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

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

Key indicators

• Single-crystal X-ray study
• T = 113 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.045
• wR factor = 0.108
• Data-to-parameter ratio = 17.5

checkCIF/PLATON results

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PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical .          ?
PLAT125_ALERT_4_C No _symmetry_space_group_name_Hall Given .......          ?
PLAT220_ALERT_2_C Large Non-Solvent    C     Ueq(max)/Ueq(min) ...       2.55 Ratio

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
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   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
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S1. Comment

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

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

S2. Experimental

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).

S3. Refinement

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

Computing details

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

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

Crystal data

C15H28ClN5	Dx = 1.158 Mg m^−3
Mr = 313.87	Melting point = 94–96 K
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71070 Å
a = 19.239 (3) Å	Cell parameters from 3245 reflections
b = 7.9613 (12) Å	θ = 2.8–25.0°
c = 24.105 (4) Å	µ = 0.22 mm^−1
β = 102.684 (5)°	T = 113 K
V = 3602.0 (10) Å^3	Prism, colorless
Z = 8	0.32 × 0.22 × 0.20 mm
F(000) = 1360

Data collection

Rigaku Saturn diffractometer	3524 independent reflections
Radiation source: rotating anode	2993 reflections with I > 2s(I)
Confocal monochromator	Rint = 0.051
Detector resolution: 7.31 pixels mm^-1	θmax = 26.0°, θmin = 1.7°
ω scans	h = −23→23
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005)	k = −9→9
Tmin = 0.935, Tmax = 0.958	l = −29→29
14117 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.108	H atoms treated by a mixture of independent and constrained refinement
S = 1.10	w = 1/[σ^2(Fo^2) + (0.051P)^2 + 0.7372P] where P = (Fo^2 + 2Fc^2)/3
3524 reflections	(Δ/σ)max < 0.001
201 parameters	Δρmax = 0.28 e Å^−3
0 restraints	Δρmin = −0.27 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	0.61905 (2)	0.77094 (6)	0.160423 (18)	0.02578 (15)
N1	0.40684 (7)	0.54339 (18)	0.10629 (6)	0.0192 (3)
N2	0.50602 (7)	0.69474 (18)	0.08423 (6)	0.0197 (3)
N3	0.50886 (7)	0.61285 (18)	0.18027 (6)	0.0195 (3)
N4	0.41177 (8)	0.48292 (19)	0.20162 (7)	0.0211 (3)
N5	0.40728 (8)	0.62277 (19)	0.01429 (6)	0.0245 (4)
C1	0.44167 (9)	0.5478 (2)	0.16095 (7)	0.0183 (4)
C2	0.44069 (9)	0.6192 (2)	0.06958 (7)	0.0199 (4)
C3	0.53402 (9)	0.6820 (2)	0.13897 (7)	0.0186 (4)
C4	0.33961 (9)	0.4098 (2)	0.19432 (7)	0.0234 (4)
C5	0.32706 (9)	0.2567 (2)	0.15346 (7)	0.0205 (4)
H5A	0.3246	0.3022	0.1149	0.025*
H5B	0.2788	0.2143	0.1538	0.025*
C6	0.37619 (9)	0.0995 (2)	0.15906 (7)	0.0238 (4)
C7	0.38462 (11)	0.0073 (3)	0.21581 (8)	0.0365 (5)
H7A	0.4065	−0.1027	0.2132	0.055*
H7B	0.3377	−0.0079	0.2247	0.055*
H7C	0.4150	0.0735	0.2459	0.055*
C8	0.28372 (9)	0.5440 (2)	0.17013 (9)	0.0315 (5)
H8A	0.2920	0.6445	0.1941	0.047*
H8B	0.2360	0.4999	0.1694	0.047*
H8C	0.2875	0.5730	0.1314	0.047*
C9	0.33090 (11)	0.3647 (3)	0.25456 (8)	0.0351 (5)
H9A	0.3712	0.2952	0.2735	0.053*
H9B	0.2864	0.3022	0.2520	0.053*
H9C	0.3296	0.4679	0.2765	0.053*
C10	0.33932 (11)	−0.0216 (2)	0.11220 (8)	0.0339 (5)
H10A	0.3692	−0.1212	0.1121	0.051*
H10B	0.3321	0.0346	0.0752	0.051*
H10C	0.2931	−0.0555	0.1194	0.051*
C11	0.45047 (10)	0.1395 (3)	0.14874 (9)	0.0360 (5)
H11A	0.4762	0.2119	0.1793	0.054*
H11B	0.4456	0.1974	0.1122	0.054*
H11C	0.4771	0.0348	0.1481	0.054*
C12	0.33647 (9)	0.5470 (3)	−0.00460 (8)	0.0300 (5)
H12A	0.3111	0.6037	−0.0398	0.036*
H12B	0.3087	0.5652	0.0249	0.036*
C13	0.34036 (10)	0.3595 (3)	−0.01590 (8)	0.0347 (5)
H13A	0.3705	0.3402	−0.0432	0.052*
H13B	0.2923	0.3163	−0.0316	0.052*
H13C	0.3607	0.3012	0.0198	0.052*
C14	0.43836 (10)	0.7093 (3)	−0.02854 (8)	0.0296 (5)
H14A	0.4250	0.6482	−0.0651	0.036*
H14B	0.4910	0.7075	−0.0162	0.036*
C15	0.41314 (12)	0.8903 (3)	−0.03733 (10)	0.0466 (6)
H15A	0.3610	0.8926	−0.0490	0.070*
H15B	0.4337	0.9421	−0.0669	0.070*
H15C	0.4284	0.9527	−0.0017	0.070*
H4	0.4351 (11)	0.508 (3)	0.2348 (9)	0.035 (6)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.0212 (2)	0.0333 (3)	0.0230 (2)	−0.01011 (19)	0.00524 (18)	−0.00033 (19)
N1	0.0187 (7)	0.0192 (8)	0.0200 (7)	−0.0009 (6)	0.0049 (6)	0.0003 (6)
N2	0.0186 (7)	0.0212 (8)	0.0197 (8)	−0.0037 (6)	0.0052 (6)	−0.0005 (6)
N3	0.0181 (7)	0.0217 (8)	0.0197 (7)	−0.0034 (6)	0.0063 (6)	−0.0006 (6)
N4	0.0221 (8)	0.0231 (8)	0.0196 (8)	−0.0078 (6)	0.0075 (7)	−0.0040 (7)
N5	0.0226 (8)	0.0296 (9)	0.0198 (8)	−0.0035 (7)	0.0012 (6)	0.0034 (7)
C1	0.0191 (8)	0.0154 (9)	0.0214 (9)	0.0002 (7)	0.0068 (7)	−0.0017 (7)
C2	0.0208 (9)	0.0178 (9)	0.0211 (9)	0.0025 (7)	0.0047 (7)	0.0015 (7)
C3	0.0174 (8)	0.0172 (9)	0.0217 (9)	−0.0025 (7)	0.0053 (7)	−0.0020 (7)
C4	0.0228 (9)	0.0214 (10)	0.0292 (10)	−0.0062 (7)	0.0128 (8)	−0.0035 (8)
C5	0.0183 (9)	0.0202 (9)	0.0234 (9)	−0.0036 (7)	0.0054 (7)	−0.0002 (7)
C6	0.0256 (9)	0.0174 (9)	0.0277 (10)	0.0009 (7)	0.0045 (8)	0.0002 (7)
C7	0.0431 (12)	0.0282 (11)	0.0349 (11)	0.0011 (9)	0.0013 (9)	0.0065 (9)
C8	0.0214 (9)	0.0255 (11)	0.0519 (13)	−0.0031 (8)	0.0169 (9)	−0.0056 (9)
C9	0.0405 (12)	0.0365 (12)	0.0352 (11)	−0.0153 (10)	0.0235 (9)	−0.0073 (9)
C10	0.0417 (12)	0.0213 (10)	0.0363 (11)	0.0024 (9)	0.0032 (9)	−0.0047 (9)
C11	0.0289 (11)	0.0265 (11)	0.0555 (14)	0.0060 (9)	0.0159 (10)	0.0012 (10)
C12	0.0207 (9)	0.0400 (12)	0.0257 (10)	−0.0045 (9)	−0.0027 (8)	0.0029 (9)
C13	0.0312 (11)	0.0452 (13)	0.0278 (11)	−0.0127 (10)	0.0064 (9)	−0.0057 (9)
C14	0.0291 (10)	0.0395 (12)	0.0197 (9)	−0.0024 (9)	0.0040 (8)	0.0068 (9)
C15	0.0500 (14)	0.0439 (14)	0.0475 (14)	0.0003 (11)	0.0143 (11)	0.0218 (11)

Geometric parameters (Å, º)

Cl1—C3	1.7531 (17)	C8—H8A	0.9800
N1—C1	1.341 (2)	C8—H8B	0.9800
N1—C2	1.351 (2)	C8—H8C	0.9800
N2—C3	1.315 (2)	C9—H9A	0.9800
N2—C2	1.368 (2)	C9—H9B	0.9800
N3—C3	1.319 (2)	C9—H9C	0.9800
N3—C1	1.375 (2)	C10—H10A	0.9800
N4—C1	1.344 (2)	C10—H10B	0.9800
N4—C4	1.480 (2)	C10—H10C	0.9800
N4—H4	0.85 (2)	C11—H11A	0.9800
N5—C2	1.347 (2)	C11—H11B	0.9800
N5—C12	1.468 (2)	C11—H11C	0.9800
N5—C14	1.473 (2)	C12—C13	1.522 (3)
C4—C8	1.537 (3)	C12—H12A	0.9900
C4—C9	1.540 (2)	C12—H12B	0.9900
C4—C5	1.552 (2)	C13—H13A	0.9800
C5—C6	1.557 (2)	C13—H13B	0.9800
C5—H5A	0.9900	C13—H13C	0.9800
C5—H5B	0.9900	C14—C15	1.520 (3)
C6—C7	1.529 (3)	C14—H14A	0.9900
C6—C10	1.535 (3)	C14—H14B	0.9900
C6—C11	1.537 (2)	C15—H15A	0.9800
C7—H7A	0.9800	C15—H15B	0.9800
C7—H7B	0.9800	C15—H15C	0.9800
C7—H7C	0.9800
C1—N1—C2	115.04 (14)	C4—C8—H8C	109.5
C3—N2—C2	112.08 (13)	H8A—C8—H8C	109.5
C3—N3—C1	112.02 (14)	H8B—C8—H8C	109.5
C1—N4—C4	127.23 (15)	C4—C9—H9A	109.5
C1—N4—H4	112.0 (14)	C4—C9—H9B	109.5
C4—N4—H4	119.4 (14)	H9A—C9—H9B	109.5
C2—N5—C12	120.47 (14)	C4—C9—H9C	109.5
C2—N5—C14	121.64 (15)	H9A—C9—H9C	109.5
C12—N5—C14	117.82 (14)	H9B—C9—H9C	109.5
N1—C1—N4	120.32 (15)	C6—C10—H10A	109.5
N1—C1—N3	124.91 (14)	C6—C10—H10B	109.5
N4—C1—N3	114.76 (15)	H10A—C10—H10B	109.5
N5—C2—N1	117.63 (15)	C6—C10—H10C	109.5
N5—C2—N2	117.26 (14)	H10A—C10—H10C	109.5
N1—C2—N2	125.11 (15)	H10B—C10—H10C	109.5
N2—C3—N3	130.70 (15)	C6—C11—H11A	109.5
N2—C3—Cl1	114.51 (12)	C6—C11—H11B	109.5
N3—C3—Cl1	114.79 (13)	H11A—C11—H11B	109.5
N4—C4—C8	109.38 (14)	C6—C11—H11C	109.5
N4—C4—C9	105.84 (14)	H11A—C11—H11C	109.5
C8—C4—C9	107.93 (15)	H11B—C11—H11C	109.5
N4—C4—C5	113.30 (13)	N5—C12—C13	112.33 (16)
C8—C4—C5	107.86 (14)	N5—C12—H12A	109.1
C9—C4—C5	112.39 (14)	C13—C12—H12A	109.1
C4—C5—C6	124.73 (15)	N5—C12—H12B	109.1
C4—C5—H5A	106.1	C13—C12—H12B	109.1
C6—C5—H5A	106.1	H12A—C12—H12B	107.9
C4—C5—H5B	106.1	C12—C13—H13A	109.5
C6—C5—H5B	106.1	C12—C13—H13B	109.5
H5A—C5—H5B	106.3	H13A—C13—H13B	109.5
C7—C6—C10	107.35 (15)	C12—C13—H13C	109.5
C7—C6—C11	108.93 (16)	H13A—C13—H13C	109.5
C10—C6—C11	107.87 (16)	H13B—C13—H13C	109.5
C7—C6—C5	113.98 (15)	N5—C14—C15	112.00 (16)
C10—C6—C5	105.52 (14)	N5—C14—H14A	109.2
C11—C6—C5	112.82 (15)	C15—C14—H14A	109.2
C6—C7—H7A	109.5	N5—C14—H14B	109.2
C6—C7—H7B	109.5	C15—C14—H14B	109.2
H7A—C7—H7B	109.5	H14A—C14—H14B	107.9
C6—C7—H7C	109.5	C14—C15—H15A	109.5
H7A—C7—H7C	109.5	C14—C15—H15B	109.5
H7B—C7—H7C	109.5	H15A—C15—H15B	109.5
C4—C8—H8A	109.5	C14—C15—H15C	109.5
C4—C8—H8B	109.5	H15A—C15—H15C	109.5
H8A—C8—H8B	109.5	H15B—C15—H15C	109.5
C2—N1—C1—N4	177.07 (15)	C1—N3—C3—N2	−1.3 (3)
C2—N1—C1—N3	−4.2 (2)	C1—N3—C3—Cl1	179.02 (12)
C4—N4—C1—N1	−3.4 (3)	C1—N4—C4—C8	−60.6 (2)
C4—N4—C1—N3	177.73 (15)	C1—N4—C4—C9	−176.65 (17)
C3—N3—C1—N1	4.3 (2)	C1—N4—C4—C5	59.8 (2)
C3—N3—C1—N4	−176.88 (14)	N4—C4—C5—C6	52.9 (2)
C12—N5—C2—N1	0.3 (2)	C8—C4—C5—C6	174.13 (15)
C14—N5—C2—N1	177.13 (15)	C9—C4—C5—C6	−67.0 (2)
C12—N5—C2—N2	−178.93 (15)	C4—C5—C6—C7	58.4 (2)
C14—N5—C2—N2	−2.1 (2)	C4—C5—C6—C10	175.92 (15)
C1—N1—C2—N5	−178.17 (15)	C4—C5—C6—C11	−66.5 (2)
C1—N1—C2—N2	1.0 (2)	C2—N5—C12—C13	−85.1 (2)
C3—N2—C2—N5	−179.25 (15)	C14—N5—C12—C13	97.89 (19)
C3—N2—C2—N1	1.6 (2)	C2—N5—C14—C15	−92.2 (2)
C2—N2—C3—N3	−1.4 (3)	C12—N5—C14—C15	84.8 (2)
C2—N2—C3—Cl1	178.24 (12)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4···N3^i	0.85 (2)	2.25 (2)	3.098 (2)	172 (2)

Symmetry code: (i) −x+1, y, −z+1/2.