1-(Ferrocen-1-ylmeth­yl)-3-methyl­imidazol-3-ium hexa­fluorido­phosphate

Nyamori, V.O.; Zulu, S.M.; Omondi, B.

doi:10.1107/S1600536812008719

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 68| Part 4| April 2012| Page m353

doi:10.1107/S1600536812008719

Open

access

1-(Ferrocen-1-ylmethyl)-3-methylimidazol-3-ium hexafluoridophosphate

Vincent O. Nyamori,^a Siphesihle M. Zulu ^a and Bernard Omondi ^a ^*

^aSchool of Chemistry, University of KwaZulu-Natal, Westville Campus, Private Bag X54001, Durban 4000, South Africa
^*Correspondence e-mail: owaga@ukzn.ac.za

(Received 20 February 2012; accepted 27 February 2012; online 3 March 2012)

The crystal structure of the title compound, [Fe(C₅H₅)(C₁₀H₁₂N₂)]PF₆, consists of a ferrocene-1-methyl-(3-methylimidazolium) cation and a hexafluoridophosphate anion. The ferrocenyl rings are skewed by 6.7 (4)° from the ideal eclipsed conformation. The interplanar angle between the plane of the substituted cyclopentadienyl ring and that of the imidazole ring is 89.9 (4)°. The crystal packing is stabilized by C—H⋯F hydrogen bonds.

Related literature

For background to the chemistry of ferrocenes and their potential applications, see: Štěpnička (2008 ), Kealy & Pauson (1951 ); Togni & Hayashi (1995 ). For related work based on ferrocenylimidazolium salts, see: Nyamori et al. (2010a ); Thomas et al. (2000 , 2002 ). For the synthesis, see: Nyamori et al. (2010b ). For related structures, see Nyamori & Bala (2008 ); Nyamori et al. (2010a).

Experimental

Crystal data

[Fe(C₅H₅)(C₁₀H₁₂N₂)]PF₆
M_r = 426.13
Orthorhombic, P b c a
a = 12.4226 (2) Å
b = 13.4414 (2) Å
c = 19.2137 (3) Å
V = 3208.25 (9) Å³
Z = 8
Mo Kα radiation
μ = 1.11 mm⁻¹
T = 100 K
0.27 × 0.17 × 0.11 mm

Data collection

Bruker SMART APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2008 ) T_min = 0.755, T_max = 0.888
44208 measured reflections
4041 independent reflections
3747 reflections with I > 2σ(I)
R_int = 0.029

Refinement

R[F² > 2σ(F²)] = 0.024
wR(F²) = 0.064
S = 1.04
4041 reflections
227 parameters
H-atom parameters constrained
Δρ_max = 0.46 e Å⁻³
Δρ_min = −0.36 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C14—H14⋯F1ⁱ	0.95	2.54	3.3249 (15)	140
Symmetry code: (i) -x+1, -y+1, -z.

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT-Plus (Bruker, 2008); data reduction: SAINT-Plus and XPREP (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536812008719/fj2522sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812008719/fj2522Isup2.hkl

checkCIF report

Comment top

The discovery of ferrocene heralded a new era in the realm of organometallic chemistry (Kealy & Pauson, 1951). The ferrocene group has unique electronic properties, such as ability to stabilize carbocations. The titled compound (I) consists of a ferrocenyl moiety linked to an imidazole group via a methylene group. The electronic system is very well conjugated and the compound exhibits resonance structures if in solution. The ferrocenyl moiety represents a quite bulky group with unique spatial requirements due to its sandwich shape, and electronically, the powerful donor capacity of ferrocene is important in the stabilization of highly reactive metal centres and other electroactive species. Some of the important properties that ferrocenyl containing imidazolium salts exhibit that makes their study significant include electronic stabilization of adjacent electron-deficient centres due to participation of the iron atom in the dispersal of the positive charge; the unique steric bulk, chemical stability and reversibility of the ferrocene/ferrocenium redox couple.

The ferrocenyl rings exhibit an eclipsed conformation with a significant staggering angle of 6.7° which is smaller than that of Nyamori & Bala (2008) however, Nyamori et al., (2010a) have also synthesized ferrocenyl moiety with a significantly small staggering angle. The interplanar angle between the plane of the substituted Cp ring and that of the imidazole ring is orthogonal (89.9 (4)°) (Fig 1). In the crystal, a weak C–H···F hydrogen bond (Table 1) connects the cations and the anions.

Related literature top

For background to the chemistry of ferrocenes and their potential applications, see: Štěpnička (2008), Kealy & Pauson (1951); Togni & Hayashi (1995). For related work based on ferrocenylimidazolium salts, see: Nyamori et al. (2010a); Thomas et al. (2000, 2002). For the synthesis, see: Nyamori et al. (2010b). For related structures, see Nyamori & Bala (2008); Nyamori et al. (2010a).

Experimental top

In a two-neck round-bottom flask was added sodium hexafluoridophosphate (0.13 g, 0.76 mmol) and 1-(ferrocenylmethyl)-3-methylimidazolium iodide (0.30 g, 0.74 mmol) in acetone (20 ml). The mixture was stirred under a nitrogen atmosphere for 24 h at room temperature. The reaction mixture was filtered through a plug of celite and the filtrate was then concentrated in vacuo to yield 0.23 g, 72% of an orange crystals identified as 1-(Ferrocenylmethyl)-3-methylimidazole hexafluoridophosphate; mp 66–68 °C; IR (ATR cm_1) 3429, 1624, 1567, 1331, 1150, 812, 619,554, 500, 480; 1H NMR (CDCl3) 9.05 (1H, s, NCH), 7.11 (1H, s, NCH), 7.0868 (1H, s, NCH), 5.22 (2H, s, CH2), 4.39 (2H, t, J 1.8, C5H4), 4.23 (7H, t, J 1.8, C5H4), 4.24 (5H, s, C5H5), 3.94 (3H, s, CH3); 13 C NMR (CDCl3) 136.06, 122.79, 121.23, 78.02, 77.23, 69.97, 69.59, 69.19, 50.18; m/z 197 (2.3%), 198.6 (100%), 199.3 (13.1%), 280.6 (M±PF6, 4.5%); Anal. Calc. for C15H17N2Fe+; [M+]-PF6, 281.07411.

Structure description top

For background to the chemistry of ferrocenes and their potential applications, see: Štěpnička (2008), Kealy & Pauson (1951); Togni & Hayashi (1995). For related work based on ferrocenylimidazolium salts, see: Nyamori et al. (2010a); Thomas et al. (2000, 2002). For the synthesis, see: Nyamori et al. (2010b). For related structures, see Nyamori & Bala (2008); Nyamori et al. (2010a).

Computing details top

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT-Plus (Bruker, 2008); data reduction: SAINT-Plus and XPREP (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

Fig. 1. The asymmetric unit of the title compound with displacement ellipsoids drawn at the 50% probability level.

1-(Ferrocen-1-ylmethyl)-3-methylimidazol-3-ium hexafluoridophosphate top

Crystal data top

[Fe(C₅H₅)(C₁₀H₁₂N₂)]PF₆	F(000) = 1728
M_r = 426.13	D_x = 1.764 Mg m⁻³
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 47745 reflections
a = 12.4226 (2) Å	θ = 2.1–28.6°
b = 13.4414 (2) Å	µ = 1.11 mm⁻¹
c = 19.2137 (3) Å	T = 100 K
V = 3208.25 (9) Å³	Block, yellow
Z = 8	0.27 × 0.17 × 0.11 mm

Data collection top

Bruker SMART APEXII CCD diffractometer	3747 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.029
φ and ω scans	θ_max = 28.6°, θ_min = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −16→16
T_min = 0.755, T_max = 0.888	k = −18→17
44208 measured reflections	l = −25→25
4041 independent 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)] = 0.024	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.064	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0307P)² + 2.2775P] where P = (F_o² + 2F_c²)/3
4041 reflections	(Δ/σ)_max = 0.001
227 parameters	Δρ_max = 0.46 e Å⁻³
0 restraints	Δρ_min = −0.36 e Å⁻³

Crystal data top

[Fe(C₅H₅)(C₁₀H₁₂N₂)]PF₆	V = 3208.25 (9) Å³
M_r = 426.13	Z = 8
Orthorhombic, Pbca	Mo Kα radiation
a = 12.4226 (2) Å	µ = 1.11 mm⁻¹
b = 13.4414 (2) Å	T = 100 K
c = 19.2137 (3) Å	0.27 × 0.17 × 0.11 mm

Data collection top

Bruker SMART APEXII CCD diffractometer	4041 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2008)	3747 reflections with I > 2σ(I)
T_min = 0.755, T_max = 0.888	R_int = 0.029
44208 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.024	0 restraints
wR(F²) = 0.064	H-atom parameters constrained
S = 1.04	Δρ_max = 0.46 e Å⁻³
4041 reflections	Δρ_min = −0.36 e Å⁻³
227 parameters

Special details top

Experimental. Carbon-bound H-atoms were placed in calculated positions [C—H = 0.98 Å for Me H atoms, 0.99 Å for Methylene H atoms, 0.99 for methine H atoms and 0.95 Å for aromatic H atoms; U_iso(H) = 1.2U_eq(C) (1.5 for Me groups)] and were included in the refinement in the riding model approximation. The N—H H-atom was located in a difference map and freely refined with N—H = 0.88 Å (U_iso(H) = 1.2U_eq(N).

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. The following ALERTS were generated. Each ALERT has the format test-name_ALERT_alert-type_alert-level. PLAT244_ALERT_4_C Low 'Solvent' U_eq as Compared to Neighbors of P1 PLAT912_ALERT_4_C Missing # of FCF Reflections Above STh/L= 0.600 62 PLAT960_ALERT_3_G Number of Intensities with I. LT. - 2*sig(I) ··· 4 Noted:

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

	x	y	z	U_iso*/U_eq
C1	0.70208 (10)	0.06956 (9)	0.08674 (7)	0.0187 (2)
H1	0.6918	0.0677	0.1383	0.022*
C2	0.63898 (10)	0.01756 (9)	0.03683 (7)	0.0190 (2)
H2	0.5772	−0.0278	0.0471	0.023*
C3	0.67965 (11)	0.04158 (10)	−0.03054 (7)	0.0216 (3)
H3	0.6515	0.0158	−0.0758	0.026*
C4	0.76762 (11)	0.10892 (10)	−0.02199 (7)	0.0219 (3)
H4	0.8118	0.1387	−0.0602	0.026*
C5	0.78092 (10)	0.12621 (10)	0.05054 (7)	0.0203 (3)
H5	0.8359	0.1708	0.0723	0.024*
C6	0.50453 (10)	0.22435 (9)	−0.03703 (7)	0.0163 (2)
H6	0.4707	0.1933	−0.079	0.02*
C7	0.47250 (10)	0.20950 (9)	0.03352 (7)	0.0183 (2)
H7	0.4127	0.1654	0.0497	0.022*
C8	0.54191 (11)	0.26670 (9)	0.07702 (7)	0.0189 (2)
H8	0.5392	0.2697	0.129	0.023*
C9	0.61633 (11)	0.31834 (9)	0.03367 (7)	0.0168 (2)
H9	0.6748	0.364	0.0498	0.02*
C10	0.59352 (10)	0.29181 (9)	−0.03694 (6)	0.0144 (2)
C11	0.65066 (11)	0.32967 (9)	−0.10021 (7)	0.0178 (2)
H11A	0.7149	0.3681	−0.0859	0.021*
H11B	0.675	0.2728	−0.1289	0.021*
C12	0.55414 (10)	0.37912 (9)	−0.20841 (6)	0.0165 (2)
H12	0.5825	0.328	−0.2372	0.02*
C13	0.52134 (10)	0.47496 (9)	−0.11803 (7)	0.0174 (2)
H13	0.5234	0.502	−0.0724	0.021*
C14	0.46165 (10)	0.50875 (9)	−0.17209 (7)	0.0174 (2)
H14	0.4139	0.5639	−0.1716	0.021*
C15	0.43846 (11)	0.45908 (10)	−0.29794 (7)	0.0213 (3)
H15A	0.4663	0.5202	−0.3191	0.032*
H15B	0.3598	0.4628	−0.295	0.032*
H15C	0.4591	0.4018	−0.3265	0.032*
N1	0.57853 (8)	0.39380 (8)	−0.14182 (5)	0.0149 (2)
N2	0.48347 (9)	0.44783 (8)	−0.22797 (5)	0.0152 (2)
F1	0.68267 (7)	0.32029 (6)	0.25538 (6)	0.0312 (2)
F2	0.83765 (8)	0.29514 (8)	0.31564 (5)	0.0337 (2)
F3	0.78054 (9)	0.34815 (8)	0.15824 (5)	0.0390 (2)
F4	0.93499 (7)	0.32338 (7)	0.21887 (5)	0.0332 (2)
F5	0.80333 (8)	0.20561 (7)	0.21913 (5)	0.0346 (2)
F6	0.81291 (7)	0.43793 (6)	0.25467 (5)	0.0303 (2)
Fe1	0.629560 (14)	0.167551 (12)	0.019064 (9)	0.01225 (6)
P1	0.80910 (3)	0.32180 (2)	0.236862 (17)	0.01482 (8)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0200 (6)	0.0167 (6)	0.0193 (6)	0.0016 (5)	−0.0043 (5)	0.0048 (5)
C2	0.0192 (6)	0.0114 (5)	0.0265 (6)	0.0006 (4)	−0.0035 (5)	0.0019 (5)
C3	0.0267 (7)	0.0166 (6)	0.0216 (6)	0.0081 (5)	−0.0035 (5)	−0.0036 (5)
C4	0.0201 (6)	0.0204 (6)	0.0252 (7)	0.0075 (5)	0.0046 (5)	0.0053 (5)
C5	0.0140 (5)	0.0189 (6)	0.0280 (7)	0.0006 (5)	−0.0047 (5)	0.0047 (5)
C6	0.0148 (5)	0.0145 (5)	0.0196 (6)	0.0021 (4)	−0.0032 (4)	0.0010 (5)
C7	0.0153 (5)	0.0164 (6)	0.0233 (6)	0.0028 (5)	0.0022 (5)	0.0026 (5)
C8	0.0243 (6)	0.0157 (5)	0.0167 (6)	0.0036 (5)	0.0026 (5)	−0.0008 (4)
C9	0.0211 (6)	0.0120 (5)	0.0172 (6)	0.0009 (4)	−0.0013 (5)	−0.0012 (4)
C10	0.0157 (5)	0.0120 (5)	0.0155 (5)	0.0026 (4)	−0.0007 (4)	0.0014 (4)
C11	0.0171 (5)	0.0189 (6)	0.0174 (6)	0.0043 (5)	0.0003 (5)	0.0053 (4)
C12	0.0188 (6)	0.0138 (5)	0.0168 (6)	−0.0001 (4)	0.0000 (4)	0.0001 (4)
C13	0.0209 (6)	0.0155 (5)	0.0159 (6)	0.0027 (5)	0.0016 (5)	0.0002 (4)
C14	0.0192 (6)	0.0149 (5)	0.0182 (6)	0.0017 (5)	0.0014 (5)	0.0009 (4)
C15	0.0263 (7)	0.0217 (6)	0.0158 (6)	0.0013 (5)	−0.0058 (5)	0.0009 (5)
N1	0.0161 (5)	0.0134 (5)	0.0154 (5)	0.0011 (4)	0.0005 (4)	0.0028 (4)
N2	0.0165 (5)	0.0140 (5)	0.0152 (5)	−0.0012 (4)	−0.0017 (4)	0.0010 (4)
F1	0.0143 (4)	0.0267 (4)	0.0526 (6)	−0.0019 (3)	−0.0009 (4)	0.0108 (4)
F2	0.0334 (5)	0.0497 (6)	0.0180 (4)	−0.0015 (4)	−0.0067 (4)	0.0080 (4)
F3	0.0562 (6)	0.0405 (5)	0.0202 (4)	−0.0019 (5)	−0.0115 (4)	0.0082 (4)
F4	0.0205 (4)	0.0331 (5)	0.0459 (6)	0.0019 (4)	0.0112 (4)	0.0017 (4)
F5	0.0383 (5)	0.0165 (4)	0.0490 (6)	0.0017 (4)	−0.0128 (4)	−0.0042 (4)
F6	0.0241 (4)	0.0188 (4)	0.0481 (6)	−0.0028 (3)	−0.0019 (4)	−0.0082 (4)
Fe1	0.01293 (10)	0.01083 (9)	0.01299 (9)	0.00042 (6)	−0.00162 (6)	0.00074 (6)
P1	0.01470 (15)	0.01456 (14)	0.01521 (15)	−0.00112 (11)	−0.00222 (11)	0.00146 (11)

Geometric parameters (Å, º) top

C1—C2	1.4222 (18)	C9—Fe1	2.0527 (12)
C1—C5	1.4223 (18)	C9—H9	1
C1—Fe1	2.0585 (12)	C10—C11	1.4968 (17)
C1—H1	1	C10—Fe1	2.0367 (12)
C2—C3	1.4267 (19)	C11—N1	1.4782 (15)
C2—Fe1	2.0482 (13)	C11—H11A	0.99
C2—H2	1	C11—H11B	0.99
C3—C4	1.428 (2)	C12—N2	1.3285 (16)
C3—Fe1	2.0403 (13)	C12—N1	1.3296 (16)
C3—H3	1	C12—H12	0.95
C4—C5	1.4225 (19)	C13—C14	1.3547 (17)
C4—Fe1	2.0456 (13)	C13—N1	1.3797 (16)
C4—H4	1	C13—H13	0.95
C5—Fe1	2.0519 (13)	C14—N2	1.3772 (16)
C5—H5	1	C14—H14	0.95
C6—C7	1.4269 (18)	C15—N2	1.4637 (16)
C6—C10	1.4299 (17)	C15—H15A	0.98
C6—Fe1	2.0389 (12)	C15—H15B	0.98
C6—H6	1	C15—H15C	0.98
C7—C8	1.4258 (19)	F1—P1	1.6106 (9)
C7—Fe1	2.0498 (13)	F2—P1	1.5954 (9)
C7—H7	1	F3—P1	1.5917 (9)
C8—C9	1.4249 (18)	F4—P1	1.6018 (9)
C8—Fe1	2.0497 (13)	F5—P1	1.6001 (9)
C8—H8	1	F6—P1	1.5988 (9)
C9—C10	1.4310 (17)

C2—C1—C5	108.23 (12)	N2—C14—H14	126.6
C2—C1—Fe1	69.35 (7)	N2—C15—H15A	109.5
C5—C1—Fe1	69.50 (7)	N2—C15—H15B	109.5
C2—C1—H1	125.9	H15A—C15—H15B	109.5
C5—C1—H1	125.9	N2—C15—H15C	109.5
Fe1—C1—H1	125.9	H15A—C15—H15C	109.5
C1—C2—C3	107.78 (12)	H15B—C15—H15C	109.5
C1—C2—Fe1	70.13 (7)	C12—N1—C13	108.59 (10)
C3—C2—Fe1	69.28 (7)	C12—N1—C11	124.89 (11)
C1—C2—H2	126.1	C13—N1—C11	126.45 (11)
C3—C2—H2	126.1	C12—N2—C14	108.84 (10)
Fe1—C2—H2	126.1	C12—N2—C15	125.74 (11)
C2—C3—C4	108.06 (12)	C14—N2—C15	125.40 (11)
C2—C3—Fe1	69.87 (7)	C10—Fe1—C6	41.08 (5)
C4—C3—Fe1	69.74 (8)	C10—Fe1—C3	120.05 (5)
C2—C3—H3	126	C6—Fe1—C3	107.22 (5)
C4—C3—H3	126	C10—Fe1—C4	107.24 (5)
Fe1—C3—H3	126	C6—Fe1—C4	125.38 (5)
C5—C4—C3	107.76 (12)	C3—Fe1—C4	40.93 (6)
C5—C4—Fe1	69.92 (7)	C10—Fe1—C2	155.21 (5)
C3—C4—Fe1	69.34 (8)	C6—Fe1—C2	120.01 (5)
C5—C4—H4	126.1	C3—Fe1—C2	40.85 (5)
C3—C4—H4	126.1	C4—Fe1—C2	68.73 (5)
Fe1—C4—H4	126.1	C10—Fe1—C8	68.72 (5)
C1—C5—C4	108.16 (12)	C6—Fe1—C8	68.84 (5)
C1—C5—Fe1	70.01 (7)	C3—Fe1—C8	162.82 (6)
C4—C5—Fe1	69.45 (7)	C4—Fe1—C8	154.87 (6)
C1—C5—H5	125.9	C2—Fe1—C8	125.44 (5)
C4—C5—H5	125.9	C10—Fe1—C7	68.70 (5)
Fe1—C5—H5	125.9	C6—Fe1—C7	40.85 (5)
C7—C6—C10	107.64 (11)	C3—Fe1—C7	125.58 (6)
C7—C6—Fe1	69.99 (7)	C4—Fe1—C7	162.98 (6)
C10—C6—Fe1	69.38 (7)	C2—Fe1—C7	107.61 (5)
C7—C6—H6	126.2	C8—Fe1—C7	40.70 (5)
C10—C6—H6	126.2	C10—Fe1—C5	125.40 (5)
Fe1—C6—H6	126.2	C6—Fe1—C5	162.81 (5)
C8—C7—C6	108.23 (11)	C3—Fe1—C5	68.50 (6)
C8—C7—Fe1	69.65 (7)	C4—Fe1—C5	40.63 (5)
C6—C7—Fe1	69.17 (7)	C2—Fe1—C5	68.40 (5)
C8—C7—H7	125.9	C8—Fe1—C5	120.18 (6)
C6—C7—H7	125.9	C7—Fe1—C5	155.07 (6)
Fe1—C7—H7	125.9	C10—Fe1—C9	40.97 (5)
C9—C8—C7	108.20 (11)	C6—Fe1—C9	69.00 (5)
C9—C8—Fe1	69.79 (7)	C3—Fe1—C9	155.19 (6)
C7—C8—Fe1	69.65 (7)	C4—Fe1—C9	120.01 (6)
C9—C8—H8	125.9	C2—Fe1—C9	162.50 (6)
C7—C8—H8	125.9	C8—Fe1—C9	40.65 (5)
Fe1—C8—H8	125.9	C7—Fe1—C9	68.51 (5)
C8—C9—C10	107.72 (11)	C5—Fe1—C9	107.49 (5)
C8—C9—Fe1	69.57 (7)	C10—Fe1—C1	162.69 (5)
C10—C9—Fe1	68.92 (7)	C6—Fe1—C1	155.08 (5)
C8—C9—H9	126.1	C3—Fe1—C1	68.32 (5)
C10—C9—H9	126.1	C4—Fe1—C1	68.30 (5)
Fe1—C9—H9	126.1	C2—Fe1—C1	40.52 (5)
C6—C10—C9	108.20 (11)	C8—Fe1—C1	107.78 (5)
C6—C10—C11	125.54 (11)	C7—Fe1—C1	120.46 (5)
C9—C10—C11	126.25 (11)	C5—Fe1—C1	40.49 (5)
C6—C10—Fe1	69.54 (7)	C9—Fe1—C1	125.48 (5)
C9—C10—Fe1	70.12 (7)	F3—P1—F2	179.87 (7)
C11—C10—Fe1	127.13 (9)	F3—P1—F6	89.57 (6)
N1—C11—C10	110.49 (10)	F2—P1—F6	90.55 (6)
N1—C11—H11A	109.6	F3—P1—F5	90.29 (6)
C10—C11—H11A	109.6	F2—P1—F5	89.58 (6)
N1—C11—H11B	109.6	F6—P1—F5	179.13 (5)
C10—C11—H11B	109.6	F3—P1—F4	90.57 (6)
H11A—C11—H11B	108.1	F2—P1—F4	89.46 (5)
N2—C12—N1	108.65 (11)	F6—P1—F4	90.25 (5)
N2—C12—H12	125.7	F5—P1—F4	90.62 (5)
N1—C12—H12	125.7	F3—P1—F1	89.71 (6)
C14—C13—N1	107.04 (11)	F2—P1—F1	90.25 (5)
C14—C13—H13	126.5	F6—P1—F1	89.65 (5)
N1—C13—H13	126.5	F5—P1—F1	89.49 (5)
C13—C14—N2	106.90 (11)	F4—P1—F1	179.70 (6)
C13—C14—H14	126.6

C5—C1—C2—C3	0.48 (14)	C5—C4—Fe1—C3	−119.01 (11)
Fe1—C1—C2—C3	59.27 (9)	C5—C4—Fe1—C2	−81.21 (8)
C5—C1—C2—Fe1	−58.79 (9)	C3—C4—Fe1—C2	37.80 (8)
C1—C2—C3—C4	−0.30 (15)	C5—C4—Fe1—C8	48.21 (15)
Fe1—C2—C3—C4	59.51 (9)	C3—C4—Fe1—C8	167.22 (11)
C1—C2—C3—Fe1	−59.80 (9)	C5—C4—Fe1—C7	−161.85 (16)
C2—C3—C4—C5	0.00 (15)	C3—C4—Fe1—C7	−42.8 (2)
Fe1—C3—C4—C5	59.60 (9)	C3—C4—Fe1—C5	119.01 (11)
C2—C3—C4—Fe1	−59.59 (9)	C5—C4—Fe1—C9	81.93 (9)
C2—C1—C5—C4	−0.48 (15)	C3—C4—Fe1—C9	−159.06 (8)
Fe1—C1—C5—C4	−59.17 (9)	C5—C4—Fe1—C1	−37.51 (8)
C2—C1—C5—Fe1	58.70 (9)	C3—C4—Fe1—C1	81.50 (8)
C3—C4—C5—C1	0.29 (15)	C1—C2—Fe1—C10	166.23 (11)
Fe1—C4—C5—C1	59.52 (9)	C3—C2—Fe1—C10	47.29 (15)
C3—C4—C5—Fe1	−59.23 (9)	C1—C2—Fe1—C6	−159.41 (8)
C10—C6—C7—C8	−0.54 (14)	C3—C2—Fe1—C6	81.65 (9)
Fe1—C6—C7—C8	58.86 (9)	C1—C2—Fe1—C3	118.94 (11)
C10—C6—C7—Fe1	−59.39 (8)	C1—C2—Fe1—C4	81.07 (8)
C6—C7—C8—C9	0.78 (14)	C3—C2—Fe1—C4	−37.87 (8)
Fe1—C7—C8—C9	59.34 (9)	C1—C2—Fe1—C8	−75.18 (9)
C6—C7—C8—Fe1	−58.56 (9)	C3—C2—Fe1—C8	165.88 (8)
C7—C8—C9—C10	−0.73 (14)	C1—C2—Fe1—C7	−116.57 (8)
Fe1—C8—C9—C10	58.53 (8)	C3—C2—Fe1—C7	124.49 (8)
C7—C8—C9—Fe1	−59.26 (9)	C1—C2—Fe1—C5	37.27 (8)
C7—C6—C10—C9	0.09 (14)	C3—C2—Fe1—C5	−81.67 (8)
Fe1—C6—C10—C9	−59.69 (8)	C1—C2—Fe1—C9	−42.3 (2)
C7—C6—C10—C11	−178.54 (11)	C3—C2—Fe1—C9	−161.25 (16)
Fe1—C6—C10—C11	121.69 (12)	C3—C2—Fe1—C1	−118.94 (11)
C7—C6—C10—Fe1	59.77 (8)	C9—C8—Fe1—C10	−37.78 (7)
C8—C9—C10—C6	0.39 (14)	C7—C8—Fe1—C10	81.67 (8)
Fe1—C9—C10—C6	59.33 (8)	C9—C8—Fe1—C6	−82.00 (8)
C8—C9—C10—C11	179.01 (11)	C7—C8—Fe1—C6	37.45 (7)
Fe1—C9—C10—C11	−122.06 (12)	C9—C8—Fe1—C3	−161.81 (16)
C8—C9—C10—Fe1	−58.94 (9)	C7—C8—Fe1—C3	−42.4 (2)
C6—C10—C11—N1	66.58 (15)	C9—C8—Fe1—C4	47.57 (15)
C9—C10—C11—N1	−111.80 (14)	C7—C8—Fe1—C4	167.01 (11)
Fe1—C10—C11—N1	156.70 (9)	C9—C8—Fe1—C2	165.49 (8)
N1—C13—C14—N2	−0.09 (14)	C7—C8—Fe1—C2	−75.06 (9)
N2—C12—N1—C13	−0.05 (14)	C9—C8—Fe1—C7	−119.45 (11)
N2—C12—N1—C11	176.98 (11)	C9—C8—Fe1—C5	81.73 (9)
C14—C13—N1—C12	0.09 (14)	C7—C8—Fe1—C5	−158.82 (7)
C14—C13—N1—C11	−176.88 (11)	C7—C8—Fe1—C9	119.45 (11)
C10—C11—N1—C12	−123.38 (13)	C9—C8—Fe1—C1	124.22 (8)
C10—C11—N1—C13	53.11 (16)	C7—C8—Fe1—C1	−116.34 (8)
N1—C12—N2—C14	−0.01 (14)	C8—C7—Fe1—C10	−81.71 (8)
N1—C12—N2—C15	178.28 (11)	C6—C7—Fe1—C10	38.17 (7)
C13—C14—N2—C12	0.06 (14)	C8—C7—Fe1—C6	−119.88 (11)
C13—C14—N2—C15	−178.23 (12)	C8—C7—Fe1—C3	165.83 (8)
C9—C10—Fe1—C6	119.29 (11)	C6—C7—Fe1—C3	−74.28 (9)
C11—C10—Fe1—C6	−119.72 (14)	C8—C7—Fe1—C4	−160.96 (17)
C6—C10—Fe1—C3	81.77 (9)	C6—C7—Fe1—C4	−41.1 (2)
C9—C10—Fe1—C3	−158.93 (8)	C8—C7—Fe1—C2	124.32 (8)
C11—C10—Fe1—C3	−37.94 (13)	C6—C7—Fe1—C2	−115.80 (8)
C6—C10—Fe1—C4	124.51 (8)	C6—C7—Fe1—C8	119.88 (11)
C9—C10—Fe1—C4	−116.19 (8)	C8—C7—Fe1—C5	47.80 (15)
C11—C10—Fe1—C4	4.80 (12)	C6—C7—Fe1—C5	167.69 (11)
C6—C10—Fe1—C2	48.05 (15)	C8—C7—Fe1—C9	−37.56 (7)
C9—C10—Fe1—C2	167.34 (12)	C6—C7—Fe1—C9	82.32 (8)
C11—C10—Fe1—C2	−71.67 (17)	C8—C7—Fe1—C1	81.92 (9)
C6—C10—Fe1—C8	−81.80 (8)	C6—C7—Fe1—C1	−158.19 (7)
C9—C10—Fe1—C8	37.50 (8)	C1—C5—Fe1—C10	166.27 (7)
C11—C10—Fe1—C8	158.48 (13)	C4—C5—Fe1—C10	−74.35 (9)
C6—C10—Fe1—C7	−37.97 (7)	C1—C5—Fe1—C6	−160.03 (16)
C9—C10—Fe1—C7	81.33 (8)	C4—C5—Fe1—C6	−40.7 (2)
C11—C10—Fe1—C7	−157.68 (12)	C1—C5—Fe1—C3	−81.37 (8)
C6—C10—Fe1—C5	165.55 (8)	C4—C5—Fe1—C3	38.01 (8)
C9—C10—Fe1—C5	−75.16 (9)	C1—C5—Fe1—C4	−119.38 (11)
C11—C10—Fe1—C5	45.83 (13)	C1—C5—Fe1—C2	−37.30 (8)
C6—C10—Fe1—C9	−119.29 (11)	C4—C5—Fe1—C2	82.08 (9)
C11—C10—Fe1—C9	120.99 (14)	C1—C5—Fe1—C8	82.11 (9)
C6—C10—Fe1—C1	−163.26 (16)	C4—C5—Fe1—C8	−158.51 (8)
C9—C10—Fe1—C1	−44.0 (2)	C1—C5—Fe1—C7	48.13 (16)
C11—C10—Fe1—C1	77.0 (2)	C4—C5—Fe1—C7	167.51 (11)
C7—C6—Fe1—C10	−118.80 (10)	C1—C5—Fe1—C9	124.63 (8)
C7—C6—Fe1—C3	124.95 (8)	C4—C5—Fe1—C9	−115.99 (8)
C10—C6—Fe1—C3	−116.25 (8)	C4—C5—Fe1—C1	119.38 (11)
C7—C6—Fe1—C4	166.36 (8)	C8—C9—Fe1—C10	119.45 (11)
C10—C6—Fe1—C4	−74.85 (9)	C8—C9—Fe1—C6	81.59 (8)
C7—C6—Fe1—C2	82.31 (9)	C10—C9—Fe1—C6	−37.87 (7)
C10—C6—Fe1—C2	−158.90 (7)	C8—C9—Fe1—C3	167.31 (12)
C7—C6—Fe1—C8	−37.32 (7)	C10—C9—Fe1—C3	47.85 (16)
C10—C6—Fe1—C8	81.47 (8)	C8—C9—Fe1—C4	−158.77 (8)
C10—C6—Fe1—C7	118.80 (10)	C10—C9—Fe1—C4	81.77 (9)
C7—C6—Fe1—C5	−162.29 (16)	C8—C9—Fe1—C2	−42.8 (2)
C10—C6—Fe1—C5	−43.5 (2)	C10—C9—Fe1—C2	−162.21 (16)
C7—C6—Fe1—C9	−81.03 (8)	C10—C9—Fe1—C8	−119.45 (11)
C10—C6—Fe1—C9	37.77 (7)	C8—C9—Fe1—C7	37.61 (8)
C7—C6—Fe1—C1	49.47 (15)	C10—C9—Fe1—C7	−81.84 (8)
C10—C6—Fe1—C1	168.26 (11)	C8—C9—Fe1—C5	−116.25 (8)
C2—C3—Fe1—C10	−159.15 (7)	C10—C9—Fe1—C5	124.30 (8)
C4—C3—Fe1—C10	81.69 (9)	C8—C9—Fe1—C1	−75.24 (9)
C2—C3—Fe1—C6	−116.24 (8)	C10—C9—Fe1—C1	165.30 (7)
C4—C3—Fe1—C6	124.60 (8)	C2—C1—Fe1—C10	−160.41 (16)
C2—C3—Fe1—C4	119.16 (11)	C5—C1—Fe1—C10	−40.6 (2)
C4—C3—Fe1—C2	−119.16 (11)	C2—C1—Fe1—C6	46.28 (16)
C2—C3—Fe1—C8	−42.3 (2)	C5—C1—Fe1—C6	166.14 (11)
C4—C3—Fe1—C8	−161.45 (16)	C2—C1—Fe1—C3	−38.02 (8)
C2—C3—Fe1—C7	−75.00 (9)	C5—C1—Fe1—C3	81.84 (9)
C4—C3—Fe1—C7	165.84 (8)	C2—C1—Fe1—C4	−82.22 (9)
C2—C3—Fe1—C5	81.42 (8)	C5—C1—Fe1—C4	37.64 (8)
C4—C3—Fe1—C5	−37.74 (8)	C5—C1—Fe1—C2	119.86 (11)
C2—C3—Fe1—C9	166.68 (11)	C2—C1—Fe1—C8	124.19 (8)
C4—C3—Fe1—C9	47.53 (16)	C5—C1—Fe1—C8	−115.95 (8)
C2—C3—Fe1—C1	37.73 (8)	C2—C1—Fe1—C7	81.50 (9)
C4—C3—Fe1—C1	−81.43 (8)	C5—C1—Fe1—C7	−158.64 (8)
C5—C4—Fe1—C10	124.73 (8)	C2—C1—Fe1—C5	−119.86 (11)
C3—C4—Fe1—C10	−116.26 (8)	C2—C1—Fe1—C9	165.61 (8)
C5—C4—Fe1—C6	166.34 (7)	C5—C1—Fe1—C9	−74.54 (10)
C3—C4—Fe1—C6	−74.65 (9)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C14—H14···F1ⁱ	0.95	2.54	3.3249 (15)	140

Symmetry code: (i) −x+1, −y+1, −z.

Experimental details

Crystal data
Chemical formula	[Fe(C₅H₅)(C₁₀H₁₂N₂)]PF₆
M_r	426.13
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	100
a, b, c (Å)	12.4226 (2), 13.4414 (2), 19.2137 (3)
V (Å³)	3208.25 (9)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	1.11
Crystal size (mm)	0.27 × 0.17 × 0.11

Data collection
Diffractometer	Bruker SMART APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2008)
T_min, T_max	0.755, 0.888
No. of measured, independent and observed [I > 2σ(I)] reflections	44208, 4041, 3747
R_int	0.029
(sin θ/λ)_max (Å⁻¹)	0.673

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.024, 0.064, 1.04
No. of reflections	4041
No. of parameters	227
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.46, −0.36

Computer programs: APEX2 (Bruker, 2008), SAINT-Plus (Bruker, 2008), SAINT-Plus and XPREP (Bruker, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C14—H14···F1ⁱ	0.95	2.54	3.3249 (15)	140

Symmetry code: (i) −x+1, −y+1, −z.

Acknowledgements

We thank the University of KwaZulu-Natal and the National Research Foundation (NRF) for financial support.

References

Bruker (2008). APEX2, SAINT-Plus, XPREP and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838. CrossRef CAS IUCr Journals Google Scholar
Kealy, T. J. & Pauson, P. L. (1951). Nature (London), 168, 1039–1040. CrossRef CAS Web of Science Google Scholar
Nyamori, V. O. & Bala, M. D. (2008). Acta Cryst. E64, m1376. Web of Science CSD CrossRef IUCr Journals Google Scholar
Nyamori, V. O., Bala, M. D. & Levendis, D. C. (2010a). Acta Cryst. E66, m412. Web of Science CrossRef IUCr Journals Google Scholar
Nyamori, V. O., Gumede, M. & Bala, M. D. (2010b). Organomet. Chem. 695, 1126–1132. CrossRef CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Štěpnička, P. (2008). In Ferrocenes: Ligands, Materials and Biomolecules. Chichester: John Wiley and Sons. Google Scholar
Thomas, J.-L., Howarth, J., Hanlon, K. & McGuirk, D. (2000). Tetrahedron Lett. 41, 413–416. Web of Science CrossRef CAS Google Scholar
Thomas, J.-L., Howarth, J. & Kennedy, A. M. (2002). Molecules, 7, 861–866. Web of Science CrossRef CAS Google Scholar
Togni, A. & Hayashi, T. (1995). In Ferrocenes. Weinheim: VCH. Google Scholar