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Acta Crystallogr Sect E Struct Rep Online. 2010 November 1; 66(Pt 11): o2946.
Published online 2010 October 30. doi:  10.1107/S1600536810042418
PMCID: PMC3009022

2,4-Dichloro-6-[2-meth­oxy-4-(prop-2-en-1-yl)phen­oxy]-1,3,5-triazine

Abstract

The title compound, C13H11Cl2N3O2, was obtained by the reaction of eugenol and cyanuric chloride. The dihedral angle between the benzene and triazine rings is 87.56 (4)°. Two C atoms of the allyl group are disordered over two sites in a 0.72 (2):0.28 (2) ratio.

Related literature

For background to the Williamson reaction in organic synthesis, see: Dermer (1934 [triangle]). For related structures, see: Ma et al.(2010a [triangle],b [triangle],c [triangle]). For agricultural applications of the title compound, see: Manning et al. (1987 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-66-o2946-scheme1.jpg

Experimental

Crystal data

  • C13H11Cl2N3O2
  • M r = 312.15
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-o2946-efi1.jpg
  • a = 11.4771 (12) Å
  • b = 8.6050 (9) Å
  • c = 14.7189 (13) Å
  • β = 103.077 (1)°
  • V = 1415.9 (2) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.46 mm−1
  • T = 298 K
  • 0.42 × 0.35 × 0.33 mm

Data collection

  • Siemens SMART CCD area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 1996 [triangle]) T min = 0.830, T max = 0.862
  • 6755 measured reflections
  • 2499 independent reflections
  • 1595 reflections with I > 2σ(I)
  • R int = 0.027

Refinement

  • R[F 2 > 2σ(F 2)] = 0.038
  • wR(F 2) = 0.099
  • S = 1.02
  • 2499 reflections
  • 201 parameters
  • H-atom parameters constrained
  • Δρmax = 0.23 e Å−3
  • Δρmin = −0.23 e Å−3

Data collection: SMART (Siemens, 1996 [triangle]); cell refinement: SAINT (Siemens, 1996 [triangle]); data reduction: SAINT; 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.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810042418/rn2069sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810042418/rn2069Isup2.hkl

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

Acknowledgments

We would like to acknowledge funding support from the National Natural Science Foundation of China (grant No. 30971882), the Program of Natural Science Basic Research in Shaanxi (No. 2009JM3010) and the Program of Northwest A&F University (No. Z111020908)

supplementary crystallographic information

Comment

In this paper, we used the Williamson reaction (Dermer, 1934) to form the title compound, (I), which was synthesized by the reaction of eugenol, sodium hydroxide and cyanuric chloride at 278 K. We have previously reported three compounds of this type [Ma et al.(2010a, 2010b and 2010c)]. In (I)(Fig.1), the dihedral angle between the benzene ring C4—C9 and the triazine ring C2N3C3N1C1N2 is 87.56 (4)°. There are no significantly short intermolecular contacts in the crystal lattice.

Experimental

492 mg eugenol (3 mmol) was dissolved in 1.2 g 10% sodium hydroxide (3 mmol) in a 100 mL round-bottom flask and the water was then removed in vacuo. Added 30 ml acetonitrile into the flask in an ice bath and after stirring 10 min cyanuric chloride (3 mmol) was added and kept stirred for 2 h at 278 K. The reaction mixture was filtered and solvent was evaporated under vacuum to dryness. The solid mass was dissolved in EtOAc, washed with saturated NaHCO3 and brine, dried over anhydrous Na2SO4, concentrated and purified with column chromatography to afford the crude product. White crystals suitable for X-ray analysis were obtained by slow evaporation of a solution of the title compound in n-hexane/ethyl acetate (1:1 V/V) at room temperature.

Refinement

The atoms C12 and C13 were found to be disordered over two sites, and the ratio of the occupancy factors refined to 0.718 (7):0.282 (7) and 0.718 (7):0.282 (7) for atoms C12: C12' and C13: C13' respectively.The positions of all H atoms were determined geometrically and refined using a riding model with C—H = 0.93–0.97 Å and Uiso(methyl H) = 1.5Ueq(C) and 1.2Ueq for other H atoms.

Figures

Fig. 1.
The molecular structure of (I), with atom labels and displacement ellipsoids drawn at the 30% probability level.The disordered atoms C12 and C13 of the allyl group are the major component.

Crystal data

C13H11Cl2N3O2Dx = 1.464 Mg m3
Mr = 312.15Melting point = 385–386 K
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
a = 11.4771 (12) ÅCell parameters from 2205 reflections
b = 8.6050 (9) Åθ = 2.8–25.7°
c = 14.7189 (13) ŵ = 0.46 mm1
β = 103.077 (1)°T = 298 K
V = 1415.9 (2) Å3Monoclinic, colourless
Z = 40.42 × 0.35 × 0.33 mm
F(000) = 640

Data collection

Siemens SMART CCD area-detector diffractometer2499 independent reflections
Radiation source: fine-focus sealed tube1595 reflections with I > 2σ(I)
graphiteRint = 0.027
phi and ω scansθmax = 25.0°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)h = −13→12
Tmin = 0.830, Tmax = 0.862k = −10→7
6755 measured reflectionsl = −17→17

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.038Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.099H-atom parameters constrained
S = 1.02w = 1/[σ2(Fo2) + (0.0303P)2 + 0.7779P] where P = (Fo2 + 2Fc2)/3
2499 reflections(Δ/σ)max = 0.001
201 parametersΔρmax = 0.23 e Å3
0 restraintsΔρmin = −0.23 e Å3

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*/UeqOcc. (<1)
Cl10.23031 (7)0.11286 (10)0.56145 (6)0.0754 (3)
Cl20.08975 (7)0.41854 (15)0.81780 (6)0.1061 (4)
N10.29775 (19)0.4567 (3)0.78327 (14)0.0541 (6)
N20.36101 (18)0.3198 (2)0.66250 (14)0.0459 (5)
N30.16967 (19)0.2701 (3)0.69226 (16)0.0621 (7)
O10.47642 (15)0.5029 (2)0.75543 (11)0.0524 (5)
O20.47302 (16)0.6829 (2)0.60769 (12)0.0583 (5)
C10.3757 (2)0.4227 (3)0.73157 (17)0.0450 (6)
C20.2573 (2)0.2488 (3)0.64855 (18)0.0525 (7)
C30.1983 (2)0.3770 (4)0.7582 (2)0.0613 (8)
C40.5660 (2)0.4821 (3)0.70437 (17)0.0439 (6)
C50.5664 (2)0.5829 (3)0.63087 (17)0.0433 (6)
C60.6619 (2)0.5747 (3)0.58824 (17)0.0486 (7)
H60.66440.64110.53890.058*
C70.7537 (2)0.4693 (3)0.61776 (18)0.0499 (7)
C80.7481 (2)0.3691 (3)0.6892 (2)0.0567 (7)
H80.80820.29580.70820.068*
C90.6542 (2)0.3762 (3)0.73313 (19)0.0543 (7)
H90.65130.30900.78200.065*
C100.4713 (3)0.7868 (3)0.5320 (2)0.0654 (8)
H10A0.53820.85650.54780.098*
H10B0.39830.84560.51980.098*
H10C0.47630.72850.47740.098*
C110.8576 (2)0.4640 (4)0.5703 (2)0.0653 (8)
H11A0.87790.56930.55630.078*0.72 (2)
H11B0.92650.41990.61310.078*0.72 (2)
H11C0.84640.54380.52260.078*0.28 (2)
H11D0.93070.48830.61570.078*0.28 (2)
C120.8333 (7)0.3729 (13)0.4838 (7)0.066 (2)0.72 (2)
H120.76610.39940.43820.079*0.72 (2)
C130.8975 (13)0.2594 (16)0.4660 (11)0.086 (3)0.72 (2)
H13A0.96540.22920.50990.103*0.72 (2)
H13B0.87590.20740.40930.103*0.72 (2)
C12'0.876 (2)0.317 (2)0.527 (2)0.067 (6)0.28 (2)
H12'0.88990.22720.56340.080*0.28 (2)
C13'0.873 (3)0.310 (5)0.433 (2)0.082 (8)0.28 (2)
H13C0.85870.39920.39700.099*0.28 (2)
H13D0.88440.21520.40600.099*0.28 (2)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Cl10.0806 (5)0.0678 (5)0.0734 (5)−0.0163 (4)0.0081 (4)−0.0086 (4)
Cl20.0585 (5)0.1906 (12)0.0795 (6)−0.0079 (6)0.0370 (4)−0.0104 (7)
N10.0501 (13)0.0681 (16)0.0488 (13)0.0005 (12)0.0208 (11)0.0046 (12)
N20.0491 (13)0.0447 (13)0.0449 (13)−0.0015 (11)0.0129 (10)0.0040 (11)
N30.0480 (13)0.0831 (19)0.0547 (15)−0.0086 (13)0.0105 (11)0.0101 (14)
O10.0533 (11)0.0569 (12)0.0531 (11)−0.0097 (10)0.0246 (9)−0.0077 (9)
O20.0602 (11)0.0621 (12)0.0580 (12)0.0142 (10)0.0244 (9)0.0081 (10)
C10.0452 (15)0.0491 (17)0.0422 (15)0.0015 (13)0.0127 (12)0.0103 (13)
C20.0545 (16)0.0548 (18)0.0453 (15)−0.0022 (15)0.0052 (13)0.0124 (13)
C30.0517 (17)0.086 (2)0.0493 (17)0.0026 (17)0.0182 (14)0.0151 (17)
C40.0440 (14)0.0464 (16)0.0439 (15)−0.0098 (13)0.0155 (12)−0.0053 (13)
C50.0459 (14)0.0401 (15)0.0452 (15)−0.0030 (12)0.0133 (11)−0.0048 (13)
C60.0520 (15)0.0490 (17)0.0481 (15)−0.0064 (14)0.0177 (12)0.0004 (13)
C70.0448 (15)0.0508 (17)0.0573 (17)−0.0077 (14)0.0181 (13)−0.0059 (14)
C80.0484 (15)0.0515 (18)0.0705 (19)0.0048 (14)0.0142 (14)0.0019 (15)
C90.0589 (17)0.0510 (17)0.0547 (17)−0.0030 (15)0.0165 (14)0.0066 (14)
C100.0724 (19)0.060 (2)0.0636 (19)0.0131 (17)0.0160 (15)0.0119 (17)
C110.0523 (17)0.071 (2)0.080 (2)−0.0070 (16)0.0292 (16)−0.0036 (18)
C120.051 (3)0.090 (5)0.064 (4)0.000 (3)0.027 (3)0.004 (4)
C130.074 (6)0.086 (8)0.108 (11)−0.012 (5)0.044 (6)−0.021 (6)
C12'0.068 (11)0.068 (10)0.078 (15)0.013 (8)0.043 (11)0.010 (9)
C13'0.074 (15)0.10 (2)0.081 (19)−0.010 (14)0.036 (13)0.007 (12)

Geometric parameters (Å, °)

Cl1—C21.711 (3)C8—H80.9300
Cl2—C31.715 (3)C9—H90.9300
N1—C31.312 (3)C10—H10A0.9600
N1—C11.332 (3)C10—H10B0.9600
N2—C21.312 (3)C10—H10C0.9600
N2—C11.330 (3)C11—C12'1.451 (18)
N3—C31.323 (4)C11—C121.466 (7)
N3—C21.324 (3)C11—H11A0.9700
O1—C11.324 (3)C11—H11B0.9700
O1—C41.416 (3)C11—H11C0.9700
O2—C51.356 (3)C11—H11D0.9700
O2—C101.425 (3)C12—C131.29 (2)
C4—C91.356 (4)C12—H120.9300
C4—C51.387 (3)C13—H13A0.9300
C5—C61.382 (3)C13—H13B0.9300
C6—C71.384 (3)C12'—C13'1.38 (5)
C6—H60.9300C12'—H12'0.9300
C7—C81.372 (4)C13'—H13C0.9300
C7—C111.513 (3)C13'—H13D0.9300
C8—C91.378 (3)
C3—N1—C1112.3 (2)H10B—C10—H10C109.5
C2—N2—C1112.5 (2)C12'—C11—C1234.3 (9)
C3—N3—C2111.3 (2)C12'—C11—C7115.8 (6)
C1—O1—C4119.25 (19)C12—C11—C7113.7 (3)
C5—O2—C10117.7 (2)C12'—C11—H11A131.1
O1—C1—N2120.1 (2)C12—C11—H11A108.8
O1—C1—N1113.1 (2)C7—C11—H11A108.8
N2—C1—N1126.7 (2)C12'—C11—H11B76.4
N2—C2—N3128.4 (3)C12—C11—H11B108.8
N2—C2—Cl1116.1 (2)C7—C11—H11B108.8
N3—C2—Cl1115.5 (2)H11A—C11—H11B107.7
N1—C3—N3128.7 (3)C12'—C11—H11C108.1
N1—C3—Cl2115.7 (2)C12—C11—H11C77.4
N3—C3—Cl2115.6 (2)C7—C11—H11C108.9
C9—C4—C5122.0 (2)H11A—C11—H11C35.2
C9—C4—O1120.0 (2)H11B—C11—H11C134.6
C5—C4—O1117.7 (2)C12'—C11—H11D107.5
O2—C5—C6125.5 (2)C12—C11—H11D132.7
O2—C5—C4116.8 (2)C7—C11—H11D108.9
C6—C5—C4117.7 (2)H11A—C11—H11D74.5
C5—C6—C7121.1 (2)H11B—C11—H11D35.4
C5—C6—H6119.4H11C—C11—H11D107.4
C7—C6—H6119.4C13—C12—C11125.3 (14)
C8—C7—C6119.2 (2)C13—C12—H11C140.6
C8—C7—C11120.9 (3)C11—C12—H11C37.0
C6—C7—C11119.9 (3)C13—C12—H12117.4
C7—C8—C9120.6 (3)C11—C12—H12117.4
C7—C8—H8119.7H11C—C12—H1291.6
C9—C8—H8119.7C12—C13—H13A120.0
C4—C9—C8119.4 (3)C12—C13—H13B120.0
C4—C9—H9120.3H13A—C13—H13B120.0
C8—C9—H9120.3C13'—C12'—C11120 (3)
O2—C10—H10A109.5C13'—C12'—H12'119.9
O2—C10—H10B109.5C11—C12'—H12'119.9
H10A—C10—H10B109.5C12'—C13'—H13C120.0
O2—C10—H10C109.5C12'—C13'—H13D120.0
H10A—C10—H10C109.5H13C—C13'—H13D120.0
C4—O1—C1—N22.3 (3)C9—C4—C5—C6−1.4 (4)
C4—O1—C1—N1−178.1 (2)O1—C4—C5—C6172.4 (2)
C2—N2—C1—O1179.1 (2)O2—C5—C6—C7179.3 (2)
C2—N2—C1—N1−0.5 (4)C4—C5—C6—C70.2 (4)
C3—N1—C1—O1179.5 (2)C5—C6—C7—C81.5 (4)
C3—N1—C1—N2−0.9 (4)C5—C6—C7—C11−179.5 (2)
C1—N2—C2—N31.6 (4)C6—C7—C8—C9−2.0 (4)
C1—N2—C2—Cl1−179.54 (18)C11—C7—C8—C9179.0 (3)
C3—N3—C2—N2−1.0 (4)C5—C4—C9—C80.9 (4)
C3—N3—C2—Cl1−180.0 (2)O1—C4—C9—C8−172.7 (2)
C1—N1—C3—N31.5 (4)C7—C8—C9—C40.8 (4)
C1—N1—C3—Cl2−177.49 (19)C8—C7—C11—C12'58.8 (16)
C2—N3—C3—N1−0.7 (4)C6—C7—C11—C12'−120.3 (16)
C2—N3—C3—Cl2178.3 (2)C8—C7—C11—C1296.6 (7)
C1—O1—C4—C9−92.5 (3)C6—C7—C11—C12−82.5 (7)
C1—O1—C4—C593.6 (3)C12'—C11—C12—C13−23.9 (13)
C10—O2—C5—C61.2 (4)C7—C11—C12—C13−125.3 (10)
C10—O2—C5—C4−179.6 (2)C12—C11—C12'—C13'26 (2)
C9—C4—C5—O2179.4 (2)C7—C11—C12'—C13'121 (2)
O1—C4—C5—O2−6.8 (3)

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: RN2069).

References

  • Dermer, O. C. (1934). Chem. Rev.14, 385–430.
  • Ma, Y.-T., Shi, X.-W., Shuai, Q. & Gao, J.-M. (2010b). Acta Cryst. E66, o2293. [PMC free article] [PubMed]
  • Ma, Y.-T., Wang, J.-J., Liu, X.-W., Yang, S.-X. & Gao, J.-M. (2010a). Acta Cryst. E66, o52. [PMC free article] [PubMed]
  • Ma, Y.-T., Zhang, A.-L., Yuan, M.-S. & Gao, J.-M. (2010c). Acta Cryst. E66, o2468. [PMC free article] [PubMed]
  • Manning, D. T., Cappy, J. J., Cooke, A. R., Sheads, R. E., Wu, T. T., Lopes, A., Phillips, J. L. & Outcalt, R. J. (1987). PCT Int. Appl. WO8704321(A2).
  • Sheldrick, G. M. (1996). SADABS University of Göttingen, Germany.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Siemens (1996). SMART and SAINT Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA.

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