(E)-1-Ferrocenyl-3-(3-nitro­phen­yl)prop-2-en-1-one

Yong-Hong Liu; Jun Ye; Xiao-Lan Liu; Wen-Long Liu; Yao-Cheng Shi

doi:10.1107/S1600536808027815

. 2008 Sep 6;64(Pt 10):m1241. doi: 10.1107/S1600536808027815

(E)-1-Ferrocenyl-3-(3-nitrophenyl)prop-2-en-1-one

Yong-Hong Liu ^a,^*, Jun Ye ^a, Xiao-Lan Liu ^a, Wen-Long Liu ^a, Yao-Cheng Shi ^a

PMCID: PMC2959240 PMID: 21200999

Abstract

In the title compound, [Fe(C₅H₅)(C₁₄H₁₀NO₃)], one cyclopentadiene ring is substituted and one is unsubstituted. The two rings are almost parallel and are eclipsed and ordered. The conjugated substituent is slightly twisted with respect to the cyclopentadiene ring. The crystal structure contains four intermolecular C—H⋯O hydrogen-bonds in the range 3.324 (3)–3.539 (3) Å and one π(aryl ring)–π (Cp ring) stacking interaction with a ring–centroid distance of 3.894 (2) Å.

Related literature

For related literature, see: Allen et al. (1987 ▶); Bernstein et al. (1995 ▶); Harrison et al. (2006 ▶); Kealy & Pauson (1951 ▶); Liang et al. (1998 ▶); Liu et al. (2001 ▶, 2003 ▶, 2008 ▶); Mrisra & Tenari (1973 ▶); Shi et al. (2004 ▶). Yarishkin et al. (2008 ▶); Zhai et al. (1999 ▶).

Experimental

Crystal data

[Fe(C₅H₅)(C₁₄H₁₀NO₃)]
M _r = 361.17
Triclinic,
a = 5.8691 (7) Å
b = 10.8636 (12) Å
c = 12.6193 (14) Å
α = 77.038 (2)°
β = 81.562 (2)°
γ = 83.565 (2)°
V = 772.99 (15) Å³
Z = 2
Mo Kα radiation
μ = 0.99 mm⁻¹
T = 296 (2) K
0.30 × 0.30 × 0.20 mm

Data collection

Bruker SMART 1000 CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2007 ▶) T _min = 0.755, T _max = 0.826
5617 measured reflections
2686 independent reflections
2462 reflections with I > 2σ(I)
R _int = 0.058

Refinement

R[F ² > 2σ(F ²)] = 0.043
wR(F ²) = 0.116
S = 1.10
2686 reflections
217 parameters
H-atom parameters constrained
Δρ_max = 0.73 e Å⁻³
Δρ_min = −0.52 e Å⁻³

Data collection: SMART (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: PLATON (Spek, 2003 ▶); software used to prepare material for publication: SHELXTL (Sheldrick, 2008 ▶).

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808027815/om2257sup1.cif

e-64-m1241-sup1.cif^{(28.9KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808027815/om2257Isup2.hkl

e-64-m1241-Isup2.hkl^{(131.9KB, 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
C7—H7⋯O3ⁱ	0.93	2.54	3.324 (3)	143
C14—H14⋯O2ⁱ	0.93	2.67	3.377 (3)	134
C3—H3⋯O1ⁱⁱ	0.93	2.66	3.278 (3)	124
C17—H17⋯O1ⁱⁱⁱ	0.93	2.68	3.539 (3)	154

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

Acknowledgments

We gratefully acknowledge the support of the National Natural Science Foundation of China (No. 20572091) and the Natural Science Foundation of Yangzhou University (No. 2006XJJ03).

supplementary crystallographic information

Comment

α, β-unsaturated ketones are important as intermediates in many addition reactions and they are also used widely in synthesizing of spice and medicament and materials (Mrisra et al., 1973; Zhai et al.,1999; Liu et al., 2001, 2003; Yarishkin et al., 2008). Since the discovery of ferrocene (Kealy & Pauson, 1951), ferrocene has played an important role in the development of electronic structures of organometallic compounds and materials chemistry. A considerable number of ferrocene derivatives have been prepared directly or indirectly from ferrocene and their properties have been extensively studied. As part of our search for new biological active compounds (Liang et al., 1998; Shi et al., 2004; Liu et al., 2008), we report herein the synthesis and crystal structure of the tltle compound.

The molecule of the title compound exists as the most stable configuration of (E)-isomer (Scheme 1, Fig.1, Table 1). The Cps ring is connected to the phenyl group through the C6—C7=C8—C9—C10 chain with the C=C bond length being 1.330 (3) Å and the three single C_sp2—C_sp2 bond lengths ranging from 1.472 (3) to 1.477 (3) Å, which are the same with the result of our early works (Liu et al., 2008). This rang compares well with the statistical values for such bond lengths in conjugated C=C—C(=O)—C system [1.464 (18) Å] and for C_sp2—C_aryl bonds (lower quartile 1.472 Å) (Allen et al., 1987). The C9=O3 and C4—N1 bond distances are 1.226 (3) and 1.473 (3) Å, The Cp and Cps rings are nearly parallel [dihedral angle 0.99 (11)°]. The dihedral angle between the benzene ring and Cps ring is 6.6 (10)°, which is in agreement with the literature (Harrison et al., 2006). The nitro group is well ordered and makes a dihedral angle of 4.57 (3)° with respect to the benzene ring.

In its packing structure, along b axis two neighboring molecules are linked into R₂²(12)R₂²(12)R₂²(12) (Bernstein et al., 1995) dimer by two pairs of C14–H14(Cps)···O2(nitro) and C7–H7···O3=C inter-molecular hydrogen-bonds and the two neighboring dimers are linked into R₂²(10) ladder-shape by two C3–H3(aryl)···O1(nitro) inter-molecular hydrogen-bonds, thus forming cross edge-fused R₂²(10)R₂²(12)R₂²(12)R₂²(12) sheet (Fig. 2, Table 2). At same time, along c axis the two neighboring dimers linked into R₄⁴(16) chains and the neighboring chains above and below are assemble into a block via π(aryl ring)···π(Cp ring) inter-molecular stacking interactions (the corresponding ring-centroid separation is 3.894 (2) Å) (Fig. 3). All of the above mentioned inter-molecular hydrogen-bonds link the molecules into a three-dimensional structure of considerable complexity.

Experimental

Acetylferrocene (1.98 g, 0.01 mol) in ethanol (25 ml) was mixed with 3-nitrobenzaldehyde (1.51 g, 0.01 mol) in ethanol (25 ml) and the mixture was treated with an aqueous solution (20 ml) of potassium hydroxide (20 ml, 5%). The resulting mixture was stirred well and left for 24 h, and the solid product was collected by filtration and dried. Crystals of the product were obtained from ethanol recrystallization (yield 80%; m.p. 463 K). Analysis, found (calculated) for C₁₉H₁₅O₃NFe (%): C 63.16 (63.29), H 4.16 (4.12), N 3.88 (3.65).