3,3′-Diphenyl-1,1′-(butane-1,4-di­yl)dithio­urea

Pramod Pansuriya; Holger B Friedrich; Glenn E M Maguire

doi:10.1107/S1600536811033071

. 2011 Aug 27;67(Pt 9):o2380. doi: 10.1107/S1600536811033071

3,3′-Diphenyl-1,1′-(butane-1,4-diyl)dithiourea

Pramod Pansuriya ^a, Holger B Friedrich ^a, Glenn E M Maguire ^a,^*

PMCID: PMC3200795 PMID: 22058981

Abstract

The asymmetric unit of the title compound, C₁₈H₂₂N₄S₂, contains one half-molecule, the complete molecule being generated by crystallographic inversion symmetry. The crystal structure features two intermolecular N—H⋯S hydrogen-bonding interactions, the first generating an infinite chain along the b axis and the second an infinite chain along the a axis, together forming an interlocking structure.

Related literature

Thiourea derivatives are conspicuous for their biological activity as they form strong hydrogen-bonding interactions and coordinate to metal ions, see: Wittkopp & Schreiner (2003 ▶); Li et al. (2008 ▶). For appliactions of thiourea, see Abdallah et al. (2006 ▶); Karamé et al. (2003 ▶); Nan et al. (2000 ▶); Breuzard et al. (2000 ▶); Tommasino et al., (2000 ▶); Reinoso García et al. (2004 ▶); Leung et al. (2008 ▶). For synthesis of the title compound, see: Lee et al. (1985 ▶).

Experimental

Crystal data

C₁₈H₂₂N₄S₂
M _r = 358.52
Monoclinic,
a = 9.6795 (3) Å
b = 7.8677 (3) Å
c = 12.3213 (4) Å
β = 105.816 (2)°
V = 902.81 (5) Å³
Z = 2
Mo Kα radiation
μ = 0.30 mm⁻¹
T = 173 K
0.46 × 0.45 × 0.13 mm

Data collection

Bruker APEXII CCD diffractometer
9210 measured reflections
2192 independent reflections
1710 reflections with I > 2σ(I)
R _int = 0.042

Refinement

R[F ² > 2σ(F ²)] = 0.034
wR(F ²) = 0.093
S = 1.06
2192 reflections
117 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.45 e Å⁻³
Δρ_min = −0.23 e Å⁻³

Data collection: APEX2 (Bruker, 2006 ▶); cell refinement: SAINT-Plus (Bruker, 2006 ▶); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: OLEX2 (Dolomanov et al., 2009 ▶); software used to prepare material for publication: SHELXTL (Sheldrick, 2008 ▶).

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811033071/om2458sup1.cif

e-67-o2380-sup1.cif^{(14.6KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811033071/om2458Isup2.hkl

e-67-o2380-Isup2.hkl^{(105.6KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811033071/om2458Isup3.cml

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
N1—H1N⋯S1ⁱ	0.855 (18)	2.508 (18)	3.3465 (13)	167.1 (15)
N2—H2N⋯S1ⁱⁱ	0.806 (15)	2.713 (16)	3.3755 (14)	140.7 (13)

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

Acknowledgments

The authors wish to thank Dr Manuel Fernandes from the Chemistry Department of the University of the Witwatersrand for his assistance with the data collection and c*change for financial support.

supplementary crystallographic information

Comment

Thiourea derivatives are conspicuous for their biological activity as they form strong hydrogen bonding interactions and coordinate metal ions (Wittkopp & Schreiner, 2003; Li et al., 2008). In recent years the use of thiourea groups as potential catalytic ligands has been extensively studied in reactions such as hydroformylation (Abdallah et al., 2006), hydrosilylation (Karamé et al., 2003), asymmetric reduction (Nan et al., 2000), cyclization (Breuzard et al., 2000) and hydrogenation (Tommasino et al., 2000). Other applications include their use as synthetic cation-anion ionophores (Reinoso García et al., 2004; Leung et al., 2008).

Here we report the crystal structure of the title compound (Lee et al., 1985) (Fig. 1). The structure shows two distinct intermolecular hydrogen bonding interactions. The first occurs between between N1–H1 and S1 2.508 (18) Å, that creates an infinite chain of molecules along the b axis. The second occurs between N2–H2 and S1 2.713 (16) Å, that generates an infinite chain along the a axis. Due to these interactions an interlocking molecular structure is formed (Fig. 2).

Experimental

A solution of phenyl isothiocyanate (6.75 g, 50 mmol) in diethyl ether (15 ml) was added dropwise at 15°C to a vigorously stirred solution of anhydrous butane-1,4-diamine (8.81 g, 100 mmol) in isopropyl alcohol (100 ml) over a period of 30 min.The reaction mixture was stirred for 2 hrs at room temperature and quenched with water (200 ml). The reaction mixture was maintained overnight at room temperature. Then the reaction mixture was acidified with conc. HCl up to pH 2.6. The solvents were evaporated under vacuum, the residue was suspended in hot water for 30 min and the resulting precipitate was filtered off. The product was washed with ice cold water and dried. The yield was 2.36 g (35%).

Crystals suitable for single-crystal X-ray diffraction were grown in methanol: methylene chloride (1:2) at room temperature. M.p. = 458 K.

¹H NMR (CDCl₃, 400 MHz) d (p.p.m.): 7.64 (br.s., 2H, NH—CS), 7.40- 7.46 (m, 4H, H-arom), 7.29–7.33 (t, 2H, H-arom), 7.19–7.21 (d, 4H, H-arom), 6.18 (br.s., 2H, –NH—CH₂), 3.65 (m, 4H, –CH₂–CH₂), 1.61 (m, 4H, –CH₂–CH₂).

¹³C NMR (CDCl₃, 400 MHz): 26.12, 44.75, 125.45, 127.55, 130.34, 180.92

IR. (ν, cm^-1) 3155, 3005, 2933, 1591, 1518, 1492, 1294, 1254, 1178,1071.