11-Bromo-1-ferrocenylundecan-1-one

In the title compound, [Fe(C₅H₅)(C₁₆H₂₄BrO)], the η⁵-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...π inter­actions between neighbouring cyclo­penta­diene rings, forming zigzag chains along the c axis.

Key indicators

• Single-crystal X-ray study
• T = 85 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.050
• wR factor = 0.120
• Data-to-parameter ratio = 33.0

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT480_ALERT_4_C Long H...A H-Bond Reported H17    ..  BR1     ..       3.01 Ang.

Alert level G
REFLT03_ALERT_1_G ALERT: Expected hkl max differ from CIF values
           From the CIF: _diffrn_reflns_theta_max           34.65
           From the CIF: _reflns_number_total               7152
           From the CIF: _diffrn_reflns_limit_ max hkl    8.   14.   53.
           From the CIF: _diffrn_reflns_limit_ min hkl   -8.  -15.  -52.
           TEST1: Expected hkl limits for theta max
           Calculated maximum hkl    8.   15.   55.
           Calculated minimum hkl   -8.  -15.  -55.

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

   1 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
   1 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

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

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).

S2. Experimental

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.

S3. Refinement

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

Computing details

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

	Fig. 1. The molecular structure of (I), with the atom-labelling scheme and 50% probability displacement ellipsoids.
	Fig. 2. Formation of inversion related dimers of (I) with hydrogen bonds drawn as dashed lines.
	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

Crystal data

[Fe(C5H5)(C15H24BrO)]	F(000) = 896
Mr = 433.20	Dx = 1.486 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 6638 reflections
a = 5.6027 (2) Å	θ = 2.4–32.0°
b = 9.8858 (4) Å	µ = 2.85 mm^−1
c = 35.0048 (15) Å	T = 85 K
β = 92.576 (2)°	Rectangular plate, yellow
V = 1936.86 (13) Å^3	0.53 × 0.12 × 0.03 mm
Z = 4

Data collection

Bruker APEXII CCD area-detector diffractometer	7152 independent reflections
Radiation source: fine-focus sealed tube	5902 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.041
φ and ω scans	θmax = 34.7°, θmin = 1.2°
Absorption correction: multi-scan (SADABS; Bruker, 2004)	h = −8→8
Tmin = 0.700, Tmax = 0.918	k = −15→14
37380 measured reflections	l = −52→53

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)] = 0.050	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.120	H-atom parameters constrained
S = 1.22	w = 1/[σ^2(Fo^2) + (0.0441P)^2 + 2.8882P] where P = (Fo^2 + 2Fc^2)/3
7152 reflections	(Δ/σ)max = 0.001
217 parameters	Δρmax = 0.97 e Å^−3
0 restraints	Δρmin = −2.43 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
Br1	0.44415 (5)	0.29956 (3)	0.174591 (8)	0.02083 (8)
C1	0.6436 (5)	0.2608 (3)	0.13114 (7)	0.0179 (5)
H1A	0.8027	0.2291	0.1408	0.022*
H1B	0.5691	0.1874	0.1155	0.022*
C2	0.6732 (5)	0.3844 (2)	0.10645 (7)	0.0168 (5)
H2A	0.7894	0.3630	0.0868	0.020*
H2B	0.7425	0.4579	0.1226	0.020*
C3	0.4447 (5)	0.4366 (3)	0.08631 (8)	0.0186 (5)
H3A	0.3292	0.4610	0.1058	0.022*
H3B	0.3729	0.3633	0.0703	0.022*
C4	0.4869 (5)	0.5596 (3)	0.06113 (8)	0.0198 (5)
H4A	0.5480	0.6347	0.0775	0.024*
H4B	0.6119	0.5370	0.0431	0.024*
C5	0.2652 (5)	0.6077 (3)	0.03841 (8)	0.0191 (5)
H5A	0.1404	0.6312	0.0564	0.023*
H5B	0.2033	0.5326	0.0221	0.023*
C6	0.3113 (5)	0.7300 (3)	0.01325 (8)	0.0184 (5)
H6A	0.3603	0.8072	0.0298	0.022*
H6B	0.4458	0.7090	−0.0032	0.022*
C7	0.0957 (5)	0.7721 (3)	−0.01212 (7)	0.0177 (5)
H7A	−0.0379	0.7950	0.0043	0.021*
H7B	0.0446	0.6945	−0.0284	0.021*
C8	0.1459 (5)	0.8929 (3)	−0.03771 (7)	0.0159 (4)
H8A	0.2858	0.8718	−0.0530	0.019*
H8B	0.1879	0.9719	−0.0214	0.019*
C9	−0.0648 (5)	0.9311 (3)	−0.06499 (7)	0.0167 (5)
H9A	−0.1051	0.8533	−0.0819	0.020*
H9B	−0.2060	0.9513	−0.0500	0.020*
C10	−0.0073 (4)	1.0539 (2)	−0.08942 (7)	0.0146 (4)
H10A	0.0461	1.1287	−0.0723	0.017*
H10B	0.1274	1.0306	−0.1056	0.017*
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	−0.4880	1.2448	−0.1745	0.015*
C14	−0.1994 (5)	1.3668 (2)	−0.19158 (7)	0.0151 (4)
H14	−0.2645	1.4185	−0.2124	0.018*
C15	0.0394 (5)	1.3739 (2)	−0.17642 (7)	0.0143 (4)
H15	0.1610	1.4313	−0.1853	0.017*
C16	0.0661 (4)	1.2797 (2)	−0.14536 (7)	0.0131 (4)
H16	0.2078	1.2631	−0.1301	0.016*
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	−0.0588	0.9063	−0.1859	0.019*
C18	−0.1625 (4)	1.0354 (3)	−0.23260 (7)	0.0159 (4)
H18	−0.3248	1.0132	−0.2386	0.019*
C19	−0.0246 (4)	1.1347 (3)	−0.25143 (7)	0.0154 (4)
H19	−0.0794	1.1904	−0.2721	0.018*
C20	0.2096 (4)	1.1356 (3)	−0.23371 (7)	0.0146 (4)
H20	0.3382	1.1919	−0.2406	0.018*
C21	0.2170 (4)	1.0369 (2)	−0.20378 (7)	0.0148 (4)
H21	0.3514	1.0160	−0.1873	0.018*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Br1	0.02858 (15)	0.01801 (13)	0.01621 (13)	0.00177 (10)	0.00468 (10)	0.00173 (9)
C1	0.0245 (12)	0.0152 (11)	0.0143 (11)	0.0046 (9)	0.0026 (9)	0.0018 (9)
C2	0.0224 (12)	0.0128 (10)	0.0153 (11)	0.0012 (9)	0.0002 (9)	0.0025 (8)
C3	0.0226 (12)	0.0162 (11)	0.0166 (12)	−0.0005 (9)	−0.0028 (9)	0.0043 (9)
C4	0.0249 (13)	0.0178 (11)	0.0163 (12)	0.0011 (10)	−0.0037 (10)	0.0047 (9)
C5	0.0236 (12)	0.0161 (11)	0.0172 (12)	−0.0001 (9)	−0.0022 (10)	0.0044 (9)
C6	0.0248 (13)	0.0139 (11)	0.0163 (12)	0.0016 (9)	−0.0022 (10)	0.0035 (9)
C7	0.0234 (12)	0.0158 (11)	0.0140 (11)	0.0022 (9)	0.0005 (9)	0.0046 (9)
C8	0.0192 (11)	0.0149 (10)	0.0134 (11)	0.0027 (8)	−0.0010 (9)	0.0027 (8)
C9	0.0202 (11)	0.0148 (10)	0.0155 (11)	−0.0002 (9)	0.0034 (9)	0.0044 (9)
C10	0.0160 (10)	0.0153 (10)	0.0124 (10)	−0.0008 (8)	0.0007 (8)	0.0028 (8)
C11	0.0149 (10)	0.0125 (10)	0.0106 (10)	0.0014 (8)	0.0028 (8)	0.0004 (8)
O11	0.0142 (8)	0.0210 (9)	0.0218 (9)	−0.0029 (7)	0.0019 (7)	0.0068 (7)
C12	0.0134 (9)	0.0099 (9)	0.0103 (10)	0.0005 (7)	0.0013 (8)	−0.0002 (7)
C13	0.0137 (10)	0.0116 (10)	0.0133 (10)	0.0033 (8)	0.0008 (8)	−0.0001 (8)
C14	0.0216 (12)	0.0098 (9)	0.0138 (11)	0.0039 (8)	0.0006 (9)	0.0013 (8)
C15	0.0202 (11)	0.0104 (9)	0.0126 (10)	−0.0026 (8)	0.0031 (9)	−0.0013 (8)
C16	0.0169 (10)	0.0113 (9)	0.0108 (10)	−0.0019 (8)	−0.0003 (8)	−0.0011 (8)
Fe1	0.01107 (14)	0.00823 (14)	0.00895 (15)	0.00050 (11)	0.00024 (11)	−0.00029 (11)
C17	0.0162 (11)	0.0104 (10)	0.0207 (12)	0.0016 (8)	0.0010 (9)	−0.0034 (9)
C18	0.0130 (10)	0.0162 (11)	0.0184 (11)	−0.0012 (8)	0.0009 (8)	−0.0072 (9)
C19	0.0171 (11)	0.0186 (11)	0.0105 (10)	0.0029 (9)	0.0004 (8)	−0.0022 (8)
C20	0.0149 (10)	0.0155 (10)	0.0137 (11)	0.0013 (8)	0.0037 (8)	−0.0019 (8)
C21	0.0145 (10)	0.0133 (10)	0.0168 (11)	0.0032 (8)	0.0022 (8)	−0.0012 (8)

Geometric parameters (Å, º)

Br1—C1	1.965 (3)	C11—O11	1.225 (3)
C1—C2	1.511 (3)	C11—C12	1.477 (3)
C1—H1A	0.9900	C12—C13	1.436 (3)
C1—H1B	0.9900	C12—C16	1.439 (3)
C2—C3	1.523 (4)	C12—Fe1	2.038 (2)
C2—H2A	0.9900	C13—C14	1.421 (3)
C2—H2B	0.9900	C13—Fe1	2.050 (2)
C3—C4	1.526 (4)	C13—H13	0.9500
C3—H3A	0.9900	C14—C15	1.419 (4)
C3—H3B	0.9900	C14—Fe1	2.057 (2)
C4—C5	1.521 (4)	C14—H14	0.9500
C4—H4A	0.9900	C15—C16	1.434 (3)
C4—H4B	0.9900	C15—Fe1	2.053 (2)
C5—C6	1.525 (4)	C15—H15	0.9500
C5—H5A	0.9900	C16—Fe1	2.042 (2)
C5—H5B	0.9900	C16—H16	0.9500
C6—C7	1.525 (4)	Fe1—C20	2.042 (2)
C6—H6A	0.9900	Fe1—C19	2.048 (2)
C6—H6B	0.9900	Fe1—C21	2.050 (2)
C7—C8	1.527 (3)	Fe1—C17	2.057 (2)
C7—H7A	0.9900	Fe1—C18	2.060 (2)
C7—H7B	0.9900	C17—C21	1.427 (3)
C8—C9	1.532 (4)	C17—C18	1.432 (4)
C8—H8A	0.9900	C17—H17	0.9500
C8—H8B	0.9900	C18—C19	1.428 (4)
C9—C10	1.528 (3)	C18—H18	0.9500
C9—H9A	0.9900	C19—C20	1.426 (4)
C9—H9B	0.9900	C19—H19	0.9500
C10—C11	1.517 (3)	C20—C21	1.431 (3)
C10—H10A	0.9900	C20—H20	0.9500
C10—H10B	0.9900	C21—H21	0.9500
C2—C1—Br1	111.46 (17)	C14—C15—H15	125.8
C2—C1—H1A	109.3	C16—C15—H15	125.8
Br1—C1—H1A	109.3	Fe1—C15—H15	126.8
C2—C1—H1B	109.3	C15—C16—C12	107.2 (2)
Br1—C1—H1B	109.3	C15—C16—Fe1	69.94 (14)
H1A—C1—H1B	108.0	C12—C16—Fe1	69.19 (13)
C1—C2—C3	115.3 (2)	C15—C16—H16	126.4
C1—C2—H2A	108.5	C12—C16—H16	126.4
C3—C2—H2A	108.5	Fe1—C16—H16	126.0
C1—C2—H2B	108.5	C12—Fe1—C16	41.32 (9)
C3—C2—H2B	108.5	C12—Fe1—C20	156.54 (10)
H2A—C2—H2B	107.5	C16—Fe1—C20	119.64 (10)
C2—C3—C4	112.9 (2)	C12—Fe1—C19	161.95 (10)
C2—C3—H3A	109.0	C16—Fe1—C19	154.77 (10)
C4—C3—H3A	109.0	C20—Fe1—C19	40.80 (10)
C2—C3—H3B	109.0	C12—Fe1—C13	41.13 (9)
C4—C3—H3B	109.0	C16—Fe1—C13	69.27 (10)
H3A—C3—H3B	107.8	C20—Fe1—C13	159.94 (10)
C5—C4—C3	114.0 (2)	C19—Fe1—C13	123.98 (10)
C5—C4—H4A	108.7	C12—Fe1—C21	121.93 (10)
C3—C4—H4A	108.7	C16—Fe1—C21	107.01 (10)
C5—C4—H4B	108.7	C20—Fe1—C21	40.95 (10)
C3—C4—H4B	108.7	C19—Fe1—C21	68.70 (10)
H4A—C4—H4B	107.6	C13—Fe1—C21	158.13 (10)
C4—C5—C6	113.2 (2)	C12—Fe1—C15	68.85 (9)
C4—C5—H5A	108.9	C16—Fe1—C15	41.00 (9)
C6—C5—H5A	108.9	C20—Fe1—C15	105.66 (10)
C4—C5—H5B	108.9	C19—Fe1—C15	119.31 (10)
C6—C5—H5B	108.9	C13—Fe1—C15	68.40 (10)
H5A—C5—H5B	107.7	C21—Fe1—C15	123.76 (10)
C7—C6—C5	113.7 (2)	C12—Fe1—C14	68.63 (9)
C7—C6—H6A	108.8	C16—Fe1—C14	68.75 (10)
C5—C6—H6A	108.8	C20—Fe1—C14	122.80 (10)
C7—C6—H6B	108.8	C19—Fe1—C14	106.35 (10)
C5—C6—H6B	108.8	C13—Fe1—C14	40.49 (10)
H6A—C6—H6B	107.7	C21—Fe1—C14	160.00 (10)
C6—C7—C8	113.1 (2)	C15—Fe1—C14	40.38 (10)
C6—C7—H7A	109.0	C12—Fe1—C17	108.99 (10)
C8—C7—H7A	109.0	C16—Fe1—C17	125.29 (10)
C6—C7—H7B	109.0	C20—Fe1—C17	68.64 (10)
C8—C7—H7B	109.0	C19—Fe1—C17	68.59 (10)
H7A—C7—H7B	107.8	C13—Fe1—C17	122.84 (10)
C7—C8—C9	113.7 (2)	C21—Fe1—C17	40.65 (10)
C7—C8—H8A	108.8	C15—Fe1—C17	161.56 (10)
C9—C8—H8A	108.8	C14—Fe1—C17	157.40 (10)
C7—C8—H8B	108.8	C12—Fe1—C18	125.88 (10)
C9—C8—H8B	108.8	C16—Fe1—C18	162.88 (10)
H8A—C8—H8B	107.7	C20—Fe1—C18	68.53 (10)
C10—C9—C8	111.6 (2)	C19—Fe1—C18	40.69 (10)
C10—C9—H9A	109.3	C13—Fe1—C18	108.40 (10)
C8—C9—H9A	109.3	C21—Fe1—C18	68.47 (10)
C10—C9—H9B	109.3	C15—Fe1—C18	155.31 (10)
C8—C9—H9B	109.3	C14—Fe1—C18	121.22 (10)
H9A—C9—H9B	108.0	C17—Fe1—C18	40.69 (10)
C11—C10—C9	114.5 (2)	C21—C17—C18	108.0 (2)
C11—C10—H10A	108.6	C21—C17—Fe1	69.38 (14)
C9—C10—H10A	108.6	C18—C17—Fe1	69.75 (14)
C11—C10—H10B	108.6	C21—C17—H17	126.0
C9—C10—H10B	108.6	C18—C17—H17	126.0
H10A—C10—H10B	107.6	Fe1—C17—H17	126.4
O11—C11—C12	121.3 (2)	C19—C18—C17	108.0 (2)
O11—C11—C10	122.3 (2)	C19—C18—Fe1	69.22 (14)
C12—C11—C10	116.4 (2)	C17—C18—Fe1	69.56 (14)
C13—C12—C16	108.0 (2)	C19—C18—H18	126.0
C13—C12—C11	125.5 (2)	C17—C18—H18	126.0
C16—C12—C11	126.3 (2)	Fe1—C18—H18	126.8
C13—C12—Fe1	69.88 (13)	C20—C19—C18	108.0 (2)
C16—C12—Fe1	69.49 (13)	C20—C19—Fe1	69.38 (14)
C11—C12—Fe1	122.06 (16)	C18—C19—Fe1	70.09 (14)
C14—C13—C12	107.8 (2)	C20—C19—H19	126.0
C14—C13—Fe1	70.03 (14)	C18—C19—H19	126.0
C12—C13—Fe1	68.99 (13)	Fe1—C19—H19	126.1
C14—C13—H13	126.1	C19—C20—C21	108.1 (2)
C12—C13—H13	126.1	C19—C20—Fe1	69.83 (14)
Fe1—C13—H13	126.5	C21—C20—Fe1	69.80 (14)
C15—C14—C13	108.6 (2)	C19—C20—H20	126.0
C15—C14—Fe1	69.68 (14)	C21—C20—H20	126.0
C13—C14—Fe1	69.48 (13)	Fe1—C20—H20	126.0
C15—C14—H14	125.7	C17—C21—C20	108.0 (2)
C13—C14—H14	125.7	C17—C21—Fe1	69.97 (13)
Fe1—C14—H14	126.7	C20—C21—Fe1	69.26 (13)
C14—C15—C16	108.4 (2)	C17—C21—H21	126.0
C14—C15—Fe1	69.94 (14)	C20—C21—H21	126.0
C16—C15—Fe1	69.06 (13)	Fe1—C21—H21	126.3

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C17—H17···Br1^i	0.95	3.01	3.797 (3)	142
C1—H1B···O11^i	0.99	2.55	3.422 (3)	147
C14—H14···Cg2^ii	0.95	2.94	3.647 (3)	133

Symmetry codes: (i) −x, −y+1, −z; (ii) −x+2, y−1/2, −z+1/2.