Arene–perfluoro­arene inter­actions in crystal engineering. XV. Ferrocene–deca­fluoro­biphenyl (1/1)

Batsanov, A.S.; Collings, J.C.; Marder, T.B.

doi:10.1107/S0108270106014090

metal-organic compounds

STRUCTURAL
CHEMISTRY

ISSN: 2053-2296

Volume 62| Part 6| June 2006| Pages m229-m231

doi:10.1107/S0108270106014090

Arene–perfluoroarene interactions in crystal engineering. XV. Ferrocene–decafluorobiphenyl (1/1)†

Andrei S. Batsanov,^a ^* Jonathan C. Collings ^a and Todd B. Marder ^a ^*

^aDepartment of Chemistry, University of Durham, South Road, Durham DH1 3LE, England
^*Correspondence e-mail: a.s.batsanov@durham.ac.uk, todd.marder@durham.ac.uk

(Received 10 March 2006; accepted 18 April 2006; online 16 May 2006)

The title crystal, [Fe(C₅H₅)₂]·C₁₂F₁₀, comprises infinite chains of alternating component molecules, linked through face-to-face contacts of nearly parallel cyclopentadienyl and pentafluorophenyl rings. The decafluorobiphenyl molecule has a crystallographic twofold axis and the Fe atom of the ferrocene molecule is on a crystallographic inversion centre, with both cyclopentadienyl rings disordered.

Comment

The propensity of perfluoroarenes to form 1:1 cocrystals with arenes is now well known [for references to earlier work, see Dahl (1988 ) and Collings, Roscoe et al. (2002 )]. A recurrent feature of such solids is a mixed stack of alternating arene and perfluoroarene molecules, with parallel or nearly parallel planes. Contrary to original expectations, a geometric match between the components is unnecessary, and stable combinations can include molecules of very disparate size and form (Bunz & Enkelmann, 1999 ; Batsanov et al., 2001 ; Collings, Roscoe et al., 2002; Collings, Batsanov et al., 2002 ; Collings et al., 2005 , 2006 ). Thus, sandwich π-complexes of transition metals can also form mixed infinite stacks with perfluoroarenes. Beck et al. (1998 ) were the first to prove this, with a 1:1 adduct of decamethylferrocene with perfluorophenanthrene. Unlike ordinary arenes, however, π-complexes show a variety of other structural motifs. Thus, a 1:1 adduct of ferrocene with perfluorophenanthrene (Burdeniuc et al., 1997 ) presents a sandwich of two ferrocene molecules enclosed between two perfluorophenanthrene molecules. The complex between ferrocene and octafluoronaphthalene (OFN) has an unusual 2:3 stoichiometry (Clyburne et al., 2001 ). Nevetheless, the structure contains mixed stacks of 1:1 composition, with additional perpendicularly oriented OFN molecules inserted between the stacks. In 1:2 complexes of ferrocene or nickelocene with Hg₃(C₆F₄)₂, recently reported by Haneline & Gabbai (2004 ), the cyclopentadienyl ring is stacked with an organomercury heterocycle rather than a tetrafluorobenzene moiety. Probably the most interesting structure is the 1:1 adduct of ferrocene with perfluorotetraphenylene, reported by Day et al. (2001 ). In this structure, a continuous chain is formed through face-to-face contacts of cyclopentadienyl and tetrafluorophenylene rings, notwithstanding substantial non-planarity of the perfluoroarene molecule.

With these examples in mind, we undertook a cocrystallization of ferrocene with decafluorobiphenyl (DFB). The latter molecule must have a twisted conformation to avoid unfavourable contacts between peri-F atoms. In the gas phase, the dihedral angle between the benzene rings is 70° (Almenningen et al., 1968 ); in pure solid DFB, it decreases to 59.6° at room temperature (Gleason & Britton, 1976 ) and 57.0° at 100 K (Batsanov & Howard, 2003 ), while in 1:1 cocrystals with biphenyl (Naae, 1979 ) and naphthalene (Foss et al., 1984 ) it is smaller still, at 50.8 and 55.3°, respectively. Both cocrystals contain mixed stacks of alternating nearly parallel arene and perfluoroarene rings, in contrast with the herring-bone motif of pure DFB. Note that non-panarity of both biphenyl and DFB molecules does not preclude parallel stacking of their individual rings.

The title decafluorobiphenyl–ferrocene adduct, (I), has a 1:1 stoichiometry (Fig. 1), the asymmmetric unit comprising one-half of the formula unit. The DFB molecule possesses crystallographic C₂ symmetry, the twofold axis passing through the mid-point of the C11—C11ⁱ bond. The twist of this molecule [55.3 (1)°] is similar to that in other molecular complexes, as well as that in solid DFB. Such a conformation results in intramolecular contacts F2⋯F2ⁱ = 2.845 (2) Å and F6⋯F6ⁱ = 2.841 (2) Å, which are only moderately shorter than the normal intermolecular F⋯F contact of 3.00 Å (Rowland & Taylor, 1996 ). In fact, the shortest F⋯F contacts in the structure are intermolecular, viz. F2⋯F6(1 − x, 1 + y, $[{1\over 2}]$ − z) and its equivalents, at 2.642 (2) Å. Each DFB molecule participates in four such contacts, with two adjacent molecules related by the translations ±b.

The Fe atom is situated on a crystallographic inversion centre. Each cyclopentadienyl (Cp) ring is disordered between two orientations which differ by a ca 32° rotation around the fivefold axis, thus creating an ambiguity as to whether the actual conformation of an individual molecule is eclipsed or staggered. We presume, by analogy with the disorder in the monoclinic phase of pure ferrocene (Seiler & Dunitz, 1979 ), that the actual conformation is eclipsed, as shown in Fig. 1. The Cp rings are parallel within experimental error; the Fe-to-ring plane distance [mean 1.65 (1) Å], as in other ferrocene–perfluoroarene adducts, agrees with the absence of charge transfer, in contrast with the HFB–bis(benzene)chromium(0) complex, which does show charge-transfer character (Aspley et al., 1999 ).

The ferrocene molecule is sandwiched between two (inversion-related) pentafluorophenyl moieties. The contacting Cp and benzene rings are nearly parallel [dihedral angles of 9.1 (3) and 8.8 (3)° for the two Cp orientations], with an average interplanar separation of ca 3.3 Å. The resulting motif is a zigzag chain of alternating ferrocene and DFB molecules, running in the general direction of the c axis (Fig. 2). On the `rear' side, the pentafluorophenyl moiety is contacted by a perfluorophenyl group of an adjacent chain, in a herring-bone manner [dihedral angle = 55.3 (1)°].

Most arene–perfluoroarene complexes are remarkable for having higher melting points than either of the components, as was first observed by Patrick & Prosser (1960 ) on the seminal benzene–HFB complex, which has a melting point of 296.9 K, cf. 278.6 K for benzene and 278.2 K for HFB (see also Collings et al., 2001 ; Collings, Roscoe et al., 2002; Collings et al., 2006). Therefore, we studied the thermal behaviour of (I), the components of which have melting points of 342 (DFB) and 446 K (ferrocene) and boiling points of 479 and 522 K, respectively. Thermal gravimetric analysis (TGA) of (I) shows the loss of mass starting at 333 K and ending at 403 K, probably due to sublimation. Differential scanning calorimetry (DSC) at a rate of 5 K min⁻¹ showed two sharp endotherms at 369 and 381 K, with ΔH = 16 and 25 J g⁻¹, respectively (ca 8 and 13 kJ mol⁻¹, if we presume the original molecular weight). Both endotherms appeared on the first heating cycle only, with subsequent cycles showing a completely featurless curve in the same range, presumably due to sublimation. Transmission polarized light microscopy on a sample of (I) enclosed between two glass slides showed (I) to begin partial melting at ca 377 K, and to have completely evaporated by ca 440 K. Thus, complex (I) displays an intriguing phase behaviour which deserves further investigation.

Figure 1
(a) The molecular structure of (I)

, not showing the disorder. (b) The disorder in the ferrocene molecule. Displacement ellipsoids are drawn at the 50% probability level. [Symmetry codes: (i) 1 − x, y, −z + $[{1\over 2}]$ ; (ii) 1 − x, 1 − y, 1 − z.]

Figure 2
The crystal packing of (I)

. H atoms and the disorder have been omitted. Displacement ellipsoids are drawn at the 50% probability level.

Experimental

Single crystals of ferrocene–decafluorobiphenyl (1/1) were grown by slow evaporation of a 1:1 molar mixture of the two compounds in solution in dichloromethane. Analysis calculated for C₂₂H₁₀F₁₀Fe: C 50.80, H 1.94%; found: C 50.41, H 1.89%.

Crystal data

[Fe(C₅H₅)₂]·C₁₂F₁₀
M_r = 520.15
Monoclinic, C 2/c
a = 13.3025 (12) Å
b = 6.1690 (6) Å
c = 23.026 (2) Å
β = 98.69 (1)°
V = 1867.9 (3) Å³
Z = 4
D_x = 1.847 Mg m⁻³
Mo Kα radiation
μ = 0.91 mm⁻¹
T = 120 (2) K
Block, yellow
0.36 × 0.22 × 0.20 mm

Data collection

Bruker SMART 1K CCD area-detector diffractometer
ω scans
Absorption correction: multi-scan (SADABS; Bruker, 2001 ) T_min = 0.708, T_max = 0.839
10117 measured reflections
2143 independent reflections
1714 reflections with I > 2σ(I)
R_int = 0.045
θ_max = 27.5°

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.039
wR(F²) = 0.098
S = 1.06
2143 reflections
146 parameters
H-atom parameters constrained
w = 1/[σ²(F_o²) + (0.0424P)² + 2.913P] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max = 0.002
Δρ_max = 0.52 e Å⁻³
Δρ_min = −0.39 e Å⁻³

Table 1
Selected bond lengths (Å)

Fe—C1	2.078 (5)
Fe—C2	2.075 (5)
Fe—C3	2.054 (5)
Fe—C4	2.033 (5)
Fe—C5	2.034 (5)
Fe—C6	2.040 (5)
Fe—C7	2.045 (5)
Fe—C8	2.036 (5)
Fe—C9	2.003 (6)
Fe—C10	2.013 (5)
C11—C11ⁱ	1.487 (4)
Symmetry code: (i) $[-x+1, y, -z+{\script{1\over 2}}]$ .

All H atoms were treated as riding on their parent C atoms, with C—H = 0.95 Å and U_iso(H) = 1.2U_eq(C).

Data collection: SMART (Bruker, 1998 ); cell refinement: SMART; data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXTL (Bruker, 2001); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S0108270106014090/bg3003sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S0108270106014090/bg3003Isup2.hkl

Comment top

The propensity of perfluoroarenes to form 1:1 co-crystals with arenes is now well known [for references to earlier work see, for example, Dahl (1988) and Collings et al. (2002) Collings, Roscoe et al. or Collings, Batsanov et al.?]. A recurrent feature of such solids is a mixed stack of alternating arene and perfluoroarene molecules, with parallel or nearly parallel planes. Contrary to original expectations, a geometric match between the components is unnecessary, and stable combinations can include molecules of very disparate size and form (Bunz & Enkelmann, 1999; Batsanov et al., 2001; Collings, Roscoe et al., 2002; Collings, Batsanov et al., 2002; Collings et al., 2005, 2006). Thus, sandwich π-complexes of transition metals can also form mixed infinite stacks with perfluoroarenes. Beck et al. (1998) were the first to prove this, with a 1:1 adduct of decamethylferrocene with perfluorophenanthrene. Unlike ordinary arenes, however, π-complexes show a variety of other structural motifs. Thus, a 1:1 adduct of ferrocene with perfluorophenanthrene (Burdeniuc et al., 1997) presents a sandwich of two ferrocene molecules enclosed between two perfluorophenanthrene molecules. The complex between ferrocene and octafluoronaphthalene (OFN) has an unusual 2:3 stoichiometry (Clyburne et al., 2001). Nevetheless, the structure contains mixed stacks of 1:1 composition, with additional perpendicularly oriented OFN molecules inserted between the stacks. In 1:2 complexes of ferrocene or nickelocene with Hg₃(C₆F₄)₂, recently reported by Haneline & Gabbai (2004), the cyclopentadienyl ring is stacked with an organomercury heterocycle rather than a tetrafluorobenzene moiety. Probably the most interesting is the 1:1 adduct of ferrocene with perfluorotetraphenylene, reported by Day et al. (2001). In this structure, a continuous chain is formed through face-to-face contacts of cyclopentadienyl and tetrafluorophenylene rings, notwithstanding substantial non-planarity of the perfluoroarene molecule.

With these examples in view, we undertook a co-crystallization of ferrocene with decafluorobiphenyl (DFB). The latter molecule must have a twisted conformation to avoid unfavourable contacts between peri-F atoms. In the gas phase, the dihedral angle between the phenyl rings is 70° (Almenningen et al., 1968); in pure solid DFB, it decreases to 59.6° at room temperature (Gleason & Britton, 1976) and 57.0° at 100 K (Batsanov & Howard, 2003), while in 1:1 co-crystals with biphenyl (Naae, 1979) and naphthalene (Foss et al., 1984) it is smaller still, at 50.8 and 55.3°, respectively. Both co-crystals contain mixed stacks of alternating nearly parallel arene and perfluoroarene rings, in contrast with the herring-bone motif of pure DFB. Note that non-panarity of both biphenyl and DFB molecules does not preclude parallel stacking of their individual rings.

The title decafluorobiphenyl–ferrocene adduct, (I), has a 1:1 stoichiometry (Fig. 1), the asymmmetric unit comprising one-half of the formula unit. The DFB molecule possesses crystallographic C₂ symmetry, the twofold axis passing through the midpoint of the C11—C11ⁱ bond. The twist of this molecule [55.3 (1)°] is similar to that in other molecular complexes, as well as that in solid DFB. Such a conformation results in intramolecular contacts F2···F2ⁱ = 2.845 (2) and F6···F6ⁱ = 2.841 (2) Å, which are only moderately shorter than the normal intermolecular F···F contact of 3.00 Å (Rowland & Taylor, 1996). In fact, the shortest F···F contacts in the structure are intermolecular, viz. F2···F6(1 − x, 1 + y, 1/2 − z) and its equivalents, at 2.642 (2) Å. Each DFB molecule participates in four such contacts, with two adjacent molecules related by the translations ±b.

The Fe atom is situated on a crystallographic inversion centre. Each cyclopentadienyl (Cp) ring is disordered between two orientations which differ by a ca 32° rotation around the fivefold axis, thus creating an ambiguity as to whether the actual conformation of an individual molecule is eclipsed or staggered. We presume, by analogy with the disorder in the monoclinic phase of pure ferrocene (Seiler & Dunitz, 1979), that the actual conformation is eclipsed, as shown in Fig. 1. The Cp rings are parallel to within experimental error; the Fe–ring plane distance [mean 1.65 (1) Å], as in other ferrocene–perfluoroarene adducts, agrees with the absence of charge transfer, in contrast with the HFB.bis(benzene)chromium(0) complex, which does show charge-transfer character (Aspley et al., 1999).

The ferrocene molecule is sandwiched between two (inversion-related) pentafluorophenyl moieties. The contacting Cp and phenyl rings are nearly parallel [dihedral angles 9.1 (3) and 8.8 (3)° for the two Cp orientations)], with an average interplanar separation of ca 3.3 Å. The resulting motif is a zigzag chain of alternating ferrocene and DFB molecules, running in the general direction of the c axis (Fig. 2). On the `rear' side, the pentafluorophenyl moiety is contacted by a perfluorophenyl group of an adjacent chain, in a herring-bone manner [dihedral angle 55.3 (1)°].

Most arene–perfluoroarene complexes are remarkable for having higher melting points than either of the components, as was first observed by Patrick & Prosser (1960) on the seminal benzene–HFB complex, which has a melting point of 296.9 K, cf. 278.6 K for benzene and 278.2 K for HFB (see also Collings et al., 2001; Collings, Roscoe et al., 2002; Collings et al., 2006). Therefore, we studied the thermal behaviour of (I), the components of which have melting points of 342 K (DFB) and 446 K (ferrocene) and boiling points of 479 and 522 K, respectively. Thermal gravimetric analysis (TGA) of (I) shows the loss of mass beginning at 333 K and ending at 403 K, probably due to sublimation. Differential scanning calorimetry (DSC) at a rate of 5 K min⁻¹ showed two sharp endotherms at 369 and 381 K, with ΔH = 16 and 25 J g⁻¹, respectively (ca 8 and 13 kJ mol⁻¹, if we presume the original molecular weight). Both endotherms appeared on the first heating cycle only, with subsequent cycles showing a completely featurless curve in the same range, presumably due to sublimation. Transmission polarized light microscopy on a sample of (I) enclosed between two glass slides showed (I) to begin partial melting at ca 377 K, and to have completely evaporated by ca 440 K. Thus, complex (I) displays an intriguing phase behaviour which deserves further investigation.

Experimental top

Single crystals of ferrocene–decafluorobiphenyl (1:1) were grown by slow evaporation of a 1:1 molar mixture of the two compounds in solution in dichloromethane. Analysis, calculated for C₂₂H₁₀F₁₀Fe: C 50.80, H 1.94%; found: C 50.41, H 1.89%.

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SMART; data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXTL (Bruker, 2001); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Figures top

	Fig. 1. (a) The molecular structure of (I), not showing the disorder. (b) The disorder in the ferrocene molecule. Displacement ellipsoids are drawn at the 50% probability level. [Symmetry codes: (i) 1 − x, y, −z + 1/2; (ii) 1 − x, 1 − y, 1 − z.]
	Fig. 2. The crystal packing of (I). H atoms and the disorder have been omitted. Displacement ellipsoids are drawn at the 50% probability level.

Ferrocene–decafluorobiphenyl (1/1) top

Crystal data top

[Fe(C₅H₅)₂]·C₁₂F₁₀	F(000) = 1032
M_r = 520.15	D_x = 1.847 Mg m⁻³
Monoclinic, C2/c	Melting point: 377 K
Hall symbol: -C 2yc	Mo Kα radiation, λ = 0.71073 Å
a = 13.3025 (12) Å	Cell parameters from 930 reflections
b = 6.1690 (6) Å	θ = 10.2–24.1°
c = 23.026 (2) Å	µ = 0.91 mm⁻¹
β = 98.69 (1)°	T = 120 K
V = 1867.9 (3) Å³	Block, yellow
Z = 4	0.36 × 0.22 × 0.20 mm

Data collection top

Bruker SMART 1K CCD area-detector diffractometer	2143 independent reflections
Radiation source: fine-focus sealed tube	1714 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.045
Detector resolution: 8 pixels mm^-1	θ_max = 27.5°, θ_min = 1.8°
ω scans	h = −16→17
Absorption correction: multi-scan (SADABS; Bruker, 2001)	k = −7→8
T_min = 0.708, T_max = 0.839	l = −29→29
10117 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.098	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.0424P)² + 2.913P] where P = (F_o² + 2F_c²)/3
2143 reflections	(Δ/σ)_max = 0.002
146 parameters	Δρ_max = 0.52 e Å⁻³
0 restraints	Δρ_min = −0.39 e Å⁻³

Crystal data top

[Fe(C₅H₅)₂]·C₁₂F₁₀	V = 1867.9 (3) Å³
M_r = 520.15	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 13.3025 (12) Å	µ = 0.91 mm⁻¹
b = 6.1690 (6) Å	T = 120 K
c = 23.026 (2) Å	0.36 × 0.22 × 0.20 mm
β = 98.69 (1)°

Data collection top

Bruker SMART 1K CCD area-detector diffractometer	2143 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2001)	1714 reflections with I > 2σ(I)
T_min = 0.708, T_max = 0.839	R_int = 0.045
10117 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.039	0 restraints
wR(F²) = 0.098	H-atom parameters constrained
S = 1.06	Δρ_max = 0.52 e Å⁻³
2143 reflections	Δρ_min = −0.39 e Å⁻³
146 parameters

Special details top

Experimental. The data collection nominally covered a full sphere of reciprocal space, by a combination of 5 sets of ω scans; each set at different ϕ and/or 2θ angles and each scan (20 sec exposure) covering 0.3° in ω. Crystal to detector distance 4.43 cm. Before the absorption correction, R_int = 0.052.

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
Fe	0.5000	0.5000	0.5000	0.02156 (14)
F2	0.59664 (10)	0.6891 (2)	0.23070 (6)	0.0234 (3)
F3	0.77374 (10)	0.6984 (2)	0.30388 (6)	0.0301 (3)
F4	0.82534 (10)	0.3668 (3)	0.38007 (6)	0.0335 (4)
F5	0.69800 (12)	0.0225 (2)	0.38181 (6)	0.0312 (3)
F6	0.51663 (11)	0.0204 (2)	0.31240 (6)	0.0264 (3)
C1	0.5164 (4)	0.2348 (8)	0.4466 (2)	0.0207 (10)*	0.50
H1	0.4856	0.0968	0.4481	0.025*	0.50
C2	0.4765 (3)	0.4134 (9)	0.41189 (19)	0.0152 (8)*	0.50
H2	0.4139	0.4147	0.3860	0.018*	0.50
C3	0.5434 (4)	0.5880 (7)	0.4214 (2)	0.0152 (8)*	0.50
H3	0.5342	0.7263	0.4035	0.018*	0.50
C4	0.6290 (4)	0.5234 (10)	0.4631 (3)	0.0264 (10)*	0.50
H4	0.6864	0.6095	0.4775	0.032*	0.50
C5	0.6125 (4)	0.3050 (9)	0.4789 (2)	0.0219 (10)*	0.50
H5	0.6565	0.2197	0.5060	0.026*	0.50
C6	0.4019 (5)	0.4075 (9)	0.5554 (3)	0.0282 (11)*	0.50
H6	0.3737	0.2676	0.5584	0.034*	0.50
C7	0.3592 (4)	0.5755 (10)	0.5195 (2)	0.0208 (9)*	0.50
H7	0.2966	0.5687	0.4936	0.025*	0.50
C8	0.4238 (5)	0.7570 (9)	0.5277 (2)	0.0233 (10)*	0.50
H8	0.4130	0.8936	0.5090	0.028*	0.50
C9	0.5089 (5)	0.6989 (12)	0.5693 (3)	0.0369 (14)*	0.50
H9	0.5654	0.7881	0.5833	0.044*	0.50
C10	0.4961 (5)	0.4845 (11)	0.5870 (2)	0.0318 (11)*	0.50
H10	0.5411	0.4041	0.6147	0.038*	0.50
C11	0.54998 (16)	0.3550 (3)	0.26946 (9)	0.0169 (4)
C12	0.61827 (17)	0.5253 (3)	0.26897 (9)	0.0183 (4)
C13	0.70970 (17)	0.5311 (4)	0.30568 (10)	0.0218 (5)
C14	0.73680 (17)	0.3610 (4)	0.34389 (10)	0.0226 (5)
C15	0.67193 (18)	0.1874 (4)	0.34479 (10)	0.0218 (5)
C16	0.57985 (17)	0.1875 (3)	0.30853 (10)	0.0195 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Fe	0.0203 (2)	0.0274 (3)	0.0179 (2)	0.0066 (2)	0.00576 (17)	0.00131 (19)
F2	0.0239 (7)	0.0210 (6)	0.0253 (7)	−0.0009 (5)	0.0033 (5)	0.0077 (5)
F3	0.0234 (7)	0.0356 (8)	0.0315 (8)	−0.0120 (6)	0.0044 (6)	−0.0016 (6)
F4	0.0194 (7)	0.0523 (9)	0.0262 (8)	0.0042 (6)	−0.0052 (6)	−0.0027 (7)
F5	0.0422 (9)	0.0280 (7)	0.0216 (7)	0.0131 (6)	−0.0004 (6)	0.0065 (6)
F6	0.0370 (8)	0.0176 (6)	0.0242 (7)	−0.0068 (6)	0.0035 (6)	0.0030 (5)
C11	0.0190 (11)	0.0166 (10)	0.0156 (10)	0.0003 (8)	0.0048 (8)	−0.0015 (8)
C12	0.0188 (10)	0.0195 (11)	0.0174 (10)	0.0012 (8)	0.0055 (8)	0.0012 (8)
C13	0.0195 (11)	0.0250 (12)	0.0218 (11)	−0.0034 (9)	0.0060 (9)	−0.0034 (9)
C14	0.0163 (11)	0.0331 (12)	0.0179 (11)	0.0054 (9)	0.0005 (9)	−0.0046 (9)
C15	0.0284 (12)	0.0222 (11)	0.0150 (11)	0.0090 (9)	0.0039 (9)	0.0005 (8)
C16	0.0253 (12)	0.0166 (10)	0.0174 (11)	0.0011 (9)	0.0064 (9)	−0.0018 (8)

Geometric parameters (Å, º) top

Fe—C1	2.078 (5)	C3—H3	0.9477
Fe—C2	2.075 (5)	C4—C5	1.422 (7)
Fe—C3	2.054 (5)	C4—H4	0.9478
Fe—C4	2.033 (5)	C5—H5	0.9476
Fe—C5	2.034 (5)	C6—C7	1.393 (7)
Fe—C6	2.040 (5)	C6—C10	1.431 (8)
Fe—C7	2.045 (5)	C6—H6	0.9478
Fe—C8	2.036 (5)	C7—C8	1.407 (7)
Fe—C9	2.003 (6)	C7—H7	0.9477
Fe—C10	2.013 (5)	C8—C9	1.414 (8)
F2—C12	1.343 (2)	C8—H8	0.9477
F3—C13	1.343 (3)	C9—C10	1.401 (9)
F4—C14	1.336 (3)	C9—H9	0.9479
F5—C15	1.339 (2)	C10—H10	0.9477
F6—C16	1.341 (2)	C11—C16	1.389 (3)
C1—C2	1.416 (6)	C11—C12	1.390 (3)
C1—C5	1.446 (7)	C11—C11ⁱ	1.487 (4)
C1—H1	0.9478	C12—C13	1.373 (3)
C2—C3	1.392 (6)	C13—C14	1.382 (3)
C2—H2	0.9477	C14—C15	1.378 (3)
C3—C4	1.431 (7)	C15—C16	1.374 (3)

C9—Fe—C10	40.8 (3)	C10—C6—Fe	68.3 (3)
C9—Fe—C4	109.8 (2)	C7—C6—H6	126.2
C10—Fe—C4	124.7 (2)	C10—C6—H6	126.3
C9—Fe—C5	126.5 (2)	Fe—C6—H6	126.7
C10—Fe—C5	109.8 (2)	C6—C7—C8	109.0 (4)
C4—Fe—C5	40.9 (2)	C6—C7—Fe	69.9 (3)
C9—Fe—C8	41.0 (2)	C8—C7—Fe	69.5 (3)
C10—Fe—C8	68.7 (2)	C6—C7—H7	125.5
C4—Fe—C8	124.6 (2)	C8—C7—H7	125.5
C5—Fe—C8	162.56 (16)	Fe—C7—H7	126.8
C9—Fe—C6	68.8 (2)	C7—C8—C9	107.5 (5)
C10—Fe—C6	41.4 (2)	C7—C8—Fe	70.2 (3)
C4—Fe—C6	160.42 (17)	C9—C8—Fe	68.3 (3)
C5—Fe—C6	123.1 (2)	C7—C8—H8	126.8
C8—Fe—C6	68.0 (2)	C9—C8—H8	125.8
C2—C1—C5	106.5 (4)	Fe—C8—H8	126.7
C2—C1—Fe	70.0 (3)	C10—C9—C8	108.4 (5)
C5—C1—Fe	67.8 (3)	C10—C9—Fe	70.0 (3)
C2—C1—H1	126.4	C8—C9—Fe	70.7 (3)
C5—C1—H1	127.1	C10—C9—H9	125.0
Fe—C1—H1	126.9	C8—C9—H9	126.6
C3—C2—C1	109.7 (4)	Fe—C9—H9	125.1
C3—C2—Fe	69.5 (2)	C9—C10—C6	107.6 (5)
C1—C2—Fe	70.1 (3)	C9—C10—Fe	69.2 (3)
C3—C2—H2	124.9	C6—C10—Fe	70.3 (3)
C1—C2—H2	125.4	C9—C10—H10	126.7
Fe—C2—H2	126.9	C6—C10—H10	125.7
C2—C3—C4	108.4 (4)	Fe—C10—H10	125.9
C2—C3—Fe	71.1 (3)	C16—C11—C12	116.4 (2)
C4—C3—Fe	68.7 (3)	C16—C11—C11ⁱ	122.20 (16)
C2—C3—H3	126.2	C12—C11—C11ⁱ	121.41 (16)
C4—C3—H3	125.5	F2—C12—C13	117.80 (19)
Fe—C3—H3	125.9	F2—C12—C11	119.89 (19)
C5—C4—C3	107.3 (5)	C13—C12—C11	122.3 (2)
C5—C4—Fe	69.6 (3)	F3—C13—C12	120.6 (2)
C3—C4—Fe	70.3 (3)	F3—C13—C14	119.8 (2)
C5—C4—H4	126.1	C12—C13—C14	119.6 (2)
C3—C4—H4	126.6	F4—C14—C15	120.4 (2)
Fe—C4—H4	125.4	F4—C14—C13	119.8 (2)
C4—C5—C1	108.1 (5)	C15—C14—C13	119.8 (2)
C4—C5—Fe	69.5 (3)	F5—C15—C16	120.6 (2)
C1—C5—Fe	71.0 (3)	F5—C15—C14	119.8 (2)
C4—C5—H5	126.2	C16—C15—C14	119.6 (2)
C1—C5—H5	125.7	F6—C16—C15	118.00 (19)
Fe—C5—H5	125.1	F6—C16—C11	119.60 (19)
C7—C6—C10	107.6 (5)	C15—C16—C11	122.4 (2)
C7—C6—Fe	70.3 (3)

Symmetry code: (i) −x+1, y, −z+1/2.

Experimental details

Crystal data
Chemical formula	[Fe(C₅H₅)₂]·C₁₂F₁₀
M_r	520.15
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	120
a, b, c (Å)	13.3025 (12), 6.1690 (6), 23.026 (2)
β (°)	98.69 (1)
V (Å³)	1867.9 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.91
Crystal size (mm)	0.36 × 0.22 × 0.20

Data collection
Diffractometer	Bruker SMART 1K CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2001)
T_min, T_max	0.708, 0.839
No. of measured, independent and observed [I > 2σ(I)] reflections	10117, 2143, 1714
R_int	0.045
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.098, 1.06
No. of reflections	2143
No. of parameters	146
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.52, −0.39

Computer programs: SMART (Bruker, 1998), SMART, SAINT (Bruker, 2001), SHELXTL (Bruker, 2001), SHELXTL.

Selected bond lengths (Å) top

Fe—C1	2.078 (5)	Fe—C7	2.045 (5)
Fe—C2	2.075 (5)	Fe—C8	2.036 (5)
Fe—C3	2.054 (5)	Fe—C9	2.003 (6)
Fe—C4	2.033 (5)	Fe—C10	2.013 (5)
Fe—C5	2.034 (5)	C11—C11ⁱ	1.487 (4)
Fe—C6	2.040 (5)

Symmetry code: (i) −x+1, y, −z+1/2.

Footnotes

†For Part XIV, see Collings et al. (2006).

Acknowledgements

The authors thank D. Carswell and K. Wonghan for assistance with measurements of the thermal behaviour. TBM thanks One NorthEast for funding.

References

Almenningen, A., Hartmann, A. O. & Seip, H. M. (1968). Acta Chem. Scand. 22, 1013–1024. CrossRef CAS Google Scholar
Aspley, C. J., Boxwell, C., Buil, M. L., Higgitt, C. L., Long, C. & Perutz, R. N. (1999). Chem. Commun. pp. 1027–1028. Web of Science CSD CrossRef Google Scholar
Batsanov, A. S. & Howard, J. A. K. (2003). Private communication to the Cambridge Structural Database, No. CCDC-207400. CCDC, 12 Union Road, Cambridge, England. Google Scholar
Batsanov, A. S., Howard, J. A. K., Marder, T. B. & Robins, E. G. (2001). Acta Cryst. C57, 1303–1305. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Beck, C. M., Burdeniuc, J., Crabtree, R. H., Rheingold, A. L. & Yap, G. P. A. (1998). Inorg. Chim. Acta, 270, 559–562. Web of Science CSD CrossRef CAS Google Scholar
Bruker (1998). SMART. Version 5.049. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bruker (2001). SAINT (Version 6.02a), SADABS (Version 2.03) and SHELXTL (Version 6.12). Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bunz, U. H. F. & Enkelmann, V. (1999). Chem. Eur. J. 5, 263–266. CrossRef CAS Google Scholar
Burdeniuc, J., Crabtree, R. H., Rheingold, A. L. & Yap, G. P. A. (1997). Bull. Soc. Chim. Fr. 134, 955–958. CAS Google Scholar
Clyburne, J. A., Hamilton, T. & Jenkins, H. A. (2001). Cryst. Eng. 4, 1–9. Web of Science CSD CrossRef CAS Google Scholar
Collings, J. C., Batsanov, A. S., Howard, J. A. K., Dickie, D. A., Clyburne, J. A. C., Jenkins, H. A. & Marder, T. B. (2005). J. Fluorine Chem. 126, 515–518. CrossRef CAS Google Scholar
Collings, J. C., Batsanov, A. S., Howard, J. A. K. & Marder, T. B. (2002). Cryst. Eng. 5, 37–46. Web of Science CSD CrossRef CAS Google Scholar
Collings, J. C., Batsanov, A. S., Howard, J. A. K. & Marder, T. B. (2006). Can. J. Chem. 84, 238–242. Web of Science CSD CrossRef CAS Google Scholar
Collings, J. C., Roscoe, K. P., Robins, E. G., Batsanov, A. S., Stimson, L. M., Howard, J. A. K., Clark, S. J. & Marder, T. B. (2002). New J. Chem. 26, 1740–1746. Web of Science CSD CrossRef CAS Google Scholar
Collings, J. C., Roscoe, K. P., Thomas, R. Ll., Batsanov, A. S., Stimson, L. M., Howard, J. A. K. & Marder, T. B. (2001). New J. Chem. 25, 1410–1417. Web of Science CSD CrossRef CAS Google Scholar
Dahl, T. (1988). Acta Chem. Scand. Ser. A, 42, 1–7. CrossRef Google Scholar
Day, M. W., Matxger, A. J. & Grubbs, R. H. (2001). Private communication to the Cambridge Structural Database, No. CCDC-130854. CCDC, 12 Union Road, Cambridge, England. Google Scholar
Foss, L. I., Syed, A., Stevens, E. D. & Klein, C. L. (1984). Acta Cryst. C40, 272–274. CSD CrossRef CAS Web of Science IUCr Journals Google Scholar
Gleason, W. B. & Britton, D. (1976). Cryst. Struct. Commun. 5, 483–488. CAS Google Scholar
Haneline, M. R. & Gabbai, F. P. (2004). Angew. Chem. Int. Ed. 43, 5471–5474. Web of Science CSD CrossRef CAS Google Scholar
Naae, D. G. (1979). Acta Cryst. B35, 2765–2768. CSD CrossRef CAS IUCr Journals Web of Science Google Scholar
Patrick, C. R. & Prosser, G. S. (1960). Nature, 187, 1021. CrossRef Web of Science Google Scholar
Rowland, B. S. & Taylor, R. (1996). J. Phys. Chem. 100, 7384–7391. CrossRef CAS Web of Science Google Scholar
Seiler, P. & Dunitz, J. D. (1979). Acta Cryst. B35, 2020–2032. CSD CrossRef CAS IUCr Journals Web of Science Google Scholar

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