5-(Pyridin-2-yl)-3,3′-bi(1H-1,2,4-triazole)

Xu, Z.; Zhao, X.; Wang, Q.

doi:10.1107/S1600536811027449

organic compounds

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Volume 67| Part 8| August 2011| Page o2037

doi:10.1107/S1600536811027449

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5-(Pyridin-2-yl)-3,3′-bi(1H-1,2,4-triazole)

Zhouqing Xu,^a Xinping Zhao ^b and Qiang Wang ^a ^*

^aThe Department of Physics–Chemistry, Henan Polytechnic University, Jiao Zuo, 454000, People's Republic of China, and ^bThe Hospital of Henan Polytechnic University, Jiao Zuo, 454000, People's Republic of China
^*Correspondence e-mail: wangqiang@hpu.edu.cn

(Received 5 July 2011; accepted 8 July 2011; online 13 July 2011)

In the title molecule, C₉H₇N₇, the two triazole rings are twisted by an angle of 3.8 (5)°; the central triazole ring is twisted by 32.3 (6)° with respect to the pyridyl ring. The crystal packing consists of layers generated by intermolecular N—H⋯N hydrogen bonds.

Related literature

For related structures, see: Mai et al. (2009 ); Zhang et al. (2010 ). For the synthesis, see: Potts (1960 ); Wiley & Hart (1953 ).

Experimental

Crystal data

C₉H₇N₇
M_r = 213.22
Monoclinic, P 2₁ /c
a = 12.372 (3) Å
b = 7.5361 (15) Å
c = 10.007 (2) Å
β = 93.670 (4)°
V = 931.1 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 296 K
0.24 × 0.20 × 0.20 mm

Data collection

Bruker SMART APEX diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.975, T_max = 0.979
5150 measured reflections
1832 independent reflections
1072 reflections with I > 2σ(I)
R_int = 0.055

Refinement

R[F² > 2σ(F²)] = 0.050
wR(F²) = 0.156
S = 0.94
1832 reflections
154 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.26 e Å⁻³
Δρ_min = −0.22 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N6—H1⋯N4ⁱ	0.98 (4)	1.93 (4)	2.891 (3)	165 (3)
N2—H2⋯N3ⁱⁱ	0.99 (3)	1.90 (4)	2.878 (3)	167 (3)
Symmetry codes: (i) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (ii) $[x, -y-{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2003 ); cell refinement: SAINT (Bruker, 2003); 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/S1600536811027449/ng5195sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811027449/ng5195Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811027449/ng5195Isup3.cml

checkCIF report

Comment top

During the past decads, copounds containling trazole subunits have been intensively studied due to their diverse biological activities, such as fungicide, herbicide, medicine, etc., and have become a central focus in the sudy of agricultural, medicinal and material chemicals. Furthermore, the study on crystal structures and properties of the new metal-organic frameworks (MOFs) of N-containing ligands have attracted considerable attentions during the past years for the their potential applications in polymeric materials, catalytic materials, biological materials optical materials and so on (Zhang, et al., 2010). Therefore, in search for new multidentate ligands, we have synthesized the title compound and determined its structure.

The molecule structure of title compound was shown in the Fig.1, the lengths and angles are within normal ranges. In triazol ring, the average C—N bond length is 1.336 (5) Å, which is shorter than C—N (mean 1.461 (2) Å) (Zhang, et al., 2010), but longer than C=N (mean 1.269 (3) Å) (Mai, et al., 2009). This is caused probably by electron delocalization in heterocyclic systems. In the crystal structure, the two triazole rings are almost coplanar, they are twisted by an angle of 3.8 (5)°. the central triazole ring form dihedral angles of 32.3 (6)° with the pyridyl ring. The crystal packing (Fig. 2) consists of two-dimensional infinite plane along the b axis generated by intermolecular interactions of N—H···N hydrogen bonds.

Related literature top

For related structures, see: Mai et al. (2009); Zhang et al. (2010). For the synthesis, see: Potts (1960); Wiley & Hart (1953).

Experimental top

5-(Pyridin-2-yl)-1H,1'H-3,3'-bi(1,2,4-triazole)was prepared according to Wiley & Hart (1953) and Potts et al. (1960). The crystals suitable for crystallographic analysis were grown by recrystallization from DMF and ethanol solution as colorless block.

Computing details top

Data collection: APEX2 (Bruker, 2003); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT (Bruker, 2003); 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 molecule, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. A partial packing diagram of the title compound. Hydrogen bonds are shown as dashed lines, viewed down the b axis.

5-(Pyridin-2-yl)-3,3'-bi(1H-1,2,4-triazole) top

Crystal data top

C₉H₇N₇	F(000) = 440
M_r = 213.22	D_x = 1.521 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 12.372 (3) Å	Cell parameters from 6322 reflections
b = 7.5361 (15) Å	θ = 2.0–27.9°
c = 10.007 (2) Å	µ = 0.11 mm⁻¹
β = 93.670 (4)°	T = 296 K
V = 931.1 (3) Å³	Block, colourless
Z = 4	0.24 × 0.20 × 0.20 mm

Data collection top

Bruker SMART APEX diffractometer	1832 independent reflections
Radiation source: fine-focus sealed tube	1072 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.055
ω scan	θ_max = 26.0°, θ_min = 1.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −15→12
T_min = 0.975, T_max = 0.979	k = −9→9
5150 measured reflections	l = −12→12

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)] = 0.050	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.156	w = 1/[σ²(F_o²) + (0.0843P)²] where P = (F_o² + 2F_c²)/3
S = 0.94	(Δ/σ)_max < 0.001
1832 reflections	Δρ_max = 0.26 e Å⁻³
154 parameters	Δρ_min = −0.22 e Å⁻³
0 restraints	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.018 (5)

Crystal data top

C₉H₇N₇	V = 931.1 (3) Å³
M_r = 213.22	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 12.372 (3) Å	µ = 0.11 mm⁻¹
b = 7.5361 (15) Å	T = 296 K
c = 10.007 (2) Å	0.24 × 0.20 × 0.20 mm
β = 93.670 (4)°

Data collection top

Bruker SMART APEX diffractometer	1832 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1072 reflections with I > 2σ(I)
T_min = 0.975, T_max = 0.979	R_int = 0.055
5150 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.050	0 restraints
wR(F²) = 0.156	H atoms treated by a mixture of independent and constrained refinement
S = 0.94	Δρ_max = 0.26 e Å⁻³
1832 reflections	Δρ_min = −0.22 e Å⁻³
154 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
N4	0.22980 (16)	0.2080 (3)	0.46400 (19)	0.0342 (6)
N6	0.23958 (18)	0.2161 (3)	0.6818 (2)	0.0370 (6)
N2	0.07056 (18)	−0.2247 (3)	0.2744 (2)	0.0394 (6)
N3	0.06963 (16)	−0.2067 (3)	0.4914 (2)	0.0367 (6)
N5	0.18243 (17)	0.0672 (3)	0.6502 (2)	0.0372 (6)
C1	0.1252 (2)	−0.0720 (3)	0.4381 (2)	0.0311 (6)
N1	0.12802 (17)	−0.0763 (3)	0.3067 (2)	0.0387 (6)
C2	0.26642 (19)	0.2993 (3)	0.5708 (2)	0.0329 (6)
C3	0.1792 (2)	0.0682 (3)	0.5182 (2)	0.0324 (6)
C4	0.0376 (2)	−0.2994 (3)	0.3838 (3)	0.0388 (7)
H4	−0.0028	−0.4034	0.3851	0.047*
N7	0.40073 (18)	0.4877 (3)	0.6744 (2)	0.0446 (6)
C5	0.4476 (2)	0.7649 (4)	0.5774 (3)	0.0543 (8)
H5	0.4900	0.8669	0.5828	0.065*
C6	0.3285 (2)	0.4650 (3)	0.5701 (2)	0.0343 (6)
C7	0.3123 (2)	0.5856 (3)	0.4680 (3)	0.0417 (7)
H7	0.2620	0.5636	0.3969	0.050*
C8	0.3724 (2)	0.7401 (4)	0.4729 (3)	0.0531 (8)
H8	0.3618	0.8257	0.4064	0.064*
C9	0.4592 (2)	0.6366 (4)	0.6738 (3)	0.0547 (8)
H9	0.5113	0.6543	0.7437	0.066*
H1	0.249 (2)	0.252 (4)	0.776 (4)	0.088 (11)*
H2	0.062 (2)	−0.262 (4)	0.179 (3)	0.081 (11)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N4	0.0456 (13)	0.0338 (12)	0.0232 (11)	0.0004 (10)	0.0025 (9)	−0.0019 (9)
N6	0.0522 (14)	0.0363 (13)	0.0222 (12)	−0.0021 (11)	0.0009 (10)	−0.0032 (10)
N2	0.0552 (15)	0.0364 (13)	0.0262 (13)	0.0000 (11)	−0.0009 (10)	−0.0045 (10)
N3	0.0461 (13)	0.0346 (13)	0.0291 (12)	−0.0022 (10)	−0.0010 (10)	0.0007 (9)
N5	0.0483 (14)	0.0354 (13)	0.0276 (12)	−0.0030 (10)	−0.0001 (10)	−0.0029 (9)
C1	0.0411 (15)	0.0302 (14)	0.0220 (13)	0.0052 (11)	0.0015 (11)	0.0005 (11)
N1	0.0539 (15)	0.0371 (13)	0.0248 (12)	−0.0014 (11)	0.0011 (10)	−0.0023 (9)
C2	0.0402 (15)	0.0325 (15)	0.0257 (14)	0.0036 (12)	0.0003 (11)	−0.0006 (11)
C3	0.0422 (15)	0.0304 (14)	0.0246 (13)	0.0019 (11)	0.0022 (11)	−0.0009 (11)
C4	0.0485 (17)	0.0348 (15)	0.0329 (15)	0.0001 (12)	−0.0002 (12)	−0.0018 (12)
N7	0.0514 (14)	0.0434 (14)	0.0379 (14)	−0.0093 (12)	−0.0042 (11)	−0.0014 (11)
C5	0.061 (2)	0.0467 (19)	0.056 (2)	−0.0133 (15)	0.0099 (16)	−0.0040 (16)
C6	0.0399 (15)	0.0334 (15)	0.0299 (14)	0.0039 (12)	0.0041 (11)	−0.0020 (11)
C7	0.0461 (17)	0.0409 (16)	0.0380 (16)	0.0001 (13)	0.0017 (12)	0.0001 (13)
C8	0.057 (2)	0.0426 (17)	0.060 (2)	0.0022 (15)	0.0098 (16)	0.0114 (16)
C9	0.057 (2)	0.058 (2)	0.0487 (19)	−0.0165 (16)	−0.0029 (15)	−0.0037 (16)

Geometric parameters (Å, º) top

N4—C2	1.326 (3)	C2—C6	1.467 (3)
N4—C3	1.356 (3)	C4—H4	0.9300
N6—C2	1.336 (3)	N7—C9	1.336 (3)
N6—N5	1.353 (3)	N7—C6	1.341 (3)
N6—H1	0.98 (4)	C5—C9	1.366 (4)
N2—C4	1.319 (3)	C5—C8	1.368 (4)
N2—N1	1.353 (3)	C5—H5	0.9300
N2—H2	0.99 (3)	C6—C7	1.372 (4)
N3—C4	1.322 (3)	C7—C8	1.380 (4)
N3—C1	1.354 (3)	C7—H7	0.9300
N5—C3	1.319 (3)	C8—H8	0.9300
C1—N1	1.318 (3)	C9—H9	0.9300
C1—C3	1.461 (3)

C2—N4—C3	102.9 (2)	N2—C4—N3	111.0 (2)
C2—N6—N5	110.4 (2)	N2—C4—H4	124.5
C2—N6—H1	131 (2)	N3—C4—H4	124.5
N5—N6—H1	119 (2)	C9—N7—C6	115.9 (2)
C4—N2—N1	109.8 (2)	C9—C5—C8	118.6 (3)
C4—N2—H2	131.2 (19)	C9—C5—H5	120.7
N1—N2—H2	118.9 (19)	C8—C5—H5	120.7
C4—N3—C1	102.0 (2)	N7—C6—C7	123.6 (2)
C3—N5—N6	102.2 (2)	N7—C6—C2	115.3 (2)
N1—C1—N3	114.9 (2)	C7—C6—C2	121.1 (2)
N1—C1—C3	121.6 (2)	C6—C7—C8	118.7 (3)
N3—C1—C3	123.5 (2)	C6—C7—H7	120.7
C1—N1—N2	102.3 (2)	C8—C7—H7	120.7
N4—C2—N6	109.7 (2)	C5—C8—C7	118.7 (3)
N4—C2—C6	126.1 (2)	C5—C8—H8	120.6
N6—C2—C6	124.2 (2)	C7—C8—H8	120.6
N5—C3—N4	114.8 (2)	N7—C9—C5	124.5 (3)
N5—C3—C1	121.9 (2)	N7—C9—H9	117.8
N4—C3—C1	123.3 (2)	C5—C9—H9	117.8

C2—N6—N5—C3	0.7 (3)	N1—C1—C3—N4	4.1 (4)
C4—N3—C1—N1	0.6 (3)	N3—C1—C3—N4	−176.4 (2)
C4—N3—C1—C3	−179.1 (2)	N1—N2—C4—N3	0.5 (3)
N3—C1—N1—N2	−0.3 (3)	C1—N3—C4—N2	−0.6 (3)
C3—C1—N1—N2	179.4 (2)	C9—N7—C6—C7	−0.9 (4)
C4—N2—N1—C1	−0.2 (3)	C9—N7—C6—C2	178.9 (2)
C3—N4—C2—N6	0.6 (3)	N4—C2—C6—N7	−147.8 (3)
C3—N4—C2—C6	179.8 (2)	N6—C2—C6—N7	31.2 (3)
N5—N6—C2—N4	−0.9 (3)	N4—C2—C6—C7	32.0 (4)
N5—N6—C2—C6	180.0 (2)	N6—C2—C6—C7	−149.0 (2)
N6—N5—C3—N4	−0.3 (3)	N7—C6—C7—C8	−0.8 (4)
N6—N5—C3—C1	179.4 (2)	C2—C6—C7—C8	179.5 (2)
C2—N4—C3—N5	−0.2 (3)	C9—C5—C8—C7	−0.9 (5)
C2—N4—C3—C1	−179.9 (2)	C6—C7—C8—C5	1.7 (4)
N1—C1—C3—N5	−175.6 (2)	C6—N7—C9—C5	1.7 (4)
N3—C1—C3—N5	3.9 (4)	C8—C5—C9—N7	−0.9 (5)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N6—H1···N4ⁱ	0.98 (4)	1.93 (4)	2.891 (3)	165 (3)
N2—H2···N3ⁱⁱ	0.99 (3)	1.90 (4)	2.878 (3)	167 (3)

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

Experimental details

Crystal data
Chemical formula	C₉H₇N₇
M_r	213.22
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	12.372 (3), 7.5361 (15), 10.007 (2)
β (°)	93.670 (4)
V (Å³)	931.1 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.11
Crystal size (mm)	0.24 × 0.20 × 0.20

Data collection
Diffractometer	Bruker SMART APEX diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.975, 0.979
No. of measured, independent and observed [I > 2σ(I)] reflections	5150, 1832, 1072
R_int	0.055
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.050, 0.156, 0.94
No. of reflections	1832
No. of parameters	154
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.26, −0.22

Computer programs: APEX2 (Bruker, 2003), SAINT (Bruker, 2003), 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
N6—H1···N4ⁱ	0.98 (4)	1.93 (4)	2.891 (3)	165 (3)
N2—H2···N3ⁱⁱ	0.99 (3)	1.90 (4)	2.878 (3)	167 (3)

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

Acknowledgements

This work was supported by the Natural Science Research Program of the Education Department of Henan Province (2011 A150015), the Henan Polytechnic University Foundation for Youths (P051102) and the Henan Polytechnic University Foundation for Doctor Teachers (B2010–65). The authors thank Dr D. Zhao for help with the diffraction analysis.

References

Bruker (2003). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Mai, X., Xia, H.-Y., Cao, Y.-S., Lu, X.-S. & Liao, Y.-J. (2009). Z. Kristallogr. New Cryst. Struct. 224, 547–548. CAS Google Scholar
Potts, K. T. (1960). Chem. Rev. 61, 87–127. CrossRef Web of Science Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Wiley, R. H. & Hart, A. J. (1953). J. Org. Chem. 18, 1368–1371. CrossRef CAS Web of Science Google Scholar
Zhang, C.-H., Zhang, J.-J., Li, W. & Liu, B.-H. (2010). Z. Kristallogr. New Cryst. Struct. 225, 599–600. CAS Google Scholar