N-[4-(Dimethyl­amino)­benzyl­idene]-4H-1,2,4-triazol-4-amine

Zhou, H.-L.; Zhang, X.-M.

doi:10.1107/S1600536812014511

organic compounds

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Volume 68| Part 5| May 2012| Page o1343

doi:10.1107/S1600536812014511

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N-[4-(Dimethylamino)benzylidene]-4H-1,2,4-triazol-4-amine

Hui-Liang Zhou ^a ^* and Xiao-Min Zhang ^a

^aCollege of Chemistry and Chemical Engineering, Ningxia University, Yinchuan 750021, Ninxia, People's Republic of China
^*Correspondence e-mail: zhouhl@nxu.edu.cn

(Received 1 April 2012; accepted 3 April 2012; online 13 April 2012)

The title compound, C₁₁H₁₃N₅, is a Schiff base synthesized by the reaction of 4-amino-4H-1,2,4-triazole and 4-(dimethylamino)benzaldehyde. The dihedral angle between the benzene and triazole rings is 43.09 (11)°. The crystal structure displays weak C—H⋯N interactions.

Related literature

For the biological activity of triazole derivatives, see: Modzelewska & Kalabun (1999 ); Rollas et al. (1993 ); Todoulou et al. (1994 ); Demirbas et al. (2002 ); Kahveci et al. (2003 ). For 4-amino-1,2,4-triazole Schiff bases, see: Desenko & Khim (1995 ); Kargin et al. (1988 ).

Experimental

Crystal data

C₁₁H₁₃N₅
M_r = 215.26
Monoclinic, P 2₁ /c
a = 10.3665 (16) Å
b = 11.1585 (19) Å
c = 9.5248 (12) Å
β = 90.257 (1)°
V = 1101.8 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 298 K
0.52 × 0.15 × 0.11 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2002 ) T_min = 0.957, T_max = 0.991
5465 measured reflections
1940 independent reflections
1184 reflections with I > 2σ(I)
R_int = 0.062

Refinement

R[F² > 2σ(F²)] = 0.047
wR(F²) = 0.119
S = 1.00
1940 reflections
148 parameters
H-atom parameters constrained
Δρ_max = 0.17 e Å⁻³
Δρ_min = −0.18 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1⋯N4ⁱ	0.93	2.57	3.448 (3)	157
C2—H2⋯N2ⁱⁱ	0.93	2.43	3.284 (3)	152
C11—H11B⋯N1ⁱⁱⁱ	0.96	2.60	3.543 (3)	166
Symmetry codes: (i) -x+1, -y, -z+1; (ii) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (iii) x+1, y, z+1.

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812014511/ff2062sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812014511/ff2062Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812014511/ff2062Isup3.cml

checkCIF report

Comment top

1,2,4-Triazole and their derivatives have been used as starting materials for synthesis of many heterocycles. The aroyl Schiff bases of 4-amino-1,2,4-triazole have received considerable attention over the past few decades (Desenko et al., 1995; Kargin et al., 1988; Modzelewska & Kalabun, 1999). In recent years, various 1,2,4-triazoles and their derivatives have been found to be associated with diverse pharmacological activities such as anticonvulsant, antifungal, anticancer, anti-inflammatory and antibacterial (Rollas et al., 1993; Todoulou et al., 1994). The present X-ray crystal structure analysis was undertaken in order to study the stereochemistry and crystal packing of the title compound (I).

The molecular structure and the atom-numbering scheme of the title compound are shown in Fig. 1. In the molecule, all bond lengths and angles are normal. As shown in Fig 1, the title compound is composed of two planar segments. One segment is a triazole ring, which is contains N3, C1, N2, C2, N1, and another segment is a benzene ring. The dihedral angle between the two planar segments is 43.09 (11)°. In the triazole ring, the N1=C2 and N2=C1 bonds display double-bond character, with bond distances of 1.303 (3) and 1.295 (2) Å, respectively.

Related literature top

For the biological activity of triazole derivatives, see: Modzelewska & Kalabun (1999); Rollas et al. (1993); Todoulou et al. (1994); Demirbas et al. (2002); Kahveci et al. (2003). For 4-amino-1,2,4-triazole Schiff bases, see: Desenko & Khim (1995); Kargin et al. (1988).

Experimental top

A mixture of 4-amino-4H-1,2,4-triazole 1 (0.51 g, 6 mmol) and 4-Dimethylaminobenzaldehyde (0.85 g, 6 mmol) was reacted in 40 ml ethanol at 353 K for 0.3 h. Single crystals suitable for X-ray diffraction analysis were obtained by slow evaporation of the ethanol solution.

Computing details top

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT (Bruker, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of the title compound, showing 30% displacement ellipsoids for the non-hydrogen atoms. Hydrogen atoms are drawn as spheres of arbitrary radius.

N-[4-(Dimethylamino)benzylidene]-4H-1,2,4-triazol-4-amine top

Crystal data top

C₁₁H₁₃N₅	F(000) = 456
M_r = 215.26	D_x = 1.298 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1214 reflections
a = 10.3665 (16) Å	θ = 2.7–23.0°
b = 11.1585 (19) Å	µ = 0.08 mm⁻¹
c = 9.5248 (12) Å	T = 298 K
β = 90.257 (1)°	Cuboid, colourless
V = 1101.8 (3) Å³	0.52 × 0.15 × 0.11 mm
Z = 4

Data collection top

Bruker SMART CCD area-detector diffractometer	1940 independent reflections
Radiation source: fine-focus sealed tube	1184 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.062
phi and ω scans	θ_max = 25.0°, θ_min = 2.0°
Absorption correction: multi-scan (SADABS; Bruker, 2002)	h = −12→12
T_min = 0.957, T_max = 0.991	k = −13→9
5465 measured reflections	l = −11→11

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.047	H-atom parameters constrained
wR(F²) = 0.119	w = 1/[σ²(F_o²) + (0.0462P)²] where P = (F_o² + 2F_c²)/3
S = 1.00	(Δ/σ)_max < 0.001
1940 reflections	Δρ_max = 0.17 e Å⁻³
148 parameters	Δρ_min = −0.18 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.086 (5)

Crystal data top

C₁₁H₁₃N₅	V = 1101.8 (3) Å³
M_r = 215.26	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 10.3665 (16) Å	µ = 0.08 mm⁻¹
b = 11.1585 (19) Å	T = 298 K
c = 9.5248 (12) Å	0.52 × 0.15 × 0.11 mm
β = 90.257 (1)°

Data collection top

Bruker SMART CCD area-detector diffractometer	1940 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2002)	1184 reflections with I > 2σ(I)
T_min = 0.957, T_max = 0.991	R_int = 0.062
5465 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.047	0 restraints
wR(F²) = 0.119	H-atom parameters constrained
S = 1.00	Δρ_max = 0.17 e Å⁻³
1940 reflections	Δρ_min = −0.18 e Å⁻³
148 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
N1	0.20167 (17)	0.23656 (19)	0.4358 (2)	0.0665 (6)
N2	0.24339 (17)	0.13578 (17)	0.36475 (19)	0.0599 (5)
N3	0.34969 (14)	0.14765 (14)	0.56204 (17)	0.0461 (4)
N4	0.43764 (14)	0.11434 (15)	0.66817 (17)	0.0498 (5)
N5	0.87803 (15)	0.16192 (15)	1.14369 (18)	0.0590 (5)
C1	0.33047 (19)	0.08539 (19)	0.4428 (2)	0.0540 (6)
H1	0.3740	0.0154	0.4195	0.065*
C2	0.26690 (19)	0.2406 (2)	0.5530 (2)	0.0588 (6)
H2	0.2576	0.2996	0.6212	0.071*
C3	0.49452 (17)	0.20274 (18)	0.7270 (2)	0.0469 (5)
H3	0.4751	0.2797	0.6959	0.056*
C4	0.58726 (17)	0.18934 (17)	0.8392 (2)	0.0437 (5)
C5	0.61841 (19)	0.07978 (19)	0.8997 (2)	0.0539 (6)
H5	0.5744	0.0114	0.8707	0.065*
C6	0.7122 (2)	0.06956 (19)	1.0008 (2)	0.0581 (6)
H6	0.7301	−0.0051	1.0396	0.070*
C7	0.78200 (17)	0.17091 (18)	1.0468 (2)	0.0458 (5)
C8	0.74731 (17)	0.28123 (18)	0.9884 (2)	0.0491 (6)
H8	0.7890	0.3504	1.0186	0.059*
C9	0.65320 (18)	0.28964 (18)	0.8876 (2)	0.0477 (6)
H9	0.6329	0.3644	0.8505	0.057*
C10	0.9193 (3)	0.0473 (2)	1.1988 (3)	0.0853 (9)
H10A	0.8525	0.0144	1.2566	0.128*
H10B	0.9963	0.0579	1.2539	0.128*
H10C	0.9366	−0.0064	1.1224	0.128*
C11	0.9429 (2)	0.2687 (2)	1.1945 (2)	0.0691 (7)
H11A	0.9861	0.3074	1.1180	0.104*
H11B	1.0049	0.2468	1.2652	0.104*
H11C	0.8806	0.3225	1.2340	0.104*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0658 (12)	0.0829 (14)	0.0507 (13)	0.0148 (10)	−0.0210 (10)	−0.0039 (11)
N2	0.0641 (11)	0.0706 (13)	0.0448 (12)	−0.0003 (10)	−0.0169 (9)	0.0003 (10)
N3	0.0464 (9)	0.0559 (11)	0.0359 (10)	−0.0001 (8)	−0.0119 (8)	0.0019 (9)
N4	0.0521 (10)	0.0569 (11)	0.0403 (11)	0.0002 (8)	−0.0165 (8)	0.0024 (9)
N5	0.0578 (10)	0.0678 (13)	0.0512 (12)	0.0076 (10)	−0.0251 (9)	−0.0019 (10)
C1	0.0651 (13)	0.0536 (13)	0.0432 (14)	−0.0038 (11)	−0.0132 (11)	−0.0005 (11)
C2	0.0547 (13)	0.0712 (16)	0.0503 (15)	0.0103 (12)	−0.0140 (11)	−0.0079 (12)
C3	0.0441 (11)	0.0530 (13)	0.0436 (14)	0.0054 (10)	−0.0059 (10)	−0.0006 (11)
C4	0.0454 (11)	0.0481 (12)	0.0374 (13)	0.0048 (9)	−0.0075 (9)	−0.0018 (10)
C5	0.0642 (13)	0.0516 (13)	0.0456 (14)	−0.0066 (10)	−0.0164 (11)	−0.0038 (11)
C6	0.0744 (14)	0.0508 (13)	0.0488 (14)	0.0075 (11)	−0.0204 (12)	0.0025 (11)
C7	0.0472 (11)	0.0536 (13)	0.0364 (13)	0.0077 (10)	−0.0068 (9)	−0.0039 (10)
C8	0.0462 (11)	0.0535 (13)	0.0475 (14)	−0.0016 (10)	−0.0104 (10)	−0.0063 (11)
C9	0.0489 (11)	0.0493 (13)	0.0448 (14)	0.0051 (9)	−0.0099 (10)	−0.0002 (10)
C10	0.0898 (17)	0.089 (2)	0.0766 (19)	0.0287 (15)	−0.0392 (15)	0.0001 (16)
C11	0.0548 (13)	0.0922 (18)	0.0602 (17)	−0.0066 (12)	−0.0212 (12)	−0.0041 (14)

Geometric parameters (Å, º) top

N1—C2	1.303 (3)	C4—C9	1.389 (3)
N1—N2	1.383 (2)	C5—C6	1.370 (3)
N2—C1	1.295 (2)	C5—H5	0.9300
N3—C1	1.346 (2)	C6—C7	1.411 (3)
N3—C2	1.349 (2)	C6—H6	0.9300
N3—N4	1.408 (2)	C7—C8	1.397 (3)
N4—C3	1.277 (2)	C8—C9	1.369 (3)
N5—C7	1.358 (2)	C8—H8	0.9300
N5—C10	1.446 (3)	C9—H9	0.9300
N5—C11	1.450 (3)	C10—H10A	0.9600
C1—H1	0.9300	C10—H10B	0.9600
C2—H2	0.9300	C10—H10C	0.9600
C3—C4	1.442 (3)	C11—H11A	0.9600
C3—H3	0.9300	C11—H11B	0.9600
C4—C5	1.389 (3)	C11—H11C	0.9600

C2—N1—N2	106.54 (17)	C5—C6—C7	120.83 (19)
C1—N2—N1	106.92 (17)	C5—C6—H6	119.6
C1—N3—C2	104.55 (17)	C7—C6—H6	119.6
C1—N3—N4	124.23 (17)	N5—C7—C8	121.48 (18)
C2—N3—N4	131.21 (17)	N5—C7—C6	121.64 (18)
C3—N4—N3	114.03 (17)	C8—C7—C6	116.88 (18)
C7—N5—C10	121.78 (18)	C9—C8—C7	121.39 (19)
C7—N5—C11	120.24 (17)	C9—C8—H8	119.3
C10—N5—C11	117.98 (18)	C7—C8—H8	119.3
N2—C1—N3	111.1 (2)	C8—C9—C4	121.70 (19)
N2—C1—H1	124.4	C8—C9—H9	119.1
N3—C1—H1	124.4	C4—C9—H9	119.1
N1—C2—N3	110.9 (2)	N5—C10—H10A	109.5
N1—C2—H2	124.6	N5—C10—H10B	109.5
N3—C2—H2	124.6	H10A—C10—H10B	109.5
N4—C3—C4	123.37 (19)	N5—C10—H10C	109.5
N4—C3—H3	118.3	H10A—C10—H10C	109.5
C4—C3—H3	118.3	H10B—C10—H10C	109.5
C5—C4—C9	117.30 (18)	N5—C11—H11A	109.5
C5—C4—C3	123.47 (18)	N5—C11—H11B	109.5
C9—C4—C3	119.19 (18)	H11A—C11—H11B	109.5
C6—C5—C4	121.84 (19)	N5—C11—H11C	109.5
C6—C5—H5	119.1	H11A—C11—H11C	109.5
C4—C5—H5	119.1	H11B—C11—H11C	109.5

C2—N1—N2—C1	0.1 (2)	C3—C4—C5—C6	176.31 (19)
C1—N3—N4—C3	143.42 (19)	C4—C5—C6—C7	−0.5 (3)
C2—N3—N4—C3	−38.0 (3)	C10—N5—C7—C8	−176.5 (2)
N1—N2—C1—N3	−0.3 (2)	C11—N5—C7—C8	3.2 (3)
C2—N3—C1—N2	0.5 (2)	C10—N5—C7—C6	3.8 (3)
N4—N3—C1—N2	179.38 (16)	C11—N5—C7—C6	−176.49 (19)
N2—N1—C2—N3	0.2 (2)	C5—C6—C7—N5	−177.92 (19)
C1—N3—C2—N1	−0.4 (2)	C5—C6—C7—C8	2.4 (3)
N4—N3—C2—N1	−179.24 (17)	N5—C7—C8—C9	177.99 (18)
N3—N4—C3—C4	179.31 (16)	C6—C7—C8—C9	−2.3 (3)
N4—C3—C4—C5	−3.8 (3)	C7—C8—C9—C4	0.4 (3)
N4—C3—C4—C9	173.89 (18)	C5—C4—C9—C8	1.5 (3)
C9—C4—C5—C6	−1.4 (3)	C3—C4—C9—C8	−176.33 (18)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···N4ⁱ	0.93	2.57	3.448 (3)	157
C2—H2···N2ⁱⁱ	0.93	2.43	3.284 (3)	152
C11—H11B···N1ⁱⁱⁱ	0.96	2.60	3.543 (3)	166

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

Experimental details

Crystal data
Chemical formula	C₁₁H₁₃N₅
M_r	215.26
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	298
a, b, c (Å)	10.3665 (16), 11.1585 (19), 9.5248 (12)
β (°)	90.257 (1)
V (Å³)	1101.8 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.08
Crystal size (mm)	0.52 × 0.15 × 0.11

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2002)
T_min, T_max	0.957, 0.991
No. of measured, independent and observed [I > 2σ(I)] reflections	5465, 1940, 1184
R_int	0.062
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.047, 0.119, 1.00
No. of reflections	1940
No. of parameters	148
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.17, −0.18

Computer programs: SMART (Bruker, 2002), SAINT (Bruker, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···N4ⁱ	0.93	2.57	3.448 (3)	157
C2—H2···N2ⁱⁱ	0.93	2.43	3.284 (3)	152
C11—H11B···N1ⁱⁱⁱ	0.96	2.60	3.543 (3)	166

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

Acknowledgements

We thank the Instrumental Analysis Center of LiaoCheng University for the data collection on the Bruker SMART CCD facility.

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