Decamethyl­ferrocenium hexa­fluoro­phosphate

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.

Key indicators

• Single-crystal X-ray study
• T = 173 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.033
• wR factor = 0.092
• Data-to-parameter ratio = 13.8

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT244_ALERT_4_C Low   'Solvent' Ueq as Compared to Neighbors for         P1
PLAT380_ALERT_4_C Check Incorrectly? Oriented X(sp2)-Methyl Moiety         C4
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #          1
            C1  -FE1 -C1  -C2     59.05  0.08   5.555   1.555   1.555   6.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #          9
            C1  -FE1 -C1  -C2    -59.05  0.17   5.555   1.555   1.555   1.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         17
            C1  -FE1 -C1  -C4    180.00  0.07   5.555   1.555   1.555   1.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         37
            C2  -FE1 -C2  -C3    132.00 16.00   5.555   1.555   1.555   1.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         44
            C2  -FE1 -C2  -C1   -109.00 16.00   5.555   1.555   1.555   1.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         53
            C2  -FE1 -C2  -C5     11.00 16.00   5.555   1.555   1.555   1.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         73
            C3  -FE1 -C3  -C3    -91.00  2.00   5.555   1.555   1.555   6.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         81
            C3  -FE1 -C3  -C2     28.00  2.00   5.555   1.555   1.555   1.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         90
            C3  -FE1 -C3  -C6    149.00  2.00   5.555   1.555   1.555   1.555
PLAT742_ALERT_1_C Angle   Calc    90.00(1), Rep       90.00 ......    Missing su
              F2   -P1   -F3      1.555   1.555   1.555
PLAT742_ALERT_1_C Angle   Calc    90.00(1), Rep       90.00 ......    Missing su
              F2   -P1   -F1      1.555   1.555   1.555

Alert level G
PLAT794_ALERT_5_G Check Predicted Bond Valency for Fe1         (3)       3.24

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
  13 ALERT level C = Check and explain
   1 ALERT level G = General alerts; check

   2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 ALERT type 2 Indicator that the structure model may be wrong or deficient
   0 ALERT type 3 Indicator that the structure quality may be low
  11 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check

---

S1. Comment

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

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

S2. Experimental

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.

S3. Refinement

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

Computing details

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

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

Crystal data

[Fe(C10H15)2]PF6	F(000) = 490
Mr = 471.26	Dx = 1.460 Mg m^−3
Monoclinic, C2/m	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2y	Cell parameters from 2101 reflections
a = 14.186 (2) Å	θ = 4.1–25.2°
b = 8.9579 (11) Å	µ = 0.83 mm^−1
c = 8.9902 (13) Å	T = 173 K
β = 110.277 (13)°	Plate, green
V = 1071.6 (3) Å^3	0.34 × 0.32 × 0.19 mm
Z = 2

Data collection

Stoe IPDSII two-circle diffractometer	1050 independent reflections
Radiation source: fine-focus sealed tube	980 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.030
ω scans	θmax = 25.3°, θmin = 2.4°
Absorption correction: multi-scan (MULABS; Spek, 2003; Blessing, 1995)	h = −17→16
Tmin = 0.765, Tmax = 0.858	k = 0→10
8050 measured reflections	l = 0→10

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.033	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.092	H-atom parameters constrained
S = 1.11	w = 1/[σ^2(Fo^2) + (0.0564P)^2 + 0.6562P] where P = (Fo^2 + 2Fc^2)/3
1050 reflections	(Δ/σ)max < 0.001
76 parameters	Δρmax = 0.36 e Å^−3
0 restraints	Δρmin = −0.54 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
Fe1	0.0000	0.0000	0.0000	0.0139 (2)
C1	0.1113 (2)	0.0000	−0.1024 (3)	0.0247 (6)
C2	0.12225 (13)	0.1297 (2)	−0.0034 (2)	0.0224 (4)
C3	0.14081 (13)	0.0798 (2)	0.1560 (2)	0.0207 (4)
C4	0.0977 (3)	0.0000	−0.2774 (4)	0.0475 (11)
H4A	0.0611	0.0891	−0.3301	0.071*
H4B	0.1666	0.0000	−0.2782	0.071*
C5	0.11647 (17)	0.2895 (3)	−0.0577 (4)	0.0439 (7)
H5A	0.0978	0.3534	0.0162	0.066*
H5B	0.0658	0.2985	−0.1640	0.066*
H5C	0.1820	0.3206	−0.0605	0.066*
C6	0.16194 (17)	0.1773 (3)	0.2996 (3)	0.0410 (6)
H6A	0.1325	0.2762	0.2672	0.061*
H6B	0.2347	0.1870	0.3526	0.061*
H6C	0.1324	0.1323	0.3727	0.061*
P1	0.5000	0.0000	0.5000	0.0218 (3)
F1	0.45456 (15)	0.0000	0.6409 (2)	0.0373 (5)
F2	0.5000	0.1787 (2)	0.5000	0.0512 (6)
F3	0.38896 (16)	0.0000	0.3702 (2)	0.0532 (6)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Fe1	0.0142 (3)	0.0147 (3)	0.0126 (3)	0.000	0.0043 (2)	0.000
C1	0.0194 (13)	0.0368 (18)	0.0193 (14)	0.000	0.0084 (11)	0.000
C2	0.0155 (8)	0.0221 (11)	0.0284 (10)	−0.0026 (8)	0.0061 (8)	0.0044 (9)
C3	0.0135 (9)	0.0248 (11)	0.0216 (9)	−0.0017 (8)	0.0035 (7)	−0.0066 (8)
C4	0.0378 (18)	0.088 (3)	0.0218 (15)	0.000	0.0162 (14)	0.000
C5	0.0303 (11)	0.0307 (14)	0.0664 (17)	−0.0022 (10)	0.0114 (11)	0.0206 (13)
C6	0.0292 (11)	0.0513 (17)	0.0370 (12)	−0.0035 (11)	0.0045 (9)	−0.0258 (12)
P1	0.0303 (6)	0.0173 (6)	0.0191 (5)	0.000	0.0101 (4)	0.000
F1	0.0541 (12)	0.0360 (11)	0.0311 (10)	0.000	0.0266 (9)	0.000
F2	0.0998 (18)	0.0194 (11)	0.0481 (12)	0.000	0.0430 (12)	0.000
F3	0.0355 (11)	0.0796 (19)	0.0374 (11)	0.000	0.0037 (9)	0.000

Geometric parameters (Å, º)

Fe1—C1	2.085 (3)	C3—C6	1.500 (3)
Fe1—C1^i	2.085 (3)	C4—H4A	0.9798
Fe1—C2^ii	2.0962 (18)	C4—H4B	0.9804
Fe1—C2^i	2.0962 (18)	C5—H5A	0.9800
Fe1—C2^iii	2.0962 (18)	C5—H5B	0.9800
Fe1—C2	2.0963 (18)	C5—H5C	0.9800
Fe1—C3^ii	2.1275 (18)	C6—H6A	0.9800
Fe1—C3	2.1275 (18)	C6—H6B	0.9800
Fe1—C3^i	2.1276 (18)	C6—H6C	0.9800
Fe1—C3^iii	2.1276 (18)	P1—F2^iv	1.601 (2)
C1—C2^ii	1.439 (3)	P1—F2	1.601 (2)
C1—C2	1.439 (3)	P1—F3^iv	1.603 (2)
C1—C4	1.517 (4)	P1—F3	1.603 (2)
C2—C3	1.435 (3)	P1—F1^iv	1.6085 (17)
C2—C5	1.506 (3)	P1—F1	1.6085 (17)
C3—C3^ii	1.430 (4)
C1—Fe1—C1^i	180.00 (6)	C2—C1—C4	126.10 (12)
C1—Fe1—C2^ii	40.25 (7)	C2^ii—C1—Fe1	70.29 (12)
C1^i—Fe1—C2^ii	139.75 (7)	C2—C1—Fe1	70.29 (12)
C1—Fe1—C2^i	139.75 (7)	C4—C1—Fe1	127.9 (2)
C1^i—Fe1—C2^i	40.25 (7)	C3—C2—C1	108.03 (18)
C2^ii—Fe1—C2^i	112.69 (11)	C3—C2—C5	126.2 (2)
C1—Fe1—C2^iii	139.75 (7)	C1—C2—C5	125.8 (2)
C1^i—Fe1—C2^iii	40.25 (7)	C3—C2—Fe1	71.31 (11)
C2^ii—Fe1—C2^iii	180.00 (6)	C1—C2—Fe1	69.45 (13)
C2^i—Fe1—C2^iii	67.30 (11)	C5—C2—Fe1	125.40 (14)
C1—Fe1—C2	40.25 (7)	C3^ii—C3—C2	108.13 (12)
C1^i—Fe1—C2	139.75 (7)	C3^ii—C3—C6	125.59 (15)
C2^ii—Fe1—C2	67.31 (11)	C2—C3—C6	126.2 (2)
C2^i—Fe1—C2	180.0	C3^ii—C3—Fe1	70.36 (6)
C2^iii—Fe1—C2	112.69 (11)	C2—C3—Fe1	68.96 (10)
C1—Fe1—C3^ii	67.01 (9)	C6—C3—Fe1	128.67 (14)
C1^i—Fe1—C3^ii	112.99 (9)	C1—C4—H4A	110.9
C2^ii—Fe1—C3^ii	39.72 (8)	C1—C4—H4B	103.8
C2^i—Fe1—C3^ii	113.37 (7)	H4A—C4—H4B	111.1
C2^iii—Fe1—C3^ii	140.28 (8)	C2—C5—H5A	109.5
C2—Fe1—C3^ii	66.63 (7)	C2—C5—H5B	109.5
C1—Fe1—C3	67.01 (9)	H5A—C5—H5B	109.5
C1^i—Fe1—C3	112.99 (9)	C2—C5—H5C	109.5
C2^ii—Fe1—C3	66.63 (7)	H5A—C5—H5C	109.5
C2^i—Fe1—C3	140.28 (8)	H5B—C5—H5C	109.5
C2^iii—Fe1—C3	113.37 (7)	C3—C6—H6A	109.5
C2—Fe1—C3	39.72 (8)	C3—C6—H6B	109.5
C3^ii—Fe1—C3	39.27 (11)	H6A—C6—H6B	109.5
C1—Fe1—C3^i	112.99 (9)	C3—C6—H6C	109.5
C1^i—Fe1—C3^i	67.01 (9)	H6A—C6—H6C	109.5
C2^ii—Fe1—C3^i	113.37 (7)	H6B—C6—H6C	109.5
C2^i—Fe1—C3^i	39.72 (8)	F2^iv—P1—F2	179.999 (1)
C2^iii—Fe1—C3^i	66.63 (7)	F2^iv—P1—F3^iv	90.0
C2—Fe1—C3^i	140.27 (8)	F2—P1—F3^iv	90.0
C3^ii—Fe1—C3^i	140.73 (11)	F2^iv—P1—F3	90.0
C3—Fe1—C3^i	180.0	F2—P1—F3	90.0
C1—Fe1—C3^iii	112.99 (9)	F3^iv—P1—F3	180.0
C1^i—Fe1—C3^iii	67.01 (9)	F2^iv—P1—F1^iv	90.0
C2^ii—Fe1—C3^iii	140.28 (8)	F2—P1—F1^iv	90.0
C2^i—Fe1—C3^iii	66.63 (7)	F3^iv—P1—F1^iv	90.73 (11)
C2^iii—Fe1—C3^iii	39.72 (8)	F3—P1—F1^iv	89.27 (11)
C2—Fe1—C3^iii	113.37 (7)	F2^iv—P1—F1	90.001 (1)
C3^ii—Fe1—C3^iii	180.0	F2—P1—F1	90.0
C3—Fe1—C3^iii	140.73 (11)	F3^iv—P1—F1	89.27 (11)
C3^i—Fe1—C3^iii	39.27 (11)	F3—P1—F1	90.73 (11)
C2^ii—C1—C2	107.7 (2)	F1^iv—P1—F1	179.999 (1)
C2^ii—C1—C4	126.11 (12)
C1^i—Fe1—C1—C2^ii	59.05 (8)	C3—Fe1—C2—C1	118.41 (18)
C2^i—Fe1—C1—C2^ii	−61.9 (2)	C3^i—Fe1—C2—C1	−61.59 (18)
C2^iii—Fe1—C1—C2^ii	180.0	C3^iii—Fe1—C2—C1	−98.51 (14)
C2—Fe1—C1—C2^ii	118.1 (2)	C1—Fe1—C2—C5	120.0 (2)
C3^ii—Fe1—C1—C2^ii	37.63 (12)	C1^i—Fe1—C2—C5	−60.0 (2)
C3—Fe1—C1—C2^ii	80.46 (14)	C2^ii—Fe1—C2—C5	158.17 (18)
C3^i—Fe1—C1—C2^ii	−99.54 (14)	C2^i—Fe1—C2—C5	11 (16)
C3^iii—Fe1—C1—C2^ii	−142.36 (12)	C2^iii—Fe1—C2—C5	−21.83 (18)
C1^i—Fe1—C1—C2	−59.05 (17)	C3^ii—Fe1—C2—C5	−158.5 (2)
C2^ii—Fe1—C1—C2	−118.1 (2)	C3—Fe1—C2—C5	−121.6 (3)
C2^i—Fe1—C1—C2	180.0	C3^i—Fe1—C2—C5	58.4 (3)
C2^iii—Fe1—C1—C2	61.9 (2)	C3^iii—Fe1—C2—C5	21.5 (2)
C3^ii—Fe1—C1—C2	−80.46 (14)	C1—C2—C3—C3^ii	−0.34 (17)
C3—Fe1—C1—C2	−37.64 (12)	C5—C2—C3—C3^ii	−179.64 (16)
C3^i—Fe1—C1—C2	142.36 (12)	Fe1—C2—C3—C3^ii	59.68 (5)
C3^iii—Fe1—C1—C2	99.54 (14)	C1—C2—C3—C6	176.75 (19)
C1^i—Fe1—C1—C4	180.00 (7)	C5—C2—C3—C6	−2.6 (3)
C2^ii—Fe1—C1—C4	120.95 (11)	Fe1—C2—C3—C6	−123.23 (19)
C2^i—Fe1—C1—C4	59.05 (11)	C1—C2—C3—Fe1	−60.02 (15)
C2^iii—Fe1—C1—C4	−59.05 (11)	C5—C2—C3—Fe1	120.7 (2)
C2—Fe1—C1—C4	−120.95 (11)	C1—Fe1—C3—C3^ii	−81.29 (5)
C3^ii—Fe1—C1—C4	158.59 (6)	C1^i—Fe1—C3—C3^ii	98.71 (5)
C3—Fe1—C1—C4	−158.59 (6)	C2^ii—Fe1—C3—C3^ii	−37.33 (7)
C3^i—Fe1—C1—C4	21.41 (6)	C2^i—Fe1—C3—C3^ii	60.58 (11)
C3^iii—Fe1—C1—C4	−21.41 (6)	C2^iii—Fe1—C3—C3^ii	142.67 (7)
C2^ii—C1—C2—C3	0.5 (3)	C2—Fe1—C3—C3^ii	−119.42 (11)
C4—C1—C2—C3	−175.7 (3)	C3^i—Fe1—C3—C3^ii	−91 (2)
Fe1—C1—C2—C3	61.19 (13)	C3^iii—Fe1—C3—C3^ii	180.0
C2^ii—C1—C2—C5	179.85 (14)	C1—Fe1—C3—C2	38.13 (11)
C4—C1—C2—C5	3.6 (4)	C1^i—Fe1—C3—C2	−141.87 (11)
Fe1—C1—C2—C5	−119.5 (2)	C2^ii—Fe1—C3—C2	82.09 (16)
C2^ii—C1—C2—Fe1	−60.65 (17)	C2^i—Fe1—C3—C2	180.0
C4—C1—C2—Fe1	123.1 (3)	C2^iii—Fe1—C3—C2	−97.91 (16)
C1—Fe1—C2—C3	−118.41 (18)	C3^ii—Fe1—C3—C2	119.42 (11)
C1^i—Fe1—C2—C3	61.59 (18)	C3^i—Fe1—C3—C2	28 (2)
C2^ii—Fe1—C2—C3	−80.24 (12)	C3^iii—Fe1—C3—C2	−60.58 (11)
C2^i—Fe1—C2—C3	132 (16)	C1—Fe1—C3—C6	158.3 (2)
C2^iii—Fe1—C2—C3	99.76 (12)	C1^i—Fe1—C3—C6	−21.7 (2)
C3^ii—Fe1—C2—C3	−36.92 (13)	C2^ii—Fe1—C3—C6	−157.7 (2)
C3^i—Fe1—C2—C3	180.0	C2^i—Fe1—C3—C6	−59.8 (3)
C3^iii—Fe1—C2—C3	143.08 (13)	C2^iii—Fe1—C3—C6	22.3 (2)
C1^i—Fe1—C2—C1	180.0	C2—Fe1—C3—C6	120.2 (3)
C2^ii—Fe1—C2—C1	38.16 (14)	C3^ii—Fe1—C3—C6	−120.4 (2)
C2^i—Fe1—C2—C1	−109 (16)	C3^i—Fe1—C3—C6	149 (2)
C2^iii—Fe1—C2—C1	−141.84 (14)	C3^iii—Fe1—C3—C6	59.6 (2)
C3^ii—Fe1—C2—C1	81.49 (14)

Symmetry codes: (i) −x, −y, −z; (ii) x, −y, z; (iii) −x, y, −z; (iv) −x+1, −y, −z+1.