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access1-[3-(4-Chlorophenyl)-6-methyl-1,6-dihydro-1,2,4,5-tetrazin-1-yl]ethanone
aDepartment of Biological & Chemical Engineering, Taizhou Vocational & Technical College, Taizhou, 318000, People's Republic of China
*Correspondence e-mail: xufeng901@126.com
In the title compound, C11H11ClN4O, the tetrazine ring adopts a non-symmetrical boat conformation. The crystal packing exhibits relatively short intermolecular C⋯N contacts of 3.118 (3) Å.
Related literature
For related structures, see: Hu et al. (2004![[Hu, W. X., Rao, G. W. & Sun, Y. Q. (2004). Bioorg. Med. Chem. Lett. 14, 1177-1181.]](../../../../../../logos/arrows/e_arr.gif "Hu, W. X., Rao, G. W. & Sun, Y. Q. (2004). Bioorg. Med. Chem. Lett. 14, 1177-1181.")
, 2005); Jennison et al. (1986); Stam et al. (1982); Xu et al. (2010); Yang et al. (2010). For applications of 1,2,4,5-tetrazine derivatives, see: Sauer (1996).
![[Scheme 1]](cv2768scheme1.gif)
Experimental
Crystal data
|
Data collection: CrystalClear (Rigaku/MSC, 2008); cell CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97.
Supporting information
contains datablocks global, I. DOI: 10.1107/S1600536810037839/cv2768sup1.cif
Structure factors: contains datablock I. DOI: 10.1107/S1600536810037839/cv2768Isup2.hkl
3-(4-Chlorophenyl)-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. Acetyl 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-acetyl-3-(4-chlorophenyl)-6-methyl- 1,6-dihydro-1,2,4,5-tetrazine was obtained and purified by preparative 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. 352–354 K).1H NMR (CDCl3) δ p.p.m.: 8.10 (d,2H, J = 8.0 Hz), 7.49 (d,2H, J = 8.0 Hz), 6.87 (q,1H, J = 6.7 Hz), 2.49(s,3H), 1.05(d,3H, J = 6.4 Hz).
Methyl H atoms were placed in calculated positions with C—H = 0.96 Å and torsion angles were refined to fit the electron density, Uiso(H) = 1.5Ueq(C). Other H atoms were placed in calculated positions with C—H = 0.93 and N—H = 0.86 Å, and refined in riding mode, with Uiso(H) = 1.2Ueq(C,N).
Data collection: CrystalClear (Rigaku/MSC, 2008); cell 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: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).
![[Figure 1]](./cv2768fig1thm.gif)
| C11H11ClN4O | F(000) = 1040 |
| Mr = 250.69 | Dx = 1.411 Mg m−3 |
| Orthorhombic, Pbca | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: -P 2ac 2ab | Cell parameters from 6560 reflections |
| a = 15.165 (3) Å | θ = 3.1–27.5° |
| b = 8.0452 (15) Å | µ = 0.31 mm−1 |
| c = 19.349 (4) Å | T = 93 K |
| V = 2360.7 (8) Å3 | Block, orange |
| Z = 8 | 0.47 × 0.40 × 0.37 mm |
| Rigaku AFC10/Saturn724+ diffractometer | 2599 reflections with I > 2σ(I) |
| Radiation source: Rotating Anode | Rint = 0.038 |
| Graphite monochromator | θmax = 27.5°, θmin = 3.4° |
| Detector resolution: 28.5714 pixels mm-1 | h = −15→19 |
| phi and ω scans | k = −7→10 |
| 17617 measured reflections | l = −25→25 |
| 2705 independent reflections |
| 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)] = 0.049 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.152 | H-atom parameters constrained |
| S = 1.01 | w = 1/[σ2(Fo2) + (0.1P)2 + 1.56P] where P = (Fo2 + 2Fc2)/3 |
| 2705 reflections | (Δ/σ)max = 0.001 |
| 156 parameters | Δρmax = 0.28 e Å−3 |
| 0 restraints | Δρmin = −0.23 e Å−3 |
| C11H11ClN4O | V = 2360.7 (8) Å3 |
| Mr = 250.69 | Z = 8 |
| Orthorhombic, Pbca | Mo Kα radiation |
| a = 15.165 (3) Å | µ = 0.31 mm−1 |
| b = 8.0452 (15) Å | T = 93 K |
| c = 19.349 (4) Å | 0.47 × 0.40 × 0.37 mm |
| Rigaku AFC10/Saturn724+ diffractometer | 2599 reflections with I > 2σ(I) |
| 17617 measured reflections | Rint = 0.038 |
| 2705 independent reflections |
| R[F2 > 2σ(F2)] = 0.049 | 0 restraints |
| wR(F2) = 0.152 | H-atom parameters constrained |
| S = 1.01 | Δρmax = 0.28 e Å−3 |
| 2705 reflections | Δρmin = −0.23 e Å−3 |
| 156 parameters |
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. |
| x | y | z | Uiso*/Ueq | ||
| Cl1 | 0.92289 (3) | 0.63612 (7) | 0.27240 (2) | 0.02638 (19) | |
| O1 | 0.28242 (9) | 0.51349 (19) | 0.42261 (8) | 0.0260 (4) | |
| N1 | 0.42522 (10) | 0.5869 (2) | 0.41004 (8) | 0.0165 (3) | |
| N2 | 0.50513 (10) | 0.5506 (2) | 0.38219 (8) | 0.0167 (3) | |
| N3 | 0.56159 (11) | 0.7128 (2) | 0.47435 (8) | 0.0191 (4) | |
| N4 | 0.48695 (11) | 0.7527 (2) | 0.49690 (9) | 0.0203 (4) | |
| C1 | 0.73156 (13) | 0.6887 (3) | 0.41229 (10) | 0.0226 (4) | |
| H1 | 0.7261 | 0.7262 | 0.4586 | 0.027* | |
| C2 | 0.81377 (13) | 0.6872 (3) | 0.38052 (10) | 0.0234 (4) | |
| H2 | 0.8647 | 0.7229 | 0.4050 | 0.028* | |
| C3 | 0.82041 (13) | 0.6332 (2) | 0.31290 (10) | 0.0194 (4) | |
| C4 | 0.74733 (13) | 0.5800 (3) | 0.27600 (9) | 0.0202 (4) | |
| H4 | 0.7531 | 0.5428 | 0.2296 | 0.024* | |
| C5 | 0.66569 (13) | 0.5822 (3) | 0.30804 (10) | 0.0200 (4) | |
| H5 | 0.6149 | 0.5472 | 0.2832 | 0.024* | |
| C6 | 0.65710 (12) | 0.6353 (2) | 0.37632 (10) | 0.0168 (4) | |
| C7 | 0.56927 (13) | 0.6386 (2) | 0.40816 (10) | 0.0164 (4) | |
| C8 | 0.41462 (13) | 0.7456 (2) | 0.44422 (10) | 0.0184 (4) | |
| H8 | 0.3564 | 0.7475 | 0.4685 | 0.022* | |
| C9 | 0.42014 (14) | 0.8936 (3) | 0.39576 (12) | 0.0251 (5) | |
| H9A | 0.4757 | 0.8890 | 0.3699 | 0.030* | |
| H9B | 0.4179 | 0.9966 | 0.4227 | 0.030* | |
| H9C | 0.3705 | 0.8906 | 0.3634 | 0.030* | |
| C10 | 0.35516 (13) | 0.4761 (2) | 0.40099 (10) | 0.0192 (4) | |
| C11 | 0.37533 (13) | 0.3182 (2) | 0.36325 (11) | 0.0217 (4) | |
| H11A | 0.3268 | 0.2393 | 0.3697 | 0.026* | |
| H11B | 0.4300 | 0.2700 | 0.3814 | 0.026* | |
| H11C | 0.3825 | 0.3418 | 0.3139 | 0.026* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Cl1 | 0.0169 (3) | 0.0416 (4) | 0.0206 (3) | −0.00189 (19) | 0.00381 (16) | −0.00357 (19) |
| O1 | 0.0156 (7) | 0.0260 (8) | 0.0363 (8) | −0.0012 (6) | 0.0001 (6) | 0.0006 (6) |
| N1 | 0.0153 (8) | 0.0168 (8) | 0.0175 (8) | 0.0002 (6) | 0.0009 (6) | 0.0000 (6) |
| N2 | 0.0153 (8) | 0.0174 (8) | 0.0174 (8) | 0.0010 (6) | 0.0005 (6) | 0.0019 (6) |
| N3 | 0.0181 (8) | 0.0232 (9) | 0.0158 (8) | −0.0004 (6) | 0.0016 (6) | −0.0013 (6) |
| N4 | 0.0195 (8) | 0.0231 (8) | 0.0184 (8) | −0.0015 (7) | 0.0008 (6) | −0.0024 (6) |
| C1 | 0.0195 (10) | 0.0334 (11) | 0.0148 (8) | −0.0025 (8) | 0.0011 (7) | −0.0034 (8) |
| C2 | 0.0161 (9) | 0.0357 (12) | 0.0186 (9) | −0.0050 (8) | −0.0018 (7) | −0.0049 (8) |
| C3 | 0.0158 (9) | 0.0237 (10) | 0.0186 (9) | 0.0000 (7) | 0.0024 (7) | 0.0008 (7) |
| C4 | 0.0200 (10) | 0.0251 (10) | 0.0153 (8) | 0.0012 (8) | 0.0005 (7) | −0.0035 (7) |
| C5 | 0.0178 (9) | 0.0247 (10) | 0.0175 (9) | −0.0008 (8) | −0.0015 (7) | −0.0027 (7) |
| C6 | 0.0163 (9) | 0.0170 (9) | 0.0172 (9) | −0.0010 (7) | 0.0002 (7) | 0.0005 (6) |
| C7 | 0.0170 (10) | 0.0172 (9) | 0.0150 (9) | 0.0015 (7) | −0.0008 (6) | 0.0004 (6) |
| C8 | 0.0178 (9) | 0.0191 (9) | 0.0184 (9) | 0.0024 (7) | 0.0010 (7) | −0.0025 (7) |
| C9 | 0.0264 (11) | 0.0180 (10) | 0.0309 (11) | 0.0030 (8) | −0.0019 (8) | 0.0014 (8) |
| C10 | 0.0174 (9) | 0.0205 (10) | 0.0198 (9) | −0.0011 (7) | −0.0027 (7) | 0.0042 (7) |
| C11 | 0.0208 (10) | 0.0182 (9) | 0.0263 (10) | −0.0036 (8) | −0.0034 (7) | 0.0007 (7) |
| Cl1—C3 | 1.741 (2) | C4—C5 | 1.385 (3) |
| O1—C10 | 1.218 (2) | C4—H4 | 0.9500 |
| N1—N2 | 1.358 (2) | C5—C6 | 1.395 (3) |
| N1—C10 | 1.398 (3) | C5—H5 | 0.9500 |
| N1—C8 | 1.447 (2) | C6—C7 | 1.468 (3) |
| N2—C7 | 1.304 (2) | C8—C9 | 1.518 (3) |
| N3—N4 | 1.255 (2) | C8—H8 | 1.0000 |
| N3—C7 | 1.418 (2) | C9—H9A | 0.9800 |
| N4—C8 | 1.499 (2) | C9—H9B | 0.9800 |
| C1—C2 | 1.390 (3) | C9—H9C | 0.9800 |
| C1—C6 | 1.394 (3) | C10—C11 | 1.497 (3) |
| C1—H1 | 0.9500 | C11—H11A | 0.9800 |
| C2—C3 | 1.382 (3) | C11—H11B | 0.9800 |
| C2—H2 | 0.9500 | C11—H11C | 0.9800 |
| C3—C4 | 1.386 (3) | ||
| N2—N1—C10 | 119.42 (16) | N2—C7—N3 | 121.02 (17) |
| N2—N1—C8 | 118.06 (15) | N2—C7—C6 | 120.36 (17) |
| C10—N1—C8 | 122.38 (16) | N3—C7—C6 | 117.48 (16) |
| C7—N2—N1 | 113.33 (16) | N1—C8—N4 | 105.26 (15) |
| N4—N3—C7 | 119.73 (16) | N1—C8—C9 | 113.80 (16) |
| N3—N4—C8 | 114.46 (16) | N4—C8—C9 | 110.49 (16) |
| C2—C1—C6 | 120.20 (17) | N1—C8—H8 | 109.1 |
| C2—C1—H1 | 119.9 | N4—C8—H8 | 109.1 |
| C6—C1—H1 | 119.9 | C9—C8—H8 | 109.1 |
| C3—C2—C1 | 119.11 (18) | C8—C9—H9A | 109.5 |
| C3—C2—H2 | 120.4 | C8—C9—H9B | 109.5 |
| C1—C2—H2 | 120.4 | H9A—C9—H9B | 109.5 |
| C2—C3—C4 | 121.77 (18) | C8—C9—H9C | 109.5 |
| C2—C3—Cl1 | 119.14 (15) | H9A—C9—H9C | 109.5 |
| C4—C3—Cl1 | 119.08 (15) | H9B—C9—H9C | 109.5 |
| C5—C4—C3 | 118.70 (17) | O1—C10—N1 | 119.20 (18) |
| C5—C4—H4 | 120.7 | O1—C10—C11 | 124.23 (18) |
| C3—C4—H4 | 120.7 | N1—C10—C11 | 116.56 (17) |
| C4—C5—C6 | 120.77 (18) | C10—C11—H11A | 109.5 |
| C4—C5—H5 | 119.6 | C10—C11—H11B | 109.5 |
| C6—C5—H5 | 119.6 | H11A—C11—H11B | 109.5 |
| C1—C6—C5 | 119.45 (17) | C10—C11—H11C | 109.5 |
| C1—C6—C7 | 121.32 (17) | H11A—C11—H11C | 109.5 |
| C5—C6—C7 | 119.21 (17) | H11B—C11—H11C | 109.5 |
| C10—N1—N2—C7 | −163.54 (16) | N4—N3—C7—C6 | 163.93 (18) |
| C8—N1—N2—C7 | 20.6 (2) | C1—C6—C7—N2 | −162.04 (18) |
| C7—N3—N4—C8 | −11.1 (3) | C5—C6—C7—N2 | 19.9 (3) |
| C6—C1—C2—C3 | 0.4 (3) | C1—C6—C7—N3 | 5.9 (3) |
| C1—C2—C3—C4 | −0.2 (3) | C5—C6—C7—N3 | −172.22 (17) |
| C1—C2—C3—Cl1 | 178.44 (17) | N2—N1—C8—N4 | −54.1 (2) |
| C2—C3—C4—C5 | 0.3 (3) | C10—N1—C8—N4 | 130.11 (17) |
| Cl1—C3—C4—C5 | −178.33 (16) | N2—N1—C8—C9 | 67.0 (2) |
| C3—C4—C5—C6 | −0.6 (3) | C10—N1—C8—C9 | −108.8 (2) |
| C2—C1—C6—C5 | −0.7 (3) | N3—N4—C8—N1 | 47.4 (2) |
| C2—C1—C6—C7 | −178.79 (19) | N3—N4—C8—C9 | −75.8 (2) |
| C4—C5—C6—C1 | 0.8 (3) | N2—N1—C10—O1 | −175.83 (17) |
| C4—C5—C6—C7 | 178.96 (19) | C8—N1—C10—O1 | −0.1 (3) |
| N1—N2—C7—N3 | 22.6 (2) | N2—N1—C10—C11 | 2.9 (2) |
| N1—N2—C7—C6 | −169.92 (16) | C8—N1—C10—C11 | 178.63 (17) |
| N4—N3—C7—N2 | −28.2 (3) |
Experimental details
| Crystal data | |
| Chemical formula | C11H11ClN4O |
| Mr | 250.69 |
| Crystal system, space group | Orthorhombic, Pbca |
| Temperature (K) | 93 |
| a, b, c (Å) | 15.165 (3), 8.0452 (15), 19.349 (4) |
| V (Å3) | 2360.7 (8) |
| Z | 8 |
| Radiation type | Mo Kα |
| µ (mm−1) | 0.31 |
| Crystal size (mm) | 0.47 × 0.40 × 0.37 |
| Data collection | |
| Diffractometer | Rigaku AFC10/Saturn724+ diffractometer |
| Absorption correction | – |
| No. of measured, independent and observed [I > 2σ(I)] reflections | 17617, 2705, 2599 |
| Rint | 0.038 |
| (sin θ/λ)max (Å−1) | 0.649 |
| Refinement | |
| R[F2 > 2σ(F2)], wR(F2), S | 0.049, 0.152, 1.01 |
| No. of reflections | 2705 |
| No. of parameters | 156 |
| H-atom treatment | H-atom parameters constrained |
| Δρmax, Δρmin (e Å−3) | 0.28, −0.23 |
Computer programs: CrystalClear (Rigaku/MSC, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009).
Acknowledgements
We are very grateful to the Science Foundation for the Excellent Youth Scholars of the Department of Education of Zhejiang Province and the Educational Commission of Zhejiang Province of China (grant No. Y201018289).
References
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| CRYSTALLOGRAPHIC COMMUNICATIONS |
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 have obtained the title compound, (I) (Fig.1).
In the tetrazine ring of (I), atoms N1, N2, N3 and N4 are coplanar, while atoms C7 and C8 deviate from the plane by 0.254 (3) and 0.621 (3) Å, respectively. The N2/C7/N3 and N1/C8/N4 planes make dihedral angles of 7.61 (2)° and 44.04 (2)°, respectively, with the N1/N2/N3/N4 plane, the tetrazine ring adopts an unsymmetrical boat conformation. The benzene ring make dihedral angle of 18.5 (2)° with the N1/N2/N3/N4 plane. N1 is almost sp2 hybridized due to the angles around it add up to 359.9 (2)°. Compairing 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), 1-acetyl-3,6-dimethyl-1,2,4,5-tetrazine (Jennison et al.,1986) and 1-[3-(4-Methoxyphenyl)-6-methyl-1,6-dihydro-1,2,4,5- tetrazin-1-yl]propanone (Yang et al., 2010), one can state that the molecule in (I) is homoaromatic.