3-({[Bis(2-methyl­prop­yl)carbamo­thio­yl]amino}­carbon­yl)benzamide

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

doi:10.1107/S1600536813017455

. 2013 Jun 29;69(Pt 7):o1183. doi: 10.1107/S1600536813017455

3-({[Bis(2-methylpropyl)carbamothioyl]amino}carbonyl)benzamide

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

PMCID: PMC3770438 PMID: 24046723

Abstract

In the title compound, C₁₇H₂₅N₃O₂S, the terminal and central amide groups are, respectively, twisted and coplanar with the attached benzene ring [O—C—C—C torsion angles = 22.7 (3) and 5.4 (3)°]. In the central part of the molecule, the amide and thioamide residues are approximately perpendicular [C—N—C—S torsion angle = −104.98 (18)°]. Supramolecular layers with a zigzag topology are formed in the crystal packing by N—H⋯O, N—H⋯S and C—H⋯O interactions; these stack along c, being separated by hydrophobic interactions.

Related literature

For the preparation of bipodal acylthiourea derivatives, see: Bourne et al. (2005 ▶). For a related structure, see: Selvakumaran et al. (2013 ▶).

Experimental

Crystal data

C₁₇H₂₅N₃O₂S
M _r = 335.46
Orthorhombic,
a = 13.9870 (4) Å
b = 15.7103 (4) Å
c = 8.5532 (3) Å
V = 1879.48 (10) Å³
Z = 4
Mo Kα radiation
μ = 0.18 mm⁻¹
T = 100 K
0.40 × 0.30 × 0.20 mm

Data collection

Agilent SuperNova Dual diffractometer with an Atlas detector
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2013 ▶) T _min = 0.930, T _max = 0.964
6635 measured reflections
4007 independent reflections
3694 reflections with I > 2σ(I)
R _int = 0.020

Refinement

R[F ² > 2σ(F ²)] = 0.039
wR(F ²) = 0.097
S = 1.00
4007 reflections
218 parameters
30 restraints
H-atom parameters constrained
Δρ_max = 0.27 e Å⁻³
Δρ_min = −0.24 e Å⁻³
Absolute structure: Flack (1983) ▶, 1590 Friedel pairs
Flack parameter: −0.03 (8)

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) global, I. DOI: 10.1107/S1600536813017455/hg5326sup1.cif

e-69-o1183-sup1.cif^{(22KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813017455/hg5326Isup2.hkl

e-69-o1183-Isup2.hkl^{(196.4KB, hkl)}

Click here for additional data file.^{(6.8KB, cml)}

Supplementary material file. DOI: 10.1107/S1600536813017455/hg5326Isup3.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—H12⋯O2ⁱ	0.88	2.09	2.887 (2)	150
N2—H2⋯O1ⁱⁱ	0.88	1.97	2.797 (2)	155
N1—H11⋯S1ⁱⁱ	0.88	2.54	3.3908 (18)	163
C7—H7⋯O1ⁱⁱ	0.95	2.32	3.210 (2)	155

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

Acknowledgments

NS thanks the 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/03).

supplementary crystallographic information

Comment

The title compound, (I), was obtained as a by-product in an attempt to prepare a bipodal acylthiourea derivative (Bourne et al., 2005) from diisobutylamine, isophthaloyl dichloride and potassium thiocyanate in acetone. Crystals were grown from a solution of the compound in acetonitrile/dimethyl formamide mixture (1:1). In (I), Fig. 1, the terminal [O1—C1—C2—C7 torsion angle = 22.7 (3)°] and central [C5—C6—C8—O2 = 5.4 (3)°] amide substituents are twisted and co-planar with the attached benzene ring, respectively. A twist is also noted between the amide and adjacent thioamide residues as seen in the C8—N2—C9—S1 torsion angle of -104.98 (18)°. The methylpropyl substituents lie to either side and are approximately perpendicular to the C₃N plane with the C9—N3—C10—C11/C11' (50:50 disorder in the isopropyl group) torsion angles being 126.0 (3) and 87.5 (3)°, respectively, and 100.4 (2)° for C9—N3—C14—C1. The aforementioned conformation matches that found in the accompanying paper (Selvakumaran et al., 2013). In the crystal packing, supramolecular layers with a zigzag topology are formed by N—H···O, N—H···S and C—H···O interactions, Fig. 2 and Table 1. Layers stack along the c axis being separated by hydrophobic intertactions.

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 N₂ atmosphere, in a three-necked round bottom flask. The mixture was heated to reflux for 30 minutes 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 at room temperature. Then, 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 acetonitrile/dimethyl formamide mixture (1:1) F T—IR (KBr): ν(NH₂) 3217 & 3192, ν(N—H) 3405, ν(C═O) 1671 (with adjacent NH₂), ν(C═O) 1652 (with adjacent NH), ν(C═C) 1593, ν(C═S) 1257 cm^-1. UV-Visible (DMF): ν_max; 264, 283, 363 nm.