metal-organic papers
m216
Michael Bolteet al. [Fe(C4H8O)6][Fe2Cl6O] DOI: 101107/S1600536801007115 Acta Cryst.(2001). E57, m216±m217 Acta Crystallographica Section EStructure Reports Online
ISSN 1600-5368
[Fe(thf)
6][Cl
3Fe±O±FeCl
3]
Michael Bolte,a* Hans-Wolfram Lernerband Stefan Scholzb
aInstitut fuÈr Organische Chemie, J. W.
Goethe-UniversitaÈt Frankfurt, Marie-Curie-Straûe 11, 60439 Frankfurt/Main, Germany, andbInstitut fuÈr Anorganische Chemie, J. W. Goethe-UniversitaÈt Frankfurt, Marie-Curie-Straûe 11, 60439 Frankfurt/Main, Germany
Correspondence e-mail: [email protected]
Key indicators
Single-crystal X-ray study
T= 173 K
Mean(C±C) = 0.009 AÊ
Rfactor = 0.056
wRfactor = 0.133
Data-to-parameter ratio = 22.7
For details of how these key indicators were automatically derived from the article, see http://journals.iucr.org/e.
#2001 International Union of Crystallography Printed in Great Britain ± all rights reserved
The title compound, hexakis(tetrahydrofuran)iron(II) -oxo-bis[trichloroferrate(III)], [Fe(C4H8O)6][Fe2Cl6O], was
obtained by oxidation of FeCl2 in tetrahydrofuran. The O
atom of the anion and the Fe atom of the cation are located on special positions of site symmetry 3; the Fe atoms of the anion are located on a threefold rotation axis and, as a result, there is just1
6of both ions in the asymmetric unit.
Comment
In contrast to established ferrocene, only a few compounds with two bonds, RÐFeÐR, are known. Therefore, we became interested in the synthesis of the supersilylated compound tBu
3SiÐFeÐSitBu3, which we obtained from
sodium supersilanide,tBu
3SiNa, and iron(II) chloride, FeCl2,
in tetrahydrofuran at 195 K.
FeCl2+ 2tBu3SiNa!2tBu3SiÐFeÐSitBu3+ 2NaCl
In this context, we have prepared a calibrated solution (0.5M) of FeCl2 in tetrahydrofuran. After several
investiga-tions, the Fe2+in this calibrated solution was partially oxidized.
3FeCl2+ 0.5O2![Fe(thf)6]2+[Cl3FeÐOÐFeCl3]2ÿ
While in biological systems oxidation with oxygen from Fe2+
to Fe3+ is important, the molecular structure of the title
compound, (I), is of general interest.
The O atom of the anion and the Fe atom of the cation are located on special positions of site symmetry 3; the Fe atoms of the anion are located on a threefold rotation axis and, as a result, there is just1
6of both ions in the asymmetric unit. The
FeÐOÐFe system in the anion is linear for symmetry reasons.
Experimental
A solution of 1.072 g (8.51 mmol) FeCl2in 17 ml tetrahydrofuran was oxidized with dry air. Red cubic crystals of the title compound were obtained from this solution at 248 K.
Crystal data
[Fe(C4H8O)6][Fe2Cl6O]
Mr= 828.87
Cubic,Pa3
a= 15.244 (2) AÊ
V= 3542.4 (8) AÊ3
Z= 4
Dx= 1.554 Mg mÿ3
MoKradiation
Cell parameters from 502 re¯ections
= 2.7±20.1
= 1.70 mmÿ1
T= 173 (2) K Plate, red
0.280.280.12 mm
Data collection
Siemens CCD three-circle diffract-ometer
!scans
Absorption correction: empirical (SADABS; Sheldrick, 1996)
Tmin= 0.647,Tmax= 0.822 36 645 measured re¯ections 1405 independent re¯ections 792 re¯ections withI> 2(I)
Rint= 0.068 max= 28.2
h=ÿ19!19
k=ÿ20!17
l=ÿ19!20 123 standard re¯ections
frequency: 1200 min intensity decay: none
Re®nement
Re®nement onF2
R[F2> 2(F2)] = 0.056
wR(F2) = 0.133
S= 1.03 1405 re¯ections 62 parameters
H-atom parameters constrained
w= 1/[2(F
o2) + (0.0415P)2
+ 11.6567P]
whereP= (Fo2+ 2Fc2)/3
(/)max< 0.001 max= 0.46 e AÊÿ3 min=ÿ0.46 e AÊÿ3
Table 1
Selected geometric parameters (AÊ,).
Fe1ÐO1 1.7510 (12)
Fe1ÐCl1 2.2273 (14) Fe2ÐO2 2.171 (3) O1ÐFe1ÐCl1 110.54 (5) O2ÐFe2ÐO2i 90.44 (11)
Symmetry code: (i)3
2ÿz;1ÿx;12y.
All H atoms were located by difference Fourier synthesis and re®ned with ®xed individual displacement parameters [U(H) = 1.2Ueq(C)] using a riding model with CÐH = 0.99 AÊ.
Data collection: SMART (Siemens, 1995); cell re®nement:
SMART; data reduction:SAINT(Siemens, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to re®ne structure:SHELXL97 (Sheldrick, 1997); molecular graphics:
XPinSHELXTL-Plus(Sheldrick, 1991).
References
Sheldrick, G. M. (1990).Acta Cryst.A46, 467 - 473.
Sheldrick, G. M. (1991).SHELXTL-Plus.Release 4.1. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA.
Sheldrick, G. M. (1996).SADABS. University of GoÈttingen, Germany. Sheldrick, G. M. (1997).SHELXL97. University of GoÈttingen, Germany. Siemens (1995).SMARTandSAINT. Siemens Analytical X-ray Instruments
Inc., Madison, Wisconsin, USA.
Figure 1
supporting information
sup-1 Acta Cryst. (2001). E57, m216–m217
supporting information
Acta Cryst. (2001). E57, m216–m217 [https://doi.org/10.1107/S1600536801007115]
[Fe(thf)
6][Cl
3Fe
–
O
–
FeCl
3]
Michael Bolte, Hans-Wolfram Lerner and Stefan Scholz
(I)
Crystal data
[Fe(C4H8O)6][Fe2Cl6O]
Mr = 828.87
Cubic, Pa3
a = 15.244 (2) Å
V = 3542.4 (8) Å3
Z = 4
F(000) = 1712
Dx = 1.554 Mg m−3
Mo Kα radiation, λ = 0.71073 Å Cell parameters from 502 reflections
θ = 2.7–20.1°
µ = 1.70 mm−1
T = 173 K Plate, red
0.28 × 0.28 × 0.12 mm
Data collection
Siemens CCD three-circle diffractometer
Radiation source: fine-focus sealed tube Graphite monochromator
ω scans
Absorption correction: empirical (using intensity measurements)
(SADABS; Sheldrick, 1996)
Tmin = 0.647, Tmax = 0.822
36645 measured reflections 1405 independent reflections 792 reflections with I > 2σ(I)
Rint = 0.068
θmax = 28.2°, θmin = 2.3°
h = −19→19
k = −20→17
l = −19→20
Refinement
Refinement on F2 Least-squares matrix: full
R[F2 > 2σ(F2)] = 0.056
wR(F2) = 0.133
S = 1.03 1405 reflections 62 parameters 0 restraints
Primary atom site location: structure-invariant direct methods
Secondary atom site location: difference Fourier map
Hydrogen site location: inferred from neighbouring sites
H-atom parameters constrained
w = 1/[σ2(F
o2) + (0.0415P)2 + 11.6567P] where P = (Fo2 + 2Fc2)/3
(Δ/σ)max < 0.001 Δρmax = 0.46 e Å−3 Δρmin = −0.46 e Å−3
Special details
Experimental. ;
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
x y z Uiso*/Ueq
Fe1 0.56632 (4) 0.56632 (4) 0.56632 (4) 0.0277 (3)
Cl1 0.48436 (9) 0.64660 (9) 0.65679 (9) 0.0408 (4)
O1 0.5000 0.5000 0.5000 0.044 (2)
Fe2 0.5000 0.5000 1.0000 0.0219 (4)
O2 0.45429 (18) 0.4252 (2) 0.88772 (18) 0.0243 (7)
C2 0.5008 (3) 0.4178 (4) 0.8049 (3) 0.0365 (12)
H2A 0.5472 0.3725 0.8085 0.044*
H2B 0.5281 0.4745 0.7887 0.044*
C3 0.4336 (5) 0.3929 (6) 0.7411 (4) 0.079 (2)
H3A 0.4139 0.4453 0.7081 0.094*
H3B 0.4582 0.3502 0.6987 0.094*
C4 0.3614 (4) 0.3547 (5) 0.7862 (4) 0.066 (2)
H4A 0.3617 0.2902 0.7788 0.079*
H4B 0.3054 0.3780 0.7630 0.079*
C5 0.3717 (3) 0.3783 (4) 0.8807 (3) 0.0361 (12)
H5A 0.3224 0.4158 0.9002 0.043*
H5B 0.3728 0.3247 0.9174 0.043*
Atomic displacement parameters (Å2)
U11 U22 U33 U12 U13 U23
Fe1 0.0277 (3) 0.0277 (3) 0.0277 (3) −0.0022 (3) −0.0022 (3) −0.0022 (3)
Cl1 0.0441 (8) 0.0421 (8) 0.0364 (7) 0.0078 (6) 0.0072 (6) −0.0008 (6)
O1 0.044 (2) 0.044 (2) 0.044 (2) 0.001 (3) 0.001 (3) 0.001 (3)
Fe2 0.0219 (4) 0.0219 (4) 0.0219 (4) −0.0002 (4) −0.0002 (4) 0.0002 (4)
O2 0.0242 (17) 0.0309 (18) 0.0177 (16) −0.0026 (14) 0.0004 (13) −0.0024 (14)
C2 0.039 (3) 0.048 (3) 0.022 (2) −0.003 (3) 0.004 (2) −0.005 (2)
C3 0.078 (5) 0.123 (7) 0.035 (3) −0.037 (5) −0.004 (4) −0.012 (4)
C4 0.050 (4) 0.101 (6) 0.047 (4) −0.019 (4) −0.010 (3) −0.024 (4)
C5 0.029 (3) 0.042 (3) 0.038 (3) −0.008 (2) −0.005 (2) −0.001 (2)
Geometric parameters (Å, º)
Fe1—O1 1.7510 (12) O2—C2 1.453 (5)
Fe1—Cl1i 2.2273 (14) C2—C3 1.463 (8)
Fe1—Cl1 2.2273 (14) C2—H2A 0.9900
Fe1—Cl1ii 2.2273 (14) C2—H2B 0.9900
O1—Fe1iii 1.7510 (12) C3—C4 1.422 (9)
Fe2—O2iv 2.171 (3) C3—H3A 0.9900
supporting information
sup-3 Acta Cryst. (2001). E57, m216–m217
Fe2—O2v 2.171 (3) C4—C5 1.492 (7)
Fe2—O2vi 2.171 (3) C4—H4A 0.9900
Fe2—O2vii 2.171 (3) C4—H4B 0.9900
Fe2—O2viii 2.171 (3) C5—H5A 0.9900
O2—C5 1.452 (5) C5—H5B 0.9900
O1—Fe1—Cl1i 110.55 (5) O2—C2—C3 104.9 (4)
O1—Fe1—Cl1 110.54 (5) O2—C2—H2A 110.8
Cl1i—Fe1—Cl1 108.38 (5) C3—C2—H2A 110.8
O1—Fe1—Cl1ii 110.54 (5) O2—C2—H2B 110.8
Cl1i—Fe1—Cl1ii 108.38 (5) C3—C2—H2B 110.8
Cl1—Fe1—Cl1ii 108.38 (5) H2A—C2—H2B 108.9
Fe1iii—O1—Fe1 180.0 C4—C3—C2 109.0 (5)
O2iv—Fe2—O2 180.00 (14) C4—C3—H3A 109.9
O2iv—Fe2—O2v 90.44 (11) C2—C3—H3A 109.9
O2—Fe2—O2v 89.56 (11) C4—C3—H3B 109.9
O2iv—Fe2—O2vi 89.57 (11) C2—C3—H3B 109.9
O2—Fe2—O2vi 90.44 (11) H3A—C3—H3B 108.3
O2v—Fe2—O2vi 89.57 (11) C3—C4—C5 106.7 (5)
O2iv—Fe2—O2vii 90.43 (11) C3—C4—H4A 110.4
O2—Fe2—O2vii 89.57 (11) C5—C4—H4A 110.4
O2v—Fe2—O2vii 90.43 (11) C3—C4—H4B 110.4
O2vi—Fe2—O2vii 180.0 C5—C4—H4B 110.4
O2iv—Fe2—O2viii 89.56 (11) H4A—C4—H4B 108.6
O2—Fe2—O2viii 90.44 (11) O2—C5—C4 106.3 (4)
O2v—Fe2—O2viii 179.998 (1) O2—C5—H5A 110.5
O2vi—Fe2—O2viii 90.43 (11) C4—C5—H5A 110.5
O2vii—Fe2—O2viii 89.57 (11) O2—C5—H5B 110.5
C5—O2—C2 108.7 (3) C4—C5—H5B 110.5
C5—O2—Fe2 126.5 (3) H5A—C5—H5B 108.7
C2—O2—Fe2 124.7 (3)
O2vi—Fe2—O2—C5 −173.4 (4) C5—O2—C2—C3 18.8 (6)
O2vii—Fe2—O2—C5 6.6 (4) Fe2—O2—C2—C3 −158.5 (4)
O2viii—Fe2—O2—C5 96.1 (4) O2—C2—C3—C4 −21.5 (8)
O2iv—Fe2—O2—C2 −160 (5) C2—C3—C4—C5 15.7 (9)
O2v—Fe2—O2—C2 93.0 (3) C2—O2—C5—C4 −9.6 (6)
O2vi—Fe2—O2—C2 3.4 (3) Fe2—O2—C5—C4 167.7 (4)
O2vii—Fe2—O2—C2 −176.6 (3) C3—C4—C5—O2 −3.8 (8)
O2viii—Fe2—O2—C2 −87.0 (3)
