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Acta Crystallogr Sect E Struct Rep Online. 2008 July 1; 64(Pt 7): o1269.
Published online 2008 June 13. doi:  10.1107/S160053680801742X
PMCID: PMC2961757

3,6-Di-4-pyridyl-1,4-dihydro-1,2,4,5-tetra­zine

Abstract

The mol­ecule of the title compound, C12H10N6, which is V-shaped due to the boat conformation of the dihydro­tetra­zine ring, has crystallographic C 2 symmetry. The dihedral angle between the planes of the two pyridine rings is 31.57 (3)°. Mol­ecules are linked by weak N—H(...)N and C—H(...)N hydrogen bonds, forming a two-dimensional polymeric structure.

Related literature

For related structures, see: Bradford et al. (2004 [triangle]); Caira et al. (1976 [triangle]); Liou et al. (1996 [triangle]); Zachara et al. (2004 [triangle]); Rao & Hu (2005 [triangle]). For related literature on tetra­zines, see: Sauer (1996 [triangle]).

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Object name is e-64-o1269-scheme1.jpg

Experimental

Crystal data

  • C12H10N6
  • M r = 238.26
  • Orthorhombic, An external file that holds a picture, illustration, etc.
Object name is e-64-o1269-efi3.jpg
  • a = 11.2862 (18) Å
  • b = 14.481 (2) Å
  • c = 6.8864 (12) Å
  • V = 1125.4 (3) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.09 mm−1
  • T = 293 (2) K
  • 0.50 × 0.10 × 0.10 mm

Data collection

  • Bruker SMART CCD area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2000 [triangle]) T min = 0.955, T max = 0.991
  • 4214 measured reflections
  • 1105 independent reflections
  • 938 reflections with I > 2σ(I)
  • R int = 0.032

Refinement

  • R[F 2 > 2σ(F 2)] = 0.050
  • wR(F 2) = 0.128
  • S = 1.08
  • 1105 reflections
  • 86 parameters
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.20 e Å−3
  • Δρmin = −0.14 e Å−3

Data collection: SMART (Bruker, 2000 [triangle]); cell refinement: SMART; data reduction: SAINT (Bruker, 2000 [triangle]); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXTL.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053680801742X/gk2149sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S160053680801742X/gk2149Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

The authors thank the Program for Young Excellent Talents in Southeast University for financial support.

supplementary crystallographic information

Comment

Tetrazine derivatives have been widely used in pesticides and herbicides as they have a high potential for biological activity and possess a wide range of antiviral and antitumor properties (Sauer, 1996). Herein, we report the crystal structure of a new tetrazine derivative, 3,6-di(pyridin-4-yl)-1,4-dihydro-1,2,4,5-tetrazine.

The molecule of the title compound, which has a crystallographic C2 symmetry is shown in Fig. 1. The title compound can be regarded as a V-shaped tetrazine with the dihedral angle between the pyridine rings of 31.57 (3) °. In the crystalline state, each molecule is connected to four adjacent molecules to form a two-dimensional (4,4) hydrogen-bonding network by the intermolecular N—H···N and weak C—H···N hydrogen bonds (Fig. 2.). Crystal structures of several other tetrazine derivatives with a similar shape have been reported (Bradford et al., 2004; Caira et al., 1976; Liou et al., 1996; Zachara et al., 2004; Rao & Hu, 2005).

Experimental

A mixture of 4-cyanopyridine (0.416g, 4.0 mmol), 80% hydrazine hydrate (5 ml), CoCl2.6H2O (0.238g, 1.0 mmol) and 95% ethanol (4 ml) was heated in a 15-mL Teflon-lined autoclave at 120°C deg for 3 days, followed by slow cooling (5°/h deg) to room temperature. The resulting mixture was washed with 95% ethanol, and red block crystals were collected and dried in air [yield 3.0% (14.3 mg) based on 4-cyanopyridine].

Refinement

H atoms bonded to N atoms were located in an electron-density difference map and refined isotropically without any restraints. Other H atoms were positioned geometrically and refined using a riding model with C—H = 0.93 Å and with Uiso(H) = 1.2Ueq(C).

Figures

Fig. 1.
The molecular structure of the title compound with 30% displacement ellipsoids. Symmetry code for the atoms designated with A: -1/2 - x, 1/2 - y, z.
Fig. 2.
A two-dimensional (4,4) hydrogen-bond network of the title compound viewed along the c axis

Crystal data

C12H10N6F000 = 496
Mr = 238.26Dx = 1.406 Mg m3
Orthorhombic, PccnMo Kα radiation λ = 0.71073 Å
Hall symbol: -P 2ab 2acCell parameters from 820 reflections
a = 11.2862 (18) Åθ = 2.5–28.0º
b = 14.481 (2) ŵ = 0.09 mm1
c = 6.8864 (12) ÅT = 293 (2) K
V = 1125.4 (3) Å3Block, red
Z = 40.50 × 0.10 × 0.10 mm

Data collection

Bruker SMART CCD area-detector diffractometer1105 independent reflections
Radiation source: fine-focus sealed tube938 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.032
Detector resolution: 0 pixels mm-1θmax = 26.0º
T = 293(2) Kθmin = 2.8º
[var phi] and ω scansh = −13→10
Absorption correction: multi-scan(SADABS; Bruker, 2000)k = −17→17
Tmin = 0.955, Tmax = 0.991l = −3→8
4214 measured reflections

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.050H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.128  w = 1/[σ2(Fo2) + (0.0618P)2 + 0.3052P] where P = (Fo2 + 2Fc2)/3
S = 1.08(Δ/σ)max < 0.001
1105 reflectionsΔρmax = 0.20 e Å3
86 parametersΔρmin = −0.14 e Å3
Primary atom site location: structure-invariant direct methodsExtinction correction: none

Special details

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)

xyzUiso*/Ueq
C10.56160 (17)0.17370 (13)0.1811 (4)0.0589 (7)
H1A0.57690.23510.15000.071*
C20.65246 (19)0.11530 (16)0.2327 (4)0.0683 (8)
H2A0.72860.13970.23700.082*
C30.52968 (17)−0.00510 (13)0.2686 (3)0.0463 (5)
H3A0.5172−0.06710.29710.056*
C40.43215 (16)0.04780 (12)0.2202 (3)0.0390 (5)
H4A0.35710.02140.21760.047*
C50.44678 (15)0.13961 (11)0.1762 (3)0.0322 (4)
C60.34693 (13)0.20078 (11)0.1238 (2)0.0296 (4)
N10.63928 (15)0.02634 (11)0.2770 (3)0.0526 (5)
N20.36287 (11)0.28776 (9)0.1283 (2)0.0331 (4)
N30.26087 (12)0.33789 (10)0.0671 (2)0.0332 (4)
H3B0.2708 (17)0.3931 (14)0.097 (3)0.047 (6)*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
C10.0310 (11)0.0379 (11)0.108 (2)−0.0006 (8)−0.0039 (11)0.0119 (11)
C20.0282 (11)0.0536 (13)0.123 (2)0.0004 (9)−0.0073 (12)0.0094 (14)
C30.0396 (13)0.0355 (10)0.0639 (14)0.0077 (8)−0.0012 (9)0.0042 (9)
C40.0294 (10)0.0324 (9)0.0553 (12)0.0011 (7)−0.0008 (8)0.0023 (8)
C50.0273 (9)0.0314 (9)0.0379 (9)0.0025 (7)0.0029 (7)−0.0026 (7)
C60.0255 (9)0.0272 (8)0.0360 (9)−0.0013 (6)0.0027 (7)−0.0009 (7)
N10.0357 (10)0.0463 (10)0.0756 (13)0.0111 (7)−0.0021 (8)0.0028 (9)
N20.0238 (8)0.0283 (7)0.0471 (9)0.0007 (6)0.0036 (6)0.0006 (6)
N30.0270 (8)0.0239 (7)0.0487 (9)0.0011 (6)0.0019 (6)0.0030 (6)

Geometric parameters (Å, °)

C1—C21.376 (3)C4—C51.374 (2)
C1—C51.387 (2)C4—H4A0.9300
C1—H1A0.9300C5—C61.478 (2)
C2—N11.332 (3)C6—N21.273 (2)
C2—H2A0.9300C6—N3i1.395 (2)
C3—N11.319 (2)N2—N31.4249 (18)
C3—C41.382 (3)N3—C6i1.395 (2)
C3—H3A0.9300N3—H3B0.83 (2)
C2—C1—C5118.94 (18)C4—C5—C1116.82 (16)
C2—C1—H1A120.5C4—C5—C6122.84 (15)
C5—C1—H1A120.5C1—C5—C6120.33 (16)
N1—C2—C1124.8 (2)N2—C6—N3i121.83 (14)
N1—C2—H2A117.6N2—C6—C5118.64 (15)
C1—C2—H2A117.6N3i—C6—C5119.51 (14)
N1—C3—C4124.48 (18)C3—N1—C2115.36 (17)
N1—C3—H3A117.8C6—N2—N3112.51 (13)
C4—C3—H3A117.8C6i—N3—N2114.66 (12)
C5—C4—C3119.61 (17)C6i—N3—H3B115.7 (14)
C5—C4—H4A120.2N2—N3—H3B107.9 (14)
C3—C4—H4A120.2

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

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N3—H3B···N1ii0.83 (2)2.35 (2)3.142 (2)159.8 (18)
C3—H3A···N2iii0.932.553.312 (2)139
C4—H4A···N1iv0.932.553.475 (3)171

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: GK2149).

References

  • Bradford, F. E., Connor, L. P., Kilner, C. A. & Halcrow, M. A. (2004). Polyhedron, 23, 2141–2151.
  • Bruker (2000). SMART, SAINT andSADABS Bruker AXS Inc., Madison, Wisconsin, USA.
  • Caira, M. R., Giles, R. G. F., Nassimbeni, L. R., Sheldrick, G. M. & Hazell, R. G. (1976). Acta Cryst. B32, 1467–1469.
  • Liou, L.-S., Chen, P.-S., Sun, C.-H. & Wang, J.-C. (1996). Acta Cryst. C52, 1841–1843.
  • Rao, G.-W. & Hu, W.-X. (2005). Acta Cryst. E61, o3664–o3665.
  • Sauer, J. (1996). Comprehensive Heterocyclic Chemistry, 2nd ed., edited by A. J. Boulton, Vol. 6, pp. 901–955. Oxford: Elsevier.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Zachara, J., Madura, I. & Włostowski, M. (2004). Acta Cryst. C60, o57–o59. [PubMed]

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography