3,3′-Bis(3,4,5-trimethoxy­benzo­yl)-1,1′-(o-phenyl­ene)dithio­urea ethanol solvate

Hai-Tang Du; Hai-Jun Du

doi:10.1107/S1600536808023556

. 2008 Jul 31;64(Pt 8):o1632–o1633. doi: 10.1107/S1600536808023556

3,3′-Bis(3,4,5-trimethoxybenzoyl)-1,1′-(o-phenylene)dithiourea ethanol solvate

Hai-Tang Du ^a,^*, Hai-Jun Du ^b

PMCID: PMC2962238 PMID: 21203322

Abstract

In the molecule of the title compound, C₂₈H₃₀N₄O₈S₂·C₂H₆O, the benzene ring is oriented at dihedral angles of 38.50 (6) and 5.68 (5)° with respect to the trimethoxyphenyl rings, while the two trimethoxyphenyl rings are oriented at a dihedral angle of 44.18 (5)°. Intramolecular N—H⋯O and N—H⋯S hydrogen bonds result in the formation of non-planar six-, seven- and eight-membered rings. The twisting modes of the two side arms are different [C—N—C—O and C—N—C—N torsion angles = 0.1 (3) and 11.8 (3)°, respectively, in one arm, and 4.6 (3) and −11.5 (3)° in the other]. In the crystal structure, intermolecular N—H⋯O and O—H⋯O hydrogen bonds link the molecules.

Related literature

For a related structure, see: Thiam et al. (2008 ▶). For ring conformation puckering parameters, see: Cremer & Pople (1975 ▶).

Experimental

Crystal data

C₂₈H₃₀N₄O₈S₂·C₂H₆O
M _r = 660.75
Triclinic,
a = 7.7619 (15) Å
b = 14.473 (3) Å
c = 15.810 (3) Å
α = 67.113 (10)°
β = 73.069 (9)°
γ = 78.210 (12)°
V = 1556.9 (5) Å³
Z = 2
Mo Kα radiation
μ = 0.23 mm⁻¹
T = 113 (2) K
0.14 × 0.12 × 0.10 mm

Data collection

Rigaku Saturn CCD area-detector diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005 ▶) T _min = 0.968, T _max = 0.977
18692 measured reflections
6824 independent reflections
5694 reflections with I > 2σ(I)
R _int = 0.046

Refinement

R[F ² > 2σ(F ²)] = 0.050
wR(F ²) = 0.115
S = 1.07
6824 reflections
433 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.26 e Å⁻³
Δρ_min = −0.32 e Å⁻³

Data collection: CrystalClear (Rigaku/MSC, 2005 ▶); cell refinement: CrystalClear; data reduction: CrystalStructure (Rigaku/MSC, 2005 ▶); 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 datablocks I, global. DOI: 10.1107/S1600536808023556/hk2504sup1.cif

e-64-o1632-sup1.cif^{(27.7KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808023556/hk2504Isup2.hkl

e-64-o1632-Isup2.hkl^{(333.9KB, 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
N4—H4A⋯O1ⁱ	0.90 (2)	2.51 (2)	3.403 (2)	173 (2)
N2—H2⋯S1	0.88 (2)	2.69 (2)	3.3527 (19)	133.0 (18)
N2—H2⋯O2	0.88 (2)	1.97 (2)	2.677 (2)	136 (2)
N1—H1⋯O1	0.89 (2)	1.90 (2)	2.621 (2)	137 (2)
N3—H3A⋯O9	0.84 (2)	2.23 (2)	2.949 (2)	145 (2)
O9—H9⋯O2	0.80 (3)	2.13 (3)	2.905 (2)	163 (3)

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Symmetry code: (i) Inline graphic .

Acknowledgments

The authors thank Guiyang College for financial support.

supplementary crystallographic information

Comment

In the molecule of the title compound (Fig. 1) the bond lengths and angles are within normal ranges. Rings A (C1-C6), B (C9-C14) and C (C17-C22) are, of course, planar, and the dihedral angles between them are A/B = 38.50 (6)°, A/C = 5.68 (5)° and B/C = 44.18 (5)°.

The intramolecular N-H···O and N-H···S hydrogen bonds (Table 1) result in the formation of non-planar six-, seven- and eight-membered rings: D (O1/N1/N3/C7/C8/H1), E (O2/N2/N4/C15/C16/H2), F (S1/N1/N2/C1/C2/C7/H2) and G (S1/O2/O9/N3/C7/H2/H3A/H9). Rings D and E adopt flattened-boat [φ = 171.38 (2)°, θ = 109.10 (3)° (for ring D) and φ = -20.28 (3)°, θ = 96.87 (3)° (for ring E)] conformations, while rings F and G adopt highly twisted conformations having total puckering amplitudes, Q_T, of 0.160 (3), 0.109 (3), 2.486 (4) and 2.064 (4) Å, respectively (Cremer & Pople, 1975). The two side arms are not twisted in the same way, as evidenced by the torsion angles: C7-N3-C8-O1 [0.1 (3)°], C8-N3-C7-N1 [11.8 (3)°] and C15-N4-C16-O2 [4.6 (3)°], C16-N4-C15-N2 [-11.5 (3)°], as in 1,2-bis(N'-benzoylthioureido)- benzene (Thiam et al., 2008).

In the crystal structure, intermolecular N-H···O hydrogen bonds link the molecules (Fig. 2), in which they may be effective in the stabilization of the structure.

Experimental

For the preparation of the title compound, ammonium thiocyanate (30 mmol), 3,4,5-trimethoxylbenzoyl chloride (20 mmol), PEG-400 (0.2 mmol) and acetone (50 mL) were placed in a dried round-bottomed flask containing a magnetic stirrer bar and stirred at room temperature for 1 h, then benzene-1,2-diamine (9.5 mmol) was added, and the mixture was stirred for 2 h. The mixture was poured into water (20 ml). The resulting solid was filtered, washed with water, and then dried. Crystals suitable for X-ray analysis were obtained by the recrystallization of the solid residue from a mixture of N,N-dimethyl- formamide/ethanol (1:1) by slow evaporation at room temperature.