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

Wang, H.; Dong, H.-Z.; Lu, N.; Zhu, H.-B.

doi:10.1107/S160053680801742X

organic compounds

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ISSN: 2056-9890

Volume 64| Part 7| July 2008| Page o1269

doi:10.1107/S160053680801742X

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

Hai Wang,^a Hua-Ze Dong,^b Ning Lu ^b and Hai-Bin Zhu ^a ^*

^aDepartment of Chemistry and Chemical Engineering, Southeast University, Nanjing, People's Republic of China, and ^bDepartment of Chemistry and Chemical Engineering, State Key Laboratory of Coordination Chemistry, Nanjing University, Nanjing, People's Republic of China
^*Correspondence e-mail: cep02chl@yahoo.cn

(Received 26 May 2008; accepted 10 June 2008; online 13 June 2008)

The molecule of the title compound, C₁₂H₁₀N₆, which is V-shaped due to the boat conformation of the dihydrotetrazine ring, has crystallographic C₂ 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 ); Caira et al. (1976 ); Liou et al. (1996 ); Zachara et al. (2004 ); Rao & Hu (2005 ). For related literature on tetrazines, see: Sauer (1996 ).

Experimental

Crystal data

C₁₂H₁₀N₆
M_r = 238.26
Orthorhombic, P c c n
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 ) 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[F² > 2σ(F²)] = 0.050
wR(F²) = 0.128
S = 1.08
1105 reflections
86 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.20 e Å⁻³
Δρ_min = −0.14 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3B⋯N1ⁱ	0.83 (2)	2.35 (2)	3.142 (2)	159.8 (18)
C3—H3A⋯N2ⁱⁱ	0.93	2.55	3.312 (2)	139
C4—H4A⋯N1ⁱⁱⁱ	0.93	2.55	3.475 (3)	171
Symmetry codes: (i) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iii) $[x-{\script{1\over 2}}, -y, -z+{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 2000); cell refinement: SMART; data reduction: SAINT (Bruker, 2000); 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/S160053680801742X/gk2149sup1.cif

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

checkCIF report

Comment top

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).

Related literature top

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

Experimental top

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].

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SMART (Bruker, 2000); data reduction: SAINT (Bruker, 2000); 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 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

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

Crystal data top

C₁₂H₁₀N₆	F(000) = 496
M_r = 238.26	D_x = 1.406 Mg m⁻³
Orthorhombic, Pccn	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ab 2ac	Cell parameters from 820 reflections
a = 11.2862 (18) Å	θ = 2.5–28.0°
b = 14.481 (2) Å	µ = 0.09 mm⁻¹
c = 6.8864 (12) Å	T = 293 K
V = 1125.4 (3) Å³	Block, red
Z = 4	0.50 × 0.10 × 0.10 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	1105 independent reflections
Radiation source: fine-focus sealed tube	938 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.032
Detector resolution: 0 pixels mm^-1	θ_max = 26.0°, θ_min = 2.8°
ϕ and ω scans	h = −13→10
Absorption correction: multi-scan (SADABS; Bruker, 2000)	k = −17→17
T_min = 0.955, T_max = 0.991	l = −3→8
4214 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.050	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.128	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	w = 1/[σ²(F_o²) + (0.0618P)² + 0.3052P] where P = (F_o² + 2F_c²)/3
1105 reflections	(Δ/σ)_max < 0.001
86 parameters	Δρ_max = 0.20 e Å⁻³
0 restraints	Δρ_min = −0.14 e Å⁻³

Crystal data top

C₁₂H₁₀N₆	V = 1125.4 (3) Å³
M_r = 238.26	Z = 4
Orthorhombic, Pccn	Mo Kα radiation
a = 11.2862 (18) Å	µ = 0.09 mm⁻¹
b = 14.481 (2) Å	T = 293 K
c = 6.8864 (12) Å	0.50 × 0.10 × 0.10 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	1105 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2000)	938 reflections with I > 2σ(I)
T_min = 0.955, T_max = 0.991	R_int = 0.032
4214 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.050	0 restraints
wR(F²) = 0.128	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	Δρ_max = 0.20 e Å⁻³
1105 reflections	Δρ_min = −0.14 e Å⁻³
86 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
C1	0.56160 (17)	0.17370 (13)	0.1811 (4)	0.0589 (7)
H1A	0.5769	0.2351	0.1500	0.071*
C2	0.65246 (19)	0.11530 (16)	0.2327 (4)	0.0683 (8)
H2A	0.7286	0.1397	0.2370	0.082*
C3	0.52968 (17)	−0.00510 (13)	0.2686 (3)	0.0463 (5)
H3A	0.5172	−0.0671	0.2971	0.056*
C4	0.43215 (16)	0.04780 (12)	0.2202 (3)	0.0390 (5)
H4A	0.3571	0.0214	0.2176	0.047*
C5	0.44678 (15)	0.13961 (11)	0.1762 (3)	0.0322 (4)
C6	0.34693 (13)	0.20078 (11)	0.1238 (2)	0.0296 (4)
N1	0.63928 (15)	0.02634 (11)	0.2770 (3)	0.0526 (5)
N2	0.36287 (11)	0.28776 (9)	0.1283 (2)	0.0331 (4)
N3	0.26087 (12)	0.33789 (10)	0.0671 (2)	0.0332 (4)
H3B	0.2708 (17)	0.3931 (14)	0.097 (3)	0.047 (6)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0310 (11)	0.0379 (11)	0.108 (2)	−0.0006 (8)	−0.0039 (11)	0.0119 (11)
C2	0.0282 (11)	0.0536 (13)	0.123 (2)	0.0004 (9)	−0.0073 (12)	0.0094 (14)
C3	0.0396 (13)	0.0355 (10)	0.0639 (14)	0.0077 (8)	−0.0012 (9)	0.0042 (9)
C4	0.0294 (10)	0.0324 (9)	0.0553 (12)	0.0011 (7)	−0.0008 (8)	0.0023 (8)
C5	0.0273 (9)	0.0314 (9)	0.0379 (9)	0.0025 (7)	0.0029 (7)	−0.0026 (7)
C6	0.0255 (9)	0.0272 (8)	0.0360 (9)	−0.0013 (6)	0.0027 (7)	−0.0009 (7)
N1	0.0357 (10)	0.0463 (10)	0.0756 (13)	0.0111 (7)	−0.0021 (8)	0.0028 (9)
N2	0.0238 (8)	0.0283 (7)	0.0471 (9)	0.0007 (6)	0.0036 (6)	0.0006 (6)
N3	0.0270 (8)	0.0239 (7)	0.0487 (9)	0.0011 (6)	0.0019 (6)	0.0030 (6)

Geometric parameters (Å, º) top

C1—C2	1.376 (3)	C4—C5	1.374 (2)
C1—C5	1.387 (2)	C4—H4A	0.9300
C1—H1A	0.9300	C5—C6	1.478 (2)
C2—N1	1.332 (3)	C6—N2	1.273 (2)
C2—H2A	0.9300	C6—N3ⁱ	1.395 (2)
C3—N1	1.319 (2)	N2—N3	1.4249 (18)
C3—C4	1.382 (3)	N3—C6ⁱ	1.395 (2)
C3—H3A	0.9300	N3—H3B	0.83 (2)

C2—C1—C5	118.94 (18)	C4—C5—C1	116.82 (16)
C2—C1—H1A	120.5	C4—C5—C6	122.84 (15)
C5—C1—H1A	120.5	C1—C5—C6	120.33 (16)
N1—C2—C1	124.8 (2)	N2—C6—N3ⁱ	121.83 (14)
N1—C2—H2A	117.6	N2—C6—C5	118.64 (15)
C1—C2—H2A	117.6	N3ⁱ—C6—C5	119.51 (14)
N1—C3—C4	124.48 (18)	C3—N1—C2	115.36 (17)
N1—C3—H3A	117.8	C6—N2—N3	112.51 (13)
C4—C3—H3A	117.8	C6ⁱ—N3—N2	114.66 (12)
C5—C4—C3	119.61 (17)	C6ⁱ—N3—H3B	115.7 (14)
C5—C4—H4A	120.2	N2—N3—H3B	107.9 (14)
C3—C4—H4A	120.2

Symmetry code: (i) −x+1/2, −y+1/2, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3B···N1ⁱⁱ	0.83 (2)	2.35 (2)	3.142 (2)	159.8 (18)
C3—H3A···N2ⁱⁱⁱ	0.93	2.55	3.312 (2)	139
C4—H4A···N1^iv	0.93	2.55	3.475 (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.

Experimental details

Crystal data
Chemical formula	C₁₂H₁₀N₆
M_r	238.26
Crystal system, space group	Orthorhombic, Pccn
Temperature (K)	293
a, b, c (Å)	11.2862 (18), 14.481 (2), 6.8864 (12)
V (Å³)	1125.4 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.50 × 0.10 × 0.10

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2000)
T_min, T_max	0.955, 0.991
No. of measured, independent and observed [I > 2σ(I)] reflections	4214, 1105, 938
R_int	0.032
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.050, 0.128, 1.08
No. of reflections	1105
No. of parameters	86
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.20, −0.14

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), 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
N3—H3B···N1ⁱ	0.83 (2)	2.35 (2)	3.142 (2)	159.8 (18)
C3—H3A···N2ⁱⁱ	0.93	2.55	3.312 (2)	139.0
C4—H4A···N1ⁱⁱⁱ	0.93	2.55	3.475 (3)	171.0

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

Acknowledgements

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

References

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