Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536802013521/ci6147sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536802013521/ci6147Isup2.hkl |
CCDC reference: 197458
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.
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).
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.
Fig. 1. The molecular structure of (I), showing 30% probability displacement ellipsoids. | |
Fig. 2. Packing of the molecules viewed down the a axis. |
C12H10N6 | F(000) = 496 |
Mr = 238.26 | Dx = 1.478 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 4216 reflections |
a = 13.176 (4) Å | θ = 1.6–25.0° |
b = 7.125 (2) Å | µ = 0.10 mm−1 |
c = 11.859 (4) Å | T = 293 K |
β = 105.936 (6)° | Prism, colorless |
V = 1070.5 (5) Å3 | 0.30 × 0.20 × 0.20 mm |
Z = 4 |
Bruker SMART 1000 diffractometer | 968 reflections with I > 2.0σ(I) |
ω scans | Rint = 0.080 |
Absorption correction: empirical (using intensity measurements) SADABS (Sheldrick, 1997) | θmax = 25.0° |
Tmin = 0.971, Tmax = 0.981 | h = −15→8 |
4288 measured reflections | k = −8→8 |
1884 independent reflections | l = −11→14 |
Refinement on F2 | H-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 = 1.00 | Δρmax = 0.25 e Å−3 |
1884 reflections | Δρmin = −0.34 e Å−3 |
163 parameters |
C12H10N6 | V = 1070.5 (5) Å3 |
Mr = 238.26 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 13.176 (4) Å | µ = 0.10 mm−1 |
b = 7.125 (2) Å | T = 293 K |
c = 11.859 (4) Å | 0.30 × 0.20 × 0.20 mm |
β = 105.936 (6)° |
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 = 0.981 | Rint = 0.080 |
4288 measured reflections |
R[F2 > 2σ(F2)] = 0.054 | 163 parameters |
wR(F2) = 0.180 | H-atom parameters constrained |
S = 1.00 | Δρmax = 0.25 e Å−3 |
1884 reflections | Δρmin = −0.34 e Å−3 |
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 |
x | y | z | Uiso*/Ueq | ||
N1 | 0.6078 (3) | 0.1678 (5) | 0.9376 (3) | 0.0415 (10) | |
N2 | 0.2406 (2) | 0.1706 (5) | 0.6521 (3) | 0.0377 (9) | |
N3 | 0.1318 (2) | 0.1650 (5) | 0.6258 (3) | 0.0383 (9) | |
N4 | 0.1949 (2) | 0.1285 (4) | 0.8148 (3) | 0.0305 (8) | |
N5 | 0.1975 (2) | 0.0766 (5) | 0.9304 (3) | 0.0377 (9) | |
H5A | 0.2270 | −0.0378 | 0.9458 | 0.057* | |
H5B | 0.2360 | 0.1605 | 0.9813 | 0.057* | |
N6 | −0.2215 (3) | 0.1177 (5) | 0.7161 (4) | 0.0489 (11) | |
C1 | 0.4623 (3) | 0.0826 (6) | 0.7746 (4) | 0.0382 (11) | |
H1 | 0.4389 | 0.0277 | 0.7009 | 0.046* | |
C2 | 0.5683 (3) | 0.0916 (6) | 0.8309 (4) | 0.0412 (11) | |
H2 | 0.6154 | 0.0421 | 0.7930 | 0.049* | |
C3 | 0.5375 (3) | 0.2401 (6) | 0.9885 (4) | 0.0402 (11) | |
H3 | 0.5630 | 0.2952 | 1.0620 | 0.048* | |
C4 | 0.4300 (3) | 0.2380 (6) | 0.9390 (4) | 0.0363 (11) | |
H4 | 0.3846 | 0.2901 | 0.9782 | 0.044* | |
C5 | 0.3906 (3) | 0.1563 (6) | 0.8290 (3) | 0.0296 (10) | |
C6 | 0.2780 (3) | 0.1507 (5) | 0.7658 (4) | 0.0304 (10) | |
C7 | 0.1061 (3) | 0.1382 (5) | 0.7239 (3) | 0.0296 (10) | |
C8 | −0.0051 (3) | 0.1256 (5) | 0.7280 (4) | 0.0305 (10) | |
C9 | −0.0820 (3) | 0.0958 (6) | 0.6225 (4) | 0.0380 (11) | |
H9 | −0.0628 | 0.0778 | 0.5535 | 0.046* | |
C10 | −0.1878 (3) | 0.0933 (6) | 0.6213 (4) | 0.0453 (12) | |
H10 | −0.2380 | 0.0734 | 0.5500 | 0.054* | |
C11 | −0.1471 (3) | 0.1451 (6) | 0.8168 (4) | 0.0485 (13) | |
H11 | −0.1688 | 0.1616 | 0.8844 | 0.058* | |
C12 | −0.0396 (3) | 0.1507 (6) | 0.8275 (4) | 0.0395 (11) | |
H12 | 0.0085 | 0.1710 | 0.9002 | 0.047* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.033 (2) | 0.046 (2) | 0.043 (2) | −0.0001 (18) | 0.0069 (18) | −0.0003 (19) |
N2 | 0.029 (2) | 0.053 (2) | 0.031 (2) | −0.0043 (17) | 0.0086 (15) | −0.0007 (18) |
N3 | 0.0268 (19) | 0.057 (2) | 0.029 (2) | −0.0015 (18) | 0.0044 (15) | 0.0008 (18) |
N4 | 0.0321 (19) | 0.038 (2) | 0.0218 (19) | 0.0024 (16) | 0.0077 (15) | 0.0010 (16) |
N5 | 0.040 (2) | 0.047 (2) | 0.026 (2) | −0.0016 (17) | 0.0086 (16) | 0.0042 (17) |
N6 | 0.033 (2) | 0.058 (3) | 0.057 (3) | −0.0011 (19) | 0.014 (2) | 0.002 (2) |
C1 | 0.032 (3) | 0.047 (3) | 0.037 (3) | 0.001 (2) | 0.011 (2) | −0.004 (2) |
C2 | 0.034 (3) | 0.047 (3) | 0.046 (3) | 0.004 (2) | 0.017 (2) | 0.000 (2) |
C3 | 0.041 (3) | 0.040 (3) | 0.037 (3) | −0.007 (2) | 0.005 (2) | −0.002 (2) |
C4 | 0.030 (2) | 0.042 (3) | 0.038 (3) | 0.002 (2) | 0.010 (2) | −0.002 (2) |
C5 | 0.029 (2) | 0.033 (2) | 0.026 (2) | 0.0010 (19) | 0.0074 (18) | 0.0028 (19) |
C6 | 0.029 (2) | 0.034 (2) | 0.031 (2) | 0.0020 (19) | 0.0126 (18) | −0.004 (2) |
C7 | 0.031 (2) | 0.033 (2) | 0.024 (2) | 0.0004 (19) | 0.0056 (18) | −0.0025 (19) |
C8 | 0.032 (2) | 0.027 (2) | 0.033 (3) | 0.0015 (19) | 0.0080 (19) | −0.0001 (19) |
C9 | 0.031 (3) | 0.045 (3) | 0.036 (3) | 0.002 (2) | 0.005 (2) | −0.001 (2) |
C10 | 0.031 (3) | 0.054 (3) | 0.046 (3) | −0.001 (2) | 0.003 (2) | 0.000 (2) |
C11 | 0.046 (3) | 0.059 (3) | 0.046 (3) | 0.000 (3) | 0.022 (2) | 0.003 (3) |
C12 | 0.038 (3) | 0.047 (3) | 0.034 (3) | −0.003 (2) | 0.009 (2) | 0.000 (2) |
N1—C3 | 1.340 (5) | C2—H2 | 0.93 |
N1—C2 | 1.343 (5) | C3—C4 | 1.377 (5) |
N2—C6 | 1.310 (5) | C3—H3 | 0.93 |
N2—N3 | 1.381 (4) | C4—C5 | 1.391 (5) |
N3—C7 | 1.312 (5) | C4—H4 | 0.93 |
N4—C7 | 1.358 (4) | C5—C6 | 1.468 (5) |
N4—C6 | 1.382 (5) | C7—C8 | 1.481 (5) |
N4—N5 | 1.411 (4) | C8—C12 | 1.388 (5) |
N5—H5A | 0.90 | C8—C9 | 1.393 (5) |
N5—H5B | 0.90 | C9—C10 | 1.390 (5) |
N6—C10 | 1.328 (6) | C9—H9 | 0.93 |
N6—C11 | 1.335 (5) | C10—H10 | 0.93 |
C1—C2 | 1.375 (5) | C11—C12 | 1.387 (6) |
C1—C5 | 1.385 (5) | C11—H11 | 0.93 |
C1—H1 | 0.93 | C12—H12 | 0.93 |
C3—N1—C2 | 116.3 (4) | C1—C5—C6 | 118.3 (4) |
C6—N2—N3 | 107.7 (3) | C4—C5—C6 | 123.7 (4) |
C7—N3—N2 | 108.0 (3) | N2—C6—N4 | 109.1 (3) |
C7—N4—C6 | 105.6 (3) | N2—C6—C5 | 124.4 (3) |
C7—N4—N5 | 124.8 (3) | N4—C6—C5 | 126.5 (4) |
C6—N4—N5 | 128.9 (3) | N3—C7—N4 | 109.6 (3) |
N4—N5—H5A | 109.2 | N3—C7—C8 | 122.4 (3) |
N4—N5—H5B | 109.7 | N4—C7—C8 | 128.0 (4) |
H5A—N5—H5B | 109.5 | C12—C8—C9 | 117.1 (4) |
C10—N6—C11 | 116.3 (4) | C12—C8—C7 | 125.3 (4) |
C2—C1—C5 | 119.2 (4) | C9—C8—C7 | 117.5 (4) |
C2—C1—H1 | 120.4 | C10—C9—C8 | 119.4 (4) |
C5—C1—H1 | 120.4 | C10—C9—H9 | 120.3 |
N1—C2—C1 | 123.8 (4) | C8—C9—H9 | 120.3 |
N1—C2—H2 | 118.1 | N6—C10—C9 | 123.8 (4) |
C1—C2—H2 | 118.1 | N6—C10—H10 | 118.1 |
N1—C3—C4 | 124.1 (4) | C9—C10—H10 | 118.1 |
N1—C3—H3 | 117.9 | N6—C11—C12 | 124.6 (4) |
C4—C3—H3 | 117.9 | N6—C11—H11 | 117.7 |
C3—C4—C5 | 118.7 (4) | C12—C11—H11 | 117.7 |
C3—C4—H4 | 120.7 | C8—C12—C11 | 118.8 (4) |
C5—C4—H4 | 120.7 | C8—C12—H12 | 120.6 |
C1—C5—C4 | 117.9 (4) | C11—C12—H12 | 120.6 |
D—H···A | D—H | H···A | D···A | D—H···A |
N5—H5A···N1i | 0.90 | 2.42 | 3.139 (4) | 137 |
N5—H5B···N2ii | 0.90 | 2.34 | 3.108 (5) | 143 |
Symmetry codes: (i) −x+1, −y, −z+2; (ii) x, −y+1/2, z+1/2. |
Experimental details
Crystal data | |
Chemical formula | C12H10N6 |
Mr | 238.26 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 293 |
a, b, c (Å) | 13.176 (4), 7.125 (2), 11.859 (4) |
β (°) | 105.936 (6) |
V (Å3) | 1070.5 (5) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.10 |
Crystal size (mm) | 0.30 × 0.20 × 0.20 |
Data collection | |
Diffractometer | Bruker SMART 1000 diffractometer |
Absorption correction | Empirical (using intensity measurements) SADABS (Sheldrick, 1997) |
Tmin, Tmax | 0.971, 0.981 |
No. of measured, independent and observed [I > 2.0σ(I)] reflections | 4288, 1884, 968 |
Rint | 0.080 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.054, 0.180, 1.00 |
No. of reflections | 1884 |
No. of parameters | 163 |
No. of restraints | ? |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.25, −0.34 |
Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1998), SAINT, SHELXTL (Bruker, 1998), SHELXTL.
N1—C3 | 1.340 (5) | N4—C7 | 1.358 (4) |
N1—C2 | 1.343 (5) | N4—C6 | 1.382 (5) |
N2—C6 | 1.310 (5) | N4—N5 | 1.411 (4) |
N2—N3 | 1.381 (4) | N6—C10 | 1.328 (6) |
N3—C7 | 1.312 (5) | N6—C11 | 1.335 (5) |
C3—N1—C2 | 116.3 (4) | C7—N4—N5 | 124.8 (3) |
C6—N2—N3 | 107.7 (3) | C6—N4—N5 | 128.9 (3) |
C7—N3—N2 | 108.0 (3) | C10—N6—C11 | 116.3 (4) |
C7—N4—C6 | 105.6 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
N5—H5A···N1i | 0.90 | 2.42 | 3.139 (4) | 137 |
N5—H5B···N2ii | 0.90 | 2.34 | 3.108 (5) | 143 |
Symmetry codes: (i) −x+1, −y, −z+2; (ii) x, −y+1/2, z+1/2. |
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 π–π-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 π–π 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.