Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807042857/is2197sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807042857/is2197Isup2.hkl |
CCDC reference: 663565
Tris[(2-pyridinium)methyl]amine perchlorate (0.6017 g, 1.017 mmol), triethylamine (0.63 ml, 4.5 mmol) and sodium acetate (0.0417 g, 1.023 mmol) were dissolved in 40 ml MeOH. Fe(ClO4)3.10H2O (0.5465 g, 1.023 mmol) was dissolved in 2 ml MeOH and this solution was added to the ligand solution. Na2S.9H2O (0.1482 g, 0.6170 mmol) was then added. The mixture was stirred for approximately 20 minutes and then allowed to sit for 20 minutes until a yellow precipitate formed, which was removed by filtration. The resultant filtrate turned bright green and was allowed to sit for four days. Small green rectangular plates formed which were isolated with cold MeOH, dried and dissolved in CH3CN. The solution was placed in a sealed vessel containing ethyl acetate. Yellow-green rectangular plates formed after two days, one of which was selected for structure determination.
Initially the structure was modeled with a single acetonitrile in the asymmetric unit with full occupancy. During refinement, the thermal parameters for this acetontrile grew larger and there was a persistent peak of electron density near the nitrile carbon atom (C1). Since this feature was not in a chemically reasonable position, it was assigned as an oxygen atom (O6) of a water molecule at 25% occupancy and the occupancy of the acetonitrile atoms was fixed at 75%. This produces an apparent close contact between O6 and C1 of 1.15 (2) Å.
The populations of C1, C2, N1 and O6 were refined to evaluate the 3:1 acetonitrile:water ratio. All of the populations increased as did the thermal parameters for the acetonitrile atoms. At the same time R and wR decreased, but not significantly. This model was rejected and the populations were fixed to preserve the 3:1 ratio.
With the exception of the disordered water, the hydrogen atoms were placed in calculated positions and assigned thermal parameters 1.2 times larger than the atoms to which theyµ-Sulfato-1κO:2κO-µ-oxo-bis[tris(2-pyridylmethyl)amine-κ4 N,N',N",N'"]diiron(III) diperchlorate acetonitrile/water (0.75/0.25) solvate are bound. The hydrogen atoms for the water were located in difference maps, and were also assigned thermal parameters 1.2 times larger than the oxygen atom to which they are bound.
As the result of an attempt to synthesize a new class of diiron complexes with a µ-sulfido-µ-carboxylato diiron core using tris-(2-pyridylmethyl)amine (TPA), the title complex, (I), was prepared and structurally characterized. Since the replacement of a µ-oxo ligand by a µ-sulfido ligand has been little studied (Mukherjee et al., 1988), we were not entirely sure what spectroscopic changes would accompany this replacement. To determine whether we had synthesized the desired sulfido-bridged species, we determined the structure. Surprisingly, instead of a µ-sulfido-µ-acetato diiron TPA species we had produced a µ-oxo-µ-sulfato diiron(III) TPA species. The sulfate must have been formed by oxidation of sulfide as no sulfate was added. The source of oxidant is undetermined, but presumably is either perchlorate or atmospheric oxygen. Similarly, a µ-oxo-µ-formato diiron(III) TPA species was produced by aerobic oxidation of a methanol solution of Fe(III) and TPA (Norman et al., 1998).
The structures and spectral properties of several µ-oxo diiron(III) complexes with the TPA ligand have been previously reported (see for example, Norman et al., 1997, or Norman et al., 1998 and references therein). The title complex displays the typical pattern of inequivalent iron sites (Fe1 has the tertiary amine nitrogen atom of TPA trans to the oxo bridge, while Fe2 has the tertiary amine nitrogen atom of TPA cis to the oxo bridge) and a distinctly asymmetric oxo bridge [Fe1—O1 is 1.788 (2) Å and Fe2—O1 is 1.807 (2) Å], with pronounced lengthening of the bonds trans to the oxo bridge (Fig. 1).
Figure 2 is provided to indicate the numbering of atoms in the TPA ligands. Nxy provides the identifiers where x refers to the Fe number and the y identifies the ring. For both TPA ligands, Nx1 is in the Fe1—O1—Fe2 plane. Nx4 is the tertiary amine nitrogen atom.
The preparation of [Fe2(TPA)2O(SO4)](ClO4)2 has been reported at least twice previously (Holz et al., 1993; Hazell et al., 1994), but its structure was not determined. Interestingly, the Fe—O—Fe angle was predicted, based on electronic spectroscopy, to be 134° (Holz et al., 1993) which agrees well with the 133.0 (1)° reported here.
The compound has been reported previously (Holz et al., 1993; Hazell et al., 1994). The structure is typical of a bent µ-oxo–diiron(III) complex with TPA (Norman et al., 1997). The sulfate bridge was produced by oxidation of sulfide, a result similar to the oxidation of methanol to formate in an FeIII TPA system (Norman et al., 1998).
For related literature, see: Mukherjee et al. (1988).
Data collection: COLLECT (Nonius, 2000); cell refinement: HKL SCALEPACK (Otwinowski & Minor, 1997); data reduction: HKL DENZO and SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: TEXSAN for Windows (Molecular Structure Corporation, 1999); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: TEXSAN for Windows (Molecular Structure Corporation, 1999.
[Fe2(C18H18N4)2O(SO4)]4(ClO4)8·3C2H3N·H2O | F(000) = 2132.00 |
Mr = 4154.72 | Dx = 1.675 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.7107 Å |
Hall symbol: -P 2yn | Cell parameters from 14215 reflections |
a = 12.7031 (10) Å | θ = 2.5–32.0° |
b = 24.477 (3) Å | µ = 0.96 mm−1 |
c = 13.6165 (11) Å | T = 90 K |
β = 103.357 (5)° | Lath, yellow-green |
V = 4119.3 (6) Å3 | 0.30 × 0.17 × 0.05 mm |
Z = 1 |
Nonius KappaCCD (with Oxford Cryostream) diffractometer | 14279 independent reflections |
Radiation source: fine-focus sealed tube | 8172 reflections with I > 3σ(I) |
Graphite monochromator | Rint = 0.042 |
ω scans with κ offsets | θmax = 32.0°, θmin = 2.5° |
Absorption correction: multi-scan HKL SCALEPACK (Otwinowski & Minor, 1997) | h = −18→18 |
Tmin = 0.728, Tmax = 0.946 | k = −36→36 |
81911 measured reflections | l = −20→20 |
Refinement on F2 | 0 restraints |
Least-squares matrix: full | 0 constraints |
R[F2 > 2σ(F2)] = 0.054 | H-atom parameters constrained |
wR(F2) = 0.093 | Weighting scheme based on measured s.u.'s w = 1/[σ2(Fo) + 0.000841|Fo|2] |
S = 0.90 | (Δ/σ)max = 0.001 |
8172 reflections | Δρmax = 0.78 e Å−3 |
595 parameters | Δρmin = −0.71 e Å−3 |
[Fe2(C18H18N4)2O(SO4)]4(ClO4)8·3C2H3N·H2O | V = 4119.3 (6) Å3 |
Mr = 4154.72 | Z = 1 |
Monoclinic, P21/n | Mo Kα radiation |
a = 12.7031 (10) Å | µ = 0.96 mm−1 |
b = 24.477 (3) Å | T = 90 K |
c = 13.6165 (11) Å | 0.30 × 0.17 × 0.05 mm |
β = 103.357 (5)° |
Nonius KappaCCD (with Oxford Cryostream) diffractometer | 14279 independent reflections |
Absorption correction: multi-scan HKL SCALEPACK (Otwinowski & Minor, 1997) | 8172 reflections with I > 3σ(I) |
Tmin = 0.728, Tmax = 0.946 | Rint = 0.042 |
81911 measured reflections |
R[F2 > 2σ(F2)] = 0.054 | 0 restraints |
wR(F2) = 0.093 | H-atom parameters constrained |
S = 0.90 | Δρmax = 0.78 e Å−3 |
8172 reflections | Δρmin = −0.71 e Å−3 |
595 parameters |
Refinement. Refinement of F2. The weighted R-factor wR and goodness of fit are based on F2, conventional R-factors R are based on F. R-factors based on F2 are statistically about twice as large as those based on F. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Fe1 | 0.22087 (3) | 0.26340 (2) | 0.93084 (2) | 0.01043 (8) | |
Fe2 | 0.29912 (3) | 0.15787 (2) | 0.81495 (2) | 0.01094 (8) | |
Cl1 | 0.35062 (5) | 0.36704 (3) | 0.38755 (4) | 0.0136 (1) | |
Cl2 | 0.16176 (5) | 0.02549 (3) | 0.36029 (4) | 0.0150 (1) | |
S5 | 0.46963 (5) | 0.23004 (3) | 0.96923 (4) | 0.0123 (1) | |
O1 | 0.20634 (13) | 0.20867 (7) | 0.84171 (11) | 0.0124 (4) | |
O2 | 0.37397 (13) | 0.25008 (7) | 1.00798 (11) | 0.0129 (4) | |
O3 | 0.43271 (13) | 0.17723 (7) | 0.91148 (12) | 0.0161 (4) | |
O4 | 0.55651 (13) | 0.21686 (8) | 1.05476 (12) | 0.0166 (5) | |
O5 | 0.4959 (1) | 0.26959 (8) | 0.89952 (12) | 0.0198 (5) | |
O6 | 0.0659 (13) | 0.4065 (8) | 0.6270 (8) | 0.119 (6) | 0.25 |
O11 | 0.4197 (1) | 0.32356 (8) | 0.36660 (12) | 0.0185 (5) | |
O12 | 0.24272 (13) | 0.34587 (8) | 0.37924 (13) | 0.0204 (5) | |
O13 | 0.3478 (2) | 0.41082 (8) | 0.31582 (13) | 0.0223 (5) | |
O14 | 0.3926 (2) | 0.38753 (8) | 0.48880 (12) | 0.0215 (5) | |
O21 | 0.0775 (1) | −0.00452 (8) | 0.3920 (1) | 0.0244 (5) | |
O22 | 0.1767 (2) | 0.07740 (8) | 0.4111 (1) | 0.0313 (6) | |
O23 | 0.1307 (2) | 0.03407 (9) | 0.25307 (13) | 0.0298 (6) | |
O24 | 0.2609 (1) | −0.00557 (9) | 0.3862 (1) | 0.0264 (5) | |
N1 | 0.0615 (5) | 0.4712 (3) | 0.6607 (5) | 0.112 (3) | 0.75 |
N11 | 0.0673 (2) | 0.30205 (9) | 0.8705 (1) | 0.0125 (5) | |
N12 | 0.2774 (2) | 0.33111 (9) | 0.8582 (1) | 0.0130 (5) | |
N13 | 0.1708 (2) | 0.22604 (9) | 1.0547 (1) | 0.0119 (5) | |
N14 | 0.2234 (2) | 0.33223 (8) | 1.03999 (13) | 0.0121 (5) | |
N21 | 0.3982 (2) | 0.09698 (9) | 0.7557 (2) | 0.0153 (5) | |
N22 | 0.2472 (2) | 0.09465 (9) | 0.9014 (1) | 0.0135 (5) | |
N23 | 0.3084 (2) | 0.19461 (9) | 0.6755 (1) | 0.0134 (5) | |
N24 | 0.1760 (2) | 0.11150 (9) | 0.7049 (1) | 0.0124 (5) | |
C1 | 0.0943 (4) | 0.4470 (2) | 0.5982 (4) | 0.041 (1) | 0.75 |
C2 | 0.1257 (3) | 0.4167 (2) | 0.5289 (3) | 0.0231 (10) | 0.75 |
C111 | 0.0045 (2) | 0.28996 (11) | 0.7787 (2) | 0.0150 (6) | |
C112 | −0.0826 (2) | 0.32136 (12) | 0.7327 (2) | 0.0189 (7) | |
C113 | −0.1098 (2) | 0.36695 (12) | 0.7842 (2) | 0.0206 (7) | |
C114 | −0.0454 (2) | 0.37946 (11) | 0.8778 (2) | 0.0181 (7) | |
C115 | 0.0439 (2) | 0.34687 (10) | 0.9182 (2) | 0.0132 (6) | |
C116 | 0.1165 (2) | 0.35992 (11) | 1.0196 (2) | 0.0153 (6) | |
C121 | 0.2846 (2) | 0.33099 (11) | 0.7613 (2) | 0.0157 (6) | |
C122 | 0.3387 (2) | 0.37159 (11) | 0.7221 (2) | 0.0184 (7) | |
C123 | 0.3848 (2) | 0.41413 (12) | 0.7840 (2) | 0.0191 (7) | |
C124 | 0.3736 (2) | 0.41542 (11) | 0.8834 (2) | 0.0168 (6) | |
C125 | 0.3194 (2) | 0.37323 (10) | 0.9184 (2) | 0.0144 (6) | |
C126 | 0.3123 (2) | 0.36916 (11) | 1.0274 (2) | 0.0164 (6) | |
C131 | 0.1278 (2) | 0.17545 (10) | 1.0520 (2) | 0.0130 (6) | |
C132 | 0.1007 (2) | 0.15191 (11) | 1.1349 (2) | 0.0146 (6) | |
C133 | 0.1142 (2) | 0.18243 (12) | 1.2231 (2) | 0.0163 (6) | |
C134 | 0.1573 (2) | 0.23451 (11) | 1.2264 (2) | 0.0146 (6) | |
C135 | 0.1879 (2) | 0.25491 (10) | 1.1420 (2) | 0.0128 (6) | |
C136 | 0.2468 (2) | 0.30805 (11) | 1.1426 (2) | 0.0144 (6) | |
C211 | 0.5072 (2) | 0.09782 (11) | 0.7736 (2) | 0.0181 (7) | |
C212 | 0.5643 (2) | 0.06486 (12) | 0.7223 (2) | 0.0189 (7) | |
C213 | 0.5072 (2) | 0.03167 (12) | 0.6458 (2) | 0.0217 (7) | |
C214 | 0.3957 (2) | 0.03125 (11) | 0.6247 (2) | 0.0194 (7) | |
C215 | 0.3433 (2) | 0.06357 (10) | 0.6826 (2) | 0.0149 (6) | |
C216 | 0.2224 (2) | 0.06104 (11) | 0.6700 (2) | 0.0145 (6) | |
C221 | 0.3020 (2) | 0.07783 (11) | 0.9932 (2) | 0.0190 (7) | |
C222 | 0.2591 (2) | 0.03969 (12) | 1.0487 (2) | 0.0229 (7) | |
C223 | 0.1578 (2) | 0.01815 (12) | 1.0076 (2) | 0.0229 (7) | |
C224 | 0.1017 (2) | 0.03533 (11) | 0.9122 (2) | 0.0191 (7) | |
C225 | 0.1484 (2) | 0.07404 (11) | 0.8619 (2) | 0.0156 (6) | |
C226 | 0.0923 (2) | 0.09717 (11) | 0.7605 (2) | 0.0151 (6) | |
C231 | 0.3918 (2) | 0.22496 (11) | 0.6615 (2) | 0.0152 (6) | |
C232 | 0.4004 (2) | 0.24110 (11) | 0.5658 (2) | 0.0160 (6) | |
C233 | 0.3215 (2) | 0.22475 (11) | 0.4830 (2) | 0.0157 (6) | |
C234 | 0.2350 (2) | 0.19409 (11) | 0.4975 (2) | 0.0143 (6) | |
C235 | 0.2300 (2) | 0.18008 (10) | 0.5949 (2) | 0.0128 (6) | |
C236 | 0.1359 (2) | 0.14990 (11) | 0.6194 (2) | 0.0146 (6) | |
H1 | 0.1659 | 0.3862 | 0.5606 | 0.028* | 0.75 |
H2 | 0.1698 | 0.4380 | 0.4960 | 0.028* | 0.75 |
H3 | 0.0639 | 0.4042 | 0.4807 | 0.028* | 0.75 |
H4 | 0.0786 | 0.4258 | 0.6894 | 0.143* | 0.25 |
H5 | 0.1336 | 0.3869 | 0.6254 | 0.143* | 0.25 |
H111 | 0.0213 | 0.2584 | 0.7445 | 0.018* | |
H112 | −0.1237 | 0.3124 | 0.6672 | 0.023* | |
H113 | −0.1711 | 0.3887 | 0.7554 | 0.025* | |
H114 | −0.0619 | 0.4101 | 0.9144 | 0.022* | |
H115 | 0.0804 | 0.3492 | 1.0703 | 0.018* | |
H116 | 0.1284 | 0.3983 | 1.0231 | 0.018* | |
H121 | 0.2516 | 0.3022 | 0.7184 | 0.019* | |
H122 | 0.3440 | 0.3703 | 0.6537 | 0.022* | |
H123 | 0.4236 | 0.4421 | 0.7592 | 0.023* | |
H124 | 0.4027 | 0.4449 | 0.9266 | 0.020* | |
H125 | 0.2996 | 0.4046 | 1.0508 | 0.020* | |
H126 | 0.3789 | 0.3555 | 1.0663 | 0.020* | |
H131 | 0.1156 | 0.1553 | 0.9908 | 0.016* | |
H132 | 0.0735 | 0.1157 | 1.1318 | 0.018* | |
H133 | 0.0940 | 0.1676 | 1.2806 | 0.020* | |
H134 | 0.1659 | 0.2561 | 1.2857 | 0.018* | |
H135 | 0.3224 | 0.3018 | 1.1646 | 0.017* | |
H136 | 0.2241 | 0.3327 | 1.1875 | 0.017* | |
H211 | 0.5461 | 0.1220 | 0.8235 | 0.022* | |
H212 | 0.6411 | 0.0649 | 0.7389 | 0.023* | |
H213 | 0.5447 | 0.0093 | 0.6081 | 0.026* | |
H214 | 0.3554 | 0.0093 | 0.5716 | 0.023* | |
H215 | 0.2059 | 0.0309 | 0.7078 | 0.017* | |
H216 | 0.1898 | 0.0557 | 0.6005 | 0.017* | |
H221 | 0.3718 | 0.0925 | 1.0207 | 0.023* | |
H222 | 0.2986 | 0.0286 | 1.1136 | 0.027* | |
H223 | 0.1268 | −0.0081 | 1.0440 | 0.027* | |
H224 | 0.0325 | 0.0206 | 0.8823 | 0.023* | |
H225 | 0.0526 | 0.1289 | 0.7697 | 0.018* | |
H226 | 0.0443 | 0.0707 | 0.7235 | 0.018* | |
H231 | 0.4463 | 0.2357 | 0.7185 | 0.018* | |
H232 | 0.4595 | 0.2630 | 0.5574 | 0.019* | |
H233 | 0.3267 | 0.2345 | 0.4168 | 0.019* | |
H234 | 0.1798 | 0.1828 | 0.4416 | 0.017* | |
H235 | 0.0993 | 0.1299 | 0.5619 | 0.018* | |
H236 | 0.0875 | 0.1754 | 0.6379 | 0.018* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Fe1 | 0.0114 (2) | 0.0108 (2) | 0.0095 (2) | −0.0013 (1) | 0.00342 (12) | −0.00123 (13) |
Fe2 | 0.0098 (2) | 0.0122 (2) | 0.0114 (2) | −0.0019 (1) | 0.00351 (12) | −0.00255 (13) |
Cl1 | 0.0139 (3) | 0.0142 (3) | 0.0123 (3) | 0.0003 (2) | 0.0022 (2) | 0.0000 (2) |
Cl2 | 0.0176 (3) | 0.0125 (3) | 0.0155 (3) | 0.0005 (2) | 0.0050 (2) | −0.0008 (2) |
S5 | 0.0105 (3) | 0.0150 (3) | 0.0115 (3) | −0.0023 (2) | 0.0024 (2) | −0.0025 (2) |
O1 | 0.0120 (8) | 0.0125 (9) | 0.0129 (8) | −0.0013 (7) | 0.0036 (6) | −0.0017 (7) |
O2 | 0.0113 (8) | 0.0155 (9) | 0.0117 (8) | 0.0003 (7) | 0.0025 (6) | −0.0022 (7) |
O3 | 0.0128 (8) | 0.0158 (10) | 0.0185 (9) | −0.0016 (7) | 0.0013 (7) | −0.0064 (7) |
O4 | 0.0133 (8) | 0.0214 (10) | 0.0140 (8) | −0.0006 (8) | 0.0006 (7) | −0.0029 (7) |
O5 | 0.0187 (9) | 0.0236 (11) | 0.0189 (9) | −0.0047 (8) | 0.0076 (7) | 0.0028 (8) |
O6 | 0.122 (12) | 0.21 (2) | 0.032 (6) | 0.14 (1) | 0.034 (7) | 0.041 (9) |
O11 | 0.0195 (9) | 0.0171 (10) | 0.0204 (9) | 0.0031 (8) | 0.0077 (7) | −0.0017 (7) |
O12 | 0.0131 (9) | 0.0247 (11) | 0.0242 (9) | −0.0046 (8) | 0.0060 (7) | −0.0014 (8) |
O13 | 0.0272 (10) | 0.0174 (10) | 0.0215 (10) | −0.0002 (8) | 0.0037 (8) | 0.0055 (8) |
O14 | 0.0242 (10) | 0.0238 (11) | 0.0143 (9) | 0.0007 (9) | 0.0000 (7) | −0.0058 (8) |
O21 | 0.0178 (10) | 0.0219 (11) | 0.0356 (11) | −0.0002 (8) | 0.0106 (8) | 0.0062 (9) |
O22 | 0.0470 (13) | 0.0149 (11) | 0.0315 (11) | −0.0017 (10) | 0.0077 (10) | −0.0082 (9) |
O23 | 0.0487 (13) | 0.0268 (12) | 0.0147 (9) | 0.0088 (10) | 0.0090 (9) | 0.0040 (8) |
O24 | 0.0153 (9) | 0.0271 (12) | 0.0364 (11) | 0.0071 (9) | 0.0048 (8) | 0.0000 (9) |
N1 | 0.115 (5) | 0.126 (6) | 0.117 (5) | −0.037 (4) | 0.072 (4) | −0.091 (5) |
N11 | 0.0140 (10) | 0.0121 (11) | 0.0121 (9) | −0.0021 (8) | 0.0045 (8) | −0.0008 (8) |
N12 | 0.0132 (10) | 0.0111 (11) | 0.0147 (10) | −0.0012 (8) | 0.0030 (8) | −0.0017 (8) |
N13 | 0.0102 (9) | 0.0138 (11) | 0.0117 (9) | 0.0004 (8) | 0.0027 (8) | 0.0002 (8) |
N14 | 0.0138 (10) | 0.0117 (11) | 0.0103 (9) | −0.0017 (8) | 0.0015 (7) | −0.0004 (8) |
N21 | 0.0121 (10) | 0.0167 (12) | 0.0173 (10) | −0.0013 (9) | 0.0040 (8) | −0.0027 (8) |
N22 | 0.0141 (10) | 0.0131 (11) | 0.0144 (10) | 0.0002 (9) | 0.0054 (8) | −0.0019 (8) |
N23 | 0.0122 (10) | 0.0158 (11) | 0.0130 (9) | −0.0022 (8) | 0.0044 (8) | −0.0035 (8) |
N24 | 0.0118 (10) | 0.0115 (11) | 0.0145 (10) | −0.0006 (8) | 0.0046 (8) | −0.0012 (8) |
C1 | 0.031 (2) | 0.039 (3) | 0.051 (3) | −0.014 (2) | 0.007 (2) | 0.000 (2) |
C2 | 0.023 (2) | 0.023 (2) | 0.021 (2) | −0.003 (2) | −0.000 (1) | −0.002 (2) |
C111 | 0.0164 (12) | 0.0146 (13) | 0.0147 (11) | −0.0034 (10) | 0.0053 (10) | −0.0024 (10) |
C112 | 0.0143 (12) | 0.024 (2) | 0.0167 (12) | −0.0028 (11) | −0.0002 (9) | −0.0003 (11) |
C113 | 0.0162 (13) | 0.017 (1) | 0.027 (1) | 0.0021 (11) | 0.0021 (10) | 0.0022 (11) |
C114 | 0.0199 (13) | 0.015 (1) | 0.0186 (12) | 0.0004 (11) | 0.0031 (10) | −0.0016 (10) |
C115 | 0.0153 (11) | 0.0123 (12) | 0.0135 (11) | −0.0013 (10) | 0.0063 (9) | 0.0011 (9) |
C116 | 0.0155 (12) | 0.0146 (13) | 0.0164 (12) | 0.0030 (10) | 0.0048 (10) | −0.0027 (10) |
C121 | 0.0164 (12) | 0.0146 (13) | 0.0170 (12) | 0.0012 (10) | 0.0056 (10) | 0.0009 (10) |
C122 | 0.0206 (13) | 0.020 (2) | 0.0154 (12) | 0.0015 (11) | 0.0066 (10) | 0.0047 (10) |
C123 | 0.0175 (13) | 0.018 (1) | 0.0229 (13) | −0.0010 (11) | 0.0072 (10) | 0.0059 (11) |
C124 | 0.0150 (12) | 0.0124 (13) | 0.0213 (13) | −0.0010 (10) | 0.0006 (10) | −0.0000 (10) |
C125 | 0.0129 (12) | 0.0132 (13) | 0.0168 (12) | 0.0003 (10) | 0.0029 (9) | 0.0005 (10) |
C126 | 0.0197 (13) | 0.0134 (13) | 0.0159 (12) | −0.0062 (11) | 0.0040 (10) | −0.0034 (10) |
C131 | 0.0093 (11) | 0.0166 (13) | 0.0127 (11) | 0.0004 (10) | 0.0020 (9) | −0.0017 (9) |
C132 | 0.0106 (11) | 0.0142 (13) | 0.0179 (12) | 0.0007 (10) | 0.0010 (9) | 0.0035 (10) |
C133 | 0.0132 (12) | 0.023 (2) | 0.0118 (11) | 0.0006 (11) | 0.0021 (9) | 0.0037 (10) |
C134 | 0.0132 (11) | 0.022 (1) | 0.0091 (11) | 0.0022 (11) | 0.0028 (9) | −0.0003 (10) |
C135 | 0.0113 (11) | 0.0137 (13) | 0.0128 (11) | 0.0024 (10) | 0.0018 (9) | −0.0003 (9) |
C136 | 0.0176 (12) | 0.0146 (13) | 0.0109 (11) | −0.0007 (10) | 0.0030 (9) | −0.0009 (9) |
C211 | 0.0135 (12) | 0.020 (2) | 0.0210 (13) | −0.0023 (11) | 0.0043 (10) | −0.0063 (10) |
C212 | 0.0128 (12) | 0.018 (1) | 0.027 (1) | 0.0010 (11) | 0.0070 (10) | −0.0025 (11) |
C213 | 0.0197 (13) | 0.020 (2) | 0.030 (1) | −0.0000 (11) | 0.0130 (11) | −0.0070 (11) |
C214 | 0.0169 (12) | 0.018 (1) | 0.0239 (13) | −0.0013 (11) | 0.0061 (10) | −0.0084 (11) |
C215 | 0.0155 (12) | 0.0116 (13) | 0.0192 (12) | −0.0018 (10) | 0.0070 (10) | −0.0027 (10) |
C216 | 0.0136 (11) | 0.0141 (13) | 0.0160 (11) | −0.0030 (10) | 0.0038 (9) | −0.0039 (9) |
C221 | 0.0190 (13) | 0.015 (1) | 0.0239 (13) | 0.0029 (11) | 0.0065 (10) | 0.0002 (11) |
C222 | 0.029 (2) | 0.018 (2) | 0.0222 (13) | 0.0064 (12) | 0.0086 (12) | 0.0051 (11) |
C223 | 0.030 (2) | 0.015 (1) | 0.030 (1) | 0.0012 (12) | 0.0183 (12) | 0.0026 (11) |
C224 | 0.0188 (13) | 0.016 (1) | 0.0263 (13) | −0.0020 (11) | 0.0130 (11) | −0.0030 (11) |
C225 | 0.0166 (12) | 0.0124 (13) | 0.0201 (12) | 0.0009 (10) | 0.0089 (10) | −0.0043 (10) |
C226 | 0.0111 (11) | 0.0153 (13) | 0.0203 (12) | −0.0023 (10) | 0.0066 (9) | −0.0044 (10) |
C231 | 0.0139 (12) | 0.017 (1) | 0.0158 (12) | −0.0032 (10) | 0.0048 (9) | −0.0028 (10) |
C232 | 0.0143 (12) | 0.018 (1) | 0.0164 (12) | −0.0036 (10) | 0.0058 (9) | −0.0019 (10) |
C233 | 0.0192 (13) | 0.0144 (13) | 0.0139 (11) | 0.0023 (10) | 0.0049 (10) | 0.0013 (9) |
C234 | 0.0149 (12) | 0.0156 (13) | 0.0119 (11) | 0.0022 (10) | 0.0017 (9) | −0.0011 (9) |
C235 | 0.0100 (11) | 0.0130 (13) | 0.0155 (11) | 0.0010 (9) | 0.0035 (9) | −0.0023 (9) |
C236 | 0.0106 (11) | 0.017 (1) | 0.0154 (11) | −0.0008 (10) | 0.0016 (9) | −0.0031 (10) |
Fe1—O1 | 1.788 (2) | C135—C136 | 1.499 (3) |
Fe1—O2 | 2.012 (2) | C211—C212 | 1.379 (3) |
Fe1—N11 | 2.153 (2) | C212—C213 | 1.386 (4) |
Fe1—N12 | 2.138 (2) | C213—C214 | 1.379 (4) |
Fe1—N13 | 2.140 (2) | C214—C215 | 1.391 (3) |
Fe1—N14 | 2.242 (2) | C215—C216 | 1.506 (3) |
Fe2—O1 | 1.807 (2) | C221—C222 | 1.389 (4) |
Fe2—O3 | 1.950 (2) | C222—C223 | 1.384 (4) |
Fe2—N21 | 2.220 (2) | C223—C224 | 1.395 (4) |
Fe2—N22 | 2.138 (2) | C224—C225 | 1.380 (3) |
Fe2—N23 | 2.129 (2) | C225—C226 | 1.511 (4) |
Fe2—N24 | 2.213 (2) | C231—C232 | 1.390 (3) |
Cl1—O11 | 1.449 (2) | C232—C233 | 1.383 (3) |
Cl1—O12 | 1.445 (2) | C233—C234 | 1.382 (3) |
Cl1—O13 | 1.445 (2) | C234—C235 | 1.385 (3) |
Cl1—O14 | 1.448 (2) | C235—C236 | 1.507 (3) |
Cl2—O21 | 1.444 (2) | O6—H4 | 0.951 |
Cl2—O22 | 1.438 (2) | O6—H5 | 0.991 |
Cl2—O23 | 1.437 (2) | C2—H1 | 0.950 |
Cl2—O24 | 1.444 (2) | C2—H2 | 0.950 |
S5—O2 | 1.514 (2) | C2—H3 | 0.950 |
S5—O3 | 1.529 (2) | C111—H111 | 0.950 |
S5—O4 | 1.444 (2) | C112—H112 | 0.950 |
S5—O5 | 1.448 (2) | C113—H113 | 0.950 |
N1—C1 | 1.188 (7) | C114—H114 | 0.950 |
N11—C111 | 1.351 (3) | C116—H115 | 0.950 |
N11—C115 | 1.343 (3) | C116—H116 | 0.950 |
N12—C121 | 1.344 (3) | C121—H121 | 0.950 |
N12—C125 | 1.348 (3) | C122—H122 | 0.950 |
N13—C131 | 1.351 (3) | C123—H123 | 0.950 |
N13—C135 | 1.356 (3) | C124—H124 | 0.950 |
N14—C116 | 1.486 (3) | C126—H125 | 0.950 |
N14—C126 | 1.487 (3) | C126—H126 | 0.950 |
N14—C136 | 1.482 (3) | C131—H131 | 0.950 |
N21—C211 | 1.349 (3) | C132—H132 | 0.950 |
N21—C215 | 1.351 (3) | C133—H133 | 0.950 |
N22—C221 | 1.347 (3) | C134—H134 | 0.950 |
N22—C225 | 1.345 (3) | C136—H135 | 0.950 |
N23—C231 | 1.343 (3) | C136—H136 | 0.950 |
N23—C235 | 1.348 (3) | C211—H211 | 0.950 |
N24—C216 | 1.492 (3) | C212—H212 | 0.950 |
N24—C226 | 1.483 (3) | C213—H213 | 0.950 |
N24—C236 | 1.491 (3) | C214—H214 | 0.950 |
C1—C2 | 1.332 (6) | C216—H215 | 0.950 |
C111—C112 | 1.373 (4) | C216—H216 | 0.950 |
C112—C113 | 1.403 (4) | C221—H221 | 0.950 |
C113—C114 | 1.380 (4) | C222—H222 | 0.950 |
C114—C115 | 1.392 (4) | C223—H223 | 0.950 |
C115—C116 | 1.506 (3) | C224—H224 | 0.950 |
C121—C122 | 1.383 (3) | C226—H225 | 0.950 |
C122—C123 | 1.382 (4) | C226—H226 | 0.950 |
C123—C124 | 1.392 (3) | C231—H231 | 0.950 |
C124—C125 | 1.385 (3) | C232—H232 | 0.950 |
C125—C126 | 1.511 (3) | C233—H233 | 0.950 |
C131—C132 | 1.379 (3) | C234—H234 | 0.950 |
C132—C133 | 1.390 (4) | C236—H235 | 0.950 |
C133—C134 | 1.384 (4) | C236—H236 | 0.950 |
C134—C135 | 1.389 (3) | ||
O14···C132i | 3.074 (3) | O14···C223iv | 3.263 (4) |
O22···C234 | 3.113 (3) | O4···C111ii | 3.269 (3) |
O4···O6ii | 3.17 (2) | O24···C212iii | 3.277 (3) |
O24···C213iii | 3.141 (3) | O12···C2 | 3.281 (4) |
O5···C234ii | 3.150 (3) | N1···N21iv | 3.282 (7) |
N1···C215iv | 3.152 (6) | O23···C132vi | 3.282 (3) |
O13···O23v | 3.190 (3) | O11···C233 | 3.291 (3) |
N1···C214iv | 3.204 (6) | O14···C131i | 3.294 (3) |
O11···C131i | 3.206 (3) | ||
O1—Fe1—O2 | 99.71 (7) | C212—C213—C214 | 119.6 (2) |
O1—Fe1—N11 | 97.34 (8) | C213—C214—C215 | 118.8 (2) |
O1—Fe1—N12 | 105.07 (7) | N21—C215—C214 | 121.9 (2) |
O1—Fe1—N13 | 102.23 (8) | N21—C215—C216 | 116.7 (2) |
O1—Fe1—N14 | 175.05 (7) | C214—C215—C216 | 121.4 (2) |
O2—Fe1—N11 | 162.14 (8) | N24—C216—C215 | 113.4 (2) |
O2—Fe1—N12 | 88.82 (7) | N22—C221—C222 | 121.8 (2) |
O2—Fe1—N13 | 86.95 (7) | C221—C222—C223 | 118.8 (2) |
O2—Fe1—N14 | 84.91 (7) | C222—C223—C224 | 119.2 (2) |
N11—Fe1—N12 | 81.63 (8) | C223—C224—C225 | 118.9 (2) |
N11—Fe1—N13 | 94.63 (7) | N22—C225—C224 | 121.9 (2) |
N11—Fe1—N14 | 78.23 (7) | N22—C225—C226 | 115.1 (2) |
N12—Fe1—N13 | 152.70 (8) | C224—C225—C226 | 123.0 (2) |
N12—Fe1—N14 | 76.64 (7) | N24—C226—C225 | 108.2 (2) |
N13—Fe1—N14 | 76.12 (7) | N23—C231—C232 | 121.8 (2) |
O1—Fe2—O3 | 101.74 (7) | C231—C232—C233 | 118.8 (2) |
O1—Fe2—N21 | 170.51 (7) | C232—C233—C234 | 119.4 (2) |
O1—Fe2—N22 | 95.09 (7) | C233—C234—C235 | 119.0 (2) |
O1—Fe2—N23 | 93.57 (8) | N23—C235—C234 | 121.7 (2) |
O1—Fe2—N24 | 95.61 (7) | N23—C235—C236 | 115.1 (2) |
O3—Fe2—N21 | 85.97 (7) | C234—C235—C236 | 123.2 (2) |
O3—Fe2—N22 | 97.82 (7) | N24—C236—C235 | 109.7 (2) |
O3—Fe2—N23 | 106.23 (8) | H4—O6—H5 | 106.94 |
O3—Fe2—N24 | 161.81 (8) | C1—C2—H1 | 109.47 |
N21—Fe2—N22 | 89.26 (8) | C1—C2—H2 | 109.47 |
N21—Fe2—N23 | 78.83 (8) | C1—C2—H3 | 109.47 |
N21—Fe2—N24 | 77.34 (7) | H1—C2—H2 | 109.47 |
N22—Fe2—N23 | 152.16 (8) | H1—C2—H3 | 109.47 |
N22—Fe2—N24 | 75.04 (7) | H2—C2—H3 | 109.47 |
N23—Fe2—N24 | 77.81 (7) | N11—C111—H111 | 118.65 |
O11—Cl1—O12 | 109.2 (1) | C112—C111—H111 | 118.65 |
O11—Cl1—O13 | 109.4 (1) | C111—C112—H112 | 120.57 |
O11—Cl1—O14 | 109.6 (1) | C113—C112—H112 | 120.57 |
O12—Cl1—O13 | 109.8 (1) | C112—C113—H113 | 120.78 |
O12—Cl1—O14 | 109.5 (1) | C114—C113—H113 | 120.78 |
O13—Cl1—O14 | 109.4 (1) | C113—C114—H114 | 120.23 |
O21—Cl2—O22 | 109.3 (1) | C115—C114—H114 | 120.23 |
O21—Cl2—O23 | 109.2 (1) | N14—C116—H115 | 108.21 |
O21—Cl2—O24 | 108.9 (1) | N14—C116—H116 | 108.21 |
O22—Cl2—O23 | 109.5 (1) | C115—C116—H115 | 108.21 |
O22—Cl2—O24 | 109.7 (1) | C115—C116—H116 | 108.21 |
O23—Cl2—O24 | 110.2 (1) | H115—C116—H116 | 109.46 |
O2—S5—O3 | 106.1 (1) | N12—C121—H121 | 119.01 |
O2—S5—O4 | 108.47 (9) | C122—C121—H121 | 119.02 |
O2—S5—O5 | 109.7 (1) | C121—C122—H122 | 120.51 |
O3—S5—O4 | 108.2 (1) | C123—C122—H122 | 120.51 |
O3—S5—O5 | 108.5 (1) | C122—C123—H123 | 120.48 |
O4—S5—O5 | 115.4 (1) | C124—C123—H123 | 120.48 |
Fe1—O1—Fe2 | 133.0 (1) | C123—C124—H124 | 120.40 |
Fe1—O2—S5 | 128.9 (1) | C125—C124—H124 | 120.40 |
Fe2—O3—S5 | 131.9 (1) | N14—C126—H125 | 108.86 |
Fe1—N11—C111 | 123.1 (2) | N14—C126—H126 | 108.86 |
Fe1—N11—C115 | 117.1 (2) | C125—C126—H125 | 108.86 |
C111—N11—C115 | 118.5 (2) | C125—C126—H126 | 108.86 |
Fe1—N12—C121 | 124.0 (2) | H125—C126—H126 | 109.46 |
Fe1—N12—C125 | 116.1 (2) | N13—C131—H131 | 118.78 |
C121—N12—C125 | 119.4 (2) | C132—C131—H131 | 118.78 |
Fe1—N13—C131 | 124.2 (2) | C131—C132—H132 | 120.73 |
Fe1—N13—C135 | 116.8 (2) | C133—C132—H132 | 120.73 |
C131—N13—C135 | 118.9 (2) | C132—C133—H133 | 120.26 |
Fe1—N14—C116 | 110.2 (1) | C134—C133—H133 | 120.26 |
Fe1—N14—C126 | 106.0 (1) | C133—C134—H134 | 120.38 |
Fe1—N14—C136 | 107.1 (1) | C135—C134—H134 | 120.38 |
C116—N14—C126 | 112.8 (2) | N14—C136—H135 | 109.22 |
C116—N14—C136 | 109.5 (2) | N14—C136—H136 | 109.22 |
C126—N14—C136 | 111.1 (2) | C135—C136—H135 | 109.22 |
Fe2—N21—C211 | 124.6 (2) | C135—C136—H136 | 109.22 |
Fe2—N21—C215 | 115.7 (2) | H135—C136—H136 | 109.46 |
C211—N21—C215 | 118.5 (2) | N21—C211—H211 | 118.75 |
Fe2—N22—C221 | 125.0 (2) | C212—C211—H211 | 118.75 |
Fe2—N22—C225 | 115.5 (2) | C211—C212—H212 | 120.69 |
C221—N22—C225 | 119.4 (2) | C213—C212—H212 | 120.69 |
Fe2—N23—C231 | 124.7 (2) | C212—C213—H213 | 120.18 |
Fe2—N23—C235 | 115.6 (2) | C214—C213—H213 | 120.18 |
C231—N23—C235 | 119.3 (2) | C213—C214—H214 | 120.62 |
Fe2—N24—C216 | 111.8 (1) | C215—C214—H214 | 120.62 |
Fe2—N24—C226 | 104.7 (1) | N24—C216—H215 | 108.49 |
Fe2—N24—C236 | 105.4 (1) | N24—C216—H216 | 108.49 |
C216—N24—C226 | 110.4 (2) | C215—C216—H215 | 108.49 |
C216—N24—C236 | 111.2 (2) | C215—C216—H216 | 108.49 |
C226—N24—C236 | 113.0 (2) | H215—C216—H216 | 109.46 |
N1—C1—C2 | 175.5 (6) | N22—C221—H221 | 119.10 |
N11—C111—C112 | 122.7 (2) | C222—C221—H221 | 119.10 |
C111—C112—C113 | 118.9 (2) | C221—C222—H222 | 120.61 |
C112—C113—C114 | 118.4 (2) | C223—C222—H222 | 120.61 |
C113—C114—C115 | 119.5 (2) | C222—C223—H223 | 120.38 |
N11—C115—C114 | 121.8 (2) | C224—C223—H223 | 120.38 |
N11—C115—C116 | 117.4 (2) | C223—C224—H224 | 120.54 |
C114—C115—C116 | 120.7 (2) | C225—C224—H224 | 120.54 |
N14—C116—C115 | 114.5 (2) | N24—C226—H225 | 109.78 |
N12—C121—C122 | 122.0 (2) | N24—C226—H226 | 109.78 |
C121—C122—C123 | 119.0 (2) | C225—C226—H225 | 109.78 |
C122—C123—C124 | 119.0 (2) | C225—C226—H226 | 109.78 |
C123—C124—C125 | 119.2 (2) | H225—C226—H226 | 109.46 |
N12—C125—C124 | 121.3 (2) | N23—C231—H231 | 119.12 |
N12—C125—C126 | 116.2 (2) | C232—C231—H231 | 119.12 |
C124—C125—C126 | 122.3 (2) | C231—C232—H232 | 120.59 |
N14—C126—C125 | 111.9 (2) | C233—C232—H232 | 120.59 |
N13—C131—C132 | 122.4 (2) | C232—C233—H233 | 120.30 |
C131—C132—C133 | 118.5 (2) | C234—C233—H233 | 120.30 |
C132—C133—C134 | 119.5 (2) | C233—C234—H234 | 120.49 |
C133—C134—C135 | 119.2 (2) | C235—C234—H234 | 120.49 |
N13—C135—C134 | 121.3 (2) | N24—C236—H235 | 109.42 |
N13—C135—C136 | 115.8 (2) | N24—C236—H236 | 109.42 |
C134—C135—C136 | 122.8 (2) | C235—C236—H235 | 109.42 |
N14—C136—C135 | 110.5 (2) | C235—C236—H236 | 109.42 |
N21—C211—C212 | 122.5 (2) | H235—C236—H236 | 109.46 |
C211—C212—C213 | 118.6 (2) | ||
Fe1—O1—Fe2—O3 | −0.8 (1) | N13—Fe1—N11—C111 | −116.5 (2) |
Fe1—O1—Fe2—N21 | −144.7 (4) | N13—Fe1—N11—C115 | 76.4 (2) |
Fe1—O1—Fe2—N22 | 98.3 (1) | N13—Fe1—N12—C121 | −171.6 (2) |
Fe1—O1—Fe2—N23 | −108.2 (1) | N13—Fe1—N12—C125 | 16.3 (3) |
Fe1—O1—Fe2—N24 | 173.7 (1) | N13—Fe1—N14—C116 | −90.0 (1) |
Fe1—O2—S5—O3 | −53.0 (2) | N13—Fe1—N14—C126 | 147.7 (2) |
Fe1—O2—S5—O4 | −169.0 (1) | N13—Fe1—N14—C136 | 29.0 (1) |
Fe1—O2—S5—O5 | 64.1 (2) | N13—C131—C132—C133 | 2.8 (4) |
Fe1—N11—C111—C112 | −167.5 (2) | N13—C135—C134—C133 | 3.7 (4) |
Fe1—N11—C115—C114 | 170.6 (2) | N13—C135—C136—N14 | 30.5 (3) |
Fe1—N11—C115—C116 | −11.2 (3) | N14—Fe1—N11—C111 | 168.8 (2) |
Fe1—N12—C121—C122 | −168.6 (2) | N14—Fe1—N11—C115 | 1.6 (2) |
Fe1—N12—C125—C124 | 169.9 (2) | N14—Fe1—N12—C121 | −167.6 (2) |
Fe1—N12—C125—C126 | −5.1 (3) | N14—Fe1—N12—C125 | 20.4 (2) |
Fe1—N13—C131—C132 | 177.2 (2) | N14—Fe1—N13—C131 | 168.2 (2) |
Fe1—N13—C135—C134 | 179.3 (2) | N14—Fe1—N13—C135 | −14.4 (2) |
Fe1—N13—C135—C136 | −3.9 (3) | N14—C116—C115—C114 | −163.5 (2) |
Fe1—N14—C116—C115 | −15.7 (2) | N14—C126—C125—C124 | 161.7 (2) |
Fe1—N14—C126—C125 | 37.3 (2) | N14—C136—C135—C134 | −152.8 (2) |
Fe1—N14—C136—C135 | −39.7 (2) | N21—Fe2—N22—C221 | 84.7 (2) |
Fe2—O1—Fe1—O2 | −4.8 (1) | N21—Fe2—N22—C225 | −100.5 (2) |
Fe2—O1—Fe1—N11 | 169.9 (1) | N21—Fe2—N23—C231 | −82.7 (2) |
Fe2—O1—Fe1—N12 | 86.6 (1) | N21—Fe2—N23—C235 | 89.0 (2) |
Fe2—O1—Fe1—N13 | −93.7 (1) | N21—Fe2—N24—C216 | 11.2 (1) |
Fe2—O1—Fe1—N14 | −163.8 (8) | N21—Fe2—N24—C226 | 130.8 (2) |
Fe2—O3—S5—O2 | 43.9 (2) | N21—Fe2—N24—C236 | −109.8 (1) |
Fe2—O3—S5—O4 | 160.1 (1) | N21—C211—C212—C213 | 3.4 (4) |
Fe2—O3—S5—O5 | −73.9 (2) | N21—C215—C214—C213 | 2.9 (4) |
Fe2—N21—C211—C212 | −169.0 (2) | N21—C215—C216—N24 | 25.8 (3) |
Fe2—N21—C215—C214 | 166.9 (2) | N22—Fe2—N21—C211 | −115.4 (2) |
Fe2—N21—C215—C216 | −15.8 (3) | N22—Fe2—N21—C215 | 77.2 (2) |
Fe2—N22—C221—C222 | 174.5 (2) | N22—Fe2—N23—C231 | −149.0 (2) |
Fe2—N22—C225—C224 | −176.1 (2) | N22—Fe2—N23—C235 | 22.7 (3) |
Fe2—N22—C225—C226 | 2.7 (3) | N22—Fe2—N24—C216 | −81.4 (2) |
Fe2—N23—C231—C232 | 170.4 (2) | N22—Fe2—N24—C226 | 38.1 (1) |
Fe2—N23—C235—C234 | −170.0 (2) | N22—Fe2—N24—C236 | 157.6 (1) |
Fe2—N23—C235—C236 | 12.4 (3) | N22—C221—C222—C223 | 0.6 (4) |
Fe2—N24—C216—C215 | −22.5 (2) | N22—C225—C224—C223 | 1.5 (4) |
Fe2—N24—C226—C225 | −47.8 (2) | N22—C225—C226—N24 | 31.7 (3) |
Fe2—N24—C236—C235 | 43.0 (2) | N23—Fe2—N21—C211 | 89.9 (2) |
S5—O2—Fe1—O1 | 36.1 (1) | N23—Fe2—N21—C215 | −77.5 (2) |
S5—O2—Fe1—N11 | −126.4 (2) | N23—Fe2—N22—C221 | 148.7 (2) |
S5—O2—Fe1—N12 | −68.9 (1) | N23—Fe2—N22—C225 | −36.5 (3) |
S5—O2—Fe1—N13 | 138.0 (1) | N23—Fe2—N24—C216 | 92.3 (2) |
S5—O2—Fe1—N14 | −145.6 (1) | N23—Fe2—N24—C226 | −148.1 (2) |
S5—O3—Fe2—O1 | −20.1 (1) | N23—Fe2—N24—C236 | −28.6 (1) |
S5—O3—Fe2—N21 | 154.3 (1) | N23—C231—C232—C233 | −0.8 (4) |
S5—O3—Fe2—N22 | −117.0 (1) | N23—C235—C234—C233 | −1.4 (4) |
S5—O3—Fe2—N23 | 77.2 (1) | N23—C235—C236—N24 | −38.6 (3) |
S5—O3—Fe2—N24 | 177.6 (2) | N24—Fe2—N21—C211 | 169.8 (2) |
O1—Fe1—N11—C111 | −13.5 (2) | N24—Fe2—N21—C215 | 2.3 (2) |
O1—Fe1—N11—C115 | 179.4 (2) | N24—Fe2—N22—C221 | 161.8 (2) |
O1—Fe1—N12—C121 | 7.6 (2) | N24—Fe2—N22—C225 | −23.4 (2) |
O1—Fe1—N12—C125 | −164.4 (2) | N24—Fe2—N23—C231 | −162.0 (2) |
O1—Fe1—N13—C131 | −7.0 (2) | N24—Fe2—N23—C235 | 9.7 (2) |
O1—Fe1—N13—C135 | 170.4 (2) | N24—C216—C215—C214 | −156.9 (2) |
O1—Fe1—N14—C116 | −18.8 (9) | N24—C226—C225—C224 | −149.5 (2) |
O1—Fe1—N14—C126 | −141.2 (8) | N24—C236—C235—C234 | 143.8 (2) |
O1—Fe1—N14—C136 | 100.2 (8) | C111—N11—C115—C114 | 2.9 (3) |
O1—Fe2—N21—C211 | 127.2 (4) | C111—N11—C115—C116 | −178.9 (2) |
O1—Fe2—N21—C215 | −40.2 (6) | C111—C112—C113—C114 | 2.2 (4) |
O1—Fe2—N22—C221 | −103.7 (2) | C112—C111—N11—C115 | −0.5 (3) |
O1—Fe2—N22—C225 | 71.1 (2) | C112—C113—C114—C115 | 0.0 (4) |
O1—Fe2—N23—C231 | 103.0 (2) | C113—C114—C115—C116 | 179.2 (2) |
O1—Fe2—N23—C235 | −85.2 (2) | C115—C116—N14—C126 | 102.6 (2) |
O1—Fe2—N24—C216 | −175.2 (1) | C115—C116—N14—C136 | −133.2 (2) |
O1—Fe2—N24—C226 | −55.7 (2) | C116—N14—C126—C125 | −83.4 (2) |
O1—Fe2—N24—C236 | 63.8 (1) | C116—N14—C136—C135 | 79.8 (2) |
O2—Fe1—N11—C111 | 149.1 (2) | C121—N12—C125—C124 | −2.5 (4) |
O2—Fe1—N11—C115 | −18.0 (3) | C121—N12—C125—C126 | −177.5 (2) |
O2—Fe1—N12—C121 | 107.3 (2) | C121—C122—C123—C124 | −1.3 (4) |
O2—Fe1—N12—C125 | −64.7 (2) | C122—C121—N12—C125 | 3.2 (4) |
O2—Fe1—N13—C131 | −106.3 (2) | C122—C123—C124—C125 | 1.9 (4) |
O2—Fe1—N13—C135 | 71.1 (2) | C123—C124—C125—C126 | 174.6 (2) |
O2—Fe1—N14—C116 | −178.1 (1) | C125—C126—N14—C136 | 153.3 (2) |
O2—Fe1—N14—C126 | 59.6 (1) | C126—N14—C136—C135 | −155.0 (2) |
O2—Fe1—N14—C136 | −59.1 (1) | C131—N13—C135—C134 | −3.1 (3) |
O3—Fe2—N21—C211 | −17.5 (2) | C131—N13—C135—C136 | 173.6 (2) |
O3—Fe2—N21—C215 | 175.1 (2) | C131—C132—C133—C134 | −2.1 (4) |
O3—Fe2—N22—C221 | −1.1 (2) | C132—C131—N13—C135 | −0.2 (3) |
O3—Fe2—N22—C225 | 173.7 (2) | C132—C133—C134—C135 | −1.1 (4) |
O3—Fe2—N23—C231 | −0.3 (2) | C133—C134—C135—C136 | −172.8 (2) |
O3—Fe2—N23—C235 | 171.4 (2) | C211—N21—C215—C214 | −1.4 (4) |
O3—Fe2—N24—C216 | −12.7 (3) | C211—N21—C215—C216 | 175.9 (2) |
O3—Fe2—N24—C226 | 106.9 (2) | C211—C212—C213—C214 | −1.7 (4) |
O3—Fe2—N24—C236 | −133.6 (2) | C212—C211—N21—C215 | −1.8 (4) |
N11—Fe1—N12—C121 | −87.8 (2) | C212—C213—C214—C215 | −1.3 (4) |
N11—Fe1—N12—C125 | 100.2 (2) | C213—C214—C215—C216 | −174.2 (2) |
N11—Fe1—N13—C131 | 91.5 (2) | C215—C216—N24—C226 | −138.6 (2) |
N11—Fe1—N13—C135 | −91.1 (2) | C215—C216—N24—C236 | 95.0 (2) |
N11—Fe1—N14—C116 | 7.8 (1) | C216—N24—C226—C225 | 72.6 (2) |
N11—Fe1—N14—C126 | −114.5 (2) | C216—N24—C236—C235 | −78.3 (2) |
N11—Fe1—N14—C136 | 126.9 (1) | C221—N22—C225—C224 | −1.0 (4) |
N11—C111—C112—C113 | −2.0 (4) | C221—N22—C225—C226 | 177.8 (2) |
N11—C115—C114—C113 | −2.6 (4) | C221—C222—C223—C224 | −0.1 (4) |
N11—C115—C116—N14 | 18.3 (3) | C222—C221—N22—C225 | −0.1 (4) |
N12—Fe1—N11—C111 | 90.8 (2) | C222—C223—C224—C225 | −0.9 (4) |
N12—Fe1—N11—C115 | −76.4 (2) | C223—C224—C225—C226 | −177.2 (2) |
N12—Fe1—N13—C131 | 172.2 (2) | C225—C226—N24—C236 | −162.0 (2) |
N12—Fe1—N13—C135 | −10.4 (3) | C226—N24—C236—C235 | 156.8 (2) |
N12—Fe1—N14—C116 | 91.9 (2) | C231—N23—C235—C234 | 2.2 (4) |
N12—Fe1—N14—C126 | −30.4 (1) | C231—N23—C235—C236 | −175.4 (2) |
N12—Fe1—N14—C136 | −149.1 (2) | C231—C232—C233—C234 | 1.6 (4) |
N12—C121—C122—C123 | −1.3 (4) | C232—C231—N23—C235 | −1.1 (4) |
N12—C125—C124—C123 | −0.1 (4) | C232—C233—C234—C235 | −0.6 (4) |
N12—C125—C126—N14 | −23.4 (3) | C233—C234—C235—C236 | 176.0 (2) |
Symmetry codes: (i) x+1/2, −y+1/2, z−1/2; (ii) x+1/2, −y+1/2, z+1/2; (iii) −x+1, −y, −z+1; (iv) −x+1/2, y+1/2, −z+3/2; (v) −x+1/2, y+1/2, −z+1/2; (vi) x, y, z−1. |
Experimental details
Crystal data | |
Chemical formula | [Fe2(C18H18N4)2O(SO4)]4(ClO4)8·3C2H3N·H2O |
Mr | 4154.72 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 90 |
a, b, c (Å) | 12.7031 (10), 24.477 (3), 13.6165 (11) |
β (°) | 103.357 (5) |
V (Å3) | 4119.3 (6) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 0.96 |
Crystal size (mm) | 0.30 × 0.17 × 0.05 |
Data collection | |
Diffractometer | Nonius KappaCCD (with Oxford Cryostream) |
Absorption correction | Multi-scan HKL SCALEPACK (Otwinowski & Minor, 1997) |
Tmin, Tmax | 0.728, 0.946 |
No. of measured, independent and observed [I > 3σ(I)] reflections | 81911, 14279, 8172 |
Rint | 0.042 |
(sin θ/λ)max (Å−1) | 0.746 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.054, 0.093, 0.90 |
No. of reflections | 8172 |
No. of parameters | 595 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.78, −0.71 |
Computer programs: COLLECT (Nonius, 2000), HKL SCALEPACK (Otwinowski & Minor, 1997), HKL DENZO and SCALEPACK (Otwinowski & Minor, 1997), SIR92 (Altomare et al., 1993), TEXSAN for Windows (Molecular Structure Corporation, 1999), ORTEPII (Johnson, 1976), TEXSAN for Windows (Molecular Structure Corporation, 1999.
Fe1—O1 | 1.788 (2) | Fe2—O1 | 1.807 (2) |
Fe1—O2 | 2.012 (2) | Fe2—O3 | 1.950 (2) |
Fe1—N11 | 2.153 (2) | Fe2—N21 | 2.220 (2) |
Fe1—N12 | 2.138 (2) | Fe2—N22 | 2.138 (2) |
Fe1—N13 | 2.140 (2) | Fe2—N23 | 2.129 (2) |
Fe1—N14 | 2.242 (2) | Fe2—N24 | 2.213 (2) |
Fe1—O1—Fe2 | 133.0 (1) |
As the result of an attempt to synthesize a new class of diiron complexes with a µ-sulfido-µ-carboxylato diiron core using tris-(2-pyridylmethyl)amine (TPA), the title complex, (I), was prepared and structurally characterized. Since the replacement of a µ-oxo ligand by a µ-sulfido ligand has been little studied (Mukherjee et al., 1988), we were not entirely sure what spectroscopic changes would accompany this replacement. To determine whether we had synthesized the desired sulfido-bridged species, we determined the structure. Surprisingly, instead of a µ-sulfido-µ-acetato diiron TPA species we had produced a µ-oxo-µ-sulfato diiron(III) TPA species. The sulfate must have been formed by oxidation of sulfide as no sulfate was added. The source of oxidant is undetermined, but presumably is either perchlorate or atmospheric oxygen. Similarly, a µ-oxo-µ-formato diiron(III) TPA species was produced by aerobic oxidation of a methanol solution of Fe(III) and TPA (Norman et al., 1998).
The structures and spectral properties of several µ-oxo diiron(III) complexes with the TPA ligand have been previously reported (see for example, Norman et al., 1997, or Norman et al., 1998 and references therein). The title complex displays the typical pattern of inequivalent iron sites (Fe1 has the tertiary amine nitrogen atom of TPA trans to the oxo bridge, while Fe2 has the tertiary amine nitrogen atom of TPA cis to the oxo bridge) and a distinctly asymmetric oxo bridge [Fe1—O1 is 1.788 (2) Å and Fe2—O1 is 1.807 (2) Å], with pronounced lengthening of the bonds trans to the oxo bridge (Fig. 1).
Figure 2 is provided to indicate the numbering of atoms in the TPA ligands. Nxy provides the identifiers where x refers to the Fe number and the y identifies the ring. For both TPA ligands, Nx1 is in the Fe1—O1—Fe2 plane. Nx4 is the tertiary amine nitrogen atom.
The preparation of [Fe2(TPA)2O(SO4)](ClO4)2 has been reported at least twice previously (Holz et al., 1993; Hazell et al., 1994), but its structure was not determined. Interestingly, the Fe—O—Fe angle was predicted, based on electronic spectroscopy, to be 134° (Holz et al., 1993) which agrees well with the 133.0 (1)° reported here.