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Acta Cryst. (2007). E63, o3367    [ doi:10.1107/S1600536807031637 ]

2-Butylamino-6-chloro-4-(2,4,4-trimethylpentan-2-ylamino)-1,3,5-triazine

R.-Z. Wen, S.-F. Li and J.-J. Li

Abstract top

The crystal structure of the title compound, C15H28ClN5, is stabilized by intermolecular N-H...N hydrogen bonds, forming zigzag chains running along the c axis.

Comment top

The title compound is an intermediate in the synthesis of hindered light stabilizers (Borzatta & Carrozza, 1991). This kind of compounds is widely used (Deng et al., 2006).

The triazine ring is essentially planar. The r.m.s. deviation from the mean plane is 0.014 (3) Å.

Intermolecular N—H···N hydrogen bonds link the molecules into zigzag-like chains running along the c axis.

Related literature top

For general background, see: Borzatta & Carrozza (1991). For related structures, see: Deng et al. (2006). For related literature, see: 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. 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, 1-butylamine(15.5 g, 0.213 mol) 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 (57.8 g) was obtained as a powder form in a yield of 86.5%. Crystals were obtained by slow evaporation of a solution of methanol.

Refinement top

The coordinates of the H atoms bonded to N were refined with Uiso(H) = 1.2Ueq(N). All H atoms bonded to C were positioned geometrically (C—H = 0.96–0.97 Å) and refined as riding with Uiso(H) = 1.2Ueq(C) or 1.5eq(Cmethyl).

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SMART; data reduction: SAINT (Bruker, 1997); 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: SHELXTL.

Figures top
[Figure 1] Fig. 1. A view of the molecule (I). Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii.
2-Butylamino-6-chloro-4-(2,4,4-trimethylpentan-2-ylamino)-1,3,5-triazine top
Crystal data top
C15H28ClN5Dx = 1.146 Mg m−3
Mr = 313.87Melting point = 156–158 K
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
a = 19.411 (4) ÅCell parameters from 2586 reflections
b = 8.2182 (17) Åθ = 2.5–23.1°
c = 23.245 (5) ŵ = 0.21 mm−1
β = 101.091 (4)°T = 294 K
V = 3638.9 (13) Å3Block, colourless
Z = 80.22 × 0.20 × 0.18 mm
F(000) = 1360
Data collection top
Bruker SMART CCD area-detector
diffractometer		3213 independent reflections
Radiation source: fine-focus sealed tube2283 reflections with I > 2σ(I)
graphiteRint = 0.032
φ and ω scansθmax = 25.0°, θmin = 1.8°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −22→22
Tmin = 0.955, Tmax = 0.963k = −9→9
8608 measured reflectionsl = −27→11
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)] = 0.054Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.161H atoms treated by a mixture of independent and constrained refinement
S = 1.04 w = 1/[σ2(Fo2) + (0.0795P)2 + 3.6231P]
where P = (Fo2 + 2Fc2)/3
3213 reflections(Δ/σ)max = 0.002
200 parametersΔρmax = 0.56 e Å−3
0 restraintsΔρmin = −0.29 e Å−3
Crystal data top
C15H28ClN5V = 3638.9 (13) Å3
Mr = 313.87Z = 8
Monoclinic, C2/cMo Kα radiation
a = 19.411 (4) ŵ = 0.21 mm−1
b = 8.2182 (17) ÅT = 294 K
c = 23.245 (5) Å0.22 × 0.20 × 0.18 mm
β = 101.091 (4)°
Data collection top
Bruker SMART CCD area-detector
diffractometer		3213 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		2283 reflections with I > 2σ(I)
Tmin = 0.955, Tmax = 0.963Rint = 0.032
8608 measured reflectionsθmax = 25.0°
Refinement top
R[F2 > 2σ(F2)] = 0.054H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.161Δρmax = 0.56 e Å−3
S = 1.04Δρmin = −0.29 e Å−3
3213 reflectionsAbsolute structure: ?
200 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
Cl11.11711 (4)−0.02496 (10)0.15825 (3)0.0586 (3)
N11.00664 (10)0.0414 (3)0.08007 (9)0.0376 (5)
N21.00846 (10)0.1316 (3)0.17761 (8)0.0375 (5)
N30.90867 (10)0.1911 (3)0.10248 (8)0.0367 (5)
N40.91215 (12)0.1087 (3)0.00839 (9)0.0441 (6)
H40.9338 (16)0.063 (4)−0.0112 (14)0.053*
N50.91392 (11)0.2638 (3)0.19970 (9)0.0406 (6)
H50.9351 (15)0.245 (4)0.2334 (13)0.049*
C11.03346 (12)0.0595 (3)0.13587 (11)0.0358 (6)
C20.94263 (12)0.1942 (3)0.15820 (10)0.0338 (6)
C30.94272 (12)0.1153 (3)0.06501 (10)0.0344 (6)
C80.84288 (13)0.3361 (3)0.19418 (11)0.0420 (7)
C90.78787 (14)0.2044 (4)0.17388 (15)0.0580 (8)
H9A0.79020.17160.13470.087*
H9B0.74200.24660.17460.087*
H9C0.79690.11220.19960.087*
C100.83748 (17)0.3866 (4)0.25678 (13)0.0659 (9)
H10A0.87190.46880.27040.099*
H10B0.84580.29360.28220.099*
H10C0.79140.42900.25690.099*
C110.82914 (15)0.4783 (3)0.15022 (13)0.0478 (7)
H11A0.78110.51250.14940.057*
H11B0.82990.43160.11200.057*
C120.87304 (19)0.6361 (4)0.15384 (16)0.0684 (10)
C130.9485 (2)0.6015 (5)0.1488 (3)0.124 (2)
H13A0.94910.54040.11380.185*
H13B0.97100.53990.18230.185*
H13C0.97300.70240.14730.185*
C140.8716 (3)0.7385 (5)0.2077 (2)0.131 (2)
H14A0.89700.68390.24180.196*
H14B0.82380.75450.21200.196*
H14C0.89290.84210.20360.196*
C150.8392 (3)0.7383 (5)0.1007 (2)0.1218 (18)
H15A0.86440.83880.10070.183*
H15B0.79120.76070.10290.183*
H15C0.84090.67930.06540.183*
C40.84612 (15)0.1883 (4)−0.01574 (12)0.0559 (8)
H4A0.81340.16880.01020.067*
H4B0.82670.1389−0.05330.067*
C50.8518 (2)0.3659 (5)−0.02418 (16)0.0793 (11)
H5A0.80510.4089−0.03840.095*
H5B0.86940.41540.01370.095*
C60.8958 (2)0.4149 (5)−0.0636 (2)0.0987 (14)
H6A0.87820.3671−0.10170.118*
H6B0.94270.3730−0.04960.118*
C70.8997 (3)0.6042 (6)−0.0704 (2)0.149 (2)
H7A0.92260.6297−0.10230.223*
H7B0.92580.6503−0.03480.223*
H7C0.85310.6485−0.07810.223*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.0456 (4)0.0801 (6)0.0485 (4)0.0282 (4)0.0048 (3)−0.0040 (4)
N10.0381 (12)0.0436 (13)0.0323 (11)0.0069 (9)0.0096 (9)−0.0024 (10)
N20.0337 (11)0.0484 (13)0.0314 (11)0.0066 (9)0.0089 (9)−0.0011 (10)
N30.0357 (11)0.0443 (12)0.0312 (11)0.0055 (9)0.0089 (9)−0.0029 (10)
N40.0415 (13)0.0603 (16)0.0312 (12)0.0123 (11)0.0087 (9)−0.0062 (11)
N50.0383 (12)0.0559 (14)0.0287 (11)0.0112 (10)0.0092 (9)−0.0030 (11)
C10.0332 (13)0.0395 (14)0.0359 (14)0.0056 (11)0.0097 (11)0.0013 (11)
C20.0349 (13)0.0365 (14)0.0314 (13)0.0008 (10)0.0103 (10)−0.0003 (11)
C30.0372 (13)0.0365 (14)0.0307 (13)0.0010 (11)0.0098 (10)0.0005 (11)
C80.0371 (14)0.0516 (17)0.0409 (15)0.0100 (12)0.0163 (11)−0.0002 (13)
C90.0413 (16)0.0580 (19)0.079 (2)0.0018 (14)0.0215 (15)0.0076 (17)
C100.072 (2)0.081 (2)0.0524 (18)0.0291 (18)0.0321 (16)0.0016 (17)
C110.0474 (16)0.0467 (16)0.0521 (17)0.0094 (13)0.0168 (13)0.0014 (14)
C120.083 (2)0.0458 (18)0.084 (2)0.0018 (17)0.036 (2)−0.0050 (18)
C130.090 (3)0.069 (3)0.229 (6)−0.028 (2)0.073 (4)−0.005 (3)
C140.216 (6)0.061 (3)0.131 (4)−0.027 (3)0.071 (4)−0.039 (3)
C150.180 (5)0.061 (3)0.132 (4)−0.001 (3)0.048 (4)0.034 (3)
C40.0498 (17)0.079 (2)0.0374 (15)0.0144 (16)0.0053 (13)−0.0014 (15)
C50.083 (3)0.090 (3)0.062 (2)0.020 (2)0.0057 (19)0.010 (2)
C60.091 (3)0.095 (3)0.112 (3)−0.015 (3)0.024 (3)−0.002 (3)
C70.202 (7)0.114 (4)0.128 (5)−0.052 (4)0.028 (4)0.032 (4)
Geometric parameters (Å, °) top
Cl1—C11.750 (2)C12—C141.514 (5)
N1—C11.310 (3)C12—C131.518 (5)
N1—C31.365 (3)C12—C151.532 (5)
N2—C11.307 (3)C13—H13A0.9600
N2—C21.371 (3)C13—H13B0.9600
N3—C21.336 (3)C13—H13C0.9600
N3—C31.344 (3)C14—H14A0.9600
N4—C31.337 (3)C14—H14B0.9600
N4—C41.452 (3)C14—H14C0.9600
N4—H40.77 (3)C15—H15A0.9600
N5—C21.333 (3)C15—H15B0.9600
N5—C81.484 (3)C15—H15C0.9600
N5—H50.83 (3)C4—C51.480 (5)
C8—C91.530 (4)C4—H4A0.9700
C8—C101.536 (4)C4—H4B0.9700
C8—C111.541 (4)C5—C61.425 (5)
C9—H9A0.9600C5—H5A0.9700
C9—H9B0.9600C5—H5B0.9700
C9—H9C0.9600C6—C71.567 (6)
C10—H10A0.9600C6—H6A0.9700
C10—H10B0.9600C6—H6B0.9700
C10—H10C0.9600C7—H7A0.9600
C11—C121.545 (4)C7—H7B0.9600
C11—H11A0.9700C7—H7C0.9600
C11—H11B0.9700
C1—N1—C3111.8 (2)C14—C12—C11114.4 (3)
C1—N2—C2112.4 (2)C13—C12—C11111.6 (3)
C2—N3—C3115.1 (2)C15—C12—C11105.6 (3)
C3—N4—C4123.6 (2)C12—C13—H13A109.5
C3—N4—H4114 (2)C12—C13—H13B109.5
C4—N4—H4122 (2)H13A—C13—H13B109.5
C2—N5—C8128.3 (2)C12—C13—H13C109.5
C2—N5—H5114 (2)H13A—C13—H13C109.5
C8—N5—H5116 (2)H13B—C13—H13C109.5
N2—C1—N1130.8 (2)C12—C14—H14A109.5
N2—C1—Cl1114.49 (18)C12—C14—H14B109.5
N1—C1—Cl1114.74 (18)H14A—C14—H14B109.5
N5—C2—N3120.8 (2)C12—C14—H14C109.5
N5—C2—N2114.6 (2)H14A—C14—H14C109.5
N3—C2—N2124.6 (2)H14B—C14—H14C109.5
N4—C3—N3118.5 (2)C12—C15—H15A109.5
N4—C3—N1116.3 (2)C12—C15—H15B109.5
N3—C3—N1125.2 (2)H15A—C15—H15B109.5
N5—C8—C9109.0 (2)C12—C15—H15C109.5
N5—C8—C10104.9 (2)H15A—C15—H15C109.5
C9—C8—C10108.2 (2)H15B—C15—H15C109.5
N5—C8—C11113.6 (2)N4—C4—C5114.4 (3)
C9—C8—C11108.1 (2)N4—C4—H4A108.7
C10—C8—C11112.9 (2)C5—C4—H4A108.7
C8—C9—H9A109.5N4—C4—H4B108.7
C8—C9—H9B109.5C5—C4—H4B108.7
H9A—C9—H9B109.5H4A—C4—H4B107.6
C8—C9—H9C109.5C6—C5—C4115.6 (3)
H9A—C9—H9C109.5C6—C5—H5A108.4
H9B—C9—H9C109.5C4—C5—H5A108.4
C8—C10—H10A109.5C6—C5—H5B108.4
C8—C10—H10B109.5C4—C5—H5B108.4
H10A—C10—H10B109.5H5A—C5—H5B107.4
C8—C10—H10C109.5C5—C6—C7113.1 (4)
H10A—C10—H10C109.5C5—C6—H6A109.0
H10B—C10—H10C109.5C7—C6—H6A109.0
C8—C11—C12125.2 (3)C5—C6—H6B109.0
C8—C11—H11A106.0C7—C6—H6B109.0
C12—C11—H11A106.0H6A—C6—H6B107.8
C8—C11—H11B106.0C6—C7—H7A109.5
C12—C11—H11B106.0C6—C7—H7B109.5
H11A—C11—H11B106.3H7A—C7—H7B109.5
C14—C12—C13109.9 (4)C6—C7—H7C109.5
C14—C12—C15106.8 (3)H7A—C7—H7C109.5
C13—C12—C15108.1 (4)H7B—C7—H7C109.5
C2—N2—C1—N11.4 (4)C1—N1—C3—N4177.6 (2)
C2—N2—C1—Cl1−179.32 (17)C1—N1—C3—N3−3.2 (4)
C3—N1—C1—N21.7 (4)C2—N5—C8—C960.6 (3)
C3—N1—C1—Cl1−177.58 (17)C2—N5—C8—C10176.3 (3)
C8—N5—C2—N34.2 (4)C2—N5—C8—C11−60.0 (4)
C8—N5—C2—N2−177.0 (2)N5—C8—C11—C12−58.3 (3)
C3—N3—C2—N5−179.1 (2)C9—C8—C11—C12−179.4 (3)
C3—N3—C2—N22.3 (4)C10—C8—C11—C1261.0 (3)
C1—N2—C2—N5177.7 (2)C8—C11—C12—C14−63.0 (4)
C1—N2—C2—N3−3.6 (4)C8—C11—C12—C1362.5 (4)
C4—N4—C3—N34.2 (4)C8—C11—C12—C15179.8 (3)
C4—N4—C3—N1−176.5 (3)C3—N4—C4—C577.2 (4)
C2—N3—C3—N4−179.5 (2)N4—C4—C5—C661.1 (4)
C2—N3—C3—N11.4 (4)C4—C5—C6—C7−179.8 (4)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N4—H4···N1i0.77 (3)2.31 (3)3.079 (3)171 (3)
N5—H5···N2ii0.83 (3)2.34 (3)3.151 (3)167 (3)
Symmetry codes: (i) −x+2, −y, −z; (ii) −x+2, y, −z+1/2.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N4—H4···N1i0.77 (3)2.31 (3)3.079 (3)171 (3)
N5—H5···N2ii0.83 (3)2.34 (3)3.151 (3)167 (3)
Symmetry codes: (i) −x+2, −y, −z; (ii) −x+2, y, −z+1/2.
references
References top

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

Bruker (1997). SMART, SAINT and 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.

Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.

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