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Acta Cryst. (2007). E63, o3017    [ doi:10.1107/S1600536807024099 ]

6-Chloro-2-diethylamino-4-[(1,1,3,3-tetramethylbutyl)amino]-1,3,5-triazine

J.-P. Wang, F. Wen, Q.-M. Zang and S. Liu

Abstract top

The crystal structure of the title compound, C15H28ClN5, is stabilized by intermolecular N-H...N hydrogen bonds.

Comment top

The title compound (Fig. 1) is an important intermediate for the synthesis of hindered light stabilizers (Borzatta & Carrozza, 1991). These compounds containing a triazine ring are widely used (Deng et al., 2006).

The triazine ring is essentially planar with an r.m.s. deviation of 0.013 Å. The molecules are linked by intermolecular N—H···N hydrogen bonds.

Related literature top

For related literature, see: Borzatta & Carrozza (1991); Deng et al. (2006); Kaiser & Thurston (1951).

Experimental top

The title compound was prepared according to the method of Kaiser & Thurston (1951). 2,4,6-Trichloro-1,3,5-triazine (40.0 g, 0.217 mol) was dissolved in toluene (120 ml) and then cooled to 278 K. With stirring, a solution of 2,4,4-trimethylpentan-2-amine (27.5 g, 0.213 mol) in toluene (50 ml) was then added dropwise to the mixture over a period of 0.5 h. Then a solution of Na2CO3 (23.02 g, 0.217 mol) in water (50 ml) was then added dropwise for 0.5 h. The mixture was stirred at 273–278 K for a further 3 h. Diethylamine(15.84 g, 0.217 mol) was and solid Na2CO3 (23.02 g, 0.217 mol) were added to the mixture, maintaining the temperature at 338 k for 5 h. The organic layer was washed with water and then concentrated in vacuo. The title compound (54.50 g) was obtained in powder form in a yield of 80.0%. Crystals of (I) were obtained by slow evaporation of a solution of methanol (m.p. 427–429 K).

Refinement top

H atoms bonded to C were positioned geometrically (C—H=0.98–0.99 Å), and refined as riding with Uiso(H)=1.2Ueq(C) or 1.5eq(methyl groups). The methyl groups were allowed to rotate but not to tip. The H atom bonded to N was freely refined.

Computing details top

Data collection: CrystalClear (Rigaku/MSC, 2005); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: CrystalStructure (Rigaku/MSC, 2005).

Figures top
[Figure 1] Fig. 1. A view of the molecular of (I). Displacement ellopsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii.
6-chloro-2-diethylamino-4-[(1,1,3,3-tetramethylbutyl)amino] -1,3,5-triazine top
Crystal data top
C15H28ClN5Dx = 1.158 Mg m−3
Mr = 313.87Melting point = 94–96 K
Monoclinic, C2/cMo Kα radiation, λ = 0.71070 Å
a = 19.239 (3) ÅCell parameters from 3245 reflections
b = 7.9613 (12) Åθ = 2.8–25.0°
c = 24.105 (4) ŵ = 0.22 mm−1
β = 102.684 (5)°T = 113 K
V = 3602.0 (10) Å3Prism, colorless
Z = 80.32 × 0.22 × 0.20 mm
F(000) = 1360
Data collection top
Rigaku Saturn
diffractometer		3524 independent reflections
Radiation source: rotating anode2993 reflections with I > 2s(I)
confocalRint = 0.051
Detector resolution: 7.31 pixels mm-1θmax = 26.0°, θmin = 1.7°
ω scansh = −23→23
Absorption correction: multi-scan
(CrystalClear; Rigaku/MSC, 2005)		k = −9→9
Tmin = 0.935, Tmax = 0.958l = −29→29
14117 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.045Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.108H atoms treated by a mixture of independent and constrained refinement
S = 1.10 w = 1/[σ2(Fo2) + (0.051P)2 + 0.7372P]
where P = (Fo2 + 2Fc2)/3
3524 reflections(Δ/σ)max < 0.001
201 parametersΔρmax = 0.28 e Å−3
0 restraintsΔρmin = −0.27 e Å−3
Crystal data top
C15H28ClN5V = 3602.0 (10) Å3
Mr = 313.87Z = 8
Monoclinic, C2/cMo Kα radiation
a = 19.239 (3) ŵ = 0.22 mm−1
b = 7.9613 (12) ÅT = 113 K
c = 24.105 (4) Å0.32 × 0.22 × 0.20 mm
β = 102.684 (5)°
Data collection top
Rigaku Saturn
diffractometer		3524 independent reflections
Absorption correction: multi-scan
(CrystalClear; Rigaku/MSC, 2005)		2993 reflections with I > 2s(I)
Tmin = 0.935, Tmax = 0.958Rint = 0.051
14117 measured reflectionsθmax = 26.0°
Refinement top
R[F2 > 2σ(F2)] = 0.045H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.108Δρmax = 0.28 e Å−3
S = 1.10Δρmin = −0.27 e Å−3
3524 reflectionsAbsolute structure: ?
201 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
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
xyzUiso*/Ueq
Cl10.61905 (2)0.77094 (6)0.160423 (18)0.02578 (15)
N10.40684 (7)0.54339 (18)0.10629 (6)0.0192 (3)
N20.50602 (7)0.69474 (18)0.08423 (6)0.0197 (3)
N30.50886 (7)0.61285 (18)0.18027 (6)0.0195 (3)
N40.41177 (8)0.48292 (19)0.20162 (7)0.0211 (3)
N50.40728 (8)0.62277 (19)0.01429 (6)0.0245 (4)
C10.44167 (9)0.5478 (2)0.16095 (7)0.0183 (4)
C20.44069 (9)0.6192 (2)0.06958 (7)0.0199 (4)
C30.53402 (9)0.6820 (2)0.13897 (7)0.0186 (4)
C40.33961 (9)0.4098 (2)0.19432 (7)0.0234 (4)
C50.32706 (9)0.2567 (2)0.15346 (7)0.0205 (4)
H5A0.32460.30220.11490.025*
H5B0.27880.21430.15380.025*
C60.37619 (9)0.0995 (2)0.15906 (7)0.0238 (4)
C70.38462 (11)0.0073 (3)0.21581 (8)0.0365 (5)
H7A0.4065−0.10270.21320.055*
H7B0.3377−0.00790.22470.055*
H7C0.41500.07350.24590.055*
C80.28372 (9)0.5440 (2)0.17013 (9)0.0315 (5)
H8A0.29200.64450.19410.047*
H8B0.23600.49990.16940.047*
H8C0.28750.57300.13140.047*
C90.33090 (11)0.3647 (3)0.25456 (8)0.0351 (5)
H9A0.37120.29520.27350.053*
H9B0.28640.30220.25200.053*
H9C0.32960.46790.27650.053*
C100.33932 (11)−0.0216 (2)0.11220 (8)0.0339 (5)
H10A0.3692−0.12120.11210.051*
H10B0.33210.03460.07520.051*
H10C0.2931−0.05550.11940.051*
C110.45047 (10)0.1395 (3)0.14874 (9)0.0360 (5)
H11A0.47620.21190.17930.054*
H11B0.44560.19740.11220.054*
H11C0.47710.03480.14810.054*
C120.33647 (9)0.5470 (3)−0.00460 (8)0.0300 (5)
H12A0.31110.6037−0.03980.036*
H12B0.30870.56520.02490.036*
C130.34036 (10)0.3595 (3)−0.01590 (8)0.0347 (5)
H13A0.37050.3402−0.04320.052*
H13B0.29230.3163−0.03160.052*
H13C0.36070.30120.01980.052*
C140.43836 (10)0.7093 (3)−0.02854 (8)0.0296 (5)
H14A0.42500.6482−0.06510.036*
H14B0.49100.7075−0.01620.036*
C150.41314 (12)0.8903 (3)−0.03733 (10)0.0466 (6)
H15A0.36100.8926−0.04900.070*
H15B0.43370.9421−0.06690.070*
H15C0.42840.9527−0.00170.070*
H40.4351 (11)0.508 (3)0.2348 (9)0.035 (6)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.0212 (2)0.0333 (3)0.0230 (2)−0.01011 (19)0.00524 (18)−0.00033 (19)
N10.0187 (7)0.0192 (8)0.0200 (7)−0.0009 (6)0.0049 (6)0.0003 (6)
N20.0186 (7)0.0212 (8)0.0197 (8)−0.0037 (6)0.0052 (6)−0.0005 (6)
N30.0181 (7)0.0217 (8)0.0197 (7)−0.0034 (6)0.0063 (6)−0.0006 (6)
N40.0221 (8)0.0231 (8)0.0196 (8)−0.0078 (6)0.0075 (7)−0.0040 (7)
N50.0226 (8)0.0296 (9)0.0198 (8)−0.0035 (7)0.0012 (6)0.0034 (7)
C10.0191 (8)0.0154 (9)0.0214 (9)0.0002 (7)0.0068 (7)−0.0017 (7)
C20.0208 (9)0.0178 (9)0.0211 (9)0.0025 (7)0.0047 (7)0.0015 (7)
C30.0174 (8)0.0172 (9)0.0217 (9)−0.0025 (7)0.0053 (7)−0.0020 (7)
C40.0228 (9)0.0214 (10)0.0292 (10)−0.0062 (7)0.0128 (8)−0.0035 (8)
C50.0183 (9)0.0202 (9)0.0234 (9)−0.0036 (7)0.0054 (7)−0.0002 (7)
C60.0256 (9)0.0174 (9)0.0277 (10)0.0009 (7)0.0045 (8)0.0002 (7)
C70.0431 (12)0.0282 (11)0.0349 (11)0.0011 (9)0.0013 (9)0.0065 (9)
C80.0214 (9)0.0255 (11)0.0519 (13)−0.0031 (8)0.0169 (9)−0.0056 (9)
C90.0405 (12)0.0365 (12)0.0352 (11)−0.0153 (10)0.0235 (9)−0.0073 (9)
C100.0417 (12)0.0213 (10)0.0363 (11)0.0024 (9)0.0032 (9)−0.0047 (9)
C110.0289 (11)0.0265 (11)0.0555 (14)0.0060 (9)0.0159 (10)0.0012 (10)
C120.0207 (9)0.0400 (12)0.0257 (10)−0.0045 (9)−0.0027 (8)0.0029 (9)
C130.0312 (11)0.0452 (13)0.0278 (11)−0.0127 (10)0.0064 (9)−0.0057 (9)
C140.0291 (10)0.0395 (12)0.0197 (9)−0.0024 (9)0.0040 (8)0.0068 (9)
C150.0500 (14)0.0439 (14)0.0475 (14)0.0003 (11)0.0143 (11)0.0218 (11)
Geometric parameters (Å, °) top
Cl1—C31.7531 (17)C8—H8A0.9800
N1—C11.341 (2)C8—H8B0.9800
N1—C21.351 (2)C8—H8C0.9800
N2—C31.315 (2)C9—H9A0.9800
N2—C21.368 (2)C9—H9B0.9800
N3—C31.319 (2)C9—H9C0.9800
N3—C11.375 (2)C10—H10A0.9800
N4—C11.344 (2)C10—H10B0.9800
N4—C41.480 (2)C10—H10C0.9800
N4—H40.85 (2)C11—H11A0.9800
N5—C21.347 (2)C11—H11B0.9800
N5—C121.468 (2)C11—H11C0.9800
N5—C141.473 (2)C12—C131.522 (3)
C4—C81.537 (3)C12—H12A0.9900
C4—C91.540 (2)C12—H12B0.9900
C4—C51.552 (2)C13—H13A0.9800
C5—C61.557 (2)C13—H13B0.9800
C5—H5A0.9900C13—H13C0.9800
C5—H5B0.9900C14—C151.520 (3)
C6—C71.529 (3)C14—H14A0.9900
C6—C101.535 (3)C14—H14B0.9900
C6—C111.537 (2)C15—H15A0.9800
C7—H7A0.9800C15—H15B0.9800
C7—H7B0.9800C15—H15C0.9800
C7—H7C0.9800
C1—N1—C2115.04 (14)C4—C8—H8C109.5
C3—N2—C2112.08 (13)H8A—C8—H8C109.5
C3—N3—C1112.02 (14)H8B—C8—H8C109.5
C1—N4—C4127.23 (15)C4—C9—H9A109.5
C1—N4—H4112.0 (14)C4—C9—H9B109.5
C4—N4—H4119.4 (14)H9A—C9—H9B109.5
C2—N5—C12120.47 (14)C4—C9—H9C109.5
C2—N5—C14121.64 (15)H9A—C9—H9C109.5
C12—N5—C14117.82 (14)H9B—C9—H9C109.5
N1—C1—N4120.32 (15)C6—C10—H10A109.5
N1—C1—N3124.91 (14)C6—C10—H10B109.5
N4—C1—N3114.76 (15)H10A—C10—H10B109.5
N5—C2—N1117.63 (15)C6—C10—H10C109.5
N5—C2—N2117.26 (14)H10A—C10—H10C109.5
N1—C2—N2125.11 (15)H10B—C10—H10C109.5
N2—C3—N3130.70 (15)C6—C11—H11A109.5
N2—C3—Cl1114.51 (12)C6—C11—H11B109.5
N3—C3—Cl1114.79 (13)H11A—C11—H11B109.5
N4—C4—C8109.38 (14)C6—C11—H11C109.5
N4—C4—C9105.84 (14)H11A—C11—H11C109.5
C8—C4—C9107.93 (15)H11B—C11—H11C109.5
N4—C4—C5113.30 (13)N5—C12—C13112.33 (16)
C8—C4—C5107.86 (14)N5—C12—H12A109.1
C9—C4—C5112.39 (14)C13—C12—H12A109.1
C4—C5—C6124.73 (15)N5—C12—H12B109.1
C4—C5—H5A106.1C13—C12—H12B109.1
C6—C5—H5A106.1H12A—C12—H12B107.9
C4—C5—H5B106.1C12—C13—H13A109.5
C6—C5—H5B106.1C12—C13—H13B109.5
H5A—C5—H5B106.3H13A—C13—H13B109.5
C7—C6—C10107.35 (15)C12—C13—H13C109.5
C7—C6—C11108.93 (16)H13A—C13—H13C109.5
C10—C6—C11107.87 (16)H13B—C13—H13C109.5
C7—C6—C5113.98 (15)N5—C14—C15112.00 (16)
C10—C6—C5105.52 (14)N5—C14—H14A109.2
C11—C6—C5112.82 (15)C15—C14—H14A109.2
C6—C7—H7A109.5N5—C14—H14B109.2
C6—C7—H7B109.5C15—C14—H14B109.2
H7A—C7—H7B109.5H14A—C14—H14B107.9
C6—C7—H7C109.5C14—C15—H15A109.5
H7A—C7—H7C109.5C14—C15—H15B109.5
H7B—C7—H7C109.5H15A—C15—H15B109.5
C4—C8—H8A109.5C14—C15—H15C109.5
C4—C8—H8B109.5H15A—C15—H15C109.5
H8A—C8—H8B109.5H15B—C15—H15C109.5
C2—N1—C1—N4177.07 (15)C1—N3—C3—N2−1.3 (3)
C2—N1—C1—N3−4.2 (2)C1—N3—C3—Cl1179.02 (12)
C4—N4—C1—N1−3.4 (3)C1—N4—C4—C8−60.6 (2)
C4—N4—C1—N3177.73 (15)C1—N4—C4—C9−176.65 (17)
C3—N3—C1—N14.3 (2)C1—N4—C4—C559.8 (2)
C3—N3—C1—N4−176.88 (14)N4—C4—C5—C652.9 (2)
C12—N5—C2—N10.3 (2)C8—C4—C5—C6174.13 (15)
C14—N5—C2—N1177.13 (15)C9—C4—C5—C6−67.0 (2)
C12—N5—C2—N2−178.93 (15)C4—C5—C6—C758.4 (2)
C14—N5—C2—N2−2.1 (2)C4—C5—C6—C10175.92 (15)
C1—N1—C2—N5−178.17 (15)C4—C5—C6—C11−66.5 (2)
C1—N1—C2—N21.0 (2)C2—N5—C12—C13−85.1 (2)
C3—N2—C2—N5−179.25 (15)C14—N5—C12—C1397.89 (19)
C3—N2—C2—N11.6 (2)C2—N5—C14—C15−92.2 (2)
C2—N2—C3—N3−1.4 (3)C12—N5—C14—C1584.8 (2)
C2—N2—C3—Cl1178.24 (12)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N4—H4···N3i0.85 (2)2.25 (2)3.098 (2)172 (2)
Symmetry codes: (i) −x+1, y, −z+1/2.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N4—H4···N3i0.85 (2)2.25 (2)3.098 (2)172 (2)
Symmetry codes: (i) −x+1, y, −z+1/2.
references
References top

Borzatta, V. & Carrozza, P. (1991). European Patent EP 0462069.

Bruker (1997). SHELXTL. Bruker AXS Inc., Madison, Wisconsin, USA.

Deng, Y., Wang, X.-J., Wen, F., Wang, L. & Zhang, Y. (2006). Acta Cryst. E62, o5207–o5208.

Kaiser, D. W. & Thurston, J. T. (1951). J. Am. Chem. Soc. 73, 2984–2986.

Rigaku/MSC (2005). CrystalClear and CrystalStructure. Rigaku/MSC, 9009 New Trails Drive, The Woodlands, TX 77381, USA.

Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.