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Acta Cryst. (2007). E63, m2145-m2146    [ doi:10.1107/S1600536807033892 ]

1'-Acetylferrocene-1-carbonitrile

M. Erben, A. Ruzicka, J. Vinklárek, V. Stáva and K. Handlír

Abstract top

In the title compound, [Fe(C6H4N)(C7H7O)], the two cyclopentadienyl rings are nearly parallel, making a dihedral angle of 2.3 (1) Å, and are almost eclipsed as viewed down the normal to each ring. In the crystal structure, the molecules are stacked along the b axis, with a short distance of 3.749 (1) Å between the centroids of the cyclopentadienyl rings of neighbouring molecules. Weak intermolecular C-H...N and C-H...O hydrogen bonds link these stacks into two-dimensional sheets parallel to the bc plane.

Comment top

Ferrocenes are well known class of organometallic compounds and the wealth of its derivatives is described in literature. Ferrocene compounds are widely used in homogenous catalysis, organic or organometallic synthesis and in material science. In last three years, utilization of ferrocene derivatives in drying of oxidizable paints has been investigated, and it was observed that ferrocenes bearing electron-withdrawing substituents showed the highest activity in drying processes Šťáva et al., 2007). In the framework of investigation of ferrocene derivatives we prepared, spectroscopically characterized the title compound (I) and determined its molecular structure in the solid state.

Figure 1 shows typical sandwich structure of (I) with cyclopentadienyl ligands being very close to be eclipsed. The dihedral angle between a ring carbon, the two ring centroids and the carbon atom of opposite ring varies from 6.9 (2) to 8.2 (2)°. The exocyclic bond lengths C8—C13 and C1—C6 of 1.429 (3) Å and 1.466 (3) Å, respectively, are very close to those found in cyanoferrocene [1.432 (6) Å, (Bell et al., 1996)] and diacetylferrocene [1.747 (8) Å, 1.768 (8) Å (Palenik, 1970)]. The interatomic distances and angles in the molecule of (I) are comparable to those observed for similar ferrocene derivatives, the principial interest lies in the intermolecular interactions.

The ring Cp2 of molecule at (x, y, z) is nearly coplanar with ring Cp1 of the molecule at (x, 1 + y, z) with dihedral angle of 2.3 (1)°. The distance between the centriods of Cp rings was found to be 3.749 (1) Å indicating significant intermolecular π···π interaction between neighboring molecules of (I) along b axis.. Atom N1 in the molecule at (x, y, z) acts as hydrogen-bond acceptor from cyclopentadienyl carbon atoms C4 and C9 of the molecule at (2 − x, 1 − y, 1 − z), i.e. (i), with C···N distances of 3.411 (3) and 3.464 (3) Å, respectively. Simultaneously, N1i atom serves as hydrogen-bond acceptor from atoms C4 and C9 of molecule at (x, y, z) generating molecular pairs connected by four C—H···N hydrogen bonds. Thus each nitrogen atom exhibits trigonal coordination; an angle H4i···N1···H9i was found to be 73°. Oxygen atom O1 of acetyl group also participates in intermolecular interactions, being hydrogen-bond acceptor from atom C11 of the molecule at (2 − x, − y, − z). Reversely, atom C11 in the molecule at (x, y, z) acts as donor to the oxygen atom of the molecule at (2 − x, − y, − z). Figure 2 depicts three molecules of (I) interconnected by weak hydrogen bonds.

The interplay of π···π stacking and weak hydrogen bonds is responsible for the observed structure giving two-dimensional sheets parallel to bc-plane

Related literature top

Transition metal complexes bearing a strongly electron-withdrawing cyano group at the cyclopentadienyl ring are relatively sparse and only three related structures have been published previously: (η5-cyanocyclopentadienyl)-(η4-tetraphenylcyclobutadiene)cobalt (Villa et al., 1974), (η5-cyanocyclopentadienyl)dicarbonylnitrosylchromium (Rogers et al., 1988) and cyanoferrocene (Bell et al., 1996). For related literature dealing with acetyl- and cyano-substituted ferrocenes, see: Nesmeyanov et al. (1962); Palenik (1970); Šťáva et al. (2007).

Experimental top

The title compound (I) was synthesized by direct cyanation of acetylferrocene following published procedure (Nesmeyanov et al., 1962). Melting point, IR, Raman and NMR spectra confirmed identity and purity of prepared compound. Crystals of (I) suitable for X-ray diffraction analysis were grown by sublimation in sealed ampoule at 0.1 Pa and 353 K.

Refinement top

All H atoms were positioned geometrically and refined as riding on their parent C atoms, with C—H = 0.93 Å, Uiso(H) = 1.2Ueq(C) and C—H = 0.96 Å, Uiso(H) = 1.5Ueq(C) for cyclopentadienyl and methyl H atoms, respectively.

Computing details top

Data collection: COLLECT (Hooft, 1998) and DENZO (Otwinowski & Minor, 1997); cell refinement: COLLECT and DENZO; data reduction: COLLECT and DENZO; program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: enCIFer (Allen et al., 2004).

Figures top
[Figure 1] Fig. 1. ORTEP view of the title compound (I) with displacement ellipsoids drawn at the 50% probability.
[Figure 2] Fig. 2. A view of three molecules of (I) linked by weak C—H···N and C—H···O hydrogen bonds (dashed lines). H atoms not involved in contacts have been omitted. [Symmetry codes: (i) 2 − x, 1 − y, 1 − z; (ii) 2 − x, − y, − z]
1'-Acetylferrocene-1-carbonitrile top
Crystal data top
[Fe(C6H4N)(C7H7O)]Z = 2
Mr = 253.08F(000) = 260
Triclinic, P1Dx = 1.609 Mg m−3
Hall symbol: -P 1Melting point: 370 K
a = 5.7610 (5) ÅMo Kα radiation, λ = 0.71073 Å
b = 6.8431 (5) ÅCell parameters from 7054 reflections
c = 14.1940 (14) Åθ = 1–27.5°
α = 99.264 (7)°µ = 1.42 mm−1
β = 99.666 (6)°T = 150 K
γ = 104.277 (7)°Plate, red
V = 522.45 (8) Å30.16 × 0.10 × 0.05 mm
Data collection top
Bruker–Nonius KappaCCD area-detector
diffractometer		2383 independent reflections
Radiation source: fine-focus sealed tube2151 reflections with I > 2σ(I)
graphiteRint = 0.052
Detector resolution: 9.091 pixels mm-1θmax = 27.5°, θmin = 3.7°
φ and ω scans to fill the Ewald sphereh = −7→7
Absorption correction: integration
(Gaussian; Coppens et al., 1970)		k = −8→8
Tmin = 0.801, Tmax = 0.931l = −18→18
6982 measured reflections
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)] = 0.032Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.082H-atom parameters constrained
S = 1.08 w = 1/[σ2(Fo2) + (0.0403P)2 + 0.3168P]
where P = (Fo2 + 2Fc2)/3
2383 reflections(Δ/σ)max < 0.001
145 parametersΔρmax = 0.45 e Å−3
0 restraintsΔρmin = −0.59 e Å−3
Crystal data top
[Fe(C6H4N)(C7H7O)]γ = 104.277 (7)°
Mr = 253.08V = 522.45 (8) Å3
Triclinic, P1Z = 2
a = 5.7610 (5) ÅMo Kα radiation
b = 6.8431 (5) ŵ = 1.42 mm−1
c = 14.1940 (14) ÅT = 150 K
α = 99.264 (7)°0.16 × 0.10 × 0.05 mm
β = 99.666 (6)°
Data collection top
Bruker–Nonius KappaCCD area-detector
diffractometer		2383 independent reflections
Absorption correction: integration
(Gaussian; Coppens et al., 1970)		2151 reflections with I > 2σ(I)
Tmin = 0.801, Tmax = 0.931Rint = 0.052
6982 measured reflectionsθmax = 27.5°
Refinement top
R[F2 > 2σ(F2)] = 0.032H-atom parameters constrained
wR(F2) = 0.082Δρmax = 0.45 e Å−3
S = 1.08Δρmin = −0.59 e Å−3
2383 reflectionsAbsolute structure: ?
145 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
Special details top

Experimental. Melting point: 370–371 K. Spectroscopic analysis: 1H NMR (CDCl3, δ, p.p.m.): 2.40 (s, 3H), 4.40 (s, 2H), 4.62 (s, 4H), 4.87 (s, 2H). 13C NMR (CDCl3, δ, p.p.m.): 27.9, 53.9, 71.8, 72.4, 73.2, 74.5, 81.3, 118.9, 200.9. Uv-Vis (cyclohexane, maxima at nm): 447, 350s h, 314s h. IR (KBr disc, cm−1): 3121 (m), 3104 (m), 3092 (m), 3078 (s), 2925 (m), 2856 (m), 2231 (versus), 1655 (versus), 1455 (s), 1400 (m), 1375 (s), 1356 (m), 1279 (versus), 1235 (m), 1117 (m), 1069 (w), 1039 (m), 966 (w), 917 (m), 896 (m), 854 (w), 833 (s), 667 (w), 623 (m), 556 (s), 527 (s), 512 (m), 483 (s). Raman (quartz capillary, cm−1): 3122 (m), 3108 (s), 3092 (w), 3077 (m), 2925 (m), 2232 (versus), 1654 (versus), 1457 (w), 1446 (m), 1401 (w), 1378 (w), 1283 (m), 1234 (s), 1119 (m), 1077 (m), 1042 (m), 1034 (m), 917 (w), 673 (m), 641 (m), 625 (w), 555 (w), 527 (w), 483 (w), 358 (m), 314 (versus), 218 (m), 186 (m), 115 (m).

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
Fe10.92112 (5)0.18493 (4)0.26947 (2)0.01257 (10)
C121.0895 (4)0.4420 (3)0.22364 (15)0.0183 (4)
H121.24600.47340.21080.022*
O11.1803 (3)−0.1467 (3)0.09502 (12)0.0281 (4)
C40.8082 (4)−0.0211 (3)0.35489 (16)0.0192 (4)
H40.7015−0.01300.39690.023*
C70.7473 (4)−0.2488 (4)0.03850 (17)0.0277 (5)
H7A0.7866−0.2852−0.02390.042*
H7B0.6589−0.14710.03620.042*
H7C0.6478−0.36930.05370.042*
C10.9600 (4)−0.0971 (3)0.21714 (15)0.0151 (4)
C90.7666 (4)0.4179 (3)0.30431 (15)0.0180 (4)
H90.67720.43080.35260.022*
C100.6706 (4)0.3170 (3)0.20418 (15)0.0184 (4)
H100.50610.25210.17570.022*
C50.7397 (4)−0.1180 (3)0.25418 (15)0.0163 (4)
H50.5806−0.18330.21850.020*
C31.0686 (4)0.0617 (3)0.38067 (15)0.0191 (4)
H31.16040.13400.44220.023*
C110.8676 (4)0.3322 (3)0.15519 (15)0.0184 (4)
H110.85380.27910.08930.022*
C21.1633 (4)0.0151 (3)0.29684 (15)0.0171 (4)
H21.32790.05080.29370.021*
C60.9806 (4)−0.1621 (3)0.11602 (15)0.0184 (4)
N11.3441 (4)0.6917 (3)0.47474 (15)0.0311 (5)
C81.0275 (4)0.4956 (3)0.31641 (15)0.0173 (4)
C131.2006 (4)0.6036 (3)0.40509 (16)0.0212 (4)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Fe10.01291 (15)0.01076 (16)0.01458 (16)0.00420 (11)0.00143 (10)0.00445 (10)
C120.0214 (10)0.0129 (9)0.0237 (11)0.0062 (8)0.0075 (8)0.0078 (8)
O10.0228 (8)0.0363 (10)0.0250 (8)0.0086 (7)0.0077 (7)0.0026 (7)
C40.0236 (11)0.0160 (10)0.0217 (10)0.0069 (8)0.0075 (8)0.0101 (8)
C70.0257 (12)0.0293 (12)0.0219 (11)0.0039 (10)−0.0006 (9)0.0000 (9)
C10.0154 (9)0.0094 (9)0.0209 (10)0.0044 (7)0.0026 (8)0.0044 (8)
C90.0213 (10)0.0159 (10)0.0208 (10)0.0099 (8)0.0059 (8)0.0063 (8)
C100.0165 (10)0.0178 (10)0.0224 (11)0.0082 (8)0.0001 (8)0.0073 (8)
C50.0155 (9)0.0111 (9)0.0219 (10)0.0021 (7)0.0027 (8)0.0061 (8)
C30.0251 (11)0.0162 (10)0.0169 (10)0.0087 (8)−0.0003 (8)0.0067 (8)
C110.0248 (11)0.0165 (10)0.0169 (10)0.0086 (8)0.0037 (8)0.0083 (8)
C20.0145 (9)0.0149 (10)0.0237 (10)0.0067 (8)0.0014 (8)0.0077 (8)
C60.0212 (10)0.0130 (9)0.0196 (10)0.0037 (8)0.0027 (8)0.0034 (8)
N10.0316 (11)0.0258 (11)0.0293 (11)0.0040 (9)−0.0009 (9)0.0010 (9)
C80.0202 (10)0.0121 (9)0.0199 (10)0.0054 (8)0.0032 (8)0.0039 (8)
C130.0244 (11)0.0134 (10)0.0254 (11)0.0052 (9)0.0049 (9)0.0039 (8)
Geometric parameters (Å, °) top
Fe1—C82.026 (2)C7—H7A0.9600
Fe1—C12.0332 (19)C7—H7B0.9600
Fe1—C52.036 (2)C7—H7C0.9600
Fe1—C92.042 (2)C1—C51.438 (3)
Fe1—C122.049 (2)C1—C21.440 (3)
Fe1—C22.052 (2)C1—C61.466 (3)
Fe1—C102.055 (2)C9—C101.426 (3)
Fe1—C42.060 (2)C9—C81.436 (3)
Fe1—C112.062 (2)C9—H90.9300
Fe1—C32.063 (2)C10—C111.419 (3)
C12—C111.420 (3)C10—H100.9300
C12—C81.436 (3)C5—H50.9300
C12—H120.9300C3—C21.413 (3)
O1—C61.221 (3)C3—H30.9300
C4—C51.419 (3)C11—H110.9300
C4—C31.426 (3)C2—H20.9300
C4—H40.9300N1—C131.145 (3)
C7—C61.506 (3)C8—C131.429 (3)
C8—Fe1—C1156.37 (9)C6—C7—H7B109.5
C8—Fe1—C5160.78 (8)H7A—C7—H7B109.5
C1—Fe1—C541.38 (8)C6—C7—H7C109.5
C8—Fe1—C941.34 (8)H7A—C7—H7C109.5
C1—Fe1—C9161.58 (8)H7B—C7—H7C109.5
C5—Fe1—C9122.75 (8)C5—C1—C2107.46 (18)
C8—Fe1—C1241.27 (8)C5—C1—C6127.67 (18)
C1—Fe1—C12121.50 (8)C2—C1—C6124.73 (18)
C5—Fe1—C12155.76 (9)C5—C1—Fe169.43 (11)
C9—Fe1—C1269.39 (8)C2—C1—Fe170.06 (11)
C8—Fe1—C2120.61 (8)C6—C1—Fe1122.50 (14)
C1—Fe1—C241.27 (8)C10—C9—C8107.00 (18)
C5—Fe1—C269.15 (8)C10—C9—Fe170.11 (12)
C9—Fe1—C2154.11 (9)C8—C9—Fe168.71 (11)
C12—Fe1—C2109.65 (8)C10—C9—H9126.5
C8—Fe1—C1068.63 (8)C8—C9—H9126.5
C1—Fe1—C10125.75 (8)Fe1—C9—H9126.2
C5—Fe1—C10106.12 (8)C11—C10—C9108.71 (18)
C9—Fe1—C1040.74 (8)C11—C10—Fe170.12 (11)
C12—Fe1—C1068.34 (8)C9—C10—Fe169.15 (11)
C2—Fe1—C10164.69 (9)C11—C10—H10125.6
C8—Fe1—C4124.28 (9)C9—C10—H10125.6
C1—Fe1—C468.66 (8)Fe1—C10—H10126.7
C5—Fe1—C440.54 (8)C4—C5—C1107.80 (18)
C9—Fe1—C4104.96 (8)C4—C5—Fe170.63 (12)
C12—Fe1—C4163.19 (9)C1—C5—Fe169.19 (11)
C2—Fe1—C468.14 (8)C4—C5—H5126.1
C10—Fe1—C4118.35 (9)C1—C5—H5126.1
C8—Fe1—C1168.51 (8)Fe1—C5—H5125.7
C1—Fe1—C11109.10 (8)C2—C3—C4108.44 (18)
C5—Fe1—C11120.23 (8)C2—C3—Fe169.49 (11)
C9—Fe1—C1168.56 (8)C4—C3—Fe169.65 (11)
C12—Fe1—C1140.41 (8)C2—C3—H3125.8
C2—Fe1—C11128.46 (9)C4—C3—H3125.8
C10—Fe1—C1140.31 (8)Fe1—C3—H3126.7
C4—Fe1—C11153.79 (9)C10—C11—C12108.58 (18)
C8—Fe1—C3107.35 (8)C10—C11—Fe169.56 (11)
C1—Fe1—C368.57 (8)C12—C11—Fe169.28 (11)
C5—Fe1—C368.50 (8)C10—C11—H11125.7
C9—Fe1—C3118.52 (9)C12—C11—H11125.7
C12—Fe1—C3127.16 (9)Fe1—C11—H11127.0
C2—Fe1—C340.17 (8)C3—C2—C1107.97 (18)
C10—Fe1—C3153.12 (9)C3—C2—Fe170.34 (12)
C4—Fe1—C340.48 (8)C1—C2—Fe168.68 (11)
C11—Fe1—C3165.04 (9)C3—C2—H2126.0
C11—C12—C8107.36 (18)C1—C2—H2126.0
C11—C12—Fe170.31 (11)Fe1—C2—H2126.5
C8—C12—Fe168.50 (11)O1—C6—C1121.19 (19)
C11—C12—H12126.3O1—C6—C7120.82 (19)
C8—C12—H12126.3C1—C6—C7117.99 (18)
Fe1—C12—H12126.4C13—C8—C9126.81 (19)
C5—C4—C3108.33 (19)C13—C8—C12124.83 (19)
C5—C4—Fe168.83 (11)C9—C8—C12108.35 (18)
C3—C4—Fe169.87 (12)C13—C8—Fe1124.42 (15)
C5—C4—H4125.8C9—C8—Fe169.95 (11)
C3—C4—H4125.8C12—C8—Fe170.23 (11)
Fe1—C4—H4127.0N1—C13—C8178.1 (2)
C6—C7—H7A109.5
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C4—H4···N1i0.932.723.411 (3)132
C9—H9···N1i0.932.733.463 (3)137
C11—H11···O1ii0.932.593.514 (3)178
Symmetry codes: (i) −x+2, −y+1, −z+1; (ii) −x+2, −y, −z.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C4—H4···N1i0.932.723.411 (3)132
C9—H9···N1i0.932.733.463 (3)137
C11—H11···O1ii0.932.593.514 (3)178
Symmetry codes: (i) −x+2, −y+1, −z+1; (ii) −x+2, −y, −z.
Table 2
Selected geometric parameters (Å, °). top
Fe1···Cg11.6505 (10)
Fe1···Cg21.6479 (10)
Cg2···Cg1iii3.749 (1)
Cg1 and Cg2 are the centroids defined by atoms C1–C5 and C8–C12, respectively. Symmetry code: (iii) x, 1 + y, z.
Acknowledgements top

The authors thank the Ministry of Education, Youth and Sports of the Czech Republic for financial support of this work within the framework of research project MSM 0021627501.

references
References top

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