ligand to 1617 cm-1 in the complex. The UV–vis–NIR spectrum of the solid compound shows a broad absorption in the range between 700 and 230 nm. The UV–vis–NIR spectrum of [Fe(phox)3] in a methanol solution shows an absorption band at 461 nm, which can be assigned to the phenolate to FeIII ligand to metal charge transfer (LMCT) band. Bands observed at 307 and 222 nm, which are also present in the free ligand, can be assigned to π → π* transitions of the ligand. The magnetic moment of [Fe(phox)3] (5.70 µB) is close to the spin-only value of 5.92µB expected for an S = 5/2 system of an octahedral high-spin FeIII ion. During variable temperature measurements, the compound shows a strict Curie–Weiss behaviour, indicating an isolated paramagnetic ion as the plot of 1/χ against T can be extrapolated to zero.