Crystal structure and Hirshfeld surface analysis of 5-methyl-1,2,4-triazolo[1,5-a]pyrimidine

Lahmidi, S.; Sebbar, N.K.; Hökelek, T.; Chkirate, K.; Mague, J.T.; Essassi, E.M.

doi:10.1107/S2056989018016225

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ISSN: 2056-9890

Volume 74| Part 12| December 2018| Pages 1833-1837

https://doi.org/10.1107/S2056989018016225

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Crystal structure and Hirshfeld surface analysis of 5-methyl-1,2,4-triazolo[1,5-a]pyrimidine

Sanae Lahmidi,^a ^* Nada Kheira Sebbar,^b Tuncer Hökelek,^c Karim Chkirate,^a Joel T. Mague ^d and El Mokhtar Essassi ^a

^aLaboratoire de Chimie Organique Hétérocyclique URAC 21, Pôle de Compétence Pharmacochimie, Av. Ibn Battouta, BP 1014, Faculté des Sciences, Université Mohammed V, Rabat, Morocco, ^bLaboratoire de Chimie Bioorganique Appliquée, Faculté des Sciences, Université Ibn Zohr, Agadir, Morocco, ^cDepartment of Physics, Hacettepe University, 06800 Beytepe, Ankara, Turkey, and ^dDepartment of Chemistry, Tulane University, New Orleans, LA 70118, USA
^*Correspondence e-mail: sanaelahmidi2018@gmail.com

Edited by A. J. Lough, University of Toronto, Canada (Received 7 November 2018; accepted 15 November 2018; online 22 November 2018)

The nine-membered ring system of the title compound, C₆H₆N₄, is essentially planar. In the crystal, molecules are linked via C—H_Trz⋯N_Trz and C—H_Pyrm⋯N_Trz (Trz = triazole and Pyrm = pyrimidine) hydrogen bonds together with weaker C—H_Pyrm⋯N_Pyrm hydrogen bonds to form layers parallel to ( $[\overline{1}]$ 02). The layers are further connected by π–π-stacking interactions between the nine-membered ring system [centroid–centroid = 3.7910 (8) Å], forming oblique stacks along the a-axis direction. The Hirshfeld surface analysis of the crystal structure indicates that the most important contributions for the crystal packing are from H⋯N/N⋯H (40.1%), H⋯H (35.3%), H⋯C/C⋯H (9.5%), N⋯C/C⋯N (9.0%), N⋯N (3.1%) and C⋯C (3.0%) interactions and that hydrogen-bonding and van der Waals interactions are the dominant interactions in the crystal packing. No significant C—H⋯π interactions are observed.

Keywords: crystal structure; triazole; pyrimidine; hydrogen bond; π⋯π-stacking; Hirshfeld surface analysis.

CCDC reference: 1879279

1. Chemical context

In recent years, much attention has been paid to the development of new methods for the synthesis and investigation of biological and pharmacological properties of [1,2,4]triazolo[1,5-a]pyrimidine derivatives (Chebanov et al., 2010 ; Lahmidi et al., 2016a ,b , 2018 ; Sedash et al., 2012 ). Thus, these compounds have also received successful applications for the preparation of new poly-condensed heterocycles (Beck et al., 2011 ). Among the various classes of nitrogen-containing heterocyclic compounds such as triazolopyrimidine derivatives display a broad spectrum of biological activities, including anti-inflammatory (Ashour et al., 2013 ), anticancer (Hoffmann et al., 2017 ) and antibacterial (Mabkhot et al., 2016 ) activities. In a continuation of our research on the elaboration of new methods for the synthesis of various heterocyclic systems, we investigated the reaction of bis(2-chloroethyl)amine hydrochloride with ethyl 2-(5-methyl-1-1,2,4-triazolo[1,5-a]pyrimidin-7-yl)acetate under phase-transfer catalysis conditions using tetra-n-butyl ammoniumbromide (TBAB) as catalyst and potassium carbonate as base to afford the title compound, 5-methyl-1,2,4-triazolo[1,5-a]pyrimidine, (I). We report herein its molecular and crystal structures along with the results of a Hirshfeld surface analysis.

2. Structural commentary

In the title compound (Fig. 1), the nine-membered ring is planar to within 0.004 (1) Å (for atom C5), and the r.m.s. deviation of the fitted atoms is 0.009 Å. Methyl atom C6 is displaced by 0.032 (1) Å from the ring system.

Figure 1
The title molecule with the atom-labelling scheme and 50% probability ellipsoids.

3. Supramolecular features

In the crystal, C—H_Trz⋯N_Trz and C—H_Pyrm⋯N_Trz (Trz = triazole and Pyrm = pyrimidine) hydrogen bonds (Table 1), together with weaker C—H_Pyrm⋯N_Pyrm hydrogen bonds, link the molecules, forming layers parallel to ( $[\overline{1}]$ 02) (Fig. 2). The layers are further connected by π–π-stacking interactions between the nine-membered rings [centroid–centroid distance = 3.7910 (8) Å], forming oblique stacks along the a-axis direction (Fig. 3). No significant C—H ⋯ π interactions are observed.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2⋯N1ⁱ	1.016 (17)	2.550 (19)	3.4052 (18)	141.5 (13)
C3—H3⋯N2^vi	0.979 (18)	2.525 (18)	3.4822 (18)	165.8 (13)
C4—H4⋯N4^viii	0.946 (19)	2.642 (19)	3.5677 (17)	165.9 (14)
Symmetry codes: (i) -x+2, -y+1, -z+2; (vi) -x, -y+1, -z+1; (viii) $[x-1, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

Figure 2
The packing viewed along the a-axis direction giving a plan view of the layers. C—H⋯N hydrogen bonds are shown as black dashed lines and the orange dots mark the π–π stacking interactions.

Figure 3
Packing seen along the b-axis direction giving a side view of the layers. Hydrogen bonds are depicted as in Fig. 2

and the π-stacking interactions are shown as orange dashed lines.

4. Hirshfeld surface analysis

In order to visualize the intermolecular interactions in the crystal of the title compound, a Hirshfeld surface (HS) analysis (Hirshfeld, 1977 ; Spackman & Jayatilaka, 2009 ) was carried out using CrystalExplorer17.5 (Turner et al., 2017 ). In the HS plotted over d_norm (Fig. 4), the white surface indicates contacts with distances equal to the sum of the van der Waals radii, and the red and blue colours indicate distances shorter (in close contact) or longer (distinct contact), respectively, than the van der Waals radii (Venkatesan et al., 2016 ). The bright-red spots appearing near N2 and hydrogen atoms H2, H3 and H4 indicate their roles as the respective donors and/or acceptors in the dominant C—H⋯N hydrogen bonds; they also appear as blue and red regions corresponding to positive and negative potentials on the HS mapped over electrostatic potential (Spackman et al., 2008 ; Jayatilaka et al., 2005 ) as shown in Fig. 5. The blue regions indicate positive electrostatic potential (hydrogen-bond donors), while the red regions indicate negative electrostatic potential (hydrogen-bond acceptors). The shape-index of the HS is a tool to visualize π–π stacking by the presence of adjacent red and blue triangles; if there are no adjacent red and/or blue triangles, then there are no π–π interactions. Fig. 6 clearly suggest that there are π–π interactions present in the crystal structure of (I).

Figure 4
View of the three-dimensional Hirshfeld surface of the title compound plotted over d_norm in the range −0.1566 to 1.0057 a.u.

Figure 5
View of the three-dimensional Hirshfeld surface of the title compound plotted over electrostatic potential energy in the range −0.0500 to 0.0500 a.u. using the STO-3 G basis set at the Hartree–Fock level of theory. Hydrogen-bond donors and acceptors are shown as blue and red regions around the atoms corresponding to positive and negative potentials, respectively.

Figure 6
Hirshfeld surface of the title compound plotted over shape-index.

The overall two-dimensional fingerprint plot, Fig. 7(a), and those delineated into H⋯N/N⋯H, H⋯H, H⋯C/C⋯H, N⋯C/C⋯N, N⋯N and C⋯C contacts (McKinnon et al., 2007 ) are illustrated in Fig. 7(b)–(g), respectively, together with their relative contributions to the Hirshfeld surface. The most important interaction is H⋯N/N⋯H, contributing 40.1% to the overall crystal packing, which is reflected in Fig. 7(b) as a pair of characteristic wings with the tips at d_e + d_i = 2.40 Å arising from the C—H⋯N hydrogen bonds (Table 1) as well as from the H⋯N/N⋯H contacts (Table 3). The split thin and thick pair of wings with the tips at d_e + d_i ∼2.23 Å in Fig. 7(c), arise from the short interatomic H⋯H contacts, which make a 35.3% contribution to the HS and are seen as widely scattered points of high density arising from the large hydrogen content of the molecule. In the absence of C—H⋯π interactions, the pair of wings in the fingerprint plot delineated into H⋯C/C⋯H contacts (9.5% contribution to the HS) have a nearly symmetrical distribution of points, Fig. 7(d), with the tips at d_e + d_i ∼2.77 Å. The N⋯C/C⋯N [Fig. 7(e)] and N⋯N [Fig. 7(f)] contacts make contributions of 9.0 and 3.1%, respectively, to the HS and have widely scattered distributions of points. Finally, the C⋯C [Fig. 7(g)] contacts (3.0% contribution to the HS) have a symmetrical distribution of points, with the tip at d_e = d_i = 1.69 Å.

Table 3
Experimental details

Crystal data
Chemical formula	C₆H₆N₄
M_r	134.15
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	150
a, b, c (Å)	3.7910 (2), 18.0092 (10), 9.0069 (5)
β (°)	101.704 (2)
V (Å³)	602.14 (6)
Z	4
Radiation type	Cu Kα
μ (mm⁻¹)	0.82
Crystal size (mm)	0.29 × 0.18 × 0.13

Data collection
Diffractometer	Bruker D8 VENTURE PHOTON 100 CMOS
Absorption correction	Multi-scan (SADABS; Krause et al., 2015 )
T_min, T_max	0.67, 0.90
No. of measured, independent and observed [I > 2σ(I)] reflections	4567, 1205, 1102
R_int	0.074
(sin θ/λ)_max (Å⁻¹)	0.626

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.044, 0.113, 1.10
No. of reflections	1205
No. of parameters	116
H-atom treatment	All H-atom parameters refined
Δρ_max, Δρ_min (e Å⁻³)	0.20, −0.20
Computer programs: APEX3 and SAINT (Bruker, 2016 ), SHELXT (Sheldrick, 2015a ), SHELXL2018 (Sheldrick, 2015b ), DIAMOND (Brandenburg & Putz, 2012 ) and SHELXTL (Sheldrick, 2008 ).

Figure 7
The full two-dimensional fingerprint plots for the title compound, showing (a) all interactions, and delineated into (b) H⋯N/N⋯H, (c) H⋯H, (d) H⋯C/C⋯H, (e) N⋯C/C⋯N, (f) N⋯N and (g) C⋯C interactions. The d_i and d_e values are the closest internal and external distances (in Å) from given points on the Hirshfeld surface contacts.

The Hirshfeld surface representations with the function d_norm plotted onto the surface are shown for the H⋯N/N⋯H, H⋯H, H⋯C/C⋯H, N ⋯ C/C⋯N, N⋯N and C⋯C interactions in Fig. 8(a)–(f), respectively.

Figure 8
The Hirshfeld surface representations with the function d_norm plotted onto the surface for (a) H⋯N/N⋯H, (b) H⋯H, (c) H⋯C/C⋯H, (d) N⋯C/C⋯N, (e) N⋯N and (f) C⋯C interactions.

The Hirshfeld surface analysis confirms the importance of H-atom contacts in establishing the packing. The large number of H⋯N/N⋯H, H⋯H and H⋯C/C⋯H interactions suggest that van der Waals interactions and hydrogen bonding play the major roles in the crystal packing (Hathwar et al., 2015 ).

5. Database survey

Two structures have previously been reported in which the title compound, (I), is present as a ligand (L), namely [Fe(L)₂(SCN)₂(H₂O)₂] (Bigini Cingi et al., 1986 ) and [Cu(μ-L)₂(SCN)]_n (Cornelissen et al., 1989 ), but to the best of our knowledge, the molecule itself has not previously been structurally characterized.

6. Synthesis and crystallization

To a solution of ethyl-2-{5-methyl-1-[1,2,4]triazolo[1,5-a]pyrimidin-7-yl}acetate (1.00 g, 4.5 mmol) in DMF (25 ml) was added 2eq of bis(2-chloroethyl)amine hydrochloride (1.61g, 9 mmol), potassium carbonate (1.37 g, 9.9 mmol) and a catalytic amount of tetra-n-butylammonium bromide. The mixture was stirred at 353.15 K for 24 h. The solution was filtered and the solvent was removed under reduced pressure. The residue obtained was dissolved in dichloromethane and purified by column chromatography (EtOAc/Hexane, 1:9 v:v). The title compound was obtained as colourless crystals in 40% yield.

7. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. H atoms were located in a difference Fourier map and were freely refined.

Table 2
Selected interatomic distances (Å)

N1⋯C2ⁱ	3.4051 (19)	C1⋯C4ⁱⁱⁱ	3.5667 (19)
N2⋯C2ⁱⁱ	3.385 (2)	C2⋯C6^vii	3.5715 (18)
N3⋯C3ⁱⁱⁱ	3.4163 (19)	C2⋯C2ⁱ	3.595 (2)
N4⋯C5ⁱⁱⁱ	3.4314 (17)	C4⋯C5ⁱⁱ	3.4986 (19)
N4⋯C4ⁱⁱⁱ	3.4177 (19)	C1⋯H6B^iv	2.94 (3)
N1⋯H6B^iv	2.85 (2)	C6⋯H6Cⁱⁱⁱ	2.98 (3)
N1⋯H2ⁱ	2.553 (18)	H2⋯C6^vii	2.773 (16)
N1⋯H6C^v	2.86 (3)	H2⋯H6B^vii	2.58 (3)
N2⋯H3^vi	2.525 (18)	H2⋯H6C^vii	2.48 (3)
N4⋯H4^v	2.641 (18)	H6A⋯H4^v	2.59 (3)
N4⋯H6B^iv	2.84 (3)	H6B⋯H6Cⁱⁱⁱ	2.47 (4)
C1⋯C3ⁱⁱⁱ	3.4166 (19)
Symmetry codes: (i) -x+2, -y+1, -z+2; (ii) x-1, y, z; (iii) x+1, y, z; (iv) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (v) $[x+1, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (vi) -x, -y+1, -z+1; (vii) $[-x+1, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Supporting information

CCDC reference: 1879279

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S2056989018016225/lh5886sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989018016225/lh5886Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989018016225/lh5886Isup3.cdx

Supporting information file. DOI: https://doi.org/10.1107/S2056989018016225/lh5886Isup4.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 (Sheldrick, 2015b); molecular graphics: DIAMOND (Brandenburg & Putz, 2012); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

5-Methyl-1,2,4-triazolo[1,5-a]pyrimidine top

Crystal data top

C₆H₆N₄	F(000) = 280
M_r = 134.15	D_x = 1.480 Mg m⁻³
Monoclinic, P2₁/c	Cu Kα radiation, λ = 1.54178 Å
a = 3.7910 (2) Å	Cell parameters from 3969 reflections
b = 18.0092 (10) Å	θ = 4.9–74.7°
c = 9.0069 (5) Å	µ = 0.82 mm⁻¹
β = 101.704 (2)°	T = 150 K
V = 602.14 (6) Å³	Column, colourless
Z = 4	0.29 × 0.18 × 0.13 mm

Data collection top

Bruker D8 VENTURE PHOTON 100 CMOS diffractometer	1205 independent reflections
Radiation source: INCOATEC IµS micro-focus source	1102 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.074
Detector resolution: 10.4167 pixels mm^-1	θ_max = 74.7°, θ_min = 4.9°
ω scans	h = −4→4
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	k = −22→21
T_min = 0.67, T_max = 0.90	l = −11→10
4567 measured reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F² > 2σ(F²)] = 0.044	All H-atom parameters refined
wR(F²) = 0.113	w = 1/[σ²(F_o²) + (0.0458P)² + 0.1643P] where P = (F_o² + 2F_c²)/3
S = 1.10	(Δ/σ)_max < 0.001
1205 reflections	Δρ_max = 0.20 e Å⁻³
116 parameters	Δρ_min = −0.20 e Å⁻³
0 restraints	Extinction correction: SHELXL2018 (Sheldrick, 2015b), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.021 (4)

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. 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.

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

	x	y	z	U_iso*/U_eq
N1	0.7561 (3)	0.42236 (6)	0.88570 (13)	0.0322 (3)
N2	0.4407 (3)	0.49411 (6)	0.69436 (15)	0.0341 (3)
N3	0.3764 (3)	0.42019 (6)	0.66430 (13)	0.0281 (3)
N4	0.5532 (3)	0.30294 (6)	0.77958 (13)	0.0277 (3)
C1	0.5676 (3)	0.37780 (7)	0.78059 (15)	0.0269 (3)
C2	0.6678 (4)	0.49082 (7)	0.82759 (17)	0.0340 (4)
H2	0.776 (5)	0.5371 (9)	0.883 (2)	0.037 (4)*
C3	0.1587 (4)	0.38918 (7)	0.54119 (15)	0.0313 (3)
H3	0.025 (5)	0.4230 (9)	0.465 (2)	0.037 (4)*
C4	0.1409 (4)	0.31397 (7)	0.53851 (16)	0.0302 (3)
H4	−0.006 (5)	0.2889 (10)	0.456 (2)	0.039 (4)*
C5	0.3442 (3)	0.27179 (7)	0.66009 (15)	0.0279 (3)
C6	0.3279 (4)	0.18893 (7)	0.65408 (19)	0.0344 (4)
H6A	0.462 (6)	0.1656 (13)	0.749 (3)	0.066 (6)*
H6B	0.431 (6)	0.1705 (12)	0.576 (3)	0.071 (7)*
H6C	0.095 (7)	0.1716 (12)	0.629 (3)	0.073 (7)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0381 (6)	0.0233 (5)	0.0321 (6)	−0.0020 (4)	0.0000 (5)	−0.0010 (4)
N2	0.0434 (7)	0.0197 (5)	0.0367 (6)	−0.0011 (4)	0.0026 (5)	0.0000 (4)
N3	0.0324 (6)	0.0222 (5)	0.0281 (6)	−0.0001 (4)	0.0024 (5)	0.0005 (4)
N4	0.0311 (6)	0.0221 (5)	0.0289 (6)	−0.0004 (4)	0.0040 (5)	−0.0003 (4)
C1	0.0297 (6)	0.0224 (6)	0.0280 (7)	0.0001 (4)	0.0041 (5)	0.0011 (4)
C2	0.0414 (8)	0.0221 (6)	0.0360 (8)	−0.0023 (5)	0.0020 (6)	−0.0019 (5)
C3	0.0337 (7)	0.0304 (7)	0.0281 (7)	0.0005 (5)	0.0020 (5)	0.0005 (5)
C4	0.0319 (7)	0.0289 (7)	0.0284 (7)	−0.0030 (5)	0.0026 (5)	−0.0029 (5)
C5	0.0284 (6)	0.0250 (6)	0.0308 (7)	−0.0016 (5)	0.0074 (5)	−0.0022 (5)
C6	0.0386 (8)	0.0244 (7)	0.0393 (8)	−0.0022 (5)	0.0058 (7)	−0.0043 (5)

Geometric parameters (Å, º) top

N1—C1	1.3329 (17)	C3—C4	1.3560 (18)
N1—C2	1.3545 (17)	C3—H3	0.979 (18)
N2—C2	1.329 (2)	C4—C5	1.4241 (19)
N2—N3	1.3703 (15)	C4—H4	0.946 (19)
N3—C3	1.3607 (17)	C5—C6	1.4940 (18)
N3—C1	1.3775 (17)	C6—H6A	1.00 (2)
N4—C5	1.3245 (17)	C6—H6B	0.94 (3)
N4—C1	1.3492 (17)	C6—H6C	0.92 (3)
C2—H2	1.016 (17)

N1···C2ⁱ	3.4051 (19)	C1···C4ⁱⁱⁱ	3.5667 (19)
N2···C2ⁱⁱ	3.385 (2)	C2···C6^vii	3.5715 (18)
N3···C3ⁱⁱⁱ	3.4163 (19)	C2···C2ⁱ	3.595 (2)
N4···C5ⁱⁱⁱ	3.4314 (17)	C4···C5ⁱⁱ	3.4986 (19)
N4···C4ⁱⁱⁱ	3.4177 (19)	C1···H6B^iv	2.94 (3)
N1···H6B^iv	2.85 (2)	C6···H6Cⁱⁱⁱ	2.98 (3)
N1···H2ⁱ	2.553 (18)	H2···C6^vii	2.773 (16)
N1···H6C^v	2.86 (3)	H2···H6B^vii	2.58 (3)
N2···H3^vi	2.525 (18)	H2···H6C^vii	2.48 (3)
N4···H4^v	2.641 (18)	H6A···H4^v	2.59 (3)
N4···H6B^iv	2.84 (3)	H6B···H6Cⁱⁱⁱ	2.47 (4)
C1···C3ⁱⁱⁱ	3.4166 (19)

C1—N1—C2	102.64 (11)	N3—C3—H3	117.3 (10)
C2—N2—N3	101.05 (10)	C3—C4—C5	120.13 (12)
C3—N3—N2	127.88 (11)	C3—C4—H4	120.6 (11)
C3—N3—C1	122.05 (11)	C5—C4—H4	119.3 (11)
N2—N3—C1	110.07 (11)	N4—C5—C4	122.68 (12)
C5—N4—C1	116.45 (11)	N4—C5—C6	117.78 (12)
N1—C1—N4	128.43 (12)	C4—C5—C6	119.54 (12)
N1—C1—N3	109.26 (11)	C5—C6—H6A	112.4 (14)
N4—C1—N3	122.30 (12)	C5—C6—H6B	111.1 (13)
N2—C2—N1	116.97 (12)	H6A—C6—H6B	106.4 (19)
N2—C2—H2	122.2 (10)	C5—C6—H6C	112.2 (14)
N1—C2—H2	120.8 (10)	H6A—C6—H6C	111.5 (19)
C4—C3—N3	116.38 (12)	H6B—C6—H6C	103 (2)
C4—C3—H3	126.3 (10)

C2—N2—N3—C3	179.68 (13)	N3—N2—C2—N1	0.14 (17)
C2—N2—N3—C1	0.03 (14)	C1—N1—C2—N2	−0.24 (17)
C2—N1—C1—N4	179.97 (13)	N2—N3—C3—C4	−179.91 (12)
C2—N1—C1—N3	0.24 (14)	C1—N3—C3—C4	−0.30 (18)
C5—N4—C1—N1	−179.67 (12)	N3—C3—C4—C5	−0.18 (19)
C5—N4—C1—N3	0.04 (17)	C1—N4—C5—C4	−0.53 (17)
C3—N3—C1—N1	−179.85 (12)	C1—N4—C5—C6	178.84 (11)
N2—N3—C1—N1	−0.18 (14)	C3—C4—C5—N4	0.6 (2)
C3—N3—C1—N4	0.39 (18)	C3—C4—C5—C6	−178.74 (13)
N2—N3—C1—N4	−179.93 (11)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···N1ⁱ	1.016 (17)	2.550 (19)	3.4052 (18)	141.5 (13)
C3—H3···N2^vi	0.979 (18)	2.525 (18)	3.4822 (18)	165.8 (13)
C4—H4···N4^viii	0.946 (19)	2.642 (19)	3.5677 (17)	165.9 (14)

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

Funding information

The support of NSF–MRI grant No. 1228232 for the purchase of the diffractometer and Tulane University for support of the Tulane Crystallography Laboratory are gratefully acknowledged. TH is grateful to the Hacettepe University Scientific Research Project Unit (grant No. 013 D04 602 004).

References

Ashour, H., Shaaban, O., Rizk, O. & El-Ashmawy, I. M. (2013). Eur. J. Med. Chem. 62, 341–351. CrossRef Google Scholar
Beck, H. P., DeGraffenreid, M., Fox, B., Allen, J. G., Rew, Y., Schneider, S., Saiki, A. Y., Yu, D., Oliner, J. D., Salyers, K., Ye, Q. & Olson, S. (2011). Bioorg. Med. Chem. Lett. 21, 2752–2755. Web of Science CrossRef CAS PubMed Google Scholar
Biagini Cingi, M., Manotti Lanfredi, A. M., Tiripicchio, A., Cornelissen, J. P., Haasnoot, J. G. & Reedijk, J. (1986). Acta Cryst. C42, 1296–1298. CrossRef IUCr Journals Google Scholar
Brandenburg, K. & Putz, H. (2012). DIAMOND, Crystal Impact GbR, Bonn, Germany. Google Scholar
Bruker (2016). APEX3 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Chebanov, V. A., Gura, K. A. & Desenko, S. M. (2010). Top. Heterocycl. Chem. 23, 41–84. CrossRef CAS Google Scholar
Cornelissen, J. P., De Graaff, R. A. G., Haasnoot, J. G., Prins, R., Reedijk, J., Biagini-Cingi, M., Manotti-Lanfredi, A. M. & Tiripicchio, A. (1989). Polyhedron, 8, 2313–2320. CrossRef Google Scholar
Hathwar, V. R., Sist, M., Jørgensen, M. R. V., Mamakhel, A. H., Wang, X., Hoffmann, C. M., Sugimoto, K., Overgaard, J. & Iversen, B. B. (2015). IUCrJ, 2, 563–574. Web of Science CrossRef CAS PubMed IUCr Journals Google Scholar
Hirshfeld, H. L. (1977). Theor. Chim. Acta, 44, 129–138. CrossRef CAS Web of Science Google Scholar
Hoffmann, K., Wiśniewska, J., Wojtczak, A., Sitkowski, J., Denslow, A., Wietrzyk, J., Jakubowski, M. & Łakomska, I. (2017). J. Inorg. Biochem. 172, 34–45. CrossRef Google Scholar
Jayatilaka, D., Grimwood, D. J., Lee, A., Lemay, A., Russel, A. J., Taylor, C., Wolff, S. K., Cassam-Chenai, P. & Whitton, A. (2005). TONTO - A System for Computational Chemistry. Available at: https://hirshfeldsurface.net/ Google Scholar
Krause, L., Herbst-Irmer, R., Sheldrick, G. M. & Stalke, D. (2015). J. Appl. Cryst. 48, 3–10. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Lahmidi, S., El Hafi, M., Moussaif, A., Benchidmi, M., Essassi, E. M. & Mague, J. T. (2018). IUCrData, 3, x181280. Google Scholar
Lahmidi, S., Sebbar, N. K., Boulhaoua, M., Essassi, E. M., Mague, J. T. & Zouihri, H. (2016a). IUCrData, 1, x160870. Google Scholar
Lahmidi, S., Sebbar, N. K., Harmaoui, A., Ouzidan, Y., Essassi, E. M. & Mague, J. T. (2016b). IUCrData, 1, x161946. Google Scholar
Mabkhot, Y. N., Alatibi, F., El-Sayed, N. N. E., Kheder, N. A. & Al-Showiman, S. (2016). Molecules, 21, 1036–1045. CrossRef Google Scholar
McKinnon, J. J., Jayatilaka, D. & Spackman, M. A. (2007). Chem. Commun. pp. 3814. Google Scholar
Sedash, Y. V., Gorobets, N. Y., Chebanov, V. A., Konovalova, I. S., Shishkin, O. V. & Desenko, S. M. (2012). RSC Adv. 2, 6719–6728. CrossRef Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2015a). Acta Cryst. A71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2015b). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Spackman, M. A. & Jayatilaka, D. (2009). CrystEngComm, 11, 19–32. Web of Science CrossRef CAS Google Scholar
Spackman, M. A., McKinnon, J. J. & Jayatilaka, D. (2008). CrystEngComm, 10, 377–388. CAS Google Scholar
Turner, M. J., McKinnon, J. J., Wolff, S. K., Grimwood, D. J., Spackman, P. R., Jayatilaka, D. & Spackman, M. A. (2017). CrystalExplorer17. The University of Western Australia. Google Scholar
Venkatesan, P., Thamotharan, S., Ilangovan, A., Liang, H. & Sundius, T. (2016). Spectrochim. Acta Part A, 153, 625–636. Web of Science CrossRef CAS Google Scholar

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Volume 74| Part 12| December 2018| Pages 1833-1837

https://doi.org/10.1107/S2056989018016225

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research communications\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Crystal structure and Hirshfeld surface analysis of 5-methyl-1,2,4-triazolo[1,5-a]pyrimidine

1. Chemical context

2. Structural commentary

3. Supra­molecular features

4. Hirshfeld surface analysis

5. Database survey

6. Synthesis and crystallization

7. Refinement

Supporting information

Funding information

References

research communications

3. Supramolecular features