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Acta Cryst. (2007). E63, m1703    [ doi:10.1107/S1600536807024919 ]

Decamethylferrocenium hexafluorophosphate

A. Sánchez Perucha and M. Bolte

Abstract top

The structure of the title compound, [Fe(C10H15)2]PF6, is composed of discrete decamethylferrocenium cations and hexafluorophosphate anions. The Fe and P atoms are located on special positions of site symmetry 2/m, two C atoms and two F atoms are located on a mirror plane, and one F atom is located on a twofold rotation axis. The compound is isostructural with the cobaltocenium complex.

Comment top

Ferrocenium salts have been extensively studied to better understand the mechanisms of reactions involving ferrocene and ferrocenium-type systems.

The structure of the title compound, [C20H30Fe]+[PF6]-, is composed of discrete decamethylferrocenium cations and hexafluorophosphate anions. The Fe and P atoms are located on special positions of site symmetry 2/m, two carbon atoms and two F atoms are located on a mirror plane and one F atom is located on a twofold rotation axis. The title compound is isostructural with the cobaltocenium complex (Braga et al., 1999; Heize et al., 2002).

Related literature top

For related literature, see: Braga et al. (1999); Heize et al. (2002).

Experimental top

Decamethylferrocenium hexafluorophosphate was synthesized from the reaction between decamethylferrocene and AlCl3 in refluxing cyclohexane followed by aqueous workup with NH4PF6. Single crystals of the title compound were obtained by slow diffusion of diethyether in a concentrated solution of the ferrocenium phosphate in acetone.

Refinement top

H atoms were refined with fixed individual displacement parameters [Uiso(H) = 1.5Ueq(C)] using a riding model with C—H = 0.98 Å. Two methyl groups were allowed to rotate but not to tip.

Computing details top

Data collection: X-AREA (Stoe & Cie, 2001); cell refinement: X-AREA; data reduction: X-AREA; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP in SHELXTL-Plus (Sheldrick, 1991); software used to prepare material for publication: SHELXL97.

Figures top
[Figure 1] Fig. 1. Perspective view of the title compound with the atom numbering scheme; displacement ellipsoids are at the 50% probability level. H atoms are omitted for clarity. Symmetry operators for generating equivalent atoms: (A) -x, -y, -z; (B) -x, y, -z; (C) x, -y, z; (D) 1 - x, y, 1 - z.
Decamethylferrocenium hexafluorophosphate top
Crystal data top
[Fe(C10H15)2]PF6F(000) = 490
Mr = 471.26Dx = 1.460 Mg m−3
Monoclinic, C2/mMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yCell parameters from 2101 reflections
a = 14.186 (2) Åθ = 4.1–25.2°
b = 8.9579 (11) ŵ = 0.83 mm−1
c = 8.9902 (13) ÅT = 173 K
β = 110.277 (13)°Plate, green
V = 1071.6 (3) Å30.34 × 0.32 × 0.19 mm
Z = 2
Data collection top
Stoe IPDSII two-circle
diffractometer		1050 independent reflections
Radiation source: fine-focus sealed tube980 reflections with I > 2σ(I)
graphiteRint = 0.030
ω scansθmax = 25.3°, θmin = 2.4°
Absorption correction: multi-scan
(MULABS; Spek, 2003; Blessing, 1995)		h = −17→16
Tmin = 0.765, Tmax = 0.858k = 0→10
8050 measured reflectionsl = 0→10
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.033Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.092H-atom parameters constrained
S = 1.11 w = 1/[σ2(Fo2) + (0.0564P)2 + 0.6562P]
where P = (Fo2 + 2Fc2)/3
1050 reflections(Δ/σ)max < 0.001
76 parametersΔρmax = 0.36 e Å−3
0 restraintsΔρmin = −0.53 e Å−3
Crystal data top
[Fe(C10H15)2]PF6V = 1071.6 (3) Å3
Mr = 471.26Z = 2
Monoclinic, C2/mMo Kα radiation
a = 14.186 (2) ŵ = 0.83 mm−1
b = 8.9579 (11) ÅT = 173 K
c = 8.9902 (13) Å0.34 × 0.32 × 0.19 mm
β = 110.277 (13)°
Data collection top
Stoe IPDSII two-circle
diffractometer		1050 independent reflections
Absorption correction: multi-scan
(MULABS; Spek, 2003; Blessing, 1995)		980 reflections with I > 2σ(I)
Tmin = 0.765, Tmax = 0.858Rint = 0.030
8050 measured reflectionsθmax = 25.3°
Refinement top
R[F2 > 2σ(F2)] = 0.033H-atom parameters constrained
wR(F2) = 0.092Δρmax = 0.36 e Å−3
S = 1.11Δρmin = −0.53 e Å−3
1050 reflectionsAbsolute structure: ?
76 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Fe10.00000.00000.00000.0139 (2)
C10.1113 (2)0.0000−0.1024 (3)0.0247 (6)
C20.12225 (13)0.1297 (2)−0.0034 (2)0.0224 (4)
C30.14081 (13)0.0798 (2)0.1560 (2)0.0207 (4)
C40.0977 (3)0.0000−0.2774 (4)0.0475 (11)
H4A0.06110.0891−0.33010.071*
H4B0.16660.0000−0.27820.071*
C50.11647 (17)0.2895 (3)−0.0577 (4)0.0439 (7)
H5A0.09780.35340.01620.066*
H5B0.06580.2985−0.16400.066*
H5C0.18200.3206−0.06050.066*
C60.16194 (17)0.1773 (3)0.2996 (3)0.0410 (6)
H6A0.13250.27620.26720.061*
H6B0.23470.18700.35260.061*
H6C0.13240.13230.37270.061*
P10.50000.00000.50000.0218 (3)
F10.45456 (15)0.00000.6409 (2)0.0373 (5)
F20.50000.1787 (2)0.50000.0512 (6)
F30.38896 (16)0.00000.3702 (2)0.0532 (6)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Fe10.0142 (3)0.0147 (3)0.0126 (3)0.0000.0043 (2)0.000
C10.0194 (13)0.0368 (18)0.0193 (14)0.0000.0084 (11)0.000
C20.0155 (8)0.0221 (11)0.0284 (10)−0.0026 (8)0.0061 (8)0.0044 (9)
C30.0135 (9)0.0248 (11)0.0216 (9)−0.0017 (8)0.0035 (7)−0.0066 (8)
C40.0378 (18)0.088 (3)0.0218 (15)0.0000.0162 (14)0.000
C50.0303 (11)0.0307 (14)0.0664 (17)−0.0022 (10)0.0114 (11)0.0206 (13)
C60.0292 (11)0.0513 (17)0.0370 (12)−0.0035 (11)0.0045 (9)−0.0258 (12)
P10.0303 (6)0.0173 (6)0.0191 (5)0.0000.0101 (4)0.000
F10.0541 (12)0.0360 (11)0.0311 (10)0.0000.0266 (9)0.000
F20.0998 (18)0.0194 (11)0.0481 (12)0.0000.0430 (12)0.000
F30.0355 (11)0.0796 (19)0.0374 (11)0.0000.0037 (9)0.000
Geometric parameters (Å, °) top
Fe1—C12.085 (3)C3—C61.500 (3)
Fe1—C1i2.085 (3)C4—H4A0.9798
Fe1—C2ii2.0962 (18)C4—H4B0.9804
Fe1—C2i2.0962 (18)C5—H5A0.9800
Fe1—C2iii2.0962 (18)C5—H5B0.9800
Fe1—C22.0963 (18)C5—H5C0.9800
Fe1—C3ii2.1275 (18)C6—H6A0.9800
Fe1—C32.1275 (18)C6—H6B0.9800
Fe1—C3i2.1276 (18)C6—H6C0.9800
Fe1—C3iii2.1276 (18)P1—F2iv1.601 (2)
C1—C2ii1.439 (3)P1—F21.601 (2)
C1—C21.439 (3)P1—F3iv1.603 (2)
C1—C41.517 (4)P1—F31.603 (2)
C2—C31.435 (3)P1—F1iv1.6085 (17)
C2—C51.506 (3)P1—F11.6085 (17)
C3—C3ii1.430 (4)
C1—Fe1—C1i180.00 (6)C2—C1—C4126.10 (12)
C1—Fe1—C2ii40.25 (7)C2ii—C1—Fe170.29 (12)
C1i—Fe1—C2ii139.75 (7)C2—C1—Fe170.29 (12)
C1—Fe1—C2i139.75 (7)C4—C1—Fe1127.9 (2)
C1i—Fe1—C2i40.25 (7)C3—C2—C1108.03 (18)
C2ii—Fe1—C2i112.69 (11)C3—C2—C5126.2 (2)
C1—Fe1—C2iii139.75 (7)C1—C2—C5125.8 (2)
C1i—Fe1—C2iii40.25 (7)C3—C2—Fe171.31 (11)
C2ii—Fe1—C2iii180.00 (6)C1—C2—Fe169.45 (13)
C2i—Fe1—C2iii67.30 (11)C5—C2—Fe1125.40 (14)
C1—Fe1—C240.25 (7)C3ii—C3—C2108.13 (12)
C1i—Fe1—C2139.75 (7)C3ii—C3—C6125.59 (15)
C2ii—Fe1—C267.31 (11)C2—C3—C6126.2 (2)
C2i—Fe1—C2180.0C3ii—C3—Fe170.36 (6)
C2iii—Fe1—C2112.69 (11)C2—C3—Fe168.96 (10)
C1—Fe1—C3ii67.01 (9)C6—C3—Fe1128.67 (14)
C1i—Fe1—C3ii112.99 (9)C1—C4—H4A110.9
C2ii—Fe1—C3ii39.72 (8)C1—C4—H4B103.8
C2i—Fe1—C3ii113.37 (7)H4A—C4—H4B111.1
C2iii—Fe1—C3ii140.28 (8)C2—C5—H5A109.5
C2—Fe1—C3ii66.63 (7)C2—C5—H5B109.5
C1—Fe1—C367.01 (9)H5A—C5—H5B109.5
C1i—Fe1—C3112.99 (9)C2—C5—H5C109.5
C2ii—Fe1—C366.63 (7)H5A—C5—H5C109.5
C2i—Fe1—C3140.28 (8)H5B—C5—H5C109.5
C2iii—Fe1—C3113.37 (7)C3—C6—H6A109.5
C2—Fe1—C339.72 (8)C3—C6—H6B109.5
C3ii—Fe1—C339.27 (11)H6A—C6—H6B109.5
C1—Fe1—C3i112.99 (9)C3—C6—H6C109.5
C1i—Fe1—C3i67.01 (9)H6A—C6—H6C109.5
C2ii—Fe1—C3i113.37 (7)H6B—C6—H6C109.5
C2i—Fe1—C3i39.72 (8)F2iv—P1—F2179.999 (1)
C2iii—Fe1—C3i66.63 (7)F2iv—P1—F3iv90.0
C2—Fe1—C3i140.27 (8)F2—P1—F3iv90.0
C3ii—Fe1—C3i140.73 (11)F2iv—P1—F390.0
C3—Fe1—C3i180.0F2—P1—F390.0
C1—Fe1—C3iii112.99 (9)F3iv—P1—F3180.0
C1i—Fe1—C3iii67.01 (9)F2iv—P1—F1iv90.0
C2ii—Fe1—C3iii140.28 (8)F2—P1—F1iv90.0
C2i—Fe1—C3iii66.63 (7)F3iv—P1—F1iv90.73 (11)
C2iii—Fe1—C3iii39.72 (8)F3—P1—F1iv89.27 (11)
C2—Fe1—C3iii113.37 (7)F2iv—P1—F190.001 (1)
C3ii—Fe1—C3iii180.0F2—P1—F190.0
C3—Fe1—C3iii140.73 (11)F3iv—P1—F189.27 (11)
C3i—Fe1—C3iii39.27 (11)F3—P1—F190.73 (11)
C2ii—C1—C2107.7 (2)F1iv—P1—F1179.999 (1)
C2ii—C1—C4126.11 (12)
C1i—Fe1—C1—C2ii59.05 (8)C3—Fe1—C2—C1118.41 (18)
C2i—Fe1—C1—C2ii−61.9 (2)C3i—Fe1—C2—C1−61.59 (18)
C2iii—Fe1—C1—C2ii180.0C3iii—Fe1—C2—C1−98.51 (14)
C2—Fe1—C1—C2ii118.1 (2)C1—Fe1—C2—C5120.0 (2)
C3ii—Fe1—C1—C2ii37.63 (12)C1i—Fe1—C2—C5−60.0 (2)
C3—Fe1—C1—C2ii80.46 (14)C2ii—Fe1—C2—C5158.17 (18)
C3i—Fe1—C1—C2ii−99.54 (14)C2i—Fe1—C2—C511 (16)
C3iii—Fe1—C1—C2ii−142.36 (12)C2iii—Fe1—C2—C5−21.83 (18)
C1i—Fe1—C1—C2−59.05 (17)C3ii—Fe1—C2—C5−158.5 (2)
C2ii—Fe1—C1—C2−118.1 (2)C3—Fe1—C2—C5−121.6 (3)
C2i—Fe1—C1—C2180.0C3i—Fe1—C2—C558.4 (3)
C2iii—Fe1—C1—C261.9 (2)C3iii—Fe1—C2—C521.5 (2)
C3ii—Fe1—C1—C2−80.46 (14)C1—C2—C3—C3ii−0.34 (17)
C3—Fe1—C1—C2−37.64 (12)C5—C2—C3—C3ii−179.64 (16)
C3i—Fe1—C1—C2142.36 (12)Fe1—C2—C3—C3ii59.68 (5)
C3iii—Fe1—C1—C299.54 (14)C1—C2—C3—C6176.75 (19)
C1i—Fe1—C1—C4180.00 (7)C5—C2—C3—C6−2.6 (3)
C2ii—Fe1—C1—C4120.95 (11)Fe1—C2—C3—C6−123.23 (19)
C2i—Fe1—C1—C459.05 (11)C1—C2—C3—Fe1−60.02 (15)
C2iii—Fe1—C1—C4−59.05 (11)C5—C2—C3—Fe1120.7 (2)
C2—Fe1—C1—C4−120.95 (11)C1—Fe1—C3—C3ii−81.29 (5)
C3ii—Fe1—C1—C4158.59 (6)C1i—Fe1—C3—C3ii98.71 (5)
C3—Fe1—C1—C4−158.59 (6)C2ii—Fe1—C3—C3ii−37.33 (7)
C3i—Fe1—C1—C421.41 (6)C2i—Fe1—C3—C3ii60.58 (11)
C3iii—Fe1—C1—C4−21.41 (6)C2iii—Fe1—C3—C3ii142.67 (7)
C2ii—C1—C2—C30.5 (3)C2—Fe1—C3—C3ii−119.42 (11)
C4—C1—C2—C3−175.7 (3)C3i—Fe1—C3—C3ii−91 (2)
Fe1—C1—C2—C361.19 (13)C3iii—Fe1—C3—C3ii180.0
C2ii—C1—C2—C5179.85 (14)C1—Fe1—C3—C238.13 (11)
C4—C1—C2—C53.6 (4)C1i—Fe1—C3—C2−141.87 (11)
Fe1—C1—C2—C5−119.5 (2)C2ii—Fe1—C3—C282.09 (16)
C2ii—C1—C2—Fe1−60.65 (17)C2i—Fe1—C3—C2180.0
C4—C1—C2—Fe1123.1 (3)C2iii—Fe1—C3—C2−97.91 (16)
C1—Fe1—C2—C3−118.41 (18)C3ii—Fe1—C3—C2119.42 (11)
C1i—Fe1—C2—C361.59 (18)C3i—Fe1—C3—C228 (2)
C2ii—Fe1—C2—C3−80.24 (12)C3iii—Fe1—C3—C2−60.58 (11)
C2i—Fe1—C2—C3132 (16)C1—Fe1—C3—C6158.3 (2)
C2iii—Fe1—C2—C399.76 (12)C1i—Fe1—C3—C6−21.7 (2)
C3ii—Fe1—C2—C3−36.92 (13)C2ii—Fe1—C3—C6−157.7 (2)
C3i—Fe1—C2—C3180.0C2i—Fe1—C3—C6−59.8 (3)
C3iii—Fe1—C2—C3143.08 (13)C2iii—Fe1—C3—C622.3 (2)
C1i—Fe1—C2—C1180.0C2—Fe1—C3—C6120.2 (3)
C2ii—Fe1—C2—C138.16 (14)C3ii—Fe1—C3—C6−120.4 (2)
C2i—Fe1—C2—C1−109 (16)C3i—Fe1—C3—C6149 (2)
C2iii—Fe1—C2—C1−141.84 (14)C3iii—Fe1—C3—C659.6 (2)
C3ii—Fe1—C2—C181.49 (14)
Symmetry codes: (i) −x, −y, −z; (ii) x, −y, z; (iii) −x, y, −z; (iv) −x+1, −y, −z+1.
references
References top

Blessing, R. H. (1995). Acta Cryst. A51, 33–38.

Braga, D., Benedi, O., Maini, L. & Grepioni, F. (1999). J. Chem. Soc. Dalton Trans. pp. 2611–2618.

Heise, H., Köhler, F. H., Herker, M. & Hiller, W. (2002). J. Am. Chem. Soc. 124, 10823–10832.

Sheldrick, G. M. (1991). SHELXTL-Plus. Release 4.1. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA.

Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.

Spek, A. L. (2003). J. Appl. Cryst. 36, 7–13.

Stoe & Cie (2001). X-AREA. Stoe & Cie, Darmstadt, Germany.