Crystal structure of 1,1-di­acetyl­ferrocene dihydrazone

Namig G Shikhaliyev; Atash V Gurbanov; Vasily M Muzalevsky; Valentine G Nenajdenko; Victor N Khrustalev

doi:10.1107/S1600536814014366

. 2014 Jul 2;70(Pt 8):m286–m287. doi: 10.1107/S1600536814014366

Crystal structure of 1,1-diacetylferrocene dihydrazone

Namig G Shikhaliyev ^a,^*, Atash V Gurbanov ^a, Vasily M Muzalevsky ^b, Valentine G Nenajdenko ^b, Victor N Khrustalev ^c

PMCID: PMC4158501 PMID: 25249874

Abstract

The title compound, [Fe(C₇H₉N₂)₂], crystallizes with two crystallographically independent molecules in the unit cell. These represent the chiral atropoisomers distinguished by the mutual arrangement of the two acetyl–hydrazone groups with a cis conformation of the C=N bonds. The two cyclopentadienyl (Cp) rings are planar and nearly parallel, the tilt between the two rings being 3.16 (16)° [4.40 (18)° for the second independent molecule]. The conformation of the Cp rings is close to eclipsed, the twist angle being 0.1 (2)° [3.3 (2)°]. The two acetyl–hydrazone substituents are also planar and are inclined at 13.99 (15)/9.17 (16)° [6.83 (17)/14.59 (15)°] relative to the Cp rings. The Fe—C bond lengths range from 2.035 (3) to 2.065 (2) Å, with an average of 2.050 (3) Å [2.036 (3) to 2.069 (2), average 2.046 (3) Å], which agrees well with those reported for most ferrocene derivatives. In the crystal, the molecules form dimers via two strong N—H⋯N hydrogen bonds. The dimers are linked into a three-dimensional framework by weak N—H⋯N hydrogen bonds.

Keywords: crystal structure, ferrocene, dihydrazone, chiral atropoisomers, hydrogen bonds

Related literature

For a new catalytic olefination reaction and synthesis of 1,1-diacetylferrocene dihydrazone, see: Korotchenko et al. (2001 ▶); Nenajdenko et al. (2004 ▶); Abd-Elzaher et al. (2005 ▶). For related compounds, see: Xiao et al. (1999 ▶); Fang et al. (2001 ▶); Lopez et al. (2003 ▶); Zhang et al. (2006 ▶); Zhou et al. (2007 ▶); Qiao et al. (2009 ▶).

Experimental

Crystal data

[Fe(C₇H₉N₂)₂]
M _r = 298.17
Orthorhombic,
a = 9.2647 (3) Å
b = 12.9260 (4) Å
c = 22.0729 (7) Å
V = 2643.35 (15) Å³
Z = 8
Mo Kα radiation
μ = 1.13 mm⁻¹
T = 295 K
0.26 × 0.22 × 0.18 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2003 ▶) T _min = 0.757, T _max = 0.822
38476 measured reflections
6542 independent reflections
6096 reflections with I > 2σ(I)
R _int = 0.017

Refinement

R[F ² > 2σ(F ²)] = 0.031
wR(F ²) = 0.080
S = 1.08
6542 reflections
347 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.43 e Å⁻³
Δρ_min = −0.25 e Å⁻³
Absolute structure: Flack (1983 ▶), 3181 Friedel pairs
Absolute structure parameter: 0.475 (16)

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: SAINT (Bruker, 2001 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536814014366/rk2429sup1.cif

e-70-0m286-sup1.cif^{(54.6KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814014366/rk2429Isup2.hkl

e-70-0m286-Isup2.hkl^{(320.2KB, hkl)}

CCDC reference: 1009066

Additional supporting information: crystallographic information; 3D view; checkCIF report

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯N7ⁱ	0.90	2.53	3.287 (5)	142
N4—H4A⋯N5ⁱⁱ	0.90	2.29	3.137 (4)	157
N4—H4B⋯N2ⁱⁱⁱ	0.90	2.61	3.421 (4)	150
N6—H6A⋯N3^iv	0.90	2.24	3.073 (4)	154
N8—H8B⋯N1^v	0.90	2.60	3.497 (5)	178

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

Acknowledgments

We thank Professor Abel M. Maharramov for fruitful discussions and help with this work.

supplementary crystallographic information

S1. Comment

The Nenajdenko–Shastin catalytic olefination reaction discovered by us recently is a facile approach to functionally substituted halogen–alkenes (Korotchenko et al., 2001; Nenajdenko et al., 2004) (Fig. 1). To study the further synthetic potential of this reaction, we have investigated the olefination of 1,1–diacetylferrocene as a representative of metallocenes. The structure of the reaction product, C₁₄H₁₈FeN₄, I, has been unambiguously established by X–ray diffraction analysis. It has been revealed that the olefination of 1,1–diacetylferrocene allows the developing of a simple and convenient way to obtain the halogen–substituted ferrocene–alkenes II–V (Fig. 2).

The I crystallizes in the non–centrosymmetric orthorhombic space group Pna2₁ with two crystallographically independent molecules in the unit cell. The two crystallographically independent molecules of I represent the chiral atropoisomers (Fig. 3). The atropoisomers are distinguished by the mutual arrangement of the two acetyl–hydrazone groups having the cis–configuration of the C═N bonds (the disposition of the hydrazone groups is right/left and left/right, respectively). The two Cp rings are planar (r.m.s. deviations are 0.001, 0.003 and 0.003, 0.002 for the two crystallographically independent molecules, respectively) and nearly parallel, the ring–tilt between the two rings being 3.16 (16)° and 4.40 (18)° for the two crystallographically independent molecules, respectively. The conformation of the Cp rings is close to eclipsed, which is common for ferrocene derivatives. The twist angle of the Cp rings is defined as the torsion angle between a ring C atom, the two ring centers and the corresponding C atom on the opposite ring. The value of the twist angle in I is 0.1 (2)° and 3.3 (2)° for the two crystallographically independent molecules, respectively. The two acetyl–hydrazone substituents are also planar (r.m.s. deviations are 0.012, 0.026 and 0.018, 0.027 for the two crystallographically independent molecules, respectively) and are inclined relative to the Cp rings at 13.99 (15)°, 9.17 (16)° and 6.83 (17)°, 14.59 (15)° for the two crystallographically independent molecules, respectively. The Fe–C distances are as expected for a ferrocene derivative, ranging from 2.035 (3)Å to 2.065 (2)Å, with an average of 2.050 (3)Å and 2.046 (3)Å (for the two crystallographically independent molecules, respectively), which agree well with those reported for most of ferrocene derivatives (Xiao et al., 1999; Fang et al., 2001; Lopez et al., 2003; Zhang et al., 2006; Zhou et al., 2007; Qiao et al., 2009).

In the crystal, the molecules of I form a dimers via the two strong intermolecular N—H···N hydrogen bonds (Fig. 4, Table 1). Further, the dimers are linked into three–dimensional framework by the additional weak intermolecular N—H···N hydrogen bonds (Fig. 5, Table 1).

S2. Experimental

The product I was prepared by use of the methodics described in Abd-Elzaher et al., 2005. The single crystals of I were obtained by slow crystallization from C₂H₅OH. M.p. = 452–454 K.