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The two pyridine rings in the title compound, C12H10N6, form dihedral angles of 35.7 (2) and 16.8 (2)° with the central triazole ring. The mol­ecules exist as centrosymmetrically related dimers and form a three-dimensional network through intermolecular N—H...N hydrogen bonds.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536802013521/ci6147sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536802013521/ci6147Isup2.hkl
Contains datablock I

CCDC reference: 197458

Key indicators

  • Single-crystal X-ray study
  • T = 293 K
  • Mean [sigma](C-C) = 0.006 Å
  • R factor = 0.054
  • wR factor = 0.180
  • Data-to-parameter ratio = 11.6

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry








Comment top

Polypyridyl bridging ligands have attracted considerable attention due to their potential as building blocks for supramolecular assemblies and their ability to function as optical sensor and probes of nucleic acid (Holmlin et al., 1999; Blake et al., 1999). In particular, the ligands derived from the appropriate modification of 4,4'-bipyridine have been widely employed in order to suit those applications (Hagraman et al., 1999). The nature of the ligand, such as the length and the steric interaction, is crucial to the type of architecture observed (Withersby et al., 1999). The title compound, 4-amino-3,5-bis(4-pyridyl)-1,2,4-triazole, (I), an angular dipyridine ligand, has attracted our attention in connection with structural control of novel organic/inorganic supramolecular network. In this paper, we report the structure of this compound.

A perspective view of (I), including the atomic numbering scheme, is shown in Fig. 1. In the structure of (I), the two pyridine rings make dihedral angles of 35.7 (2) and 16.8 (2)° with the mean plane of the central triazole ring, and the dihedral angle between them is 19.7 (2)°. The C—N bond distances lie in the range of 1.310 (5)–1.382 (5) Å, which are markedly shorter than the normal C—N single-bond distance (1.47 Å; Sasada et al., 1984) and longer than the value of C—N double-bond distance (1.28 Å; Wang et al., 1998). The C—C bond distances of the pyridine rings are in the range of 1.375 (5)–1.393 (5) Å and all the bond angles are about 120°, falling within normal limits (Sasada, 1984). The angle between the center of the triazole ring and the two pyridine N-atom donors is 152.2°, and the separation of the two N-atom donors is 10.519 (2) Å. Hence, this ligand may provide both discrete and divergent products upon metal complexation under appropriate conditions.

A notable feature of this structure resides in the formation of a three-dimensional network through intermolecular N—H···N hydrogen bonds, which is further stabilized by the ππ-stacking interactions. In the crystal, the inversion-related molecules are linked by mutual N5—H5A···N1(1 − x, −y, 2 − z) hydrogen bonds to form a dimer (Table 2). In the dimer, the separation of the two opposite pyridine rings is 3.608 (5) Å, indicating ππ interactions. The dimeric pairs are interlinked by N5—H5B···N2(x, 1/2 − y, 1/2 + z) hydrogen bonds to form a three-dimensional network, as depicted in Fig. 2.

Experimental top

4-Amino-3,5-bis(4-pyridyl)-1,2,4-triazole was synthesized and purified according to the reported procedure, and characterized by NMR, IR and elemental analyses, giving results consistent with those in the literature (Bentiss et al., 1999). Well shaped colorless single crystals of the title compound suitable for X-ray diffraction were obtained by recrystallization from hot C2H5OH.

Refinement top

After checking their presence in a difference Fourier map, all the H atoms were fixed geometrically and treated as riding on their parent atoms, with C—H = 0.93 Å and N—H = 0.90 Å. The Uiso(H) values were set equal to 1.2Ueq(C) or 1.5Ueq(N).

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Bruker, 1998); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), showing 30% probability displacement ellipsoids.
[Figure 2] Fig. 2. Packing of the molecules viewed down the a axis.
4-amino-3,5-bis(4-pyridyl)-1,2,4-triazole top
Crystal data top
C12H10N6F(000) = 496
Mr = 238.26Dx = 1.478 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 4216 reflections
a = 13.176 (4) Åθ = 1.6–25.0°
b = 7.125 (2) ŵ = 0.10 mm1
c = 11.859 (4) ÅT = 293 K
β = 105.936 (6)°Prism, colorless
V = 1070.5 (5) Å30.30 × 0.20 × 0.20 mm
Z = 4
Data collection top
Bruker SMART 1000
diffractometer
968 reflections with I > 2.0σ(I)
ω scansRint = 0.080
Absorption correction: empirical (using intensity measurements)
SADABS (Sheldrick, 1997)
θmax = 25.0°
Tmin = 0.971, Tmax = 0.981h = 158
4288 measured reflectionsk = 88
1884 independent reflectionsl = 1114
Refinement top
Refinement on F2H-atom parameters constrained
R[F2 > 2σ(F2)] = 0.054 w = 1/[σ2(Fo2) + (0.076P)2]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.180(Δ/σ)max < 0.001
S = 1.00Δρmax = 0.25 e Å3
1884 reflectionsΔρmin = 0.34 e Å3
163 parameters
Crystal data top
C12H10N6V = 1070.5 (5) Å3
Mr = 238.26Z = 4
Monoclinic, P21/cMo Kα radiation
a = 13.176 (4) ŵ = 0.10 mm1
b = 7.125 (2) ÅT = 293 K
c = 11.859 (4) Å0.30 × 0.20 × 0.20 mm
β = 105.936 (6)°
Data collection top
Bruker SMART 1000
diffractometer
1884 independent reflections
Absorption correction: empirical (using intensity measurements)
SADABS (Sheldrick, 1997)
968 reflections with I > 2.0σ(I)
Tmin = 0.971, Tmax = 0.981Rint = 0.080
4288 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.054163 parameters
wR(F2) = 0.180H-atom parameters constrained
S = 1.00Δρmax = 0.25 e Å3
1884 reflectionsΔρmin = 0.34 e Å3
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. Full-matrix

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
N10.6078 (3)0.1678 (5)0.9376 (3)0.0415 (10)
N20.2406 (2)0.1706 (5)0.6521 (3)0.0377 (9)
N30.1318 (2)0.1650 (5)0.6258 (3)0.0383 (9)
N40.1949 (2)0.1285 (4)0.8148 (3)0.0305 (8)
N50.1975 (2)0.0766 (5)0.9304 (3)0.0377 (9)
H5A0.22700.03780.94580.057*
H5B0.23600.16050.98130.057*
N60.2215 (3)0.1177 (5)0.7161 (4)0.0489 (11)
C10.4623 (3)0.0826 (6)0.7746 (4)0.0382 (11)
H10.43890.02770.70090.046*
C20.5683 (3)0.0916 (6)0.8309 (4)0.0412 (11)
H20.61540.04210.79300.049*
C30.5375 (3)0.2401 (6)0.9885 (4)0.0402 (11)
H30.56300.29521.06200.048*
C40.4300 (3)0.2380 (6)0.9390 (4)0.0363 (11)
H40.38460.29010.97820.044*
C50.3906 (3)0.1563 (6)0.8290 (3)0.0296 (10)
C60.2780 (3)0.1507 (5)0.7658 (4)0.0304 (10)
C70.1061 (3)0.1382 (5)0.7239 (3)0.0296 (10)
C80.0051 (3)0.1256 (5)0.7280 (4)0.0305 (10)
C90.0820 (3)0.0958 (6)0.6225 (4)0.0380 (11)
H90.06280.07780.55350.046*
C100.1878 (3)0.0933 (6)0.6213 (4)0.0453 (12)
H100.23800.07340.55000.054*
C110.1471 (3)0.1451 (6)0.8168 (4)0.0485 (13)
H110.16880.16160.88440.058*
C120.0396 (3)0.1507 (6)0.8275 (4)0.0395 (11)
H120.00850.17100.90020.047*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.033 (2)0.046 (2)0.043 (2)0.0001 (18)0.0069 (18)0.0003 (19)
N20.029 (2)0.053 (2)0.031 (2)0.0043 (17)0.0086 (15)0.0007 (18)
N30.0268 (19)0.057 (2)0.029 (2)0.0015 (18)0.0044 (15)0.0008 (18)
N40.0321 (19)0.038 (2)0.0218 (19)0.0024 (16)0.0077 (15)0.0010 (16)
N50.040 (2)0.047 (2)0.026 (2)0.0016 (17)0.0086 (16)0.0042 (17)
N60.033 (2)0.058 (3)0.057 (3)0.0011 (19)0.014 (2)0.002 (2)
C10.032 (3)0.047 (3)0.037 (3)0.001 (2)0.011 (2)0.004 (2)
C20.034 (3)0.047 (3)0.046 (3)0.004 (2)0.017 (2)0.000 (2)
C30.041 (3)0.040 (3)0.037 (3)0.007 (2)0.005 (2)0.002 (2)
C40.030 (2)0.042 (3)0.038 (3)0.002 (2)0.010 (2)0.002 (2)
C50.029 (2)0.033 (2)0.026 (2)0.0010 (19)0.0074 (18)0.0028 (19)
C60.029 (2)0.034 (2)0.031 (2)0.0020 (19)0.0126 (18)0.004 (2)
C70.031 (2)0.033 (2)0.024 (2)0.0004 (19)0.0056 (18)0.0025 (19)
C80.032 (2)0.027 (2)0.033 (3)0.0015 (19)0.0080 (19)0.0001 (19)
C90.031 (3)0.045 (3)0.036 (3)0.002 (2)0.005 (2)0.001 (2)
C100.031 (3)0.054 (3)0.046 (3)0.001 (2)0.003 (2)0.000 (2)
C110.046 (3)0.059 (3)0.046 (3)0.000 (3)0.022 (2)0.003 (3)
C120.038 (3)0.047 (3)0.034 (3)0.003 (2)0.009 (2)0.000 (2)
Geometric parameters (Å, º) top
N1—C31.340 (5)C2—H20.93
N1—C21.343 (5)C3—C41.377 (5)
N2—C61.310 (5)C3—H30.93
N2—N31.381 (4)C4—C51.391 (5)
N3—C71.312 (5)C4—H40.93
N4—C71.358 (4)C5—C61.468 (5)
N4—C61.382 (5)C7—C81.481 (5)
N4—N51.411 (4)C8—C121.388 (5)
N5—H5A0.90C8—C91.393 (5)
N5—H5B0.90C9—C101.390 (5)
N6—C101.328 (6)C9—H90.93
N6—C111.335 (5)C10—H100.93
C1—C21.375 (5)C11—C121.387 (6)
C1—C51.385 (5)C11—H110.93
C1—H10.93C12—H120.93
C3—N1—C2116.3 (4)C1—C5—C6118.3 (4)
C6—N2—N3107.7 (3)C4—C5—C6123.7 (4)
C7—N3—N2108.0 (3)N2—C6—N4109.1 (3)
C7—N4—C6105.6 (3)N2—C6—C5124.4 (3)
C7—N4—N5124.8 (3)N4—C6—C5126.5 (4)
C6—N4—N5128.9 (3)N3—C7—N4109.6 (3)
N4—N5—H5A109.2N3—C7—C8122.4 (3)
N4—N5—H5B109.7N4—C7—C8128.0 (4)
H5A—N5—H5B109.5C12—C8—C9117.1 (4)
C10—N6—C11116.3 (4)C12—C8—C7125.3 (4)
C2—C1—C5119.2 (4)C9—C8—C7117.5 (4)
C2—C1—H1120.4C10—C9—C8119.4 (4)
C5—C1—H1120.4C10—C9—H9120.3
N1—C2—C1123.8 (4)C8—C9—H9120.3
N1—C2—H2118.1N6—C10—C9123.8 (4)
C1—C2—H2118.1N6—C10—H10118.1
N1—C3—C4124.1 (4)C9—C10—H10118.1
N1—C3—H3117.9N6—C11—C12124.6 (4)
C4—C3—H3117.9N6—C11—H11117.7
C3—C4—C5118.7 (4)C12—C11—H11117.7
C3—C4—H4120.7C8—C12—C11118.8 (4)
C5—C4—H4120.7C8—C12—H12120.6
C1—C5—C4117.9 (4)C11—C12—H12120.6
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N5—H5A···N1i0.902.423.139 (4)137
N5—H5B···N2ii0.902.343.108 (5)143
Symmetry codes: (i) x+1, y, z+2; (ii) x, y+1/2, z+1/2.

Experimental details

Crystal data
Chemical formulaC12H10N6
Mr238.26
Crystal system, space groupMonoclinic, P21/c
Temperature (K)293
a, b, c (Å)13.176 (4), 7.125 (2), 11.859 (4)
β (°) 105.936 (6)
V3)1070.5 (5)
Z4
Radiation typeMo Kα
µ (mm1)0.10
Crystal size (mm)0.30 × 0.20 × 0.20
Data collection
DiffractometerBruker SMART 1000
diffractometer
Absorption correctionEmpirical (using intensity measurements)
SADABS (Sheldrick, 1997)
Tmin, Tmax0.971, 0.981
No. of measured, independent and
observed [I > 2.0σ(I)] reflections
4288, 1884, 968
Rint0.080
(sin θ/λ)max1)0.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.054, 0.180, 1.00
No. of reflections1884
No. of parameters163
No. of restraints?
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.25, 0.34

Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1998), SAINT, SHELXTL (Bruker, 1998), SHELXTL.

Selected geometric parameters (Å, º) top
N1—C31.340 (5)N4—C71.358 (4)
N1—C21.343 (5)N4—C61.382 (5)
N2—C61.310 (5)N4—N51.411 (4)
N2—N31.381 (4)N6—C101.328 (6)
N3—C71.312 (5)N6—C111.335 (5)
C3—N1—C2116.3 (4)C7—N4—N5124.8 (3)
C6—N2—N3107.7 (3)C6—N4—N5128.9 (3)
C7—N3—N2108.0 (3)C10—N6—C11116.3 (4)
C7—N4—C6105.6 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N5—H5A···N1i0.902.423.139 (4)137
N5—H5B···N2ii0.902.343.108 (5)143
Symmetry codes: (i) x+1, y, z+2; (ii) x, y+1/2, z+1/2.
 

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