1-[3-({[Bis(2-methyl­prop­yl)carbamo­thio­yl]amino}­carbon­yl)benzoyl]-3,3-bis­(2-methyl­prop­yl)thio­urea

N Selvakumaran; R Karvembu; Seik Weng Ng; Edward R T Tiekink

doi:10.1107/S1600536813021053

. 2013 Aug 3;69(Pt 9):o1368. doi: 10.1107/S1600536813021053

1-[3-({[Bis(2-methylpropyl)carbamothioyl]amino}carbonyl)benzoyl]-3,3-bis(2-methylpropyl)thiourea

N Selvakumaran ^a, R Karvembu ^a,^‡, Seik Weng Ng ^b,^c, Edward R T Tiekink ^b,^*

PMCID: PMC3884506 PMID: 24427014

Abstract

The title compound, C₂₆H₄₂N₄O₂S₂, adopts a shallow U-shape as both pendant arms of the 1,3-substituted benzene ring are orientated in the same direction. The thione S atoms lie to the same side of the benzene ring and the carbonyl O atoms to the other. The most prominent feature of the crystal packing is the formation of inversion dimers mediated by N—H⋯S hydrogen bonds. One of the 2-methylpropyl groups is statistically disordered over two positions.

Related literature

For the use of the title compound in the synthesis of metal macrocycles, see: Nguyen et al. (2011 ▶). For the structure of the methanol solvate, see: Rodenstein et al. (2007 ▶).

Experimental

Crystal data

C₂₆H₄₂N₄O₂S₂
M _r = 506.76
Monoclinic,
a = 12.6926 (2) Å
b = 11.8015 (2) Å
c = 19.9701 (4) Å
β = 103.883 (2)°
V = 2903.97 (9) Å³
Z = 4
Cu Kα radiation
μ = 1.87 mm⁻¹
T = 100 K
0.30 × 0.25 × 0.20 mm

Data collection

Agilent SuperNova Dual diffractometer with an Atlas detector
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2013 ▶) T _min = 0.217, T _max = 1.000
11629 measured reflections
5743 independent reflections
5234 reflections with I > 2σ(I)
R _int = 0.028

Refinement

R[F ² > 2σ(F ²)] = 0.050
wR(F ²) = 0.142
S = 1.01
5743 reflections
316 parameters
30 restraints
H-atom parameters constrained
Δρ_max = 0.89 e Å⁻³
Δρ_min = −0.82 e Å⁻³

Data collection: CrysAlis PRO (Agilent, 2013 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▶) and DIAMOND (Brandenburg, 2006 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Supplementary Material

Crystal structure: contains datablock(s) general, I. DOI: 10.1107/S1600536813021053/hg5336sup1.cif

e-69-o1368-sup1.cif^{(28KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813021053/hg5336Isup2.hkl

e-69-o1368-Isup2.hkl^{(281.2KB, hkl)}

Click here for additional data file.^{(10.5KB, cml)}

Supplementary material file. DOI: 10.1107/S1600536813021053/hg5336Isup3.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
N2—H2⋯S2ⁱ	0.88	2.62	3.4745 (17)	163
N3—H3⋯S2ⁱ	0.88	2.54	3.3870 (18)	162

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Symmetry code: (i) Inline graphic .

Acknowledgments

NS thanks NITT for a Fellowship. The authors also thank the Ministry of Higher Education (Malaysia) for funding structural studies through the High-Impact Research scheme (UM.C/HIR-MOHE/SC/12).

supplementary crystallographic information

1. Comment

The title compound, (I), for which the structure of a methanol solvate is known (Rodenstein et al., 2007), plays a vital role in forming a metallamacrocyclic square-planar d⁸ metal complexes via self-assembly (Nguyen et al., 2011).

In (I), Fig. 1, there is an almost orthogonal relationship between adjacent thione and carbonyl groups as seen in the C10—N2—C9—S1 and C17—N3—C18—S2 torsion angles of -113.25 (18) and 112.56 (18)°, respectively. Globally, the molecule adopts a flattened U-shape. The thione-S atoms lie to one side of the plane through the central benzene and the carbonyl-O atoms to the other so that the molecule has approximate mirror symmetry. The structure reported here for (I) is quite distinct that that observed in the methanol solvate of (I) (Rodenstein et al., 2007). In the latter, the thione-S atoms lie to either side of the benzene ring and, to a first approximation, the carbonyl-O atoms are co-planar with the ring.

Being direct towards the centre of the U-shaped molecule, the nitrogen-bound hydrogen atoms are well placed to form two N—H···S hydrogen bonds with an inverted U-shaped molecule with the central pair forming an eight-membered {···HNCS}₂ synthon, Fig. 2 and Table 1. A detailed analysis of the crystal packing is precluded owing to the presence of disorder in the molecule.

2. Experimental

Isophthaloyl dichloride (2.0302 g, 10 mmol) dissolved in acetone (80 ml) was placed in a dropping funnel and added drop wise with stirring to potassium thiocyanate (1.9436 g, 20 mmol) dissolved in acetone (80 ml), under an N₂ atmosphere, in a three-necked round bottom flask. The mixture was heated to reflux for 30 min. and then allowed to cool. A solution of diisobutylamine (2.2850 g, 20 mmol) in acetone (80 ml) was added drop wise from a dropping funnel to the reaction mixture and the resulting mixture was stirred for 2 h. Hydrochloric acid (0.1 N, 300 ml) was added and the resulting white solid was filtered off, washed with water and dried in vacuo. Single crystals were grown at room temperature from its acetonitrile solution. FT—IR (KBr): ν(N—H) 3275, ν(C═O) 1694, ν(C═C) 1604, ν(C═S) 1262 cm^-1.