1-Ferrocenyl-3-(2-methyl­anilino)propan-1-one

Zorica Leka; Sladjana B Novaković; Anka Pejović; Goran A Bogdanović; Rastko D Vukićević

doi:10.1107/S1600536812028802

. 2012 Jun 30;68(Pt 7):m995–m996. doi: 10.1107/S1600536812028802

1-Ferrocenyl-3-(2-methylanilino)propan-1-one

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

PMCID: PMC3393239 PMID: 22807807

Abstract

In the ferrocene-containing Mannich base, [Fe(C₅H₅)(C₁₅H₁₆NO)], the dihedral angle between the mean planes of the benzene ring and the substituted cyclopentadienyl ring is 84.63 (7)°. The conformation of the title compound significantly differs from those found in corresponding m-tolylamino and p-tolylamino derivatives. In the crystal, C—H⋯O interactions connect the molecules into chains, which further interact by means of C—H⋯π interactions. It is noteworthy that the amino H atom is shielded and is not involved in hydrogen bonding.

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)(C₁₅H₁₆NO)]
M _r = 347.23
Monoclinic,
a = 12.1343 (4) Å
b = 17.8010 (7) Å
c = 7.5464 (2) Å
β = 92.946 (3)°
V = 1627.89 (9) Å³
Z = 4
Mo Kα radiation
μ = 0.93 mm⁻¹
T = 293 K
0.22 × 0.18 × 0.12 mm

Data collection

Oxford Diffraction Xcalibur Sapphire3 Gemini diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009 ▶)’ T _min = 0.923, T _max = 1.000
7605 measured reflections
3694 independent reflections
2843 reflections with I > 2σ(I)
R _int = 0.029

Refinement

R[F ² > 2σ(F ²)] = 0.039
wR(F ²) = 0.097
S = 1.04
3694 reflections
213 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.28 e Å⁻³
Δρ_min = −0.28 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/S1600536812028802/bt5950sup1.cif

e-68-0m995-sup1.cif^{(25.8KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812028802/bt5950Isup2.hkl

e-68-0m995-Isup2.hkl^{(177.5KB, hkl)}

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

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

Cg is the centroid of the C14–C19 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C12—H12A⋯O1ⁱ	0.97	2.38	3.182 (3)	139
C19—H19⋯Cg1ⁱ	0.93	2.98	3.838 (3)	160

Open in a new tab

Symmetry code: (i) Inline graphic .

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

The title compound 1-Ferrocenyl-3-(o-tolylamino)propan-1-one (I), Fig. 1, shows considerable conformational differences in comparison to the crystal structures of two closely related derivatives, 1-Ferrocenyl-4-(m-tolylamino)propan-1-one (Pejović et al., 2012) and 1-Ferrocenyl-3-(p-tolylamino)propan-1-one (Leka et al., 2012b). The torsion angles C1—C11—C12—C13, C11—C12—C13—N1 and C12—C13—N1—C4 within the aliphatic fragment have the values of -161.7 (2), 78.9 (3) and 168.9 (2)°. The latter torsion angle which defines the final orientation of the phenyl ring significantly differs from the values found in m-tolylamino [69.4 (4)°] and p-tolylamino [70.6 (3)°] derivatives. On the other hand, the conformation of the title compound is closer to the one found in those 3-(arylamino)-1-ferrocenylpropan-1-ones which comprise other ortho substituted arylamino fragments, such as previously reported 1-Ferrocenyl-3-(2-acetylphenylamino)propan-1-one (Stevanović et al., 2012) and 1-Ferrocenyl-3-(2-nitrophenylamino)propan-1-one (Damljanović et al., 2011), [the torsion angle C12—C13—N1—C4 in these compounds has the value -176.1 (6) and -175.7 (6)° respectively]. In the molecule of (I) the phenyl ring is nearly orthogonally positioned with regard to substituted Cp ring. The dihedral angle between the mean planes of the phenyl ring and the substituted Cp ring is 84.63 (7)°. The Cp rings within the Fc unit display nearly eclipsed conformation with C1—Cg1—Cg2—C6 angle of 9.93° (Cg is centroid of the corresponding Cp ring). The molecules of (I) connect via C12–H12a···O1 interaction into zigzag chain extended along c axis (Fig. 2). The chains are further related by means of extensive C—H···π interactions, C19—H19···Cg1ⁱ: H···Cg 2.98 Å, H-Perp 2.87 Å, X—H···Cg 160°, (i = x, -y + 1/2, z - 1/2); C8—H8···Cg1ⁱⁱ: H···Cg 3.02 Å, H-Perp 2.84 Å, X—H···Cg 140° (ii = -x + 1, -y, -z + 1); C13—H13b···Cg1ⁱ: H···Cg 3.35 Å, H-Perp 2.87 Å, X—H···Cg 127°; C16—H16···Cg2ⁱⁱⁱ: H···Cg 3.07 Å, H-Perp 2.97 Å, X—H···Cg 168 ° (iii = -x + 1, -y, -z + 1); C20—H20a···Cg2ⁱⁱⁱ: H···Cg 3.38 Å, H-Perp 2.95 Å, X—H···Cg 140° (Cg1 and Cg2 are centroids of phenyl and unsubstituted Cp ring respectively).

Experimental

The compound was obtained by an aza-Michael addition of the coresponding 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).