organic compounds
N-[4-(Dimethylamino)benzylidene]-4H-1,2,4-triazol-4-amine
aCollege of Chemistry and Chemical Engineering, Ningxia University, Yinchuan 750021, Ninxia, People's Republic of China
*Correspondence e-mail: zhouhl@nxu.edu.cn
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 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 see: Desenko & Khim (1995); Kargin et al. (1988).
Experimental
Crystal data
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Refinement
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Data collection: SMART (Bruker, 2002); cell 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
10.1107/S1600536812014511/ff2062sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536812014511/ff2062Isup2.hkl
Supporting information file. DOI: 10.1107/S1600536812014511/ff2062Isup3.cml
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
were obtained by slow evaporation of the ethanol solution.The H atoms were positioned geometrically, with C—H distances of 0.93–0.96 Å for aromatic, methylene and methyl H atoms, respectively, and Uiso(H) = 1.2–1.5Ueq of the parent atom.
Data collection: SMART (Bruker, 2002); cell
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).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. |
C11H13N5 | F(000) = 456 |
Mr = 215.26 | Dx = 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 |
Bruker SMART CCD area-detector diffractometer | 1940 independent reflections |
Radiation source: fine-focus sealed tube | 1184 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.062 |
phi and ω scans | θmax = 25.0°, θmin = 2.0° |
Absorption correction: multi-scan (SADABS; Bruker, 2002) | h = −12→12 |
Tmin = 0.957, Tmax = 0.991 | k = −13→9 |
5465 measured reflections | l = −11→11 |
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(Fo2) + (0.0462P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.00 | (Δ/σ)max < 0.001 |
1940 reflections | Δρmax = 0.17 e Å−3 |
148 parameters | Δρmin = −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) |
C11H13N5 | V = 1101.8 (3) Å3 |
Mr = 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)° |
Bruker SMART CCD area-detector diffractometer | 1940 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2002) | 1184 reflections with I > 2σ(I) |
Tmin = 0.957, Tmax = 0.991 | Rint = 0.062 |
5465 measured reflections |
R[F2 > 2σ(F2)] = 0.047 | 0 restraints |
wR(F2) = 0.119 | H-atom parameters constrained |
S = 1.00 | Δρmax = 0.17 e Å−3 |
1940 reflections | Δρmin = −0.18 e Å−3 |
148 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
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* |
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) |
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) |
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 |
Mr | 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) |
Tmin, Tmax | 0.957, 0.991 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5465, 1940, 1184 |
Rint | 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 |
Δρmax, Δρmin (e Å−3) | 0.17, −0.18 |
Computer programs: SMART (Bruker, 2002), SAINT (Bruker, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).
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.
References
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This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
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.