Benzyl N-[2-(1H-indol-3-yl)eth­yl]dithio­carbamate

Nagarajan Vembu; Frank R Fronczek; Celine Petit; Marc Devocelle

doi:10.1107/S1600536807066524

. 2007 Dec 18;64(Pt 1):o288–o289. doi: 10.1107/S1600536807066524

Benzyl N-[2-(1H-indol-3-yl)ethyl]dithiocarbamate

Nagarajan Vembu ^a,^*, Frank R Fronczek ^b, Celine Petit ^c, Marc Devocelle ^c

PMCID: PMC2915340 PMID: 21200854

Abstract

The indole and phenyl ring systems in the title compound, C₁₈H₁₈N₂S₂, are nearly coplanar, the indole and phenyl planes forming a dihedral angle of 6.5 (1)°. Supramolecular aggregation is effected by N—H⋯S, C—H⋯S, N—H⋯π and C—H⋯π interactions. The crystal studied exhibited inversion twinning.

Related literature

For a detailed account of the indoleamine 2,3-dioxygenase (IDO) inhibitory properties of the title compound and other brassinin derivatives, see: Gaspari et al. (2006 ▶) and references cited therein. For hydrogen-bond criteria, see: Desiraju & Steiner (1999 ▶); Desiraju (1989 ▶). For graph-set notations, see: Bernstein et al. (1995 ▶); Etter (1990 ▶).

Experimental

Crystal data

C₁₈H₁₈N₂S₂
M _r = 326.46
Monoclinic,
a = 34.554 (10) Å
b = 5.459 (2) Å
c = 8.875 (3) Å
β = 102.522 (18)°
V = 1634.3 (9) Å³
Z = 4
Mo Kα radiation
μ = 0.32 mm⁻¹
T = 90 K
0.30 × 0.27 × 0.05 mm

Data collection

Nonius KappaCCD diffractometer with an Oxford Cryosystems Cryostream cooler
Absorption correction: multi-scan (SCALEPACK; Otwinowski & Minor, 1997 ▶) T _min = 0.909, T _max = 0.984
14452 measured reflections
3638 independent reflections
2846 reflections with I > 2σ(I)
R _int = 0.013

Refinement

R[F ² > 2σ(F ²)] = 0.038
wR(F ²) = 0.083
S = 1.06
3638 reflections
271 parameters
2 restraints
All H-atom parameters refined
Δρ_max = 0.28 e Å⁻³
Δρ_min = −0.36 e Å⁻³
Absolute structure: Flack (1983 ▶), 1615 Friedel pairs
Flack parameter: 0.44 (6)

Data collection: COLLECT (Nonius, 2000 ▶); cell refinement: DENZO and SCALEPACK (Otwinowski & Minor, 1997 ▶); data reduction: DENZO and SCALEPACK; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997 ▶); molecular graphics: PLATON (Spek, 2003 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536807066524/sj2455sup1.cif

e-64-0o288-sup1.cif^{(19.6KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536807066524/sj2455Isup2.hkl

e-64-0o288-Isup2.hkl^{(178.4KB, hkl)}

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

Cg1 is the centroid of the N1/C2–C5 ring, Cg2 that of the C4–C9 ring and Cg3 that of the C17–C22 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C11—H11B⋯S14	0.95 (3)	2.65 (2)	3.103 (2)	109.6 (17)
C16—H16A⋯S14	1.00 (2)	2.80 (2)	3.222 (2)	106.1 (15)
N12—H12⋯S14ⁱ	0.84 (3)	2.50 (3)	3.283 (2)	156 (2)
C16—H16A⋯S15ⁱⁱ	1.00 (2)	2.78 (2)	3.642 (3)	144.8 (17)
N1—H1⋯Cg2ⁱⁱⁱ	0.84 (3)	2.658	3.373	143.65
C8—H8⋯Cg2ⁱⁱ	0.95 (3)	3.244	3.868	124.79
C9—H9⋯Cg1ⁱⁱ	0.94 (3)	2.807	3.574	140.03
C18—H18⋯Cg3^iv	1.04 (3)	3.174	4.053	142.60
C21—H21⋯Cg3^v	0.93 (3)	3.212	3.946	136.93

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) ; (v) .

Acknowledgments

CP and MD thank the Irish Government under its ‘Programme for Research in Third Level Institutions’ and the Research committee of the Royal College of Surgeons in Ireland for financial support. The purchase of the diffractometer was made possible by grant No. LEQSF(1999–2000)-ENH-TR-13, administered by the Louisiana Board of Regents.

supplementary crystallographic information

Comment

The enzyme indoleamine 2,3-dioxygenase (IDO) has been reported to play a role in tumour immunosuppression. IDO inhibitors have been reported to be novel therapeutics for cancer treatment. The natural product brassinin has been shown to be a moderately active competitive IDO inhibitor. The title compound, (I), Fig. 1, is a brassinin derivative and its IDO inhibitory properties have been reported (Gaspari et al., 2006). The present investigation is aimed at the study of the molecular and supramolecular architecture of the title compound. This study may serve as a forerunner to an investigation of the correlation between the molecular and supramolecular features of this compound with its biological activity.

In (I), the dithiocarbamate moiety is essentially planar, as shown by the small deviation of N12 [0.0036 (6) Å], C13 [-0.009 (2) Å], S14 [0.0032 (5) Å] & S15 [0.0027 (5) Å] atoms from their mean plane. The interplanar angle between the indole and the phenyl ring is 6.5 (1)° thereby confirming their near coplanarity.

The crystal structure of (I) is stabilized by the interplay of N—H···S, C—H···S, N—H···π and C—H···π interactions, Fig. 2, Table 1. The H-bond distances found in (I) agree with those reported in literature (Desiraju & Steiner, 1999; Desiraju, 1989). The C11—H11B···S14 interaction generates a motif of graph set (Bernstein et al., 1995; Etter, 1990) S(5). Another S(5) motif is formed by the C16—H16···S14 interaction. The N12—H12···S14ⁱ interaction generates an infinite one-dimensional chain along [001]. The N12—H12···S14ⁱ and C16—H16A···S15ⁱⁱ interactions generate a binary motif of graph set R²₂(9). The C8—H8···Cg2ⁱⁱ and C9—H9···Cg1ⁱⁱ interactions generate an R²₂(6) motif in which each of the aromatic rings are considered as single acceptor atoms. Cg1 is the centroid of the N1, C2, C3, C4 & C5 ring, Cg2 that of the C4, C5, C6, C7, C8 & C9 ring and Cg3 that of the C17, C18, C19, C20, C21 & C22 ring, Table 1.

Experimental

The title compound was prepared by the reported procedure (Gaspari et al., 2006). Diffraction quality crystals were obtained by recrystallizing the crude product from a 1:1 mixture of dichloromethane and petroleum ether.