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

Yu-Jie Ding; Xi-Bin Chang; Xiao-Qing Yang; Wen-Kui Dong

doi:10.1107/S1600536808004340

. 2008 Mar 5;64(Pt 4):o658. doi: 10.1107/S1600536808004340

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

Yu-Jie Ding ^a, Xi-Bin Chang ^b, Xiao-Qing Yang ^c, Wen-Kui Dong ^c,^*

PMCID: PMC2961008 PMID: 21202055

Abstract

In the centrosymmetric title compound, C₂₀H₂₂N₄O₂S₂, the carbonyl group forms an intramolecular hydrogen bond with the NH group attached to the butanediyl linker, resulting in a six-membered ring. There are also intermolecular C—H⋯S interactions in the crystal structure, and π–π interactions between phenyl groups [2.425 (3) Å].

Related literature

For related literature, see: Breuzard et al. (2000 ▶); Burrows et al. (1997 ▶); Dong et al. (2006 ▶); Foss et al. (2004 ▶); Huang et al., 2006 ▶; Nan et al. (2000 ▶); Teoh et al. (1999 ▶); Valdés-Martínez et al. (2004 ▶); Zhang et al. (2006 ▶).

Experimental

Crystal data

C₂₀H₂₂N₄O₂S₂
M _r = 414.54
Monoclinic,
a = 6.0405 (11) Å
b = 23.358 (2) Å
c = 7.2877 (13) Å
β = 104.018 (2)°
V = 997.6 (3) Å³
Z = 2
Mo Kα radiation
μ = 0.29 mm⁻¹
T = 298 (2) K
0.22 × 0.16 × 0.07 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.939, T _max = 0.980
4845 measured reflections
1735 independent reflections
1044 reflections with I > 2σ(I)
R _int = 0.058

Refinement

R[F ² > 2σ(F ²)] = 0.056
wR(F ²) = 0.106
S = 1.02
1735 reflections
127 parameters
H-atom parameters constrained
Δρ_max = 0.23 e Å⁻³
Δρ_min = −0.21 e Å⁻³

Data collection: SMART (Siemens, 1996 ▶); cell refinement: SAINT (Siemens, 1996 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Version 5.1; Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808004340/hg2377sup1.cif

e-64-0o658-sup1.cif^{(15.7KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808004340/hg2377Isup2.hkl

e-64-0o658-Isup2.hkl^{(85.5KB, 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—H2⋯O1	0.86	2.06	2.717 (3)	133
C2—H2A⋯S1	0.97	2.68	3.060 (3)	103
C2—H2B⋯S1ⁱ	0.97	2.72	3.468 (3)	134

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Symmetry code: (i) Inline graphic .

Acknowledgments

This work was supported by the Foundation of the Education Department of Gansu Province (grant No. 0604-01) and the Qing Lan Talent Engineering Fund of Lanzhou Jiaotong University (grant No. QL-03-01A), which are gratefully acknowledged.

supplementary crystallographic information

Comment

Acylthioureas have been the subject of extensive investigation because of their biological activity and their ability to coordinate strongly with metal ions (Teoh et al., 1999; Huang et al., 2006; Foss et al., 2004). Some thioureas are organic catalysts in the metal-catalyzed asymmetric reduction of carbonyl compounds and carbonylative cyclization of o-hydroxyarylacetylenes (Nan et al., 2000; Breuzard et al., 2000). In recent years, thiourea derivatives have been studied because they are excellent H bonding donors and acceptors (Zhang et al., 2006; Valdés-Martínez et al., 2004), and readily form an intramolecular hydrogen bonding between the benzoyl (CO) and the N—H group (Dong et al., 2006). They also easily form intermolecular hydrogen bonds, which can be applied in the design and synthesis of three-dimension supramolecular structure (Burrows et al., 1997). Here we report synthesis and crystal structure of N, N'-(1, 4-tetramethylene)bisbenzoylthiourea (I), C₂₀H₂₂N₄O₂S₂.

The crystal structure of (I) consists of discrete molecules. The carbonyl group forms an intramolecular hydrogen bond with the N2—H2 group, which forms a six-membered ring (C4/N1/C1/N2/H2/O1) structure, the H2···O1 bond length is 2.055 (3) Å. This is similar to the situation found in the structure of N-benzoyl-N'-(3-pyridyl)thiourea (Dong et al., 2006). There is intermolecular hydrogen bonding between N2—H2 and the C?S group of another molecule, the H2···S1(x + 1, y, z) bond length is 2.906 (3) Å. The C?O bond length of 1.223 (3) Å is longer than the average C?O bond length (1.200 Å), which is due to intramolecular hydrogen bonding. The torsion angles of C2—N2—C1—N1 and C2—N2—C1—S1 are 178.3 (2) and -0.9 (4)°. There are π–π interactions between phenyl groups in the crystal lattice.

Experimental

Benzoyl chloride (1.41 g, 10 mmol) was reacted with ammonium thiocyanate (1.14 g, 15 mmol) in CH₂Cl₂ (25 ml) solution under solid–liquid phase transfer catalysis, using polyethylene glycol-400 (0.18 g) as the catalyst, to give the corresponding benzoyl isothiocyanate. Then a solution of 1,4-butylenediamine (0.40 g, 4.5 mmol) in CH₂Cl₂ (15 ml) was added dropwise to benzoyl isothiocyanate, to give the title compound. Yield, 81.8%. m.p. 196–198 °C. Anal. Calc. for C₂₀H₂₂N₄O₂S₂ (%): C, 57.97; H, 5.31; N, 13.53. Found: C, 57.90; H, 5.45; N, 13.35. Selected IR data (cm^-1, KBr pellet): 3416, 3222 (ν NH), 1672 (ν C?O), 1146 (ν C?S). ¹H NMR (200 MHz, DMSO-d6, δ, p.p.m.): 1.71 (t, 4H, CH2); 3.69 (t, 4H, CH2); 7.48–7.93 (m, 10H, C6H5); 10.95 (s, 1H, NH); 11.06 (s, 1H, NH). A DMF solution of the title compound was placed in a diethyl ether atmosphere, after several days, along with diffusion of diethyl ether into the DMF solution of the title compound, colorless block-shaped single crystals suitable for X-ray crystallographic analysis were obtained.