organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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1-[3-(4-Meth­oxy­phen­yl)-6-methyl-1,6-di­hydro-1,2,4,5-tetra­zin-1-yl]propanone

aDepartment of Biological and Chemical Engineering, Taizhou Vocational and Technical college, Taizhou 318000, People's Republic of China
*Correspondence e-mail: xufeng901@126.com

(Received 22 March 2010; accepted 24 March 2010; online 27 March 2010)

In the title compound, C13H16N4O2, the central tetra­zine ring adopts an unsymmetrical boat conformation with the two C atoms as flagpoles. This compound can be considered as having homoaromaticity.

Related literature

For the biological activity of 1,2,4,5-tetra­zine derivatives, see: Sauer (1996[Sauer, J. (1996). Comprehensive Heterocyclic Chemistry, 2nd ed., edited by A. J. Boulton, Vol. 6, pp. 901-955. Oxford: Elsevier.]). For related structures, see: Jennison et al. (1986[Jennison, C. P. R., Mackay, D., Watson, K. N. & Taylor, N. J. (1986). J. Org. Chem. 51, 3043-3051.]); Stam et al. (1982[Stam, C. H., Counotte-Potman, A. D. & Van der Plas, H. C. (1982). J. Org. Chem. 47, 2856-2858.]); Xu et al. (2010[Xu, F., Yang, Z. Z., Hu, W. X. & Xi, L. M. (2010). Chin. J. Org. Chem. 30, 260-265.]). For the structure–activity relationships of 1,6-dihydro-1,2,4,5-tetra­zine derivatives, see: Hu et al. (2004[Hu, W. X., Rao, G. W. & Sun, Y. Q. (2004). Bioorg. Med. Chem. Lett. 14, 1177-1181.], 2005[Hu, W. X., Shi, H. B., Yuan, Q. & Sun, Y. Q. (2005). J. Chem. Res. pp. 291-293.]).

[Scheme 1]

Experimental

Crystal data
  • C13H16N4O2

  • Mr = 260.30

  • Triclinic, [P \overline 1]

  • a = 8.345 (2) Å

  • b = 8.4898 (19) Å

  • c = 10.245 (3) Å

  • α = 113.232 (6)°

  • β = 99.820 (15)°

  • γ = 93.268 (11)°

  • V = 651.0 (3) Å3

  • Z = 2

  • Mo Kα radiation

  • μ = 0.09 mm−1

  • T = 93 K

  • 0.50 × 0.37 × 0.23 mm

Data collection
  • Rigaku AFC10/Saturn724+ diffractometer

  • 6410 measured reflections

  • 2920 independent reflections

  • 2207 reflections with I > 2σ(I)

  • Rint = 0.022

Refinement
  • R[F2 > 2σ(F2)] = 0.036

  • wR(F2) = 0.081

  • S = 1.00

  • 2920 reflections

  • 175 parameters

  • H-atom parameters constrained

  • Δρmax = 0.32 e Å−3

  • Δρmin = −0.21 e Å−3

Data collection: CrystalClear (Rigaku/MSC, 2008[Rigaku/MSC (2008). CrystalClear. Rigaku/MSC Inc., The Woodlands, Texas, USA.]); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); software used to prepare material for publication: SHELXTL.

Supporting information


Comment top

1,2,4,5-Tetrazine derivatives have high potential for biological activity, possessing a wide spectrum of antiviral and antitumor properties. They have been widely used in pesticides and herbicides (Sauer, 1996). Dihydro-1,2,4,5- tetrazine has four isomers, namely 1,2-, 1,4-, 1,6- and 3,6-dihydro-1,2,4,5- tetrazines. The 1,6-dihydro structures (Stam et al., 1982; Jennison et al., 1986) were found, by X-ray diffraction, to be homoaromatic. In continuation of our work on the structure-activity relationship of 1,6-dihydro-1,2,4,5-tetrazine derivatives (Hu et al., 2004,2005), we report here the crystal structure of the title compound (I) (Fig. 1).

In the tetrazine ring, atoms N1, N2, N3 and N4 are coplanar, while atoms C7 and C8 deviate from the plane by 0.239 (2) and 0.595 (2) Å, respectively. The N2/C7/N3 and N1/C8/N4 planes make dihedral angles of 21.0 (2)° and 42.2 (1)°, respectively, with the N1/N2/ N3/N4 plane, i.e. the tetrazine ring adopts an unsymmetrical boat conformation. The benzene ring make dihedral angle of 16.7 (1)° with the N1/N2/N3/N4 plane. Atom N1 is almost sp2 hybridized due to the angles around it add up to 360.0 (2)°. In keeping with similar situations in 3-phenyl-6-ethyl-1,6-dihydro- 1,2,4,5-tetrazine (Stam et al., 1982), N-(2-methylphenyl)-3-phenyl-6-methyl-1,6-dihydro-1,2,4,5-tetrazine (Xu et al., 2010) and 1-acetyl-3,6-dimethyl-1,2,4,5-tetrazine (Jennison et al., 1986), it can be considered that the molecule is homoaromatic.

Related literature top

For the biological activity of 1,2,4,5-tetrazine derivatives, see: Sauer (1996). For related structures, see: Jennison et al. (1986); Stam et al. (1982); Xu et al. (2010). For the structure–activity relationship of 1,6-dihydro-1,2,4,5-tetrazine derivatives, see: Hu et al. (2004, 2005).

Experimental top

3-(4-Methoxyphenyl)-6-methyl-1,6-dihydro-1,2,4,5-tetrazine (3.0 mmol), chloroform (10 ml) and pyridine (0.25 ml,3.1 mmol) were mixed. Propionyl chloride(3.0 mmol) in chloroform (10 ml) was added dropwise with stirring at room temperature. After the starting, 1,6-dihydro-1,2,4,5-tetrazine was completely consumed (the reaction courses was monitored by TLC, dichloromethane system), evaporation of the chloroform, crude 1-propionyl-3-(4-methoxyphenyl)-6-methyl- 1,6-dihydro-1,2,4,5-tetrazine was obtained and purified by preparative thin-layer chromatography over silica gel GF254(2 mm) (dichloromethane-petroleum ether, 1:1). The solution of the compound in anhydrous ethanol was concentrated gradually at room temperature to afford single crystals, which was suitable for X-ray diffraction (m.p. 340–342 K).1H NMR (CDCl3) δ p.p.m.: 8.10 (d,2H, J = 8.8 Hz), 7.03 (d,2H, J = 8.8 Hz), 6.84 (q,1H, J = 6.4 Hz), 3.89 (s,3H), 2.95–3.05(m,1H,CH2), 2.72–2.85(m,1H,CH2),1.20(t,3H, J = 7.6 Hz), 1.04 (d,3H, J = 6.4 Hz).

Refinement top

H atoms were placed in calculated positions with N—H = 0.86 Å, C-H = 0.93 (aromatic) and 0.96 Å (methyl), and refined in riding model, with Uiso(H) = 1.2Ueq(C,N) and 1.5Ueq(Cmethyl).

Computing details top

Data collection: CrystalClear (Rigaku/MSC, 2008); cell refinement: CrystalClear (Rigaku/MSC, 2008); data reduction: CrystalClear (Rigaku/MSC, 2008); 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
[Figure 1] Fig. 1. The molecular structure of the title compound, showing 50% probability displacement ellipsoids and the atomic numbering.
1-[3-(4-Methoxyphenyl)-6-methyl-1,6-dihydro-1,2,4,5-tetrazin-1-yl]propanone top
Crystal data top
C13H16N4O2Z = 2
Mr = 260.30F(000) = 276
Triclinic, P1Dx = 1.328 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 8.345 (2) ÅCell parameters from 1846 reflections
b = 8.4898 (19) Åθ = 3.4–27.5°
c = 10.245 (3) ŵ = 0.09 mm1
α = 113.232 (6)°T = 93 K
β = 99.820 (15)°Prism, red
γ = 93.268 (11)°0.50 × 0.37 × 0.23 mm
V = 651.0 (3) Å3
Data collection top
Rigaku AFC10/Saturn724+
diffractometer
2207 reflections with I > 2σ(I)
Radiation source: Rotating AnodeRint = 0.022
Graphite monochromatorθmax = 27.5°, θmin = 3.4°
Detector resolution: 28.5714 pixels mm-1h = 1010
ϕ and ω scansk = 1111
6410 measured reflectionsl = 1312
2920 independent reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.036Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.081H-atom parameters constrained
S = 1.00 w = 1/[σ2(Fo2) + (0.0282P)2 + 0.16P]
where P = (Fo2 + 2Fc2)/3
2920 reflections(Δ/σ)max = 0.001
175 parametersΔρmax = 0.32 e Å3
0 restraintsΔρmin = 0.21 e Å3
Crystal data top
C13H16N4O2γ = 93.268 (11)°
Mr = 260.30V = 651.0 (3) Å3
Triclinic, P1Z = 2
a = 8.345 (2) ÅMo Kα radiation
b = 8.4898 (19) ŵ = 0.09 mm1
c = 10.245 (3) ÅT = 93 K
α = 113.232 (6)°0.50 × 0.37 × 0.23 mm
β = 99.820 (15)°
Data collection top
Rigaku AFC10/Saturn724+
diffractometer
2207 reflections with I > 2σ(I)
6410 measured reflectionsRint = 0.022
2920 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0360 restraints
wR(F2) = 0.081H-atom parameters constrained
S = 1.00Δρmax = 0.32 e Å3
2920 reflectionsΔρmin = 0.21 e Å3
175 parameters
Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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
O11.03435 (11)0.17376 (12)0.48191 (9)0.0240 (2)
O20.16763 (10)0.73207 (11)0.11227 (10)0.0240 (2)
N10.33360 (12)0.55086 (13)0.15664 (11)0.0189 (2)
N20.47200 (12)0.53199 (13)0.23910 (11)0.0186 (2)
N30.47565 (13)0.27926 (13)0.02813 (11)0.0209 (2)
N40.34190 (13)0.29167 (14)0.04264 (11)0.0224 (2)
C10.69924 (15)0.41266 (16)0.41273 (13)0.0193 (3)
H10.64250.50410.46310.023*
C20.82340 (15)0.36341 (16)0.49081 (13)0.0198 (3)
H20.85120.42070.59380.024*
C30.90723 (14)0.22979 (16)0.41785 (13)0.0179 (3)
C40.86288 (15)0.14452 (16)0.26693 (13)0.0213 (3)
H40.91830.05160.21690.026*
C50.73919 (15)0.19411 (16)0.18974 (13)0.0198 (3)
H50.71020.13510.08690.024*
C60.65589 (14)0.33049 (15)0.26145 (13)0.0166 (3)
C70.52322 (15)0.38258 (16)0.18025 (13)0.0174 (3)
C80.23071 (15)0.39564 (16)0.04682 (13)0.0197 (3)
H80.14750.42950.01630.024*
C90.14232 (16)0.29206 (17)0.11103 (14)0.0229 (3)
H9A0.22130.27380.18460.027*
H9B0.09080.17980.03390.027*
H9C0.05770.35560.15610.027*
C100.29499 (15)0.71638 (16)0.18095 (13)0.0188 (3)
C110.41530 (15)0.86447 (16)0.29536 (13)0.0211 (3)
H11A0.52560.85460.27200.025*
H11B0.42150.85830.39060.025*
C120.36603 (17)1.03756 (17)0.30564 (15)0.0267 (3)
H12A0.35731.04290.21090.032*
H12B0.44921.13110.37820.032*
H12C0.25981.05060.33450.032*
C131.07827 (16)0.24669 (18)0.63702 (14)0.0246 (3)
H13A1.10830.37220.67370.030*
H13B1.17190.19570.66800.030*
H13C0.98480.22220.67570.030*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0227 (5)0.0325 (5)0.0196 (5)0.0115 (4)0.0026 (4)0.0134 (4)
O20.0192 (5)0.0280 (5)0.0261 (5)0.0064 (4)0.0008 (4)0.0134 (4)
N10.0169 (5)0.0206 (5)0.0185 (5)0.0019 (4)0.0015 (4)0.0094 (4)
N20.0166 (5)0.0217 (5)0.0192 (5)0.0028 (4)0.0004 (4)0.0114 (4)
N30.0206 (6)0.0244 (6)0.0174 (5)0.0031 (4)0.0013 (4)0.0094 (5)
N40.0210 (6)0.0256 (6)0.0195 (5)0.0030 (5)0.0004 (5)0.0096 (5)
C10.0184 (6)0.0202 (6)0.0187 (6)0.0047 (5)0.0037 (5)0.0073 (5)
C20.0205 (6)0.0224 (6)0.0151 (6)0.0019 (5)0.0014 (5)0.0073 (5)
C30.0147 (6)0.0219 (6)0.0200 (6)0.0027 (5)0.0020 (5)0.0123 (5)
C40.0239 (7)0.0220 (6)0.0199 (6)0.0088 (5)0.0065 (5)0.0091 (5)
C50.0227 (7)0.0210 (6)0.0144 (6)0.0033 (5)0.0022 (5)0.0066 (5)
C60.0147 (6)0.0182 (6)0.0181 (6)0.0001 (5)0.0017 (5)0.0096 (5)
C70.0157 (6)0.0207 (6)0.0169 (6)0.0007 (5)0.0026 (5)0.0094 (5)
C80.0173 (6)0.0218 (6)0.0180 (6)0.0017 (5)0.0015 (5)0.0083 (5)
C90.0200 (6)0.0238 (7)0.0237 (7)0.0003 (5)0.0008 (5)0.0103 (5)
C100.0188 (6)0.0232 (6)0.0184 (6)0.0053 (5)0.0057 (5)0.0118 (5)
C110.0212 (7)0.0218 (7)0.0209 (7)0.0048 (5)0.0024 (5)0.0101 (5)
C120.0261 (7)0.0213 (7)0.0332 (8)0.0049 (5)0.0047 (6)0.0120 (6)
C130.0222 (7)0.0329 (7)0.0200 (7)0.0043 (6)0.0006 (5)0.0141 (6)
Geometric parameters (Å, º) top
O1—C31.3596 (14)C5—C61.3995 (17)
O1—C131.4291 (15)C5—H50.95
O2—C101.2155 (14)C6—C71.4647 (16)
N1—N21.3669 (14)C8—C91.5160 (17)
N1—C101.3941 (16)C8—H81.00
N1—C81.4531 (15)C9—H9A0.98
N2—C71.3044 (16)C9—H9B0.98
N3—N41.2571 (14)C9—H9C0.98
N3—C71.4236 (16)C10—C111.5015 (17)
N4—C81.4917 (16)C11—C121.5169 (17)
C1—C21.3852 (17)C11—H11A0.99
C1—C61.3952 (17)C11—H11B0.99
C1—H10.95C12—H12A0.98
C2—C31.3911 (17)C12—H12B0.98
C2—H20.95C12—H12C0.98
C3—C41.3939 (17)C13—H13A0.98
C4—C51.3791 (17)C13—H13B0.98
C4—H40.95C13—H13C0.98
C3—O1—C13118.23 (10)N1—C8—H8108.9
N2—N1—C10119.47 (10)N4—C8—H8108.9
N2—N1—C8118.20 (10)C9—C8—H8108.9
C10—N1—C8122.32 (10)C8—C9—H9A109.5
C7—N2—N1113.70 (10)C8—C9—H9B109.5
N4—N3—C7120.02 (11)H9A—C9—H9B109.5
N3—N4—C8115.25 (10)C8—C9—H9C109.5
C2—C1—C6121.25 (12)H9A—C9—H9C109.5
C2—C1—H1119.4H9B—C9—H9C109.5
C6—C1—H1119.4O2—C10—N1119.15 (11)
C1—C2—C3119.76 (11)O2—C10—C11124.57 (12)
C1—C2—H2120.1N1—C10—C11116.27 (10)
C3—C2—H2120.1C10—C11—C12111.53 (11)
O1—C3—C2125.16 (11)C10—C11—H11A109.3
O1—C3—C4115.33 (11)C12—C11—H11A109.3
C2—C3—C4119.50 (11)C10—C11—H11B109.3
C5—C4—C3120.48 (12)C12—C11—H11B109.3
C5—C4—H4119.8H11A—C11—H11B108.0
C3—C4—H4119.8C11—C12—H12A109.5
C4—C5—C6120.64 (11)C11—C12—H12B109.5
C4—C5—H5119.7H12A—C12—H12B109.5
C6—C5—H5119.7C11—C12—H12C109.5
C1—C6—C5118.35 (11)H12A—C12—H12C109.5
C1—C6—C7120.72 (11)H12B—C12—H12C109.5
C5—C6—C7120.91 (11)O1—C13—H13A109.5
N2—C7—N3121.12 (11)O1—C13—H13B109.5
N2—C7—C6121.13 (11)H13A—C13—H13B109.5
N3—C7—C6116.68 (11)O1—C13—H13C109.5
N1—C8—N4106.07 (9)H13A—C13—H13C109.5
N1—C8—C9112.98 (10)H13B—C13—H13C109.5
N4—C8—C9110.99 (10)
C10—N1—N2—C7159.83 (10)N4—N3—C7—C6164.47 (10)
C8—N1—N2—C720.73 (14)C1—C6—C7—N218.43 (17)
C7—N3—N4—C89.80 (16)C5—C6—C7—N2163.36 (11)
C6—C1—C2—C30.09 (18)C1—C6—C7—N3173.30 (11)
C13—O1—C3—C25.43 (17)C5—C6—C7—N34.91 (16)
C13—O1—C3—C4175.44 (11)N2—N1—C8—N452.33 (13)
C1—C2—C3—O1177.78 (11)C10—N1—C8—N4128.25 (11)
C1—C2—C3—C41.32 (18)N2—N1—C8—C969.47 (13)
O1—C3—C4—C5177.85 (11)C10—N1—C8—C9109.95 (13)
C2—C3—C4—C51.33 (18)N3—N4—C8—N145.04 (13)
C3—C4—C5—C60.12 (18)N3—N4—C8—C978.02 (13)
C2—C1—C6—C51.10 (17)N2—N1—C10—O2176.38 (11)
C2—C1—C6—C7179.36 (11)C8—N1—C10—O23.04 (17)
C4—C5—C6—C11.09 (17)N2—N1—C10—C112.16 (16)
C4—C5—C6—C7179.34 (11)C8—N1—C10—C11178.43 (10)
N1—N2—C7—N320.73 (16)O2—C10—C11—C125.10 (17)
N1—N2—C7—C6171.53 (10)N1—C10—C11—C12176.46 (11)
N4—N3—C7—N227.26 (17)

Experimental details

Crystal data
Chemical formulaC13H16N4O2
Mr260.30
Crystal system, space groupTriclinic, P1
Temperature (K)93
a, b, c (Å)8.345 (2), 8.4898 (19), 10.245 (3)
α, β, γ (°)113.232 (6), 99.820 (15), 93.268 (11)
V3)651.0 (3)
Z2
Radiation typeMo Kα
µ (mm1)0.09
Crystal size (mm)0.50 × 0.37 × 0.23
Data collection
DiffractometerRigaku AFC10/Saturn724+
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
6410, 2920, 2207
Rint0.022
(sin θ/λ)max1)0.649
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.036, 0.081, 1.00
No. of reflections2920
No. of parameters175
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.32, 0.21

Computer programs: CrystalClear (Rigaku/MSC, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

 

Acknowledgements

The authors are grateful to the Science Foundation for Excellent Youth Scholars of the Department of Education of Zhejiang province and the Foundation of Taizhou Vocational and Technical College (grant No. 2010ZD08) for financial support.

References

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First citationXu, F., Yang, Z. Z., Hu, W. X. & Xi, L. M. (2010). Chin. J. Org. Chem. 30, 260–265.  CAS Google Scholar

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