[1-(2,5-Di­chloro­anilino)-5-methyl-1H-1,2,3-triazol-4-yl]methanol

Cunha, A.C.; Jordão, A.K.; Souza, M.C.B.V. de; Ferreira, V.F.; Almeida, M.C.B. de; Wardell, J.L.; Tiekink, E.R.T.

doi:10.1107/S2414314615024475

organic compounds

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ISSN: 2414-3146

Volume 1| Part 1| January 2016| x152447

doi:10.1107/S2414314615024475

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[1-(2,5-Dichloroanilino)-5-methyl-1H-1,2,3-triazol-4-yl]methanol

Anna C. Cunha,^a Alessandro K. Jordão,^b Maria C. B. V. de Souza,^a Vitor F. Ferreira,^a Maria C. B. de Almeida,^a James L. Wardell ^c,^d ‡ and Edward R. T. Tiekink ^e ^*

^aUniversidade Federal Fluminense, Departamento de Química Orgânica, Programa de Pós-Graduaçõ em Química, 24020-141 Niterói, RJ, Brazil, ^bUnidade Universitária de Farmácia, Fundaçõ Centro Universitário Estadual da Zona Oeste, 23070-200, Rio de Janeiro, RJ, Brazil, ^cFioCruz-Fundação Oswaldo Cruz, Instituto de Tecnologia em Fármacos-Far-Manguinhos, Rua Sizenando Nabuco, 100, Manguinhos, 21041-250, Rio de Janeiro, RJ, Brazil, ^dDepartment of Chemistry, University of Aberdeen, Old Aberdeen, AB24 3UE, Scotland, UK, and ^eCentre for Crystalline Materials, Faculty of Science and Technology, Sunway University, 47500 Bandar Sunway, Selangor Darul Ehsan, Malaysia
^*Correspondence e-mail: edwardt@sunway.edu.my

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 16 December 2015; accepted 20 December 2015; online 12 January 2016)

In the title compound, C₁₀H₁₀Cl₂N₄O, the hydroxy group and benzene ring are disposed to opposite sides of the central 1,2,3-triazolyl ring. The dihedral angle between the five- and six-membered rings is 87.51 (12)°, and the C—O bond of the hydroxy group lies almost normal to the plane of the 5-membered ring [N—C—C—O = −93.2 (2)°]. An intramolecular amino-N—H⋯Cl hydrogen bond is noted. In the extended structure, supramolecular layers in the ab plane are formed via hydroxy-O—H⋯N(ring) and amine-N—H⋯O(hydroxy) hydrogen bonds. The layers are connected along the c axis by π–π contacts between benzene rings [inter-centroid distance = 3.7789 (13) Å] and by C—Cl⋯π interactions.

Keywords: crystal structure; 1,2,3-triazolyl; alcohol; hydrogen bonding.

CCDC reference: 672063

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Chemical scheme

Structure description

1,2,3-Triazole derivatives attract continuing interest as a result of their biological activities (Dehaen & Bakulev, 2014 ). Diseases that have been evaluated recently include tuberculosis (Jordão et al., 2011 ), and the susceptibility of Cantagalo virus to 1,2,3-triazoles has also been investigated (Jordão et al., 2009 ). These studies have provided a number of crystals enabling systematic studies of the influence of the electronegativity of aryl-bound substituents upon crystal packing patterns (Cunha et al., 2013 ; Seth et al., 2015 ).

The central 1,2,3-triazolyl ring (r.m.s. deviation = 0.006 Å) in the title compound, Fig. 1, is flanked by C1-bound hydroxymethyl and N2-bound amino-2,5-dichlorobenzene substituents which lie to opposite sides of the ring. The C—O grouping of the hydroxyl group lies almost normal to the ring with the N4—C1—C10—O1 torsion angle being −93.2 (2)°. The dihedral angle between the triazolyl and benzene rings is 87.51 (12)°, with the latter being almost perpendicular, forming a N2—N1—C4—C5 torsion angle of −8.9 (3)°. This alignment allows for the formation of an intramolecular amino-N—H⋯Cl hydrogen bond, Table 1.

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the C4–C9 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N⋯Cl2	0.87 (2)	2.67 (2)	2.9530 (19)	100 (2)
O1—H1O⋯N4ⁱ	0.84 (2)	2.01 (2)	2.836 (2)	169 (2)
N1—H1N⋯O1ⁱⁱ	0.87 (2)	2.01 (2)	2.848 (3)	165 (2)
C6—Cl1⋯Cg1ⁱⁱⁱ	1.74 (1)	3.73 (1)	5.411 (3)	161 (1)
Symmetry codes: (i) $[-x+2, y-{\script{1\over 2}}, -z+{\script{5\over 2}}]$ ; (ii) -x+2, -y+1, -z+2; (iii) -x+1, -y+1, -z+2.

Figure 1
The molecular structure of the title compound showing the atom-labelling scheme and displacement ellipsoids at the 50% probability level.

In the molecular packing, the hydroxy group is pivotal in the hydrogen-bonding scheme, forming donor hydroxy-O—H⋯N(ring) and acceptor amine-N—H⋯O(hydroxy) interactions, Table 1. The latter interactions assemble molecules into dimers and these are in turn connected into supramolecular layers in the ab plane by the former interactions. The connections between layers are afforded by inter-digitating benzene rings via π—π contacts [inter-centroid distance = 3.7789 (13) Å for symmetry operation 1 − x, − $[{1\over 2}]$ + y, $[{3\over 2}]$ − z] and C—Cl⋯π interactions, Table 1 and Fig. 2.

Figure 2
A view of the unit cell contents of the title compound shown in projection down the b axis. The O—H⋯O, N—H⋯O, π—π and C—Cl⋯π interactions are shown as orange, blue, green and brown dashed lines, respectively.

Synthesis and crystallization

A solution of the desired 4-carbethoxy-triazole (Cunha et al., 2013) (1.00 mmol) in anhydrous THF (5 ml) was added dropwise to a suspension of LiAlH₄ (2 mmol) in anhydrous THF (10 ml) under a nitrogen atmosphere at 0°C. The reaction mixture was stirred at room temperature for 2 h, water (10 ml) was added, the aqueous layer acidified to pH 1 with 1 M HCl, and extracted with CH₂Cl₂ (3 ×). The organic extracts were combined, dried with Na₂SO₄, and concentrated under reduced pressure. The resulting residue was washed with hexane/dichloromethane (3:1) and dried under vacuum. 44% yield. Crystals were obtained from the slow evaporation of its methanol solution. M.p. 197°C. IR (KBr) ν_max (cm⁻¹): 3184 (N—H); 3096 (O—H). ¹H NMR (300 MHz, DMSO-d₆) δ: 2.18 (s, 3H, CH₃), 4.55 (d, 2H, J = 5.6 Hz, CH₂OH), 5.19 (t, 1H, J = 5.6 Hz, CH₂OH), 5.80 (d, 1H, J = 2.4 Hz, H5), 7.00 (dd, 1H, J = 2.4 & 8.5 Hz, H7), 7.50 (d, 1H, J = 8.5 Hz, H8), 10.21 (s, 1H, NH). ¹³C NMR (75 MHz, DMSO-d₆) δ: 6.8 (CH₃), 54.8 (CH₂), 112.4 (C5), 116.4 (C6), 121.5 (C7), 131.3 (C8), 132.0 (C9), 132.7 (C1or C2), 143.6 (C1 or C2), 143.7 (C4). Anal. calcd. For C₁₀H₁₀Cl₂N4O: C, 43.98; H, 3.69; N, 20.51. Found: C, 44.01; H, 3.72; N, 20.09.

Refinement

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

Table 2
Experimental details

Crystal data
Chemical formula	C₁₀H₁₀Cl₂N₄O
M_r	273.12
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	120
a, b, c (Å)	12.1802 (5), 7.3646 (4), 13.9001 (8)
β (°)	112.276 (3)
V (Å³)	1153.81 (11)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.55
Crystal size (mm)	0.26 × 0.18 × 0.16

Data collection
Diffractometer	Bruker–Nonius 95mm CCD camera on κ-goniostat diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2003 )
T_min, T_max	0.768, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	12461, 2645, 1963
R_int	0.062
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.117, 1.06
No. of reflections	2645
No. of parameters	161
No. of restraints	2
Δρ_max, Δρ_min (e Å⁻³)	0.33, −0.40
Computer programs: DENZO (Otwinowski & Minor, 1997 ) and COLLECT (Hooft, 1998 ), SHELXS97 (Sheldrick, 2008 ), SHELXL2014 (Sheldrick, 2015 ), ORTEP-3 for Windows (Farrugia, 2012 ), DIAMOND (Brandenburg, 2006 ), publCIF (Westrip, 2010 ).

Structural data

CCDC reference: 672063

Crystal structure: contains datablocks I, global. DOI: 10.1107/S2414314615024475/hb4004sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S2414314615024475/hb4004Isup2.hkl

Supporting information file. DOI: 10.1107/S2414314615024475/hb4004Isup3.cml

checkCIF report

Structural commentary top

1,2,3-Triazoles derivatives attract continuing interest as a result of their biological activities (Dehaen & Bakulev, 2014). Diseases that have been evaluated recently include tuberculosis (Jordão et al., 2011), and the susceptibility of Cantagalo virus to 1,2,3-triazoles has also been investigated (Jordão et al., 2009). These studies have provided a number of crystals enabling systematic studies of the influence of the electronegativity of aryl-bound substituents upon crystal packing patterns (Cunha et al., 2013; Seth et al., 2015).

The central 1,2,3-triazolyl ring (r.m.s. deviation = 0.006 Å) in the title compound, Fig. 1, is flanked by C1-bound hydroxymethyl and N2-bound amino-2,5-dichlorobenzene substituents which lie to opposite sides of the ring. The hydroxyl group lie almost normal to the ring with the N4—C1—C10—O1 torsion angle being -93.2 (2)°. The dihedral angle between the triazolyl and benzene rings is 87.51 (12)°, with the latter being almost perpendicular, forming a N2—N1—C4—C5 torsion angle of -8.9 (3)°. This alignment allows for the formation of an intramolecular amino-N—H···Cl hydrogen bond, Table 1.

In the molecular packing, the hydroxy group is pivotal in the hydrogen bonding scheme, forming donor hydroxy-O—H···N(ring) and acceptor amine-N—H···O(hydroxy) interactions, Table 1. The latter interactions assemble molecules into dimers and these are in turn connected into supramolecular layers in the ab plane by the former interactions. The connections between layers are afforded by inter-digitating benzene rings via π—π contacts (inter-centroid distance = 3.7789 (13) Å for symmetry operation 1-x, -1/2+y, 3/2-z) and C—Cl···π interactions, Table 1 and Fig. 2.

Synthesis and crystallization top

A solution of the desired 4-carbethoxy-triazole (Cunha et al., 2013) (1.00 mmol) in anhydrous THF (5 ml) was added drop-wise to a suspension of LiAlH₄ (2 mmol) in anhydrous THF (10 ml) under a nitrogen atmosphere at 0°C. The reaction mixture was stirred at room temperature for 2 h, water (10 ml) was added, the aqueous layer acidified to pH 1 with 1 M HCl, and extracted with CHCl₂ (3 ×). The organic extracts were combined, dried with Na₂SO₄, and concentrated under reduced pressure. The resulting residue was washed with hexane/dichloromethane (3:1) and dried under vacuum. 44% yield. Crystals were obtained from the slow evaporation of its methanol solution. M.pt: 197 °C. IR (KBr) ν_max (cm^-1): 3184 (N—H); 3096 (O—H). ¹H NMR (300 MHz, DMSO-d6) δ: 2.18 (s, 3H, CH₃), 4.55 (d, 2H, J = 5.6 Hz, CH₂OH), 5.19 (t, 1H, J = 5.6 Hz, CH₂OH), 5.80 (d, 1H, J = 2.4 Hz, H5), 7.00 (dd, 1H, J = 2.4 & 8.5 Hz, H7), 7.50 (d, 1H, J = 8.5 Hz, H8), 10.21 (s, 1H, NH). ¹³C NMR (75 MHz, DMSO-d6) δ: 6.8 (CH₃), 54.8 (CH₂), 112.4 (C5), 116.4 (C6), 121.5 (C7), 131.3 (C8), 132.0 (C9), 132.7 (C1or C2), 143.6 (C1 or C2), 143.7 (C4). Anal. Calcd. For C₁₀H₁₀Cl₂N4O: C, 43.98; H, 3.69; N, 20.51. Found: C, 44.01; H, 3.72; N, 20.09.

Refinement top

The carbon-bound H-atoms were placed in calculated positions (C—H = 0.93–0.98 Å) and were included in the refinement in the riding model approximation, with U_iso(H) set to 1.2–1.5U_equiv(C). The oxygen and nitrogen-bound H-atoms were located in a difference Fourier map but were refined with a distance restraints of O—H = 0.84±0.01 Å and N—H = 0.88±0.01 Å, and with U_iso(H) set to 1.5U_equiv(O) or 1.2U_equiv(N).

Experimental top

A solution of the desired 4-carbethoxy-triazole (Cunha et al., 2013) (1.00 mmol) in anhydrous THF (5 ml) was added dropwise to a suspension of LiAlH₄ (2 mmol) in anhydrous THF (10 ml) under a nitrogen atmosphere at 0°C. The reaction mixture was stirred at room temperature for 2 h, water (10 ml) was added, the aqueous layer acidified to pH 1 with 1 M HCl, and extracted with CHCl₂ (3 ×). The organic extracts were combined, dried with Na₂SO₄, and concentrated under reduced pressure. The resulting residue was washed with hexane/dichloromethane (3:1) and dried under vacuum. 44% yield. Crystals were obtained from the slow evaporation of its methanol solution. M.p. 197°C. IR (KBr) ν_max (cm^-1): 3184 (N—H); 3096 (O—H). ¹H NMR (300 MHz, DMSO-d₆) δ: 2.18 (s, 3H, CH₃), 4.55 (d, 2H, J = 5.6 Hz, CH₂OH), 5.19 (t, 1H, J = 5.6 Hz, CH₂OH), 5.80 (d, 1H, J = 2.4 Hz, H5), 7.00 (dd, 1H, J = 2.4 & 8.5 Hz, H7), 7.50 (d, 1H, J = 8.5 Hz, H8), 10.21 (s, 1H, NH). ¹³C NMR (75 MHz, DMSO-d₆) δ: 6.8 (CH₃), 54.8 (CH₂), 112.4 (C5), 116.4 (C6), 121.5 (C7), 131.3 (C8), 132.0 (C9), 132.7 (C1or C2), 143.6 (C1 or C2), 143.7 (C4). Anal. calcd. For C₁₀H₁₀Cl₂N4O: C, 43.98; H, 3.69; N, 20.51. Found: C, 44.01; H, 3.72; N, 20.09.

Structure description top

The central 1,2,3-triazolyl ring (r.m.s. deviation = 0.006 Å) in the title compound, Fig. 1, is flanked by C1-bound hydroxymethyl and N2-bound amino-2,5-dichlorobenzene substituents which lie to opposite sides of the ring. The C—O grouping of the hydroxyl group lies almost normal to the ring with the N4—C1—C10—O1 torsion angle being -93.2 (2)°. The dihedral angle between the triazolyl and benzene rings is 87.51 (12)°, with the latter being almost perpendicular, forming a N2—N1—C4—C5 torsion angle of -8.9 (3)°. This alignment allows for the formation of an intramolecular amino-N—H···Cl hydrogen bond, Table 1.

In the molecular packing, the hydroxy group is pivotal in the hydrogen-bonding scheme, forming donor hydroxy-O—H···N(ring) and acceptor amine-N—H···O(hydroxy) interactions, Table 1. The latter interactions assemble molecules into dimers and these are in turn connected into supramolecular layers in the ab plane by the former interactions. The connections between layers are afforded by inter-digitating benzene rings via π—π contacts [inter-centroid distance = 3.7789 (13) Å for symmetry operation 1 - x, -1/2 + y, 3/2 - z] and C—Cl···π interactions, Table 1 and Fig. 2.

Computing details top

Data collection: COLLECT (Hooft, 1998); cell refinement: DENZO (Otwinowski & Minor, 1997) and COLLECT (Hooft, 1998); data reduction: DENZO (Otwinowski & Minor, 1997) and COLLECT (Hooft, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); 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: publCIF (Westrip, 2010).

Figures top

	Fig. 1. The molecular structure of the title compound showing the atom-labelling scheme and displacement ellipsoids at the 50% probability level.
	Fig. 2. A view of the unit cell contents of the title compound shown in projection down the b axis. The O—H···O, N—H···O, π—π and C—Cl···π interactions are shown as orange, blue, green and brown dashed lines, respectively.

[1-(2,5-Dichloroanilino)-5-methyl-1H-1,2,3-triazol-4-yl]methanol top

Crystal data top

C₁₀H₁₀Cl₂N₄O	F(000) = 560
M_r = 273.12	D_x = 1.572 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71069 Å
a = 12.1802 (5) Å	Cell parameters from 2686 reflections
b = 7.3646 (4) Å	θ = 2.9–27.5°
c = 13.9001 (8) Å	µ = 0.55 mm⁻¹
β = 112.276 (3)°	T = 120 K
V = 1153.81 (11) Å³	Block, colourless
Z = 4	0.26 × 0.18 × 0.16 mm

Data collection top

Bruker-Nonius 95mm CCD camera on κ-goniostat diffractometer	2645 independent reflections
Radiation source: Bruker-Nonius FR591 rotating anode	1963 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.062
Detector resolution: 9.091 pixels mm^-1	θ_max = 27.5°, θ_min = 3.0°
φ & ω scans	h = −15→14
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −9→9
T_min = 0.768, T_max = 1.000	l = −18→17
12461 measured reflections

Refinement top

Refinement on F²	2 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.043	w = 1/[σ²(F_o²) + (0.0528P)² + 0.5445P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.117	(Δ/σ)_max = 0.001
S = 1.06	Δρ_max = 0.33 e Å⁻³
2645 reflections	Δρ_min = −0.40 e Å⁻³
161 parameters

Crystal data top

C₁₀H₁₀Cl₂N₄O	V = 1153.81 (11) Å³
M_r = 273.12	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 12.1802 (5) Å	µ = 0.55 mm⁻¹
b = 7.3646 (4) Å	T = 120 K
c = 13.9001 (8) Å	0.26 × 0.18 × 0.16 mm
β = 112.276 (3)°

Data collection top

Bruker-Nonius 95mm CCD camera on κ-goniostat diffractometer	2645 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	1963 reflections with I > 2σ(I)
T_min = 0.768, T_max = 1.000	R_int = 0.062
12461 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.043	161 parameters
wR(F²) = 0.117	2 restraints
S = 1.06	Δρ_max = 0.33 e Å⁻³
2645 reflections	Δρ_min = −0.40 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
Cl1	0.37932 (5)	0.38765 (8)	0.87969 (5)	0.02943 (19)
Cl2	0.68215 (5)	0.39438 (8)	0.60698 (4)	0.02549 (18)
O1	1.07381 (14)	0.3879 (2)	1.25648 (13)	0.0289 (4)
H1O	1.098 (2)	0.319 (3)	1.3086 (16)	0.043*
N1	0.78023 (15)	0.4396 (3)	0.83509 (14)	0.0188 (4)
H1N	0.8125 (19)	0.503 (3)	0.8004 (17)	0.023*
N2	0.82967 (15)	0.4789 (2)	0.94015 (13)	0.0163 (4)
N3	0.83152 (15)	0.6498 (2)	0.97786 (14)	0.0190 (4)
N4	0.87624 (15)	0.6334 (2)	1.07929 (14)	0.0190 (4)
C1	0.90092 (17)	0.4551 (3)	1.10644 (16)	0.0177 (5)
C2	0.87186 (17)	0.3534 (3)	1.01696 (17)	0.0175 (5)
C3	0.8799 (2)	0.1582 (3)	0.99578 (19)	0.0249 (5)
H3A	0.8016	0.1136	0.9502	0.037*
H3B	0.9070	0.0906	1.0614	0.037*
H3C	0.9364	0.1410	0.9617	0.037*
C4	0.65537 (18)	0.4209 (3)	0.79153 (16)	0.0164 (4)
C5	0.58710 (19)	0.4161 (3)	0.85238 (17)	0.0190 (5)
H5	0.6234	0.4282	0.9258	0.023*
C6	0.46531 (19)	0.3934 (3)	0.80412 (18)	0.0195 (5)
C7	0.40899 (19)	0.3747 (3)	0.69811 (18)	0.0227 (5)
H7	0.3252	0.3615	0.6670	0.027*
C8	0.4772 (2)	0.3757 (3)	0.63790 (18)	0.0231 (5)
H8	0.4404	0.3614	0.5647	0.028*
C9	0.59873 (19)	0.3976 (3)	0.68423 (17)	0.0185 (5)
C10	0.94792 (19)	0.3937 (3)	1.21697 (17)	0.0211 (5)
H10A	0.9215	0.4782	1.2592	0.025*
H10B	0.9164	0.2715	1.2216	0.025*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0241 (3)	0.0385 (4)	0.0300 (4)	−0.0026 (2)	0.0151 (3)	−0.0009 (3)
Cl2	0.0269 (3)	0.0356 (4)	0.0139 (3)	0.0017 (2)	0.0077 (2)	−0.0017 (2)
O1	0.0178 (8)	0.0412 (11)	0.0218 (9)	−0.0036 (7)	0.0011 (7)	0.0160 (7)
N1	0.0197 (9)	0.0277 (10)	0.0083 (9)	−0.0043 (7)	0.0045 (7)	−0.0016 (7)
N2	0.0177 (8)	0.0190 (10)	0.0111 (9)	−0.0001 (7)	0.0041 (7)	−0.0008 (7)
N3	0.0193 (9)	0.0213 (10)	0.0143 (10)	−0.0011 (7)	0.0038 (7)	−0.0008 (7)
N4	0.0195 (9)	0.0230 (10)	0.0128 (10)	−0.0006 (7)	0.0043 (7)	−0.0009 (7)
C1	0.0149 (10)	0.0225 (11)	0.0155 (11)	−0.0018 (8)	0.0055 (8)	0.0003 (9)
C2	0.0147 (10)	0.0228 (12)	0.0151 (11)	−0.0004 (8)	0.0060 (8)	0.0020 (9)
C3	0.0324 (13)	0.0213 (12)	0.0226 (13)	0.0030 (9)	0.0122 (10)	0.0026 (10)
C4	0.0161 (10)	0.0163 (10)	0.0142 (11)	0.0004 (8)	0.0030 (8)	0.0005 (8)
C5	0.0211 (11)	0.0224 (12)	0.0114 (11)	−0.0003 (8)	0.0037 (9)	−0.0013 (8)
C6	0.0193 (11)	0.0182 (11)	0.0224 (12)	−0.0003 (8)	0.0095 (9)	−0.0004 (9)
C7	0.0170 (11)	0.0217 (12)	0.0242 (13)	−0.0011 (8)	0.0020 (9)	−0.0015 (9)
C8	0.0248 (12)	0.0238 (12)	0.0143 (11)	0.0000 (9)	0.0002 (9)	−0.0013 (9)
C9	0.0232 (11)	0.0176 (11)	0.0146 (11)	0.0014 (8)	0.0070 (9)	−0.0002 (8)
C10	0.0201 (11)	0.0281 (13)	0.0140 (11)	−0.0008 (9)	0.0055 (9)	0.0014 (9)

Geometric parameters (Å, º) top

Cl1—C6	1.742 (2)	C3—H3A	0.9800
Cl2—C9	1.736 (2)	C3—H3B	0.9800
O1—C10	1.420 (3)	C3—H3C	0.9800
O1—H1O	0.839 (10)	C4—C5	1.393 (3)
N1—N2	1.383 (2)	C4—C9	1.396 (3)
N1—C4	1.414 (3)	C5—C6	1.387 (3)
N1—H1N	0.866 (10)	C5—H5	0.9500
N2—C2	1.357 (3)	C6—C7	1.376 (3)
N2—N3	1.361 (3)	C7—C8	1.385 (3)
N3—N4	1.310 (3)	C7—H7	0.9500
N4—C1	1.368 (3)	C8—C9	1.382 (3)
C1—C2	1.378 (3)	C8—H8	0.9500
C1—C10	1.492 (3)	C10—H10A	0.9900
C2—C3	1.478 (3)	C10—H10B	0.9900

C10—O1—H1O	109 (2)	C9—C4—N1	119.01 (18)
N2—N1—C4	116.08 (16)	C6—C5—C4	119.0 (2)
N2—N1—H1N	111.5 (16)	C6—C5—H5	120.5
C4—N1—H1N	117.1 (16)	C4—C5—H5	120.5
C2—N2—N3	112.40 (17)	C7—C6—C5	122.5 (2)
C2—N2—N1	124.87 (18)	C7—C6—Cl1	118.26 (16)
N3—N2—N1	122.50 (17)	C5—C6—Cl1	119.24 (17)
N4—N3—N2	105.56 (16)	C6—C7—C8	118.48 (19)
N3—N4—C1	110.12 (17)	C6—C7—H7	120.8
N4—C1—C2	108.56 (19)	C8—C7—H7	120.8
N4—C1—C10	122.24 (19)	C9—C8—C7	120.1 (2)
C2—C1—C10	129.2 (2)	C9—C8—H8	120.0
N2—C2—C1	103.36 (18)	C7—C8—H8	120.0
N2—C2—C3	122.65 (19)	C8—C9—C4	121.3 (2)
C1—C2—C3	134.0 (2)	C8—C9—Cl2	119.02 (17)
C2—C3—H3A	109.5	C4—C9—Cl2	119.63 (16)
C2—C3—H3B	109.5	O1—C10—C1	110.11 (17)
H3A—C3—H3B	109.5	O1—C10—H10A	109.6
C2—C3—H3C	109.5	C1—C10—H10A	109.6
H3A—C3—H3C	109.5	O1—C10—H10B	109.6
H3B—C3—H3C	109.5	C1—C10—H10B	109.6
C5—C4—C9	118.58 (19)	H10A—C10—H10B	108.2
C5—C4—N1	122.34 (19)

C4—N1—N2—C2	93.4 (2)	N2—N1—C4—C9	174.27 (18)
C4—N1—N2—N3	−80.6 (2)	C9—C4—C5—C6	−1.7 (3)
C2—N2—N3—N4	0.6 (2)	N1—C4—C5—C6	−178.6 (2)
N1—N2—N3—N4	175.36 (16)	C4—C5—C6—C7	0.2 (3)
N2—N3—N4—C1	−1.0 (2)	C4—C5—C6—Cl1	−179.89 (16)
N3—N4—C1—C2	1.0 (2)	C5—C6—C7—C8	1.1 (3)
N3—N4—C1—C10	−177.30 (18)	Cl1—C6—C7—C8	−178.78 (17)
N3—N2—C2—C1	0.0 (2)	C6—C7—C8—C9	−0.9 (3)
N1—N2—C2—C1	−174.61 (17)	C7—C8—C9—C4	−0.7 (3)
N3—N2—C2—C3	−179.43 (18)	C7—C8—C9—Cl2	178.92 (17)
N1—N2—C2—C3	6.0 (3)	C5—C4—C9—C8	2.0 (3)
N4—C1—C2—N2	−0.6 (2)	N1—C4—C9—C8	178.94 (19)
C10—C1—C2—N2	177.57 (19)	C5—C4—C9—Cl2	−177.60 (16)
N4—C1—C2—C3	178.7 (2)	N1—C4—C9—Cl2	−0.6 (3)
C10—C1—C2—C3	−3.1 (4)	N4—C1—C10—O1	−93.2 (2)
N2—N1—C4—C5	−8.9 (3)	C2—C1—C10—O1	88.9 (3)

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of the C4–C9 ring.

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···Cl2	0.87 (2)	2.67 (2)	2.9530 (19)	100 (2)
O1—H1O···N4ⁱ	0.84 (2)	2.01 (2)	2.836 (2)	169 (2)
N1—H1N···O1ⁱⁱ	0.87 (2)	2.01 (2)	2.848 (3)	165 (2)
C6—Cl1···Cg1ⁱⁱⁱ	1.74 (1)	3.73 (1)	5.411 (3)	161 (1)

Symmetry codes: (i) −x+2, y−1/2, −z+5/2; (ii) −x+2, −y+1, −z+2; (iii) −x+1, −y+1, −z+2.

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of the C4–C9 ring.

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···Cl2	0.87 (2)	2.67 (2)	2.9530 (19)	100.2 (17)
O1—H1O···N4ⁱ	0.84 (2)	2.01 (2)	2.836 (2)	169 (2)
N1—H1N···O1ⁱⁱ	0.87 (2)	2.01 (2)	2.848 (3)	165 (2)
C6—Cl1···Cg1ⁱⁱⁱ	1.742 (2)	3.7326 (12)	5.411 (3)	161.12 (8)

Symmetry codes: (i) −x+2, y−1/2, −z+5/2; (ii) −x+2, −y+1, −z+2; (iii) −x+1, −y+1, −z+2.

Experimental details

Crystal data
Chemical formula	C₁₀H₁₀Cl₂N₄O
M_r	273.12
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	120
a, b, c (Å)	12.1802 (5), 7.3646 (4), 13.9001 (8)
β (°)	112.276 (3)
V (Å³)	1153.81 (11)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.55
Crystal size (mm)	0.26 × 0.18 × 0.16

Data collection
Diffractometer	Bruker-Nonius 95mm CCD camera on κ-goniostat
Absorption correction	Multi-scan (SADABS; Sheldrick, 2003)
T_min, T_max	0.768, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	12461, 2645, 1963
R_int	0.062
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.117, 1.06
No. of reflections	2645
No. of parameters	161
No. of restraints	2
Δρ_max, Δρ_min (e Å⁻³)	0.33, −0.40

Computer programs: DENZO (Otwinowski & Minor, 1997) and COLLECT (Hooft, 1998), SHELXS97 (Sheldrick, 2008), SHELXL2014 (Sheldrick, 2015), ORTEP-3 for Windows (Farrugia, 2012) and DIAMOND (Brandenburg, 2006), publCIF (Westrip, 2010).

Footnotes

‡Additional correspondence author, e-mail: j.wardell@abdn.ac.uk.

Acknowledgements

This work was supported by the Brazilian agency FAPERJ. Fellowships granted to Universidade Federal Fluminense by FAPERJ, CAPES and CNPq-PIBIC are gratefully acknowledged.

References

Brandenburg, K. (2006). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Cunha, A. C., Ferreira, V. F., Jordão, A. K., de Souza, M. C. B. V., Wardell, S. M. S. V., Wardell, J. L., Tan, P. A., Bettens, R. P. A., Seth, S. K. & Tiekink, E. R. T. (2013). CrystEngComm, 15, 4917–4929. Web of Science CSD CrossRef CAS Google Scholar
Dehaen, W. & Bakulev, V. A. (2014). Chemistry of 1,2,3-triazoles. Topics in Heterocyclic Chemistry, Vol. 40. Berlin Heidleberg: Springer-Verlag. Google Scholar
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854. Web of Science CrossRef CAS IUCr Journals Google Scholar
Hooft, R. W. W. (1998). COLLECT. Nonius BV, Delft, The Netherlands. Google Scholar
Jordão, A. K., Afonso, P. P., Ferreira, V. F., de Souza, M. C., Almeida, M. C., Beltrame, C. O., Paiva, D. P., Wardell, S. M. S. V., Wardell, J. L., Tiekink, E. R. T., Damaso, R. & Cunha, A. C. (2009). Eur. J. Med. Chem. 44, 3777–3783. Web of Science PubMed Google Scholar
Jordão, A. K., Sathler, P. C., Ferreira, V. F., Campos, V. R., de Souza, M. C. B. V., Castro, H. C., Lannes, A., Lourenco, A., Rodrigues, C. R., Bello, M. L., Lourenco, M. C. S., Carvalho, G. S. L., Almeida, M. C. B. & Cunha, A. C. (2011). Bioorg. Med. Chem. 19, 5605–5611. Web of Science PubMed Google Scholar
Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307–326. New York: Academic Press. Google Scholar
Seth, S. K., Lee, V. S., Yana, J., Zain, S. M., Cunha, A. C., Ferreira, V. F., Jordão, A. K., de Souza, M. C. B. V., Wardell, S. M. S. V., Wardell, J. L. & Tiekink, E. R. T. (2015). CrystEngComm, 17, 2255–2266. Web of Science CSD CrossRef CAS Google Scholar
Sheldrick, G. M. (2003). 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
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar

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