3,3′-Dimethyl-4,4′-(hexane-1,6-di­yl)bis­[1H-1,2,4-triazol-5(4H)-one]

Ustabaş, R.; Çoruh, U.; Ünlüer, D.; Hökelek, T.; Ermiş, E.

doi:10.1107/S1600536810037311

organic compounds

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doi:10.1107/S1600536810037311

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3,3′-Dimethyl-4,4′-(hexane-1,6-diyl)bis[1H-1,2,4-triazol-5(4H)-one]

Reşat Ustabaş,^a Ufuk Çoruh,^b ^* Dilek Ünlüer,^c Tuncer Hökelek ^d and Emel Ermiş ^e

^aDepartment of Middle Education, Educational Faculty, Ondokuz Mayıs University, 55200 Atakum, Samsun, Turkey, ^bDepartment of Computer Education and Instructional Technology, Educational Faculty, Ondokuz Mayıs University, 55200 Atakum, Samsun, Turkey, ^cDepartment of Chemistry, Faculty of Arts and Sciences, Karadeniz Teknik University, 61080 Trabzon, Turkey, ^dDepartment of Physics, Hacettepe University, Beytepe 06800, Ankara, Turkey, and ^eAnadolu University, Faculty of Science, Department of Chemistry, 26470 Yenibaĝlar, Eskişehir, Turkey
^*Correspondence e-mail: ucoruh@omu.edu.tr

(Received 7 September 2010; accepted 17 September 2010; online 25 September 2010)

The title compound, C₁₂H₂₀N₆O₂, has a centre of symmetry. The molecule consists of two triazole rings joined by an aliphatic –(CH₂)₆– chain. The crystal structure is stabilized by intermolecular N—H⋯O hydrogen bonds and by π–π stacking interactions between the triazole rings of inversion-related molecules [centroid–centroid distance = 3.277 (8) Å].

Related literature

For background information including pharmacological studies, see: Chiu & Huskey (1998 ); Clemons et al. (2004 ); Dalloul & Boyle (2006 ); Eliott et al. (1986 ); Griffin & Mannion (1986 ); Santen (2003 ); Tanaka (1974 ); Zamani et al. (2003 ). Related structures have been reported by Ustabaş et al. (2006 , 2007 , 2009 ); Ünver et al. (2008 , 2009 ); Çoruh et al. (2003 ).

Experimental

Crystal data

C₁₂H₂₀N₆O₂
M_r = 280.34
Triclinic, $[P \overline 1]$
a = 6.3641 (2) Å
b = 7.3034 (2) Å
c = 7.7774 (2) Å
α = 93.299 (2)°
β = 109.578 (2)°
γ = 94.707 (2)°
V = 338.05 (2) Å³
Z = 1
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 101 K
0.40 × 0.16 × 0.12 mm

Data collection

Bruker Kappa APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2007 ) T_min = 0.962, T_max = 0.988
6074 measured reflections
1673 independent reflections
1309 reflections with I > 2σ(I)
R_int = 0.033

Refinement

R[F² > 2σ(F²)] = 0.041
wR(F²) = 0.112
S = 1.03
1673 reflections
131 parameters
All H-atom parameters refined
Δρ_max = 0.32 e Å⁻³
Δρ_min = −0.28 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3⋯O1ⁱ	0.90 (2)	1.89 (2)	2.7707 (15)	167 (2)
Symmetry code: (i) -x+1, -y, -z+2.

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810037311/pk2267sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810037311/pk2267Isup2.hkl

checkCIF report

Comment top

The 1,2,4-triazole compounds possess important pharmacological activities that include antifungal and antiviral properties. Examples of compounds bearing the 1,2,4-triazole group are fluconazole, the powerful azole antifungal agent as well as the potent antiviral N– nucleoside ribavirin (Ünver et al., 2008; Ünver et al., 2009). Furthermore, various 1,2,4-triazole derivatives have been reported as fungicidal (Zamani et al., 2003), insecticidal (Tanaka, 1974), antimicrobial (Griffin & Mannion, 1986), and some showed antitumor activity as well as having anticonvulsant (Dalloul & Boyle, 2006), antidepressant (Chiu & Huskey, 1998) and plant growth regulator anticoagulant activity (Eliott et al., 1986). It was reported that compounds having triazole moieties, such as Vorozole, Anastrozole and Letrozole appear to be very effective aromatase inhibitors and can be useful for preventing breast cancer (Santen, 2003; Clemons et al., 2004).

The molecular structure of the compound is shown in Fig.1. The molecule consists of two triazole rings, joined by an aliphatic —(CH₂)₆— chain connected to nitrogen atoms of the rings. The molecule has an inversion center in the middle of the chain, that connects the triazole rings. The length of the N═C [N2═C5= 1.3031 (17) Å] bond in the triazole ring is close to the those similar structures in the literature [1.296 (3)Å in C₁₄H₁₆N₆O₂S (Ustabaş et al., 2007); 1.288 (2)Å in C₁₆H₂₈N₆O₂ (Çoruh et al., 2003)]. The bond length of O═C [O1═C1= 1.2421 (16) Å] is in conformity with the values mentioned before[1.218 (3)Å in C₁₆H₂₀N₆O₂S (Ustabaş et al., 2006); 1.220 (2)Å in C₂₄H₂₀N₄O₂S (Ustabaş et al., 2009)]. The triazole ring is very close to planarity, with a maximum deviation from the least-squares plane of -0.014 (13)Å for atom C1.

In the crystal structure of the compound, there is a strong intermolecular N3—H3···O1 hydrogen-bonding interaction (Table 1). The compound also exhibits π-π stacking interactions between triazole rings (Cg1···Cg1= 3.277 (8) Å; symmetry code: –X, 2-Y, –Z).

Related literature top

For background information including pharmacological studies, see: Chiu & Huskey (1998); Clemons et al. (2004); Dalloul & Boyle (2006); Eliott et al. (1986); Griffin & Mannion (1986); Santen (2003); Tanaka (1974); Zamani et al. (2003). Related structures have been reported by Ustabaş et al. (2006, 2007, 2009); Ünver et al. (2008, 2009); Çoruh et al. (2003).

Experimental top

The synthesis of 4,4'-(hexane-1,6-diyl)bis (5-ethyl-2H-1,2,4-triazol-3(4H)-one) to a solution of ethyl 2 (1-ethoxyethylidene)hydrazinecarboxylate (0.02 mol) in 50 ml water hexane-1,6-diamine (0.01 mol) was added. Having refluxed this mixture for 4 h the precipitate formed was filtered off. The solid product was washed with water and crystallized from ethanol/water (1/3)(yield 73.25%) to afford the desired compound.

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

	Fig. 1. An ellipsoid plot of the title compound, with the atom numbering scheme. Atoms with primed labels are related via an inversion center (1-x, 1-y, 1-z). Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. A packing diagram, viewed along b.

3,3'-Dimethyl-4,4'-(hexane-1,6-diyl)bis[1H-1,2,4-triazol- 5(4H)-one] top

Crystal data top

C₁₂H₂₀N₆O₂	Z = 1
M_r = 280.34	F(000) = 150
Triclinic, P1	D_x = 1.377 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.3641 (2) Å	Cell parameters from 1309 reflections
b = 7.3034 (2) Å	θ = 2.8–28.3°
c = 7.7774 (2) Å	µ = 0.10 mm⁻¹
α = 93.299 (2)°	T = 101 K
β = 109.578 (2)°	Rod-shaped, colorless
γ = 94.707 (2)°	0.40 × 0.16 × 0.12 mm
V = 338.05 (2) Å³

Data collection top

Bruker Kappa APEXII CCD area-detector diffractometer	1673 independent reflections
Radiation source: fine-focus sealed tube	1309 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.033
ϕ and ω scans	θ_max = 28.3°, θ_min = 2.8°
Absorption correction: multi-scan (SADABS; Bruker, 2007)	h = −8→8
T_min = 0.962, T_max = 0.988	k = −9→9
6074 measured reflections	l = −10→10

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.112	All H-atom parameters refined
S = 1.03	w = 1/[σ²(F_o²) + (0.062P)² + 0.0594P] where P = (F_o² + 2F_c²)/3
1673 reflections	(Δ/σ)_max < 0.001
131 parameters	Δρ_max = 0.32 e Å⁻³
0 restraints	Δρ_min = −0.28 e Å⁻³

Crystal data top

C₁₂H₂₀N₆O₂	γ = 94.707 (2)°
M_r = 280.34	V = 338.05 (2) Å³
Triclinic, P1	Z = 1
a = 6.3641 (2) Å	Mo Kα radiation
b = 7.3034 (2) Å	µ = 0.10 mm⁻¹
c = 7.7774 (2) Å	T = 101 K
α = 93.299 (2)°	0.40 × 0.16 × 0.12 mm
β = 109.578 (2)°

Data collection top

Bruker Kappa APEXII CCD area-detector diffractometer	1673 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2007)	1309 reflections with I > 2σ(I)
T_min = 0.962, T_max = 0.988	R_int = 0.033
6074 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.041	0 restraints
wR(F²) = 0.112	All H-atom parameters refined
S = 1.03	Δρ_max = 0.32 e Å⁻³
1673 reflections	Δρ_min = −0.28 e Å⁻³
131 parameters

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s 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 > σ(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
O1	0.49741 (15)	0.02539 (13)	0.76514 (13)	0.0199 (3)
N1	0.84928 (18)	0.18555 (15)	0.81036 (15)	0.0159 (3)
N2	0.98018 (18)	0.22436 (15)	1.11442 (15)	0.0183 (3)
N3	0.76344 (18)	0.13460 (15)	1.04956 (15)	0.0173 (3)
C1	0.6815 (2)	0.10507 (17)	0.86549 (18)	0.0162 (3)
C2	0.8354 (2)	0.1878 (2)	0.61861 (18)	0.0189 (3)
C3	0.7642 (2)	0.36813 (19)	0.54057 (19)	0.0202 (3)
C4	0.5280 (2)	0.40487 (19)	0.53108 (19)	0.0193 (3)
C5	1.0248 (2)	0.25341 (17)	0.96590 (18)	0.0166 (3)
C6	1.2408 (2)	0.3456 (2)	0.9639 (2)	0.0207 (3)
H21	0.981 (3)	0.163 (2)	0.609 (2)	0.019 (4)*
H61	1.220 (3)	0.461 (3)	0.914 (2)	0.030 (4)*
H32	0.772 (3)	0.361 (2)	0.415 (2)	0.025 (4)*
H41	0.512 (3)	0.397 (2)	0.655 (2)	0.018 (4)*
H31	0.876 (3)	0.476 (2)	0.614 (2)	0.028 (4)*
H42	0.414 (3)	0.309 (2)	0.446 (2)	0.022 (4)*
H22	0.732 (3)	0.087 (2)	0.551 (2)	0.025 (4)*
H3	0.696 (3)	0.089 (2)	1.125 (3)	0.036 (5)*
H62	1.310 (3)	0.273 (3)	0.887 (3)	0.035 (5)*
H63	1.348 (3)	0.368 (3)	1.093 (3)	0.041 (5)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0140 (5)	0.0240 (5)	0.0184 (5)	−0.0042 (4)	0.0030 (4)	0.0004 (4)
N1	0.0126 (6)	0.0162 (6)	0.0181 (6)	0.0005 (4)	0.0043 (5)	0.0024 (4)
N2	0.0123 (6)	0.0186 (6)	0.0213 (6)	−0.0005 (4)	0.0028 (5)	0.0012 (4)
N3	0.0127 (6)	0.0192 (6)	0.0183 (6)	−0.0006 (4)	0.0035 (5)	0.0026 (4)
C1	0.0134 (6)	0.0150 (6)	0.0197 (7)	0.0028 (5)	0.0047 (5)	0.0025 (5)
C2	0.0156 (7)	0.0230 (7)	0.0169 (7)	−0.0009 (6)	0.0049 (5)	−0.0001 (5)
C3	0.0163 (7)	0.0237 (7)	0.0202 (7)	−0.0017 (6)	0.0065 (6)	0.0039 (6)
C4	0.0160 (7)	0.0213 (7)	0.0184 (7)	−0.0029 (5)	0.0039 (6)	0.0035 (5)
C5	0.0130 (6)	0.0153 (6)	0.0198 (7)	0.0033 (5)	0.0028 (5)	0.0018 (5)
C6	0.0131 (7)	0.0208 (7)	0.0261 (8)	−0.0005 (5)	0.0045 (6)	0.0021 (6)

Geometric parameters (Å, º) top

O1—C1	1.2421 (16)	C3—C4	1.5271 (19)
N1—C5	1.3751 (17)	C3—H32	0.991 (16)
N1—C1	1.3794 (16)	C3—H31	1.017 (18)
N1—C2	1.4653 (16)	C4—C4ⁱ	1.528 (3)
N2—C5	1.3031 (17)	C4—H41	1.007 (15)
N2—N3	1.3907 (15)	C4—H42	1.000 (17)
N3—C1	1.3467 (18)	C5—C6	1.4856 (19)
N3—H3	0.902 (19)	C6—H61	0.952 (18)
C2—C3	1.521 (2)	C6—H62	1.006 (18)
C2—H21	0.985 (15)	C6—H63	1.00 (2)
C2—H22	0.945 (18)

C5—N1—C1	107.39 (11)	C2—C3—H31	110.3 (10)
C5—N1—C2	128.60 (11)	C4—C3—H31	109.3 (9)
C1—N1—C2	123.98 (11)	H32—C3—H31	107.2 (13)
C5—N2—N3	103.79 (11)	C3—C4—C4ⁱ	112.27 (14)
C1—N3—N2	112.63 (11)	C3—C4—H41	110.2 (9)
C1—N3—H3	124.9 (12)	C4ⁱ—C4—H41	108.2 (8)
N2—N3—H3	122.0 (12)	C3—C4—H42	110.5 (9)
O1—C1—N3	128.98 (12)	C4ⁱ—C4—H42	109.0 (9)
O1—C1—N1	126.86 (12)	H41—C4—H42	106.5 (13)
N3—C1—N1	104.16 (11)	N2—C5—N1	111.99 (11)
N1—C2—C3	112.31 (11)	N2—C5—C6	124.26 (13)
N1—C2—H21	108.9 (9)	N1—C5—C6	123.74 (12)
C3—C2—H21	111.3 (9)	C5—C6—H61	110.6 (10)
N1—C2—H22	107.6 (10)	C5—C6—H62	113.5 (10)
C3—C2—H22	110.7 (10)	H61—C6—H62	105.9 (14)
H21—C2—H22	105.8 (13)	C5—C6—H63	108.9 (11)
C2—C3—C4	114.14 (11)	H61—C6—H63	108.3 (15)
C2—C3—H32	106.5 (9)	H62—C6—H63	109.6 (14)
C4—C3—H32	109.1 (9)

C5—N2—N3—C1	1.87 (14)	N1—C2—C3—C4	−64.04 (15)
N2—N3—C1—O1	178.11 (12)	C2—C3—C4—C4ⁱ	174.64 (14)
N2—N3—C1—N1	−2.33 (14)	N3—N2—C5—N1	−0.58 (14)
C5—N1—C1—O1	−178.57 (12)	N3—N2—C5—C6	−179.47 (12)
C2—N1—C1—O1	−0.5 (2)	C1—N1—C5—N2	−0.81 (15)
C5—N1—C1—N3	1.86 (13)	C2—N1—C5—N2	−178.77 (12)
C2—N1—C1—N3	179.93 (11)	C1—N1—C5—C6	178.09 (12)
C5—N1—C2—C3	−84.62 (16)	C2—N1—C5—C6	0.1 (2)
C1—N1—C2—C3	97.73 (14)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3···O1ⁱⁱ	0.90 (2)	1.89 (2)	2.7707 (15)	167 (2)

Symmetry code: (ii) −x+1, −y, −z+2.

Experimental details

Crystal data
Chemical formula	C₁₂H₂₀N₆O₂
M_r	280.34
Crystal system, space group	Triclinic, P1
Temperature (K)	101
a, b, c (Å)	6.3641 (2), 7.3034 (2), 7.7774 (2)
α, β, γ (°)	93.299 (2), 109.578 (2), 94.707 (2)
V (Å³)	338.05 (2)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.40 × 0.16 × 0.12

Data collection
Diffractometer	Bruker Kappa APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2007)
T_min, T_max	0.962, 0.988
No. of measured, independent and observed [I > 2σ(I)] reflections	6074, 1673, 1309
R_int	0.033
(sin θ/λ)_max (Å⁻¹)	0.667

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.041, 0.112, 1.03
No. of reflections	1673
No. of parameters	131
H-atom treatment	All H-atom parameters refined
Δρ_max, Δρ_min (e Å⁻³)	0.32, −0.28

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3···O1ⁱ	0.90 (2)	1.89 (2)	2.7707 (15)	167 (2)

Symmetry code: (i) −x+1, −y, −z+2.

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