Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270102004948/bm1491sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270102004948/bm1491Isup2.hkl |
CCDC reference: 187908
To a solution of FeCl3 (0.32 g, 2.0 mmol) in MeOH (30 ml) was added an MeOH (30 ml) solution of 3{5}-tertbutylpyrazole (0.49 g, 4.0 mmol) and NaOH (0.080 g, 2.0 mmol). The mixture was stirred at room temperature for 2 h and then evaporated to dryness. The residue was dissolved in a minimum volume of CH2Cl2, and the filtered extracts were layered with pentane to give dark-brown crystals of (I) (yield 0.28 g, 37%). Analysis found: C 43.9, H 6.2, N 14.8%; calculated for C28H48Cl4Fe2N8O: C 43.9, H 6.3, N 14.6%.
All H atoms were placed in calculated positions, and refined using a riding model. The constraints employed were as follows: Csp2—H = 0.95 Å and Uiso(H) = 1.2Ueq(C), Cmethyl—H = 0.98 Å and Uiso(H) = 1.5Ueq(C), and N—H = 0.88 Å and Uiso(H) = 1.2Ueq(N).
Data collection: COLLECT (Nonius, 1999); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997); data reduction: DENZO-SMN; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEX (McArdle, 1995); software used to prepare material for publication: local program.
Fig. 1. A view of the molecular structure of (I) with 50% probability displacement ellipsoids, showing the atom-numbering scheme employed. All C-bound H atoms have been omitted for clarity. |
[Fe2Cl4O(C7H12N2)4] | Z = 2 |
Mr = 766.24 | F(000) = 800 |
Triclinic, P1 | Dx = 1.304 Mg m−3 |
a = 10.3075 (1) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 10.9284 (1) Å | Cell parameters from 44449 reflections |
c = 17.3424 (2) Å | θ = 2.7–27.5° |
α = 87.5556 (4)° | µ = 1.05 mm−1 |
β = 88.8661 (4)° | T = 150 K |
γ = 89.3366 (5)° | Prism, brown |
V = 1951.25 (3) Å3 | 0.43 × 0.30 × 0.20 mm |
Nonius KappaCCD area-detector diffractometer | 8944 independent reflections |
Radiation source: fine-focus sealed tube | 8129 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.054 |
Detector resolution: 9.091 pixels mm-1 | θmax = 27.5°, θmin = 2.7° |
ϕ or ω scans? | h = −13→13 |
Absorption correction: multi-scan (SORTAV; Blessing, 1995) | k = −14→14 |
Tmin = 0.661, Tmax = 0.818 | l = −22→22 |
44449 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)] = 0.033 | H-atom parameters constrained |
wR(F2) = 0.091 | w = 1/[σ2(Fo2) + (0.042P)2 + 1.185P] where P = (Fo2 + 2Fc2)/3 |
S = 1.03 | (Δ/σ)max = 0.001 |
8944 reflections | Δρmax = 0.68 e Å−3 |
401 parameters | Δρmin = −0.46 e Å−3 |
0 restraints | Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0074 (11) |
[Fe2Cl4O(C7H12N2)4] | γ = 89.3366 (5)° |
Mr = 766.24 | V = 1951.25 (3) Å3 |
Triclinic, P1 | Z = 2 |
a = 10.3075 (1) Å | Mo Kα radiation |
b = 10.9284 (1) Å | µ = 1.05 mm−1 |
c = 17.3424 (2) Å | T = 150 K |
α = 87.5556 (4)° | 0.43 × 0.30 × 0.20 mm |
β = 88.8661 (4)° |
Nonius KappaCCD area-detector diffractometer | 8944 independent reflections |
Absorption correction: multi-scan (SORTAV; Blessing, 1995) | 8129 reflections with I > 2σ(I) |
Tmin = 0.661, Tmax = 0.818 | Rint = 0.054 |
44449 measured reflections |
R[F2 > 2σ(F2)] = 0.033 | 0 restraints |
wR(F2) = 0.091 | H-atom parameters constrained |
S = 1.03 | Δρmax = 0.68 e Å−3 |
8944 reflections | Δρmin = −0.46 e Å−3 |
401 parameters |
Experimental. Detector set at 30 mm from sample with different 2theta offsets 1 degree phi exposures for chi = 0 degree settings 1 degree omega exposures for chi = 90 degree settings |
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. No disorder was detected during refinement. All non-H atoms were refined anisotropically, while H atoms were placed in calculated positions and refined using a riding model. |
x | y | z | Uiso*/Ueq | ||
Fe1 | 0.41378 (2) | 0.27268 (2) | 0.785051 (14) | 0.02569 (8) | |
Fe2 | 0.18626 (2) | 0.51040 (2) | 0.733357 (13) | 0.02143 (8) | |
O3 | 0.30286 (11) | 0.38557 (10) | 0.74966 (7) | 0.0270 (2) | |
Cl4 | 0.48973 (5) | 0.17574 (5) | 0.68300 (3) | 0.04227 (12) | |
Cl5 | 0.30469 (5) | 0.14164 (4) | 0.86208 (3) | 0.04562 (13) | |
Cl6 | 0.56810 (5) | 0.36669 (5) | 0.84687 (3) | 0.04381 (13) | |
Cl7 | 0.02717 (4) | 0.66874 (4) | 0.71027 (2) | 0.02889 (10) | |
N8 | 0.21379 (14) | 0.49550 (14) | 0.61217 (8) | 0.0279 (3) | |
N9 | 0.29234 (14) | 0.40677 (14) | 0.58331 (8) | 0.0282 (3) | |
H9 | 0.3420 | 0.3579 | 0.6119 | 0.034* | |
C10 | 0.28539 (18) | 0.40240 (19) | 0.50580 (10) | 0.0341 (4) | |
C11 | 0.1984 (2) | 0.4930 (2) | 0.48349 (11) | 0.0447 (5) | |
H11 | 0.1720 | 0.5139 | 0.4324 | 0.054* | |
C12 | 0.15653 (19) | 0.5482 (2) | 0.55084 (11) | 0.0383 (4) | |
H12 | 0.0958 | 0.6141 | 0.5527 | 0.046* | |
C13 | 0.36163 (19) | 0.3101 (2) | 0.46002 (11) | 0.0404 (5) | |
C14 | 0.3394 (3) | 0.3363 (3) | 0.37413 (13) | 0.0658 (8) | |
H14A | 0.2468 | 0.3291 | 0.3635 | 0.099* | |
H14B | 0.3890 | 0.2771 | 0.3441 | 0.099* | |
H14C | 0.3681 | 0.4194 | 0.3596 | 0.099* | |
C15 | 0.5070 (2) | 0.3187 (2) | 0.47622 (13) | 0.0434 (5) | |
H15A | 0.5373 | 0.4013 | 0.4615 | 0.065* | |
H15B | 0.5551 | 0.2587 | 0.4461 | 0.065* | |
H15C | 0.5214 | 0.3017 | 0.5313 | 0.065* | |
C16 | 0.3149 (3) | 0.1803 (2) | 0.48311 (16) | 0.0598 (7) | |
H16A | 0.3332 | 0.1620 | 0.5376 | 0.090* | |
H16B | 0.3605 | 0.1209 | 0.4513 | 0.090* | |
H16C | 0.2213 | 0.1754 | 0.4751 | 0.090* | |
N17 | 0.03181 (13) | 0.38172 (12) | 0.73012 (8) | 0.0251 (3) | |
N18 | 0.06060 (14) | 0.26120 (13) | 0.72268 (9) | 0.0283 (3) | |
H18 | 0.1392 | 0.2298 | 0.7275 | 0.034* | |
C19 | −0.04439 (17) | 0.19512 (16) | 0.70704 (10) | 0.0295 (4) | |
C20 | −0.14720 (18) | 0.27707 (17) | 0.70420 (11) | 0.0330 (4) | |
H20 | −0.2353 | 0.2596 | 0.6944 | 0.040* | |
C21 | −0.09530 (17) | 0.39078 (16) | 0.71873 (11) | 0.0301 (4) | |
H21 | −0.1441 | 0.4649 | 0.7203 | 0.036* | |
C22 | −0.0360 (2) | 0.05790 (18) | 0.69825 (13) | 0.0389 (4) | |
C23 | −0.0167 (3) | −0.0067 (2) | 0.77871 (16) | 0.0673 (8) | |
H23A | −0.0876 | 0.0167 | 0.8137 | 0.101* | |
H23B | 0.0662 | 0.0181 | 0.7996 | 0.101* | |
H23C | −0.0164 | −0.0957 | 0.7737 | 0.101* | |
C24 | 0.0785 (3) | 0.0257 (2) | 0.64687 (19) | 0.0664 (8) | |
H24A | 0.0788 | −0.0625 | 0.6386 | 0.100* | |
H24B | 0.1591 | 0.0476 | 0.6716 | 0.100* | |
H24C | 0.0717 | 0.0710 | 0.5971 | 0.100* | |
C25 | −0.1617 (3) | 0.0123 (2) | 0.6678 (2) | 0.0736 (9) | |
H25A | −0.1780 | 0.0520 | 0.6171 | 0.110* | |
H25B | −0.2329 | 0.0317 | 0.7036 | 0.110* | |
H25C | −0.1559 | −0.0766 | 0.6628 | 0.110* | |
N26 | 0.33073 (14) | 0.65078 (13) | 0.74043 (8) | 0.0262 (3) | |
N27 | 0.42701 (13) | 0.63822 (13) | 0.79259 (8) | 0.0262 (3) | |
H27 | 0.4517 | 0.5674 | 0.8139 | 0.031* | |
C28 | 0.48066 (16) | 0.74608 (15) | 0.80819 (10) | 0.0276 (3) | |
C29 | 0.41610 (18) | 0.83397 (16) | 0.76322 (12) | 0.0340 (4) | |
H29 | 0.4308 | 0.9197 | 0.7606 | 0.041* | |
C30 | 0.32477 (18) | 0.77038 (16) | 0.72253 (11) | 0.0317 (4) | |
H30 | 0.2661 | 0.8076 | 0.6868 | 0.038* | |
C31 | 0.58927 (17) | 0.75550 (17) | 0.86476 (11) | 0.0324 (4) | |
C32 | 0.6104 (2) | 0.8911 (2) | 0.88003 (15) | 0.0524 (6) | |
H32A | 0.6317 | 0.9358 | 0.8313 | 0.079* | |
H32B | 0.6820 | 0.8983 | 0.9159 | 0.079* | |
H32C | 0.5310 | 0.9259 | 0.9027 | 0.079* | |
C33 | 0.5529 (2) | 0.6864 (2) | 0.94078 (11) | 0.0404 (4) | |
H33A | 0.4700 | 0.7182 | 0.9606 | 0.061* | |
H33B | 0.6206 | 0.6980 | 0.9786 | 0.061* | |
H33C | 0.5449 | 0.5990 | 0.9317 | 0.061* | |
C34 | 0.71368 (19) | 0.6991 (2) | 0.83047 (13) | 0.0434 (5) | |
H34A | 0.6980 | 0.6136 | 0.8188 | 0.065* | |
H34B | 0.7836 | 0.7025 | 0.8678 | 0.065* | |
H34C | 0.7388 | 0.7453 | 0.7829 | 0.065* | |
N35 | 0.16108 (14) | 0.53483 (13) | 0.85458 (8) | 0.0265 (3) | |
N36 | 0.11578 (14) | 0.64142 (13) | 0.88234 (8) | 0.0275 (3) | |
H36 | 0.0775 | 0.6992 | 0.8538 | 0.033* | |
C37 | 0.13576 (16) | 0.64931 (15) | 0.95849 (10) | 0.0264 (3) | |
C38 | 0.19761 (19) | 0.54193 (17) | 0.98154 (11) | 0.0340 (4) | |
H38 | 0.2252 | 0.5187 | 1.0321 | 0.041* | |
C39 | 0.21147 (18) | 0.47424 (16) | 0.91543 (10) | 0.0313 (4) | |
H39 | 0.2514 | 0.3956 | 0.9140 | 0.038* | |
C40 | 0.09855 (17) | 0.76062 (17) | 1.00299 (11) | 0.0312 (4) | |
C41 | −0.0331 (2) | 0.81112 (19) | 0.97703 (12) | 0.0405 (4) | |
H41A | −0.0264 | 0.8411 | 0.9231 | 0.061* | |
H41B | −0.0598 | 0.8786 | 1.0095 | 0.061* | |
H41C | −0.0977 | 0.7460 | 0.9819 | 0.061* | |
C42 | 0.0885 (2) | 0.7232 (2) | 1.08944 (12) | 0.0438 (5) | |
H42A | 0.0243 | 0.6582 | 1.0974 | 0.066* | |
H42B | 0.0617 | 0.7943 | 1.1187 | 0.066* | |
H42C | 0.1732 | 0.6932 | 1.1073 | 0.066* | |
C43 | 0.2043 (2) | 0.85660 (19) | 0.99072 (16) | 0.0505 (6) | |
H43A | 0.2874 | 0.8220 | 1.0081 | 0.076* | |
H43B | 0.1820 | 0.9284 | 1.0204 | 0.076* | |
H43C | 0.2113 | 0.8809 | 0.9358 | 0.076* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Fe1 | 0.02496 (13) | 0.02369 (13) | 0.02849 (14) | 0.00402 (9) | −0.00314 (9) | −0.00194 (9) |
Fe2 | 0.02206 (12) | 0.02076 (12) | 0.02166 (13) | 0.00110 (8) | −0.00237 (9) | −0.00254 (8) |
O3 | 0.0281 (6) | 0.0246 (6) | 0.0284 (6) | 0.0039 (5) | −0.0031 (5) | −0.0029 (5) |
Cl4 | 0.0490 (3) | 0.0405 (3) | 0.0376 (3) | 0.0117 (2) | 0.0028 (2) | −0.0101 (2) |
Cl5 | 0.0500 (3) | 0.0337 (2) | 0.0517 (3) | 0.0015 (2) | 0.0109 (2) | 0.0092 (2) |
Cl6 | 0.0369 (2) | 0.0400 (3) | 0.0558 (3) | 0.00361 (19) | −0.0202 (2) | −0.0083 (2) |
Cl7 | 0.0280 (2) | 0.02482 (19) | 0.0340 (2) | 0.00477 (15) | −0.00568 (16) | −0.00191 (15) |
N8 | 0.0270 (7) | 0.0329 (7) | 0.0241 (7) | 0.0001 (6) | −0.0015 (6) | −0.0027 (6) |
N9 | 0.0276 (7) | 0.0343 (7) | 0.0229 (7) | −0.0005 (6) | 0.0000 (6) | −0.0037 (6) |
C10 | 0.0286 (9) | 0.0506 (11) | 0.0236 (8) | −0.0056 (8) | −0.0006 (7) | −0.0069 (8) |
C11 | 0.0406 (11) | 0.0700 (15) | 0.0233 (9) | 0.0060 (10) | −0.0054 (8) | −0.0008 (9) |
C12 | 0.0359 (10) | 0.0513 (11) | 0.0274 (9) | 0.0064 (8) | −0.0043 (7) | 0.0014 (8) |
C13 | 0.0345 (10) | 0.0594 (13) | 0.0283 (9) | −0.0030 (9) | 0.0030 (8) | −0.0140 (9) |
C14 | 0.0582 (15) | 0.111 (2) | 0.0292 (11) | 0.0204 (15) | 0.0001 (10) | −0.0197 (13) |
C15 | 0.0350 (10) | 0.0552 (12) | 0.0405 (11) | −0.0006 (9) | 0.0045 (8) | −0.0079 (9) |
C16 | 0.0563 (14) | 0.0624 (15) | 0.0631 (16) | −0.0161 (12) | 0.0117 (12) | −0.0314 (13) |
N17 | 0.0262 (7) | 0.0222 (6) | 0.0272 (7) | 0.0007 (5) | −0.0010 (5) | −0.0032 (5) |
N18 | 0.0242 (7) | 0.0239 (7) | 0.0372 (8) | 0.0003 (5) | −0.0011 (6) | −0.0061 (6) |
C19 | 0.0292 (8) | 0.0294 (8) | 0.0300 (9) | −0.0054 (7) | 0.0013 (7) | −0.0039 (7) |
C20 | 0.0270 (8) | 0.0351 (9) | 0.0373 (10) | −0.0042 (7) | −0.0043 (7) | −0.0031 (7) |
C21 | 0.0257 (8) | 0.0300 (8) | 0.0345 (9) | 0.0016 (6) | −0.0022 (7) | −0.0003 (7) |
C22 | 0.0398 (10) | 0.0299 (9) | 0.0478 (12) | −0.0060 (8) | 0.0018 (9) | −0.0108 (8) |
C23 | 0.113 (2) | 0.0330 (11) | 0.0562 (15) | −0.0079 (13) | −0.0130 (15) | −0.0004 (10) |
C24 | 0.0692 (17) | 0.0361 (12) | 0.094 (2) | 0.0014 (11) | 0.0262 (15) | −0.0133 (12) |
C25 | 0.0610 (16) | 0.0416 (13) | 0.121 (3) | −0.0110 (12) | −0.0189 (17) | −0.0214 (15) |
N26 | 0.0258 (7) | 0.0259 (7) | 0.0271 (7) | −0.0011 (5) | −0.0051 (5) | −0.0006 (5) |
N27 | 0.0257 (7) | 0.0256 (7) | 0.0274 (7) | −0.0005 (5) | −0.0057 (5) | 0.0002 (5) |
C28 | 0.0255 (8) | 0.0290 (8) | 0.0285 (8) | −0.0035 (6) | 0.0009 (6) | −0.0054 (7) |
C29 | 0.0331 (9) | 0.0243 (8) | 0.0447 (11) | −0.0033 (7) | −0.0048 (8) | −0.0007 (7) |
C30 | 0.0317 (9) | 0.0267 (8) | 0.0366 (10) | −0.0008 (7) | −0.0055 (7) | 0.0033 (7) |
C31 | 0.0283 (9) | 0.0370 (9) | 0.0327 (9) | −0.0031 (7) | −0.0045 (7) | −0.0091 (7) |
C32 | 0.0530 (13) | 0.0443 (12) | 0.0619 (15) | −0.0104 (10) | −0.0190 (11) | −0.0157 (11) |
C33 | 0.0359 (10) | 0.0555 (12) | 0.0304 (10) | 0.0031 (9) | −0.0047 (8) | −0.0069 (9) |
C34 | 0.0267 (9) | 0.0639 (14) | 0.0408 (11) | −0.0037 (9) | −0.0028 (8) | −0.0128 (10) |
N35 | 0.0299 (7) | 0.0242 (7) | 0.0255 (7) | 0.0019 (5) | 0.0006 (6) | −0.0048 (5) |
N36 | 0.0319 (7) | 0.0241 (7) | 0.0265 (7) | 0.0047 (5) | −0.0004 (6) | −0.0043 (5) |
C37 | 0.0264 (8) | 0.0284 (8) | 0.0248 (8) | −0.0012 (6) | 0.0007 (6) | −0.0054 (6) |
C38 | 0.0441 (10) | 0.0334 (9) | 0.0245 (8) | 0.0057 (8) | −0.0014 (7) | −0.0018 (7) |
C39 | 0.0410 (10) | 0.0268 (8) | 0.0259 (8) | 0.0044 (7) | −0.0005 (7) | −0.0010 (7) |
C40 | 0.0304 (9) | 0.0321 (9) | 0.0317 (9) | 0.0033 (7) | −0.0009 (7) | −0.0110 (7) |
C41 | 0.0424 (11) | 0.0416 (10) | 0.0378 (10) | 0.0112 (8) | −0.0038 (8) | −0.0084 (8) |
C42 | 0.0483 (12) | 0.0536 (12) | 0.0301 (10) | 0.0109 (9) | −0.0015 (8) | −0.0100 (9) |
C43 | 0.0473 (12) | 0.0326 (10) | 0.0726 (16) | −0.0064 (9) | 0.0113 (11) | −0.0186 (10) |
Fe1—O3 | 1.7710 (11) | C24—H24B | 0.9800 |
Fe1—Cl5 | 2.2168 (5) | C24—H24C | 0.9800 |
Fe1—Cl6 | 2.2214 (5) | C25—H25A | 0.9800 |
Fe1—Cl4 | 2.2256 (5) | C25—H25B | 0.9800 |
Fe2—O3 | 1.8243 (11) | C25—H25C | 0.9800 |
Fe2—N8 | 2.1280 (14) | N26—C30 | 1.331 (2) |
Fe2—N17 | 2.1395 (14) | N26—N27 | 1.3579 (19) |
Fe2—N26 | 2.1592 (14) | N27—C28 | 1.348 (2) |
Fe2—N35 | 2.1407 (14) | N27—H27 | 0.8800 |
Fe2—Cl7 | 2.3968 (4) | C28—C29 | 1.384 (3) |
N8—C12 | 1.333 (2) | C28—C31 | 1.510 (2) |
N8—N9 | 1.361 (2) | C29—C30 | 1.397 (3) |
N9—C10 | 1.350 (2) | C29—H29 | 0.9500 |
N9—H9 | 0.8800 | C30—H30 | 0.9500 |
C10—C11 | 1.377 (3) | C31—C33 | 1.533 (3) |
C10—C13 | 1.513 (3) | C31—C32 | 1.536 (3) |
C11—C12 | 1.396 (3) | C31—C34 | 1.536 (3) |
C11—H11 | 0.9500 | C32—H32A | 0.9800 |
C12—H12 | 0.9500 | C32—H32B | 0.9800 |
C13—C14 | 1.526 (3) | C32—H32C | 0.9800 |
C13—C15 | 1.535 (3) | C33—H33A | 0.9800 |
C13—C16 | 1.538 (3) | C33—H33B | 0.9800 |
C14—H14A | 0.9800 | C33—H33C | 0.9800 |
C14—H14B | 0.9800 | C34—H34A | 0.9800 |
C14—H14C | 0.9800 | C34—H34B | 0.9800 |
C15—H15A | 0.9800 | C34—H34C | 0.9800 |
C15—H15B | 0.9800 | N35—C39 | 1.333 (2) |
C15—H15C | 0.9800 | N35—N36 | 1.3539 (19) |
C16—H16A | 0.9800 | N36—C37 | 1.347 (2) |
C16—H16B | 0.9800 | N36—H36 | 0.8800 |
C16—H16C | 0.9800 | C37—C38 | 1.377 (2) |
N17—C21 | 1.331 (2) | C37—C40 | 1.510 (2) |
N17—N18 | 1.3577 (19) | C38—C39 | 1.395 (3) |
N18—C19 | 1.346 (2) | C38—H38 | 0.9500 |
N18—H18 | 0.8800 | C39—H39 | 0.9500 |
C19—C20 | 1.380 (3) | C40—C43 | 1.527 (3) |
C19—C22 | 1.515 (3) | C40—C41 | 1.528 (3) |
C20—C21 | 1.393 (2) | C40—C42 | 1.539 (3) |
C20—H20 | 0.9500 | C41—H41A | 0.9800 |
C21—H21 | 0.9500 | C41—H41B | 0.9800 |
C22—C25 | 1.507 (3) | C41—H41C | 0.9800 |
C22—C24 | 1.512 (3) | C42—H42A | 0.9800 |
C22—C23 | 1.552 (3) | C42—H42B | 0.9800 |
C23—H23A | 0.9800 | C42—H42C | 0.9800 |
C23—H23B | 0.9800 | C43—H43A | 0.9800 |
C23—H23C | 0.9800 | C43—H43B | 0.9800 |
C24—H24A | 0.9800 | C43—H43C | 0.9800 |
O3—Fe1—Cl5 | 107.90 (4) | C22—C24—H24B | 109.5 |
O3—Fe1—Cl6 | 107.98 (4) | H24A—C24—H24B | 109.5 |
Cl5—Fe1—Cl6 | 112.14 (2) | C22—C24—H24C | 109.5 |
O3—Fe1—Cl4 | 106.59 (4) | H24A—C24—H24C | 109.5 |
Cl5—Fe1—Cl4 | 109.15 (2) | H24B—C24—H24C | 109.5 |
Cl6—Fe1—Cl4 | 112.80 (2) | C22—C25—H25A | 109.5 |
O3—Fe2—N8 | 89.50 (6) | C22—C25—H25B | 109.5 |
O3—Fe2—N17 | 90.43 (5) | H25A—C25—H25B | 109.5 |
N8—Fe2—N17 | 88.92 (6) | C22—C25—H25C | 109.5 |
O3—Fe2—N35 | 92.12 (5) | H25A—C25—H25C | 109.5 |
N8—Fe2—N35 | 177.14 (6) | H25B—C25—H25C | 109.5 |
N17—Fe2—N35 | 93.43 (5) | C30—N26—N27 | 104.78 (14) |
O3—Fe2—N26 | 93.61 (5) | C30—N26—Fe2 | 130.69 (12) |
N8—Fe2—N26 | 93.52 (6) | N27—N26—Fe2 | 120.34 (10) |
N17—Fe2—N26 | 175.29 (5) | C28—N27—N26 | 112.60 (14) |
N35—Fe2—N26 | 84.02 (5) | C28—N27—H27 | 123.7 |
O3—Fe2—Cl7 | 177.77 (4) | N26—N27—H27 | 123.7 |
N8—Fe2—Cl7 | 89.81 (4) | N27—C28—C29 | 105.87 (15) |
N17—Fe2—Cl7 | 87.44 (4) | N27—C28—C31 | 122.34 (16) |
N35—Fe2—Cl7 | 88.66 (4) | C29—C28—C31 | 131.79 (16) |
N26—Fe2—Cl7 | 88.54 (4) | C28—C29—C30 | 105.67 (15) |
Fe1—O3—Fe2 | 168.50 (8) | C28—C29—H29 | 127.2 |
C12—N8—N9 | 105.06 (15) | C30—C29—H29 | 127.2 |
C12—N8—Fe2 | 133.48 (13) | N26—C30—C29 | 111.08 (16) |
N9—N8—Fe2 | 120.92 (11) | N26—C30—H30 | 124.5 |
C10—N9—N8 | 112.29 (15) | C29—C30—H30 | 124.5 |
C10—N9—H9 | 123.9 | C28—C31—C33 | 109.75 (15) |
N8—N9—H9 | 123.9 | C28—C31—C32 | 108.84 (16) |
N9—C10—C11 | 105.76 (17) | C33—C31—C32 | 109.38 (17) |
N9—C10—C13 | 122.54 (18) | C28—C31—C34 | 109.27 (15) |
C11—C10—C13 | 131.69 (18) | C33—C31—C34 | 109.48 (17) |
C10—C11—C12 | 106.42 (17) | C32—C31—C34 | 110.11 (17) |
C10—C11—H11 | 126.8 | C31—C32—H32A | 109.5 |
C12—C11—H11 | 126.8 | C31—C32—H32B | 109.5 |
N8—C12—C11 | 110.47 (18) | H32A—C32—H32B | 109.5 |
N8—C12—H12 | 124.8 | C31—C32—H32C | 109.5 |
C11—C12—H12 | 124.8 | H32A—C32—H32C | 109.5 |
C10—C13—C14 | 109.07 (19) | H32B—C32—H32C | 109.5 |
C10—C13—C15 | 110.39 (16) | C31—C33—H33A | 109.5 |
C14—C13—C15 | 109.40 (18) | C31—C33—H33B | 109.5 |
C10—C13—C16 | 109.36 (17) | H33A—C33—H33B | 109.5 |
C14—C13—C16 | 109.5 (2) | C31—C33—H33C | 109.5 |
C15—C13—C16 | 109.1 (2) | H33A—C33—H33C | 109.5 |
C13—C14—H14A | 109.5 | H33B—C33—H33C | 109.5 |
C13—C14—H14B | 109.5 | C31—C34—H34A | 109.5 |
H14A—C14—H14B | 109.5 | C31—C34—H34B | 109.5 |
C13—C14—H14C | 109.5 | H34A—C34—H34B | 109.5 |
H14A—C14—H14C | 109.5 | C31—C34—H34C | 109.5 |
H14B—C14—H14C | 109.5 | H34A—C34—H34C | 109.5 |
C13—C15—H15A | 109.5 | H34B—C34—H34C | 109.5 |
C13—C15—H15B | 109.5 | C39—N35—N36 | 104.80 (14) |
H15A—C15—H15B | 109.5 | C39—N35—Fe2 | 131.21 (12) |
C13—C15—H15C | 109.5 | N36—N35—Fe2 | 121.81 (11) |
H15A—C15—H15C | 109.5 | C37—N36—N35 | 112.56 (14) |
H15B—C15—H15C | 109.5 | C37—N36—H36 | 123.7 |
C13—C16—H16A | 109.5 | N35—N36—H36 | 123.7 |
C13—C16—H16B | 109.5 | N36—C37—C38 | 105.94 (15) |
H16A—C16—H16B | 109.5 | N36—C37—C40 | 123.14 (15) |
C13—C16—H16C | 109.5 | C38—C37—C40 | 130.87 (16) |
H16A—C16—H16C | 109.5 | C37—C38—C39 | 105.86 (16) |
H16B—C16—H16C | 109.5 | C37—C38—H38 | 127.1 |
C21—N17—N18 | 104.77 (14) | C39—C38—H38 | 127.1 |
C21—N17—Fe2 | 134.52 (12) | N35—C39—C38 | 110.84 (16) |
N18—N17—Fe2 | 119.29 (10) | N35—C39—H39 | 124.6 |
C19—N18—N17 | 112.49 (14) | C38—C39—H39 | 124.6 |
C19—N18—H18 | 123.8 | C37—C40—C43 | 108.89 (15) |
N17—N18—H18 | 123.8 | C37—C40—C41 | 110.30 (15) |
N18—C19—C20 | 105.90 (15) | C43—C40—C41 | 111.18 (17) |
N18—C19—C22 | 121.75 (16) | C37—C40—C42 | 108.83 (16) |
C20—C19—C22 | 132.32 (17) | C43—C40—C42 | 108.97 (18) |
C19—C20—C21 | 105.85 (16) | C41—C40—C42 | 108.63 (16) |
C19—C20—H20 | 127.1 | C40—C41—H41A | 109.5 |
C21—C20—H20 | 127.1 | C40—C41—H41B | 109.5 |
N17—C21—C20 | 110.98 (16) | H41A—C41—H41B | 109.5 |
N17—C21—H21 | 124.5 | C40—C41—H41C | 109.5 |
C20—C21—H21 | 124.5 | H41A—C41—H41C | 109.5 |
C25—C22—C24 | 111.8 (2) | H41B—C41—H41C | 109.5 |
C25—C22—C19 | 109.94 (18) | C40—C42—H42A | 109.5 |
C24—C22—C19 | 110.43 (17) | C40—C42—H42B | 109.5 |
C25—C22—C23 | 107.0 (2) | H42A—C42—H42B | 109.5 |
C24—C22—C23 | 108.3 (2) | C40—C42—H42C | 109.5 |
C19—C22—C23 | 109.27 (17) | H42A—C42—H42C | 109.5 |
C22—C23—H23A | 109.5 | H42B—C42—H42C | 109.5 |
C22—C23—H23B | 109.5 | C40—C43—H43A | 109.5 |
H23A—C23—H23B | 109.5 | C40—C43—H43B | 109.5 |
C22—C23—H23C | 109.5 | H43A—C43—H43B | 109.5 |
H23A—C23—H23C | 109.5 | C40—C43—H43C | 109.5 |
H23B—C23—H23C | 109.5 | H43A—C43—H43C | 109.5 |
C22—C24—H24A | 109.5 | H43B—C43—H43C | 109.5 |
D—H···A | D—H | H···A | D···A | D—H···A |
N9—H9···O3 | 0.88 | 2.45 | 2.8885 (19) | 112 |
N9—H9···Cl4 | 0.88 | 2.76 | 3.6265 (16) | 170 |
N18—H18···O3 | 0.88 | 2.46 | 2.9122 (18) | 113 |
N18—H18···Cl5 | 0.88 | 3.03 | 3.7117 (16) | 135 |
N27—H27···Cl6 | 0.88 | 2.54 | 3.3945 (15) | 165 |
N36—H36···Cl7 | 0.88 | 2.59 | 3.1392 (15) | 122 |
Experimental details
Crystal data | |
Chemical formula | [Fe2Cl4O(C7H12N2)4] |
Mr | 766.24 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 150 |
a, b, c (Å) | 10.3075 (1), 10.9284 (1), 17.3424 (2) |
α, β, γ (°) | 87.5556 (4), 88.8661 (4), 89.3366 (5) |
V (Å3) | 1951.25 (3) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 1.05 |
Crystal size (mm) | 0.43 × 0.30 × 0.20 |
Data collection | |
Diffractometer | Nonius KappaCCD area-detector diffractometer |
Absorption correction | Multi-scan (SORTAV; Blessing, 1995) |
Tmin, Tmax | 0.661, 0.818 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 44449, 8944, 8129 |
Rint | 0.054 |
(sin θ/λ)max (Å−1) | 0.651 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.033, 0.091, 1.03 |
No. of reflections | 8944 |
No. of parameters | 401 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.68, −0.46 |
Computer programs: COLLECT (Nonius, 1999), DENZO-SMN (Otwinowski & Minor, 1997), DENZO-SMN, SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), ORTEX (McArdle, 1995), local program.
Fe1—O3 | 1.7710 (11) | Fe2—N8 | 2.1280 (14) |
Fe1—Cl5 | 2.2168 (5) | Fe2—N17 | 2.1395 (14) |
Fe1—Cl6 | 2.2214 (5) | Fe2—N26 | 2.1592 (14) |
Fe1—Cl4 | 2.2256 (5) | Fe2—N35 | 2.1407 (14) |
Fe2—O3 | 1.8243 (11) | Fe2—Cl7 | 2.3968 (4) |
O3—Fe1—Cl5 | 107.90 (4) | N17—Fe2—N35 | 93.43 (5) |
O3—Fe1—Cl6 | 107.98 (4) | O3—Fe2—N26 | 93.61 (5) |
Cl5—Fe1—Cl6 | 112.14 (2) | N8—Fe2—N26 | 93.52 (6) |
O3—Fe1—Cl4 | 106.59 (4) | N17—Fe2—N26 | 175.29 (5) |
Cl5—Fe1—Cl4 | 109.15 (2) | N35—Fe2—N26 | 84.02 (5) |
Cl6—Fe1—Cl4 | 112.80 (2) | O3—Fe2—Cl7 | 177.77 (4) |
O3—Fe2—N8 | 89.50 (6) | N8—Fe2—Cl7 | 89.81 (4) |
O3—Fe2—N17 | 90.43 (5) | N17—Fe2—Cl7 | 87.44 (4) |
N8—Fe2—N17 | 88.92 (6) | N35—Fe2—Cl7 | 88.66 (4) |
O3—Fe2—N35 | 92.12 (5) | N26—Fe2—Cl7 | 88.54 (4) |
N8—Fe2—N35 | 177.14 (6) | Fe1—O3—Fe2 | 168.50 (8) |
D—H···A | D—H | H···A | D···A | D—H···A |
N9—H9···O3 | 0.88 | 2.45 | 2.8885 (19) | 112 |
N9—H9···Cl4 | 0.88 | 2.76 | 3.6265 (16) | 170 |
N18—H18···O3 | 0.88 | 2.46 | 2.9122 (18) | 113 |
N18—H18···Cl5 | 0.88 | 3.03 | 3.7117 (16) | 135 |
N27—H27···Cl6 | 0.88 | 2.54 | 3.3945 (15) | 165 |
N36—H36···Cl7 | 0.88 | 2.59 | 3.1392 (15) | 122 |
We have recently reported that complexation of CuCl2 by HpztBu in basic MeOH affords a heptacopper aggregate with a double-cubane core structure, which is templated by N—H···Cl hydrogen bonding between the pyrazole ligands and non-coordinated Cl- anions (Liu et al., 2002). As an extension of this work, we were keen to determine the products of similar reactions using other transition metal halide precursors. We report here the title compound, (I), which we isolated in moderate yield from an otherwise identical procedure using FeCl3 as starting material. Our isolation of (I) contrasts with a report of a very similar reaction using unsubstituted pyrazole as ligand, which instead afforded a unique octanuclear aggregate containing bridging oxo and pyrazolide groups (Raptis et al., 1999). Unsymmetrical diiron complexes containing the [FeOX3]- moiety (X- is Cl- or Br-) have been described previously (Gómez-Romero et al., 1989, 1990; Wang et al., 1996; James et al., 1997; Ondrejkovičová et al., 1998a,b), most relevantly in [Fe2OCl4tz4] (tz is thiazole; James et al., 1997). \sch
The asymmetric unit of (I) contains one molecule of the complex lying on a general position, with the two Fe centres linked by a bent oxo bridge having an Fe1—O3—Fe2 angle that is within the usual range for compounds containing [FeOCl3]- centres (tabulated in Ondrejkovičová et al., 1998b). The failure of atom Fe1 to achieve perfect C3v symmetry is seen in small variations in the Fe1—Cl bond lengths: the differences between individual Fe1—Cl distances are in the range 0.0042 (7)–0.0088 (7) Å. These differences may be related to the hydrogen bonds accepted by these three Cl- donors (see below), since there is a perfect correlation between each Fe1—Cl bond length (Table 1) and the strength of the hydrogen bond accepted by that Cl atom, as expressed by its N—H···Cl angle (Table 2). However, this suggestion remains to be confirmed, since [Fe2OCl4tz4] (James et al., 1997) and other compounds containing the [FeOCl3]- moiety that do not possess hydrogen bonding to the Cl- ligands (Ondrejkovičová et al., 1998b) also show unequal Fe—Cl bond lengths.
The local geometry at Fe2 is approximately C4v, but with a distribution of Fe2—N bond distances; while Fe2—N17 and Fe2—N35 are metrically equivalent, Fe2—N8 is shorter than the average of these two bonds by 0.012 (2) Å, and Fe2—N26 is longer by 0.019 (2) Å. A similar spread of Fe—N distances is also exhibited by [Fe2OCl4tz4] (James et al., 1997). The Fe2—Cl7 bond is longer than the Fe1—Cl bonds by an average of 0.1755 (10) Å, which should reflect both the higher coordination number at Fe2 and the strong trans influence of the bridging oxo ligand.
While all the pyrazole rings are coordinated as the 5-substituted tautomer, the N35—C43 ligand is rotated by ca 180° about the Fe2—N35 bond relative to the other three HpztBu ligands. This is related to the intramolecular hydrogen bonding within the compound (see below).
The four pyrazole ligands in (I) form intramolecular N—H···X (X is O or Cl) hydrogen bonds to different acceptors in the molecule. Three of these NH groups interact with atom O3, and/or a Cl- ligand bound to Fe1. Both atoms H9 and H18 form bifurcated hydrogen bonds to atom O3 and atoms Cl4 and Cl5, respectively. While the N9—H9···Cl4 interaction is quite short and close to linear, the N18—H18···Cl5 contact is much longer and is substantially bent, to the extent that this should be considered a very weak interaction. In contrast, atom H27 forms a near-linear hydrogen bond to atom Cl6 only. The irregularity of the hydrogen bonds formed by these three pyrazole groups reflects the poor complementarity between hydrogen bond-donors bound to a near-C4v-symmetric metal centre, with N—Fe2—N angles of ca 90°, and hydrogen-bond acceptors at a C3v-symmetric centre, related by ca 109.5°. The fourth pyrazole N—H atom, H36, forms a hydrogen bond to Cl7. There are no noteworthy intermolecular contacts within the crystal lattice.