5-Methyl-1-(4-methyl­phen­yl)-N′-[1-(thio­phen-2-yl)ethyl­idene]-1H-1,2,3-triazole-4-carbohydrazide

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

doi:10.1107/S2414314618013792

organic compounds

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ISSN: 2414-3146

Volume 3| Part 10| October 2018| x181379

https://doi.org/10.1107/S2414314618013792

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5-Methyl-1-(4-methylphenyl)-N′-[1-(thiophen-2-yl)ethylidene]-1H-1,2,3-triazole-4-carbohydrazide

Gamal A. El-Hiti,^a ^* Bakr F. Abdel-Wahab,^b,^c Mohammad Hayal Alotaibi,^d Emad Yousif,^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, Egypt, ^dNational Center for Petrochemicals Technology, King Abdulaziz City for Science and Technology, PO Box 6086, Riyadh 11442, Saudi Arabia, ^eDepartment of Chemistry, College of Science, Al-Nahrain University, Baghdad 64021, Iraq, and ^fSchool of Chemistry, Cardiff University, Main Building, Park Place, Cardiff CF10 3AT, UK
^*Correspondence e-mail: gelhiti@ksu.edu.sa

Edited by J. Simpson, University of Otago, New Zealand (Received 26 September 2018; accepted 28 September 2018; online 5 October 2018)

The asymmetric unit comprises a single molecule of C₁₇H₁₇N₅OS with twist angles between the planes through the thiophenyl, methyltriazolyl and tolyl groups of 12.3 (1) and 44.9 (1)°, respectively. A possible weak intramolecular hydrogen bond forms between the methyl substituent on the triazole ring and the adjacent carbonyl O atom. In the crystal structure, π–π interactions occur between phenyl rings of pairs of molecules related by inversion symmetry with a centroid–centroid separation of 3.7647 (18) Å. The shortest intermolecular hydrogen bonding contact is a C—H⋯O interaction that generates inversion dimers.

Keywords: crystal structure; thiophene; 1,2,3-triazole; π–π contacts; hydrogen bonds.

CCDC reference: 1870514

Structure description

Acyl hydrazones possess diverse biological and pharmacological properties (Narang et al., 2012 ; Popiołek 2017 ; Rollas & Küçükgüzel, 2007 ; Verma et al., 2014 ).

The asymmetric unit comprises a molecule of C₁₇H₁₇N₅OS (Fig. 1). The twist angles between the planes through the thiophenyl, methyltriazolyl and tolyl groups are 12.3 (1)° and 44.9 (1)° respectively. A weak intramolecular C10—H10B⋯O1 hydrogen bond (Table 1) imposes a degree of planarity on the section of the molecule incorporating the linked five-membered rings. In the crystal structure, inversion-related π–π interactions occur between the phenyl rings of pairs of molecules with a centroid–centroid distance Cg3⋯Cg3ⁱⁱ = 3.7647 (18) Å, symmetry code: (ii) = 1 − x, 2 − y, −1 − z. Inversion-related C16—H16⋯O1 hydrogen bonds form dimers and generate R₂²(16) ring motifs (Table 1, Fig. 2).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C10—H10B⋯O1	0.96	2.53	3.124 (4)	120
C16—H16⋯O1ⁱ	0.93	2.55	3.437 (4)	161
Symmetry code: (i) -x+1, -y+2, -z.

Figure 1
An ORTEP representation showing 50% probability ellipsoids.

Figure 2
A view of the crystal packing approximately along the b axis. The π–π contact is shown as a dotted green line with the ring centroids drawn as red spheres. Hydrogen bonds are drawn as blue dotted lines.

Synthesis and crystallization

The title compound was synthesized from the reaction of a mixture of 5-methyl-1-(4-tolyl)-1H-1,2,3-triazole-4-carbohydrazide and 1-(thiophen-2-yl)ethanone in ethanol containing acetic acid as a catalyst under reflux conditions for 4 h. The crude product was recrystallized from dimethylformamide solution to give colourless crystals (85%).

Refinement

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

Table 2
Experimental details

Crystal data
Chemical formula	C₁₇H₁₇N₅OS
M_r	339.41
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	296
a, b, c (Å)	9.0292 (7), 9.864 (1), 10.8754 (9)
α, β, γ (°)	111.021 (9), 105.103 (8), 96.945 (7)
V (Å³)	847.86 (14)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	0.21
Crystal size (mm)	0.43 × 0.18 × 0.02

Data collection
Diffractometer	Rigaku Oxford Diffraction SuperNova, Dual, Cu at home/near, Atlas
Absorption correction	Multi-scan (CrysAlis PRO; Rigaku OD, 2015 $[Rigaku OD (2015). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, England.]$ )
T_min, T_max	0.690, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	7552, 3957, 2493
R_int	0.032
(sin θ/λ)_max (Å⁻¹)	0.696

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.063, 0.174, 1.04
No. of reflections	3957
No. of parameters	220
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.27, −0.33
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 ),Mercury (Macrae et al., 2008 ) and CHEMDRAW Ultra (Cambridge Soft, 2001 ).

Structural data

CCDC reference: 1870514

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314618013792/sj4191sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314618013792/sj4191Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314618013792/sj4191Isup3.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), and Mercury (Macrae et al., 2008); software used to prepare material for publication: WinGX (Farrugia, 2012) and CHEMDRAW Ultra (Cambridge Soft, 2001).

5-Methyl-1-(4-methylphenyl)-N'-[1-(thiophen-2-yl)ethylidene]-1H-1,2,3-triazole-4-carbohydrazide top

Crystal data top

C₁₇H₁₇N₅OS	Z = 2
M_r = 339.41	F(000) = 356
Triclinic, P1	D_x = 1.329 Mg m⁻³
a = 9.0292 (7) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.864 (1) Å	Cell parameters from 1876 reflections
c = 10.8754 (9) Å	θ = 4.2–26.3°
α = 111.021 (9)°	µ = 0.21 mm⁻¹
β = 105.103 (8)°	T = 296 K
γ = 96.945 (7)°	Plate, colourless
V = 847.86 (14) Å³	0.43 × 0.18 × 0.02 mm

Data collection top

Rigaku Oxford Diffraction SuperNova, Dual, Cu at home/near, Atlas diffractometer	2493 reflections with I > 2σ(I)
ω scans	R_int = 0.032
Absorption correction: multi-scan (CrysAlis PRO; Rigaku OD, 2015)	θ_max = 29.6°, θ_min = 3.3°
T_min = 0.690, T_max = 1.000	h = −11→11
7552 measured reflections	k = −13→11
3957 independent reflections	l = −13→14

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.063	H-atom parameters constrained
wR(F²) = 0.174	w = 1/[σ²(F_o²) + (0.0711P)² + 0.2305P] where P = (F_o² + 2F_c²)/3
S = 1.04	(Δ/σ)_max < 0.001
3957 reflections	Δρ_max = 0.27 e Å⁻³
220 parameters	Δρ_min = −0.32 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.

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

	x	y	z	U_iso*/U_eq
C1	0.1112 (3)	0.4156 (4)	0.3425 (4)	0.0601 (8)
H1	0.122378	0.438200	0.435658	0.072*
C2	−0.0111 (4)	0.3116 (4)	0.2339 (4)	0.0658 (9)
H2	−0.092623	0.254289	0.244511	0.079*
C3	−0.0012 (3)	0.2998 (3)	0.1034 (3)	0.0558 (8)
H3	−0.075280	0.233982	0.018406	0.067*
C4	0.1312 (3)	0.3974 (3)	0.1160 (3)	0.0434 (6)
C5	0.1775 (3)	0.4220 (3)	0.0050 (3)	0.0429 (6)
C6	0.0912 (3)	0.3171 (3)	−0.1446 (3)	0.0584 (8)
H6A	0.055984	0.373559	−0.197589	0.088*
H6B	0.001658	0.249516	−0.149553	0.088*
H6C	0.160803	0.261177	−0.182098	0.088*
C7	0.4505 (3)	0.6844 (3)	−0.0240 (3)	0.0421 (6)
C8	0.4679 (3)	0.7032 (3)	−0.1488 (3)	0.0404 (6)
C9	0.5722 (3)	0.8129 (3)	−0.1543 (3)	0.0399 (6)
C10	0.7022 (3)	0.9388 (3)	−0.0437 (3)	0.0539 (7)
H10A	0.791056	0.948232	−0.075463	0.081*
H10B	0.732737	0.919721	0.038836	0.081*
H10C	0.666715	1.029832	−0.022930	0.081*
C11	0.6040 (3)	0.8528 (3)	−0.3642 (3)	0.0396 (6)
C12	0.6343 (3)	0.7657 (3)	−0.4820 (3)	0.0473 (7)
H12	0.611736	0.662164	−0.513414	0.057*
C13	0.6987 (3)	0.8351 (3)	−0.5525 (3)	0.0567 (8)
H13	0.717677	0.776617	−0.632754	0.068*
C14	0.7358 (3)	0.9890 (3)	−0.5071 (3)	0.0512 (7)
C15	0.7021 (3)	1.0733 (3)	−0.3892 (3)	0.0520 (7)
H15	0.725550	1.176941	−0.357128	0.062*
C16	0.6344 (3)	1.0064 (3)	−0.3184 (3)	0.0464 (6)
H16	0.609748	1.063996	−0.241044	0.056*
C17	0.8067 (4)	1.0635 (4)	−0.5852 (4)	0.0730 (10)
H17A	0.803269	1.166931	−0.551180	0.110*
H17B	0.747381	1.014761	−0.682920	0.110*
H17C	0.914343	1.056050	−0.571143	0.110*
N1	0.2922 (2)	0.5357 (2)	0.0459 (2)	0.0451 (5)
N2	0.3362 (2)	0.5630 (2)	−0.0562 (2)	0.0473 (6)
H2A	0.290362	0.502099	−0.141972	0.057*
N3	0.3746 (2)	0.6096 (2)	−0.2804 (2)	0.0472 (6)
N4	0.4142 (3)	0.6548 (2)	−0.3689 (2)	0.0482 (6)
N5	0.5345 (2)	0.7799 (2)	−0.2928 (2)	0.0409 (5)
O1	0.5302 (2)	0.7712 (2)	0.0941 (2)	0.0595 (6)
S1	0.24161 (8)	0.49989 (8)	0.28844 (8)	0.0522 (2)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0675 (19)	0.076 (2)	0.056 (2)	0.0198 (16)	0.0326 (16)	0.0388 (17)
C2	0.0576 (18)	0.078 (2)	0.072 (2)	0.0041 (16)	0.0295 (17)	0.0404 (19)
C3	0.0497 (15)	0.0606 (18)	0.055 (2)	0.0010 (13)	0.0169 (14)	0.0255 (16)
C4	0.0449 (14)	0.0430 (14)	0.0450 (16)	0.0106 (11)	0.0177 (12)	0.0188 (12)
C5	0.0432 (14)	0.0444 (15)	0.0435 (16)	0.0108 (11)	0.0164 (12)	0.0190 (12)
C6	0.0608 (17)	0.0615 (18)	0.0431 (18)	0.0035 (14)	0.0146 (14)	0.0157 (15)
C7	0.0494 (14)	0.0451 (15)	0.0360 (16)	0.0141 (11)	0.0199 (12)	0.0162 (12)
C8	0.0453 (13)	0.0402 (14)	0.0364 (15)	0.0092 (10)	0.0169 (11)	0.0142 (11)
C9	0.0463 (13)	0.0399 (14)	0.0350 (15)	0.0118 (11)	0.0151 (11)	0.0154 (11)
C10	0.0639 (17)	0.0500 (16)	0.0406 (17)	0.0021 (13)	0.0122 (14)	0.0175 (13)
C11	0.0453 (13)	0.0437 (14)	0.0332 (14)	0.0104 (11)	0.0143 (11)	0.0185 (12)
C12	0.0600 (16)	0.0440 (15)	0.0440 (17)	0.0136 (12)	0.0238 (13)	0.0194 (13)
C13	0.0719 (19)	0.0639 (19)	0.0479 (19)	0.0236 (15)	0.0332 (15)	0.0259 (15)
C14	0.0498 (15)	0.0613 (18)	0.0529 (19)	0.0113 (13)	0.0191 (14)	0.0337 (15)
C15	0.0564 (16)	0.0446 (16)	0.0527 (19)	0.0063 (12)	0.0109 (14)	0.0239 (14)
C16	0.0556 (15)	0.0453 (15)	0.0392 (16)	0.0126 (12)	0.0174 (13)	0.0166 (13)
C17	0.077 (2)	0.088 (2)	0.079 (3)	0.0165 (18)	0.0374 (19)	0.054 (2)
N1	0.0508 (12)	0.0516 (13)	0.0391 (13)	0.0097 (10)	0.0199 (10)	0.0225 (11)
N2	0.0565 (13)	0.0517 (13)	0.0335 (13)	0.0030 (10)	0.0177 (11)	0.0180 (11)
N3	0.0510 (13)	0.0505 (13)	0.0385 (13)	0.0037 (10)	0.0160 (11)	0.0180 (11)
N4	0.0544 (13)	0.0484 (13)	0.0357 (13)	0.0005 (10)	0.0138 (11)	0.0149 (11)
N5	0.0478 (12)	0.0430 (12)	0.0338 (12)	0.0092 (9)	0.0156 (10)	0.0169 (10)
O1	0.0732 (13)	0.0607 (13)	0.0347 (12)	−0.0031 (10)	0.0198 (10)	0.0131 (10)
S1	0.0562 (4)	0.0576 (5)	0.0451 (5)	0.0080 (3)	0.0177 (3)	0.0243 (4)

Geometric parameters (Å, º) top

C1—C2	1.358 (5)	C10—H10B	0.9600
C1—S1	1.703 (3)	C10—H10C	0.9600
C1—H1	0.9300	C11—C12	1.380 (4)
C2—C3	1.410 (5)	C11—C16	1.380 (4)
C2—H2	0.9300	C11—N5	1.435 (3)
C3—C4	1.385 (4)	C12—C13	1.380 (4)
C3—H3	0.9300	C12—H12	0.9300
C4—C5	1.462 (4)	C13—C14	1.384 (4)
C4—S1	1.719 (3)	C13—H13	0.9300
C5—N1	1.284 (3)	C14—C15	1.388 (4)
C5—C6	1.504 (4)	C14—C17	1.513 (4)
C6—H6A	0.9600	C15—C16	1.384 (4)
C6—H6B	0.9600	C15—H15	0.9300
C6—H6C	0.9600	C16—H16	0.9300
C7—O1	1.217 (3)	C17—H17A	0.9600
C7—N2	1.354 (3)	C17—H17B	0.9600
C7—C8	1.479 (4)	C17—H17C	0.9600
C8—N3	1.358 (3)	N1—N2	1.372 (3)
C8—C9	1.375 (3)	N2—H2A	0.8600
C9—N5	1.358 (3)	N3—N4	1.305 (3)
C9—C10	1.486 (4)	N4—N5	1.364 (3)
C10—H10A	0.9600

C2—C1—S1	112.2 (3)	H10B—C10—H10C	109.5
C2—C1—H1	123.9	C12—C11—C16	121.0 (2)
S1—C1—H1	123.9	C12—C11—N5	118.6 (2)
C1—C2—C3	112.8 (3)	C16—C11—N5	120.4 (2)
C1—C2—H2	123.6	C13—C12—C11	118.8 (3)
C3—C2—H2	123.6	C13—C12—H12	120.6
C4—C3—C2	112.3 (3)	C11—C12—H12	120.6
C4—C3—H3	123.8	C12—C13—C14	121.9 (3)
C2—C3—H3	123.8	C12—C13—H13	119.0
C3—C4—C5	128.1 (3)	C14—C13—H13	119.0
C3—C4—S1	110.7 (2)	C13—C14—C15	117.8 (3)
C5—C4—S1	121.11 (19)	C13—C14—C17	121.3 (3)
N1—C5—C4	115.4 (2)	C15—C14—C17	120.8 (3)
N1—C5—C6	125.0 (3)	C16—C15—C14	121.4 (3)
C4—C5—C6	119.6 (2)	C16—C15—H15	119.3
C5—C6—H6A	109.5	C14—C15—H15	119.3
C5—C6—H6B	109.5	C11—C16—C15	119.0 (3)
H6A—C6—H6B	109.5	C11—C16—H16	120.5
C5—C6—H6C	109.5	C15—C16—H16	120.5
H6A—C6—H6C	109.5	C14—C17—H17A	109.5
H6B—C6—H6C	109.5	C14—C17—H17B	109.5
O1—C7—N2	124.6 (3)	H17A—C17—H17B	109.5
O1—C7—C8	122.6 (2)	C14—C17—H17C	109.5
N2—C7—C8	112.8 (2)	H17A—C17—H17C	109.5
N3—C8—C9	109.3 (2)	H17B—C17—H17C	109.5
N3—C8—C7	122.5 (2)	C5—N1—N2	116.6 (2)
C9—C8—C7	128.1 (2)	C7—N2—N1	121.1 (2)
N5—C9—C8	103.6 (2)	C7—N2—H2A	119.5
N5—C9—C10	124.4 (2)	N1—N2—H2A	119.5
C8—C9—C10	131.9 (3)	N4—N3—C8	109.2 (2)
C9—C10—H10A	109.5	N3—N4—N5	107.0 (2)
C9—C10—H10B	109.5	C9—N5—N4	110.9 (2)
H10A—C10—H10B	109.5	C9—N5—C11	129.9 (2)
C9—C10—H10C	109.5	N4—N5—C11	119.1 (2)
H10A—C10—H10C	109.5	C1—S1—C4	92.00 (15)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C10—H10B···O1	0.96	2.53	3.124 (4)	120
C16—H16···O1ⁱ	0.93	2.55	3.437 (4)	161

Symmetry code: (i) −x+1, −y+2, −z.

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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