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Acta Cryst. (2007). E63, m1362    [ doi:10.1107/S1600536807016510 ]

11-Bromo-1-ferrocenylundecan-1-one

C. J. McAdam, B. H. Robinson and J. Simpson

Abstract top

In the title compound, [Fe(C5H5)(C16H24BrO)], the [eta]5-cyclopentadiene rings are essentially eclipsed, while the well ordered chain of the undecanone substituent is bowed significantly towards the Fe atom. In the crystal structure, adjacent molecules form inversion-related dimers through weak C-H...O and C-H...Br interactions. These dimers are further aggregated by intermolecular C-H...[pi] interactions between neighbouring cyclopentadiene rings, forming zigzag chains along the c axis.

Comment top

The title compound, (I), is a useful precursor for the preparation of amino ferrocenyl derivatives (McAdam et al., 2000) or redox active surfactant systems (Saji et al., 2000) and its structure is reported here (Fig. 1). The cyclopentadienyl rings of the ferrocene are approximately eclipsed, with a mean Cm—Cg1—Cg2—Cn torsion angle of 4.2 (2)° (Cg1 and Cg2 are the centroids of the cyclopentadienyl rings, m = 12–16 and n = 17–21). The dihedral angle between the Cp ring mean planes is 4.68 (15)°. The ten-membered methylene chain of the undecanone substituent is nicely ordered and is bowed significantly towards the Fe atom. While the C11 atom lies 0.070 (3) Å above the C12···C16 ring plane, atom C1 is 0.735 (5) Å below that plane in the direction of the Fe1 atom.

In the crystal structure molecules of (I) link in a head-to-tail fashion through C17—H17···Br1 and C1···H1B···O11 hydrogen bonds to form inversion related dimers (Fig 2, Table 1). Then, C14—H14···Cg2 interactions link the dimers into an extended zigzag chain along the c axis (Fig. 3).

Related literature top

The title compound was prepared using the method of Saji et al. (1991). The longest methylene chain to have been examined crystallographically (Cambridge Structural Database, Version 5.28, 2007; Allen, 2002) for a similar ferrocenyl compound is 6-bromohexanoylferrocene (Hursthouse et al., 2003), while that in an organic compound is for 1-(4-tert-butylphenyl)-4-chlorobutan-1-one (Anilkumar et al., 2005). A 1,6-diferrocenylhexane-1,6-dione has also been reported (Pugh et al., 2004).

For related literature, see: McAdam et al. (2000).

Experimental top

The title compound was prepared using the method of Saji et al. (1991). Yellow rectangular plates were grown by slow evaporation from a CH2Cl2–toluene (1:1 v/v) solvent system.

Refinement top

All H atoms were positioned geometrically, with C—H = 0.95–0.99 Å, and refined as riding, with Uiso(H) = 1.2Ueq(C).

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997) and TITAN2000 (Hunter & Simpson, 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997) and TITAN2000; molecular graphics: ORTEP-3 (Farrugia, 1997) and Mercury (Macrae et al., 2006); software used to prepare material for publication: SHELXL97, enCIFer (Allen et al., 2004), PLATON (Spek, 2003) and PARST (Nardelli, 1995).

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), with the atom-labelling scheme and 50% probability displacement ellipsoids.
[Figure 2] Fig. 2. Formation of inversion related dimers of (I) with hydrogen bonds drawn as dashed lines.
[Figure 3] Fig. 3. Part of the packing of (I), with hydrogen bonds drawn as blue dashed lines and C—H···π interactions drawn as purple dashed lines. The red circles represent centroids of the C18···C21 rings.
11-Bromo-1-ferrocenylundecan-1-one top
Crystal data top
[Fe(C5H5)(C15H24BrO)]F(000) = 896
Mr = 433.20Dx = 1.486 Mg m−3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 6638 reflections
a = 5.6027 (2) Åθ = 2.4–32.0°
b = 9.8858 (4) ŵ = 2.85 mm−1
c = 35.0048 (15) ÅT = 85 K
β = 92.576 (2)°Rectangular plate, yellow
V = 1936.86 (13) Å30.53 × 0.12 × 0.03 mm
Z = 4
Data collection top
Bruker APEXII CCD area-detector
diffractometer		7152 independent reflections
Radiation source: fine-focus sealed tube5902 reflections with I > 2σ(I)
graphiteRint = 0.041
φ and ω scansθmax = 34.7°, θmin = 1.2°
Absorption correction: multi-scan
(SADABS; Bruker, 2004)		h = −8→8
Tmin = 0.700, Tmax = 0.918k = −15→14
37380 measured reflectionsl = −52→53
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)] = 0.050Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.120H-atom parameters constrained
S = 1.22 w = 1/[σ2(Fo2) + (0.0441P)2 + 2.8882P]
where P = (Fo2 + 2Fc2)/3
7152 reflections(Δ/σ)max = 0.001
217 parametersΔρmax = 0.97 e Å−3
0 restraintsΔρmin = −2.43 e Å−3
Crystal data top
[Fe(C5H5)(C15H24BrO)]V = 1936.86 (13) Å3
Mr = 433.20Z = 4
Monoclinic, P21/cMo Kα radiation
a = 5.6027 (2) ŵ = 2.85 mm−1
b = 9.8858 (4) ÅT = 85 K
c = 35.0048 (15) Å0.53 × 0.12 × 0.03 mm
β = 92.576 (2)°
Data collection top
Bruker APEXII CCD area-detector
diffractometer		7152 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2004)		5902 reflections with I > 2σ(I)
Tmin = 0.700, Tmax = 0.918Rint = 0.041
37380 measured reflectionsθmax = 34.7°
Refinement top
R[F2 > 2σ(F2)] = 0.050H-atom parameters constrained
wR(F2) = 0.120Δρmax = 0.97 e Å−3
S = 1.22Δρmin = −2.43 e Å−3
7152 reflectionsAbsolute structure: ?
217 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
Br10.44415 (5)0.29956 (3)0.174591 (8)0.02083 (8)
C10.6436 (5)0.2608 (3)0.13114 (7)0.0179 (5)
H1A0.80270.22910.14080.022*
H1B0.56910.18740.11550.022*
C20.6732 (5)0.3844 (2)0.10645 (7)0.0168 (5)
H2A0.78940.36300.08680.020*
H2B0.74250.45790.12260.020*
C30.4447 (5)0.4366 (3)0.08631 (8)0.0186 (5)
H3A0.32920.46100.10580.022*
H3B0.37290.36330.07030.022*
C40.4869 (5)0.5596 (3)0.06113 (8)0.0198 (5)
H4A0.54800.63470.07750.024*
H4B0.61190.53700.04310.024*
C50.2652 (5)0.6077 (3)0.03841 (8)0.0191 (5)
H5A0.14040.63120.05640.023*
H5B0.20330.53260.02210.023*
C60.3113 (5)0.7300 (3)0.01325 (8)0.0184 (5)
H6A0.36030.80720.02980.022*
H6B0.44580.7090−0.00320.022*
C70.0957 (5)0.7721 (3)−0.01212 (7)0.0177 (5)
H7A−0.03790.79500.00430.021*
H7B0.04460.6945−0.02840.021*
C80.1459 (5)0.8929 (3)−0.03771 (7)0.0159 (4)
H8A0.28580.8718−0.05300.019*
H8B0.18790.9719−0.02140.019*
C9−0.0648 (5)0.9311 (3)−0.06499 (7)0.0167 (5)
H9A−0.10510.8533−0.08190.020*
H9B−0.20600.9513−0.05000.020*
C10−0.0073 (4)1.0539 (2)−0.08942 (7)0.0146 (4)
H10A0.04611.1287−0.07230.017*
H10B0.12741.0306−0.10560.017*
C11−0.2143 (4)1.1037 (2)−0.11510 (7)0.0126 (4)
O11−0.4154 (3)1.0556 (2)−0.11395 (6)0.0190 (4)
C12−0.1618 (4)1.2151 (2)−0.14154 (7)0.0112 (4)
C13−0.3250 (4)1.2695 (2)−0.17037 (7)0.0129 (4)
H13−0.48801.2448−0.17450.015*
C14−0.1994 (5)1.3668 (2)−0.19158 (7)0.0151 (4)
H14−0.26451.4185−0.21240.018*
C150.0394 (5)1.3739 (2)−0.17642 (7)0.0143 (4)
H150.16101.4313−0.18530.017*
C160.0661 (4)1.2797 (2)−0.14536 (7)0.0131 (4)
H160.20781.2631−0.13010.016*
Fe1−0.03768 (6)1.18054 (3)−0.194497 (9)0.00942 (8)
C17−0.0130 (4)0.9752 (2)−0.20303 (8)0.0157 (4)
H17−0.05880.9063−0.18590.019*
C18−0.1625 (4)1.0354 (3)−0.23260 (7)0.0159 (4)
H18−0.32481.0132−0.23860.019*
C19−0.0246 (4)1.1347 (3)−0.25143 (7)0.0154 (4)
H19−0.07941.1904−0.27210.018*
C200.2096 (4)1.1356 (3)−0.23371 (7)0.0146 (4)
H200.33821.1919−0.24060.018*
C210.2170 (4)1.0369 (2)−0.20378 (7)0.0148 (4)
H210.35141.0160−0.18730.018*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Br10.02858 (15)0.01801 (13)0.01621 (13)0.00177 (10)0.00468 (10)0.00173 (9)
C10.0245 (12)0.0152 (11)0.0143 (11)0.0046 (9)0.0026 (9)0.0018 (9)
C20.0224 (12)0.0128 (10)0.0153 (11)0.0012 (9)0.0002 (9)0.0025 (8)
C30.0226 (12)0.0162 (11)0.0166 (12)−0.0005 (9)−0.0028 (9)0.0043 (9)
C40.0249 (13)0.0178 (11)0.0163 (12)0.0011 (10)−0.0037 (10)0.0047 (9)
C50.0236 (12)0.0161 (11)0.0172 (12)−0.0001 (9)−0.0022 (10)0.0044 (9)
C60.0248 (13)0.0139 (11)0.0163 (12)0.0016 (9)−0.0022 (10)0.0035 (9)
C70.0234 (12)0.0158 (11)0.0140 (11)0.0022 (9)0.0005 (9)0.0046 (9)
C80.0192 (11)0.0149 (10)0.0134 (11)0.0027 (8)−0.0010 (9)0.0027 (8)
C90.0202 (11)0.0148 (10)0.0155 (11)−0.0002 (9)0.0034 (9)0.0044 (9)
C100.0160 (10)0.0153 (10)0.0124 (10)−0.0008 (8)0.0007 (8)0.0028 (8)
C110.0149 (10)0.0125 (10)0.0106 (10)0.0014 (8)0.0028 (8)0.0004 (8)
O110.0142 (8)0.0210 (9)0.0218 (9)−0.0029 (7)0.0019 (7)0.0068 (7)
C120.0134 (9)0.0099 (9)0.0103 (10)0.0005 (7)0.0013 (8)−0.0002 (7)
C130.0137 (10)0.0116 (10)0.0133 (10)0.0033 (8)0.0008 (8)−0.0001 (8)
C140.0216 (12)0.0098 (9)0.0138 (11)0.0039 (8)0.0006 (9)0.0013 (8)
C150.0202 (11)0.0104 (9)0.0126 (10)−0.0026 (8)0.0031 (9)−0.0013 (8)
C160.0169 (10)0.0113 (9)0.0108 (10)−0.0019 (8)−0.0003 (8)−0.0011 (8)
Fe10.01107 (14)0.00823 (14)0.00895 (15)0.00050 (11)0.00024 (11)−0.00029 (11)
C170.0162 (11)0.0104 (10)0.0207 (12)0.0016 (8)0.0010 (9)−0.0034 (9)
C180.0130 (10)0.0162 (11)0.0184 (11)−0.0012 (8)0.0009 (8)−0.0072 (9)
C190.0171 (11)0.0186 (11)0.0105 (10)0.0029 (9)0.0004 (8)−0.0022 (8)
C200.0149 (10)0.0155 (10)0.0137 (11)0.0013 (8)0.0037 (8)−0.0019 (8)
C210.0145 (10)0.0133 (10)0.0168 (11)0.0032 (8)0.0022 (8)−0.0012 (8)
Geometric parameters (Å, °) top
Br1—C11.965 (3)C11—O111.225 (3)
C1—C21.511 (3)C11—C121.477 (3)
C1—H1A0.9900C12—C131.436 (3)
C1—H1B0.9900C12—C161.439 (3)
C2—C31.523 (4)C12—Fe12.038 (2)
C2—H2A0.9900C13—C141.421 (3)
C2—H2B0.9900C13—Fe12.050 (2)
C3—C41.526 (4)C13—H130.9500
C3—H3A0.9900C14—C151.419 (4)
C3—H3B0.9900C14—Fe12.057 (2)
C4—C51.521 (4)C14—H140.9500
C4—H4A0.9900C15—C161.434 (3)
C4—H4B0.9900C15—Fe12.053 (2)
C5—C61.525 (4)C15—H150.9500
C5—H5A0.9900C16—Fe12.042 (2)
C5—H5B0.9900C16—H160.9500
C6—C71.525 (4)Fe1—C202.042 (2)
C6—H6A0.9900Fe1—C192.048 (2)
C6—H6B0.9900Fe1—C212.050 (2)
C7—C81.527 (3)Fe1—C172.057 (2)
C7—H7A0.9900Fe1—C182.060 (2)
C7—H7B0.9900C17—C211.427 (3)
C8—C91.532 (4)C17—C181.432 (4)
C8—H8A0.9900C17—H170.9500
C8—H8B0.9900C18—C191.428 (4)
C9—C101.528 (3)C18—H180.9500
C9—H9A0.9900C19—C201.426 (4)
C9—H9B0.9900C19—H190.9500
C10—C111.517 (3)C20—C211.431 (3)
C10—H10A0.9900C20—H200.9500
C10—H10B0.9900C21—H210.9500
C2—C1—Br1111.46 (17)C14—C15—H15125.8
C2—C1—H1A109.3C16—C15—H15125.8
Br1—C1—H1A109.3Fe1—C15—H15126.8
C2—C1—H1B109.3C15—C16—C12107.2 (2)
Br1—C1—H1B109.3C15—C16—Fe169.94 (14)
H1A—C1—H1B108.0C12—C16—Fe169.19 (13)
C1—C2—C3115.3 (2)C15—C16—H16126.4
C1—C2—H2A108.5C12—C16—H16126.4
C3—C2—H2A108.5Fe1—C16—H16126.0
C1—C2—H2B108.5C12—Fe1—C1641.32 (9)
C3—C2—H2B108.5C12—Fe1—C20156.54 (10)
H2A—C2—H2B107.5C16—Fe1—C20119.64 (10)
C2—C3—C4112.9 (2)C12—Fe1—C19161.95 (10)
C2—C3—H3A109.0C16—Fe1—C19154.77 (10)
C4—C3—H3A109.0C20—Fe1—C1940.80 (10)
C2—C3—H3B109.0C12—Fe1—C1341.13 (9)
C4—C3—H3B109.0C16—Fe1—C1369.27 (10)
H3A—C3—H3B107.8C20—Fe1—C13159.94 (10)
C5—C4—C3114.0 (2)C19—Fe1—C13123.98 (10)
C5—C4—H4A108.7C12—Fe1—C21121.93 (10)
C3—C4—H4A108.7C16—Fe1—C21107.01 (10)
C5—C4—H4B108.7C20—Fe1—C2140.95 (10)
C3—C4—H4B108.7C19—Fe1—C2168.70 (10)
H4A—C4—H4B107.6C13—Fe1—C21158.13 (10)
C4—C5—C6113.2 (2)C12—Fe1—C1568.85 (9)
C4—C5—H5A108.9C16—Fe1—C1541.00 (9)
C6—C5—H5A108.9C20—Fe1—C15105.66 (10)
C4—C5—H5B108.9C19—Fe1—C15119.31 (10)
C6—C5—H5B108.9C13—Fe1—C1568.40 (10)
H5A—C5—H5B107.7C21—Fe1—C15123.76 (10)
C7—C6—C5113.7 (2)C12—Fe1—C1468.63 (9)
C7—C6—H6A108.8C16—Fe1—C1468.75 (10)
C5—C6—H6A108.8C20—Fe1—C14122.80 (10)
C7—C6—H6B108.8C19—Fe1—C14106.35 (10)
C5—C6—H6B108.8C13—Fe1—C1440.49 (10)
H6A—C6—H6B107.7C21—Fe1—C14160.00 (10)
C6—C7—C8113.1 (2)C15—Fe1—C1440.38 (10)
C6—C7—H7A109.0C12—Fe1—C17108.99 (10)
C8—C7—H7A109.0C16—Fe1—C17125.29 (10)
C6—C7—H7B109.0C20—Fe1—C1768.64 (10)
C8—C7—H7B109.0C19—Fe1—C1768.59 (10)
H7A—C7—H7B107.8C13—Fe1—C17122.84 (10)
C7—C8—C9113.7 (2)C21—Fe1—C1740.65 (10)
C7—C8—H8A108.8C15—Fe1—C17161.56 (10)
C9—C8—H8A108.8C14—Fe1—C17157.40 (10)
C7—C8—H8B108.8C12—Fe1—C18125.88 (10)
C9—C8—H8B108.8C16—Fe1—C18162.88 (10)
H8A—C8—H8B107.7C20—Fe1—C1868.53 (10)
C10—C9—C8111.6 (2)C19—Fe1—C1840.69 (10)
C10—C9—H9A109.3C13—Fe1—C18108.40 (10)
C8—C9—H9A109.3C21—Fe1—C1868.47 (10)
C10—C9—H9B109.3C15—Fe1—C18155.31 (10)
C8—C9—H9B109.3C14—Fe1—C18121.22 (10)
H9A—C9—H9B108.0C17—Fe1—C1840.69 (10)
C11—C10—C9114.5 (2)C21—C17—C18108.0 (2)
C11—C10—H10A108.6C21—C17—Fe169.38 (14)
C9—C10—H10A108.6C18—C17—Fe169.75 (14)
C11—C10—H10B108.6C21—C17—H17126.0
C9—C10—H10B108.6C18—C17—H17126.0
H10A—C10—H10B107.6Fe1—C17—H17126.4
O11—C11—C12121.3 (2)C19—C18—C17108.0 (2)
O11—C11—C10122.3 (2)C19—C18—Fe169.22 (14)
C12—C11—C10116.4 (2)C17—C18—Fe169.56 (14)
C13—C12—C16108.0 (2)C19—C18—H18126.0
C13—C12—C11125.5 (2)C17—C18—H18126.0
C16—C12—C11126.3 (2)Fe1—C18—H18126.8
C13—C12—Fe169.88 (13)C20—C19—C18108.0 (2)
C16—C12—Fe169.49 (13)C20—C19—Fe169.38 (14)
C11—C12—Fe1122.06 (16)C18—C19—Fe170.09 (14)
C14—C13—C12107.8 (2)C20—C19—H19126.0
C14—C13—Fe170.03 (14)C18—C19—H19126.0
C12—C13—Fe168.99 (13)Fe1—C19—H19126.1
C14—C13—H13126.1C19—C20—C21108.1 (2)
C12—C13—H13126.1C19—C20—Fe169.83 (14)
Fe1—C13—H13126.5C21—C20—Fe169.80 (14)
C15—C14—C13108.6 (2)C19—C20—H20126.0
C15—C14—Fe169.68 (14)C21—C20—H20126.0
C13—C14—Fe169.48 (13)Fe1—C20—H20126.0
C15—C14—H14125.7C17—C21—C20108.0 (2)
C13—C14—H14125.7C17—C21—Fe169.97 (13)
Fe1—C14—H14126.7C20—C21—Fe169.26 (13)
C14—C15—C16108.4 (2)C17—C21—H21126.0
C14—C15—Fe169.94 (14)C20—C21—H21126.0
C16—C15—Fe169.06 (13)Fe1—C21—H21126.3
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C17—H17···Br1i0.953.013.797 (3)142
C1—H1B···O11i0.992.553.422 (3)147
C14—H14···Cg2ii0.952.943.647 (3)133
Symmetry codes: (i) −x, −y+1, −z; (ii) −x+2, y−1/2, −z+1/2.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C17—H17···Br1i0.953.013.797 (3)142
C1—H1B···O11i0.992.553.422 (3)147
C14—H14···Cg2ii0.952.943.647 (3)133
Symmetry codes: (i) −x, −y+1, −z; (ii) −x+2, y−1/2, −z+1/2.
Acknowledgements top

The authors are grateful to students in the CHEM303 class of 2007 at the University of Otago for preparation of the title compound. We also thank the New Zealand Foundation for Research Science and Technology for a Postdoctoral Fellowship to CJM and the University of Otago for purchase of the diffractometer.

references
References top

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