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

Abstract

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,

• a = 8.1943 (10) Å

• b = 11.0948 (17) Å

• c = 11.8333 (18) Å

• β = 94.383 (14)°

• V = 1072.7 (3) ų

• 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[F ² > 2σ(F ²)] = 0.038

• wR(F ²) = 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

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 ▶).

Supplementary Material

Supplementary material file. DOI: 10.1107/S1600536812026578/zs2206Isup3.cml

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

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) .

supplementary crystallographic information

Comment

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].

Experimental

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.

Refinement

All H atoms were positioned geometrically and treated as riding, with C—H bond lengths constrained to 0.98 Å (methyl) and 0.99 Å (methylene), and with U_iso(H) = 1.2U_eq (methylene C) and 1.5U_eq(methyl C).

Figures

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.

Crystal data

C8H10Cl2N4O	F(000) = 512
Mr = 249.10	Dx = 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

Rigaku Saturn724 CCD-detector diffractometer	2547 independent reflections
Radiation source: rotating anode	1592 reflections with I > 2σ(I)
Multilayer monochromator	Rint = 0.058
Detector resolution: 14.22 pixels mm-1	θmax = 27.8°, θmin = 2.5°
ω and φ scans	h = −10→10
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	k = −14→14
Tmin = 0.892, Tmax = 0.966	l = −15→15
13220 measured reflections

Refinement

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(Fo2) + (0.0381P)2] where P = (Fo2 + 2Fc2)/3
2547 reflections	(Δ/σ)max = 0.001
138 parameters	Δρmax = 0.40 e Å−3
0 restraints	Δρmin = −0.40 e Å−3

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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	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)

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)

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.