7-Chloro-4-[(7-chloro­quinolin-4-yl)sulfan­yl]quinoline dihydrate

James L Wardell; Edward R T Tiekink

doi:10.1107/S1600536812011087

. 2012 Mar 21;68(Pt 4):o1117. doi: 10.1107/S1600536812011087

7-Chloro-4-[(7-chloroquinolin-4-yl)sulfanyl]quinoline dihydrate

James L Wardell ^a,^‡, Edward R T Tiekink ^b,^*

PMCID: PMC3344064 PMID: 22589973

Abstract

In the title thioether dihydrate, C₁₈H₁₀Cl₂N₂S·2H₂O, the S-bound quinolinyl residues are almost orthogonal, forming a dihedral angle of 72.36 (4)°. In the crystal, the four water molecules are connected via an eight-membered {⋯OH}₄ synthon with each of the four pendent water H atoms hydrogen bonded to a pyridine N atom to stabilize a three-dimensional architecture.

Related literature

For background to the significant biological activities exhibited by quinoline derivatives, see: Natarajan et al. (2008 ▶). For an earlier synthesis, see: Surrey (1948 ▶).

Experimental

Crystal data

C₁₈H₁₀Cl₂N₂S·2H₂O
M _r = 393.27
Monoclinic,
a = 7.8228 (2) Å
b = 11.5596 (3) Å
c = 19.2421 (13) Å
β = 97.384 (7)°
V = 1725.60 (13) Å³
Z = 4
Mo Kα radiation
μ = 0.51 mm⁻¹
T = 120 K
0.07 × 0.07 × 0.03 mm

Data collection

Rigaku Saturn724+ diffractometer
Absorption correction: multi-scan (CrystalClear-SM Expert; Rigaku, 2011 ▶) T _min = 0.930, T _max = 1.000
36518 measured reflections
3943 independent reflections
3512 reflections with I > 2σ(I)
R _int = 0.029

Refinement

R[F ² > 2σ(F ²)] = 0.027
wR(F ²) = 0.076
S = 1.04
3943 reflections
238 parameters
6 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.46 e Å⁻³
Δρ_min = −0.19 e Å⁻³

Data collection: CrystalClear-SM Expert (Rigaku, 2011 ▶); cell refinement: CrystalClear-SM Expert; data reduction: CrystalClear-SM Expert; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶) 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/S1600536812011087/pk2399sup1.cif

e-68-o1117-sup1.cif^{(19.6KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812011087/pk2399Isup2.hkl

e-68-o1117-Isup2.hkl^{(189.4KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536812011087/pk2399Isup3.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—H1W⋯N1	0.85 (1)	2.02 (1)	2.8530 (15)	171 (2)
O1W—H2W⋯O2Wⁱ	0.84 (1)	1.94 (1)	2.7723 (14)	173 (2)
O2W—H3W⋯N2	0.85 (2)	2.01 (2)	2.8429 (14)	165 (1)
O2W—H4W⋯O1Wⁱⁱ	0.85 (1)	1.94 (2)	2.7683 (14)	166 (2)

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

Acknowledgments

The use of the EPSRC X-ray crystallographic service at the University of Southampton, England, and the valuable assistance of the staff there is gratefully acknowledged. JLW acknowledges support from CAPES (Brazil). Support from the Ministry of Higher Education, Malaysia, High-Impact Research scheme (UM.C/HIR/MOHE/SC/12) is gratefully acknowledged.

supplementary crystallographic information

Comment

Interest in the title compound, bis(7-chloroquinolin-4-yl)sulfide, crystallized as a dihydrate, rests with the biological activity of related quinoline derivatives, in particular against chloroquine-resistant malaria (Natarajan et al., 2008).

In (I), Fig. 1, the dihedral angle between the two quinolinyl residues [r.m.s. deviation for the 10 atoms of the N1- and N2-systems = 0.018 and 0.011 Å, respectively] of 72.36 (4)° indicates an almost orthogonal relationship.

The water molecules play a pivotal role in stabilizing the crystal structure, forming hydrogen bonds to each other and to the quinolinyl-N atoms, Table 1. The water···water interactions each to eight-membered {···OH}₄ synthons with each pendent water-H atom hydrogen bonded to a quinolinyl-N atom to stabilize a three-dimensional architecture, Fig. 2.

Experimental

A modification of a published procedure was adopted (Natarajan et al., 2008). A solution of 4,7-dichloroquinoline (0.5 g) in EtOH (20 ml) was heated to 323 K. Thiourea (0.20 g.) was added and the mixture was stirred for 5 min. and then cooled to room temperature. The white solid was filtered off and was extracted into 0.2 M NaOH solution. The precipitate, bis(7-chloroquinolin-4-yl)sulfide, was collected and recrystallized from EtOH as the dihydrate; M.pt. 436–439 K; lit. M.pt: 439–440 K (Surrey, 1948).