1-[(Ferrocen-1-yl)meth­yl]-3-(naphthalen-1-yl)thio­urea

Xia Li; Wei Liu

doi:10.1107/S1600536811046629

. 2011 Nov 12;67(Pt 12):m1744. doi: 10.1107/S1600536811046629

1-[(Ferrocen-1-yl)methyl]-3-(naphthalen-1-yl)thiourea

Xia Li ^a,^*, Wei Liu ^a

PMCID: PMC3238652 PMID: 22199543

Abstract

In the title compound, [Fe(C₅H₅)(C₁₇H₁₅N₂S)], the cyclopentadienyl (Cp) rings are almost parallel and essentially eclipsed, with a dihedral angle between the Cp ring planes of 0.807 (11)°. The Fe atom is slightly closer to the substituted cyclopentadienyl ring, with an Fe–centroid distance of 1.6510 (8) Å, compared with 1.6597 (8) Å for the unsubstituted ring. The bridging unit between the substituted Cp ring and the naphthyl ring system is planar within 0.0174 Å and makes dihedral angles of 59.032 (10) and 66.02 (2)°, respectively, with these two rings. The angle between the substituted Cp ring and the naphthyl ring system is 72.094 (18)°. The H atoms of the NH groups of the thiourea moiety are positioned anti with respect to each other. In the crystal, molecules form centrosymmetric dimers via pairs of N—H⋯S hydrogen bonds.

Related literature

For applications of thiourea in the field of medicine, see: Di Grandi et al. (2004 ▶); Suh et al. (2005 ▶); Kaymakcioglu et al. (2005 ▶); Han et al. (2006 ▶), in bioorganic chemistry, see: Rostom (2006 ▶) and in supramolecular chemistry, see: Henderson et al. (2001 ▶); Heck & Marsura (2003 ▶).

Experimental

Crystal data

[Fe(C₅H₅)(C₁₇H₁₅N₂S)]
M _r = 400.31
Triclinic,
a = 7.958 (3) Å
b = 10.890 (5) Å
c = 12.357 (5) Å
α = 66.886 (6)°
β = 78.637 (8)°
γ = 73.306 (8)°
V = 939.1 (7) Å³
Z = 2
Mo Kα radiation
μ = 0.92 mm⁻¹
T = 296 K
0.39 × 0.24 × 0.16 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2001 ▶) T _min = 0.755, T _max = 0.867
5178 measured reflections
3645 independent reflections
2741 reflections with I > 2σ(I)
R _int = 0.018

Refinement

R[F ² > 2σ(F ²)] = 0.040
wR(F ²) = 0.105
S = 1.04
3645 reflections
241 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.35 e Å⁻³
Δρ_min = −0.32 e Å⁻³

Data collection: SMART (Bruker, 2001 ▶); cell refinement: SAINT (Bruker, 2001 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811046629/fj2464sup1.cif

e-67-m1744-sup1.cif^{(28.6KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811046629/fj2464Isup2.hkl

e-67-m1744-Isup2.hkl^{(178.7KB, 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—H2A⋯S1ⁱ	0.90 (3)	2.45 (3)	3.326 (3)	167 (2)

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Symmetry code: (i) Inline graphic .

Acknowledgments

We gratefully acknowledge financial support from the Foundation of Henan Educational Committee (2011B150001) and the Foundation of Henan University of Urban Construction (2010JYB007).

supplementary crystallographic information

Comment

Thiourea and its derivatives have attracted great attention because of their potential applications in the field of medicine (Di Grandi et al., 2004; Suh et al., 2005; Kaymakcioglu et al., 2005; Han et al., 2006), bioorganic (Rostom et al., 2006) and supramolecular chemistry (Henderson et al., 2001; Heck et al., 2003). Detailed information on their molecular and crystal structures is necessary to understand their biologic activity and coordination possibility. Here we want to report the crystal structure of a new ferrocene-containing thiourea, 1-((ferroecen-1-yl)methyl)-3-(naphthalen-1-yl)thiourea.

The molecular structure of the title compound is composed of a (ferroecen-1-yl)methyl group and a naphthalen group joined by an organic thiourea spacer. The Fe—C bond distances within the ferrocene group are in the range of 2.043 (3)–2.048 (3) Å for the substituted cyclopentadienyl (Cp) ring [C1—C5] and 2.033 (3)–2.048 (3) Å for the unsubstituted Cp ring [C6—C10]. The Cp rings are almost parallel and are essentially eclipsed, and the dihedral angle between the Cp ring planes is 0.807 (11) °. The Fe atom is slightly closer to the substituted cyclopentadienyl ring, with a Fe-centroid distance of 1.6510 (8) Å, compared with 1.6597 (8) Å for the unsubstituted ring. The bridging unit between the substituted Cp ring and naphthyl rings is planar within 0.0174 Å and makes dihedral angles of 59.032 (10) ° and 66.019 (21) °, respectively, with these two rings, while the angle between the substituted Cp ring and naphthyl rings is 72.094 (18) °. The H atoms of the NH groups of thiourea are positioned anti to each other. In the crystal, the molecules form centrosymmetric dimers via intermolecular N—H···S hydrogen bonds.

Experimental

To a solution of (ferrocene-1-yl)methanamine (1.075 g, 5 mmol) in MeOH (30 ml), 1-naphthyl isothiocyanate (0.925 g, 5 mmol) was added. The reaction mixture was stirred at room temperature for 12 h. The resulting solution was concentrated to about 10 ml and then cooled at ice-bath. The yellow precipitate was collected by filtration and washed with Ether several times. The crude product was purified by recrystallization from CH₂Cl₂ / MeOH to give 1-((ferroecen-1-yl)methyl)-3-(naphthalen-1-yl)thiourea as yellow block crystals.