3,3′-Dibenzoyl-1,1′-(3,6-dioxaoctane-1,8-di­yl)dithio­urea

Mouhamadou Moustapha Sow; Ousmane Diouf; Aliou Hamady Barry; Mohamed Gaye; Abdou Salam Sall

doi:10.1107/S1600536809005662

. 2009 Feb 21;65(Pt 3):o569. doi: 10.1107/S1600536809005662

3,3′-Dibenzoyl-1,1′-(3,6-dioxaoctane-1,8-diyl)dithiourea

Mouhamadou Moustapha Sow ^a, Ousmane Diouf ^a, Aliou Hamady Barry ^b, Mohamed Gaye ^a,^*, Abdou Salam Sall ^a

PMCID: PMC2968616 PMID: 21582224

Abstract

In the molecule of the title compound, C₂₂H₂₆N₄O₄S₂, the central O—CH₂—CH₂—O chain adopts a synclinal conformation [torsion angle = 65.0 (2)°]. The crystal structure is stabilized by intramolecular N—H⋯O=C and intermolecular N—H⋯O—C hydrogen bonds.

Related literature

For related structures, see: Avşar et al. (2003 ▶); Arslan et al. (2004 ▶); Du & Du (2008 ▶); Ding et al. (2008 ▶).

Experimental

Crystal data

C₂₂H₂₆N₄O₄S₂
M _r = 474.59
Triclinic,
a = 7.9718 (2) Å
b = 9.2177 (3) Å
c = 16.4106 (5) Å
α = 81.018 (2)°
β = 83.364 (2)°
γ = 80.450 (2)°
V = 1169.60 (6) Å³
Z = 2
Mo Kα radiation
μ = 0.26 mm⁻¹
T = 293 K
0.10 × 0.10 × 0.10 mm

Data collection

Nonius Kappa CCD diffractometer
Absorption correction: none
7989 measured reflections
4211 independent reflections
2737 reflections with I > 2σ(I)
R _int = 0.030

Refinement

R[F ² > 2σ(F ²)] = 0.045
wR(F ²) = 0.128
S = 1.02
4211 reflections
305 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.41 e Å⁻³
Δρ_min = −0.50 e Å⁻³

Data collection: COLLECT (Nonius, 1998 ▶); cell refinement: DENZO and SCALEPACK (Otwinowski & Minor, 1997 ▶); data reduction: DENZO and SCALEPACK; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: PLATON (Spek, 2009 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809005662/bh2217sup1.cif

e-65-0o569-sup1.cif^{(19.9KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809005662/bh2217Isup2.hkl

e-65-0o569-Isup2.hkl^{(202.2KB, 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	0.82 (3)	1.99 (3)	2.648 (3)	136 (2)
N3—H3⋯O4	0.83 (3)	2.01 (3)	2.632 (3)	132 (3)
N4—H4⋯O2ⁱ	0.82 (3)	2.48 (3)	3.290 (3)	170 (2)

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Symmetry code: (i) Inline graphic .

Acknowledgments

The authors thank the Agence Universitaire de la Francophonie for financial support (AUF-PSCI No.6314PS804).

supplementary crystallographic information

Comment

The title compound, C₂₂H₂₆N₄O₄S₂, was characterized by ¹H and ¹³C NMR, solid-state IR and X-ray crystallographic techniques. The X-ray structure determination reveals that the compound crystallizes in the triclinic space group P1 with one molecule in the asymmetric unit. The molecular geometry is illustrated in Fig. 1. The C—S bond lengths of 1.665 (3) Å and 1.659 (2) Å and the C—O bond lengths of 1.220 (3) Å and 1.222 (3) Å are double bonds character and are comparable to those observed for 1-(biphenyl-4-carbonyl)-3-p-tolyl-thiourea [1.647 (3) Å for C—S, 1.217 (3) and 1.224 (3) Å for C—O respectively (Arslan et al., 2004)]. The C—N bond lengths are in the range 1.310 (3)–1.451 (3) Å, and are shorter than the normal single C—N bond length (Avşar et al., 2003). The carbonyl group forms an intramolecular hydrogen bonds with the N2—H2 and the N3—H3 groups, which forms two six-membered rings (C8/N1/C7/O1/H2/N2 and C15/N4/C16/O4/H3/N3) structure (Fig. 2); H2···O1 and the H3···O4 separations are respectively 1.99 (3) Å and 2.01 (3) Å. There is an intermolecular hydrogen bonding between N4—H4 and the O atom of the ethoxy group of a symmetry-related molecule, the H4···O2 (-x + 2, -y, -z + 1) separation being 2.48 (3) Å (Table 1). The structure of the title compound is related to other thiourea derivatives (e.g. Ding et al., 2008; Du & Du, 2008).

Experimental

Benzoyl chloride (7.10 g, 50 mmol) was reacted with potassium thiocyanate (4.86 g, 50 mmol) in CH₃OCH₃ (50 ml) solution, to give the corresponding benzoyl isothiocyanate after one hour under refluxing. After cooling to room temperature, a solution of 2-(2-(2-aminoethoxy)ethoxy)ethanamine (3.70 g, 25 mmol) in CH₃OCH₃ (20 ml) was added dropwise to benzoyl isothiocyanate. After three hours under stirring, 200 ml of HCl 1 M was added. A yellow oil was isolated and treated with diethyl ether to give the title compound which is washed with diethyl ether twice. Yield: 55.9%. m.p. 415–419 K. Anal. Calc. for C₂₂H₂₆N₄O₄S₂: C 55.68, H 5.52, N 11.81%. Found: C 55.70, H 5.45, N 11.65%. Selected IR data (cm^-1, KBr pellet): 3424, 3218 (ν NH), 1667 (ν C?O), 1160 (ν C?S). ¹H-NMR (200 MHz, DMSO-d₆, δ, p.p.m.): 3.45 (t, 4H, N—CH₂); 3.63 (s, 4H, O—CH₂); 3.70 (t, 4H, O—CH₂); 7.21–7.92 (m, 10H, C₆H₅); 11.01 (s, 2H, NH); 11.41 (s, 2H, NH). ¹³C-NMR (50 MHz, DMSO-d₆, δ, p.p.m.): 45.21 (N—CH₂); 68.09 (O—CH₂); 70.12 (O—CH₂); 133.31–127.62 (C₆H₅); 1168.60 (C?O); 180.81 (C?S). A CH₃Cl solution of the title compound was mixed with ethanol (1/1). After several days, colorless block-shaped single crystals suitable for X-ray crystallographic analysis were obtained.