3-(3-Acetyl­anilino)-1-ferrocenylpropan-1-one

Sladjana B Novaković; Dragana Stevanović; Vladimir Divjaković; Goran A Bogdanović; Rastko D Vukićević

doi:10.1107/S1600536812028796

. 2012 Jun 30;68(Pt 7):m979–m980. doi: 10.1107/S1600536812028796

3-(3-Acetylanilino)-1-ferrocenylpropan-1-one

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

PMCID: PMC3393229 PMID: 22807797

Abstract

The title ferrocene-containing Mannich base, [Fe(C₅H₅)(C₁₆H₁₆NO₂)], crystallizes with two independent molecules (A and B) in the asymmetric unit. Molecules A and B have similar conformations. The dihedral angles between the best planes of the benzene and substituted cyclopentadienyl rings are 88.59 (9) and 84.39 (10)° in A and B, respectively. In the crystal, the independent molecules form centrosymmetric dimers via corresponding N—H⋯O hydrogen bonds. The dimers further arrange via C—H⋯π and C—H⋯O interactions. There are no significant interactions between the A and B molecules.

Related literature

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

Experimental

Crystal data

[Fe(C₅H₅)(C₁₆H₁₆NO₂)]
M _r = 375.24
Monoclinic,
a = 22.7768 (8) Å
b = 7.3978 (1) Å
c = 22.2118 (7) Å
β = 109.642 (4)°
V = 3524.87 (19) Å³
Z = 8
Mo Kα radiation
μ = 0.87 mm⁻¹
T = 293 K
0.14 × 0.10 × 0.08 mm

Data collection

Oxford Diffraction Xcalibur Sapphire3 Gemini diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009 ▶) T _min = 0.947, T _max = 1.000
21526 measured reflections
8197 independent reflections
6146 reflections with I > 2σ(I)
R _int = 0.029

Refinement

R[F ² > 2σ(F ²)] = 0.057
wR(F ²) = 0.112
S = 1.13
8197 reflections
461 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.29 e Å⁻³
Δρ_min = −0.36 e Å⁻³

Data collection: CrysAlis PRO (Oxford Diffraction, 2009 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; 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 Mercury (Macrae et al., 2006 ▶); 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/S1600536812028796/bt5949sup1.cif

e-68-0m979-sup1.cif^{(43KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812028796/bt5949Isup2.hkl

e-68-0m979-Isup2.hkl^{(392.9KB, hkl)}

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

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

Cg2A and Cg2B are the centroids of the C6A–C10A and C6B–C10B rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1A—H1NA⋯O1A ⁱ	0.78 (4)	2.40 (3)	3.162 (4)	166 (3)
N1B—H1NB⋯O1B ⁱⁱ	0.80 (4)	2.46 (3)	3.253 (4)	167 (3)
C9A—H9A⋯O2A ⁱⁱⁱ	0.93	2.49	3.403 (3)	166
C12A—H12A⋯O1A ^iv	0.97	2.67	3.517 (4)	146
C19A—H19A⋯O1A ⁱ	0.93	2.69	3.449 (4)	139
C18B—H18B⋯O2B ^v	0.93	2.49	3.336 (4)	152
C7A—H7A⋯Cg2A^vi	0.93	2.98	3.721 (4)	137
C7B—H7B⋯Cg2B^vii	0.93	2.96	3.781 (5)	148

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) ; (v) ; (vi) ; (vii) .

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 (Togni & Hayashi, 1995). In the course of our studies of different ferrocene derivatives containing two or more heteroatoms, we have synthesized and determined the crystal structures of a series of 3-(arylamino)-1-ferrocenylpropan-1-ones (Damljanović et al. 2011, Pejović et al. 2012, Stevanović et al. 2012 Leka et al. 2012a,b,c). The present derivative 1-ferrocenyl-3-(3-acetylphenylamino)propan-1-one, crystallizes with two independent molecules (A and B) in the asymmetric unit (Fig. 1). The cyclopentadienyl rings (Cp) within the Fc unit of molecules A and B take a nearly eclipsed geometry; the corresponding torsion angle C1—Cg1—Cg2—C6 has a value of 2.8 and 3.2°, respectively (Cg is centroid of the corresponding Cp ring). Both molecules display a conformation similar to that of previously reported derivatives containing meta-substituted phenyl rings.

The torsion angles C1—C11—C12—C13, C11—C12—C13—N1 and C12—C13—N1—C4 within the aliphatic fragment are -172.0 (2)/167.2 (2), 68.4 (3)/-70.4 (3) and 76.0 (4)/-77.0 (4)° (first value corresponds to molecule A, while the second one corresponds to molecule B). Inversion related molecules arrange into AA and BB dimers via corresponding N1—H1n···O1 hydrogen bonds. The AA and BB dimers further arrange into separate chains via dissimilar C—H···O interactions. In these interactions the acetyl O2 atom engages as an acceptor. On the other hand, the C—H donors engaged in these interactions are not equivalent as the A molecules use cyclopentadienyl while B molecules use phenyl fragments (Fig. 2). The molecules of the same type also interact by relatively strong C—H···π interaction which in both cases include the unsubstituted Cp ring, C7a— H7a···Cg2aⁱ: H···Cg 2.98 Å, H—Perp 2.91 Å, X—H···Cg 137°, (i = -x, y + 1/2, -z + 1/2) and C7b—H7b···Cg2 bⁱⁱ H···Cg 2.96 Å H—Perp 2.72 Å, X—H···Cg 148 °, (ii = -x + 1, y - 1/2, -z + 3/2). There are no significant interactions between the A and B molecules.

Experimental

An aza-Michael addition of arylamines to a conjugated enone, acryloylferrocene, has been achieved by ultrasonic irradiation of the mixture of these reactants and the catalyst - montmorillonite K-10. This solvent-free reaction, yielding ferrocene containing Mannich bases (3-(arylamino)-1-ferrocenylpropan-1-ones), has been performed through the use of a simple ultrasonic cleaner. The details of the synthesis are described by Pejović et al. (2012b).