4-(4-Acetyl-5-methyl-1H-1,2,3-triazol-1-yl)benzo­nitrile: crystal structure and Hirshfeld surface analysis

Zukerman-Schpector, J.; Dias, C. da S.; Schwab, R.S.; Jotani, M.M.; Tiekink, E.R.T.

doi:10.1107/S2056989018010885

research communications

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ISSN: 2056-9890

Volume 74| Part 9| September 2018| Pages 1195-1200

https://doi.org/10.1107/S2056989018010885

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4-(4-Acetyl-5-methyl-1H-1,2,3-triazol-1-yl)benzonitrile: crystal structure and Hirshfeld surface analysis

Julio Zukerman-Schpector,^a ^* Cássio da S. Dias,^b Ricardo S. Schwab,^b Mukesh M. Jotani ^c and Edward R. T. Tiekink ^d ‡

^aLaboratório de Cristalografia, Esterodinâmica e Modelagem Molecular, Departamento de Química, Universidade Federal de São Carlos, 13565-905 São Carlos, SP, Brazil, ^bDepartamento de Química, Universidade Federal de São Carlos, 13565-905 São Carlos, SP, Brazil, ^cDepartment of Physics, Bhavan's Sheth R. A. College of Science, Ahmedabad, Gujarat 380001, India, and ^dResearch Centre for Crystalline Materials, School of Science and Technology, Sunway University, 47500 Bandar Sunway, Selangor Darul Ehsan, Malaysia
^*Correspondence e-mail: julio@power.ufscar.br

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 27 July 2018; accepted 29 July 2018; online 10 August 2018)

The title compound, C₁₂H₁₀N₄O, comprises a central 1,2,3-triazole ring (r.m.s. deviation = 0.0030 Å) flanked by N-bound 4-cyanophenyl and C-bound acetyl groups, which make dihedral angles of 54.64 (5) and 6.8 (3)° with the five-membered ring, indicating a twisted molecule. In the crystal, the three-dimensional architecture is sustained by carbonyl-C=O⋯π(triazoyl), cyano-C≡N⋯π(triazoyl) (these interactions are shown to be attractive based on non-covalent interaction plots) and π–π stacking interactions [intercentroid separation = 3.9242 (9) Å]. An analysis of the Hirshfeld surface shows the important contributions made by H⋯H (35.9%) and N⋯H (26.2%) contacts to the overall surface, as well as notable contributions by O⋯H (9.9%), C⋯H (8.7%), C⋯C (7.3%) and C⋯N (7.2%) contacts.

Keywords: crystal structure; 1,2,3-triazol-1-yl; nitrile; Hirshfeld surface analysis; NCI plots.

CCDC reference: 1859008

1. Chemical context

The 1,2,3-triazoles comprise an interesting class of heterocyclic compounds, with diverse applications in biological and material chemistry (Struthers et al., 2010 ; Bonandi et al., 2017 ; Dheer et al., 2017 ). In particular, 1,2,3-triazoles containing a carbonyl or carboxyl group in their structures have received considerable attention as they are found in a great number of biologically and pharmaceutically active molecules that exhibit a broad spectrum of properties (Shu et al., 2009 ; Morzherin et al., 2011 ; Cheng et al., 2012 ; Gilchrist et al., 2014 ). In this context, the organocatalytic cycloaddition reaction of organic azides with β-ketoesters, β-ketoamides, enones and allyl ketones has proven to be a powerful strategy for the synthesis of such class of compounds (John et al., 2015 ; Lima et al., 2015 ). Although much progress has been achieved, most of the available methodologies usually employ a homogenous catalyst, which can be difficult to recover. In view of environmental concerns, very recently, we reported for the first time, a heterogeneous strategy for the synthesis of 1,4,5-tris-substituted-1,2,3-triazoles through the 1,3-dipolar cycloaddition between aryl azides and active methylene compounds using CuO nanoparticles as catalyst in DMSO under microwave irradiation (Dias et al., 2018 ). The title compound, (I), was prepared in this study and despite having been prepared by another route in a different study (Kamalraj et al., 2008 ), no crystal structure is available. The availability of crystals in the latter study prompted the present structural analysis.

2. Structural commentary

The molecular structure of (I), Fig. 1, comprises an essentially planar 1,2,3-triazolyl ring with a r.m.s. deviation of the fitted atoms of 0.0030 Å; the maximum deviation of 0.0037 (9) Å is found for the N2 atom. A 4-cyanophenyl residue is connected to the 1,2,3-triazolyl ring at the N1-position and forms a dihedral angle of 54.64 (5)° with it, indicating a significant twist between the rings. By contrast, the acetyl group connected at the C2-position is approximately co-planar with the central ring, forming a dihedral angle of 6.8 (3)°. The dihedral angle between the phenyl and acetyl groups is 60.82 (13)°, indicating a dis-rotatory relationship. The acetyl-carbonyl group occupies a position approximately syn to the ring-bound methyl substituent with the C1—C2—C3—O1 and C4—C1—C2—C3 torsion angles being 6.2 (3) and −1.5 (3)°, respectively.

Figure 1
The molecular structure of (I)

, showing the atom-labelling scheme and displacement ellipsoids at the 50% probability level.

3. Supramolecular features

The molecular packing of (I) features interactions involving both the five- and six-membered rings. Centrosymmetrically related molecules are connected via carbonyl-C=O⋯π(triazoyl) interactions, Table 1. Further connections between molecules are of the type cyano-C≡N⋯π(triazoyl) to the opposite face of the five-membered ring (Fig. 2, Table 1), which together lead to a supramolecular layer parallel to ( $[\overline{1}]$ 01). The O⋯π or N⋯π separations for these interactions are significantly longer that the van der Waals' separations for these species (3.32 and 3.35 Å, respectively) but the non-covalent interactions plots (see below) indicate that they are weakly attractive in nature. Connections between the layers giving rise to a three-dimensional architecture are weak π–π stacking interactions between centrosymmetrically related phenyl rings, with the inter-centroid separation being 3.9242 (9) Å; symmetry operation (i): 2 − x, 2 − y, 1 − z. A view of the unit cell contents is shown in Fig. 2. The specified and other weak intermolecular interactions are discussed in more detail below in Hirshfeld surface analysis.

Table 1
π(Triazolyl) interaction geometry (Å, °)

Cg1 is the centroid of the N1–N3/C1/C2 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—O1⋯Cg1ⁱ	1.21 (1)	3.69 (1)	3.7359 (17)	83 (1)
C12—N4⋯Cg1ⁱⁱ	1.14 (1)	3.68 (1)	3.8468 (19)	90 (1)
Symmetry codes: (i) -x+1, -y+2, -z+1; (ii) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

Figure 2
A view of the unit-cell contents shown in projection down the b axis. The C= O⋯π(triazoyl), C≡N⋯π(triazoyl) and π(tolyl)–π(tolyl) contacts are shown as orange, blue and purple dashed lines, respectively.

4. Hirshfeld surface analysis

The Hirshfeld surface calculations for (I) were performed in accord with related studies (Caracelli et al., 2018 ) and provide information on the influence of other weak intermolecular interactions instrumental in the molecular packing. In addition to the presence of carbonyl-C=O⋯π(triazolyl) and cyano-C≡N⋯π(triazolyl) interactions (Table 1) in the formation of three-dimensional architecture as discussed above, the molecular packing also features weak C—H⋯N interactions. On the Hirshfeld surface mapped over d_norm in Fig. 3, these interactions are characterized as the bright-red spots near the triazolyl-N3, cyano-N4 (Fig. 3a), phenyl-H8 and H10 atoms (Fig. 3b), and the diminutive-red spots near cyano-N4 (Fig. 3b) and phenyl-H7 (Fig. 3a) atoms. The influence of short interatomic C⋯O/O⋯C contacts involving methyl-C4 and carbonyl-O1 atoms (Table 2) is also observed as the faint-red spots near these atoms in Fig. 3b. The donors and acceptors of intermolecular C—H⋯N interactions are also evident as the blue and red regions corresponding to positive and negative electrostatic potentials, respectively, on the Hirshfeld surface mapped over electrostatic potential shown in Fig. 4. Views of the immediate environment about a reference molecule within the Hirshfeld surface mapped over the shape-index property, highlighting intermolecular C=O⋯π, C≡N⋯π and π–π stacking interactions, are illustrated in Fig. 5.

Table 2
Summary of short interatomic contacts (Å) in (I)

Contact	Distance	Symmetry operation
H4C⋯H4C	2.39	1 − x, 1 − y, 1 − z
H10⋯N3	2.48	$[{1\over 2}]$ + x, $[{5\over 2}]$ − y, $[{1\over 2}]$ + z
H7⋯N4	2.58	− $[{1\over 2}]$ + x, $[{3\over 2}]$ − y, − $[{1\over 2}]$ + z
H8⋯N4	2.53	$[{5\over 2}]$ − x, − $[{1\over 2}]$ + y, $[{3\over 2}]$ − z
C4⋯O1	3.208 (2)	1 − x, 1 − y, 1 − z

Figure 3
Two views of the Hirshfeld surface for (I)

mapped over d_norm in the range −0.065 to +1.215 a.u.

Figure 4
Two views of the Hirshfeld surface mapped over the electrostatic potential in the range −0.092 to +0.055 a.u. The red and blue regions represent negative and positive electrostatic potentials, respectively.

Figure 5
Views of the Hirshfeld surface mapped the shape-index property showing (a) π–π and C≡N⋯π interactions with black and sky-blue dotted lines, respectively and (b) C=O⋯π contacts with red-dotted lines.

The overall two-dimensional fingerprint plot for (I) (Fig. 6a) and those delineated into H⋯H, N⋯H/H⋯N, O⋯H/H⋯O, C⋯H/H⋯C, C⋯C, C⋯N/N⋯C and N⋯N contacts (McKinnon et al., 2007 ) are illustrated in Fig. 6b–i, respectively; the percentage contributions from identified interatomic contacts to the Hirshfeld surface are summarized in Table 3. The short interatomic H⋯H contact involving symmetry-related methyl-H4C atoms (Table 2) is viewed as the cone-shaped tip at d_e + d_i ∼ 2.3 Å in the fingerprint plot delineated into H⋯H contacts (Fig. 6b). The second largest contribution to the Hirshfeld surface, i.e. 26.2%, is from N⋯H/H⋯N contacts (Fig. 6c) and arise from the intermolecular C—H⋯N contacts involving cyano-N4 and triazolyl-N3 atoms (Table 2) and are viewed as the pair of overlapping green and blue spikes with their tips at d_e + d_i ∼2.5 Å. Although the carbonyl-O1 atom makes a significant contribution of 9.9% to the overall surface owing to interatomic O⋯H/H⋯O contacts, it is evident from the respective delineated fingerprint plot (Fig. 6d) that these are beyond van der Waals separations. The relatively small contribution from C⋯H/H⋯C contacts to the Hirshfeld surface (Table 3) is indicative of the absence of C—H⋯π contacts in the molecular packing, Fig. 6e. The weak π–π stacking interactions between symmetry related phenyl-(C6–C11) rings are evident from the fingerprint delineated into C⋯C contacts (Fig. 6f) as the rocket-like tip at d_e + d_i ∼ 3.6 Å. The involvement of the triazolyl ring in intermolecular triazolyl-C≡N⋯π and carbonyl C=O⋯π contacts in the crystal is reflected from the percentage contributions due to C⋯N/N⋯C, C⋯O/O⋯C, N⋯N and N⋯O/O⋯N contacts to the Hirshfeld surface (Table 3). These intermolecular interactions are also evident from the fingerprint plots delineated into C⋯N/N⋯C, C⋯O/O⋯C and N⋯N contacts in Fig. 6f–h, respectively.

Table 3
Percentage contributions of interatomic contacts to the Hirshfeld surface for (I)

Contact	Percentage contribution
H⋯H	35.9
N⋯H/H⋯N	26.2
O⋯H/H⋯O	9.9
C⋯H/H⋯C	8.7
C⋯C	7.3
C⋯N/N⋯C	7.2
N⋯N	2.1
C⋯O/O⋯C	1.4
N⋯O/O⋯N	1.4

Figure 6
(a) The full two-dimensional fingerprint plot for (I)

and (b)-(h) those delineated into H⋯H, N⋯H/H⋯N, O⋯H/H⋯O, C⋯H/H⋯C, C⋯C, C⋯N/N⋯C and N⋯N contacts, respectively.

5. Non-covalent interaction plots

Non-covalent interaction (NCI) plots are a convenient means by which the nature of an interaction between residues may be assessed in terms of being attractive or otherwise (Johnson et al., 2010 ; Contreras-García et al., 2011 ). In NCI plots, a weakly attractive interaction will appear green on the isosurface, whereas attractive and repulsive interactions will result in blue and red isosurfaces, respectively. The NCI plots for the interacting entities of the carbonyl-C=O⋯π(triazolyl) and cyano-C≡N⋯π(triazolyl) interactions are shown in Fig. 7a,b, indicating the weakly attractive nature of these interactions. The arrows in Fig. 7b, highlight a weak phenyl-C—H⋯N(cyano) interaction (Table 2).

Figure 7
Non-covalent interaction plots for the (a) carbonyl-C= O⋯π(triazolyl) and (b) cyano-C≡N⋯π(triazolyl) interactions. The arrows in (b) indicate attractive phenyl-C—H⋯N(cyano) interactions (see text).

6. Database survey

There are four closely related compounds in the literature whereby the cyano group of (I) is replaced by chloride and bromide, which are isostructural (Zeghada et al., 2011 ), methyl (El-Hiti et al., 2017 ) and nitro (Vinutha et al. (2013 ); two independent molecules comprise the asymmetric unit of the nitro compound. Key dihedral angle data are included in Table 4. This shows that the greatest variations in dihedral angles between the phenyl and acetyl residues is found for the two independent molecules of the nitro compound. The different relative conformations in the aforementioned molecules is highlighted in the overlay diagram of Fig. 8.

Table 4
Dihedral angle data (°) for (I) and 4-X-phenyl derivatives

X	triazolyl/phenyl	triazolyl/acetyl	phenyl/acetyl	Ref.
Me	50.11 (7)	6.12 (18)	50.14 (12)	El-Hiti et al. (2017)
Cl	45.60 (4)	6.97 (9)	45.19 (6)	Zeghada et al. (2011)
Br	47.03 (5)	7.08 (12)	46.5 (7)	Zeghada et al. (2011)
NO₂^a	38.26 (15)	13.4 (4)	27.9 (3)	Vinutha et al. (2013)
	87.11 (18)	15.2 (3)	74.4 (2)
C≡N	54.64 (5)	6.8 (3)	60.82 (13)	This work
Note: (a) Two independent molecules comprise the asymmetric unit.

Figure 8
Overlay diagram for (I)

and 4-X-phenyl derivatives: (I)

(red image), X = Cl (green), X = Br (blue), X = Me (pink), X = NO₂ (first independent molecule; aqua) and X = NO₂ (second molecule; yellow). The molecules have been overlapped so that the triazolyl rings are coincident.

7. Synthesis and crystallization

Compound (I) was prepared as described in the literature (Dias et al., 2018) and crystals were obtained by the slow evaporation from its ethyl acetate/hexane (v/v) solution. M.p. 426–428 K. ¹H NMR (400 MHz, CDCl₃) δ = 7.91 (d, J = 8.7 Hz, 2H), 7.65 (d, J = 8.7 Hz, 2H), 2.76 (s, 3H), 2.66 (s, 3H). ¹³C NMR (100 MHz,CDCl₃) δ = 194.30, 144.20, 138.89, 137.42, 133.85, 125.84, 117.51, 114.23, 28.10, 10.43 ppm.

8. Refinement details

Crystal data, data collection and structure refinement details are summarized in Table 5. The carbon-bound H atoms were placed in calculated positions (C—H = 0.93–0.96 Å) and were included in the refinement in the riding model approximation, with U_iso(H) set to 1.2–1.5U_eq(C).

Table 5
Experimental details

Crystal data
Chemical formula	C₁₂H₁₀N₄O
M_r	226.24
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	293
a, b, c (Å)	11.8533 (5), 6.8299 (3), 14.7329 (6)
β (°)	107.477 (1)
V (Å³)	1137.67 (8)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.09
Crystal size (mm)	0.44 × 0.27 × 0.12

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996 )
T_min, T_max	0.726, 0.745
No. of measured, independent and observed [I > 2σ(I)] reflections	30812, 2333, 2083
R_int	0.023
(sin θ/λ)_max (Å⁻¹)	0.625

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.044, 0.126, 1.10
No. of reflections	2333
No. of parameters	156
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.21, −0.20
Computer programs: APEX2 and SAINT (Bruker, 2009 ), SIR2014 (Burla et al., 2015 ), SHELXL2014 (Sheldrick, 2015 ), ORTEP-3 for Windows (Farrugia, 2012 ), DIAMOND (Brandenburg, 2006 ), MarvinSketch (ChemAxon, 2010 ) and publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 1859008

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S2056989018010885/hb7764sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989018010885/hb7764Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989018010885/hb7764Isup3.cml

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SIR2014 (Burla et al., 2015); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and DIAMOND (Brandenburg, 2006); software used to prepare material for publication: MarvinSketch (ChemAxon, 2010) and publCIF (Westrip, 2010).

4-(4-Acetyl-5-methyl-1H-1,2,3-triazol-1-yl)benzonitrile top

Crystal data top

C₁₂H₁₀N₄O	F(000) = 472
M_r = 226.24	D_x = 1.321 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 11.8533 (5) Å	Cell parameters from 9978 reflections
b = 6.8299 (3) Å	θ = 2.6–26.3°
c = 14.7329 (6) Å	µ = 0.09 mm⁻¹
β = 107.477 (1)°	T = 293 K
V = 1137.67 (8) Å³	Irregular, colourless
Z = 4	0.44 × 0.27 × 0.12 mm

Data collection top

Bruker APEXII CCD diffractometer	2083 reflections with I > 2σ(I)
φ and ω scans	R_int = 0.023
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	θ_max = 26.4°, θ_min = 1.9°
T_min = 0.726, T_max = 0.745	h = −14→14
30812 measured reflections	k = −8→8
2333 independent reflections	l = −18→18

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.044	H-atom parameters constrained
wR(F²) = 0.126	w = 1/[σ²(F_o²) + (0.0573P)² + 0.3916P] where P = (F_o² + 2F_c²)/3
S = 1.10	(Δ/σ)_max < 0.001
2333 reflections	Δρ_max = 0.21 e Å⁻³
156 parameters	Δρ_min = −0.20 e Å⁻³
0 restraints

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
O1	0.39515 (11)	0.7197 (2)	0.36712 (11)	0.0785 (5)
N1	0.73587 (10)	0.95924 (17)	0.48424 (8)	0.0357 (3)
N2	0.70535 (11)	1.13354 (19)	0.43684 (10)	0.0476 (3)
N3	0.59641 (11)	1.11608 (19)	0.38456 (10)	0.0462 (3)
N4	1.27442 (13)	0.8725 (3)	0.80947 (11)	0.0623 (4)
C1	0.64418 (11)	0.8326 (2)	0.46207 (10)	0.0364 (3)
C2	0.55549 (12)	0.9350 (2)	0.39775 (10)	0.0364 (3)
C3	0.43345 (13)	0.8728 (2)	0.34833 (11)	0.0451 (4)
C4	0.64687 (15)	0.6346 (3)	0.50374 (14)	0.0614 (5)
H4A	0.7168	0.6210	0.5570	0.092*
H4B	0.6473	0.5378	0.4566	0.092*
H4C	0.5782	0.6168	0.5246	0.092*
C5	0.35961 (15)	1.0069 (3)	0.27426 (14)	0.0668 (6)
H5A	0.3902	1.0108	0.2209	0.100*
H5B	0.3615	1.1361	0.3004	0.100*
H5C	0.2795	0.9602	0.2538	0.100*
C6	0.85161 (11)	0.9389 (2)	0.55064 (9)	0.0354 (3)
C7	0.92321 (13)	0.7849 (2)	0.54291 (11)	0.0454 (4)
H7	0.8976	0.6944	0.4938	0.054*
C8	1.03376 (14)	0.7662 (2)	0.60904 (11)	0.0482 (4)
H8	1.0827	0.6622	0.6050	0.058*
C9	1.07120 (12)	0.9032 (2)	0.68124 (10)	0.0403 (3)
C10	0.99970 (13)	1.0600 (3)	0.68695 (11)	0.0494 (4)
H10	1.0261	1.1532	0.7347	0.059*
C11	0.88901 (13)	1.0776 (2)	0.62138 (11)	0.0472 (4)
H11	0.8401	1.1820	0.6249	0.057*
C12	1.18561 (13)	0.8846 (3)	0.75178 (11)	0.0470 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0477 (7)	0.0734 (9)	0.0927 (10)	−0.0232 (7)	−0.0117 (7)	0.0290 (8)
N1	0.0288 (6)	0.0351 (6)	0.0380 (6)	−0.0012 (4)	0.0023 (5)	0.0037 (5)
N2	0.0366 (6)	0.0393 (7)	0.0589 (8)	−0.0023 (5)	0.0022 (6)	0.0124 (6)
N3	0.0334 (6)	0.0443 (7)	0.0534 (7)	0.0003 (5)	0.0020 (5)	0.0125 (6)
N4	0.0443 (8)	0.0714 (11)	0.0552 (9)	0.0006 (7)	−0.0094 (7)	−0.0012 (7)
C1	0.0307 (6)	0.0376 (7)	0.0364 (7)	−0.0032 (5)	0.0036 (5)	0.0021 (6)
C2	0.0302 (7)	0.0401 (7)	0.0361 (7)	−0.0003 (5)	0.0054 (5)	0.0049 (6)
C3	0.0317 (7)	0.0553 (9)	0.0424 (8)	−0.0039 (6)	0.0024 (6)	0.0068 (7)
C4	0.0469 (9)	0.0476 (10)	0.0732 (12)	−0.0105 (7)	−0.0071 (8)	0.0224 (8)
C5	0.0377 (8)	0.0836 (14)	0.0641 (11)	−0.0017 (9)	−0.0074 (8)	0.0234 (10)
C6	0.0273 (6)	0.0391 (7)	0.0358 (7)	−0.0026 (5)	0.0033 (5)	0.0015 (6)
C7	0.0376 (8)	0.0462 (8)	0.0436 (8)	0.0026 (6)	−0.0009 (6)	−0.0114 (6)
C8	0.0383 (8)	0.0475 (9)	0.0512 (9)	0.0077 (6)	0.0019 (7)	−0.0067 (7)
C9	0.0301 (7)	0.0493 (8)	0.0365 (7)	−0.0029 (6)	0.0025 (5)	0.0008 (6)
C10	0.0388 (8)	0.0544 (9)	0.0477 (8)	−0.0026 (7)	0.0018 (7)	−0.0157 (7)
C11	0.0356 (8)	0.0460 (8)	0.0538 (9)	0.0032 (6)	0.0038 (7)	−0.0120 (7)
C12	0.0385 (8)	0.0526 (9)	0.0434 (8)	−0.0017 (7)	0.0025 (7)	−0.0012 (7)

Geometric parameters (Å, º) top

O1—C3	1.205 (2)	C5—H5A	0.9600
N1—C1	1.3500 (17)	C5—H5B	0.9600
N1—N2	1.3726 (17)	C5—H5C	0.9600
N1—C6	1.4326 (16)	C6—C7	1.378 (2)
N2—N3	1.2952 (17)	C6—C11	1.379 (2)
N3—C2	1.3634 (19)	C7—C8	1.384 (2)
N4—C12	1.140 (2)	C7—H7	0.9300
C1—C2	1.3762 (19)	C8—C9	1.385 (2)
C1—C4	1.482 (2)	C8—H8	0.9300
C2—C3	1.4734 (19)	C9—C10	1.384 (2)
C3—C5	1.491 (2)	C9—C12	1.4452 (19)
C4—H4A	0.9600	C10—C11	1.381 (2)
C4—H4B	0.9600	C10—H10	0.9300
C4—H4C	0.9600	C11—H11	0.9300

C1—N1—N2	111.26 (11)	C3—C5—H5C	109.5
C1—N1—C6	129.75 (12)	H5A—C5—H5C	109.5
N2—N1—C6	118.91 (11)	H5B—C5—H5C	109.5
N3—N2—N1	106.62 (11)	C7—C6—C11	121.37 (13)
N2—N3—C2	109.42 (12)	C7—C6—N1	120.33 (12)
N1—C1—C2	103.53 (12)	C11—C6—N1	118.29 (13)
N1—C1—C4	124.68 (12)	C6—C7—C8	119.25 (14)
C2—C1—C4	131.77 (13)	C6—C7—H7	120.4
N3—C2—C1	109.16 (12)	C8—C7—H7	120.4
N3—C2—C3	121.99 (13)	C7—C8—C9	119.71 (14)
C1—C2—C3	128.84 (14)	C7—C8—H8	120.1
O1—C3—C2	121.25 (14)	C9—C8—H8	120.1
O1—C3—C5	121.51 (15)	C10—C9—C8	120.56 (13)
C2—C3—C5	117.25 (14)	C10—C9—C12	118.92 (14)
C1—C4—H4A	109.5	C8—C9—C12	120.52 (14)
C1—C4—H4B	109.5	C11—C10—C9	119.66 (14)
H4A—C4—H4B	109.5	C11—C10—H10	120.2
C1—C4—H4C	109.5	C9—C10—H10	120.2
H4A—C4—H4C	109.5	C6—C11—C10	119.42 (14)
H4B—C4—H4C	109.5	C6—C11—H11	120.3
C3—C5—H5A	109.5	C10—C11—H11	120.3
C3—C5—H5B	109.5	N4—C12—C9	177.85 (18)
H5A—C5—H5B	109.5

C1—N1—N2—N3	−0.81 (17)	C1—C2—C3—C5	−173.75 (16)
C6—N1—N2—N3	−177.77 (12)	C1—N1—C6—C7	57.1 (2)
N1—N2—N3—C2	0.54 (17)	N2—N1—C6—C7	−126.64 (15)
N2—N1—C1—C2	0.72 (16)	C1—N1—C6—C11	−123.36 (17)
C6—N1—C1—C2	177.26 (13)	N2—N1—C6—C11	52.95 (19)
N2—N1—C1—C4	−177.72 (16)	C11—C6—C7—C8	1.7 (2)
C6—N1—C1—C4	−1.2 (2)	N1—C6—C7—C8	−178.73 (14)
N2—N3—C2—C1	−0.10 (18)	C6—C7—C8—C9	−0.6 (3)
N2—N3—C2—C3	179.34 (14)	C7—C8—C9—C10	−1.0 (3)
N1—C1—C2—N3	−0.38 (16)	C7—C8—C9—C12	179.08 (15)
C4—C1—C2—N3	177.90 (17)	C8—C9—C10—C11	1.5 (3)
N1—C1—C2—C3	−179.78 (14)	C12—C9—C10—C11	−178.55 (15)
C4—C1—C2—C3	−1.5 (3)	C7—C6—C11—C10	−1.2 (2)
N3—C2—C3—O1	−173.09 (17)	N1—C6—C11—C10	179.25 (14)
C1—C2—C3—O1	6.2 (3)	C9—C10—C11—C6	−0.4 (3)
N3—C2—C3—C5	6.9 (2)

Hydrogen-bond geometry (Å, º) top

π(Triazolyl) interaction geometry (Å, °) for (I). Cg1 is the centroid of the N1–N3/C1/C2 ring.

D—H···A	D—H	H···A	D···A	D—H···A
C3—O1···Cg1ⁱ	1.21 (1)	3.69 (1)	3.7359 (17)	83 (1)
C12—N4···Cg1ⁱⁱ	1.14 (1)	3.68 (1)	3.8468 (19)	90 (1)

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

Summary of short interatomic contacts (Å) in (I) top

Contact	Distance	Symmetry operation
H4C···H4C	2.39	1 - x, 1 - y, 1 - z
H10···N3	2.48	1/2 + x, 5/2 - y, 1/2 + z
H7···N4	2.58	-1/2 + x, 3/2 - y, -1/2 + z
H8···N4	2.53	5/2 - x, -1/2 + y, 3/2 - z
C4···O1	3.208 (2)	1 - x, 1 - y, 1 - z

Percentage contributions of interatomic contacts to the Hirshfeld surface for (I) top

Contact	Percentage contribution
H···H	35.9
N···H/H···N	26.2
O···H/H···O	9.9
C···H/H···C	8.7
C···C	7.3
C···N/N···C	7.2
N···N	2.1
C···O/O···C	1.4
N···O/O···N	1.4

Dihedral angle data (°) for (I) and 4-X-phenyl derivatives top

X	triazolyl/phenyl	triazolyl/acetyl	phenyl/acetyl	Ref.
Me	50.11 (7)	6.12 (18)	50.14 (12)	El-Hiti et al. (2017)
Cl	45.60 (4)	6.97 (9)	45.19 (6)	Zeghada et al. (2011)
Br	47.03 (5)	7.08 (12)	46.5 (7)	Zeghada et al. (2011)
NO₂^a	38.26 (15)	13.4 (4)	27.9 (3)	Vinutha et al. (2013)
	87.11 (18)	15.2 (3)	74.4 (2)
C≡N	54.64 (5)	6.8 (3)	60.82 (13)	This work

Note: (a) Two independent molecules comprise the asymmetric unit.

Footnotes

‡Additional correspondence author, e-mail: edwardt@sunway.edu.my.

Acknowledgements

The Brazilian agencies Coordination for the Improvement of Higher Education Personnel, CAPES, National Council for Scientific and Technological Development, CNPq, for a scholarship to JZ-S (303207/2017–5) are acknowledged for support. Funding for this research was provided by the National Council for Scientific and Technological Development, CNPq, (awards No. 303207/2017–5; 475203/2013–5), São Paulo Research Foundation-FAPESP (2013/06558–3) and GlaxoSmithKline-FAPESP (2014/50249–8). We thank Professor Regina H. A. Santos from IQSC-USP for the X-ray data collection.

Funding information

Funding for this research was provided by: National Council for Scientific and Technological Development, CNPq (grant No. 303207/2017–5); National Council for Scientific and Technological Development, CNPq (grant No. 475203/2013–5); São Paulo Research Foundation-FAPESP (grant No. 2013/06558-3); GlaxoSmithKline-FAPESP (grant No. 2014/50249-8).

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