Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270104028148/av1198sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270104028148/av1198Isup2.hkl |
CCDC reference: 243531
To a solution of the BPHPA ligand [prepared as described by He et al. (2000)] (0.006 g, 0.187 mol) in methanol (2 ml) was added a solution of Fe(ClO4)3·9H2O (0.097 g, 0.187 mmol) in methanol (2 mm l). The solution was stirred for 20 min and diethyl ether was added dropwise until a solid precipitated completely, then the precipitate was collected by filtration and dried in vacuo. Yield 0.063 g (58%). The complex was redissolved in CH3CN and left to stand at room temperature for a week, yielding red crystals. ESI-MS: m/z [((BPHPAFe)2O) + ClO4-2H]+ 865, [(BPHPAFe)2O]-2H]2+ 383; IR (KBr cm−1): 3434 (m), 3079 (w), 2927 (w), 1606 (s), 1581 (w), 1484 (m), 1444 (s), 1349 (w), 1311 (w), 1288 (w), 1089 (s) (ClO4), 1025 (s), 902 (w), 881 (w), 833 (s) (Fe—O—Fe), 765 (s), 734 (w), 649 (w), 622 (s) (ClO4), 532 (w) UV λmax nm (εmax M−1 cm−1): 252 (2.8 x 104), 323 (1.0 x 104), 358 (8.5 x 103), 487 (613), 658 (178).
H atoms bonded to C atoms were placed at calculated positions, with C—H distances of 0.93 and 0.97 Å, and treated as riding atoms. The H atom of the hydroxy group was located from difference maps and refined isotropically, with an O—H distance restraint of 0.85 (s.u.?) Å.
Data collection: SMART (Siemens,1996); cell refinement: SMART and SAINT (Siemens,1994); data reduction: SAINT? and XPREP in SHELXTL (Siemens, 1994); program(s) used to solve structure: SHELXTL; program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
[Fe2O(C19H20N4O)2](ClO4)4 | F(000) = 2384 |
Mr = 1166.28 | Dx = 1.697 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2yc | Cell parameters from 3348 reflections |
a = 24.0733 (9) Å | θ = 1.8–25.1° |
b = 9.9223 (3) Å | µ = 0.96 mm−1 |
c = 20.5055 (8) Å | T = 293 K |
β = 111.220 (2)° | Block, red |
V = 4565.9 (3) Å3 | 0.34 × 0.28 × 0.16 mm |
Z = 4 |
Siemens SMART CCD area-detector diffractometer | 4002 independent reflections |
Radiation source: fine-focus sealed tube | 3000 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.045 |
ϕ and ω scans | θmax = 25.1°, θmin = 1.8° |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | h = −28→25 |
Tmin = 0.713, Tmax = 0.856 | k = −11→11 |
7191 measured reflections | l = −12→24 |
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)] = 0.075 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.191 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.09 | w = 1/[σ2(Fo2) + (0.0536P)2 + 58.9568P] where P = (Fo2 + 2Fc2)/3 |
4002 reflections | (Δ/σ)max < 0.001 |
326 parameters | Δρmax = 0.66 e Å−3 |
1 restraint | Δρmin = −0.48 e Å−3 |
[Fe2O(C19H20N4O)2](ClO4)4 | V = 4565.9 (3) Å3 |
Mr = 1166.28 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 24.0733 (9) Å | µ = 0.96 mm−1 |
b = 9.9223 (3) Å | T = 293 K |
c = 20.5055 (8) Å | 0.34 × 0.28 × 0.16 mm |
β = 111.220 (2)° |
Siemens SMART CCD area-detector diffractometer | 4002 independent reflections |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | 3000 reflections with I > 2σ(I) |
Tmin = 0.713, Tmax = 0.856 | Rint = 0.045 |
7191 measured reflections |
R[F2 > 2σ(F2)] = 0.075 | 1 restraint |
wR(F2) = 0.191 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.09 | w = 1/[σ2(Fo2) + (0.0536P)2 + 58.9568P] where P = (Fo2 + 2Fc2)/3 |
4002 reflections | Δρmax = 0.66 e Å−3 |
326 parameters | Δρmin = −0.48 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 | ||
Fe1 | 0.29296 (4) | 0.79664 (9) | 0.08823 (5) | 0.0304 (3) | |
O1 | 0.3169 (2) | 0.6180 (5) | 0.1415 (3) | 0.0451 (12) | |
O2 | 0.2500 | 0.7500 | 0.0000 | 0.0445 (17) | |
O3 | 0.4608 (4) | 0.3527 (12) | 0.0495 (4) | 0.144 (4) | |
O4 | 0.4874 (4) | 0.4481 (9) | 0.1561 (5) | 0.119 (3) | |
O5 | 0.4691 (4) | 0.2171 (8) | 0.1403 (5) | 0.130 (3) | |
O6 | 0.3914 (3) | 0.3699 (7) | 0.1005 (5) | 0.102 (3) | |
O7 | 0.1601 (3) | 0.3947 (9) | 0.1270 (4) | 0.108 (3) | |
O8 | 0.2578 (3) | 0.3888 (5) | 0.1329 (3) | 0.0619 (15) | |
O9 | 0.2360 (3) | 0.4851 (6) | 0.2249 (3) | 0.0765 (19) | |
O10 | 0.2281 (3) | 0.2526 (6) | 0.2063 (3) | 0.0686 (17) | |
N1 | 0.2182 (2) | 0.8654 (6) | 0.1099 (3) | 0.0360 (13) | |
N2 | 0.2995 (2) | 1.0166 (5) | 0.0817 (3) | 0.0330 (12) | |
N3 | 0.3697 (2) | 0.8181 (6) | 0.0602 (3) | 0.0377 (13) | |
N4 | 0.3547 (2) | 0.8471 (6) | 0.1896 (3) | 0.0366 (13) | |
C1 | 0.1858 (3) | 0.7920 (8) | 0.1383 (4) | 0.0444 (17) | |
H1 | 0.1989 | 0.7062 | 0.1551 | 0.053* | |
C2 | 0.1338 (3) | 0.8394 (9) | 0.1435 (4) | 0.057 (2) | |
H2 | 0.1122 | 0.7870 | 0.1636 | 0.068* | |
C3 | 0.1144 (3) | 0.9659 (10) | 0.1180 (4) | 0.062 (2) | |
H3 | 0.0789 | 0.9989 | 0.1199 | 0.074* | |
C4 | 0.1473 (3) | 1.0440 (8) | 0.0899 (4) | 0.051 (2) | |
H4 | 0.1350 | 1.1307 | 0.0739 | 0.062* | |
C5 | 0.1996 (3) | 0.9903 (7) | 0.0859 (3) | 0.0402 (16) | |
C6 | 0.2364 (3) | 1.0635 (7) | 0.0511 (4) | 0.0420 (16) | |
H6A | 0.2206 | 1.0458 | 0.0012 | 0.050* | |
H6B | 0.2346 | 1.1598 | 0.0581 | 0.050* | |
C7 | 0.3320 (3) | 1.0455 (7) | 0.0336 (4) | 0.0440 (17) | |
H7A | 0.3528 | 1.1308 | 0.0467 | 0.053* | |
H7B | 0.3034 | 1.0544 | −0.0137 | 0.053* | |
C8 | 0.3762 (3) | 0.9382 (7) | 0.0349 (3) | 0.0394 (16) | |
C9 | 0.4190 (3) | 0.9582 (8) | 0.0047 (4) | 0.0502 (19) | |
H9 | 0.4233 | 1.0419 | −0.0133 | 0.060* | |
C10 | 0.4547 (3) | 0.8514 (9) | 0.0020 (5) | 0.060 (2) | |
H10 | 0.4831 | 0.8620 | −0.0186 | 0.072* | |
C11 | 0.4482 (3) | 0.7299 (8) | 0.0297 (4) | 0.0490 (19) | |
H11 | 0.4727 | 0.6579 | 0.0289 | 0.059* | |
C12 | 0.4057 (3) | 0.7147 (7) | 0.0586 (4) | 0.0428 (16) | |
H12 | 0.4014 | 0.6319 | 0.0775 | 0.051* | |
C13 | 0.3296 (3) | 1.0761 (7) | 0.1530 (3) | 0.0401 (16) | |
H13A | 0.3514 | 1.1562 | 0.1494 | 0.048* | |
H13B | 0.2997 | 1.1027 | 0.1720 | 0.048* | |
C14 | 0.3716 (3) | 0.9777 (7) | 0.2016 (3) | 0.0344 (14) | |
C15 | 0.4222 (3) | 1.0126 (8) | 0.2575 (4) | 0.0476 (18) | |
H15 | 0.4340 | 1.1022 | 0.2659 | 0.057* | |
C16 | 0.4549 (4) | 0.9118 (9) | 0.3004 (4) | 0.059 (2) | |
H16 | 0.4889 | 0.9337 | 0.3384 | 0.071* | |
C17 | 0.4379 (3) | 0.7788 (8) | 0.2880 (4) | 0.052 (2) | |
H17 | 0.4600 | 0.7106 | 0.3170 | 0.063* | |
C18 | 0.3866 (3) | 0.7498 (7) | 0.2306 (3) | 0.0399 (16) | |
C19 | 0.3628 (3) | 0.6109 (7) | 0.2110 (4) | 0.0505 (19) | |
H19A | 0.3945 | 0.5506 | 0.2108 | 0.061* | |
H19B | 0.3461 | 0.5771 | 0.2444 | 0.061* | |
Cl1 | 0.45259 (9) | 0.3448 (2) | 0.11403 (12) | 0.0582 (5) | |
Cl2 | 0.21960 (9) | 0.38082 (18) | 0.17381 (10) | 0.0492 (5) | |
H20 | 0.297 (3) | 0.546 (5) | 0.133 (4) | 0.07 (3)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Fe1 | 0.0316 (5) | 0.0293 (5) | 0.0298 (5) | −0.0013 (4) | 0.0104 (4) | −0.0016 (4) |
O1 | 0.051 (3) | 0.035 (3) | 0.047 (3) | −0.005 (2) | 0.015 (2) | 0.003 (2) |
O2 | 0.034 (4) | 0.058 (4) | 0.037 (4) | −0.005 (3) | 0.008 (3) | −0.011 (3) |
O3 | 0.122 (7) | 0.235 (12) | 0.093 (6) | 0.048 (7) | 0.062 (6) | 0.026 (7) |
O4 | 0.092 (5) | 0.110 (6) | 0.157 (8) | −0.039 (5) | 0.047 (5) | −0.045 (6) |
O5 | 0.112 (7) | 0.067 (5) | 0.179 (9) | 0.026 (5) | 0.015 (6) | 0.040 (5) |
O6 | 0.063 (4) | 0.077 (5) | 0.185 (8) | −0.003 (4) | 0.069 (5) | −0.010 (5) |
O7 | 0.064 (4) | 0.144 (7) | 0.094 (5) | 0.021 (5) | 0.002 (4) | 0.024 (5) |
O8 | 0.087 (4) | 0.051 (3) | 0.064 (3) | −0.016 (3) | 0.046 (3) | −0.008 (3) |
O9 | 0.121 (6) | 0.045 (3) | 0.080 (4) | −0.010 (3) | 0.056 (4) | −0.015 (3) |
O10 | 0.101 (5) | 0.044 (3) | 0.069 (4) | 0.000 (3) | 0.040 (4) | 0.012 (3) |
N1 | 0.033 (3) | 0.044 (3) | 0.031 (3) | −0.004 (2) | 0.011 (2) | −0.010 (2) |
N2 | 0.033 (3) | 0.030 (3) | 0.036 (3) | 0.003 (2) | 0.012 (2) | 0.003 (2) |
N3 | 0.037 (3) | 0.043 (3) | 0.035 (3) | −0.004 (3) | 0.015 (2) | −0.001 (2) |
N4 | 0.034 (3) | 0.043 (3) | 0.031 (3) | −0.001 (2) | 0.011 (2) | 0.001 (2) |
C1 | 0.043 (4) | 0.051 (4) | 0.043 (4) | −0.001 (3) | 0.019 (3) | −0.004 (3) |
C2 | 0.045 (4) | 0.074 (6) | 0.057 (5) | −0.006 (4) | 0.025 (4) | −0.004 (4) |
C3 | 0.036 (4) | 0.081 (7) | 0.071 (6) | −0.006 (4) | 0.021 (4) | −0.025 (5) |
C4 | 0.032 (4) | 0.049 (4) | 0.064 (5) | 0.009 (3) | 0.006 (4) | −0.015 (4) |
C5 | 0.036 (4) | 0.045 (4) | 0.032 (3) | 0.003 (3) | 0.002 (3) | −0.007 (3) |
C6 | 0.038 (4) | 0.037 (4) | 0.043 (4) | 0.006 (3) | 0.005 (3) | 0.001 (3) |
C7 | 0.059 (4) | 0.030 (4) | 0.046 (4) | −0.005 (3) | 0.022 (4) | 0.006 (3) |
C8 | 0.031 (3) | 0.040 (4) | 0.042 (4) | −0.007 (3) | 0.007 (3) | 0.001 (3) |
C9 | 0.040 (4) | 0.053 (5) | 0.059 (5) | −0.013 (4) | 0.020 (4) | 0.008 (4) |
C10 | 0.045 (4) | 0.073 (6) | 0.071 (6) | −0.011 (4) | 0.033 (4) | −0.005 (5) |
C11 | 0.038 (4) | 0.057 (5) | 0.057 (5) | 0.000 (3) | 0.022 (4) | −0.013 (4) |
C12 | 0.039 (4) | 0.043 (4) | 0.043 (4) | 0.002 (3) | 0.010 (3) | −0.006 (3) |
C13 | 0.042 (4) | 0.036 (4) | 0.037 (4) | −0.005 (3) | 0.009 (3) | −0.007 (3) |
C14 | 0.037 (4) | 0.037 (4) | 0.030 (3) | −0.005 (3) | 0.011 (3) | −0.005 (3) |
C15 | 0.043 (4) | 0.055 (5) | 0.038 (4) | −0.009 (3) | 0.007 (3) | −0.006 (3) |
C16 | 0.051 (5) | 0.075 (6) | 0.040 (4) | −0.018 (4) | 0.003 (4) | 0.000 (4) |
C17 | 0.039 (4) | 0.063 (5) | 0.045 (4) | 0.010 (4) | 0.004 (3) | 0.012 (4) |
C18 | 0.041 (4) | 0.041 (4) | 0.039 (4) | 0.000 (3) | 0.017 (3) | 0.001 (3) |
C19 | 0.061 (5) | 0.046 (4) | 0.046 (4) | 0.013 (4) | 0.020 (4) | 0.012 (3) |
Cl1 | 0.0503 (11) | 0.0496 (11) | 0.0760 (14) | 0.0032 (9) | 0.0245 (10) | 0.0023 (10) |
Cl2 | 0.0592 (11) | 0.0429 (10) | 0.0476 (10) | −0.0020 (8) | 0.0218 (9) | 0.0027 (8) |
Fe1—O2 | 1.7896 (9) | C3—H3 | 0.9300 |
Fe1—O1 | 2.052 (5) | C4—C5 | 1.396 (9) |
Fe1—N1 | 2.117 (5) | C4—H4 | 0.9300 |
Fe1—N4 | 2.132 (5) | C5—C6 | 1.510 (10) |
Fe1—N3 | 2.134 (5) | C6—H6A | 0.9700 |
Fe1—N2 | 2.196 (5) | C6—H6B | 0.9700 |
O1—C19 | 1.455 (9) | C7—C8 | 1.498 (9) |
O1—H20 | 0.84 (6) | C7—H7A | 0.9700 |
O2—Fe1i | 1.7896 (9) | C7—H7B | 0.9700 |
O3—Cl1 | 1.409 (8) | C8—C9 | 1.395 (9) |
O4—Cl1 | 1.404 (8) | C9—C10 | 1.378 (11) |
O5—Cl1 | 1.378 (7) | C9—H9 | 0.9300 |
O6—Cl1 | 1.418 (6) | C10—C11 | 1.365 (11) |
O7—Cl2 | 1.413 (7) | C10—H10 | 0.9300 |
O8—Cl2 | 1.454 (5) | C11—C12 | 1.363 (10) |
O9—Cl2 | 1.423 (6) | C11—H11 | 0.9300 |
O10—Cl2 | 1.415 (6) | C12—H12 | 0.9300 |
N1—C1 | 1.346 (9) | C13—C14 | 1.496 (9) |
N1—C5 | 1.349 (9) | C13—H13A | 0.9700 |
N2—C7 | 1.492 (8) | C13—H13B | 0.9700 |
N2—C6 | 1.492 (8) | C14—C15 | 1.379 (9) |
N2—C13 | 1.499 (8) | C15—C16 | 1.376 (11) |
N3—C8 | 1.332 (8) | C15—H15 | 0.9300 |
N3—C12 | 1.351 (8) | C16—C17 | 1.377 (11) |
N4—C18 | 1.328 (8) | C16—H16 | 0.9300 |
N4—C14 | 1.354 (8) | C17—C18 | 1.393 (10) |
C1—C2 | 1.376 (10) | C17—H17 | 0.9300 |
C1—H1 | 0.9300 | C18—C19 | 1.491 (10) |
C2—C3 | 1.374 (12) | C19—H19A | 0.9700 |
C2—H2 | 0.9300 | C19—H19B | 0.9700 |
C3—C4 | 1.374 (11) | ||
O2—Fe1—O1 | 105.26 (15) | N2—C7—H7B | 109.0 |
O2—Fe1—N1 | 94.12 (14) | C8—C7—H7B | 109.0 |
O1—Fe1—N1 | 105.2 (2) | H7A—C7—H7B | 107.8 |
O2—Fe1—N4 | 172.06 (15) | N3—C8—C9 | 120.7 (7) |
O1—Fe1—N4 | 73.8 (2) | N3—C8—C7 | 117.4 (6) |
N1—Fe1—N4 | 93.7 (2) | C9—C8—C7 | 121.6 (6) |
O2—Fe1—N3 | 89.61 (14) | C10—C9—C8 | 118.6 (7) |
O1—Fe1—N3 | 97.2 (2) | C10—C9—H9 | 120.7 |
N1—Fe1—N3 | 155.3 (2) | C8—C9—H9 | 120.7 |
N4—Fe1—N3 | 82.7 (2) | C11—C10—C9 | 119.7 (7) |
O2—Fe1—N2 | 102.90 (14) | C11—C10—H10 | 120.1 |
O1—Fe1—N2 | 151.4 (2) | C9—C10—H10 | 120.1 |
N1—Fe1—N2 | 77.1 (2) | C12—C11—C10 | 119.7 (7) |
N4—Fe1—N2 | 77.6 (2) | C12—C11—H11 | 120.2 |
N3—Fe1—N2 | 78.3 (2) | C10—C11—H11 | 120.2 |
C19—O1—Fe1 | 122.1 (4) | N3—C12—C11 | 121.1 (7) |
C19—O1—H20 | 109 (6) | N3—C12—H12 | 119.5 |
Fe1—O1—H20 | 127 (6) | C11—C12—H12 | 119.5 |
Fe1—O2—Fe1i | 180.00 (5) | C14—C13—N2 | 111.4 (5) |
C1—N1—C5 | 119.1 (6) | C14—C13—H13A | 109.3 |
C1—N1—Fe1 | 126.0 (5) | N2—C13—H13A | 109.3 |
C5—N1—Fe1 | 114.5 (4) | C14—C13—H13B | 109.3 |
C7—N2—C6 | 111.1 (5) | N2—C13—H13B | 109.3 |
C7—N2—C13 | 112.6 (5) | H13A—C13—H13B | 108.0 |
C6—N2—C13 | 110.3 (5) | N4—C14—C15 | 120.5 (6) |
C7—N2—Fe1 | 107.3 (4) | N4—C14—C13 | 114.6 (5) |
C6—N2—Fe1 | 104.5 (4) | C15—C14—C13 | 124.8 (6) |
C13—N2—Fe1 | 110.6 (4) | C16—C15—C14 | 118.5 (7) |
C8—N3—C12 | 120.2 (6) | C16—C15—H15 | 120.8 |
C8—N3—Fe1 | 115.5 (4) | C14—C15—H15 | 120.8 |
C12—N3—Fe1 | 123.8 (5) | C15—C16—C17 | 121.1 (7) |
C18—N4—C14 | 120.9 (6) | C15—C16—H16 | 119.5 |
C18—N4—Fe1 | 119.1 (5) | C17—C16—H16 | 119.5 |
C14—N4—Fe1 | 117.4 (4) | C16—C17—C18 | 117.8 (7) |
N1—C1—C2 | 122.4 (7) | C16—C17—H17 | 121.1 |
N1—C1—H1 | 118.8 | C18—C17—H17 | 121.1 |
C2—C1—H1 | 118.8 | N4—C18—C17 | 121.2 (7) |
C3—C2—C1 | 118.4 (8) | N4—C18—C19 | 115.1 (6) |
C3—C2—H2 | 120.8 | C17—C18—C19 | 123.7 (7) |
C1—C2—H2 | 120.8 | O1—C19—C18 | 107.5 (6) |
C4—C3—C2 | 120.5 (7) | O1—C19—H19A | 110.2 |
C4—C3—H3 | 119.8 | C18—C19—H19A | 110.2 |
C2—C3—H3 | 119.8 | O1—C19—H19B | 110.2 |
C3—C4—C5 | 118.6 (7) | C18—C19—H19B | 110.2 |
C3—C4—H4 | 120.7 | H19A—C19—H19B | 108.5 |
C5—C4—H4 | 120.7 | O5—Cl1—O4 | 114.0 (6) |
N1—C5—C4 | 121.1 (7) | O5—Cl1—O3 | 107.5 (7) |
N1—C5—C6 | 116.1 (6) | O4—Cl1—O3 | 106.3 (6) |
C4—C5—C6 | 122.7 (7) | O5—Cl1—O6 | 111.7 (5) |
N2—C6—C5 | 109.5 (5) | O4—Cl1—O6 | 109.8 (5) |
N2—C6—H6A | 109.8 | O3—Cl1—O6 | 107.2 (5) |
C5—C6—H6A | 109.8 | O7—Cl2—O10 | 110.2 (5) |
N2—C6—H6B | 109.8 | O7—Cl2—O9 | 111.9 (5) |
C5—C6—H6B | 109.8 | O10—Cl2—O9 | 110.7 (4) |
H6A—C6—H6B | 108.2 | O7—Cl2—O8 | 107.5 (4) |
N2—C7—C8 | 113.0 (5) | O10—Cl2—O8 | 107.9 (4) |
N2—C7—H7A | 109.0 | O9—Cl2—O8 | 108.7 (4) |
C8—C7—H7A | 109.0 |
Symmetry code: (i) −x+1/2, −y+3/2, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H20···O8 | 0.84 (6) | 1.82 (3) | 2.654 (7) | 169 (8) |
Experimental details
Crystal data | |
Chemical formula | [Fe2O(C19H20N4O)2](ClO4)4 |
Mr | 1166.28 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 293 |
a, b, c (Å) | 24.0733 (9), 9.9223 (3), 20.5055 (8) |
β (°) | 111.220 (2) |
V (Å3) | 4565.9 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.96 |
Crystal size (mm) | 0.34 × 0.28 × 0.16 |
Data collection | |
Diffractometer | Siemens SMART CCD area-detector diffractometer |
Absorption correction | Empirical (using intensity measurements) (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.713, 0.856 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7191, 4002, 3000 |
Rint | 0.045 |
(sin θ/λ)max (Å−1) | 0.597 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.075, 0.191, 1.09 |
No. of reflections | 4002 |
No. of parameters | 326 |
No. of restraints | 1 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
w = 1/[σ2(Fo2) + (0.0536P)2 + 58.9568P] where P = (Fo2 + 2Fc2)/3 | |
Δρmax, Δρmin (e Å−3) | 0.66, −0.48 |
Computer programs: SMART (Siemens,1996), SMART and SAINT (Siemens,1994), SAINT? and XPREP in SHELXTL (Siemens, 1994), SHELXTL.
Fe1—O2 | 1.7896 (9) | Fe1—N4 | 2.132 (5) |
Fe1—O1 | 2.052 (5) | Fe1—N3 | 2.134 (5) |
Fe1—N1 | 2.117 (5) | Fe1—N2 | 2.196 (5) |
O2—Fe1—O1 | 105.26 (15) | N1—Fe1—N3 | 155.3 (2) |
O2—Fe1—N1 | 94.12 (14) | N4—Fe1—N3 | 82.7 (2) |
O1—Fe1—N1 | 105.2 (2) | O2—Fe1—N2 | 102.90 (14) |
O2—Fe1—N4 | 172.06 (15) | O1—Fe1—N2 | 151.4 (2) |
O1—Fe1—N4 | 73.8 (2) | N1—Fe1—N2 | 77.1 (2) |
N1—Fe1—N4 | 93.7 (2) | N4—Fe1—N2 | 77.6 (2) |
O2—Fe1—N3 | 89.61 (14) | N3—Fe1—N2 | 78.3 (2) |
O1—Fe1—N3 | 97.2 (2) | Fe1—O2—Fe1i | 180.00 (5) |
Symmetry code: (i) −x+1/2, −y+3/2, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H20···O8 | 0.84 (6) | 1.82 (3) | 2.654 (7) | 169 (8) |
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TPA [tris(2-pyridylmethyl)amine] is a versatile tetradentate ligand, which forms stable complexes with a large number of transition metal ions (Gultneh et al., 2003; Jitsukawa et al., 2001; Mandon et al., 2002; Zhang et al., 2003); in particular, (µ-oxo)diiron(III)TPA complexes are well established by mimicing the structure of non-heme diiron proteins, such as monooxygenase (Feig et al., 1994). Besides the µ-oxo atom, these complexes often have one or two additional oxoanionic bridges (carboxylate or phosphte) or are coordinated by other small molecules (e.g. water) (Dong et al., 1995; Kojima et al., 1993; Norman et al., 1990). While only one (µ-oxo)diiron(III)TPA complex coordinated with a pentadentate TPA ligand and one bridging oxo atom has been reported (Lange et al., 1999), it is interesting to design more of these pentadentate TPA ligands in order to obtain (µ-oxo)diiron(III)TPA complexes that may significantly affect the catalytic oxidation reaction. We have obtained a novel dinuclear iron(III)–oxo–TPA complex, [(BPHPA)2Fe2O]4ClO4, (I), with a pentadentate TPA ligand substituted by a hydroxymethyl group in the α position [BPHPA is bis(2-pyridylmethyl)(6-hydroxymethyl-2-pyridylmethyl)-amine]. We report here the synthesis, crystal structure, spectroscopic properties and H2O2 dismutation activity of (I).
The crystal structure of the title complex is composed of a binuclear [(BPHPA)2Fe2O]4+ cation and four perchlorate anions as illustrated in Fig. 1.
This µ-oxo dimer has a linear Fe—O—Fe structure, because the bridging O atom lies on the inversion center. The geometry at each iron cation is distorted octahedral, with trans ligand chelating angles of less than 180° (Table 1). The flexibility of the TPA ligand is illustrated by the fact that there are? five angles smaller than 90° and two angles larger than 90°. The lengths of the Fe—N bonds range from 2.117 (5) to 2.196 (5) Å, the Fe—Oligand distance is 2.052 (5) Å and the Fe—Ooxo distance is 1.7896 (9) Å.
The Fe—Ooxo bond distance in (I) is similar to the corresponding bond distance [1.789 (1) Å] in [Fe2(µ-O)(6-C6H4O-TPA)]2(BPh4)2 (II) (Lange et al., 1999), which is the only published structure of a (µ-oxo)diiron(III)TPA complex coordinated by five atoms of substituted TPA ligand with one oxo bridge, in which the TPA ligand is substituted by one phenol group in the α position of a pyridine ring. However, the Fe—Namine distance [2.196 (5) Å] and the mean Fe—Npy distance [2.128 Å] in (I) are both shorter than the equivalent distances in the structure of (II) (by 0.014 and 0.039 Å, respectively). Hydrogen bonds exist between the OH group of the hydroxymethyl group and an O atom of a perchlorate anion [O1—H···O8 = 2.654 (7) Å] as shown in the packing diagram (Fig. 2).
The IR spectra of the diiron complex and ligand show the typical aromatic and aliphatic bands. The coordination of the pyridine moieties causes a shift of the aromatic C=N bands to higher wavenumbers. Two strong new bands in the spectrum of the diiron complex can be assigned to v(Cl—O) of ClO4 at 1089 and 622 cm−1. The presence of Fe—O—Fe linkage is also confirmed by the appearance of v(Fe—O—Fe) at 833 cm−1.
The intense peak in the UV range is slightly blue-shifted compared with that in the free ligand (from 262 to 252 nm) and is assigned to a ligand-centered π–π* transition. Upon metalation of the ligand, four peaks appear at 323, 358, 487 and 658 nm, which are assign to oxo-to-FeIII LMCT transitions (Norman et al., 1990).
The diiron–oxo complex also shows H2O2 dismutation activity in acetonitrile with a complex (1 mM)/H2O2 ratio of 1:1000 at 298 K. The turnover of the reaction for the first 20 min is 188; however, the complex has no catalytic activity for the oxidation of cyclohexane or cyclohexene. Further study of the reactive mechanism is in process.