5-[5-(4-Chloro­phen­yl)isoxazol-3-yl]-N-phenyl-1,3,4-oxa­diazol-2-amine

El-Hiti, G.A.; Abdel-Wahab, B.F.; Yousif, E.; Hayal Alotaibi, M.; Hegazy, A.S.; Kariuki, B.M.

doi:10.1107/S2414314619001366

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 4| Part 1| January 2019| x190136

https://doi.org/10.1107/S2414314619001366

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5-[5-(4-Chlorophenyl)isoxazol-3-yl]-N-phenyl-1,3,4-oxadiazol-2-amine

Gamal A. El-Hiti,^a ^* Bakr F. Abdel-Wahab,^b,^c Emad Yousif,^d Mohammad Hayal Alotaibi,^e Amany S. Hegazy ^f and Benson M. Kariuki ^f ‡

^aDepartment of Optometry, College of Applied Medical Sciences, King Saud, University, PO Box 10219, Riyadh 11433, Saudi Arabia, ^bDepartment of Chemistry, College of Science and Humanities, Shaqra University, Duwadimi, Saudi Arabia, ^cApplied Organic Chemistry Department, National Research Centre, Dokki, Giza 12622, Egypt, ^dDepartment of Chemistry, College of Science, Al-Nahrain University, Baghdad 64021, Iraq, ^eNational Center for Petrochemicals Technology, King Abdulaziz City for Science and Technology, PO Box 6086, Riyadh 11442, Saudi Arabia, and ^fSchool of Chemistry, Cardiff University, Main Building, Park Place, Cardiff CF10 3AT, UK
^*Correspondence e-mail: gelhiti@ksu.edu.sa

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 23 January 2019; accepted 24 January 2019; online 31 January 2019)

The title compound, C₁₇H₁₁ClN₄O₂, consists of chlorophenyl (A), isoxazolyl (B), oxadiazolyl (C) and phenyl (D) rings with twist angles between the planes through neighbouring rings A/B, B/C and C/D of 14.9 (1), 1.8 (1) and 8.9 (1)° respectively. In the crystal, adjacent molecules related by inversion symmetry form columns parallel to the [010] direction through π–π stacking [shortest centroid–centroid separation = 3.6203 (10) Å]; these are cross-linked by N—H⋯N interactions in the [001] direction.

Keywords: crystal structure; oxadiazole; isoxazole.

CCDC reference: 1893181

Structure description

Substituted 1,3,4-oxadiazol-2-amines can act as anticancer and antiproliferative agents (Ahsan et al., 2014 ; Gonda et al., 2017 ; Kumar et al., 2009 , 2011 ). As part of our studies in this area, we now describe the synthesis and structure of the title compound.

The molecule consists of chlorophenyl (A), isoxazolyl (B), oxadiazolyl (C) and phenyl (D) rings (Fig. 1). The molecule is close to planar, as indicated by the twist angles between the planes through neighbouring rings A/B, B/C and C/D, namely 14.9 (1), 1.8 (1) and 8.9 (1)° respectively. A short intramolecular C—H⋯N contact is observed (Table 1). In the crystal, adjacent molecules related by inversion symmetry form columns parallel to the [010] direction through π-π stacking [shortest centroid–centroid separation = 3.6203 (10) Å]. The columns of molecules are linked by N—H⋯N interactions in the [001] direction (Fig. 2).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C17—H17⋯N3	0.93	2.33	2.955 (2)	125
N4—H4⋯N2ⁱ	0.86	2.42	3.176 (2)	146
Symmetry code: (i) $[x, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ .

Figure 1
The molecular structure of the title compound showing 50% probability ellipsoids.

Figure 2
A segment of the crystal structure showing N—H⋯N hydrogen bonds as dotted lines.

Synthesis and crystallization

2-(3-(4-Chlorophenyl)isoxazole-5-carbonyl)-N-phenylhydrazinecarbothioamide was treated with anhydrous sodium acetate in ethanol under reflux for 5 h. The resulting solid was collected by filtration, washed with ethanol, dried and recrystallized from dimethylformamide solution to give colourless plates, m.p. 277–278°C.

Refinement

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

Table 2
Experimental details

Crystal data
Chemical formula	C₁₇H₁₁ClN₄O₂
M_r	338.75
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	17.8925 (15), 7.4168 (6), 11.5006 (9)
β (°)	102.061 (8)
V (Å³)	1492.5 (2)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.27
Crystal size (mm)	0.32 × 0.17 × 0.04

Data collection
Diffractometer	Rigaku Oxford Diffraction SuperNova, Dual, Cu at zero, Atlas
Absorption correction	Gaussian (CrysAlis PRO; Rigaku OD, 2015 $[Rigaku OD (2015). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, England.]$ )
T_min, T_max	0.768, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	13114, 3720, 2622
R_int	0.027
(sin θ/λ)_max (Å⁻¹)	0.699

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.045, 0.112, 1.06
No. of reflections	3720
No. of parameters	218
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.25, −0.23
Computer programs: CrysAlis PRO (Rigaku OD, 2015 $[Rigaku OD (2015). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, England.]$ ), SHELXS (Sheldrick, 2008 ), SHELXL2018 (Sheldrick, 2015 ), ORTEP-3 for Windows and WinGX (Farrugia, 2012 ) and CHEMDRAW Ultra (Cambridge Soft, 2001 ).

Structural data

CCDC reference: 1893181

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314619001366/hb4282sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314619001366/hb4282Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314619001366/hb4282Isup3.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: SHELXS (Sheldrick, 2008); program(s) used to refine structure: SHELXL2018 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows and WinGX (Farrugia, 2012); software used to prepare material for publication: CHEMDRAW Ultra (Cambridge Soft, 2001).

5-[5-(4-Chlorophenyl)isoxazol-3-yl]-N-phenyl-1,3,4-oxadiazol-2-amine top

Crystal data top

C₁₇H₁₁ClN₄O₂	F(000) = 696
M_r = 338.75	D_x = 1.508 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 17.8925 (15) Å	Cell parameters from 3445 reflections
b = 7.4168 (6) Å	θ = 3.3–26.7°
c = 11.5006 (9) Å	µ = 0.27 mm⁻¹
β = 102.061 (8)°	T = 296 K
V = 1492.5 (2) Å³	Plate, colourless
Z = 4	0.32 × 0.17 × 0.04 mm

Data collection top

Rigaku Oxford Diffraction SuperNova, Dual, Cu at zero, Atlas diffractometer	2622 reflections with I > 2σ(I)
ω scans	R_int = 0.027
Absorption correction: gaussian (CrysAlisPro; Rigaku OD, 2015)	θ_max = 29.8°, θ_min = 3.0°
T_min = 0.768, T_max = 1.000	h = −24→23
13114 measured reflections	k = −10→10
3720 independent reflections	l = −13→16

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.045	w = 1/[σ²(F_o²) + (0.039P)² + 0.4804P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.112	(Δ/σ)_max < 0.001
S = 1.06	Δρ_max = 0.25 e Å⁻³
3720 reflections	Δρ_min = −0.23 e Å⁻³
218 parameters	Extinction correction: SHELXL-2018/1 (Sheldrick 2018), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.0044 (7)
Primary atom site location: structure-invariant direct methods

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.

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

	x	y	z	U_iso*/U_eq
C1	0.27509 (9)	0.6433 (2)	0.57408 (14)	0.0354 (4)
C2	0.27554 (10)	0.5711 (2)	0.68585 (14)	0.0380 (4)
H2	0.321696	0.540461	0.735750	0.046*
C3	0.20791 (11)	0.5447 (2)	0.72307 (15)	0.0406 (4)
H3	0.208175	0.496146	0.797718	0.049*
C4	0.13988 (10)	0.5911 (2)	0.64829 (16)	0.0419 (4)
C5	0.13775 (10)	0.6597 (3)	0.53621 (16)	0.0443 (4)
H5	0.091345	0.687890	0.486141	0.053*
C6	0.20539 (10)	0.6856 (2)	0.49975 (15)	0.0410 (4)
H6	0.204587	0.732140	0.424398	0.049*
C7	0.34717 (10)	0.6763 (2)	0.53732 (14)	0.0368 (4)
C8	0.42112 (10)	0.6850 (2)	0.59279 (15)	0.0411 (4)
H8	0.441861	0.666766	0.673050	0.049*
C9	0.45996 (10)	0.7280 (2)	0.50222 (15)	0.0395 (4)
C10	0.54121 (10)	0.7559 (2)	0.50955 (14)	0.0386 (4)
C11	0.64134 (9)	0.8153 (2)	0.44570 (14)	0.0363 (4)
C12	0.76067 (9)	0.8721 (2)	0.37782 (14)	0.0348 (4)
C13	0.78904 (10)	0.9338 (2)	0.28169 (15)	0.0416 (4)
H13	0.755572	0.967507	0.211870	0.050*
C14	0.86646 (11)	0.9450 (3)	0.28962 (17)	0.0480 (5)
H14	0.885249	0.984768	0.224560	0.058*
C15	0.91682 (11)	0.8977 (3)	0.39347 (17)	0.0494 (5)
H15	0.969268	0.906781	0.398840	0.059*
C16	0.88857 (10)	0.8372 (3)	0.48854 (17)	0.0473 (5)
H16	0.922266	0.805371	0.558565	0.057*
C17	0.81049 (10)	0.8229 (2)	0.48169 (15)	0.0392 (4)
H17	0.791856	0.780592	0.546287	0.047*
N1	0.41386 (9)	0.7429 (3)	0.39846 (14)	0.0606 (5)
N2	0.59647 (9)	0.7436 (2)	0.59928 (13)	0.0490 (4)
N3	0.66384 (8)	0.7833 (2)	0.55885 (13)	0.0487 (4)
N4	0.68044 (8)	0.8585 (2)	0.36244 (12)	0.0405 (4)
H4	0.654043	0.880249	0.292363	0.049*
O1	0.34130 (7)	0.7092 (2)	0.42024 (11)	0.0600 (4)
O2	0.56429 (6)	0.80070 (17)	0.40728 (10)	0.0409 (3)
Cl1	0.05523 (3)	0.56575 (9)	0.69766 (5)	0.0682 (2)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0365 (9)	0.0360 (9)	0.0339 (8)	−0.0021 (7)	0.0078 (7)	−0.0019 (7)
C2	0.0399 (9)	0.0403 (9)	0.0324 (8)	−0.0005 (7)	0.0046 (7)	−0.0025 (7)
C3	0.0490 (11)	0.0427 (10)	0.0317 (8)	−0.0024 (8)	0.0119 (7)	−0.0009 (8)
C4	0.0389 (10)	0.0444 (10)	0.0465 (10)	−0.0004 (8)	0.0178 (8)	−0.0048 (8)
C5	0.0372 (10)	0.0494 (11)	0.0455 (10)	0.0037 (8)	0.0069 (8)	0.0012 (9)
C6	0.0422 (10)	0.0467 (10)	0.0344 (9)	0.0018 (8)	0.0088 (7)	0.0054 (8)
C7	0.0375 (9)	0.0409 (9)	0.0315 (8)	−0.0010 (7)	0.0061 (7)	0.0015 (7)
C8	0.0373 (9)	0.0538 (11)	0.0316 (8)	−0.0017 (8)	0.0062 (7)	−0.0005 (8)
C9	0.0346 (9)	0.0462 (10)	0.0373 (9)	−0.0011 (8)	0.0068 (7)	0.0013 (8)
C10	0.0348 (9)	0.0480 (10)	0.0338 (8)	−0.0012 (8)	0.0087 (7)	0.0001 (8)
C11	0.0288 (8)	0.0430 (9)	0.0362 (9)	0.0006 (7)	0.0046 (7)	−0.0043 (7)
C12	0.0326 (9)	0.0356 (9)	0.0357 (8)	−0.0002 (7)	0.0063 (7)	−0.0050 (7)
C13	0.0367 (9)	0.0515 (11)	0.0355 (9)	−0.0013 (8)	0.0049 (7)	0.0017 (8)
C14	0.0435 (11)	0.0560 (12)	0.0471 (11)	−0.0051 (9)	0.0154 (8)	0.0002 (9)
C15	0.0327 (9)	0.0614 (12)	0.0544 (11)	−0.0017 (9)	0.0101 (8)	−0.0043 (10)
C16	0.0372 (10)	0.0564 (12)	0.0443 (10)	0.0034 (9)	−0.0003 (8)	−0.0018 (9)
C17	0.0380 (9)	0.0444 (10)	0.0344 (9)	0.0005 (8)	0.0059 (7)	−0.0010 (8)
N1	0.0337 (9)	0.1058 (15)	0.0422 (9)	−0.0077 (9)	0.0076 (7)	0.0204 (9)
N2	0.0364 (8)	0.0768 (12)	0.0341 (8)	−0.0046 (8)	0.0084 (6)	0.0010 (8)
N3	0.0349 (8)	0.0784 (12)	0.0323 (8)	−0.0047 (8)	0.0059 (6)	−0.0001 (8)
N4	0.0304 (7)	0.0583 (9)	0.0316 (7)	0.0004 (7)	0.0035 (6)	0.0050 (7)
O1	0.0337 (7)	0.1065 (12)	0.0386 (7)	−0.0082 (7)	0.0048 (5)	0.0204 (7)
O2	0.0308 (6)	0.0564 (8)	0.0345 (6)	−0.0015 (5)	0.0050 (5)	0.0041 (6)
Cl1	0.0494 (3)	0.0880 (4)	0.0766 (4)	0.0034 (3)	0.0345 (3)	0.0077 (3)

Geometric parameters (Å, º) top

C1—C2	1.391 (2)	C10—O2	1.3665 (19)
C1—C6	1.393 (2)	C11—N3	1.301 (2)
C1—C7	1.459 (2)	C11—N4	1.338 (2)
C2—C3	1.379 (2)	C11—O2	1.3611 (19)
C2—H2	0.9300	C12—C17	1.382 (2)
C3—C4	1.379 (3)	C12—C13	1.387 (2)
C3—H3	0.9300	C12—N4	1.413 (2)
C4—C5	1.379 (3)	C13—C14	1.372 (3)
C4—Cl1	1.7351 (18)	C13—H13	0.9300
C5—C6	1.375 (2)	C14—C15	1.383 (3)
C5—H5	0.9300	C14—H14	0.9300
C6—H6	0.9300	C15—C16	1.372 (3)
C7—C8	1.345 (2)	C15—H15	0.9300
C7—O1	1.351 (2)	C16—C17	1.387 (2)
C8—C9	1.404 (2)	C16—H16	0.9300
C8—H8	0.9300	C17—H17	0.9300
C9—N1	1.306 (2)	N1—O1	1.3952 (19)
C9—C10	1.453 (2)	N2—N3	1.411 (2)
C10—N2	1.275 (2)	N4—H4	0.8600

C2—C1—C6	119.05 (16)	N3—C11—N4	131.36 (16)
C2—C1—C7	119.83 (15)	N3—C11—O2	113.02 (15)
C6—C1—C7	121.11 (15)	N4—C11—O2	115.62 (14)
C3—C2—C1	120.36 (16)	C17—C12—C13	119.92 (16)
C3—C2—H2	119.8	C17—C12—N4	122.98 (15)
C1—C2—H2	119.8	C13—C12—N4	117.08 (15)
C4—C3—C2	119.23 (16)	C14—C13—C12	119.99 (17)
C4—C3—H3	120.4	C14—C13—H13	120.0
C2—C3—H3	120.4	C12—C13—H13	120.0
C5—C4—C3	121.56 (16)	C13—C14—C15	120.58 (18)
C5—C4—Cl1	119.36 (14)	C13—C14—H14	119.7
C3—C4—Cl1	119.07 (14)	C15—C14—H14	119.7
C6—C5—C4	118.86 (17)	C16—C15—C14	119.29 (17)
C6—C5—H5	120.6	C16—C15—H15	120.4
C4—C5—H5	120.6	C14—C15—H15	120.4
C5—C6—C1	120.92 (16)	C15—C16—C17	120.94 (17)
C5—C6—H6	119.5	C15—C16—H16	119.5
C1—C6—H6	119.5	C17—C16—H16	119.5
C8—C7—O1	109.14 (15)	C12—C17—C16	119.28 (16)
C8—C7—C1	135.40 (16)	C12—C17—H17	120.4
O1—C7—C1	115.45 (14)	C16—C17—H17	120.4
C7—C8—C9	104.44 (15)	C9—N1—O1	104.75 (14)
C7—C8—H8	127.8	C10—N2—N3	106.85 (14)
C9—C8—H8	127.8	C11—N3—N2	105.10 (13)
N1—C9—C8	112.40 (16)	C11—N4—C12	126.68 (14)
N1—C9—C10	118.31 (15)	C11—N4—H4	116.7
C8—C9—C10	129.29 (16)	C12—N4—H4	116.7
N2—C10—O2	113.04 (15)	C7—O1—N1	109.26 (13)
N2—C10—C9	129.36 (16)	C11—O2—C10	101.99 (13)
O2—C10—C9	117.60 (14)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C17—H17···N3	0.93	2.33	2.955 (2)	125
N4—H4···N2ⁱ	0.86	2.42	3.176 (2)	146

Symmetry code: (i) x, −y+3/2, z−1/2.

Footnotes

‡Additional corresponding author, e-mail: kariukib@cardiff.ac.uk.

Funding information

MHA thanks King Abdulaziz City for Science and Technology (KACST), Saudi Arabia for financial support (award No. 020–0180).

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