3-(4,6-Dichloro-1,3,5-triazin-2-yl)-2,2-dimethyl-1,3-oxazolidine

Zou, Y.; Hu, Z.; Cao, D.

doi:10.1107/S1600536812026578

organic compounds

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ISSN: 2056-9890

Volume 68| Part 7| July 2012| Page o2142

https://doi.org/10.1107/S1600536812026578

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3-(4,6-Dichloro-1,3,5-triazin-2-yl)-2,2-dimethyl-1,3-oxazolidine

Ye-cheng Zou,^a Zhi-yong Hu ^a ^* and Duan-lin Cao ^a

^aSchool of Chemical Engineering and Environment, North University of China, Taiyuan, People's Republic of China
^*Correspondence e-mail: Huzhiyong@nuc.edu.cn

(Received 1 May 2012; accepted 12 June 2012; online 20 June 2012)

In the title compound, C₈H₁₀Cl₂N₄O, the dichloro-substituted triazine ring and the quasi-plane of the five-membered dimethyl-substituted oxazolidine unit, in which the O atom lies 0.228 (1) Å out of the least-squares plane, are close to being coplanar [dihedral angle = 4.99 (10)°]. In the crystal, molecules are linked by intermolecular C—H⋯Cl interactions, forming chains extend along the a axis. Also present are weak π–π interactions between triazine rings [minimum ring centroid separation = 3.7427 (11) Å].

Related literature

For the properties of 1,3,5-triazines, see: Xue et al. (2011 ); Zhao et al. (2010 ). For the chemistry and synthesis of the title compound, see: Li et al. (2010 ); Yang et al. (2010 ); Rankin et al. (2002 ).

Experimental

Crystal data

C₈H₁₀Cl₂N₄O
M_r = 249.10
Monoclinic, P 2₁ /n
a = 8.1943 (10) Å
b = 11.0948 (17) Å
c = 11.8333 (18) Å
β = 94.383 (14)°
V = 1072.7 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.58 mm⁻¹
T = 113 K
0.20 × 0.20 × 0.06 mm

Data collection

Rigaku Saturn724 CCD-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.892, T_max = 0.966
13220 measured reflections
2547 independent reflections
1592 reflections with I > 2σ(I)
R_int = 0.058

Refinement

R[F² > 2σ(F²)] = 0.038
wR(F²) = 0.088
S = 0.97
2547 reflections
138 parameters
H-atom parameters constrained
Δρ_max = 0.40 e Å⁻³
Δρ_min = −0.40 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2A⋯Cl2ⁱ	0.99	2.78	3.522 (2)	132
Symmetry code: (i) x+1, y, z.

Data collection: CrystalClear (Rigaku/MSC, 2000 ); cell refinement: CrystalClear; data reduction: CrystalClear; 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: CrystalStructure (Rigaku/MSC, 2000).

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536812026578/zs2206sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812026578/zs2206Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536812026578/zs2206Isup3.cml

checkCIF report

Comment top

2,4,6-Trichloro-1,3,5-triazine, because of the excellent and different reactivity of each chlorine atom, can react with organic amines or compounds containing active hydrogen to form compounds that have various substituent groups (Li et al., 2010); Xue et al., 2011; Zhao et al., 2010). The Aldol reaction is also particularly useful in organic synthesis for the facile formation of C—C bonds. A similar mechanism to that of the Aldol reaction is involved in the reaction of acetone with N-yl-2-iminoethanol (Yang et al., 2010; Rankin et al., 2002). The title compound C₈H₁₀Cl₂N₄O was the product from a combination of such reactions and the structure is reported here.

In this compound (Fig. 1), the dichloro-substituted triazine ring and the quasi-plane of the five-membered dimethyl-substituted oxazolidine moiety, in which the O-atom lies 0.228 (1) Å out of the l.s. plane, are close to coplanar [dihedral angle, 4.99 (10)°]. An intramolecular methyl C—H···N_triazine interaction is present. The crystal packing is stabilized by a single intermolecular C2—H···Cl2ⁱ interaction (Table 1), giving chains which extend along a (Fig. 2). Also present are weak π–π interactions between triazine rings [minimum ring centroid separation, 3.7427 (11) Å].

Related literature top

For the properties of 1,3,5-triazines, see: Xue et al. (2011); Zhao et al. (2010). For the chemistry and synthesis of the title compound, see: Li et al. (2010); Yang et al. (2010); Rankin et al. (2002).

Experimental top

The title compound was prepared in a two-step synthesis: 1:1 Stoichiometric quantities of 2,4,6-trichloro-1,3,5-triazine and ethanolamine were first reacted in an ice bath (Xue et al., 2011). The intermediate product from the first step was then reacted with acetone in the presence of base as a catalyst in an Aldol reaction (Yang et al., 2010; Rankin et al., 2002). Single crystals suitable for X-ray diffraction were obtained by evaporation of a solution of the title compound in toluene at room temperature.

Structure description top

For the properties of 1,3,5-triazines, see: Xue et al. (2011); Zhao et al. (2010). For the chemistry and synthesis of the title compound, see: Li et al. (2010); Yang et al. (2010); Rankin et al. (2002).

Computing details top

Data collection: CrystalClear (Rigaku/MSC, 2000); cell refinement: CrystalClear (Rigaku/MSC, 2000); data reduction: CrystalClear (Rigaku/MSC, 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: CrystalStructure (Rigaku/MSC, 2000).

Figures top

	Fig. 1. The molecular structure and atom-numbering scheme for the title compound, with atoms shown as 50% probability displacement ellipsoids.
	Fig. 2. The crystal packing of the title compound, viewed down the a axis of the unit cell.

3-(4,6-Dichloro-1,3,5-triazin-2-yl)-2,2-dimethyl-1,3-oxazolidine top

Crystal data top

C₈H₁₀Cl₂N₄O	F(000) = 512
M_r = 249.10	D_x = 1.542 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 4131 reflections
a = 8.1943 (10) Å	θ = 1.7–27.9°
b = 11.0948 (17) Å	µ = 0.58 mm⁻¹
c = 11.8333 (18) Å	T = 113 K
β = 94.383 (14)°	Plate, colorless
V = 1072.7 (3) Å³	0.20 × 0.20 × 0.06 mm
Z = 4

Data collection top

Rigaku Saturn724 CCD-detector diffractometer	2547 independent reflections
Radiation source: rotating anode	1592 reflections with I > 2σ(I)
Multilayer monochromator	R_int = 0.058
Detector resolution: 14.22 pixels mm^-1	θ_max = 27.8°, θ_min = 2.5°
ω and φ scans	h = −10→10
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	k = −14→14
T_min = 0.892, T_max = 0.966	l = −15→15
13220 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)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.088	H-atom parameters constrained
S = 0.97	w = 1/[σ²(F_o²) + (0.0381P)²] where P = (F_o² + 2F_c²)/3
2547 reflections	(Δ/σ)_max = 0.001
138 parameters	Δρ_max = 0.40 e Å⁻³
0 restraints	Δρ_min = −0.40 e Å⁻³

Crystal data top

C₈H₁₀Cl₂N₄O	V = 1072.7 (3) Å³
M_r = 249.10	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 8.1943 (10) Å	µ = 0.58 mm⁻¹
b = 11.0948 (17) Å	T = 113 K
c = 11.8333 (18) Å	0.20 × 0.20 × 0.06 mm
β = 94.383 (14)°

Data collection top

Rigaku Saturn724 CCD-detector diffractometer	2547 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1592 reflections with I > 2σ(I)
T_min = 0.892, T_max = 0.966	R_int = 0.058
13220 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.038	0 restraints
wR(F²) = 0.088	H-atom parameters constrained
S = 0.97	Δρ_max = 0.40 e Å⁻³
2547 reflections	Δρ_min = −0.40 e Å⁻³
138 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
Cl1	0.76979 (6)	0.25777 (5)	−0.13199 (4)	0.02482 (15)
Cl2	0.23647 (6)	0.16452 (5)	0.06027 (4)	0.02427 (15)
O1	0.85464 (15)	−0.10346 (12)	0.36264 (11)	0.0234 (3)
N1	0.77455 (18)	0.01989 (14)	0.21633 (12)	0.0186 (4)
N2	0.76821 (19)	0.12912 (14)	0.05072 (13)	0.0183 (4)
N3	0.51066 (18)	0.20524 (14)	−0.02873 (12)	0.0181 (4)
N4	0.52080 (18)	0.09188 (15)	0.14388 (13)	0.0192 (4)
C1	0.9986 (2)	−0.04035 (19)	0.33452 (16)	0.0256 (5)
H1A	1.0933	−0.0957	0.3342	0.031*
H1B	1.0256	0.0256	0.3891	0.031*
C2	0.9532 (2)	0.00951 (19)	0.21618 (16)	0.0244 (5)
H2A	1.0048	0.0889	0.2053	0.029*
H2B	0.9849	−0.0467	0.1567	0.029*
C3	0.7163 (2)	−0.03406 (17)	0.32222 (15)	0.0196 (4)
C4	0.5752 (2)	−0.12112 (18)	0.30178 (17)	0.0250 (5)
H4A	0.6003	−0.1792	0.2432	0.037*
H4B	0.4758	−0.0764	0.2767	0.037*
H4C	0.5579	−0.1642	0.3722	0.037*
C5	0.6822 (2)	0.06585 (18)	0.40536 (16)	0.0273 (5)
H5A	0.6539	0.0302	0.4771	0.041*
H5B	0.5907	0.1153	0.3737	0.041*
H5C	0.7798	0.1163	0.4189	0.041*
C6	0.6855 (2)	0.08098 (17)	0.13663 (15)	0.0181 (4)
C7	0.6724 (2)	0.18873 (17)	−0.02348 (16)	0.0184 (4)
C8	0.4475 (2)	0.15203 (17)	0.05908 (16)	0.0182 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0252 (3)	0.0285 (3)	0.0215 (3)	−0.0004 (2)	0.0066 (2)	0.0066 (2)
Cl2	0.0191 (3)	0.0262 (3)	0.0279 (3)	0.0008 (2)	0.0043 (2)	0.0039 (2)
O1	0.0207 (8)	0.0221 (8)	0.0271 (8)	0.0000 (6)	0.0000 (6)	0.0085 (6)
N1	0.0181 (9)	0.0191 (9)	0.0188 (9)	0.0009 (7)	0.0032 (7)	0.0050 (7)
N2	0.0205 (9)	0.0181 (9)	0.0167 (9)	−0.0003 (7)	0.0034 (7)	0.0010 (7)
N3	0.0209 (9)	0.0167 (9)	0.0168 (9)	0.0000 (7)	0.0017 (7)	−0.0003 (7)
N4	0.0184 (9)	0.0188 (9)	0.0206 (9)	0.0011 (7)	0.0024 (7)	0.0023 (7)
C1	0.0209 (11)	0.0289 (12)	0.0268 (12)	0.0012 (9)	0.0008 (9)	0.0063 (10)
C2	0.0207 (12)	0.0276 (12)	0.0254 (12)	0.0030 (9)	0.0046 (9)	0.0053 (9)
C3	0.0207 (11)	0.0206 (11)	0.0174 (10)	0.0003 (8)	0.0012 (8)	0.0040 (9)
C4	0.0267 (12)	0.0257 (12)	0.0222 (11)	−0.0075 (9)	0.0000 (9)	0.0054 (9)
C5	0.0307 (12)	0.0289 (12)	0.0229 (11)	0.0010 (10)	0.0047 (9)	−0.0022 (10)
C6	0.0229 (11)	0.0140 (10)	0.0177 (10)	−0.0018 (8)	0.0029 (8)	−0.0011 (8)
C7	0.0244 (12)	0.0156 (10)	0.0156 (10)	−0.0022 (8)	0.0037 (8)	−0.0031 (8)
C8	0.0195 (11)	0.0158 (10)	0.0194 (11)	−0.0016 (8)	0.0027 (8)	−0.0053 (8)

Geometric parameters (Å, º) top

Cl1—C7	1.7402 (19)	C1—C2	1.525 (2)
Cl2—C8	1.7360 (19)	C1—H1A	0.9900
O1—C3	1.422 (2)	C1—H1B	0.9900
O1—C1	1.432 (2)	C2—H2A	0.9900
N1—C6	1.333 (2)	C2—H2B	0.9900
N1—C2	1.469 (2)	C3—C4	1.512 (2)
N1—C3	1.499 (2)	C3—C5	1.522 (2)
N2—C7	1.311 (2)	C4—H4A	0.9800
N2—C6	1.372 (2)	C4—H4B	0.9800
N3—C8	1.333 (2)	C4—H4C	0.9800
N3—C7	1.335 (2)	C5—H5A	0.9800
N4—C8	1.312 (2)	C5—H5B	0.9800
N4—C6	1.364 (2)	C5—H5C	0.9800

C3—O1—C1	107.84 (14)	N1—C3—C5	109.60 (15)
C6—N1—C2	122.07 (16)	C4—C3—C5	113.10 (16)
C6—N1—C3	127.05 (16)	C3—C4—H4A	109.5
C2—N1—C3	110.53 (14)	C3—C4—H4B	109.5
C7—N2—C6	112.84 (16)	H4A—C4—H4B	109.5
C8—N3—C7	110.25 (16)	C3—C4—H4C	109.5
C8—N4—C6	113.21 (16)	H4A—C4—H4C	109.5
O1—C1—C2	104.09 (15)	H4B—C4—H4C	109.5
O1—C1—H1A	110.9	C3—C5—H5A	109.5
C2—C1—H1A	110.9	C3—C5—H5B	109.5
O1—C1—H1B	110.9	H5A—C5—H5B	109.5
C2—C1—H1B	110.9	C3—C5—H5C	109.5
H1A—C1—H1B	109.0	H5A—C5—H5C	109.5
N1—C2—C1	101.55 (15)	H5B—C5—H5C	109.5
N1—C2—H2A	111.5	N1—C6—N4	119.43 (17)
C1—C2—H2A	111.5	N1—C6—N2	116.57 (17)
N1—C2—H2B	111.5	N4—C6—N2	124.00 (17)
C1—C2—H2B	111.5	N2—C7—N3	129.93 (18)
H2A—C2—H2B	109.3	N2—C7—Cl1	115.56 (14)
O1—C3—N1	101.59 (14)	N3—C7—Cl1	114.51 (14)
O1—C3—C4	106.75 (16)	N4—C8—N3	129.73 (18)
N1—C3—C4	114.19 (15)	N4—C8—Cl2	115.62 (14)
O1—C3—C5	110.98 (15)	N3—C8—Cl2	114.65 (14)

C3—O1—C1—C2	−39.6 (2)	C2—N1—C6—N2	3.1 (3)
C6—N1—C2—C1	167.26 (17)	C3—N1—C6—N2	175.65 (16)
C3—N1—C2—C1	−6.4 (2)	C8—N4—C6—N1	−178.75 (17)
O1—C1—C2—N1	26.7 (2)	C8—N4—C6—N2	0.9 (3)
C1—O1—C3—N1	34.21 (18)	C7—N2—C6—N1	−179.35 (17)
C1—O1—C3—C4	154.11 (15)	C7—N2—C6—N4	1.0 (3)
C1—O1—C3—C5	−82.24 (18)	C6—N2—C7—N3	−2.3 (3)
C6—N1—C3—O1	170.59 (17)	C6—N2—C7—Cl1	177.47 (13)
C2—N1—C3—O1	−16.15 (19)	C8—N3—C7—N2	1.4 (3)
C6—N1—C3—C4	56.1 (3)	C8—N3—C7—Cl1	−178.37 (13)
C2—N1—C3—C4	−130.64 (18)	C6—N4—C8—N3	−2.1 (3)
C6—N1—C3—C5	−72.0 (2)	C6—N4—C8—Cl2	177.73 (14)
C2—N1—C3—C5	101.30 (18)	C7—N3—C8—N4	1.1 (3)
C2—N1—C6—N4	−177.19 (17)	C7—N3—C8—Cl2	−178.75 (13)
C3—N1—C6—N4	−4.7 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2A···Cl2ⁱ	0.99	2.78	3.522 (2)	132
C4—H4B···N4	0.98	2.49	3.025 (3)	114

Symmetry code: (i) x+1, y, z.

Experimental details

Crystal data
Chemical formula	C₈H₁₀Cl₂N₄O
M_r	249.10
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	113
a, b, c (Å)	8.1943 (10), 11.0948 (17), 11.8333 (18)
β (°)	94.383 (14)
V (Å³)	1072.7 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.58
Crystal size (mm)	0.20 × 0.20 × 0.06

Data collection
Diffractometer	Rigaku Saturn724 CCD-detector
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.892, 0.966
No. of measured, independent and observed [I > 2σ(I)] reflections	13220, 2547, 1592
R_int	0.058
(sin θ/λ)_max (Å⁻¹)	0.657

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.038, 0.088, 0.97
No. of reflections	2547
No. of parameters	138
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.40, −0.40

Computer programs: CrystalClear (Rigaku/MSC, 2000), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), CrystalStructure (Rigaku/MSC, 2000).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2A···Cl2ⁱ	0.99	2.78	3.522 (2)	132

Symmetry code: (i) x+1, y, z.

Acknowledgements

The authors thank Shanxi Province for financial support.

References

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