3-Anilino-1-ferrocenylpropan-1-one

Zorica Leka; Sladjana B Novaković; Dragana Stevanović; Goran A Bogdanović; Rastko D Vukićević

doi:10.1107/S1600536812003492

. 2012 Jan 31;68(Pt 2):m229. doi: 10.1107/S1600536812003492

3-Anilino-1-ferrocenylpropan-1-one

Zorica Leka ^a,^*, Sladjana B Novaković ^b, Dragana Stevanović ^c, Goran A Bogdanović ^b, Rastko D Vukićević ^c

PMCID: PMC3274941 PMID: 22346888

Abstract

In the title ferrocene derivative, [Fe(C₅H₅)(C₁₄H₁₄NO)], the dihedral angle between the mean planes of the phenyl ring and the substituted cyclopentadienyl ring is 84.4 (1)°. The molecules are connected into centrosymmetric dimers via N—H⋯O hydrogen bonds. In addition, C—H⋯O and C—H⋯N contacts stabilize the crystal packing.

Related literature

For the physico-chemical properties of ferrocene-based compounds, see: Togni & Hayashi (1995 ▶). For related crystal structures and details of the synthesis, see: Damljanović et al. (2011 ▶); Stevanović et al. (2012 ▶); Leka, Novaković, Stevanović et al. (2012 ▶); Leka, Novaković, Pejović et al. (2012 ▶).

Experimental

Crystal data

[Fe(C₅H₅)(C₁₄H₁₄NO)]
M _r = 333.20
Triclinic,
a = 7.605 (3) Å
b = 9.748 (3) Å
c = 12.098 (4) Å
α = 86.036 (4)°
β = 73.869 (4)°
γ = 68.684 (3)°
V = 802.1 (5) Å³
Z = 2
Mo Kα radiation
μ = 0.94 mm⁻¹
T = 293 K
0.26 × 0.25 × 0.18 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
3395 measured reflections
3143 independent reflections
2449 reflections with I > 2σ(I)
R _int = 0.017
3 standard reflections every 60 min intensity decay: none

Refinement

R[F ² > 2σ(F ²)] = 0.034
wR(F ²) = 0.091
S = 1.05
3143 reflections
203 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.21 e Å⁻³
Δρ_min = −0.21 e Å⁻³

Data collection: CAD-4 Software (Enraf–Nonius, 1989 ▶); cell refinement: CAD-4 Software; data reduction: CAD-4 Software; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶) and POV-RAY (Persistence of Vision, 2004 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶), PLATON (Spek, 2009 ▶) and PARST (Nardelli, 1995 ▶).

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812003492/bt5790sup1.cif

e-68-0m229-sup1.cif^{(27.4KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812003492/bt5790Isup2.hkl

e-68-0m229-Isup2.hkl^{(151KB, hkl)}

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

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N⋯O1ⁱ	0.80 (3)	2.30 (3)	3.082 (3)	164 (2)
C19—H19⋯O1ⁱ	0.93	2.65	3.425 (3)	141
C4—H4⋯N1ⁱⁱ	0.93	2.63	3.489 (3)	153

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Symmetry codes: (i) Inline graphic ; (ii) .

Acknowledgments

This work was supported by the Ministry of Education and Science of the Republic of Serbia (project Nos. 172014, 172035 and 172034).

supplementary crystallographic information

Comment

Derivatives of ferrocene have attracted great interest due to their physical, chemical and biological properties. The ease of functionalization of the ferrocene (Fc) unit led to structurally diverse compounds with numerous applications. In that context Mannich bases (Mannich ketones; β-aminoketones) containing a Fc unit might be very useful synthetic components as they can be converted into a range of other derivatives, such as 1,3-aminoalcohols. Here we report the crystal structure of the Mannich base, 1-Ferrocenyl-3-(phenylamino)propan-1- one (I), synthesized according to the previously reported procedure (Damljanović et al., 2011).

In the title compound (Figure 1) the cyclopentadienyl rings (Cp) within the Fc unit take an almost eclipsed geometry, where the smallest C—Cg1—Cg2—C torsion angle has the value of 5.1° (Cg1 and Cg2 are centroids of the corresponding Cp rings). Bond lengths of the Fc unit have the expected values and the Cp rings show only a small mutual tilting of 1.5 (2)°. The distances of Fe1 to the centroids of the two Cp rings are 1.65 and 1.66 Å, respectively. The C1—O1 carbonyl group lies approximately in the plane of the substituted Cp1 ring with the O1—C11—C1—C5 torsion angle of 3.9 (3)°. Similarly, the atoms of phenylamino moiety are approximately co-planar as evidenced from the N1—C14—C15—C16 torsion angle of 175.5 (2)°. The torsion angle C11—C12—C13—N1 of 72.3 (2)°, on the other hand, indicates a significant twisting between two aromatic parts of the molecule, eventually the phenylamino moiety takes an almost orthogonal position with respect to the substituted Cp ring. The dihedral angle between the best planes of the two rings, phenyl and substituted Cp is 84.4 (1)°.

Molecules are organized into centrosymmetric dimers via the N—H···O and C19—H19···O1 hydrogen bonds. These dimers further arrange into the chain trough the C4—H4···N1 interaction (Figure 2).

Experimental

The compound was obtained by an aza-Michael addition of the corresponding arylamine to acryloylferrocene. The reaction was performed by microwave (MW) irradiation (500 W/5 min) of a mixture of reactants and montmorillonite K-10, without a solvent as described by Damljanović et al. (2011).