5-(3-Hy­droxy­phen­yl)-1,3,4-oxa­diazole-2(3H)-thione hemihydrate

Razzoqova, S.R.; Kadirova, S.; Ashurov, J.M.; Rakhmonova, D.S.; Ziyaev, A.; Parpiev, N.A.

doi:10.1107/S2414314619015323

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 4| Part 11| November 2019| x191532

https://doi.org/10.1107/S2414314619015323

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5-(3-Hydroxyphenyl)-1,3,4-oxadiazole-2(3H)-thione hemihydrate

Surayyo Razzoqovna Razzoqova,^a Shaxnoza Kadirova,^a Jamshid Mengnorovich Ashurov,^b ^* Dilnoza Salamovna Rakhmonova,^a Abdukhakim Ziyaev ^c and Nusrat Agzamovich Parpiev ^a

^aNational University of Uzbekistan named after Mirzo Ulugbek, 4 University St, Tashkent, 100174, Uzbekistan, ^bInstitute of Bioorganic Chemistry, Academy of Sciences of Uzbekistan, 83 M. Ulugbek St, Tashkent 700125, Uzbekistan, and ^cInstitute of the Chemistry of Plant Substances, Academy of Sciences of Uzbekistan, 77 M. Ulugbek St, Tashkent 100170, Uzbekistan
^*Correspondence e-mail: atom.uz@mail.ru

Edited by M. Weil, Vienna University of Technology, Austria (Received 21 October 2019; accepted 13 November 2019; online 15 November 2019)

The title 1,3,4-oxadiazole derivative crystallizes as a hemihydrate, C₈H₆N₂O₂S·0.5H₂O, with the water molecule located on a twofold rotation axis. The 1,3,4-oxadiazole molecule is essentially planar, the r.m.s. deviation of the non-H atoms being 0.0443 Å. The dihedral angle between the mean planes of the phenyl and oxadiazole rings is 6.101 (17)°. In the crystal, molecules are linked via O—H⋯S and N—H⋯O hydrogen bonds involving the water molecule, the N—H group and the thione S atom into undulating ribbons. Additional π–π interactions generate a two-dimensional supramolecular framework extending parallel to (001).

Keywords: crystal structure; 1,3,4-oxadiazole; hydrogen bonding.

CCDC references: 1965447; 1965447

Structure description

Oxadiazoles are an important class of heterocyclic compounds because of their broad biological activities. In particular, 1,3,4-Oxadiazole derivatives are known to act as antibacterial (Ahmed et al., 2018 ), antimicrobial (Zheng et al., 2018 ), anticancer (Glomb et al., 2018 ), anti-inflammatory (Abd-Ellah et al., 2017 ), analgesic (Husain & Ajmal, 2009 ), antitubercular (Ali & Shaharyar, 2007 ; Zampieri et al., 2009 ), and vasodilatory (Shirote & Bhatia, 2010 ) agents. They are also important as starting materials for cycloaddition reactions (Vasilev et al., 2007 ), and are employed in the synthesis of furans (Wolkenberg & Boger, 2002 ), natural products (Yuan et al., 2005 ) and plant-growth hormones (Won et al., 2011 ). Several methods have been reported for the synthesis of 1,3,4-oxadiazoles, the commonly used synthetic routes including reactions of acid hydrazides with acid chlorides/carboxylic acids and direct cyclization of diacylhydrazines using a variety of dehydrating agents such as phosphorous oxychloride (Kadi et al., 2007 ), thionyl chloride (Mickevičius et al., 2009 ), or direct reaction of the acid with triphenylphosphorane (Ramazani et al., 2011 ,2013 ).

The title 1,3,4-oxadiazole is derived from the condensation of 3-hydroxybenzoic acid hydrazide with potassium butyl xanthate and crystallizes as a hemihydrate (Fig. 1), with the water molecule situated on a twofold rotation axis. The dihedral angle between the mean planes of the phenyl (C3–C8, centroid Cg2) and oxadiazole (C1/O1/C2/N2/N, centroid1 Cg1) rings is 6.101 (17)°.

Figure 1
Structures of the molecular entities of the title compound. Displacement ellipsoids are drawn at the 30% probability level; hydrogen bonds are indicated by dashed lines.

In the crystal, the organic molecules are linked into dimers by pairs of N—H⋯O hydrogen bonds (Table 1), with the O atom of the hydroxy group as the acceptor. Simultaneously, the hydroxy group is also the donor group of a weak hydrogen bond to the S atom of a neighbouring molecule. The water molecule is likewise involved in hydrogen bonding both as a donor and an acceptor, with the S atom and the N—H group as the corresponding acceptor and donor groups, respectively (Table 1). The above-mentioned hydrogen bonds give rise to R₂²(16) and R₂²(6) graph-set motifs (Fig. 2), and eventually lead to the formation of undulating ribbons (Fig. 3). Additional π–π stacking between the phenyl and oxadiazole rings [Cg1⋯ Cg2 (x, 1 + y, z) = 3.6283 (16) Å, slippage = 1.684 Å] consolidates a two-dimensional supramolecular framework extending parallel (001).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O1W	0.86	2.26	2.995 (3)	143
N1—H1⋯O2ⁱ	0.86	2.42	3.064 (3)	133
O1W—H1W⋯S1	0.85 (4)	2.72 (4)	3.2814 (9)	125 (3)
O2—H2⋯S1ⁱⁱ	0.82	2.51	3.319 (2)	168
Symmetry codes: (i) -x+1, -y+1, -z+1; (ii) $[x-{\script{1\over 2}}, -y+1, z]$ .

Figure 2
Formation of N—H⋯O and O—H⋯S hydrogen bonds (dashed lines) in the crystal structure, leading to R₂²(16) and R₂²(6) graph-set motifs.

Figure 3
Packing of the molecular entities in the crystal structure, in a view along the b axis. Hydrogen bonds are shown as dashed lines.

Synthesis and crystallization

A mixture of 50 mmol of 3-hydroxybenzoic acid hydrazide and 50 mmol of potassium butyl xanthate was dissolved in 100 ml of ethanol and boiled for 8 h. The solvent was distilled off, the residue was diluted with water and acidified with hydrochloric acid to pH = 5–6 (Fig. 4). The resulting mass was filtered, washed with water, dried in air and recrystallized from aqueous ethanol. Small needle-shaped crystals the colour of pale milk were obtained; m.p. 477–478 K.

Figure 4
Synthetic scheme for the preparation of the title compound.

Refinement

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

Table 2
Experimental details

Crystal data
Chemical formula	2C₈H₆N₂O₂S·H₂O
M_r	406.43
Crystal system, space group	Monoclinic, I2/a
Temperature (K)	293
a, b, c (Å)	16.3881 (12), 4.6912 (3), 22.4928 (18)
β (°)	97.512 (7)
V (Å³)	1714.4 (2)
Z	4
Radiation type	Cu Kα
μ (mm⁻¹)	3.17
Crystal size (mm)	0.4 × 0.28 × 0.2

Data collection
Diffractometer	Rigaku Xcalibur Ruby
Absorption correction	Multi-scan (CrysAlis PRO; Rigaku OD, 2015 $[Rigaku OD. (2015). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, England.]$ )
T_min, T_max	0.953, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	5850, 1767, 1256
R_int	0.061
(sin θ/λ)_max (Å⁻¹)	0.629

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.117, 1.04
No. of reflections	1767
No. of parameters	128
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.22, −0.23
Computer programs: CrysAlis PRO (Rigaku OD, 2015 $[Rigaku OD. (2015). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, England.]$ ), SHELXT (Sheldrick, 2015a ), SHELXL2014 (Sheldrick, 2015b ), Mercury (Macrae et al., 2006 ) and publCIF (Westrip, 2010 ).

Structural data

CCDC references: 1965447; 1965447

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314619015323/wm4116sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314619015323/wm4116Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314619015323/wm4116Isup3.cml

checkCIF report

Computing details top

Data collection: CrysAlis PRO (Rigaku OD, 2015); cell refinement: CrysAlis PRO (Rigaku OD, 2015); data reduction: CrysAlis PRO (Rigaku OD, 2015); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: Mercury (Macrae et al., 2006); software used to prepare material for publication: publCIF (Westrip, 2010).

5-(3-Hydroxyphenyl)-1,3,4-oxadiazole-2(3H)-thione hemihydrate top

Crystal data top

2C₈H₆N₂O₂S·H₂O	F(000) = 840
M_r = 406.43	D_x = 1.575 Mg m⁻³
Monoclinic, I2/a	Cu Kα radiation, λ = 1.54184 Å
a = 16.3881 (12) Å	Cell parameters from 1053 reflections
b = 4.6912 (3) Å	θ = 5.4–74.2°
c = 22.4928 (18) Å	µ = 3.17 mm⁻¹
β = 97.512 (7)°	T = 293 K
V = 1714.4 (2) Å³	Block, colourless
Z = 4	0.4 × 0.28 × 0.2 mm

Data collection top

Rigaku Xcalibur Ruby diffractometer	1256 reflections with I > 2σ(I)
Detector resolution: 10.2576 pixels mm^-1	R_int = 0.061
ω scans	θ_max = 76.1°, θ_min = 4.0°
Absorption correction: multi-scan (CrysAlis PRO; Rigaku OD, 2015)	h = −18→20
T_min = 0.953, T_max = 1.000	k = −4→5
5850 measured reflections	l = −27→27
1767 independent reflections

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.043	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.117	w = 1/[σ²(F_o²) + (0.0512P)²] where P = (F_o² + 2F_c²)/3
S = 1.04	(Δ/σ)_max < 0.001
1767 reflections	Δρ_max = 0.22 e Å⁻³
128 parameters	Δρ_min = −0.23 e Å⁻³

Special details top

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. The hydrogen atom of the water molecule was located from a difference electron-density map and was refined with O—H = 0.85 (4) Å, and U_iso(H) = 1.3U_eq(O).

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

	x	y	z	U_iso*/U_eq
S1	0.67502 (4)	1.34393 (15)	0.35767 (3)	0.0449 (2)
O1	0.55444 (11)	0.9588 (4)	0.35221 (8)	0.0373 (4)
O2	0.32072 (15)	0.0756 (5)	0.42672 (10)	0.0555 (6)
H2	0.290571	−0.045956	0.409275	0.083*
O1W	0.750000	1.3852 (8)	0.500000	0.0597 (9)
N1	0.60967 (15)	1.0310 (5)	0.44201 (11)	0.0447 (6)
H1	0.640309	1.100099	0.472576	0.054*
N0AA	0.55104 (15)	0.8229 (5)	0.44618 (11)	0.0452 (6)
C2	0.51961 (16)	0.7884 (6)	0.39152 (11)	0.0361 (6)
C3	0.45590 (16)	0.5862 (5)	0.36792 (12)	0.0365 (6)
C8	0.41731 (17)	0.4239 (6)	0.40779 (13)	0.0392 (6)
H8	0.431399	0.446199	0.448938	0.047*
C1	0.61390 (16)	1.1129 (6)	0.38633 (12)	0.0380 (6)
C7	0.35775 (17)	0.2289 (6)	0.38559 (13)	0.0401 (6)
C4	0.43517 (18)	0.5516 (6)	0.30612 (13)	0.0435 (7)
H4	0.461017	0.659969	0.279433	0.052*
C6	0.33699 (18)	0.1922 (6)	0.32463 (13)	0.0447 (7)
H6	0.297161	0.059244	0.310210	0.054*
C5	0.37544 (19)	0.3532 (7)	0.28508 (13)	0.0480 (7)
H5	0.361217	0.328550	0.244007	0.058*
H1W	0.742 (3)	1.497 (8)	0.4702 (18)	0.086 (14)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0410 (4)	0.0408 (4)	0.0533 (4)	−0.0028 (3)	0.0071 (3)	0.0054 (3)
O1	0.0366 (9)	0.0366 (9)	0.0384 (10)	−0.0010 (8)	0.0037 (7)	0.0026 (8)
O2	0.0563 (13)	0.0618 (15)	0.0488 (12)	−0.0194 (10)	0.0080 (10)	−0.0006 (10)
O1W	0.078 (2)	0.055 (2)	0.0451 (18)	0.000	0.0046 (17)	0.000
N1	0.0464 (14)	0.0494 (14)	0.0372 (12)	−0.0080 (11)	0.0013 (10)	−0.0030 (11)
N0AA	0.0479 (14)	0.0479 (14)	0.0402 (12)	−0.0076 (11)	0.0074 (10)	0.0005 (11)
C2	0.0390 (14)	0.0355 (13)	0.0350 (13)	0.0023 (10)	0.0094 (11)	0.0024 (11)
C3	0.0350 (13)	0.0328 (13)	0.0426 (15)	0.0039 (10)	0.0080 (11)	0.0008 (10)
C8	0.0390 (14)	0.0396 (15)	0.0391 (14)	0.0003 (11)	0.0054 (11)	−0.0018 (11)
C1	0.0346 (13)	0.0357 (14)	0.0433 (15)	0.0035 (10)	0.0035 (11)	−0.0007 (11)
C7	0.0381 (14)	0.0386 (14)	0.0453 (15)	0.0012 (11)	0.0122 (12)	0.0012 (12)
C4	0.0464 (16)	0.0427 (15)	0.0418 (15)	−0.0032 (12)	0.0072 (12)	0.0026 (12)
C6	0.0402 (15)	0.0429 (16)	0.0503 (17)	−0.0027 (12)	0.0034 (12)	−0.0066 (13)
C5	0.0516 (16)	0.0518 (17)	0.0395 (15)	−0.0033 (14)	0.0013 (12)	−0.0033 (14)

Geometric parameters (Å, º) top

S1—C1	1.662 (3)	C2—C3	1.458 (4)
O1—C1	1.366 (3)	C3—C8	1.390 (4)
O1—C2	1.371 (3)	C3—C4	1.396 (4)
O2—C7	1.374 (3)	C8—C7	1.382 (4)
O2—H2	0.8200	C8—H8	0.9300
O1W—H1W	0.85 (4)	C7—C6	1.380 (4)
O1W—H1Wⁱ	0.85 (4)	C4—C5	1.388 (4)
N1—C1	1.321 (4)	C4—H4	0.9300
N1—N0AA	1.381 (3)	C6—C5	1.380 (4)
N1—H1	0.8600	C6—H6	0.9300
N0AA—C2	1.280 (4)	C5—H5	0.9300

C1—O1—C2	105.8 (2)	N1—C1—O1	104.9 (2)
C7—O2—H2	109.5	N1—C1—S1	131.8 (2)
H1W—O1W—H1Wⁱ	104 (6)	O1—C1—S1	123.3 (2)
C1—N1—N0AA	113.2 (2)	O2—C7—C6	122.0 (3)
C1—N1—H1	123.4	O2—C7—C8	117.1 (3)
N0AA—N1—H1	123.4	C6—C7—C8	120.8 (3)
C2—N0AA—N1	102.7 (2)	C5—C4—C3	119.1 (3)
N0AA—C2—O1	113.4 (2)	C5—C4—H4	120.5
N0AA—C2—C3	127.7 (2)	C3—C4—H4	120.5
O1—C2—C3	118.9 (2)	C7—C6—C5	119.9 (3)
C8—C3—C4	120.4 (3)	C7—C6—H6	120.1
C8—C3—C2	119.1 (2)	C5—C6—H6	120.1
C4—C3—C2	120.5 (2)	C6—C5—C4	120.5 (3)
C7—C8—C3	119.2 (3)	C6—C5—H5	119.7
C7—C8—H8	120.4	C4—C5—H5	119.7
C3—C8—H8	120.4

Symmetry code: (i) −x+3/2, y, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1W	0.86	2.26	2.995 (3)	143
N1—H1···O2ⁱⁱ	0.86	2.42	3.064 (3)	133
O1W—H1W···S1	0.85 (4)	2.72 (4)	3.2814 (9)	125 (3)
O2—H2···S1ⁱⁱⁱ	0.82	2.51	3.319 (2)	168

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

Funding information

This work was supported by a Grant for Fundamental Research (No. BA—FA–F7–004) from the Center of Science and Technology, Uzbekistan.

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