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

Ma, Y.-T.; Li, H.-Q.; Shi, X.-W.; Zhang, A.-L.; Gao, J.-M.

doi:10.1107/S1600536810042418

organic compounds

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ISSN: 2056-9890

Volume 66| Part 11| November 2010| Page o2946

https://doi.org/10.1107/S1600536810042418

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

Ya-Tuan Ma,^a ‡ Hong-Quan Li,^a Xin-Wei Shi,^a An-Ling Zhang ^a and Jin-Ming Gao ^a ^*

^aCollege of Science, Northwest A&F University, Yangling Shaanxi 712100, People's Republic of China
^*Correspondence e-mail: jinminggaocn@yahoo.com.cn

(Received 15 September 2010; accepted 19 October 2010; online 30 October 2010)

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 ). For related structures, see: Ma et al.(2010a ,b ,c). For agricultural applications of the title compound, see: Manning et al. (1987 ).

Experimental

Crystal data

C₁₃H₁₁Cl₂N₃O₂
M_r = 312.15
Monoclinic, P 2₁ /c
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 ) 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[F² > 2σ(F²)] = 0.038
wR(F²) = 0.099
S = 1.02
2499 reflections
201 parameters
H-atom parameters constrained
Δρ_max = 0.23 e Å⁻³
Δρ_min = −0.23 e Å⁻³

Data collection: SMART (Siemens, 1996 ); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT; 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: https://doi.org/10.1107/S1600536810042418/rn2069sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810042418/rn2069Isup2.hkl

checkCIF report

Comment top

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.

Related literature top

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

Experimental top

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.

Structure description top

Computing details top

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT (Siemens, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXS97 (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 (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.

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

Crystal data top

C₁₃H₁₁Cl₂N₃O₂	D_x = 1.464 Mg m⁻³
M_r = 312.15	Melting point = 385–386 K
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 11.4771 (12) Å	Cell parameters from 2205 reflections
b = 8.6050 (9) Å	θ = 2.8–25.7°
c = 14.7189 (13) Å	µ = 0.46 mm⁻¹
β = 103.077 (1)°	T = 298 K
V = 1415.9 (2) Å³	Monoclinic, colourless
Z = 4	0.42 × 0.35 × 0.33 mm
F(000) = 640

Data collection top

Siemens SMART CCD area-detector diffractometer	2499 independent reflections
Radiation source: fine-focus sealed tube	1595 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.027
phi and ω scans	θ_max = 25.0°, θ_min = 1.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −13→12
T_min = 0.830, T_max = 0.862	k = −10→7
6755 measured reflections	l = −17→17

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)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.099	H-atom parameters constrained
S = 1.02	w = 1/[σ²(F_o²) + (0.0303P)² + 0.7779P] where P = (F_o² + 2F_c²)/3
2499 reflections	(Δ/σ)_max = 0.001
201 parameters	Δρ_max = 0.23 e Å⁻³
0 restraints	Δρ_min = −0.23 e Å⁻³

Crystal data top

C₁₃H₁₁Cl₂N₃O₂	V = 1415.9 (2) Å³
M_r = 312.15	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 11.4771 (12) Å	µ = 0.46 mm⁻¹
b = 8.6050 (9) Å	T = 298 K
c = 14.7189 (13) Å	0.42 × 0.35 × 0.33 mm
β = 103.077 (1)°

Data collection top

Siemens SMART CCD area-detector diffractometer	2499 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1595 reflections with I > 2σ(I)
T_min = 0.830, T_max = 0.862	R_int = 0.027
6755 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.038	0 restraints
wR(F²) = 0.099	H-atom parameters constrained
S = 1.02	Δρ_max = 0.23 e Å⁻³
2499 reflections	Δρ_min = −0.23 e Å⁻³
201 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	Occ. (<1)
Cl1	0.23031 (7)	0.11286 (10)	0.56145 (6)	0.0754 (3)
Cl2	0.08975 (7)	0.41854 (15)	0.81780 (6)	0.1061 (4)
N1	0.29775 (19)	0.4567 (3)	0.78327 (14)	0.0541 (6)
N2	0.36101 (18)	0.3198 (2)	0.66250 (14)	0.0459 (5)
N3	0.16967 (19)	0.2701 (3)	0.69226 (16)	0.0621 (7)
O1	0.47642 (15)	0.5029 (2)	0.75543 (11)	0.0524 (5)
O2	0.47302 (16)	0.6829 (2)	0.60769 (12)	0.0583 (5)
C1	0.3757 (2)	0.4227 (3)	0.73157 (17)	0.0450 (6)
C2	0.2573 (2)	0.2488 (3)	0.64855 (18)	0.0525 (7)
C3	0.1983 (2)	0.3770 (4)	0.7582 (2)	0.0613 (8)
C4	0.5660 (2)	0.4821 (3)	0.70437 (17)	0.0439 (6)
C5	0.5664 (2)	0.5829 (3)	0.63087 (17)	0.0433 (6)
C6	0.6619 (2)	0.5747 (3)	0.58824 (17)	0.0486 (7)
H6	0.6644	0.6411	0.5389	0.058*
C7	0.7537 (2)	0.4693 (3)	0.61776 (18)	0.0499 (7)
C8	0.7481 (2)	0.3691 (3)	0.6892 (2)	0.0567 (7)
H8	0.8082	0.2958	0.7082	0.068*
C9	0.6542 (2)	0.3762 (3)	0.73313 (19)	0.0543 (7)
H9	0.6513	0.3090	0.7820	0.065*
C10	0.4713 (3)	0.7868 (3)	0.5320 (2)	0.0654 (8)
H10A	0.5382	0.8565	0.5478	0.098*
H10B	0.3983	0.8456	0.5198	0.098*
H10C	0.4763	0.7285	0.4774	0.098*
C11	0.8576 (2)	0.4640 (4)	0.5703 (2)	0.0653 (8)
H11A	0.8779	0.5693	0.5563	0.078*	0.72 (2)
H11B	0.9265	0.4199	0.6131	0.078*	0.72 (2)
H11C	0.8464	0.5438	0.5226	0.078*	0.28 (2)
H11D	0.9307	0.4883	0.6157	0.078*	0.28 (2)
C12	0.8333 (7)	0.3729 (13)	0.4838 (7)	0.066 (2)	0.72 (2)
H12	0.7661	0.3994	0.4382	0.079*	0.72 (2)
C13	0.8975 (13)	0.2594 (16)	0.4660 (11)	0.086 (3)	0.72 (2)
H13A	0.9654	0.2292	0.5099	0.103*	0.72 (2)
H13B	0.8759	0.2074	0.4093	0.103*	0.72 (2)
C12'	0.876 (2)	0.317 (2)	0.527 (2)	0.067 (6)	0.28 (2)
H12'	0.8899	0.2272	0.5634	0.080*	0.28 (2)
C13'	0.873 (3)	0.310 (5)	0.433 (2)	0.082 (8)	0.28 (2)
H13C	0.8587	0.3992	0.3970	0.099*	0.28 (2)
H13D	0.8844	0.2152	0.4060	0.099*	0.28 (2)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0806 (5)	0.0678 (5)	0.0734 (5)	−0.0163 (4)	0.0081 (4)	−0.0086 (4)
Cl2	0.0585 (5)	0.1906 (12)	0.0795 (6)	−0.0079 (6)	0.0370 (4)	−0.0104 (7)
N1	0.0501 (13)	0.0681 (16)	0.0488 (13)	0.0005 (12)	0.0208 (11)	0.0046 (12)
N2	0.0491 (13)	0.0447 (13)	0.0449 (13)	−0.0015 (11)	0.0129 (10)	0.0040 (11)
N3	0.0480 (13)	0.0831 (19)	0.0547 (15)	−0.0086 (13)	0.0105 (11)	0.0101 (14)
O1	0.0533 (11)	0.0569 (12)	0.0531 (11)	−0.0097 (10)	0.0246 (9)	−0.0077 (9)
O2	0.0602 (11)	0.0621 (12)	0.0580 (12)	0.0142 (10)	0.0244 (9)	0.0081 (10)
C1	0.0452 (15)	0.0491 (17)	0.0422 (15)	0.0015 (13)	0.0127 (12)	0.0103 (13)
C2	0.0545 (16)	0.0548 (18)	0.0453 (15)	−0.0022 (15)	0.0052 (13)	0.0124 (13)
C3	0.0517 (17)	0.086 (2)	0.0493 (17)	0.0026 (17)	0.0182 (14)	0.0151 (17)
C4	0.0440 (14)	0.0464 (16)	0.0439 (15)	−0.0098 (13)	0.0155 (12)	−0.0053 (13)
C5	0.0459 (14)	0.0401 (15)	0.0452 (15)	−0.0030 (12)	0.0133 (11)	−0.0048 (13)
C6	0.0520 (15)	0.0490 (17)	0.0481 (15)	−0.0064 (14)	0.0177 (12)	0.0004 (13)
C7	0.0448 (15)	0.0508 (17)	0.0573 (17)	−0.0077 (14)	0.0181 (13)	−0.0059 (14)
C8	0.0484 (15)	0.0515 (18)	0.0705 (19)	0.0048 (14)	0.0142 (14)	0.0019 (15)
C9	0.0589 (17)	0.0510 (17)	0.0547 (17)	−0.0030 (15)	0.0165 (14)	0.0066 (14)
C10	0.0724 (19)	0.060 (2)	0.0636 (19)	0.0131 (17)	0.0160 (15)	0.0119 (17)
C11	0.0523 (17)	0.071 (2)	0.080 (2)	−0.0070 (16)	0.0292 (16)	−0.0036 (18)
C12	0.051 (3)	0.090 (5)	0.064 (4)	0.000 (3)	0.027 (3)	0.004 (4)
C13	0.074 (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, º) top

Cl1—C2	1.711 (3)	C8—H8	0.9300
Cl2—C3	1.715 (3)	C9—H9	0.9300
N1—C3	1.312 (3)	C10—H10A	0.9600
N1—C1	1.332 (3)	C10—H10B	0.9600
N2—C2	1.312 (3)	C10—H10C	0.9600
N2—C1	1.330 (3)	C11—C12'	1.451 (18)
N3—C3	1.323 (4)	C11—C12	1.466 (7)
N3—C2	1.324 (3)	C11—H11A	0.9700
O1—C1	1.324 (3)	C11—H11B	0.9700
O1—C4	1.416 (3)	C11—H11C	0.9700
O2—C5	1.356 (3)	C11—H11D	0.9700
O2—C10	1.425 (3)	C12—C13	1.29 (2)
C4—C9	1.356 (4)	C12—H12	0.9300
C4—C5	1.387 (3)	C13—H13A	0.9300
C5—C6	1.382 (3)	C13—H13B	0.9300
C6—C7	1.384 (3)	C12'—C13'	1.38 (5)
C6—H6	0.9300	C12'—H12'	0.9300
C7—C8	1.372 (4)	C13'—H13C	0.9300
C7—C11	1.513 (3)	C13'—H13D	0.9300
C8—C9	1.378 (3)

C3—N1—C1	112.3 (2)	H10B—C10—H10C	109.5
C2—N2—C1	112.5 (2)	C12'—C11—C12	34.3 (9)
C3—N3—C2	111.3 (2)	C12'—C11—C7	115.8 (6)
C1—O1—C4	119.25 (19)	C12—C11—C7	113.7 (3)
C5—O2—C10	117.7 (2)	C12'—C11—H11A	131.1
O1—C1—N2	120.1 (2)	C12—C11—H11A	108.8
O1—C1—N1	113.1 (2)	C7—C11—H11A	108.8
N2—C1—N1	126.7 (2)	C12'—C11—H11B	76.4
N2—C2—N3	128.4 (3)	C12—C11—H11B	108.8
N2—C2—Cl1	116.1 (2)	C7—C11—H11B	108.8
N3—C2—Cl1	115.5 (2)	H11A—C11—H11B	107.7
N1—C3—N3	128.7 (3)	C12'—C11—H11C	108.1
N1—C3—Cl2	115.7 (2)	C12—C11—H11C	77.4
N3—C3—Cl2	115.6 (2)	C7—C11—H11C	108.9
C9—C4—C5	122.0 (2)	H11A—C11—H11C	35.2
C9—C4—O1	120.0 (2)	H11B—C11—H11C	134.6
C5—C4—O1	117.7 (2)	C12'—C11—H11D	107.5
O2—C5—C6	125.5 (2)	C12—C11—H11D	132.7
O2—C5—C4	116.8 (2)	C7—C11—H11D	108.9
C6—C5—C4	117.7 (2)	H11A—C11—H11D	74.5
C5—C6—C7	121.1 (2)	H11B—C11—H11D	35.4
C5—C6—H6	119.4	H11C—C11—H11D	107.4
C7—C6—H6	119.4	C13—C12—C11	125.3 (14)
C8—C7—C6	119.2 (2)	C13—C12—H11C	140.6
C8—C7—C11	120.9 (3)	C11—C12—H11C	37.0
C6—C7—C11	119.9 (3)	C13—C12—H12	117.4
C7—C8—C9	120.6 (3)	C11—C12—H12	117.4
C7—C8—H8	119.7	H11C—C12—H12	91.6
C9—C8—H8	119.7	C12—C13—H13A	120.0
C4—C9—C8	119.4 (3)	C12—C13—H13B	120.0
C4—C9—H9	120.3	H13A—C13—H13B	120.0
C8—C9—H9	120.3	C13'—C12'—C11	120 (3)
O2—C10—H10A	109.5	C13'—C12'—H12'	119.9
O2—C10—H10B	109.5	C11—C12'—H12'	119.9
H10A—C10—H10B	109.5	C12'—C13'—H13C	120.0
O2—C10—H10C	109.5	C12'—C13'—H13D	120.0
H10A—C10—H10C	109.5	H13C—C13'—H13D	120.0

C4—O1—C1—N2	2.3 (3)	C9—C4—C5—C6	−1.4 (4)
C4—O1—C1—N1	−178.1 (2)	O1—C4—C5—C6	172.4 (2)
C2—N2—C1—O1	179.1 (2)	O2—C5—C6—C7	179.3 (2)
C2—N2—C1—N1	−0.5 (4)	C4—C5—C6—C7	0.2 (4)
C3—N1—C1—O1	179.5 (2)	C5—C6—C7—C8	1.5 (4)
C3—N1—C1—N2	−0.9 (4)	C5—C6—C7—C11	−179.5 (2)
C1—N2—C2—N3	1.6 (4)	C6—C7—C8—C9	−2.0 (4)
C1—N2—C2—Cl1	−179.54 (18)	C11—C7—C8—C9	179.0 (3)
C3—N3—C2—N2	−1.0 (4)	C5—C4—C9—C8	0.9 (4)
C3—N3—C2—Cl1	−180.0 (2)	O1—C4—C9—C8	−172.7 (2)
C1—N1—C3—N3	1.5 (4)	C7—C8—C9—C4	0.8 (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—Cl2	178.3 (2)	C8—C7—C11—C12	96.6 (7)
C1—O1—C4—C9	−92.5 (3)	C6—C7—C11—C12	−82.5 (7)
C1—O1—C4—C5	93.6 (3)	C12'—C11—C12—C13	−23.9 (13)
C10—O2—C5—C6	1.2 (4)	C7—C11—C12—C13	−125.3 (10)
C10—O2—C5—C4	−179.6 (2)	C12—C11—C12'—C13'	26 (2)
C9—C4—C5—O2	179.4 (2)	C7—C11—C12'—C13'	121 (2)
O1—C4—C5—O2	−6.8 (3)

Experimental details

Crystal data
Chemical formula	C₁₃H₁₁Cl₂N₃O₂
M_r	312.15
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	298
a, b, c (Å)	11.4771 (12), 8.6050 (9), 14.7189 (13)
β (°)	103.077 (1)
V (Å³)	1415.9 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.46
Crystal size (mm)	0.42 × 0.35 × 0.33

Data collection
Diffractometer	Siemens SMART CCD area-detector
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.830, 0.862
No. of measured, independent and observed [I > 2σ(I)] reflections	6755, 2499, 1595
R_int	0.027

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.038, 0.099, 1.02
No. of reflections	2499
No. of parameters	201
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.23, −0.23

Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SHELXS97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Footnotes

‡Additional address: College of Life Sciences, Northwest A&F University, Yangling Shaanxi 712100, People's Republic of China.

Acknowledgements

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)

References

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