1,4-Bis(1H-1,2,4-triazol-1-yl)benzene

Du, R.; Meng, L.; Lu, L.-P.

doi:10.1107/S2414314617002723

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 2| Part 2| February 2017| x170272

https://doi.org/10.1107/S2414314617002723

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1,4-Bis(1H-1,2,4-triazol-1-yl)benzene

Ran Du,^a Li Meng ^a and Li-Ping Lu ^a ^*

^aInstitute of Molecular Science, Shanxi University, Taiyuan, Shanxi 030006, People's Republic of China
^*Correspondence e-mail: luliping@sxu.edu.cn

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 19 January 2017; accepted 17 February 2017; online 21 February 2017)

The complete molecule of the title compound, C₁₀H₈N₆, is generated by crystallographic inversion symmetry; the dihedral angle between the planes of the benzene and triazole rings is 16.7 (2)°. In the crystal, inversion dimers linked by pairs of weak C—H⋯N hydrogen bonds generate R₂²(6) loops. Weak aromatic π–π stacking interactions [centroid–centroid separation = 3.809 (1) Å] are also observed.

Keywords: crystal structure; 1,4-bis(1H-1,2,4-triazol-1-yl)benzene; C—H⋯N hydrogen bonding; π–π interaction.

CCDC reference: 1533318

Structure description

Derivatives of 1,2,4-triazole exhibit a wide range of bioactivities, including anticancer activity, antitubercular activity and kinase inhibition (Kaur et al., 2016 ; Keri et al., 2015 ). Their copper complexes can inhibit the activity of protein tyrosine phosphatase (Lu & Zhu, 2014 ). Thus, we reacted 2,5-bis(1H-1,2,4-triazol-1-yl)terephthalic acid with CuCl₂ under hydrothermal conditions in an attempt to form a complex, but instead crystals of the title compound, (I), were obtained.

The molecular structure of (I) is illustrated in Fig. 1. The asymmetric unit consists of half a molecule; the complete molecule is generated by an inversion operation. The planes of the benzene and triazole rings are inclined at an angle of 16.7 (2)°. In the crystal, molecules are connected through weak C—H⋯N hydrogen bonds (Table 1) and π–π interactions [centroid–centroid separation = 3.809 (1) Å], leading to the formation of a supramolecular network (Fig. 2).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1⋯N3ⁱ	0.93	2.55	3.3563 (19)	146
C5—H5⋯N2ⁱⁱ	0.93	2.71	3.6184 (18)	165
Symmetry codes: (i) -x+1, -y+1, -z+1; (ii) $[-x+2, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Figure 1
The molecular structure of the title compound, with displacement ellipsoids for non-H atoms drawn at the 50% probability level. [Symmetry code: (i) 2 − x, 1 − y, −z.]

Figure 2
The C—H⋯N hydrogen-bonded (dotted lines) network of (I).

Synthesis and crystallization

A mixture containing CuCl₂·4H₂O (0.10 mmol, 17 mg), 2,5-bis(1H-1,2,4-triazol-1-yl)terephthalic acid (0.05 mmol, 15 mg), 1,10-phenanthroline (0.05 mmol, 8.5 mg), dimethylformamide (1.0 ml) and H₂O (6.0 ml) was stirred for 30 min at room temperature. The reaction mixture was sealed in a Teflon-lined stainless steel vessel and then heated to 433 K for 3 d and then allowed to cool gradually to room temperature. Colourless blocks of the title compound were collected by filtration and washed with water.

Refinement

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

Table 2
Experimental details

Crystal data
Chemical formula	C₁₀H₈N₆
M_r	212.22
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	298
a, b, c (Å)	3.8091 (3), 10.2616 (9), 11.9768 (11)
β (°)	96.165 (3)
V (Å³)	465.44 (7)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	0.10
Crystal size (mm)	0.20 × 0.20 × 0.20

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996 )
T_min, T_max	0.669, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	4210, 1057, 875
R_int	0.029
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.114, 1.03
No. of reflections	1057
No. of parameters	73
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.23, −0.17
Computer programs: APEX2 and SAINT (Bruker, 2000 ), SHELXS97 and SHELXTL (Sheldrick, 2008 ) and SHELXL2016 (Sheldrick, 2015 ).

Structural data

CCDC reference: 1533318

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314617002723/hb4114sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314617002723/hb4114Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314617002723/hb4114Isup3.cml

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2016 (Sheldrick, 2015); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

1,4-Bis(1H-1,2,4-triazol-1-yl)benzene top

Crystal data top

C₁₀H₈N₆	F(000) = 220
M_r = 212.22	D_x = 1.514 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 3.8091 (3) Å	Cell parameters from 2111 reflections
b = 10.2616 (9) Å	θ = 3.4–27.5°
c = 11.9768 (11) Å	µ = 0.10 mm⁻¹
β = 96.165 (3)°	T = 298 K
V = 465.44 (7) Å³	Block, colorless
Z = 2	0.20 × 0.20 × 0.20 mm

Data collection top

Bruker APEXII CCD diffractometer	875 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.029
φ and ω scans	θ_max = 27.5°, θ_min = 3.4°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −3→4
T_min = 0.669, T_max = 0.746	k = −13→13
4210 measured reflections	l = −15→15
1057 independent reflections

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)] = 0.043	H-atom parameters constrained
wR(F²) = 0.114	w = 1/[σ²(F_o²) + (0.0567P)² + 0.1337P] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max = 0.001
1057 reflections	Δρ_max = 0.23 e Å⁻³
73 parameters	Δρ_min = −0.17 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
N1	0.8017 (3)	0.48118 (10)	0.21842 (9)	0.0307 (3)
N2	0.7691 (4)	0.58859 (12)	0.28330 (10)	0.0451 (4)
N3	0.6288 (4)	0.40718 (13)	0.37506 (11)	0.0459 (4)
C1	0.6654 (5)	0.53760 (15)	0.37491 (13)	0.0467 (4)
H1	0.620016	0.588563	0.435947	0.056*
C2	0.7160 (4)	0.37557 (14)	0.27543 (12)	0.0417 (4)
H2	0.718064	0.290825	0.247992	0.050*
C3	0.9038 (3)	0.49129 (12)	0.10767 (11)	0.0282 (3)
C4	0.8869 (4)	0.61044 (13)	0.05306 (11)	0.0331 (3)
H4	0.811019	0.684228	0.088642	0.040*
C5	1.0163 (4)	0.38103 (13)	0.05481 (11)	0.0341 (4)
H5	1.026722	0.301276	0.091893	0.041*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0397 (7)	0.0278 (6)	0.0257 (6)	−0.0006 (5)	0.0082 (5)	−0.0003 (4)
N2	0.0729 (9)	0.0319 (7)	0.0343 (7)	−0.0005 (6)	0.0228 (6)	−0.0043 (5)
N3	0.0651 (9)	0.0412 (7)	0.0346 (7)	−0.0032 (6)	0.0199 (6)	0.0029 (5)
C1	0.0691 (11)	0.0401 (8)	0.0344 (8)	0.0005 (7)	0.0224 (7)	−0.0017 (6)
C2	0.0623 (10)	0.0307 (7)	0.0342 (7)	−0.0038 (7)	0.0153 (7)	0.0024 (6)
C3	0.0309 (7)	0.0302 (7)	0.0239 (6)	−0.0018 (5)	0.0045 (5)	−0.0004 (5)
C4	0.0439 (8)	0.0260 (7)	0.0306 (7)	0.0025 (5)	0.0099 (6)	−0.0025 (5)
C5	0.0471 (8)	0.0261 (6)	0.0301 (7)	0.0035 (6)	0.0095 (6)	0.0039 (5)

Geometric parameters (Å, º) top

N1—C2	1.3397 (17)	C2—H2	0.9300
N1—N2	1.3620 (15)	C3—C4	1.3848 (18)
N1—C3	1.4255 (16)	C3—C5	1.3867 (18)
N2—C1	1.3141 (19)	C4—C5ⁱ	1.3839 (17)
N3—C2	1.3133 (18)	C4—H4	0.9300
N3—C1	1.346 (2)	C5—H5	0.9300
C1—H1	0.9300

C2—N1—N2	108.77 (11)	N1—C2—H2	124.4
C2—N1—C3	129.70 (11)	C4—C3—C5	120.38 (12)
N2—N1—C3	121.51 (10)	C4—C3—N1	120.02 (11)
C1—N2—N1	102.01 (12)	C5—C3—N1	119.60 (11)
C2—N3—C1	102.01 (12)	C5ⁱ—C4—C3	119.55 (12)
N2—C1—N3	115.95 (13)	C5ⁱ—C4—H4	120.2
N2—C1—H1	122.0	C3—C4—H4	120.2
N3—C1—H1	122.0	C4ⁱ—C5—C3	120.07 (12)
N3—C2—N1	111.26 (13)	C4ⁱ—C5—H5	120.0
N3—C2—H2	124.4	C3—C5—H5	120.0

C2—N1—N2—C1	0.02 (17)	N2—N1—C3—C4	−16.2 (2)
C3—N1—N2—C1	178.56 (13)	C2—N1—C3—C5	−17.3 (2)
N1—N2—C1—N3	0.1 (2)	N2—N1—C3—C5	164.48 (13)
C2—N3—C1—N2	−0.2 (2)	C5—C3—C4—C5ⁱ	−0.1 (2)
C1—N3—C2—N1	0.19 (19)	N1—C3—C4—C5ⁱ	−179.45 (12)
N2—N1—C2—N3	−0.14 (19)	C4—C3—C5—C4ⁱ	0.1 (2)
C3—N1—C2—N3	−178.52 (13)	N1—C3—C5—C4ⁱ	179.46 (13)
C2—N1—C3—C4	162.05 (15)

Symmetry code: (i) −x+2, −y+1, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···N3ⁱⁱ	0.93	2.55	3.3563 (19)	146
C5—H5···N2ⁱⁱⁱ	0.93	2.71	3.6184 (18)	165

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

Funding information

Funding for this research was provided by: National Natural Science Foundation of China (award No. 21571118).

References

Bruker (2000). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Kaur, R., Dwivedi, A. R., Kumar, B. & Kumar, V. (2016). Anticancer Agents Med. Chem. 16, 465–489. CrossRef CAS PubMed Google Scholar
Keri, R. S., Patil, S. A., Budagumpi, S. & Nagaraja, B. M. (2015). Chem. Biol. Drug Des. 86, 410–423. CrossRef CAS PubMed Google Scholar
Lu, L. P. & Zhu, M. L. (2014). Antioxid. Redox Signal. 20, 2210–2224. CrossRef CAS PubMed Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2015). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar

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ISSN: 2414-3146

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https://doi.org/10.1107/S2414314617002723

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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

1,4-Bis(1H-1,2,4-triazol-1-yl)benzene

Structure description

Synthesis and crystallization

Refinement

Structural data

Funding information

References

organic compounds