Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801020542/ya6079sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536801020542/ya6079Isup2.hkl |
CCDC reference: 180514
Key indicators
- Single-crystal X-ray study
- T = 120 K
- Mean (C-C) = 0.003 Å
- Disorder in solvent or counterion
- R factor = 0.032
- wR factor = 0.034
- Data-to-parameter ratio = 16.2
checkCIF results
No syntax errors found ADDSYM reports no extra symmetry
Alert Level B:
PLAT_420 Alert B D-H Without Acceptor >O10 - >HO10A ?
Alert Level C:
PLAT_302 Alert C Anion/Solvent Disorder ....................... 36.00 Perc.
0 Alert Level A = Potentially serious problem
1 Alert Level B = Potential problem
1 Alert Level C = Please check
Red crystals of the title compound (1) were prepared by the method described by Hazell et al. (1995).
The H atoms of the ligand were constrained to have C—H = 0.95 Å and Uiso = 1.2Ueq for the atom to which they are attached. The H atoms of the water molecules O10 were obtained from a difference map and kept fixed. One of the perchlorate ions (with the central Cl4 atom) was disordered, appearing on the Fourier map as a very anisotropic heavy atom surrounded by six light atoms, and was modelled as two interpenetrating perchlorate ions which were constrained to have regular tetrahedral geometry with all Cl—O distances the same. Site-occupation factors for the two ions were set, arbitrarily, to be 0.5. The site-occupation factor for the water molecule was refined and found to be 0.751 (5).
Data collection: SMART (Siemens, 1995); cell refinement: SAINT (Siemens, 1995); data reduction: SAINT; program(s) used to solve structure: SIR97 (Altomare et al., 1997) and KRYSTAL (Hazell, 1995); program(s) used to refine structure: modified ORFLS (Busing et al., 1962) and KRYSTAL; molecular graphics: ORTEPIII (Burnett & Johnson, 1996) and KRYSTAL; software used to prepare material for publication: KRYSTAL.
Fig. 1. View of the title cation showing the labelling of the non-H atoms. Displacement ellipsoids are shown at 50% probability levels; H atoms have been omitted. |
[Fe2Cl2O(C16H22N4)2](ClO4)2·0.751H2O | F(000) = 1966.04 |
Mr = 951.83 | Dx = 1.572 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yc | Cell parameters from 8666 reflections |
a = 13.632 (3) Å | θ = 2.3–30.5° |
b = 17.956 (4) Å | µ = 1.05 mm−1 |
c = 16.489 (3) Å | T = 120 K |
β = 94.938 (4)° | Needle, red |
V = 4021 (1) Å3 | 0.50 × 0.13 × 0.12 mm |
Z = 4 |
Siemens SMART CCD diffractometer | 12123 independent reflections |
Radiation source: x-ray tube | 8461 reflections with I > 3σ(I) |
Graphite monochromator | Rint = 0.042 |
ω rotation scans with narrow frames | θmax = 30.5°, θmin = 2.3° |
Absorption correction: integration (XPREP; Siemens, 1995) | h = −19→18 |
Tmin = 0.647, Tmax = 0.899 | k = −25→24 |
45381 measured reflections | l = −22→23 |
Refinement on F | 0 restraints |
Least-squares matrix: full | 1 constraint |
R[F2 > 2σ(F2)] = 0.032 | H-atom parameters constrained |
wR(F2) = 0.034 | w = 1/{[σcs(F2) + B + (1 + A)F2]1/2-|F|}2, where A = 0.03, B = 0.10 |
S = 0.88 | (Δ/σ)max = 0.001 |
8461 reflections | Δρmax = 0.72 (8) e Å−3 |
521 parameters | Δρmin = −0.51 (8) e Å−3 |
[Fe2Cl2O(C16H22N4)2](ClO4)2·0.751H2O | V = 4021 (1) Å3 |
Mr = 951.83 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 13.632 (3) Å | µ = 1.05 mm−1 |
b = 17.956 (4) Å | T = 120 K |
c = 16.489 (3) Å | 0.50 × 0.13 × 0.12 mm |
β = 94.938 (4)° |
Siemens SMART CCD diffractometer | 12123 independent reflections |
Absorption correction: integration (XPREP; Siemens, 1995) | 8461 reflections with I > 3σ(I) |
Tmin = 0.647, Tmax = 0.899 | Rint = 0.042 |
45381 measured reflections |
R[F2 > 2σ(F2)] = 0.032 | 0 restraints |
wR(F2) = 0.034 | H-atom parameters constrained |
S = 0.88 | Δρmax = 0.72 (8) e Å−3 |
8461 reflections | Δρmin = −0.51 (8) e Å−3 |
521 parameters |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Fe1 | 0.61790 (2) | 0.23117 (1) | 0.47934 (2) | 0.0142 (1) | |
Fe2 | 0.88440 (2) | 0.22588 (1) | 0.50562 (2) | 0.0137 (1) | |
Cl1 | 0.57692 (4) | 0.18339 (3) | 0.60298 (3) | 0.0222 (2) | |
Cl2 | 0.91849 (3) | 0.16269 (3) | 0.38755 (3) | 0.0189 (2) | |
O1 | 0.7513 (1) | 0.23165 (7) | 0.49289 (7) | 0.0156 (6) | |
N1 | 0.5972 (1) | 0.34514 (9) | 0.51623 (10) | 0.0195 (8) | |
N2 | 0.6143 (1) | 0.29613 (9) | 0.36461 (9) | 0.0181 (8) | |
N3 | 0.4553 (1) | 0.22114 (9) | 0.43131 (10) | 0.0200 (8) | |
N4 | 0.6020 (1) | 0.12359 (9) | 0.42168 (10) | 0.0206 (8) | |
N5 | 0.9157 (1) | 0.33305 (9) | 0.45299 (10) | 0.0179 (8) | |
N6 | 0.8967 (1) | 0.30488 (9) | 0.61008 (9) | 0.0193 (8) | |
N7 | 1.0454 (1) | 0.21039 (9) | 0.55344 (10) | 0.0189 (8) | |
N8 | 0.8897 (1) | 0.12447 (9) | 0.57680 (9) | 0.0186 (8) | |
C1 | 0.5687 (1) | 0.3677 (1) | 0.5888 (1) | 0.025 (1) | |
C2 | 0.5748 (2) | 0.4411 (1) | 0.6133 (1) | 0.033 (1) | |
C3 | 0.6104 (2) | 0.4933 (1) | 0.5620 (2) | 0.033 (1) | |
C4 | 0.6367 (1) | 0.4715 (1) | 0.4866 (1) | 0.028 (1) | |
C5 | 0.6296 (1) | 0.3967 (1) | 0.4652 (1) | 0.021 (1) | |
C6 | 0.6623 (1) | 0.3679 (1) | 0.3869 (1) | 0.023 (1) | |
C7 | 0.6699 (2) | 0.2586 (1) | 0.3034 (1) | 0.026 (1) | |
C8 | 0.5103 (1) | 0.3098 (1) | 0.3317 (1) | 0.022 (1) | |
C9 | 0.4488 (1) | 0.2416 (1) | 0.3436 (1) | 0.023 (1) | |
C10 | 0.3853 (1) | 0.2670 (1) | 0.4736 (1) | 0.027 (1) | |
C11 | 0.4292 (1) | 0.1419 (1) | 0.4387 (1) | 0.027 (1) | |
C12 | 0.5114 (1) | 0.0932 (1) | 0.4141 (1) | 0.024 (1) | |
C13 | 0.4961 (2) | 0.0212 (1) | 0.3856 (2) | 0.034 (1) | |
C14 | 0.5749 (2) | −0.0204 (1) | 0.3638 (2) | 0.038 (1) | |
C15 | 0.6678 (2) | 0.0112 (1) | 0.3708 (1) | 0.033 (1) | |
C16 | 0.6791 (2) | 0.0831 (1) | 0.4005 (1) | 0.025 (1) | |
C17 | 0.9439 (1) | 0.3439 (1) | 0.3777 (1) | 0.021 (1) | |
C18 | 0.9427 (2) | 0.4131 (1) | 0.3415 (1) | 0.026 (1) | |
C19 | 0.9122 (2) | 0.4740 (1) | 0.3846 (1) | 0.028 (1) | |
C20 | 0.8868 (1) | 0.4641 (1) | 0.4630 (1) | 0.025 (1) | |
C21 | 0.8888 (1) | 0.3927 (1) | 0.4958 (1) | 0.019 (1) | |
C22 | 0.8556 (1) | 0.3764 (1) | 0.5786 (1) | 0.022 (1) | |
C23 | 0.8390 (2) | 0.2794 (1) | 0.6768 (1) | 0.026 (1) | |
C24 | 1.0026 (1) | 0.3147 (1) | 0.6395 (1) | 0.023 (1) | |
C25 | 1.0562 (1) | 0.2412 (1) | 0.6376 (1) | 0.022 (1) | |
C26 | 1.1193 (1) | 0.2450 (1) | 0.5041 (1) | 0.026 (1) | |
C27 | 1.0634 (1) | 0.1292 (1) | 0.5567 (1) | 0.022 (1) | |
C28 | 0.9771 (1) | 0.0888 (1) | 0.5869 (1) | 0.020 (1) | |
C29 | 0.9859 (2) | 0.0184 (1) | 0.6214 (1) | 0.025 (1) | |
C30 | 0.9033 (2) | −0.0159 (1) | 0.6468 (1) | 0.026 (1) | |
C31 | 0.8136 (2) | 0.0212 (1) | 0.6385 (1) | 0.026 (1) | |
C32 | 0.8095 (1) | 0.0908 (1) | 0.6027 (1) | 0.023 (1) | |
Cl3 | 0.70397 (4) | 0.61278 (3) | 0.31004 (3) | 0.0273 (3) | |
O2 | 0.6623 (2) | 0.5405 (1) | 0.2916 (1) | 0.056 (1) | |
O3 | 0.6259 (1) | 0.6647 (1) | 0.3194 (1) | 0.047 (1) | |
O4 | 0.7602 (1) | 0.6359 (1) | 0.2452 (1) | 0.054 (1) | |
O5 | 0.7650 (1) | 0.6092 (1) | 0.3850 (1) | 0.052 (1) | |
Cl4a | 0.7985 (2) | 0.8915 (1) | 0.1886 (1) | 0.027 (1) | 0.5 |
O6a | 0.6968 (2) | 0.8895 (3) | 0.2056 (1) | 0.032 (1) | 0.5 |
O7a | 0.8075 (2) | 0.9313 (2) | 0.1139 (2) | 0.040 (3) | 0.5 |
O8a | 0.8556 (2) | 0.9286 (2) | 0.2541 (2) | 0.045 (2) | 0.5 |
O9a | 0.8343 (3) | 0.8167 (1) | 0.1809 (2) | 0.045 (2) | 0.5 |
Cl4b | 0.8017 (2) | 0.9086 (1) | 0.1822 (1) | 0.027 (1) | 0.5 |
O6b | 0.7000 (2) | 0.8971 (2) | 0.1960 (2) | 0.032 (1) | 0.5 |
O7b | 0.8346 (3) | 0.9787 (2) | 0.2170 (2) | 0.066 (3) | 0.5 |
O8b | 0.8603 (3) | 0.8492 (2) | 0.2197 (3) | 0.084 (4) | 0.5 |
O9b | 0.8118 (3) | 0.9092 (2) | 0.0960 (1) | 0.042 (3) | 0.5 |
O10 | 0.6891 (2) | 0.8185 (1) | 0.3539 (1) | 0.035 (1) | 0.751 (5) |
HO10a | 0.6989 | 0.8371 | 0.3040 | 0.050* | 0.751 (5) |
HO10b | 0.6682 | 0.7714 | 0.3407 | 0.050* | 0.751 (5) |
H1 | 0.5436 | 0.3319 | 0.6240 | 0.030* | |
H2 | 0.5548 | 0.4555 | 0.6648 | 0.040* | |
H3 | 0.6168 | 0.5439 | 0.5784 | 0.040* | |
H4 | 0.6593 | 0.5071 | 0.4499 | 0.034* | |
H6a | 0.6457 | 0.4031 | 0.3450 | 0.028* | |
H6b | 0.7317 | 0.3609 | 0.3927 | 0.028* | |
H7a | 0.6390 | 0.2124 | 0.2890 | 0.031* | |
H7b | 0.7356 | 0.2499 | 0.3255 | 0.031* | |
H7c | 0.6705 | 0.2891 | 0.2564 | 0.031* | |
H8a | 0.5087 | 0.3209 | 0.2753 | 0.027* | |
H8b | 0.4845 | 0.3507 | 0.3596 | 0.027* | |
H9a | 0.3821 | 0.2517 | 0.3253 | 0.028* | |
H9b | 0.4722 | 0.2015 | 0.3131 | 0.028* | |
H10a | 0.3895 | 0.2540 | 0.5297 | 0.032* | |
H10b | 0.3203 | 0.2584 | 0.4501 | 0.032* | |
H10c | 0.4013 | 0.3182 | 0.4684 | 0.032* | |
H11a | 0.3712 | 0.1318 | 0.4043 | 0.032* | |
H11b | 0.4176 | 0.1315 | 0.4936 | 0.032* | |
H13 | 0.4317 | 0.0006 | 0.3811 | 0.041* | |
H14 | 0.5655 | −0.0699 | 0.3443 | 0.046* | |
H15 | 0.7231 | −0.0160 | 0.3555 | 0.040* | |
H16 | 0.7430 | 0.1045 | 0.4061 | 0.030* | |
H17 | 0.9654 | 0.3023 | 0.3484 | 0.025* | |
H18 | 0.9624 | 0.4190 | 0.2880 | 0.032* | |
H19 | 0.9088 | 0.5220 | 0.3603 | 0.034* | |
H20 | 0.8682 | 0.5055 | 0.4942 | 0.031* | |
H22a | 0.8773 | 0.4152 | 0.6150 | 0.026* | |
H22b | 0.7858 | 0.3738 | 0.5748 | 0.026* | |
H23a | 0.8655 | 0.2334 | 0.6970 | 0.031* | |
H23b | 0.7721 | 0.2728 | 0.6568 | 0.031* | |
H23c | 0.8430 | 0.3154 | 0.7192 | 0.031* | |
H24a | 1.0071 | 0.3331 | 0.6937 | 0.028* | |
H24b | 1.0320 | 0.3493 | 0.6053 | 0.028* | |
H25a | 1.1241 | 0.2486 | 0.6540 | 0.027* | |
H25b | 1.0291 | 0.2072 | 0.6738 | 0.027* | |
H26a | 1.1124 | 0.2254 | 0.4504 | 0.031* | |
H26b | 1.1836 | 0.2346 | 0.5283 | 0.031* | |
H26c | 1.1094 | 0.2974 | 0.5021 | 0.031* | |
H27a | 1.1203 | 0.1195 | 0.5924 | 0.027* | |
H27b | 1.0736 | 0.1118 | 0.5037 | 0.027* | |
H29 | 1.0480 | −0.0059 | 0.6274 | 0.030* | |
H30 | 0.9077 | −0.0644 | 0.6699 | 0.032* | |
H31 | 0.7563 | −0.0009 | 0.6570 | 0.031* | |
H32 | 0.7480 | 0.1159 | 0.5960 | 0.028* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Fe1 | 0.0126 (1) | 0.0166 (1) | 0.0130 (1) | −0.0005 (1) | −0.0006 (1) | −0.0002 (1) |
Fe2 | 0.0127 (1) | 0.0145 (1) | 0.0138 (1) | −0.0002 (1) | −0.0006 (1) | 0.0016 (1) |
Cl1 | 0.0197 (2) | 0.0305 (2) | 0.0164 (2) | −0.0041 (2) | 0.0011 (2) | 0.0047 (2) |
Cl2 | 0.0205 (2) | 0.0186 (2) | 0.0175 (2) | 0.0040 (2) | 0.0005 (2) | −0.0018 (2) |
O1 | 0.0143 (5) | 0.0162 (6) | 0.0160 (6) | −0.0004 (5) | −0.0002 (4) | 0.0005 (5) |
N1 | 0.0159 (8) | 0.0220 (8) | 0.0204 (8) | 0.0018 (6) | 0.0001 (6) | −0.0029 (6) |
N2 | 0.0149 (7) | 0.0232 (8) | 0.0162 (7) | 0.0038 (6) | 0.0012 (6) | 0.0014 (6) |
N3 | 0.0162 (8) | 0.0241 (8) | 0.0194 (7) | −0.0004 (6) | −0.0003 (6) | −0.0007 (6) |
N4 | 0.0188 (8) | 0.0201 (8) | 0.0221 (8) | −0.0019 (6) | −0.0034 (6) | −0.0017 (6) |
N5 | 0.0161 (7) | 0.0175 (7) | 0.0199 (8) | −0.0003 (6) | 0.0009 (6) | 0.0005 (6) |
N6 | 0.0168 (7) | 0.0238 (8) | 0.0170 (7) | −0.0033 (6) | 0.0001 (6) | −0.0009 (6) |
N7 | 0.0153 (7) | 0.0211 (8) | 0.0201 (8) | −0.0006 (6) | −0.0004 (6) | 0.0032 (6) |
N8 | 0.0170 (8) | 0.0187 (8) | 0.0195 (8) | 0.0010 (6) | −0.0018 (6) | 0.0040 (6) |
C1 | 0.019 (1) | 0.033 (1) | 0.024 (1) | 0.004 (1) | 0.001 (1) | −0.007 (1) |
C2 | 0.026 (1) | 0.039 (1) | 0.033 (1) | 0.009 (1) | −0.005 (1) | −0.017 (1) |
C3 | 0.024 (1) | 0.024 (1) | 0.050 (1) | 0.005 (1) | −0.010 (1) | −0.013 (1) |
C4 | 0.017 (1) | 0.022 (1) | 0.044 (1) | 0.002 (1) | −0.004 (1) | 0.001 (1) |
C5 | 0.013 (1) | 0.022 (1) | 0.027 (1) | 0.002 (1) | −0.002 (1) | 0.000 (1) |
C6 | 0.018 (1) | 0.025 (1) | 0.025 (1) | 0.000 (1) | 0.001 (1) | 0.007 (1) |
C7 | 0.023 (1) | 0.038 (1) | 0.017 (1) | 0.010 (1) | 0.004 (1) | 0.002 (1) |
C8 | 0.018 (1) | 0.031 (1) | 0.018 (1) | 0.007 (1) | −0.002 (1) | 0.003 (1) |
C9 | 0.018 (1) | 0.031 (1) | 0.019 (1) | 0.004 (1) | −0.005 (1) | −0.003 (1) |
C10 | 0.016 (1) | 0.037 (1) | 0.026 (1) | 0.002 (1) | 0.003 (1) | 0.000 (1) |
C11 | 0.017 (1) | 0.030 (1) | 0.032 (1) | −0.006 (1) | −0.002 (1) | 0.000 (1) |
C12 | 0.020 (1) | 0.024 (1) | 0.026 (1) | −0.005 (1) | −0.006 (1) | 0.001 (1) |
C13 | 0.027 (1) | 0.027 (1) | 0.046 (1) | −0.009 (1) | −0.006 (1) | −0.004 (1) |
C14 | 0.038 (1) | 0.022 (1) | 0.052 (2) | −0.005 (1) | −0.010 (1) | −0.010 (1) |
C15 | 0.032 (1) | 0.023 (1) | 0.043 (1) | 0.003 (1) | −0.003 (1) | −0.008 (1) |
C16 | 0.022 (1) | 0.023 (1) | 0.030 (1) | −0.001 (1) | −0.002 (1) | −0.004 (1) |
C17 | 0.019 (1) | 0.023 (1) | 0.022 (1) | 0.000 (1) | 0.004 (1) | 0.004 (1) |
C18 | 0.022 (1) | 0.030 (1) | 0.028 (1) | −0.001 (1) | 0.004 (1) | 0.011 (1) |
C19 | 0.025 (1) | 0.020 (1) | 0.039 (1) | −0.003 (1) | −0.001 (1) | 0.010 (1) |
C20 | 0.021 (1) | 0.019 (1) | 0.037 (1) | −0.001 (1) | −0.002 (1) | −0.002 (1) |
C21 | 0.015 (1) | 0.018 (1) | 0.024 (1) | −0.001 (1) | −0.001 (1) | −0.001 (1) |
C22 | 0.021 (1) | 0.022 (1) | 0.022 (1) | 0.001 (1) | 0.000 (1) | −0.004 (1) |
C23 | 0.025 (1) | 0.036 (1) | 0.017 (1) | −0.004 (1) | 0.004 (1) | −0.002 (1) |
C24 | 0.018 (1) | 0.027 (1) | 0.024 (1) | −0.004 (1) | −0.003 (1) | −0.003 (1) |
C25 | 0.018 (1) | 0.028 (1) | 0.020 (1) | −0.004 (1) | −0.005 (1) | 0.001 (1) |
C26 | 0.016 (1) | 0.034 (1) | 0.028 (1) | −0.002 (1) | 0.003 (1) | 0.005 (1) |
C27 | 0.018 (1) | 0.024 (1) | 0.024 (1) | 0.005 (1) | −0.001 (1) | 0.004 (1) |
C28 | 0.022 (1) | 0.021 (1) | 0.018 (1) | 0.001 (1) | −0.003 (1) | 0.000 (1) |
C29 | 0.026 (1) | 0.022 (1) | 0.025 (1) | 0.006 (1) | −0.003 (1) | 0.003 (1) |
C30 | 0.033 (1) | 0.019 (1) | 0.026 (1) | 0.000 (1) | −0.003 (1) | 0.006 (1) |
C31 | 0.025 (1) | 0.025 (1) | 0.027 (1) | −0.004 (1) | 0.001 (1) | 0.006 (1) |
C32 | 0.019 (1) | 0.024 (1) | 0.025 (1) | −0.002 (1) | −0.001 (1) | 0.005 (1) |
Cl3 | 0.0260 (3) | 0.0258 (3) | 0.0297 (3) | 0.0036 (2) | 0.0003 (2) | 0.0038 (2) |
O2 | 0.072 (1) | 0.047 (1) | 0.050 (1) | −0.027 (1) | 0.002 (1) | −0.008 (1) |
O3 | 0.042 (1) | 0.060 (1) | 0.039 (1) | 0.025 (1) | 0.010 (1) | 0.014 (1) |
O4 | 0.059 (1) | 0.043 (1) | 0.067 (1) | −0.001 (1) | 0.039 (1) | −0.002 (1) |
O5 | 0.049 (1) | 0.043 (1) | 0.058 (1) | 0.006 (1) | −0.029 (1) | 0.000 (1) |
O6a | 0.021 (1) | 0.046 (1) | 0.030 (1) | −0.006 (1) | 0.002 (1) | 0.016 (1) |
Cl4a | 0.0215 (3) | 0.0366 (10) | 0.027 (4) | −0.0057 (5) | −0.0018 (3) | 0.0128 (5) |
O7a | 0.033 (2) | 0.060 (3) | 0.030 (2) | 0.017 (2) | 0.018 (2) | 0.021 (2) |
O8a | 0.025 (2) | 0.068 (3) | 0.041 (2) | −0.005 (2) | −0.007 (1) | −0.019 (2) |
O9a | 0.047 (3) | 0.042 (2) | 0.047 (2) | 0.012 (2) | 0.004 (2) | −0.001 (2) |
O6b | 0.021 (1) | 0.046 (1) | 0.030 (1) | −0.006 (1) | 0.002 (1) | 0.016 (1) |
Cl4b | 0.0215 (3) | 0.0366 (10) | 0.027 (4) | −0.0057 (5) | −0.0018 (3) | 0.0128 (5) |
O7b | 0.063 (3) | 0.078 (3) | 0.057 (3) | −0.035 (3) | 0.012 (2) | −0.015 (2) |
O8b | 0.034 (2) | 0.108 (5) | 0.108 (5) | 0.018 (3) | 0.006 (3) | 0.091 (4) |
O9b | 0.044 (3) | 0.059 (3) | 0.026 (2) | 0.024 (2) | 0.017 (2) | 0.003 (2) |
O10 | 0.039 (1) | 0.036 (1) | 0.031 (1) | 0.000 (1) | 0.005 (1) | 0.006 (1) |
Fe1—Fe2 | 3.623 (1) | Cl3—O4 | 1.430 (2) |
Fe1—Cl1 | 2.324 (1) | Cl3—O5 | 1.432 (2) |
Fe1—O1 | 1.814 (1) | Cl4a—O6a | 1.439 (1) |
Fe1—N1 | 2.161 (2) | Cl4a—O7a | 1.439 |
Fe1—N2 | 2.219 (2) | Cl4a—O8a | 1.439 |
Fe1—N3 | 2.296 (2) | Cl4a—O9a | 1.439 |
Fe1—N4 | 2.156 (2) | Cl4b—O6b | 1.439 |
Fe2—Cl2 | 2.334 (1) | Cl4b—O7b | 1.439 |
Fe2—O1 | 1.811 (1) | Cl4b—O8b | 1.439 |
Fe2—N5 | 2.169 (2) | Cl4b—O9b | 1.439 |
Fe2—N6 | 2.227 (2) | C1—H1 | 0.950 |
Fe2—N7 | 2.284 (2) | C2—H2 | 0.950 |
Fe2—N8 | 2.164 (2) | C3—H3 | 0.950 |
N1—C1 | 1.351 (2) | C4—H4 | 0.950 |
N1—C5 | 1.350 (2) | C6—H6a | 0.950 |
N2—C6 | 1.477 (3) | C6—H6b | 0.950 |
N2—C7 | 1.477 (2) | C7—H7a | 0.950 |
N2—C8 | 1.493 (2) | C7—H7b | 0.950 |
N3—C9 | 1.488 (2) | C7—H7c | 0.950 |
N3—C10 | 1.480 (2) | C8—H8a | 0.950 |
N3—C11 | 1.475 (3) | C8—H8b | 0.950 |
N4—C12 | 1.346 (2) | C9—H9a | 0.950 |
N4—C16 | 1.349 (3) | C9—H9b | 0.950 |
N5—C17 | 1.345 (2) | C10—H10a | 0.950 |
N5—C21 | 1.351 (2) | C10—H10b | 0.950 |
N6—C22 | 1.477 (2) | C10—H10c | 0.950 |
N6—C23 | 1.479 (2) | C11—H11a | 0.950 |
N6—C24 | 1.493 (2) | C11—H11b | 0.950 |
N7—C27 | 1.479 (2) | C13—H13 | 0.950 |
N7—C25 | 1.490 (2) | C14—H14 | 0.950 |
N7—C26 | 1.485 (2) | C15—H15 | 0.950 |
N8—C28 | 1.350 (2) | C16—H16 | 0.950 |
N8—C32 | 1.349 (2) | C17—H17 | 0.950 |
C1—C2 | 1.380 (3) | C18—H18 | 0.950 |
C2—C3 | 1.378 (4) | C19—H19 | 0.950 |
C3—C4 | 1.379 (3) | C20—H20 | 0.950 |
C4—C5 | 1.391 (3) | C22—H22a | 0.950 |
C5—C6 | 1.495 (3) | C22—H22b | 0.950 |
C8—C9 | 1.507 (3) | C23—H23a | 0.950 |
C11—C12 | 1.505 (3) | C23—H23b | 0.950 |
C12—C13 | 1.385 (3) | C23—H23c | 0.950 |
C13—C14 | 1.382 (3) | C24—H24a | 0.950 |
C14—C15 | 1.384 (3) | C24—H24b | 0.950 |
C15—C16 | 1.383 (3) | C25—H25a | 0.950 |
C17—C18 | 1.378 (3) | C25—H25b | 0.950 |
C18—C19 | 1.386 (3) | C26—H26a | 0.950 |
C19—C20 | 1.379 (3) | C26—H26b | 0.950 |
C20—C21 | 1.391 (3) | C26—H26c | 0.950 |
C21—C22 | 1.504 (3) | C27—H27a | 0.950 |
C24—C25 | 1.510 (3) | C27—H27b | 0.950 |
C27—C28 | 1.502 (3) | C29—H29 | 0.950 |
C28—C29 | 1.387 (3) | C30—H30 | 0.950 |
C29—C30 | 1.381 (3) | C31—H31 | 0.950 |
C30—C31 | 1.388 (3) | C32—H32 | 0.950 |
C31—C32 | 1.382 (3) | O10—HO10a | 0.909 |
Cl3—O2 | 1.438 (2) | O10—HO10b | 0.914 |
Cl3—O3 | 1.433 (2) | ||
O1—Fe1—N1 | 96.59 (6) | O6a—Cl4a—O7a | 109.47 |
O1—Fe1—N2 | 92.93 (6) | O6a—Cl4a—O8a | 109.47 |
O1—Fe1—N3 | 166.23 (6) | O6a—Cl4a—O9a | 109.47 |
O1—Fe1—N4 | 96.91 (6) | O7a—Cl4a—O8a | 109.47 |
O1—Fe1—Cl1 | 102.00 (4) | O7a—Cl4a—O9a | 109.47 |
N1—Fe1—N2 | 75.42 (6) | O8a—Cl4a—O9a | 109.47 |
N1—Fe1—N3 | 91.48 (6) | O6b—Cl4b—O7b | 109.47 |
N1—Fe1—N4 | 164.24 (6) | O6b—Cl4b—O8b | 109.47 |
N1—Fe1—Cl1 | 93.19 (5) | O6b—Cl4b—O9b | 109.47 |
N2—Fe1—N3 | 78.29 (6) | O7b—Cl4b—O8b | 109.47 |
N2—Fe1—N4 | 95.80 (6) | O7b—Cl4b—O9b | 109.47 |
N2—Fe1—Cl1 | 162.25 (4) | O8b—Cl4b—O9b | 109.47 |
N3—Fe1—N4 | 73.75 (6) | N1—C1—H1 | 119.0 |
N3—Fe1—Cl1 | 88.62 (4) | C2—C1—H1 | 119.0 |
N4—Fe1—Cl1 | 91.92 (5) | C3—C2—H2 | 120.4 |
O1—Fe2—N5 | 97.62 (6) | C1—C2—H2 | 120.4 |
O1—Fe2—N6 | 93.51 (6) | C2—C3—H3 | 120.3 |
O1—Fe2—N7 | 165.92 (6) | C4—C3—H3 | 120.3 |
O1—Fe2—N8 | 95.58 (6) | C3—C4—H4 | 120.5 |
O1—Fe2—Cl2 | 101.56 (4) | C5—C4—H4 | 120.5 |
N5—Fe2—N6 | 74.92 (6) | H6a—C6—H6b | 109.5 |
N5—Fe2—N7 | 91.71 (6) | N2—C6—H6a | 109.1 |
N5—Fe2—N8 | 164.83 (6) | C5—C6—H6a | 109.1 |
N5—Fe2—Cl2 | 92.15 (5) | N2—C6—H6b | 109.1 |
N6—Fe2—N7 | 78.71 (6) | C5—C6—H6b | 109.1 |
N6—Fe2—N8 | 96.87 (6) | H7a—C7—H7b | 109.6 |
N6—Fe2—Cl2 | 161.39 (4) | H7a—C7—H7c | 109.6 |
N7—Fe2—N8 | 73.99 (6) | N2—C7—H7a | 109.0 |
N7—Fe2—Cl2 | 88.54 (4) | H7b—C7—H7c | 109.5 |
N8—Fe2—Cl2 | 92.50 (5) | N2—C7—H7b | 109.6 |
Fe1—O1—Fe2 | 176.43 (8) | N2—C7—H7c | 109.6 |
Fe1—N1—C1 | 126.0 (1) | H8a—C8—H8b | 109.5 |
Fe1—N1—C5 | 114.6 (1) | N2—C8—H8a | 109.4 |
Fe1—N2—C6 | 105.6 (1) | C9—C8—H8a | 109.4 |
Fe1—N2—C7 | 111.6 (1) | N2—C8—H8b | 109.4 |
Fe1—N2—C8 | 110.3 (1) | C9—C8—H8b | 109.4 |
Fe1—N3—C9 | 106.9 (1) | H9a—C9—H9b | 109.5 |
Fe1—N3—C10 | 115.8 (1) | N3—C9—H9a | 109.4 |
Fe1—N3—C11 | 106.3 (1) | C8—C9—H9a | 109.4 |
Fe1—N4—C12 | 117.4 (1) | N3—C9—H9b | 109.4 |
Fe1—N4—C16 | 123.2 (1) | C8—C9—H9b | 109.4 |
Fe2—N5—C17 | 125.4 (1) | H10a—C10—H10b | 109.5 |
Fe2—N5—C21 | 115.0 (1) | H10a—C10—H10c | 109.5 |
Fe2—N6—C22 | 106.3 (1) | N3—C10—H10a | 109.5 |
Fe2—N6—C23 | 111.6 (1) | H10b—C10—H10c | 109.5 |
Fe2—N6—C24 | 109.4 (1) | N3—C10—H10b | 109.5 |
Fe2—N7—C25 | 107.0 (1) | N3—C10—H10c | 109.5 |
Fe2—N7—C26 | 115.9 (1) | H11a—C11—H11b | 109.5 |
Fe2—N7—C27 | 106.5 (1) | N3—C11—H11a | 109.3 |
Fe2—N8—C28 | 116.9 (1) | C12—C11—H11a | 109.3 |
Fe2—N8—C32 | 123.9 (1) | N3—C11—H11b | 109.3 |
C1—N1—C5 | 118.7 (2) | C12—C11—H11b | 109.3 |
C6—N2—C7 | 109.0 (2) | C14—C13—H13 | 120.2 |
C6—N2—C8 | 109.5 (1) | C12—C13—H13 | 120.2 |
C7—N2—C8 | 110.7 (1) | C13—C14—H14 | 120.5 |
C9—N3—C11 | 108.9 (2) | C15—C14—H14 | 120.5 |
C10—N3—C11 | 109.2 (2) | C16—C15—H15 | 120.5 |
C9—N3—C10 | 109.5 (1) | C14—C15—H15 | 120.5 |
C12—N4—C16 | 119.1 (2) | N4—C16—H16 | 119.0 |
C17—N5—C21 | 118.6 (2) | C15—C16—H16 | 119.0 |
C22—N6—C23 | 108.7 (2) | N5—C17—H17 | 118.8 |
C22—N6—C24 | 109.8 (1) | C18—C17—H17 | 118.8 |
C23—N6—C24 | 110.9 (1) | C17—C18—H18 | 120.6 |
C26—N7—C27 | 108.3 (2) | C19—C18—H18 | 120.6 |
C25—N7—C27 | 109.2 (1) | C20—C19—H19 | 120.3 |
C25—N7—C26 | 109.7 (1) | C18—C19—H19 | 120.3 |
C28—N8—C32 | 118.6 (2) | C19—C20—H20 | 120.5 |
N1—C1—C2 | 122.0 (2) | C21—C20—H20 | 120.5 |
C1—C2—C3 | 119.1 (2) | H22a—C22—H22b | 109.5 |
C2—C3—C4 | 119.5 (2) | N6—C22—H22a | 109.2 |
C3—C4—C5 | 119.0 (2) | C21—C22—H22a | 109.2 |
N1—C5—C4 | 121.6 (2) | N6—C22—H22b | 109.2 |
N1—C5—C6 | 116.0 (2) | C21—C22—H22b | 109.2 |
C4—C5—C6 | 122.3 (2) | H23a—C23—H23b | 109.7 |
N2—C6—C5 | 111.0 (2) | H23a—C23—H23c | 109.7 |
N2—C8—C9 | 109.9 (2) | N6—C23—H23a | 108.7 |
N3—C9—C8 | 109.9 (2) | H23b—C23—H23c | 109.5 |
N3—C11—C12 | 110.3 (2) | N6—C23—H23b | 109.7 |
N4—C12—C13 | 121.4 (2) | N6—C23—H23c | 109.7 |
N4—C12—C11 | 116.0 (2) | H24a—C24—H24b | 109.5 |
C11—C12—C13 | 122.6 (2) | N6—C24—H24a | 109.3 |
C12—C13—C14 | 119.6 (2) | C25—C24—H24a | 109.3 |
C13—C14—C15 | 118.9 (2) | N6—C24—H24b | 109.3 |
C14—C15—C16 | 119.0 (2) | C25—C24—H24b | 109.3 |
N4—C16—C15 | 122.0 (2) | H25a—C25—H25b | 109.5 |
N5—C17—C18 | 122.5 (2) | N7—C25—H25a | 109.5 |
C17—C18—C19 | 118.8 (2) | C24—C25—H25a | 109.5 |
C18—C19—C20 | 119.4 (2) | N7—C25—H25b | 109.5 |
C19—C20—C21 | 119.0 (2) | C24—C25—H25b | 109.5 |
N5—C21—C20 | 121.7 (2) | H26a—C26—H26b | 109.4 |
N5—C21—C22 | 115.9 (2) | H26a—C26—H26c | 109.4 |
C20—C21—C22 | 122.3 (2) | N7—C26—H26a | 109.7 |
N6—C22—C21 | 110.7 (2) | H26b—C26—H26c | 109.5 |
N6—C24—C25 | 110.3 (2) | N7—C26—H26b | 109.4 |
N7—C25—C24 | 109.5 (2) | N7—C26—H26c | 109.4 |
N7—C27—C28 | 110.8 (2) | H27a—C27—H27b | 109.5 |
N8—C28—C29 | 121.8 (2) | N7—C27—H27a | 109.1 |
N8—C28—C27 | 116.0 (2) | C28—C27—H27a | 109.1 |
C27—C28—C29 | 122.2 (2) | N7—C27—H27b | 109.1 |
C28—C29—C30 | 119.2 (2) | C28—C27—H27b | 109.1 |
C29—C30—C31 | 119.4 (2) | C30—C29—H29 | 120.4 |
C30—C31—C32 | 118.6 (2) | C28—C29—H29 | 120.4 |
N8—C32—C31 | 122.4 (2) | C29—C30—H30 | 120.3 |
O2—Cl3—O3 | 109.0 (1) | C31—C30—H30 | 120.3 |
O2—Cl3—O4 | 109.3 (1) | C32—C31—H31 | 120.7 |
O2—Cl3—O5 | 109.4 (1) | C30—C31—H31 | 120.7 |
O3—Cl3—O4 | 110.0 (1) | N8—C32—H32 | 118.8 |
O3—Cl3—O5 | 108.6 (1) | C31—C32—H32 | 118.8 |
O4—Cl3—O5 | 110.5 (1) | HO10a—O10—HO10b | 101.0 |
Cl1—Fe1—Fe2—Cl2 | 128.21 (2) |
Experimental details
Crystal data | |
Chemical formula | [Fe2Cl2O(C16H22N4)2](ClO4)2·0.751H2O |
Mr | 951.83 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 120 |
a, b, c (Å) | 13.632 (3), 17.956 (4), 16.489 (3) |
β (°) | 94.938 (4) |
V (Å3) | 4021 (1) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.05 |
Crystal size (mm) | 0.50 × 0.13 × 0.12 |
Data collection | |
Diffractometer | Siemens SMART CCD diffractometer |
Absorption correction | Integration (XPREP; Siemens, 1995) |
Tmin, Tmax | 0.647, 0.899 |
No. of measured, independent and observed [I > 3σ(I)] reflections | 45381, 12123, 8461 |
Rint | 0.042 |
(sin θ/λ)max (Å−1) | 0.714 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.032, 0.034, 0.88 |
No. of reflections | 8461 |
No. of parameters | 521 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.72 (8), −0.51 (8) |
Computer programs: SMART (Siemens, 1995), SAINT (Siemens, 1995), SAINT, SIR97 (Altomare et al., 1997) and KRYSTAL (Hazell, 1995), modified ORFLS (Busing et al., 1962) and KRYSTAL, ORTEPIII (Burnett & Johnson, 1996) and KRYSTAL, KRYSTAL.
Fe1—Fe2 | 3.623 (1) | Fe2—Cl2 | 2.334 (1) |
Fe1—Cl1 | 2.324 (1) | Fe2—O1 | 1.811 (1) |
Fe1—O1 | 1.814 (1) | Fe2—N5 | 2.169 (2) |
Fe1—N1 | 2.161 (2) | Fe2—N6 | 2.227 (2) |
Fe1—N2 | 2.219 (2) | Fe2—N7 | 2.284 (2) |
Fe1—N3 | 2.296 (2) | Fe2—N8 | 2.164 (2) |
Fe1—N4 | 2.156 (2) | ||
O1—Fe1—N1 | 96.59 (6) | O1—Fe2—N6 | 93.51 (6) |
O1—Fe1—N2 | 92.93 (6) | O1—Fe2—N7 | 165.92 (6) |
O1—Fe1—N3 | 166.23 (6) | O1—Fe2—N8 | 95.58 (6) |
O1—Fe1—N4 | 96.91 (6) | O1—Fe2—Cl2 | 101.56 (4) |
O1—Fe1—Cl1 | 102.00 (4) | N5—Fe2—N6 | 74.92 (6) |
N1—Fe1—N2 | 75.42 (6) | N5—Fe2—N7 | 91.71 (6) |
N1—Fe1—N3 | 91.48 (6) | N5—Fe2—N8 | 164.83 (6) |
N1—Fe1—N4 | 164.24 (6) | N5—Fe2—Cl2 | 92.15 (5) |
N1—Fe1—Cl1 | 93.19 (5) | N6—Fe2—N7 | 78.71 (6) |
N2—Fe1—N3 | 78.29 (6) | N6—Fe2—N8 | 96.87 (6) |
N2—Fe1—N4 | 95.80 (6) | N6—Fe2—Cl2 | 161.39 (4) |
N2—Fe1—Cl1 | 162.25 (4) | N7—Fe2—N8 | 73.99 (6) |
N3—Fe1—N4 | 73.75 (6) | N7—Fe2—Cl2 | 88.54 (4) |
N3—Fe1—Cl1 | 88.62 (4) | N8—Fe2—Cl2 | 92.50 (5) |
N4—Fe1—Cl1 | 91.92 (5) | Fe1—O1—Fe2 | 176.43 (8) |
O1—Fe2—N5 | 97.62 (6) |
The structure of the title complex dinuclear cation (Fig. 1) shows that the two Fe atoms are linked by a µ-oxo bridge; each Fe atom is octahedrally coordinated by the bridging O atom, four N atoms of the bispicMe2en ligand and a Cl atom. The Fe···Fe distance is 3.623 (1) Å; the Fe—O distances are 1.811 (1) and 1.814 (1) Å; Fe—Npyridine distances vary between 2.156 (2) and 2.169 (2) Å (mean 2.163 Å) and are considerably shorter than the Fe—Namine distances which fall into two categories, viz. Fe—N = 2.284 (2) and 2.296 (2) Å for the N atoms trans to the bridging O atom, and 2.219 (2) and 2.227 (2) Å for those trans to Cl. The Fe—Cl distances are 2.324 (1) and 2.334 (1) Å. These distances are similar to those found in the corresponding bispicen complex (2) (see Scheme; Arulsamy et al., 1993) and in the bispicMeen (3) and the trispicMeen (4) complexes (Nivorozhkin et al., 1997). The main differences in the geometries of these compounds are in the angle at the bridging O atom and the orientation of the ligands about the Fe—Fe axis. The Fe—O—Fe angles are 176.43 (8)° in (1), 180.0° in (2) (the O atom is in a special position in the inversion centre), 152.3 (3)° in (3) (the O atom is on a twofold axis) and 177.4 (7)° in (4). The Cl—Fe···Fe—Cl pseudo-torsion angles are 128.21 (2)° in (1), 180.0° in (2), 110.2° in (3) and 141.0° in (4).
The crystals pack with the cations lying in the xy planes at z ≈ 0 or 1/2 which accounts for the crystals growing as needles parallel to the c axis.
The near linearity of the Fe—O—Fe angle in (1) is in agreement with the prediction based on the observed νsym(Fe—O—Fe) in the resonance-Raman spectrum (Hazell et al., 1995). However, this resonance Raman result was not entirely corroborated by magnetic susceptibility measurements (Hazell et al., 1995). Usually strong magnetic exchange coupling is observed for oxo-bridged diiron(III) complexes. The structural characterization now reported sheds some light on this apparent inconsistency. The Fe—O distances in (1) are significantly longer than those found in most singly bridged µ-oxo-diiron(III) units, the mean Fe—O distance, from the Cambridge Structural database (April 2001 release; Allen & Kennard, 1993) is 1.775 Å with an s.u. of 0.001 Å, the three longest Fe—O distances, out of 162 entries are between 1.811 and 1.815 Å, cf. 1.811 and 1.814 Å found for (1). Thus, a markedly weaker exchange coupling for this particular group is consistent with the observed geometry. The electronegative chloride ions cis to the µ-oxo group and the Cl—Fe···Fe—Cl pseudo-torsion angle will influence the Fe—O bond length and consequent overlap integral of the magnetic orbitals.