N,N-Bis(quinolin-8-yl)-2,2′-[(1,3,4-thia­diazole-2,5-di­yl)bis­(sulfanedi­yl)]diacetamide monohydrate

Xiao-Feng Li; Yan An; Qing-Hua Huang; Yong-Hong Wen

doi:10.1107/S1600536811047222

. 2011 Nov 12;67(Pt 12):o3291. doi: 10.1107/S1600536811047222

N,N-Bis(quinolin-8-yl)-2,2′-[(1,3,4-thiadiazole-2,5-diyl)bis(sulfanediyl)]diacetamide monohydrate

Xiao-Feng Li ^a, Yan An ^a, Qing-Hua Huang ^b, Yong-Hong Wen ^b,^*

PMCID: PMC3238945 PMID: 22199794

Abstract

In the title compound, C₂₄H₁₈N₆O₂S₃·H₂O, the thiadiazole ring makes dihedral angles of 78.00 (13) and 77.27 (13)° with the quinoline ring systems. In the crystal, molecules are linked into a two-dimensional network by O—H⋯O and C—H⋯O hydrogen bonds.

Related literature

For background to the applications of 2,5-dimercapto-1,3,4-thiadiazole, see: Vullo et al. (2003 ▶); Gurn (2001 ▶). For related 2,5-dimercapto-1,3,4-thiadiazole structures, see: Wen et al. (2005 ▶); Zhang et al. (2005 ▶).

Experimental

Crystal data

C₂₄H₁₈N₆O₂S₃·H₂O
M _r = 536.64
Monoclinic,
a = 10.8215 (8) Å
b = 10.2355 (8) Å
c = 21.5510 (16) Å
β = 90.068 (1)°
V = 2387.1 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.35 mm⁻¹
T = 293 K
0.15 × 0.10 × 0.10 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.949, T _max = 0.966
12711 measured reflections
4542 independent reflections
3469 reflections with I > 2σ(I)
R _int = 0.031

Refinement

R[F ² > 2σ(F ²)] = 0.044
wR(F ²) = 0.109
S = 1.02
4542 reflections
333 parameters
3 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.28 e Å⁻³
Δρ_min = −0.19 e Å⁻³

Data collection: APEX2 (Bruker 2001 ▶); cell refinement: SAINT (Bruker 2001 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811047222/hg5124sup1.cif

e-67-o3291-sup1.cif^{(23.3KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811047222/hg5124Isup2.hkl

e-67-o3291-Isup2.hkl^{(222.5KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811047222/hg5124Isup3.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
O1W—H1WA⋯O1	0.95 (7)	2.07 (7)	2.990 (3)	162 (6)
O1W—H1WB⋯O2ⁱ	0.94 (4)	1.91 (4)	2.841 (3)	175 (4)
C11—H11B⋯O1Wⁱⁱ	0.97	2.49	3.332 (4)	145
C23—H23⋯O1ⁱⁱⁱ	0.93	2.55	3.411 (4)	155

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

Acknowledgments

The authors acknowledge the Project of the Shanghai Municipal Education Commission (09YZ245, 10YZ111, 10ZZ98), the ‘Chen Guang’ project supported by the Shanghai Municipal Education Commission and the Shanghai Education Development Foundation (09 C G52), the State Key Laboratory of Pollution Control and the Resource Reuse Foundation (PCRRF09001) for financial support.

supplementary crystallographic information

Comment

Thiodiazole and its derivatives have attracted much attention in the development of the new kind pesticide. 2,5-Dimercapto-1,3,4-thiadiazole (DMTD) is an effective stabilizer for emulsions, and its derivatives can be absorbed by plant cells, so they can be prepared as bactericides, herbicides and insecticides, etc (Vullo et al., 2003; Gurn, 2001). In this paper, a new DMTD derivative of amide-based open-chain crown-ether, 2,5-di(quinolin-8-ylcarbamoylmethylthio)-1,3,4-thiodiazole, was synthesized and an X-ray crystal structure undertaken to elucidate its molecular conformation (Fig. 1).

The crystal structure of the title compound, consists of a C₂₄H₁₈N₆O₂S₃ molecule and a crystal water molecule. All bond lengths and angles in the title compound are within normal ranges, and are comparable with the structural related compounds (Wen et al., 2005; Zhang et al., 2005). The bond lengths in thiadiazole ring show a character intermediate between single and double bond because of the π-conjugation. The thiadiazole ring and two quinoline rings are each coplanar with their attached atoms, excluding the H atoms attached to them, while the whole molecule is not planar, with dihedral angles of 78.00 (13) and 77.27 (13)° between the thiadiazole ring and the two quinoline rings, respectively. The N1 atom adopts a planar configuration with the sum of the bond angles around atom N1 being 360.00°.

In the crystal packing, the molecules are linked into network structure by O1W—H1WA···O1, O1W—H1WB···O2, C11—H11B···O1W and C23—H23A···O1 hydrogen bond interactions (Table 1, Fig. 2).

Experimental

After stirring the 40 ml acetone solution of 2,5-dimercapto-1,3,4-thiodiazole (1.50 g, 10 mmole), K₂CO₃ (1.52 g, 11 mmole) and NaI (0.5 g) at room temperature for 30 minutes, a 20 ml solution of 2-chloro-N-quinolin-8-ylacetamide (4.41 g, 20 mmoles) in acetone was added drop by drop, and the mixture was refluxed at 329 K for 3 h. After cooling to room temperature, the mixture was washed three times with water (3 × 5 ml) and then filtered. The filter cake was washed three times with acetone (3 × 5 ml). 2,5-di(quinolin-8-ylcarbamoylmethylthio)-1,3,4-thiodiazole was obtained after dryness of the resulting coffee powders at room temperature for 48 h. Yield 3.91 g (80.1%), mp 166.5–167.5°C. Anal. Calcd. (%) for C₂₄H₁₈N₆O₂S₃: C, 55.58; H, 3.50; N, 16.20; S, 18.55. Found (%): C, 55.62; H, 3.55; N, 16.26; S, 18.53.

Brown single crystals suitable for X-ray diffraction analysis were obtained by slow evaporation at room temperature from CH₃CH₂OH for 15 days.