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The title compound, C19H13N5O2, crystallizes in two monoclinic forms depending on the solvent used. From methanol or acetone, a yellow form [(Ia), m.p. 533 K] in the space group P21 is obtained, while with ethanol as the solvent, an orange form [(Ib), m.p. 541 K] in the space group Cc results. The conformers observed in the two polymorphs differ primarily in the relative orientation of pyridine/phenyl and triazole rings. Mol­ecules of both polymorphs form chains through carboxyl O-H...N hydrogen bonding; however, in each crystal structure, a different group acts as acceptor, viz. a triazole and a pyridyl N atom for (Ia) and (Ib), respectively. This is the first case of polymorphism observed for crystals of a 3,4,5-tri­substituted 1,2,4-triazole derivative.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270108029806/sq3157sup1.cif
Contains datablocks global, Ia, Ib

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270108029806/sq3157Iasup2.hkl
Contains datablock Ia

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270108029806/sq3157Ibsup3.hkl
Contains datablock Ib

CCDC references: 707222; 707223

Comment top

The phenomenon of polymorphism plays a vital role in the manufacture of pharmaceuticals, as well as in other biological and chemical fields. Polymorphic solids of the same chemical compound differ in internal solid-state structure and, as a consequence, possess different chemical and physical properties, including thermodynamic, spectroscopic, kinetic or mechanic ones. These properties can have a direct impact on a substance's stability, solubility, bioavailability or activity. However, polymorphism is not very well understood either at the crystallographic or at the molecular level. Its occurrence is unpredictable and may be caused by small differences in crystallization temperature, pressure, acidity or the nature of the mother liquor from which the substance was crystallized (solvent-dependent polymorphism) (Bernstein, 2002).

The present study is a continuation of our investigations on the structural characterization of aromatic derivatives of 4H-1,2,4-triazole (Mazur et al., 2004a,b, 2007). The conformational flexibility of these molecules, arising from a potential rotation between aryl and triazole rings, gives the possibility of formation of polymorphic forms. However, thus far, no polymorphs have been found for 3,4,5-trisubstituted 1,2,4-triazole derivatives, both aromatic and aliphatic.

In this work, we report the crystal structures of two polymorphic forms of 5-(3-carboxyl-2-pyridyl)-4-(phenyl)-3-(2-pyridyl)-4H-1,2,4-triazole (Ia and Ib). The molecular structures observed in (Ia) and (Ib) (Fig. 1) are composed of a central 1,2,4-triazole ring, substituted at C5 by the 3-carboxyl-2-pyridyl group, at C3 by the 2-pyridyl group and at N4 by a phenyl group. The interatomic distances within the triazole rings are not equal, ranging from 1.300 (2) to 1.389 (2) Å (Tables 1 and 3). The C3—N4 and N4—C5 bond lengths indicate single-bond character, whereas the N1—C5 and N2—C3 distances are indicative of significant double-bond character. The substituent atoms C22 and C31 in both polymorphs as well as atom C12 in (Ib) are almost coplanar with the central triazole ring, whereas the C12 atom in (Ia) is displaced from the triazole plane by 0.151 (2) Å. This out-of-plane deformation may result from intermolecular interactions. The N21—C22 bonds in the pyridyl groups and N1—N2 bonds in the triazole rings are also influenced by intermolecular contacts. All four rings in both polymorphic forms are almost perfectly planar. As in all similar compounds reported in the Cambridge Structural Database (CSD, Version 5.29; Allen, 2002; refcodes: AYEFOZ, FAXRAY, FAXSON, HIYFAW, IWOROB, MATKOH, MEGWIF, MEGXAY, NIFJUH, NUBCES, QAYVOB, QUIWVOH, TAWMAG, VERYEX), these aromatic rings are not coplanar (Fig. 2). The interplanar angles between the triazole and its substituent rings are in the range 40.7 (2)-83.0 (2)° (Table 5). Moreover, the relative orientation of the N atoms of the 2-pyridyl substituents at C3 and C5 is opposite for the forms (Ia) and (Ib). Molecule (Ia) possesses transoidally oriented pyridyl groups, while (Ib) is a cisoid conformer (Fig. 2). Besides the orientation of the rings, another significant difference between polymorphic conformers is observed, which is the relative orientation of the N11—C16 pyridyl ring and the COOH group (substituted in its C13 position). The O1—C1—C13—C12 torsion angles indicate that the protonated carboxyl O1 atom is oriented trans in (Ia) and cis in (Ib) with respect to the pyridine C12 atom (Fig. 2). All these conformational differences are accompanied by different intermolecular O—H···N hydrogen-bonding patterns.

Substantial differences in the molecular packing of the polymorphs are observed (Figs. 3 and 4). The molecules of the yellow phase (Ia) are linked by strong O1—H1O···N2i [symmetry code (i): 2 - x, y + 1/2, 1 - z] hydrogen bonds (Table 2) forming a C(8) chain (Bernstein et al., 1995) parallel to the y axis (Fig. 5). These chains are enforced by weaker multicentre C—H···O/N intermolecular interactions, giving a complex three-dimensional framework.

In the structure of the orange polymorph (Ib) the carboxylic O1—H1O bond participates in formation of a strong hydrogen bond with the pyridyl N21 atom of the second molecule transformed by the c-glide plane (Table 4, Fig. 5). The resulting infinite chain (running along the z axis) is described as a C(10) motif. Moreover, short directional contacts between the carbonyl atom O2 and the triazole N1/C5 (x, 1 - y, z - 1/2) atoms are observed (Fig. 6), which might be attractive in nature (Desiraju & Steiner, 1999). In addition to these interactions, there are also numerous weak C—H···N-type hydrogen bonds between adjacent molecular columns. Atom C26 acts as a hydrogen-bond donor to the pyridyl atom N11 (Fig. 4) in the molecule at (x - 1/2, y + 1/2, z). Simultaneously, the phenyl C34—H34 atoms participate in formation of three-centre hydrogen bonds with triazole N1—N2 atoms of the next molecule, repeated by translation along the [010] direction. Propagation of these hydrogen bonds then links all molecules into the (001) sheets.

The two crystalline forms (Ia) and (Ib) are obtained from different solvents. It seems that the polarity of solvents and their ability to form solute–solvent aggregates of different structure results in variation of intermolecular contacts during the formation of the solid. In the case of (Ib), ethanol (or water) molecules promote formation of C—H···N hydrogen bonds and electrostatic C=O···triazole interactions which are of a more hydrophobic nature. Thus, the crystals of polymorph (Ib) have higher melting point (by 8 K) and density (by 0.056 g cm-3).

Related literature top

For related literature, see: Allen (2002); Bernstein (2002); Desiraju & Steiner (1999);

Experimental top

Plate-shaped yellow single crystals of polymorph (Ia) were obtained by recrystallization of the title compound from methanol and acetone solutions at room temperature. Prismatic orange crystals of the second polymorph (Ib) were obtained by recrystallization from 95% ethanol. The melting points determined on a Boëtius microscope were 533 K and 541 K for forms (Ia) and (Ib), respectively.

Refinement top

In the absence of significant anomalous scatter, it was impossible to establish unambiguously the absolute structures of both polymorphs crystallizing in the non-centrosymmetric space groups. Nevertheless, the enantiomer selected in each case gave a value of the Flack parameter closest to zero. H atoms bonded to the O1 atoms were located in the difference Fourier map and their positions were refined with fixed isotropic displacement parameters. All remaining H atoms were positioned geometrically and constrained, with C—H bond distances of 0.93 Å. The displacement parameters of the H atoms were set to Uiso(H) = 1.2 Ueq(C).

Computing details top

For both compounds, data collection: KM-4 Software (Kuma, 1998); cell refinement: KM-4 Software (Kuma, 1998); data reduction: KM-4 Software (Kuma, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL/PC (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and enCIFer (Allen et al., 2004).

Figures top
[Figure 1] Fig. 1. Molecules of the title compound with the atom-numbering schemes: (a) polymorphic form (Ia) and (b) form (Ib). Displacement ellipsoids are drawn at the 50% probability level.
[Figure 2] Fig. 2. Molecular fit of the triazole atoms of the (Ia) (filled lines) and (Ib) (outline) conformers, showing differing orientations of the substituent rings and carboxylic acid groups.
[Figure 3] Fig. 3. The molecular packing of (Ia), viewed along the y axis. Dashed lines indicate hydrogen bonds; H atoms have been omitted (except those forming O—H···N bonds).
[Figure 4] Fig. 4. The packing arrangement of molecules of (Ib), viewed along the z axis. Dashed lines indicate C—H···N hydrogen bonds (other H atoms have been omitted). Symmetry codes: (a): x, y + 1, z; (b): x - 1/2, y + 1/2, z.
[Figure 5] Fig. 5. The chains formed by the O—H···N intermolecular hydrogen bonds in the form (Ia) (up) and (Ib) (down). H atoms have been omitted.
[Figure 6] Fig. 6. Intermolecular O—H···N hydrogen bond and accompanying carbonyl··· triazole contact in (Ib). Symmetry code: (a): x, 1 - y, z - 1/2.
(Ia) 2-[4-Phenyl-5-(2-pyridyl)-4H-1,2,4-triazol-3-yl]nicotinic acid top
Crystal data top
C19H13N5O2F(000) = 356
Mr = 343.34Dx = 1.310 Mg m3
Monoclinic, P21Cu Kα radiation, λ = 1.54178 Å
Hall symbol: P 2ybCell parameters from 48 reflections
a = 9.032 (3) Åθ = 6–18°
b = 11.758 (2) ŵ = 0.73 mm1
c = 9.208 (2) ÅT = 295 K
β = 117.11 (2)°Plate, yellow
V = 870.4 (4) Å30.58 × 0.42 × 0.36 mm
Z = 2
Data collection top
Kuma KM-4 four-circle
diffractometer
Rint = 0.026
Radiation source: fine-focus sealed tubeθmax = 80.5°, θmin = 5.4°
Graphite monochromatorh = 1010
ω–2θ scansk = 1515
3798 measured reflectionsl = 010
3577 independent reflections3 standard reflections every 100 reflections
2628 reflections with I > 2σ(I) intensity decay: 0.8%
Refinement top
Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH atoms treated by a mixture of independent and constrained refinement
R[F2 > 2σ(F2)] = 0.037 w = 1/[σ2(Fo2) + (0.0677P)2 + 0.0089P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.104(Δ/σ)max < 0.001
S = 1.06Δρmax = 0.17 e Å3
3577 reflectionsΔρmin = 0.15 e Å3
239 parametersExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
1 restraintExtinction coefficient: 0.017 (2)
Primary atom site location: structure-invariant direct methodsAbsolute structure: Flack (1983)
Secondary atom site location: difference Fourier mapAbsolute structure parameter: 0.3 (2)
Crystal data top
C19H13N5O2V = 870.4 (4) Å3
Mr = 343.34Z = 2
Monoclinic, P21Cu Kα radiation
a = 9.032 (3) ŵ = 0.73 mm1
b = 11.758 (2) ÅT = 295 K
c = 9.208 (2) Å0.58 × 0.42 × 0.36 mm
β = 117.11 (2)°
Data collection top
Kuma KM-4 four-circle
diffractometer
Rint = 0.026
3798 measured reflections3 standard reflections every 100 reflections
3577 independent reflections intensity decay: 0.8%
2628 reflections with I > 2σ(I)
Refinement top
R[F2 > 2σ(F2)] = 0.037H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.104Δρmax = 0.17 e Å3
S = 1.06Δρmin = 0.15 e Å3
3577 reflectionsAbsolute structure: Flack (1983)
239 parametersAbsolute structure parameter: 0.3 (2)
1 restraint
Special details top

Experimental. crystallizations from methanol and acetone

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
xyzUiso*/Ueq
N10.88170 (18)0.15682 (13)0.52367 (19)0.0490 (4)
N20.79779 (18)0.11734 (13)0.36563 (19)0.0488 (4)
C30.6404 (2)0.14363 (14)0.3086 (2)0.0446 (4)
N40.61739 (16)0.20125 (12)0.42533 (17)0.0412 (3)
C50.7716 (2)0.20617 (14)0.5565 (2)0.0432 (3)
N210.4002 (3)0.19321 (19)0.0643 (2)0.0755 (6)
C220.5116 (2)0.11417 (17)0.1443 (2)0.0492 (4)
C230.5157 (3)0.00945 (19)0.0794 (3)0.0644 (5)
H230.59500.04450.14060.077*
C240.3986 (4)0.0134 (2)0.0792 (3)0.0770 (7)
H240.40070.08230.12790.092*
C250.2816 (4)0.0649 (3)0.1624 (3)0.0850 (8)
H250.19940.05040.26780.102*
C260.2872 (4)0.1665 (3)0.0875 (3)0.0942 (9)
H260.20700.22070.14600.113*
C310.4674 (2)0.24733 (14)0.4213 (2)0.0431 (4)
C320.3664 (3)0.1784 (2)0.4565 (3)0.0662 (6)
H320.38970.10120.47560.079*
C330.2293 (3)0.2245 (2)0.4633 (3)0.0744 (7)
H330.15910.17840.48660.089*
C340.1964 (3)0.3393 (2)0.4357 (3)0.0687 (6)
H340.10500.37080.44180.082*
C350.2984 (3)0.4067 (2)0.3993 (4)0.0768 (7)
H350.27540.48390.37960.092*
C360.4360 (3)0.36047 (17)0.3917 (3)0.0633 (5)
H360.50560.40600.36690.076*
N110.7491 (2)0.17968 (15)0.7987 (2)0.0638 (5)
C120.8031 (2)0.24977 (15)0.7187 (2)0.0448 (4)
C10.9386 (2)0.42650 (16)0.6842 (2)0.0476 (4)
O11.0688 (2)0.48772 (16)0.7760 (2)0.0752 (5)
H1O1.113 (4)0.536 (3)0.712 (4)0.100*
O20.86796 (18)0.42958 (12)0.53827 (17)0.0598 (4)
C130.8892 (2)0.34925 (15)0.7841 (2)0.0464 (4)
C140.9276 (3)0.3752 (2)0.9435 (3)0.0635 (5)
H140.98940.43970.99340.076*
C150.8725 (3)0.3035 (3)1.0279 (3)0.0754 (7)
H150.89510.31961.13490.090*
C160.7846 (3)0.2090 (2)0.9514 (3)0.0734 (6)
H160.74690.16191.00880.088*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.0414 (7)0.0529 (8)0.0525 (9)0.0023 (6)0.0211 (6)0.0006 (6)
N20.0440 (8)0.0540 (8)0.0528 (9)0.0042 (6)0.0259 (7)0.0039 (7)
C30.0440 (9)0.0451 (9)0.0475 (10)0.0032 (6)0.0234 (7)0.0006 (6)
N40.0386 (6)0.0414 (6)0.0474 (7)0.0013 (5)0.0228 (5)0.0004 (6)
C50.0421 (8)0.0412 (7)0.0494 (9)0.0035 (6)0.0236 (7)0.0008 (7)
N210.0761 (12)0.0753 (12)0.0579 (10)0.0235 (10)0.0154 (9)0.0031 (9)
C220.0462 (9)0.0563 (10)0.0483 (10)0.0022 (7)0.0245 (7)0.0037 (7)
C230.0654 (12)0.0584 (11)0.0684 (13)0.0030 (10)0.0297 (11)0.0108 (10)
C240.0870 (17)0.0785 (16)0.0647 (14)0.0181 (14)0.0338 (13)0.0232 (12)
C250.0862 (18)0.102 (2)0.0542 (14)0.0094 (16)0.0208 (13)0.0152 (13)
C260.0861 (18)0.107 (2)0.0611 (15)0.0232 (16)0.0088 (13)0.0024 (14)
C310.0394 (8)0.0461 (8)0.0471 (9)0.0049 (7)0.0224 (7)0.0005 (7)
C320.0518 (10)0.0642 (13)0.0905 (16)0.0064 (9)0.0393 (11)0.0200 (11)
C330.0487 (11)0.0965 (19)0.0904 (17)0.0039 (11)0.0424 (11)0.0181 (14)
C340.0487 (10)0.0904 (17)0.0701 (14)0.0102 (11)0.0297 (10)0.0152 (12)
C350.0747 (15)0.0539 (12)0.106 (2)0.0150 (10)0.0446 (15)0.0130 (11)
C360.0660 (12)0.0442 (9)0.0923 (16)0.0004 (9)0.0471 (12)0.0060 (10)
N110.0754 (11)0.0586 (10)0.0674 (11)0.0107 (8)0.0414 (9)0.0061 (8)
C120.0422 (8)0.0474 (8)0.0467 (9)0.0016 (7)0.0220 (7)0.0040 (7)
C10.0454 (9)0.0499 (9)0.0476 (9)0.0097 (7)0.0213 (7)0.0049 (7)
O10.0767 (10)0.0877 (12)0.0580 (9)0.0434 (9)0.0280 (7)0.0064 (7)
O20.0651 (8)0.0602 (8)0.0492 (7)0.0133 (7)0.0218 (6)0.0036 (6)
C130.0447 (8)0.0513 (9)0.0447 (9)0.0056 (7)0.0217 (7)0.0016 (7)
C140.0676 (12)0.0768 (14)0.0482 (11)0.0159 (11)0.0282 (10)0.0107 (10)
C150.0802 (15)0.1031 (19)0.0486 (12)0.0114 (14)0.0343 (11)0.0046 (12)
C160.0873 (16)0.0868 (16)0.0588 (13)0.0092 (14)0.0443 (12)0.0131 (12)
Geometric parameters (Å, º) top
N1—C51.300 (2)C32—H320.9300
N1—N21.379 (2)C33—C341.381 (4)
N2—C31.309 (2)C33—H330.9300
C3—N41.364 (2)C34—C351.367 (4)
C3—C221.469 (3)C34—H340.9300
N4—C51.367 (2)C35—C361.387 (3)
N4—C311.444 (2)C35—H350.9300
C5—C121.479 (2)C36—H360.9300
N21—C221.320 (3)N11—C161.337 (3)
N21—C261.339 (3)N11—C121.337 (2)
C22—C231.376 (3)C12—C131.381 (2)
C23—C241.384 (3)C1—O21.197 (2)
C23—H230.9300C1—O11.307 (2)
C24—C251.347 (4)C1—C131.498 (2)
C24—H240.9300O1—H1O1.02 (3)
C25—C261.369 (4)C13—C141.380 (3)
C25—H250.9300C14—C151.384 (4)
C26—H260.9300C14—H140.9300
C31—C361.362 (3)C15—C161.360 (4)
C31—C321.365 (3)C15—H150.9300
C32—C331.379 (3)C16—H160.9300
C5—N1—N2106.5 (2)C32—C33—C34119.9 (2)
C3—N2—N1108.5 (2)C32—C33—H33120.1
N2—C3—N4109.2 (2)C34—C33—H33120.1
N2—C3—C22124.3 (2)C35—C34—C33120.0 (2)
N4—C3—C22126.5 (2)C35—C34—H34120.0
C3—N4—C5104.9 (1)C33—C34—H34120.0
C3—N4—C31130.1 (1)C34—C35—C36120.2 (2)
C5—N4—C31125.0 (1)C34—C35—H35119.9
N1—C5—N4110.8 (2)C36—C35—H35119.9
N1—C5—C12125.0 (2)C31—C36—C35118.9 (2)
N4—C5—C12123.8 (2)C31—C36—H36120.6
C22—N21—C26116.2 (2)C35—C36—H36120.6
N21—C22—C23123.5 (2)C16—N11—C12116.6 (2)
N21—C22—C3116.9 (2)N11—C12—C13123.8 (2)
C23—C22—C3119.5 (2)N11—C12—C5113.1 (2)
C22—C23—C24118.2 (2)C13—C12—C5123.0 (2)
C22—C23—H23120.9O2—C1—O1124.8 (2)
C24—C23—H23120.9O2—C1—C13123.5 (2)
C25—C24—C23119.5 (2)O1—C1—C13111.6 (2)
C25—C24—H24120.3C1—O1—H1O114 (2)
C23—C24—H24120.3C14—C13—C12118.0 (2)
C24—C25—C26118.1 (2)C14—C13—C1121.2 (2)
C24—C25—H25121.0C12—C13—C1120.8 (2)
C26—C25—H25121.0C13—C14—C15118.8 (2)
N21—C26—C25124.5 (3)C13—C14—H14120.6
N21—C26—H26117.8C15—C14—H14120.6
C25—C26—H26117.8C16—C15—C14118.8 (2)
C36—C31—C32121.8 (2)C16—C15—H15120.6
C36—C31—N4118.6 (2)C14—C15—H15120.6
C32—C31—N4119.5 (2)N11—C16—C15124.0 (2)
C31—C32—C33119.2 (2)N11—C16—H16118.0
C31—C32—H32120.4C15—C16—H16118.0
C33—C32—H32120.4
C5—N1—N2—C30.2 (2)C5—N4—C31—C3294.5 (2)
N1—N2—C3—N40.6 (2)C36—C31—C32—C330.4 (4)
N1—N2—C3—C22179.2 (2)N4—C31—C32—C33175.6 (2)
N2—C3—N4—C50.8 (2)C31—C32—C33—C340.4 (4)
C22—C3—N4—C5179.1 (2)C32—C33—C34—C350.9 (4)
N2—C3—N4—C31179.7 (2)C33—C34—C35—C360.7 (4)
C22—C3—N4—C310.2 (3)C32—C31—C36—C350.7 (4)
N2—N1—C5—N40.2 (2)N4—C31—C36—C35175.4 (2)
N2—N1—C5—C12173.0 (2)C34—C35—C36—C310.1 (4)
C3—N4—C5—N10.6 (2)C16—N11—C12—C131.1 (3)
C31—N4—C5—N1179.6 (2)C16—N11—C12—C5175.0 (2)
C3—N4—C5—C12172.7 (2)N1—C5—C12—N11100.5 (2)
C31—N4—C5—C126.3 (3)N4—C5—C12—N1171.8 (2)
C26—N21—C22—C230.2 (4)N1—C5—C12—C1375.5 (2)
C26—N21—C22—C3177.7 (2)N4—C5—C12—C13112.1 (2)
N2—C3—C22—N21138.0 (2)N11—C12—C13—C142.8 (3)
N4—C3—C22—N2142.2 (3)C5—C12—C13—C14172.8 (2)
N2—C3—C22—C2339.7 (3)N11—C12—C13—C1177.0 (2)
N4—C3—C22—C23140.2 (2)C5—C12—C13—C17.4 (3)
N21—C22—C23—C241.2 (4)O2—C1—C13—C14155.4 (2)
C3—C22—C23—C24176.3 (2)O1—C1—C13—C1425.6 (3)
C22—C23—C24—C252.4 (4)O2—C1—C13—C1224.4 (3)
C23—C24—C25—C262.2 (5)O1—C1—C13—C12154.5 (2)
C22—N21—C26—C250.4 (5)C12—C13—C14—C152.7 (3)
C24—C25—C26—N210.9 (5)C1—C13—C14—C15177.1 (2)
C3—N4—C31—C3699.6 (2)C13—C14—C15—C161.0 (4)
C5—N4—C31—C3681.7 (2)C12—N11—C16—C150.8 (4)
C3—N4—C31—C3284.3 (2)C14—C15—C16—N110.8 (4)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1O···N2i1.02 (3)1.61 (3)2.628 (2)172 (3)
C25—H25···O2ii0.932.693.474 (3)143
C34—H34···O2iii0.932.753.657 (3)164
C33—H33···N1iii0.932.693.520 (3)149
Symmetry codes: (i) x+2, y+1/2, z+1; (ii) x+1, y1/2, z; (iii) x1, y, z.
(Ib) 2-[4-Phenyl-5-(2-pyridyl)-4H-1,2,4-triazol-3-yl]nicotinic acid top
Crystal data top
C19H13N5O2F(000) = 712
Mr = 343.34Dx = 1.366 Mg m3
Monoclinic, CcCu Kα radiation, λ = 1.54178 Å
Hall symbol: C -2ycCell parameters from 43 reflections
a = 16.384 (5) Åθ = 6–16°
b = 9.725 (4) ŵ = 0.76 mm1
c = 13.181 (3) ÅT = 295 K
β = 127.36 (4)°Prism, orange
V = 1669.3 (13) Å30.46 × 0.30 × 0.26 mm
Z = 4
Data collection top
Kuma KM-4 four-circle
diffractometer
Rint = 0.028
Radiation source: fine-focus sealed tubeθmax = 80.3°, θmin = 5.7°
Graphite monochromatorh = 2020
ω–2θ scansk = 1010
6411 measured reflectionsl = 1616
3504 independent reflections3 standard reflections every 100 reflections
2716 reflections with I > 2σ(I) intensity decay: 0.1%
Refinement top
Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH atoms treated by a mixture of independent and constrained refinement
R[F2 > 2σ(F2)] = 0.040 w = 1/[σ2(Fo2) + (0.0691P)2 + 0.1803P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.109(Δ/σ)max = 0.023
S = 1.05Δρmax = 0.17 e Å3
3504 reflectionsΔρmin = 0.20 e Å3
239 parametersExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
2 restraintsExtinction coefficient: 0.0022 (2)
Primary atom site location: structure-invariant direct methodsAbsolute structure: Flack (1983)
Secondary atom site location: difference Fourier mapAbsolute structure parameter: 0.1 (3)
Crystal data top
C19H13N5O2V = 1669.3 (13) Å3
Mr = 343.34Z = 4
Monoclinic, CcCu Kα radiation
a = 16.384 (5) ŵ = 0.76 mm1
b = 9.725 (4) ÅT = 295 K
c = 13.181 (3) Å0.46 × 0.30 × 0.26 mm
β = 127.36 (4)°
Data collection top
Kuma KM-4 four-circle
diffractometer
Rint = 0.028
6411 measured reflections3 standard reflections every 100 reflections
3504 independent reflections intensity decay: 0.1%
2716 reflections with I > 2σ(I)
Refinement top
R[F2 > 2σ(F2)] = 0.040H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.109Δρmax = 0.17 e Å3
S = 1.05Δρmin = 0.20 e Å3
3504 reflectionsAbsolute structure: Flack (1983)
239 parametersAbsolute structure parameter: 0.1 (3)
2 restraints
Special details top

Experimental. crystallization from ethanol

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
xyzUiso*/Ueq
N10.45011 (13)0.22361 (17)0.19990 (17)0.0389 (4)
N20.35506 (12)0.22661 (17)0.17596 (17)0.0389 (4)
C30.32907 (14)0.3558 (2)0.16528 (18)0.0330 (4)
N40.40289 (13)0.43896 (13)0.17999 (16)0.0330 (3)
C50.47647 (14)0.35032 (19)0.20142 (17)0.0328 (4)
N210.24275 (13)0.49603 (19)0.22475 (17)0.0431 (4)
C220.23368 (14)0.4060 (2)0.14107 (18)0.0357 (4)
C230.13960 (16)0.3601 (2)0.0354 (2)0.0449 (5)
H230.13570.29690.02040.054*
C240.05133 (16)0.4102 (3)0.0141 (2)0.0535 (6)
H240.01290.38070.05610.064*
C250.05943 (17)0.5035 (3)0.0972 (3)0.0566 (6)
H250.00110.53960.08400.068*
C260.15587 (18)0.5428 (3)0.2009 (2)0.0526 (6)
H260.16100.60550.25780.063*
C310.40177 (19)0.58629 (19)0.1731 (3)0.0454 (5)
C320.3191 (3)0.6507 (3)0.0662 (4)0.0697 (8)
H320.26600.59900.00160.084*
C330.3157 (4)0.7916 (4)0.0605 (6)0.1072 (17)
H330.25990.83580.01120.129*
C340.3944 (6)0.8672 (4)0.1603 (7)0.122 (2)
H340.39100.96280.15650.147*
C350.4789 (4)0.8035 (4)0.2666 (6)0.1030 (15)
H350.53280.85580.33270.124*
C360.4829 (3)0.6582 (3)0.2743 (3)0.0657 (7)
H360.53850.61310.34540.079*
N110.65796 (13)0.3546 (2)0.33845 (17)0.0453 (4)
C120.57290 (14)0.3922 (2)0.22373 (18)0.0349 (4)
C130.57640 (16)0.4646 (2)0.13511 (19)0.0401 (4)
C10.48459 (17)0.5049 (2)0.0046 (2)0.0441 (5)
O10.40458 (12)0.42436 (17)0.04499 (15)0.0494 (4)
H1O0.345 (3)0.460 (4)0.138 (4)0.100*
O20.48704 (16)0.6016 (2)0.04985 (18)0.0708 (6)
C140.67224 (17)0.5023 (3)0.1702 (2)0.0526 (6)
H140.67730.55390.11490.063*
C150.75905 (17)0.4632 (3)0.2864 (2)0.0582 (6)
H150.82370.48650.31080.070*
C160.74845 (17)0.3884 (3)0.3667 (2)0.0536 (6)
H160.80770.36010.44470.064*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.0388 (8)0.0344 (8)0.0488 (9)0.0015 (7)0.0293 (7)0.0004 (7)
N20.0362 (8)0.0333 (9)0.0519 (9)0.0022 (7)0.0292 (8)0.0038 (7)
C30.0343 (9)0.0295 (10)0.0372 (9)0.0028 (7)0.0226 (8)0.0032 (7)
N40.0364 (6)0.0268 (7)0.0394 (7)0.0012 (7)0.0249 (6)0.0002 (7)
C50.0332 (10)0.0318 (10)0.0329 (8)0.0022 (7)0.0198 (8)0.0012 (7)
N210.0411 (9)0.0440 (10)0.0451 (9)0.0008 (7)0.0268 (8)0.0089 (7)
C220.0353 (9)0.0315 (10)0.0413 (10)0.0004 (7)0.0238 (8)0.0011 (7)
C230.0379 (11)0.0447 (12)0.0479 (11)0.0015 (8)0.0239 (10)0.0091 (9)
C240.0348 (10)0.0540 (15)0.0614 (14)0.0017 (9)0.0238 (10)0.0103 (11)
C250.0421 (13)0.0586 (15)0.0743 (16)0.0066 (10)0.0381 (13)0.0046 (12)
C260.0505 (12)0.0530 (14)0.0608 (14)0.0047 (11)0.0373 (11)0.0135 (11)
C310.0602 (11)0.0282 (9)0.0724 (13)0.0016 (11)0.0530 (11)0.0018 (11)
C320.0791 (19)0.0519 (17)0.103 (2)0.0251 (14)0.0681 (18)0.0342 (15)
C330.141 (4)0.052 (2)0.200 (5)0.041 (2)0.140 (4)0.056 (3)
C340.203 (5)0.0357 (17)0.251 (7)0.016 (3)0.202 (6)0.022 (3)
C350.165 (4)0.0495 (19)0.181 (4)0.049 (2)0.151 (4)0.049 (2)
C360.0896 (19)0.0433 (14)0.099 (2)0.0222 (13)0.0751 (18)0.0229 (13)
N110.0346 (9)0.0519 (11)0.0415 (10)0.0015 (7)0.0191 (8)0.0060 (7)
C120.0359 (9)0.0326 (10)0.0391 (10)0.0019 (7)0.0243 (8)0.0001 (8)
C130.0411 (10)0.0413 (11)0.0415 (10)0.0022 (8)0.0269 (9)0.0006 (8)
C10.0497 (11)0.0460 (12)0.0408 (9)0.0044 (9)0.0296 (9)0.0010 (8)
O10.0405 (8)0.0611 (10)0.0402 (7)0.0061 (7)0.0212 (6)0.0087 (7)
O20.0755 (12)0.0702 (12)0.0458 (8)0.0195 (9)0.0259 (8)0.0145 (8)
C140.0477 (13)0.0653 (16)0.0517 (12)0.0112 (10)0.0338 (11)0.0017 (11)
C150.0351 (11)0.0791 (17)0.0587 (14)0.0087 (11)0.0276 (10)0.0032 (12)
C160.0363 (11)0.0640 (15)0.0487 (12)0.0010 (10)0.0197 (10)0.0048 (11)
Geometric parameters (Å, º) top
N1—C51.302 (3)C32—H320.9300
N1—N21.389 (2)C33—C341.370 (8)
N2—C31.306 (3)C33—H330.9300
C3—N41.368 (2)C34—C351.382 (7)
C3—C221.476 (3)C34—H340.9300
N4—C51.365 (2)C35—C361.415 (5)
N4—C311.435 (2)C35—H350.9300
C5—C121.478 (3)C36—H360.9300
N21—C261.338 (3)N11—C161.332 (3)
N21—C221.344 (3)N11—C121.343 (3)
C22—C231.382 (3)C12—C131.395 (3)
C23—C241.384 (3)C13—C141.390 (3)
C23—H230.9300C13—C11.495 (3)
C24—C251.365 (4)C1—O21.198 (3)
C24—H240.9300C1—O11.311 (3)
C25—C261.375 (4)O1—H1O1.06 (4)
C25—H250.9300C14—C151.367 (3)
C26—H260.9300C14—H140.9300
C31—C361.372 (4)C15—C161.379 (4)
C31—C321.377 (4)C15—H150.9300
C32—C331.372 (5)C16—H160.9300
C5—N1—N2107.4 (2)C34—C33—C32120.0 (5)
C3—N2—N1107.0 (2)C34—C33—H33120.0
N2—C3—N4110.6 (2)C32—C33—H33120.0
N2—C3—C22125.1 (2)C33—C34—C35120.8 (3)
N4—C3—C22124.4 (2)C33—C34—H34119.6
C5—N4—C3104.5 (1)C35—C34—H34119.6
C5—N4—C31128.3 (2)C34—C35—C36119.7 (4)
C3—N4—C31127.3 (2)C34—C35—H35120.2
N1—C5—N4110.6 (2)C36—C35—H35120.2
N1—C5—C12124.6 (2)C31—C36—C35117.6 (4)
N4—C5—C12124.8 (2)C31—C36—H36121.2
C26—N21—C22117.2 (2)C35—C36—H36121.2
N21—C22—C23122.5 (2)C16—N11—C12117.8 (2)
N21—C22—C3117.6 (2)N11—C12—C13122.6 (2)
C23—C22—C3119.9 (2)N11—C12—C5113.8 (2)
C22—C23—C24118.7 (2)C13—C12—C5123.7 (2)
C22—C23—H23120.7C14—C13—C12117.8 (2)
C24—C23—H23120.7C14—C13—C1117.3 (2)
C25—C24—C23119.4 (2)C12—C13—C1124.9 (2)
C25—C24—H24120.3O2—C1—O1123.9 (2)
C23—C24—H24120.3O2—C1—C13121.3 (2)
C24—C25—C26118.4 (2)O1—C1—C13114.9 (2)
C24—C25—H25120.8C1—O1—H1O109 (2)
C26—C25—H25120.8C15—C14—C13119.8 (2)
N21—C26—C25123.8 (2)C15—C14—H14120.1
N21—C26—H26118.1C13—C14—H14120.1
C25—C26—H26118.1C14—C15—C16118.4 (2)
C36—C31—C32122.3 (2)C14—C15—H15120.8
C36—C31—N4118.7 (2)C16—C15—H15120.8
C32—C31—N4119.1 (2)N11—C16—C15123.6 (2)
C33—C32—C31119.5 (4)N11—C16—H16118.2
C33—C32—H32120.2C15—C16—H16118.2
C31—C32—H32120.2
C5—N1—N2—C30.5 (2)C3—N4—C31—C3254.3 (3)
N1—N2—C3—N40.6 (2)C36—C31—C32—C331.4 (4)
N1—N2—C3—C22179.3 (2)N4—C31—C32—C33177.9 (3)
N2—C3—N4—C50.4 (2)C31—C32—C33—C340.4 (5)
C22—C3—N4—C5179.4 (2)C32—C33—C34—C351.2 (6)
N2—C3—N4—C31179.1 (2)C33—C34—C35—C361.9 (6)
C22—C3—N4—C311.0 (3)C32—C31—C36—C350.7 (4)
N2—N1—C5—N40.3 (2)N4—C31—C36—C35178.5 (2)
N2—N1—C5—C12179.9 (2)C34—C35—C36—C310.9 (4)
C3—N4—C5—N10.0 (2)C16—N11—C12—C130.2 (3)
C31—N4—C5—N1179.5 (2)C16—N11—C12—C5179.9 (2)
C3—N4—C5—C12179.7 (2)N1—C5—C12—N1161.4 (3)
C31—N4—C5—C120.7 (3)N4—C5—C12—N11118.4 (2)
C26—N21—C22—C231.1 (3)N1—C5—C12—C13119.0 (2)
C26—N21—C22—C3178.9 (2)N4—C5—C12—C1361.2 (3)
N2—C3—C22—N21124.0 (2)N11—C12—C13—C142.1 (3)
N4—C3—C22—N2155.8 (3)C5—C12—C13—C14177.5 (2)
N2—C3—C22—C2356.0 (3)N11—C12—C13—C1177.8 (2)
N4—C3—C22—C23124.2 (2)C5—C12—C13—C12.6 (3)
N21—C22—C23—C240.8 (4)C14—C13—C1—O225.3 (3)
C3—C22—C23—C24179.2 (2)C12—C13—C1—O2154.8 (2)
C22—C23—C24—C250.3 (4)C14—C13—C1—O1152.7 (2)
C23—C24—C25—C261.0 (4)C12—C13—C1—O127.2 (3)
C22—N21—C26—C250.3 (4)C12—C13—C14—C152.6 (4)
C24—C25—C26—N210.7 (4)C1—C13—C14—C15177.3 (2)
C5—N4—C31—C3655.6 (3)C13—C14—C15—C160.9 (4)
C3—N4—C31—C36125.0 (2)C12—N11—C16—C152.1 (4)
C5—N4—C31—C32125.1 (2)C14—C15—C16—N111.6 (4)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1O···N21i1.06 (4)1.61 (4)2.660 (3)172 (4)
C34—H34···N1ii0.932.653.541 (4)160
C34—H34···N2ii0.932.683.582 (4)164
C26—H26···N11iii0.932.663.522 (3)155
C23—H23···N11iv0.932.573.484 (3)169
Symmetry codes: (i) x, y+1, z1/2; (ii) x, y+1, z; (iii) x1/2, y+1/2, z; (iv) x1/2, y+1/2, z1/2.

Experimental details

(Ia)(Ib)
Crystal data
Chemical formulaC19H13N5O2C19H13N5O2
Mr343.34343.34
Crystal system, space groupMonoclinic, P21Monoclinic, Cc
Temperature (K)295295
a, b, c (Å)9.032 (3), 11.758 (2), 9.208 (2)16.384 (5), 9.725 (4), 13.181 (3)
β (°) 117.11 (2) 127.36 (4)
V3)870.4 (4)1669.3 (13)
Z24
Radiation typeCu KαCu Kα
µ (mm1)0.730.76
Crystal size (mm)0.58 × 0.42 × 0.360.46 × 0.30 × 0.26
Data collection
DiffractometerKuma KM-4 four-circle
diffractometer
Kuma KM-4 four-circle
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
3798, 3577, 2628 6411, 3504, 2716
Rint0.0260.028
(sin θ/λ)max1)0.6400.639
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.037, 0.104, 1.06 0.040, 0.109, 1.05
No. of reflections35773504
No. of parameters239239
No. of restraints12
H-atom treatmentH atoms treated by a mixture of independent and constrained refinementH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.17, 0.150.17, 0.20
Absolute structureFlack (1983)Flack (1983)
Absolute structure parameter0.3 (2)0.1 (3)

Computer programs: KM-4 Software (Kuma, 1998), SHELXS97 (Sheldrick, 2008), SHELXTL/PC (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008) and enCIFer (Allen et al., 2004).

Selected geometric parameters (Å, º) for (Ia) top
N1—C51.300 (2)C3—N41.364 (2)
N1—N21.379 (2)N4—C51.367 (2)
N2—C31.309 (2)N21—C221.320 (3)
O2—C1—C13—C1224.4 (3)O1—C1—C13—C12154.5 (2)
Hydrogen-bond geometry (Å, º) for (Ia) top
D—H···AD—HH···AD···AD—H···A
O1—H1O···N2i1.02 (3)1.61 (3)2.628 (2)172 (3)
C25—H25···O2ii0.932.693.474 (3)143
C34—H34···O2iii0.932.753.657 (3)164
C33—H33···N1iii0.932.693.520 (3)149
Symmetry codes: (i) x+2, y+1/2, z+1; (ii) x+1, y1/2, z; (iii) x1, y, z.
Selected geometric parameters (Å, º) for (Ib) top
N1—C51.302 (3)C3—N41.368 (2)
N1—N21.389 (2)N4—C51.365 (2)
N2—C31.306 (3)N21—C221.344 (3)
C12—C13—C1—O2154.8 (2)C12—C13—C1—O127.2 (3)
Hydrogen-bond geometry (Å, º) for (Ib) top
D—H···AD—HH···AD···AD—H···A
O1—H1O···N21i1.06 (4)1.61 (4)2.660 (3)172 (4)
C34—H34···N1ii0.932.653.541 (4)160
C34—H34···N2ii0.932.683.582 (4)164
C26—H26···N11iii0.932.663.522 (3)155
C23—H23···N11iv0.932.573.484 (3)169
Symmetry codes: (i) x, y+1, z1/2; (ii) x, y+1, z; (iii) x1/2, y+1/2, z; (iv) x1/2, y+1/2, z1/2.
Angles (°) between triazole and aryl ring planes top
IaIb
triazole/pyridyl N11-C1674.3 (2)61.0 (2)
triazole/pyridyl N21-C2640.7 (2)55.9 (2)
triazole/phenyl C31-C3683.0 (2)54.7 (2)
phenyl/pyridyl N11-C1670.8 (2)61.1 (2)
phenyl/pyridyl N21-C2680.5 (2)55.7 (2)
 

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