2-Amino-4-(4-bromo­phen­yl)-6-ferro­cenyl­pyridine-3-carbonitrile

Run-Hong Jia; Shu-Jiang Tu

doi:10.1107/S160053680705489X

. 2007 Dec 6;64(Pt 1):m135. doi: 10.1107/S160053680705489X

2-Amino-4-(4-bromophenyl)-6-ferrocenylpyridine-3-carbonitrile

Run-Hong Jia ^a, Shu-Jiang Tu ^b,^*

PMCID: PMC2924174 PMID: 21200492

Abstract

The title compound, [Fe(C₅H₅)(C₁₇H₁₁BrN₃)], was synthesized by the reaction of 4-bromobenzaldehyde, acetylferrocene and ammonium acetate in an aqueous medium. The crystal packing is stabilized by intermolecular N—H⋯N hydrogen bonds. The dihedral angles between the phenyl ring and the pyridine and cyclopentadienyl rings are 51.67 (13) and 12.12 (21)°, respectively.

Related literature

For related literature, see: Alyoubi (2000 ▶); Desai & Shah (2003 ▶); Dombrowski et al. (1986 ▶); Murata et al. (2004 ▶).

Experimental

Crystal data

[Fe(C₅H₅)(C₁₇H₁₁BrN₃)]
M _r = 458.14
Monoclinic,
a = 12.250 (2) Å
b = 7.4511 (12) Å
c = 20.698 (3) Å
β = 97.729 (3)°
V = 1872.2 (5) Å³
Z = 4
Mo Kα radiation
μ = 2.95 mm⁻¹
T = 298 (2) K
0.16 × 0.11 × 0.07 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 1998 ▶) T _min = 0.650, T _max = 0.820
9276 measured reflections
3290 independent reflections
2327 reflections with I > 2σ(I)
R _int = 0.042

Refinement

R[F ² > 2σ(F ²)] = 0.038
wR(F ²) = 0.094
S = 1.02
3290 reflections
244 parameters
H-atom parameters constrained
Δρ_max = 0.41 e Å⁻³
Δρ_min = −0.50 e Å⁻³

Data collection: SMART (Bruker, 1998 ▶); cell refinement: SAINT (Bruker, 1999 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997 ▶); molecular graphics: SHELXTL (Bruker, 1999 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053680705489X/bq2041sup1.cif

e-64-0m135-sup1.cif^{(19.5KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S160053680705489X/bq2041Isup2.hkl

e-64-0m135-Isup2.hkl^{(161.4KB, 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
N2—H2B⋯N3ⁱ	0.86	2.29	3.050 (5)	148

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Symmetry code: (i) Inline graphic .

Acknowledgments

The authors thank the National Natural Science Foundation of China (grant No. 20672090) and the Natural Science Foundation of the Jiangsu Province (grant No. BK2006033) for financial support.

supplementary crystallographic information

Comment

Metallocenes are known to exhibit a wide range of biological activity. Among them, ferrocene has attracted special attention since it is neutral, chemically stable, non-toxic and able to cross cell membranes (Dombrowski et al., 1986). In fact, it is now well established that the incorporation of ferrocene units in organic molecules introduces significant and new properties in these materials. In addition, it has been demonstrated that molecules containing cyanopyridine moiety may be able to work as ligands towards transition-metal ions (Alyoubi, 2000), new drugs (Murata et al., 2004 and Desai et al., 2003), and significant intermediates for the synthesis of important vitamins such as nicotinic acids and nicotinamides. For these reasons, the synthesis of new compounds containing cyanopyridine derivatives is strongly desired. In this paper we report the crystal structure of the title compound (I).

In the crystal structure, the dihedral angle between the C1/C2/C3/C4/C5/N1 plane and the C17—C22 benzene ring is 51.65 (13)°.The dihedral angle between the C1/C2/C3/C4/C5/N1 plane and the C11—C16 ring is 12.21 (14)°. The molecules are connected via N—H···N hydrogen bonds, forming a three-dimensional network (Fig. 2).

Experimental

Compound (I) was prepared by the reaction of 4-bromobenzaldehyde (2 mmol), malononitrile (2 mmol), acetylferrocene (2 mmol) and ammonium acetate (4 mmol) in water (2 ml). Single crystals of (I) suitable for X-ray diffraction were obtained by slow evaporation of a 95% aqueous ethanol solution (yield 94%; m.p. >573 K). IR (cm^-1): 3457, 3354, 2211; ¹H NMR (DMSO-d₆): 4.10 (5H, s, ferrocenyl), 4.50 (2H, s, ferrocenyl), 5.04 (2H, s, ferrocenyl), 6.83 (2H, brs, NH₂), 6.94 (1H, s, ArH), 7.60 (2H, d, J = 8.0 Hz, ArH), 7.77 (2H, d, J = 8.0 Hz, ArH).7.87 (2H, brs, NH₂), 7.88–8.01 (4H, m, ArH), 11.85 (1H, s, NH).