(2,2-Dichloro-vinyl)ferrocene.

The title compound, [Fe(C(5)H(5))(C(7)H(5)Cl(2))], represents a versatile building block for the preparation of π-conjugated redox-active compounds or polymetallic organometallic systems due to the presence of the electrochemically active ferrocenyl unit. It is therefore a potential starting material for the preperation of the corresponding alkyne. In the crystal, the alkenyl unit and the cyclo-penta-dienide ring are almost parallel, with an angle between the best planes of only 10.6 (4)°.

Related literature

The title compound was first prepared in 1963, see: Schloegl et al. (1963 ▶). For an alternative synthesis using a Corey–Fuchs route, see: Luo et al. (2000 ▶). For the preparation of some other halo-vinyl ferrocenes, see: Naskar et al. (2000 ▶). For related functionalized ferrocenes, see: Clément et al. (2007a ▶) and for [2.2]paracyclo­phanes, see: Clément et al. (2007b ▶). For the parent compound, ethenylferrocene, see: McAdam et al. (2008 ▶).

Experimental

Crystal data

[Fe(C5H5)(C7H5Cl2)]

M = 280.95

Monoclinic,

a = 14.340 (3) Å

b = 7.4370 (15) Å

c = 10.932 (2) Å

β = 108.48 (3)°

V = 1105.8 (4) Å3

Z = 4

Mo Kα radiation

μ = 1.81 mm−1

T = 173 K

0.3 × 0.2 × 0.2 mm

Data collection

Bruker SMART APEX CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 1999 ▶) T min = 0.594, T max = 0.694

3293 measured reflections

1908 independent reflections

1372 reflections with I > 2σ(I)

R int = 0.05

Refinement

R[F 2 > 2σ(F 2)] = 0.063

wR(F 2) = 0.174

S = 1.02

1908 reflections

136 parameters

H-atom parameters constrained

Δρmax = 1.04 e Å−3

Δρmin = −0.46 e Å−3

Data collection: SMART (Bruker, 2001 ▶); cell refinement: SAINT-Plus (Bruker, 1999 ▶); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS90 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809006102/zl2181sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809006102/zl2181Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

[Fe(C5H5)(C7H5Cl2)]	F(000) = 568
Mr = 280.95	Dx = 1.688 Mg m−3
Monoclinic, P21/c	Melting point: 382 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 14.340 (3) Å	Cell parameters from 1338 reflections
b = 7.4370 (15) Å	θ = 1.5–25.0°
c = 10.932 (2) Å	µ = 1.81 mm−1
β = 108.48 (3)°	T = 173 K
V = 1105.8 (4) Å3	Irregular, red
Z = 4	0.3 × 0.2 × 0.2 mm

Bruker APEX CCD diffractometer	1908 independent reflections
Radiation source: fine-focus sealed tube	1372 reflections with I > 2σ(I)
graphite	Rint = 0.05
ω scans	θmax = 25.0°, θmin = 1.5°
Absorption correction: multi-scan (SADABS; Bruker, 1999)	h = −10→17
Tmin = 0.594, Tmax = 0.694	k = −8→7
3293 measured reflections	l = −12→11

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)] = 0.063	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.174	H-atom parameters constrained
S = 1.02	w = 1/[σ2(Fo2) + (0.0967P)2 + 0.0275P] where P = (Fo2 + 2Fc2)/3
1908 reflections	(Δ/σ)max < 0.001
136 parameters	Δρmax = 1.04 e Å−3
0 restraints	Δρmin = −0.46 e Å−3

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.

	x	y	z	Uiso*/Ueq
C1	0.3941 (5)	0.1149 (9)	1.0606 (6)	0.0309 (16)
C2	0.3017 (5)	0.0654 (9)	1.0059 (6)	0.0286 (16)
H2	0.2812	−0.0326	1.0468	0.034*
C3	0.2268 (5)	0.1356 (9)	0.8940 (6)	0.0262 (15)
C4	0.2322 (5)	0.2584 (8)	0.7962 (6)	0.0297 (16)
H4	0.2932	0.3182	0.7905	0.036*
C5	0.1361 (6)	0.2818 (9)	0.7090 (7)	0.0339 (17)
H5	0.1177	0.3602	0.6306	0.041*
C6	0.0706 (5)	0.1740 (10)	0.7506 (7)	0.0350 (18)
H6	−0.0018	0.1629	0.7067	0.042*
C7	0.1254 (5)	0.0827 (10)	0.8631 (6)	0.0319 (17)
H7	0.0985	−0.0039	0.9133	0.038*
C8	0.2636 (6)	−0.0694 (10)	0.6107 (7)	0.0389 (19)
H8	0.32	−0.0011	0.5981	0.047*
C9	0.2703 (6)	−0.1880 (10)	0.7137 (8)	0.0372 (18)
H9	0.3317	−0.2198	0.7847	0.045*
C10	0.1753 (5)	−0.2558 (9)	0.6980 (7)	0.0320 (17)
H10	0.1576	−0.343	0.7567	0.038*
C11	0.1090 (5)	−0.1753 (9)	0.5874 (7)	0.0327 (17)
H11	0.0365	−0.1969	0.5529	0.039*
C12	0.1664 (5)	−0.0579 (11)	0.5309 (6)	0.0366 (19)
H12	0.1408	0.0166	0.4511	0.044*
Cl1	0.45229 (14)	0.2850 (3)	1.00576 (19)	0.0410 (5)
Cl2	0.46791 (14)	0.0177 (3)	1.20093 (18)	0.0452 (6)
Fe1	0.17755 (7)	0.01793 (12)	0.71562 (9)	0.0219 (3)

	U11	U22	U33	U12	U13	U23
C1	0.031 (4)	0.032 (4)	0.022 (4)	0.001 (3)	−0.002 (3)	−0.003 (3)
C2	0.030 (4)	0.029 (4)	0.026 (4)	−0.001 (3)	0.007 (3)	0.000 (3)
C3	0.030 (4)	0.023 (4)	0.021 (3)	0.001 (3)	0.002 (3)	−0.005 (3)
C4	0.034 (4)	0.024 (4)	0.023 (3)	−0.003 (3)	−0.003 (3)	−0.001 (3)
C5	0.039 (4)	0.024 (4)	0.029 (4)	0.007 (3)	−0.002 (3)	−0.006 (3)
C6	0.030 (4)	0.039 (5)	0.034 (4)	0.008 (3)	0.007 (3)	−0.005 (3)
C7	0.036 (4)	0.036 (4)	0.023 (4)	−0.003 (3)	0.009 (3)	−0.007 (3)
C8	0.043 (5)	0.037 (4)	0.041 (5)	−0.004 (4)	0.021 (4)	−0.011 (3)
C9	0.029 (4)	0.034 (4)	0.047 (5)	0.011 (3)	0.008 (4)	−0.002 (3)
C10	0.035 (4)	0.022 (4)	0.041 (4)	−0.002 (3)	0.015 (4)	−0.009 (3)
C11	0.025 (4)	0.036 (4)	0.035 (4)	−0.008 (3)	0.006 (3)	−0.016 (3)
C12	0.034 (4)	0.054 (5)	0.020 (4)	0.012 (4)	0.006 (3)	−0.011 (3)
Cl1	0.0320 (10)	0.0469 (12)	0.0410 (10)	−0.0091 (9)	0.0072 (8)	−0.0002 (9)
Cl2	0.0374 (12)	0.0488 (13)	0.0356 (10)	0.0041 (9)	−0.0081 (9)	0.0021 (8)
Fe1	0.0202 (5)	0.0199 (6)	0.0227 (5)	−0.0013 (4)	0.0026 (4)	−0.0025 (4)

C1—C2	1.321 (9)	C7—Fe1	2.038 (7)
C1—Cl1	1.725 (7)	C7—H7	1
C1—Cl2	1.723 (7)	C8—C12	1.393 (10)
C2—C3	1.446 (9)	C8—C9	1.410 (10)
C2—H2	0.95	C8—Fe1	2.040 (7)
C3—C4	1.427 (9)	C8—H8	1
C3—C7	1.438 (10)	C9—C10	1.412 (10)
C3—Fe1	2.048 (6)	C9—Fe1	2.033 (7)
C4—C5	1.416 (10)	C9—H9	1
C4—Fe1	2.038 (6)	C10—C11	1.412 (10)
C4—H4	1	C10—Fe1	2.044 (6)
C5—C6	1.415 (10)	C10—H10	1
C5—Fe1	2.045 (7)	C11—C12	1.465 (10)
C5—H5	1	C11—Fe1	2.030 (7)
C6—C7	1.407 (9)	C11—H11	1
C6—Fe1	2.054 (7)	C12—Fe1	2.054 (6)
C6—H6	1	C12—H12	1
C2—C1—Cl1	125.0 (6)	C12—C11—Fe1	69.8 (4)
C2—C1—Cl2	122.1 (6)	C10—C11—H11	126.3
Cl1—C1—Cl2	112.9 (4)	C12—C11—H11	126.3
C1—C2—C3	130.7 (7)	Fe1—C11—H11	126.3
C1—C2—H2	114.6	C8—C12—C11	106.5 (7)
C3—C2—H2	114.6	C8—C12—Fe1	69.6 (4)
C4—C3—C2	131.5 (7)	C11—C12—Fe1	68.1 (4)
C4—C3—C7	106.8 (6)	C8—C12—H12	126.8
C2—C3—C7	121.7 (6)	C11—C12—H12	126.7
C4—C3—Fe1	69.2 (4)	Fe1—C12—H12	126.7
C2—C3—Fe1	126.2 (5)	C11—Fe1—C9	68.6 (3)
C7—C3—Fe1	69.0 (4)	C11—Fe1—C4	162.8 (3)
C5—C4—C3	108.1 (6)	C9—Fe1—C4	120.2 (3)
C5—C4—Fe1	70.0 (4)	C11—Fe1—C10	40.6 (3)
C3—C4—Fe1	69.9 (4)	C9—Fe1—C10	40.5 (3)
C5—C4—H4	125.9	C4—Fe1—C10	155.2 (3)
C3—C4—H4	126	C11—Fe1—C7	119.6 (3)
Fe1—C4—H4	126	C9—Fe1—C7	126.3 (3)
C6—C5—C4	108.5 (6)	C4—Fe1—C7	68.8 (3)
C6—C5—Fe1	70.1 (4)	C10—Fe1—C7	108.1 (3)
C4—C5—Fe1	69.4 (4)	C11—Fe1—C8	68.5 (3)
C6—C5—H5	125.7	C9—Fe1—C8	40.5 (3)
C4—C5—H5	125.7	C4—Fe1—C8	107.7 (3)
Fe1—C5—H5	125.7	C10—Fe1—C8	67.9 (3)
C5—C6—C7	108.1 (6)	C7—Fe1—C8	163.6 (3)
C5—C6—Fe1	69.5 (4)	C11—Fe1—C12	42.0 (3)
C7—C6—Fe1	69.3 (4)	C9—Fe1—C12	68.3 (3)
C5—C6—H6	126	C4—Fe1—C12	124.4 (3)
C7—C6—H6	126	C10—Fe1—C12	68.9 (3)
Fe1—C6—H6	126	C7—Fe1—C12	155.4 (3)
C6—C7—C3	108.5 (6)	C8—Fe1—C12	39.8 (3)
C6—C7—Fe1	70.5 (4)	C11—Fe1—C5	125.7 (3)
C3—C7—Fe1	69.8 (4)	C9—Fe1—C5	155.0 (3)
C6—C7—H7	125.8	C4—Fe1—C5	40.6 (3)
C3—C7—H7	125.8	C10—Fe1—C5	163.0 (3)
Fe1—C7—H7	125.8	C7—Fe1—C5	68.0 (3)
C12—C8—C9	109.8 (7)	C8—Fe1—C5	120.4 (3)
C12—C8—Fe1	70.6 (4)	C12—Fe1—C5	107.3 (3)
C9—C8—Fe1	69.5 (4)	C11—Fe1—C3	154.8 (3)
C12—C8—H8	125.1	C9—Fe1—C3	107.6 (3)
C9—C8—H8	125.1	C4—Fe1—C3	40.9 (3)
Fe1—C8—H8	125.1	C10—Fe1—C3	120.4 (3)
C8—C9—C10	108.0 (7)	C7—Fe1—C3	41.2 (3)
C8—C9—Fe1	70.0 (4)	C8—Fe1—C3	125.8 (3)
C10—C9—Fe1	70.2 (4)	C12—Fe1—C3	161.7 (3)
C8—C9—H9	126	C5—Fe1—C3	68.4 (3)
C10—C9—H9	126	C11—Fe1—C6	107.6 (3)
Fe1—C9—H9	126	C9—Fe1—C6	163.2 (3)
C9—C10—C11	108.3 (7)	C4—Fe1—C6	68.3 (3)
C9—C10—Fe1	69.3 (4)	C10—Fe1—C6	126.1 (3)
C11—C10—Fe1	69.2 (4)	C7—Fe1—C6	40.2 (3)
C9—C10—H10	125.8	C8—Fe1—C6	154.9 (3)
C11—C10—H10	125.8	C12—Fe1—C6	120.5 (3)
Fe1—C10—H10	125.8	C5—Fe1—C6	40.4 (3)
C10—C11—C12	107.4 (6)	C3—Fe1—C6	68.5 (3)
C10—C11—Fe1	70.2 (4)