5-{[(2-Hy­droxy­eth­yl)sulfan­yl]meth­yl}quinolin-8-ol

Rbaa, M.; Ramli, Y.; Lakhrissi, Y.; Mague, J.; Lakhrissi, B.

doi:10.1107/S2414314619006254

organic compounds

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ISSN: 2414-3146

Volume 4| Part 5| May 2019| x190625

https://doi.org/10.1107/S2414314619006254

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5-{[(2-Hydroxyethyl)sulfanyl]methyl}quinolin-8-ol

Mohamed Rbaa,^a Youssef Ramli,^b Younes Lakhrissi,^a ^* Joel Mague ^c and Brahim Lakhrissi ^a

^aLaboratory of Agro-resources, Polymers and Process Engineering, Ibn Tofaïl University, Faculty of Sciences, Department of Chemistry, PO Box 133, 14000, Kenitra, Morocco, ^bLaboratory of Medicinal Chemistry, Faculty of Medicine and Pharmacy, Mohammed V, University Rabat, Morocco, and ^cDepartment of Chemistry, Tulane University, New Orleans, LA 70118, USA
^*Correspondence e-mail: brahim_lakhrissi@yahoo.com

Edited by L. Van Meervelt, Katholieke Universiteit Leuven, Belgium (Received 29 April 2019; accepted 3 May 2019; online 10 May 2019)

In the title molecule, C₁₂H₁₃NO₂S, the quinolinol unit is planar (r.m.s. deviation = 0.0128 Å). In the crystal, O—H⋯N and O—H⋯S hydrogen bonds together with π-stacking interactions form layers parallel to [100] that are associated through C—H⋯O hydrogen bonds.

Keywords: crystal structure; hydrogen bond; π-stacking; quinolinol.

CCDC reference: 1913753

Structure description

Organic synthesis is a major tool for the formation of new biologically active molecules, in particular heterocyclic molecules (Rbaa et al., 2018 ). 8-Hydroxyquinoline is an important heterocyclic nucleus, thanks to its structure which presents various nucleophilic and electrophilic reactive sites that allow the synthesis of new heterocyclic derivatives. Following our interest in 8-quinolinol-based biological and anti-corrosion inhibitor compounds (El Faydy et al.,2016 ; Rbaa et al. 2017 ), we have synthesized the title compound by reaction of 5-chloromethylquinoline-8-ol hydrochloride with thioethanol in the presence of triethylamine in pure tetrahydrofuran as a solvent.

The quinolinol unit is planar to within 0.0200 (9) Å (r.m.s. deviation of the fitted atoms = 0.0128 Å) with C8 farthest from the mean plane. The side chain attached to C5 is nearly perpendicular to this plane as indicated by the C4—C5—C10—S1 torsion angle of 99.16 (10)°. There is a hydrogen bond between the oxygen atom of the phenolic ring O1and the nitrogen atom of the pyridine ring N1 (Fig. 1, Table 1).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯N1	0.87	2.29	2.7577 (12)	114
O1—H1⋯N1ⁱ	0.87	2.19	2.8395 (11)	131
O2—H2⋯S1ⁱⁱ	0.87	2.47	3.2919 (9)	159
C3—H3⋯O1ⁱⁱ	0.955 (16)	2.599 (16)	3.2858 (13)	129.1 (11)
C8—H8⋯O2ⁱⁱⁱ	0.903 (17)	2.529 (17)	3.4252 (14)	171.9 (14)
C9—H9⋯O1ⁱ	0.917 (16)	2.525 (16)	3.0446 (13)	116.3 (12)
Symmetry codes: (i) -x+1, -y+1, -z; (ii) $[x, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ ; (iii) -x, -y+1, -z+1.

Figure 1
The title molecule with the atom-labelling scheme and 50% probability ellipsoids. The intramolecular O—H⋯N hydrogen bond is shown by a dashed line.

In the crystal, the molecules form inversion dimers through O1—H1⋯N1ⁱ hydrogen bonds with a R₂²(10) graph set (Table 1 and Fig. 2). These are connected into layers parallel to [100] by O2—H2⋯S1ⁱⁱ hydrogen bonds and π-stacking interactions between inversion-related C1–C6 rings [centroid–centroid distance = 3.4044 (6) Å]. In the layers, the hydroxyethyl groups extend on either side, engaging in C7—H7⋯O2ⁱⁱ and C8—H8⋯O2ⁱⁱⁱ hydrogen bonds, which tie the layers together (Table 1 and Figs. 2–4 ). C9—H9⋯O1ⁱ hydrogen bonds also occur.

Figure 2
Detail of the intermolecular interactions. O—H⋯N, C—H⋯O and C—H⋯S hydrogen bonds are shown, respectively, by light-purple, black and gold dashed lines. The π-stacking interaction is shown by an orange dashed line.

Figure 3
Packing viewed along the c-axis direction with intermolecular interactions depicted as in Fig. 2

Figure 4
Packing viewed along the a-axis direction with intermolecular interactions depicted as in Fig. 2

Synthesis and crystallization

A mixture of 5-chloromethyl-8-hydroxyquinoline hydrochloride (0.01 mol), and thioethanol (0.02 mol) in 50 ml of absolute tetrahydrofuran (THF) in the presence of NaHCO₃ was refluxed under magnetic stirring for 8 h. The reaction was followed by TLC, after cooling. The reaction mixture was then added to 20 ml of water and then extracted with dichloromethane (3 × 20 ml). The organic layers were combined, washed twice with saturated aqueous sodium chloride, dried over anhydrous magnesium sulfate and concentrated to dryness on a rotary evaporator. The product was then purified by silica column chromatography using a mixture of acetone/hexane (85:15, v/v)), and recrystallized from ethanol solution to give crystals suitable for X-ray analysis.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	C₁₂H₁₃NO₂S
M_r	235.29
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	120
a, b, c (Å)	11.8362 (7), 11.7958 (7), 7.8459 (5)
β (°)	91.673 (1)
V (Å³)	1094.96 (12)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.28
Crystal size (mm)	0.44 × 0.43 × 0.23

Data collection
Diffractometer	Bruker SMART APEX CCD
Absorption correction	Multi-scan (SADABS; Krause et al., 2015 )
T_min, T_max	0.86, 0.94
No. of measured, independent and observed [I > 2σ(I)] reflections	33009, 2961, 2797
R_int	0.025
(sin θ/λ)_max (Å⁻¹)	0.687

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.032, 0.093, 1.05
No. of reflections	2961
No. of parameters	191
H-atom treatment	Only H-atom displacement parameters refined
Δρ_max, Δρ_min (e Å⁻³)	0.56, −0.20
Computer programs: APEX3 and SAINT (Bruker, 2016 ), SHELXT (Sheldrick, 2015a ), SHELXL2018/1 (Sheldrick, 2015b ), DIAMOND (Brandenburg & Putz, 2012 ) and SHELXTL (Sheldrick, 2008 ).

Structural data

CCDC reference: 1913753

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S2414314619006254/vm4040sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314619006254/vm4040Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314619006254/vm4040Isup3.cml

checkCIF report

Computing details top

Data collection: APEX3 (Bruker, 2016); cell refinement: SAINT (Bruker, 2016); data reduction: SAINT (Bruker, 2016); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018/1 (Sheldrick, 2015b); molecular graphics: DIAMOND (Brandenburg & Putz, 2012); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

5-{[(2-Hydroxyethyl)sulfanyl]methyl}quinolin-8-ol top

Crystal data top

C₁₂H₁₃NO₂S	F(000) = 496
M_r = 235.29	D_x = 1.427 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 11.8362 (7) Å	Cell parameters from 9809 reflections
b = 11.7958 (7) Å	θ = 2.4–29.2°
c = 7.8459 (5) Å	µ = 0.28 mm⁻¹
β = 91.673 (1)°	T = 120 K
V = 1094.96 (12) Å³	Thick plate, colourless
Z = 4	0.44 × 0.43 × 0.23 mm

Data collection top

Bruker SMART APEX CCD diffractometer	2961 independent reflections
Radiation source: fine-focus sealed tube	2797 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.025
Detector resolution: 8.3333 pixels mm^-1	θ_max = 29.2°, θ_min = 1.7°
φ and ω scans	h = −16→16
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	k = −15→16
T_min = 0.86, T_max = 0.94	l = −10→10
33009 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.032	Hydrogen site location: difference Fourier map
wR(F²) = 0.093	Only H-atom displacement parameters refined
S = 1.05	w = 1/[σ²(F_o²) + (0.0578P)² + 0.4352P] where P = (F_o² + 2F_c²)/3
2961 reflections	(Δ/σ)_max = 0.001
191 parameters	Δρ_max = 0.56 e Å⁻³
0 restraints	Δρ_min = −0.20 e Å⁻³

Special details top

Experimental. The diffraction data were obtained from 3 sets of 400 frames, each of width 0.5° in ω, colllected at φ = 0.00, 90.00 and 180.00° and 2 sets of 800 frames, each of width 0.45° in φ, collected at ω = –30.00 and 210.00°. The scan time was 5 sec/frame.

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > 2sigma(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. The hydrogen atoms attached to oxygen were placed in locations derived from a difference map, their coordinates adjusted to give O—H = 0.87 %A and were included as riding contributions.

The hydrogen atoms attached to oxygen were placed in locations derived from a difference map, their coordinates adjusted to give O—H = 0.87 Å and were included as riding contributions.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
S1	0.09756 (2)	0.62998 (2)	0.68410 (3)	0.01569 (9)
O1	0.54726 (7)	0.61574 (7)	0.18639 (10)	0.01798 (17)
H1	0.534302	0.568575	0.102876	0.039 (5)*
O2	−0.02097 (7)	0.85612 (7)	0.79986 (11)	0.02225 (18)
H2	0.021957	0.873272	0.888036	0.065 (7)*
N1	0.37596 (7)	0.46007 (7)	0.13362 (11)	0.01481 (18)
C1	0.37994 (8)	0.51945 (8)	0.28340 (12)	0.01271 (19)
C2	0.46902 (8)	0.59965 (9)	0.30686 (13)	0.01415 (19)
C3	0.47685 (9)	0.66206 (9)	0.45413 (13)	0.0163 (2)
H3	0.5355 (13)	0.7169 (13)	0.4712 (19)	0.022 (4)*
C4	0.39811 (9)	0.64610 (9)	0.58290 (13)	0.0157 (2)
H4	0.4071 (13)	0.6887 (13)	0.683 (2)	0.021 (3)*
C5	0.31138 (8)	0.56882 (9)	0.56841 (12)	0.01389 (19)
C6	0.30114 (8)	0.50343 (8)	0.41551 (12)	0.01284 (19)
C7	0.21737 (8)	0.41920 (9)	0.38675 (13)	0.0163 (2)
H7	0.1644 (13)	0.4049 (13)	0.474 (2)	0.021 (4)*
C8	0.21448 (9)	0.35904 (9)	0.23679 (14)	0.0183 (2)
H8	0.1620 (14)	0.3049 (14)	0.216 (2)	0.026 (4)*
C9	0.29511 (9)	0.38318 (9)	0.11339 (14)	0.0173 (2)
H9	0.2941 (13)	0.3434 (13)	0.013 (2)	0.022 (4)*
C10	0.23173 (9)	0.55471 (9)	0.71246 (13)	0.0157 (2)
H10A	0.2690 (13)	0.5808 (13)	0.817 (2)	0.021 (3)*
H10B	0.2087 (13)	0.4760 (14)	0.7278 (19)	0.023 (4)*
C11	0.14715 (9)	0.77525 (9)	0.66999 (14)	0.0182 (2)
H11A	0.1931 (13)	0.7926 (14)	0.771 (2)	0.025 (4)*
H11B	0.1940 (14)	0.7851 (15)	0.568 (2)	0.030 (4)*
C12	0.04781 (10)	0.85674 (10)	0.65398 (15)	0.0210 (2)
H12A	0.0778 (13)	0.9341 (14)	0.633 (2)	0.027 (4)*
H12B	−0.0047 (14)	0.8363 (14)	0.560 (2)	0.025 (4)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.01307 (14)	0.01642 (14)	0.01784 (14)	0.00009 (8)	0.00495 (9)	−0.00174 (8)
O1	0.0179 (4)	0.0194 (4)	0.0170 (4)	−0.0042 (3)	0.0076 (3)	−0.0010 (3)
O2	0.0195 (4)	0.0236 (4)	0.0240 (4)	0.0021 (3)	0.0054 (3)	−0.0036 (3)
N1	0.0140 (4)	0.0165 (4)	0.0141 (4)	0.0013 (3)	0.0028 (3)	−0.0006 (3)
C1	0.0118 (4)	0.0129 (4)	0.0135 (4)	0.0023 (3)	0.0021 (3)	0.0009 (3)
C2	0.0128 (4)	0.0143 (4)	0.0155 (4)	0.0014 (3)	0.0038 (3)	0.0025 (3)
C3	0.0145 (4)	0.0160 (4)	0.0184 (5)	−0.0019 (4)	0.0024 (4)	−0.0006 (4)
C4	0.0152 (5)	0.0174 (5)	0.0146 (4)	0.0014 (4)	0.0015 (4)	−0.0017 (3)
C5	0.0126 (4)	0.0159 (4)	0.0132 (4)	0.0031 (3)	0.0027 (3)	0.0008 (3)
C6	0.0109 (4)	0.0140 (4)	0.0137 (4)	0.0025 (3)	0.0023 (3)	0.0012 (3)
C7	0.0130 (4)	0.0178 (5)	0.0185 (5)	−0.0003 (4)	0.0047 (4)	0.0002 (4)
C8	0.0143 (5)	0.0193 (5)	0.0215 (5)	−0.0031 (4)	0.0036 (4)	−0.0030 (4)
C9	0.0161 (5)	0.0192 (5)	0.0167 (5)	−0.0003 (4)	0.0035 (4)	−0.0037 (4)
C10	0.0152 (4)	0.0192 (5)	0.0129 (4)	0.0022 (4)	0.0037 (3)	0.0011 (3)
C11	0.0175 (5)	0.0169 (5)	0.0205 (5)	−0.0015 (4)	0.0061 (4)	−0.0018 (4)
C12	0.0239 (5)	0.0186 (5)	0.0206 (5)	0.0025 (4)	0.0042 (4)	0.0001 (4)

Geometric parameters (Å, º) top

S1—C11	1.8158 (11)	C5—C6	1.4284 (13)
S1—C10	1.8273 (11)	C5—C10	1.5021 (13)
O1—C2	1.3558 (12)	C6—C7	1.4171 (14)
O1—H1	0.8698	C7—C8	1.3736 (15)
O2—C12	1.4239 (14)	C7—H7	0.956 (16)
O2—H2	0.8701	C8—C9	1.4082 (15)
N1—C9	1.3246 (14)	C8—H8	0.903 (17)
N1—C1	1.3677 (13)	C9—H9	0.916 (16)
C1—C2	1.4245 (14)	C10—H10A	0.969 (15)
C1—C6	1.4271 (13)	C10—H10B	0.976 (16)
C2—C3	1.3709 (14)	C11—C12	1.5211 (16)
C3—C4	1.4070 (14)	C11—H11A	0.967 (16)
C3—H3	0.955 (16)	C11—H11B	0.993 (17)
C4—C5	1.3751 (14)	C12—H12A	0.994 (17)
C4—H4	0.934 (16)	C12—H12B	0.978 (16)

C11—S1—C10	100.64 (5)	C7—C8—C9	118.95 (10)
C2—O1—H1	109.1	C7—C8—H8	121.5 (10)
C12—O2—H2	107.7	C9—C8—H8	119.6 (10)
C9—N1—C1	117.41 (9)	N1—C9—C8	123.90 (10)
N1—C1—C2	117.26 (9)	N1—C9—H9	116.4 (10)
N1—C1—C6	123.32 (9)	C8—C9—H9	119.7 (10)
C2—C1—C6	119.41 (9)	C5—C10—S1	114.64 (7)
O1—C2—C3	118.79 (9)	C5—C10—H10A	108.7 (9)
O1—C2—C1	121.39 (9)	S1—C10—H10A	108.7 (9)
C3—C2—C1	119.81 (9)	C5—C10—H10B	112.5 (9)
C2—C3—C4	120.23 (10)	S1—C10—H10B	103.4 (9)
C2—C3—H3	120.8 (9)	H10A—C10—H10B	108.7 (12)
C4—C3—H3	118.9 (9)	C12—C11—S1	110.55 (8)
C5—C4—C3	122.54 (9)	C12—C11—H11A	110.4 (9)
C5—C4—H4	119.4 (9)	S1—C11—H11A	109.0 (9)
C3—C4—H4	118.0 (9)	C12—C11—H11B	108.0 (10)
C4—C5—C6	118.18 (9)	S1—C11—H11B	110.4 (10)
C4—C5—C10	119.65 (9)	H11A—C11—H11B	108.5 (13)
C6—C5—C10	122.16 (9)	O2—C12—C11	112.90 (9)
C7—C6—C1	116.51 (9)	O2—C12—H12A	110.5 (9)
C7—C6—C5	123.65 (9)	C11—C12—H12A	108.4 (9)
C1—C6—C5	119.82 (9)	O2—C12—H12B	103.7 (10)
C8—C7—C6	119.89 (9)	C11—C12—H12B	112.3 (10)
C8—C7—H7	121.4 (9)	H12A—C12—H12B	109.1 (13)
C6—C7—H7	118.7 (9)

C9—N1—C1—C2	178.17 (9)	C4—C5—C6—C7	178.35 (10)
C9—N1—C1—C6	−0.86 (15)	C10—C5—C6—C7	−1.01 (15)
N1—C1—C2—O1	−0.60 (14)	C4—C5—C6—C1	0.05 (14)
C6—C1—C2—O1	178.47 (9)	C10—C5—C6—C1	−179.31 (9)
N1—C1—C2—C3	179.65 (9)	C1—C6—C7—C8	−0.74 (15)
C6—C1—C2—C3	−1.28 (15)	C5—C6—C7—C8	−179.09 (10)
O1—C2—C3—C4	−178.96 (9)	C6—C7—C8—C9	−0.43 (16)
C1—C2—C3—C4	0.80 (15)	C1—N1—C9—C8	−0.44 (16)
C2—C3—C4—C5	0.13 (16)	C7—C8—C9—N1	1.10 (17)
C3—C4—C5—C6	−0.55 (15)	C4—C5—C10—S1	99.16 (10)
C3—C4—C5—C10	178.83 (9)	C6—C5—C10—S1	−81.48 (11)
N1—C1—C6—C7	1.44 (14)	C11—S1—C10—C5	−60.60 (8)
C2—C1—C6—C7	−177.57 (9)	C10—S1—C11—C12	−177.29 (8)
N1—C1—C6—C5	179.86 (9)	S1—C11—C12—O2	63.58 (11)
C2—C1—C6—C5	0.85 (14)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1	0.87	2.29	2.7577 (12)	114
O1—H1···N1ⁱ	0.87	2.19	2.8395 (11)	131
O2—H2···S1ⁱⁱ	0.87	2.47	3.2919 (9)	159
C3—H3···O1ⁱⁱ	0.955 (16)	2.599 (16)	3.2858 (13)	129.1 (11)
C8—H8···O2ⁱⁱⁱ	0.903 (17)	2.529 (17)	3.4252 (14)	171.9 (14)
C9—H9···O1ⁱ	0.917 (16)	2.525 (16)	3.0446 (13)	116.3 (12)

Symmetry codes: (i) −x+1, −y+1, −z; (ii) x, −y+3/2, z+1/2; (iii) −x, −y+1, −z+1.

Acknowledgements

We thank Ibn Tofaïl University and Mohammed V University for supporting this study and Tulane University for support of the Tulane Crystallography Laboratory.

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