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Acta Cryst. (2007). E63, m2480-m2481    [ doi:10.1107/S1600536807042857 ]

[mu]-Sulfato-1[kappa]O:2[kappa]O-[mu]-oxo-bis[tris(2-pyridylmethyl)amine-[kappa]4N,N',N'',N''']diiron(III) diperchlorate acetonitrile/water (0.75/0.25) solvate

C. M. Smith and R. E. Norman

Abstract top

The title complex, [Fe2(C18H18N4)2O(SO4)](ClO4)2·0.75C2H3N·0.25H2O, consists of two perchlorate ions, a solvent cavity with acetonitrile and water (disordered 3/1), and an Fe complex dication. The dication is a diiron(III) unit containing an oxo bridge and a sulfato bridge. The iron(III) centers are pseudo-octahedral, six-coordinate, with tris(2-pyridylmethyl) amine (TPA) providing four N atoms. The distances and angles are typical for bent [mu]-oxo-bridged TPA complexes. The complex was the unexpected result of a reaction designed to produce a [mu]-sulfido-[mu]-carboxylato-diiron center.

Comment top

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.

Related literature top

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).

Experimental top

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.

Refinement top

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.

Computing details top

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.

Figures top
[Figure 1] Fig. 1. Perspective drawing of the [Fe2(TPA)2O(SO4)]2+ cation with displacement ellipsoids drawn at the 50% probability level. H atoms have been omitted.
[Figure 2] Fig. 2. The numbering of atoms in the TPA ligands.
µ-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 top
Crystal data top
[Fe2(C18H18N4)2O(SO4)]4(ClO4)8·3C2H3N·H2OF000 = 2132.00
Mr = 4154.72Dx = 1.675 Mg m−3
Monoclinic, P21/nMo Kα radiation
λ = 0.7107 Å
Hall symbol: -P 2ynCell parameters from 14215 reflections
a = 12.7031 (10) Åθ = 2.5–32.0º
b = 24.477 (3) ŵ = 0.96 mm−1
c = 13.6165 (11) ÅT = 90 K
β = 103.357 (5)ºLath, yellow-green
V = 4119.3 (6) Å30.30 × 0.17 × 0.05 mm
Z = 1
Data collection top
Nonius KappaCCD (with Oxford Cryostream) diffractometer14279 independent reflections
Radiation source: fine-focus sealed tube8172 reflections with I > 3σ(I)
Monochromator: graphiteRint = 0.042
T = 90 Kθmax = 32.0º
ω scans with κ offsetsθmin = 2.5º
Absorption correction: multi-scan
HKL SCALEPACK (Otwinowski & Minor, 1997)		h = −18→18
Tmin = 0.728, Tmax = 0.946k = −36→36
81911 measured reflectionsl = −20→20
Refinement top
Refinement on F2H-atom parameters constrained
Least-squares matrix: fullWeighting scheme based on measured s.u.'s w = 1/[σ2(Fo) + 0.000841|Fo|2]
R[F2 > 2σ(F2)] = 0.054(Δ/σ)max = 0.001
wR(F2) = 0.093Δρmax = 0.78 e Å−3
S = 0.90Δρmin = −0.71 e Å−3
8172 reflectionsExtinction correction: none
595 parameters
Crystal data top
[Fe2(C18H18N4)2O(SO4)]4(ClO4)8·3C2H3N·H2OV = 4119.3 (6) Å3
Mr = 4154.72Z = 1
Monoclinic, P21/nMo Kα
a = 12.7031 (10) ŵ = 0.96 mm−1
b = 24.477 (3) ÅT = 90 K
c = 13.6165 (11) Å0.30 × 0.17 × 0.05 mm
β = 103.357 (5)º
Data collection top
Nonius KappaCCD (with Oxford Cryostream) diffractometer14279 independent reflections
Absorption correction: multi-scan
HKL SCALEPACK (Otwinowski & Minor, 1997)		8172 reflections with I > 3σ(I)
Tmin = 0.728, Tmax = 0.946Rint = 0.042
81911 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.054595 parameters
wR(F2) = 0.093H-atom parameters constrained
S = 0.90Δρmax = 0.78 e Å−3
8172 reflectionsΔρmin = −0.71 e Å−3
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Fe10.22087 (3)0.26340 (2)0.93084 (2)0.01043 (8)
Fe20.29912 (3)0.15787 (2)0.81495 (2)0.01094 (8)
Cl10.35062 (5)0.36704 (3)0.38755 (4)0.0136 (1)
Cl20.16176 (5)0.02549 (3)0.36029 (4)0.0150 (1)
S50.46963 (5)0.23004 (3)0.96923 (4)0.0123 (1)
O10.20634 (13)0.20867 (7)0.84171 (11)0.0124 (4)
O20.37397 (13)0.25008 (7)1.00798 (11)0.0129 (4)
O30.43271 (13)0.17723 (7)0.91148 (12)0.0161 (4)
O40.55651 (13)0.21686 (8)1.05476 (12)0.0166 (5)
O50.4959 (1)0.26959 (8)0.89952 (12)0.0198 (5)
O60.0659 (13)0.4065 (8)0.6270 (8)0.119 (6)0.25
O110.4197 (1)0.32356 (8)0.36660 (12)0.0185 (5)
O120.24272 (13)0.34587 (8)0.37924 (13)0.0204 (5)
O130.3478 (2)0.41082 (8)0.31582 (13)0.0223 (5)
O140.3926 (2)0.38753 (8)0.48880 (12)0.0215 (5)
O210.0775 (1)−0.00452 (8)0.3920 (1)0.0244 (5)
O220.1767 (2)0.07740 (8)0.4111 (1)0.0313 (6)
O230.1307 (2)0.03407 (9)0.25307 (13)0.0298 (6)
O240.2609 (1)−0.00557 (9)0.3862 (1)0.0264 (5)
N10.0615 (5)0.4712 (3)0.6607 (5)0.112 (3)0.75
N110.0673 (2)0.30205 (9)0.8705 (1)0.0125 (5)
N120.2774 (2)0.33111 (9)0.8582 (1)0.0130 (5)
N130.1708 (2)0.22604 (9)1.0547 (1)0.0119 (5)
N140.2234 (2)0.33223 (8)1.03999 (13)0.0121 (5)
N210.3982 (2)0.09698 (9)0.7557 (2)0.0153 (5)
N220.2472 (2)0.09465 (9)0.9014 (1)0.0135 (5)
N230.3084 (2)0.19461 (9)0.6755 (1)0.0134 (5)
N240.1760 (2)0.11150 (9)0.7049 (1)0.0124 (5)
C10.0943 (4)0.4470 (2)0.5982 (4)0.041 (1)0.75
C20.1257 (3)0.4167 (2)0.5289 (3)0.0231 (10)0.75
C1110.0045 (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)
C1150.0439 (2)0.34687 (10)0.9182 (2)0.0132 (6)
C1160.1165 (2)0.35992 (11)1.0196 (2)0.0153 (6)
C1210.2846 (2)0.33099 (11)0.7613 (2)0.0157 (6)
C1220.3387 (2)0.37159 (11)0.7221 (2)0.0184 (7)
C1230.3848 (2)0.41413 (12)0.7840 (2)0.0191 (7)
C1240.3736 (2)0.41542 (11)0.8834 (2)0.0168 (6)
C1250.3194 (2)0.37323 (10)0.9184 (2)0.0144 (6)
C1260.3123 (2)0.36916 (11)1.0274 (2)0.0164 (6)
C1310.1278 (2)0.17545 (10)1.0520 (2)0.0130 (6)
C1320.1007 (2)0.15191 (11)1.1349 (2)0.0146 (6)
C1330.1142 (2)0.18243 (12)1.2231 (2)0.0163 (6)
C1340.1573 (2)0.23451 (11)1.2264 (2)0.0146 (6)
C1350.1879 (2)0.25491 (10)1.1420 (2)0.0128 (6)
C1360.2468 (2)0.30805 (11)1.1426 (2)0.0144 (6)
C2110.5072 (2)0.09782 (11)0.7736 (2)0.0181 (7)
C2120.5643 (2)0.06486 (12)0.7223 (2)0.0189 (7)
C2130.5072 (2)0.03167 (12)0.6458 (2)0.0217 (7)
C2140.3957 (2)0.03125 (11)0.6247 (2)0.0194 (7)
C2150.3433 (2)0.06357 (10)0.6826 (2)0.0149 (6)
C2160.2224 (2)0.06104 (11)0.6700 (2)0.0145 (6)
C2210.3020 (2)0.07783 (11)0.9932 (2)0.0190 (7)
C2220.2591 (2)0.03969 (12)1.0487 (2)0.0229 (7)
C2230.1578 (2)0.01815 (12)1.0076 (2)0.0229 (7)
C2240.1017 (2)0.03533 (11)0.9122 (2)0.0191 (7)
C2250.1484 (2)0.07404 (11)0.8619 (2)0.0156 (6)
C2260.0923 (2)0.09717 (11)0.7605 (2)0.0151 (6)
C2310.3918 (2)0.22496 (11)0.6615 (2)0.0152 (6)
C2320.4004 (2)0.24110 (11)0.5658 (2)0.0160 (6)
C2330.3215 (2)0.22475 (11)0.4830 (2)0.0157 (6)
C2340.2350 (2)0.19409 (11)0.4975 (2)0.0143 (6)
C2350.2300 (2)0.18008 (10)0.5949 (2)0.0128 (6)
C2360.1359 (2)0.14990 (11)0.6194 (2)0.0146 (6)
H10.16590.38620.56060.028*0.75
H20.16980.43800.49600.028*0.75
H30.06390.40420.48070.028*0.75
H40.07860.42580.68940.143*0.25
H50.13360.38690.62540.143*0.25
H1110.02130.25840.74450.018*
H112−0.12370.31240.66720.023*
H113−0.17110.38870.75540.025*
H114−0.06190.41010.91440.022*
H1150.08040.34921.07030.018*
H1160.12840.39831.02310.018*
H1210.25160.30220.71840.019*
H1220.34400.37030.65370.022*
H1230.42360.44210.75920.023*
H1240.40270.44490.92660.020*
H1250.29960.40461.05080.020*
H1260.37890.35551.06630.020*
H1310.11560.15530.99080.016*
H1320.07350.11571.13180.018*
H1330.09400.16761.28060.020*
H1340.16590.25611.28570.018*
H1350.32240.30181.16460.017*
H1360.22410.33271.18750.017*
H2110.54610.12200.82350.022*
H2120.64110.06490.73890.023*
H2130.54470.00930.60810.026*
H2140.35540.00930.57160.023*
H2150.20590.03090.70780.017*
H2160.18980.05570.60050.017*
H2210.37180.09251.02070.023*
H2220.29860.02861.11360.027*
H2230.1268−0.00811.04400.027*
H2240.03250.02060.88230.023*
H2250.05260.12890.76970.018*
H2260.04430.07070.72350.018*
H2310.44630.23570.71850.018*
H2320.45950.26300.55740.019*
H2330.32670.23450.41680.019*
H2340.17980.18280.44160.017*
H2350.09930.12990.56190.018*
H2360.08750.17540.63790.018*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Fe10.0114 (2)0.0108 (2)0.0095 (2)−0.0013 (1)0.00342 (12)−0.00123 (13)
Fe20.0098 (2)0.0122 (2)0.0114 (2)−0.0019 (1)0.00351 (12)−0.00255 (13)
Cl10.0139 (3)0.0142 (3)0.0123 (3)0.0003 (2)0.0022 (2)0.0000 (2)
Cl20.0176 (3)0.0125 (3)0.0155 (3)0.0005 (2)0.0050 (2)−0.0008 (2)
S50.0105 (3)0.0150 (3)0.0115 (3)−0.0023 (2)0.0024 (2)−0.0025 (2)
O10.0120 (8)0.0125 (9)0.0129 (8)−0.0013 (7)0.0036 (6)−0.0017 (7)
O20.0113 (8)0.0155 (9)0.0117 (8)0.0003 (7)0.0025 (6)−0.0022 (7)
O30.0128 (8)0.0158 (10)0.0185 (9)−0.0016 (7)0.0013 (7)−0.0064 (7)
O40.0133 (8)0.0214 (10)0.0140 (8)−0.0006 (8)0.0006 (7)−0.0029 (7)
O50.0187 (9)0.0236 (11)0.0189 (9)−0.0047 (8)0.0076 (7)0.0028 (8)
O60.122 (12)0.21 (2)0.032 (6)0.14 (1)0.034 (7)0.041 (9)
O110.0195 (9)0.0171 (10)0.0204 (9)0.0031 (8)0.0077 (7)−0.0017 (7)
O120.0131 (9)0.0247 (11)0.0242 (9)−0.0046 (8)0.0060 (7)−0.0014 (8)
O130.0272 (10)0.0174 (10)0.0215 (10)−0.0002 (8)0.0037 (8)0.0055 (8)
O140.0242 (10)0.0238 (11)0.0143 (9)0.0007 (9)0.0000 (7)−0.0058 (8)
O210.0178 (10)0.0219 (11)0.0356 (11)−0.0002 (8)0.0106 (8)0.0062 (9)
O220.0470 (13)0.0149 (11)0.0315 (11)−0.0017 (10)0.0077 (10)−0.0082 (9)
O230.0487 (13)0.0268 (12)0.0147 (9)0.0088 (10)0.0090 (9)0.0040 (8)
O240.0153 (9)0.0271 (12)0.0364 (11)0.0071 (9)0.0048 (8)0.0000 (9)
N10.115 (5)0.126 (6)0.117 (5)−0.037 (4)0.072 (4)−0.091 (5)
N110.0140 (10)0.0121 (11)0.0121 (9)−0.0021 (8)0.0045 (8)−0.0008 (8)
N120.0132 (10)0.0111 (11)0.0147 (10)−0.0012 (8)0.0030 (8)−0.0017 (8)
N130.0102 (9)0.0138 (11)0.0117 (9)0.0004 (8)0.0027 (8)0.0002 (8)
N140.0138 (10)0.0117 (11)0.0103 (9)−0.0017 (8)0.0015 (7)−0.0004 (8)
N210.0121 (10)0.0167 (12)0.0173 (10)−0.0013 (9)0.0040 (8)−0.0027 (8)
N220.0141 (10)0.0131 (11)0.0144 (10)0.0002 (9)0.0054 (8)−0.0019 (8)
N230.0122 (10)0.0158 (11)0.0130 (9)−0.0022 (8)0.0044 (8)−0.0035 (8)
N240.0118 (10)0.0115 (11)0.0145 (10)−0.0006 (8)0.0046 (8)−0.0012 (8)
C10.031 (2)0.039 (3)0.051 (3)−0.014 (2)0.007 (2)0.000 (2)
C20.023 (2)0.023 (2)0.021 (2)−0.003 (2)0.000 (1)−0.002 (2)
C1110.0164 (12)0.0146 (13)0.0147 (11)−0.0034 (10)0.0053 (10)−0.0024 (10)
C1120.0143 (12)0.024 (2)0.0167 (12)−0.0028 (11)−0.0002 (9)−0.0003 (11)
C1130.0162 (13)0.017 (1)0.027 (1)0.0021 (11)0.0021 (10)0.0022 (11)
C1140.0199 (13)0.015 (1)0.0186 (12)0.0004 (11)0.0031 (10)−0.0016 (10)
C1150.0153 (11)0.0123 (12)0.0135 (11)−0.0013 (10)0.0063 (9)0.0011 (9)
C1160.0155 (12)0.0146 (13)0.0164 (12)0.0030 (10)0.0048 (10)−0.0027 (10)
C1210.0164 (12)0.0146 (13)0.0170 (12)0.0012 (10)0.0056 (10)0.0009 (10)
C1220.0206 (13)0.020 (2)0.0154 (12)0.0015 (11)0.0066 (10)0.0047 (10)
C1230.0175 (13)0.018 (1)0.0229 (13)−0.0010 (11)0.0072 (10)0.0059 (11)
C1240.0150 (12)0.0124 (13)0.0213 (13)−0.0010 (10)0.0006 (10)0.0000 (10)
C1250.0129 (12)0.0132 (13)0.0168 (12)0.0003 (10)0.0029 (9)0.0005 (10)
C1260.0197 (13)0.0134 (13)0.0159 (12)−0.0062 (11)0.0040 (10)−0.0034 (10)
C1310.0093 (11)0.0166 (13)0.0127 (11)0.0004 (10)0.0020 (9)−0.0017 (9)
C1320.0106 (11)0.0142 (13)0.0179 (12)0.0007 (10)0.0010 (9)0.0035 (10)
C1330.0132 (12)0.023 (2)0.0118 (11)0.0006 (11)0.0021 (9)0.0037 (10)
C1340.0132 (11)0.022 (1)0.0091 (11)0.0022 (11)0.0028 (9)−0.0003 (10)
C1350.0113 (11)0.0137 (13)0.0128 (11)0.0024 (10)0.0018 (9)−0.0003 (9)
C1360.0176 (12)0.0146 (13)0.0109 (11)−0.0007 (10)0.0030 (9)−0.0009 (9)
C2110.0135 (12)0.020 (2)0.0210 (13)−0.0023 (11)0.0043 (10)−0.0063 (10)
C2120.0128 (12)0.018 (1)0.027 (1)0.0010 (11)0.0070 (10)−0.0025 (11)
C2130.0197 (13)0.020 (2)0.030 (1)0.0000 (11)0.0130 (11)−0.0070 (11)
C2140.0169 (12)0.018 (1)0.0239 (13)−0.0013 (11)0.0061 (10)−0.0084 (11)
C2150.0155 (12)0.0116 (13)0.0192 (12)−0.0018 (10)0.0070 (10)−0.0027 (10)
C2160.0136 (11)0.0141 (13)0.0160 (11)−0.0030 (10)0.0038 (9)−0.0039 (9)
C2210.0190 (13)0.015 (1)0.0239 (13)0.0029 (11)0.0065 (10)0.0002 (11)
C2220.029 (2)0.018 (2)0.0222 (13)0.0064 (12)0.0086 (12)0.0051 (11)
C2230.030 (2)0.015 (1)0.030 (1)0.0012 (12)0.0183 (12)0.0026 (11)
C2240.0188 (13)0.016 (1)0.0263 (13)−0.0020 (11)0.0130 (11)−0.0030 (11)
C2250.0166 (12)0.0124 (13)0.0201 (12)0.0009 (10)0.0089 (10)−0.0043 (10)
C2260.0111 (11)0.0153 (13)0.0203 (12)−0.0023 (10)0.0066 (9)−0.0044 (10)
C2310.0139 (12)0.017 (1)0.0158 (12)−0.0032 (10)0.0048 (9)−0.0028 (10)
C2320.0143 (12)0.018 (1)0.0164 (12)−0.0036 (10)0.0058 (9)−0.0019 (10)
C2330.0192 (13)0.0144 (13)0.0139 (11)0.0023 (10)0.0049 (10)0.0013 (9)
C2340.0149 (12)0.0156 (13)0.0119 (11)0.0022 (10)0.0017 (9)−0.0011 (9)
C2350.0100 (11)0.0130 (13)0.0155 (11)0.0010 (9)0.0035 (9)−0.0023 (9)
C2360.0106 (11)0.017 (1)0.0154 (11)−0.0008 (10)0.0016 (9)−0.0031 (10)
Geometric parameters (Å, °) top
Fe1—O11.788 (2)C135—C1361.499 (3)
Fe1—O22.012 (2)C211—C2121.379 (3)
Fe1—N112.153 (2)C212—C2131.386 (4)
Fe1—N122.138 (2)C213—C2141.379 (4)
Fe1—N132.140 (2)C214—C2151.391 (3)
Fe1—N142.242 (2)C215—C2161.506 (3)
Fe2—O11.807 (2)C221—C2221.389 (4)
Fe2—O31.950 (2)C222—C2231.384 (4)
Fe2—N212.220 (2)C223—C2241.395 (4)
Fe2—N222.138 (2)C224—C2251.380 (3)
Fe2—N232.129 (2)C225—C2261.511 (4)
Fe2—N242.213 (2)C231—C2321.390 (3)
Cl1—O111.449 (2)C232—C2331.383 (3)
Cl1—O121.445 (2)C233—C2341.382 (3)
Cl1—O131.445 (2)C234—C2351.385 (3)
Cl1—O141.448 (2)C235—C2361.507 (3)
Cl2—O211.444 (2)O6—H40.951
Cl2—O221.438 (2)O6—H50.991
Cl2—O231.437 (2)C2—H10.950
Cl2—O241.444 (2)C2—H20.950
S5—O21.514 (2)C2—H30.950
S5—O31.529 (2)C111—H1110.950
S5—O41.444 (2)C112—H1120.950
S5—O51.448 (2)C113—H1130.950
N1—C11.188 (7)C114—H1140.950
N11—C1111.351 (3)C116—H1150.950
N11—C1151.343 (3)C116—H1160.950
N12—C1211.344 (3)C121—H1210.950
N12—C1251.348 (3)C122—H1220.950
N13—C1311.351 (3)C123—H1230.950
N13—C1351.356 (3)C124—H1240.950
N14—C1161.486 (3)C126—H1250.950
N14—C1261.487 (3)C126—H1260.950
N14—C1361.482 (3)C131—H1310.950
N21—C2111.349 (3)C132—H1320.950
N21—C2151.351 (3)C133—H1330.950
N22—C2211.347 (3)C134—H1340.950
N22—C2251.345 (3)C136—H1350.950
N23—C2311.343 (3)C136—H1360.950
N23—C2351.348 (3)C211—H2110.950
N24—C2161.492 (3)C212—H2120.950
N24—C2261.483 (3)C213—H2130.950
N24—C2361.491 (3)C214—H2140.950
C1—C21.332 (6)C216—H2150.950
C111—C1121.373 (4)C216—H2160.950
C112—C1131.403 (4)C221—H2210.950
C113—C1141.380 (4)C222—H2220.950
C114—C1151.392 (4)C223—H2230.950
C115—C1161.506 (3)C224—H2240.950
C121—C1221.383 (3)C226—H2250.950
C122—C1231.382 (4)C226—H2260.950
C123—C1241.392 (3)C231—H2310.950
C124—C1251.385 (3)C232—H2320.950
C125—C1261.511 (3)C233—H2330.950
C131—C1321.379 (3)C234—H2340.950
C132—C1331.390 (4)C236—H2350.950
C133—C1341.384 (4)C236—H2360.950
C134—C1351.389 (3)
O14···C132i3.074 (3)O14···C223iv3.263 (4)
O22···C2343.113 (3)O4···C111ii3.269 (3)
O4···O6ii3.17 (2)O24···C212iii3.277 (3)
O24···C213iii3.141 (3)O12···C23.281 (4)
O5···C234ii3.150 (3)N1···N21iv3.282 (7)
N1···C215iv3.152 (6)O23···C132vi3.282 (3)
O13···O23v3.190 (3)O11···C2333.291 (3)
N1···C214iv3.204 (6)O14···C131i3.294 (3)
O11···C131i3.206 (3)
O1—Fe1—O299.71 (7)C212—C213—C214119.6 (2)
O1—Fe1—N1197.34 (8)C213—C214—C215118.8 (2)
O1—Fe1—N12105.07 (7)N21—C215—C214121.9 (2)
O1—Fe1—N13102.23 (8)N21—C215—C216116.7 (2)
O1—Fe1—N14175.05 (7)C214—C215—C216121.4 (2)
O2—Fe1—N11162.14 (8)N24—C216—C215113.4 (2)
O2—Fe1—N1288.82 (7)N22—C221—C222121.8 (2)
O2—Fe1—N1386.95 (7)C221—C222—C223118.8 (2)
O2—Fe1—N1484.91 (7)C222—C223—C224119.2 (2)
N11—Fe1—N1281.63 (8)C223—C224—C225118.9 (2)
N11—Fe1—N1394.63 (7)N22—C225—C224121.9 (2)
N11—Fe1—N1478.23 (7)N22—C225—C226115.1 (2)
N12—Fe1—N13152.70 (8)C224—C225—C226123.0 (2)
N12—Fe1—N1476.64 (7)N24—C226—C225108.2 (2)
N13—Fe1—N1476.12 (7)N23—C231—C232121.8 (2)
O1—Fe2—O3101.74 (7)C231—C232—C233118.8 (2)
O1—Fe2—N21170.51 (7)C232—C233—C234119.4 (2)
O1—Fe2—N2295.09 (7)C233—C234—C235119.0 (2)
O1—Fe2—N2393.57 (8)N23—C235—C234121.7 (2)
O1—Fe2—N2495.61 (7)N23—C235—C236115.1 (2)
O3—Fe2—N2185.97 (7)C234—C235—C236123.2 (2)
O3—Fe2—N2297.82 (7)N24—C236—C235109.7 (2)
O3—Fe2—N23106.23 (8)H4—O6—H5106.94
O3—Fe2—N24161.81 (8)C1—C2—H1109.47
N21—Fe2—N2289.26 (8)C1—C2—H2109.47
N21—Fe2—N2378.83 (8)C1—C2—H3109.47
N21—Fe2—N2477.34 (7)H1—C2—H2109.47
N22—Fe2—N23152.16 (8)H1—C2—H3109.47
N22—Fe2—N2475.04 (7)H2—C2—H3109.47
N23—Fe2—N2477.81 (7)N11—C111—H111118.65
O11—Cl1—O12109.2 (1)C112—C111—H111118.65
O11—Cl1—O13109.4 (1)C111—C112—H112120.57
O11—Cl1—O14109.6 (1)C113—C112—H112120.57
O12—Cl1—O13109.8 (1)C112—C113—H113120.78
O12—Cl1—O14109.5 (1)C114—C113—H113120.78
O13—Cl1—O14109.4 (1)C113—C114—H114120.23
O21—Cl2—O22109.3 (1)C115—C114—H114120.23
O21—Cl2—O23109.2 (1)N14—C116—H115108.21
O21—Cl2—O24108.9 (1)N14—C116—H116108.21
O22—Cl2—O23109.5 (1)C115—C116—H115108.21
O22—Cl2—O24109.7 (1)C115—C116—H116108.21
O23—Cl2—O24110.2 (1)H115—C116—H116109.46
O2—S5—O3106.1 (1)N12—C121—H121119.01
O2—S5—O4108.47 (9)C122—C121—H121119.02
O2—S5—O5109.7 (1)C121—C122—H122120.51
O3—S5—O4108.2 (1)C123—C122—H122120.51
O3—S5—O5108.5 (1)C122—C123—H123120.48
O4—S5—O5115.4 (1)C124—C123—H123120.48
Fe1—O1—Fe2133.0 (1)C123—C124—H124120.40
Fe1—O2—S5128.9 (1)C125—C124—H124120.40
Fe2—O3—S5131.9 (1)N14—C126—H125108.86
Fe1—N11—C111123.1 (2)N14—C126—H126108.86
Fe1—N11—C115117.1 (2)C125—C126—H125108.86
C111—N11—C115118.5 (2)C125—C126—H126108.86
Fe1—N12—C121124.0 (2)H125—C126—H126109.46
Fe1—N12—C125116.1 (2)N13—C131—H131118.78
C121—N12—C125119.4 (2)C132—C131—H131118.78
Fe1—N13—C131124.2 (2)C131—C132—H132120.73
Fe1—N13—C135116.8 (2)C133—C132—H132120.73
C131—N13—C135118.9 (2)C132—C133—H133120.26
Fe1—N14—C116110.2 (1)C134—C133—H133120.26
Fe1—N14—C126106.0 (1)C133—C134—H134120.38
Fe1—N14—C136107.1 (1)C135—C134—H134120.38
C116—N14—C126112.8 (2)N14—C136—H135109.22
C116—N14—C136109.5 (2)N14—C136—H136109.22
C126—N14—C136111.1 (2)C135—C136—H135109.22
Fe2—N21—C211124.6 (2)C135—C136—H136109.22
Fe2—N21—C215115.7 (2)H135—C136—H136109.46
C211—N21—C215118.5 (2)N21—C211—H211118.75
Fe2—N22—C221125.0 (2)C212—C211—H211118.75
Fe2—N22—C225115.5 (2)C211—C212—H212120.69
C221—N22—C225119.4 (2)C213—C212—H212120.69
Fe2—N23—C231124.7 (2)C212—C213—H213120.18
Fe2—N23—C235115.6 (2)C214—C213—H213120.18
C231—N23—C235119.3 (2)C213—C214—H214120.62
Fe2—N24—C216111.8 (1)C215—C214—H214120.62
Fe2—N24—C226104.7 (1)N24—C216—H215108.49
Fe2—N24—C236105.4 (1)N24—C216—H216108.49
C216—N24—C226110.4 (2)C215—C216—H215108.49
C216—N24—C236111.2 (2)C215—C216—H216108.49
C226—N24—C236113.0 (2)H215—C216—H216109.46
N1—C1—C2175.5 (6)N22—C221—H221119.10
N11—C111—C112122.7 (2)C222—C221—H221119.10
C111—C112—C113118.9 (2)C221—C222—H222120.61
C112—C113—C114118.4 (2)C223—C222—H222120.61
C113—C114—C115119.5 (2)C222—C223—H223120.38
N11—C115—C114121.8 (2)C224—C223—H223120.38
N11—C115—C116117.4 (2)C223—C224—H224120.54
C114—C115—C116120.7 (2)C225—C224—H224120.54
N14—C116—C115114.5 (2)N24—C226—H225109.78
N12—C121—C122122.0 (2)N24—C226—H226109.78
C121—C122—C123119.0 (2)C225—C226—H225109.78
C122—C123—C124119.0 (2)C225—C226—H226109.78
C123—C124—C125119.2 (2)H225—C226—H226109.46
N12—C125—C124121.3 (2)N23—C231—H231119.12
N12—C125—C126116.2 (2)C232—C231—H231119.12
C124—C125—C126122.3 (2)C231—C232—H232120.59
N14—C126—C125111.9 (2)C233—C232—H232120.59
N13—C131—C132122.4 (2)C232—C233—H233120.30
C131—C132—C133118.5 (2)C234—C233—H233120.30
C132—C133—C134119.5 (2)C233—C234—H234120.49
C133—C134—C135119.2 (2)C235—C234—H234120.49
N13—C135—C134121.3 (2)N24—C236—H235109.42
N13—C135—C136115.8 (2)N24—C236—H236109.42
C134—C135—C136122.8 (2)C235—C236—H235109.42
N14—C136—C135110.5 (2)C235—C236—H236109.42
N21—C211—C212122.5 (2)H235—C236—H236109.46
C211—C212—C213118.6 (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—C11576.4 (2)
Fe1—O1—Fe2—N2298.3 (1)N13—Fe1—N12—C121−171.6 (2)
Fe1—O1—Fe2—N23−108.2 (1)N13—Fe1—N12—C12516.3 (3)
Fe1—O1—Fe2—N24173.7 (1)N13—Fe1—N14—C116−90.0 (1)
Fe1—O2—S5—O3−53.0 (2)N13—Fe1—N14—C126147.7 (2)
Fe1—O2—S5—O4−169.0 (1)N13—Fe1—N14—C13629.0 (1)
Fe1—O2—S5—O564.1 (2)N13—C131—C132—C1332.8 (4)
Fe1—N11—C111—C112−167.5 (2)N13—C135—C134—C1333.7 (4)
Fe1—N11—C115—C114170.6 (2)N13—C135—C136—N1430.5 (3)
Fe1—N11—C115—C116−11.2 (3)N14—Fe1—N11—C111168.8 (2)
Fe1—N12—C121—C122−168.6 (2)N14—Fe1—N11—C1151.6 (2)
Fe1—N12—C125—C124169.9 (2)N14—Fe1—N12—C121−167.6 (2)
Fe1—N12—C125—C126−5.1 (3)N14—Fe1—N12—C12520.4 (2)
Fe1—N13—C131—C132177.2 (2)N14—Fe1—N13—C131168.2 (2)
Fe1—N13—C135—C134179.3 (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—C124161.7 (2)
Fe1—N14—C126—C12537.3 (2)N14—C136—C135—C134−152.8 (2)
Fe1—N14—C136—C135−39.7 (2)N21—Fe2—N22—C22184.7 (2)
Fe2—O1—Fe1—O2−4.8 (1)N21—Fe2—N22—C225−100.5 (2)
Fe2—O1—Fe1—N11169.9 (1)N21—Fe2—N23—C231−82.7 (2)
Fe2—O1—Fe1—N1286.6 (1)N21—Fe2—N23—C23589.0 (2)
Fe2—O1—Fe1—N13−93.7 (1)N21—Fe2—N24—C21611.2 (1)
Fe2—O1—Fe1—N14−163.8 (8)N21—Fe2—N24—C226130.8 (2)
Fe2—O3—S5—O243.9 (2)N21—Fe2—N24—C236−109.8 (1)
Fe2—O3—S5—O4160.1 (1)N21—C211—C212—C2133.4 (4)
Fe2—O3—S5—O5−73.9 (2)N21—C215—C214—C2132.9 (4)
Fe2—N21—C211—C212−169.0 (2)N21—C215—C216—N2425.8 (3)
Fe2—N21—C215—C214166.9 (2)N22—Fe2—N21—C211−115.4 (2)
Fe2—N21—C215—C216−15.8 (3)N22—Fe2—N21—C21577.2 (2)
Fe2—N22—C221—C222174.5 (2)N22—Fe2—N23—C231−149.0 (2)
Fe2—N22—C225—C224−176.1 (2)N22—Fe2—N23—C23522.7 (3)
Fe2—N22—C225—C2262.7 (3)N22—Fe2—N24—C216−81.4 (2)
Fe2—N23—C231—C232170.4 (2)N22—Fe2—N24—C22638.1 (1)
Fe2—N23—C235—C234−170.0 (2)N22—Fe2—N24—C236157.6 (1)
Fe2—N23—C235—C23612.4 (3)N22—C221—C222—C2230.6 (4)
Fe2—N24—C216—C215−22.5 (2)N22—C225—C224—C2231.5 (4)
Fe2—N24—C226—C225−47.8 (2)N22—C225—C226—N2431.7 (3)
Fe2—N24—C236—C23543.0 (2)N23—Fe2—N21—C21189.9 (2)
S5—O2—Fe1—O136.1 (1)N23—Fe2—N21—C215−77.5 (2)
S5—O2—Fe1—N11−126.4 (2)N23—Fe2—N22—C221148.7 (2)
S5—O2—Fe1—N12−68.9 (1)N23—Fe2—N22—C225−36.5 (3)
S5—O2—Fe1—N13138.0 (1)N23—Fe2—N24—C21692.3 (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—N21154.3 (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—N2377.2 (1)N23—C235—C236—N24−38.6 (3)
S5—O3—Fe2—N24177.6 (2)N24—Fe2—N21—C211169.8 (2)
O1—Fe1—N11—C111−13.5 (2)N24—Fe2—N21—C2152.3 (2)
O1—Fe1—N11—C115179.4 (2)N24—Fe2—N22—C221161.8 (2)
O1—Fe1—N12—C1217.6 (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—C2359.7 (2)
O1—Fe1—N13—C135170.4 (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—C234143.8 (2)
O1—Fe1—N14—C136100.2 (8)C111—N11—C115—C1142.9 (3)
O1—Fe2—N21—C211127.2 (4)C111—N11—C115—C116−178.9 (2)
O1—Fe2—N21—C215−40.2 (6)C111—C112—C113—C1142.2 (4)
O1—Fe2—N22—C221−103.7 (2)C112—C111—N11—C115−0.5 (3)
O1—Fe2—N22—C22571.1 (2)C112—C113—C114—C1150.0 (4)
O1—Fe2—N23—C231103.0 (2)C113—C114—C115—C116179.2 (2)
O1—Fe2—N23—C235−85.2 (2)C115—C116—N14—C126102.6 (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—C23663.8 (1)C116—N14—C136—C13579.8 (2)
O2—Fe1—N11—C111149.1 (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—C121107.3 (2)C121—C122—C123—C124−1.3 (4)
O2—Fe1—N12—C125−64.7 (2)C122—C121—N12—C1253.2 (4)
O2—Fe1—N13—C131−106.3 (2)C122—C123—C124—C1251.9 (4)
O2—Fe1—N13—C13571.1 (2)C123—C124—C125—C126174.6 (2)
O2—Fe1—N14—C116−178.1 (1)C125—C126—N14—C136153.3 (2)
O2—Fe1—N14—C12659.6 (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—C136173.6 (2)
O3—Fe2—N21—C215175.1 (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—C225173.7 (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—C235171.4 (2)C211—N21—C215—C214−1.4 (4)
O3—Fe2—N24—C216−12.7 (3)C211—N21—C215—C216175.9 (2)
O3—Fe2—N24—C226106.9 (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—C125100.2 (2)C213—C214—C215—C216−174.2 (2)
N11—Fe1—N13—C13191.5 (2)C215—C216—N24—C226−138.6 (2)
N11—Fe1—N13—C135−91.1 (2)C215—C216—N24—C23695.0 (2)
N11—Fe1—N14—C1167.8 (1)C216—N24—C226—C22572.6 (2)
N11—Fe1—N14—C126−114.5 (2)C216—N24—C236—C235−78.3 (2)
N11—Fe1—N14—C136126.9 (1)C221—N22—C225—C224−1.0 (4)
N11—C111—C112—C113−2.0 (4)C221—N22—C225—C226177.8 (2)
N11—C115—C114—C113−2.6 (4)C221—C222—C223—C224−0.1 (4)
N11—C115—C116—N1418.3 (3)C222—C221—N22—C225−0.1 (4)
N12—Fe1—N11—C11190.8 (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—C131172.2 (2)C225—C226—N24—C236−162.0 (2)
N12—Fe1—N13—C135−10.4 (3)C226—N24—C236—C235156.8 (2)
N12—Fe1—N14—C11691.9 (2)C231—N23—C235—C2342.2 (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—C2341.6 (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—C236176.0 (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.
Table 1
Selected geometric parameters (Å, °) top
Fe1—O11.788 (2)Fe2—O11.807 (2)
Fe1—O22.012 (2)Fe2—O31.950 (2)
Fe1—N112.153 (2)Fe2—N212.220 (2)
Fe1—N122.138 (2)Fe2—N222.138 (2)
Fe1—N132.140 (2)Fe2—N232.129 (2)
Fe1—N142.242 (2)Fe2—N242.213 (2)
Fe1—O1—Fe2133.0 (1)
Acknowledgements top

We thank Frank Fronczek for data collection, and the Louisiana Board of Regents Support Fund and the Robert A. Welch Foundation (x − 0011) for financial support.

references
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