6-Chloro-N⁴-(2,2,6,6-tetra­methyl­piperidin-4-yl)-N²-(2,4,4-trimethyl­pentan-2-yl)-1,3,5-triazine-2,4-diamine

In the title compound, C₂₀H₃₇ClN₆, the piperidine ring adopts a chair conformation. In the crystal structure, N—H...N hydrogen bonds link the mol­ecules into chains along b.

Key indicators

• Single-crystal X-ray study
• T = 113 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.044
• wR factor = 0.102
• Data-to-parameter ratio = 20.0

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT220_ALERT_2_C Large Non-Solvent    C     Ueq(max)/Ueq(min) ...       2.52 Ratio

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   1 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 ALERT type 2 Indicator that the structure model may be wrong or deficient
   0 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

The title compound (I) is an important intermediate in the preparation of hindered light stabilizers (Borzatta & Carrozza, 1991). Compounds containing a triazine ring are widely used in polymers, dyes, drugs and hindered amine light stabilizers (Deng et al., 2006). We report here the crystal structure of the title compound (I) (Fig. 1). In (I) the piperidine ring adopts a chair conformation and the triazine ring is essentially planar with an r.m.s. deviation from the mean plane of 0.0115Å. In the crystal structure N—H···N hydrogen bonds link the molecules into chains along b</>, Table 1.

Related literature

For the preparation and uses of (I) and similar compounds, 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) in 74.5% yield. Crystals of (I) were obtained by slow evaporation of a solution in methanol (m.p. 473–475 K).

S3. Refinement

The amine H atoms were located in a Fourier map and refined freely with isotropic displacement parameters. All other H atoms were positioned geometrically and refined using a riding model with d(C—H) = 1.00 Å, U_iso = 1.2U_eq (C) for CH, 0.99 Å, U_iso = 1.2U_eq (C) for CH₂ and 0.98 Å, U_iso = 1.5U_eq (C) for CH₃ atoms.

Computing details

Data collection: CrystalClear (Rigaku/MSC, 2005); cell refinement: CrystalClear (Rigaku/MSC, 2005); data reduction: CrystalClear (Rigaku/MSC, 2005); 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 (Version 3.7.0; Rigaku/MSC, 2005).

Figures

Fig. 1. A view of the molecular structure of (I). Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres with arbitrary radii.

6-Chloro-N4-(2,2,6,6-tetramethylpiperidin-4-yl)-N2-(2,4,4- trimethylpentan-2-yl)-1,3,5-triazine-2,4-diamine

Crystal data

C20H37ClN6	F(000) = 864
Mr = 397.01	Dx = 1.189 Mg m^−3
Monoclinic, P21/n	Melting point: 473-475 K K
Hall symbol: -P 2yn	Mo Kα radiation, λ = 0.71070 Å
a = 7.9906 (7) Å	Cell parameters from 7832 reflections
b = 20.5197 (16) Å	θ = 1.5–27.9°
c = 13.6338 (10) Å	µ = 0.19 mm^−1
β = 97.273 (3)°	T = 113 K
V = 2217.5 (3) Å^3	Block, colorless
Z = 4	0.26 × 0.22 × 0.20 mm

Data collection

Rigaku Saturn CCD diffractometer	5297 independent reflections
Radiation source: rotating anode	4972 reflections with I > 2σ(I)
Confocal monochromator	Rint = 0.035
Detector resolution: 14.63 pixels mm^-1	θmax = 27.9°, θmin = 1.8°
ω scans	h = −10→10
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005)	k = −26→27
Tmin = 0.943, Tmax = 0.963	l = −17→17
27567 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)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.102	H atoms treated by a mixture of independent and constrained refinement
S = 1.09	w = 1/[σ^2(Fo^2) + (0.0454P)^2 + 0.6837P] where P = (Fo^2 + 2Fc^2)/3
5297 reflections	(Δ/σ)max < 0.001
265 parameters	Δρmax = 0.26 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	0.01081 (4)	0.699625 (15)	0.47224 (2)	0.02317 (10)
N1	0.15950 (13)	0.66230 (5)	0.32523 (8)	0.0168 (2)
N2	0.09387 (13)	0.57989 (5)	0.43869 (8)	0.0173 (2)
N3	0.22982 (13)	0.55103 (5)	0.29729 (8)	0.0155 (2)
N4	0.28136 (14)	0.63301 (5)	0.18846 (8)	0.0170 (2)
N5	0.17778 (15)	0.47447 (5)	0.41161 (8)	0.0204 (2)
N6	0.28530 (14)	0.28875 (5)	0.29972 (8)	0.0175 (2)
C1	0.22279 (15)	0.61388 (6)	0.27161 (9)	0.0149 (2)
C2	0.09911 (16)	0.63977 (6)	0.40412 (9)	0.0162 (2)
C3	0.16769 (15)	0.53637 (6)	0.38127 (9)	0.0159 (2)
C4	0.33522 (16)	0.59015 (6)	0.11107 (9)	0.0173 (3)
C5	0.48819 (15)	0.54635 (6)	0.14791 (9)	0.0165 (2)
H5A	0.4449	0.5120	0.1890	0.020*
H5B	0.5207	0.5242	0.0886	0.020*
C6	0.65409 (16)	0.57120 (6)	0.20685 (10)	0.0197 (3)
C7	0.37084 (19)	0.63562 (7)	0.02693 (10)	0.0248 (3)
H7A	0.2657	0.6567	−0.0015	0.037*
H7B	0.4170	0.6103	−0.0244	0.037*
H7C	0.4526	0.6689	0.0528	0.037*
C8	0.18857 (17)	0.54531 (7)	0.07119 (10)	0.0228 (3)
H8A	0.1592	0.5172	0.1246	0.034*
H8B	0.2223	0.5183	0.0178	0.034*
H8C	0.0906	0.5718	0.0457	0.034*
C9	0.63165 (19)	0.59348 (8)	0.31157 (11)	0.0317 (3)
H9A	0.7423	0.6028	0.3485	0.048*
H9B	0.5762	0.5589	0.3452	0.048*
H9C	0.5620	0.6329	0.3080	0.048*
C10	0.77338 (18)	0.51252 (7)	0.21771 (11)	0.0271 (3)
H10A	0.7925	0.4971	0.1520	0.041*
H10B	0.7228	0.4775	0.2530	0.041*
H10C	0.8812	0.5254	0.2550	0.041*
C11	0.7392 (2)	0.62547 (8)	0.15494 (14)	0.0375 (4)
H11A	0.6733	0.6657	0.1562	0.056*
H11B	0.7459	0.6129	0.0862	0.056*
H11C	0.8532	0.6327	0.1890	0.056*
C12	0.24318 (17)	0.42220 (6)	0.35383 (9)	0.0187 (3)
H12	0.3114	0.4423	0.3051	0.022*
C13	0.09877 (17)	0.38406 (6)	0.29721 (10)	0.0200 (3)
H13A	0.0288	0.4142	0.2524	0.024*
H13B	0.0268	0.3662	0.3447	0.024*
C14	0.15876 (17)	0.32805 (6)	0.23626 (9)	0.0194 (3)
C15	0.42659 (16)	0.32117 (6)	0.36202 (10)	0.0187 (3)
C16	0.35639 (17)	0.37652 (6)	0.42026 (10)	0.0191 (3)
H16A	0.2913	0.3577	0.4705	0.023*
H16B	0.4514	0.4017	0.4553	0.023*
C17	0.2212 (2)	0.35397 (7)	0.14140 (10)	0.0279 (3)
H17A	0.3049	0.3884	0.1585	0.042*
H17B	0.1256	0.3717	0.0974	0.042*
H17C	0.2728	0.3183	0.1080	0.042*
C18	0.00934 (19)	0.28255 (7)	0.20586 (11)	0.0268 (3)
H18A	0.0459	0.2464	0.1668	0.040*
H18B	−0.0808	0.3068	0.1662	0.040*
H18C	−0.0327	0.2654	0.2652	0.040*
C19	0.56744 (18)	0.34602 (7)	0.30424 (12)	0.0293 (3)
H19A	0.6053	0.3104	0.2644	0.044*
H19B	0.6625	0.3616	0.3508	0.044*
H19C	0.5241	0.3818	0.2607	0.044*
C20	0.50283 (18)	0.26939 (7)	0.43525 (11)	0.0258 (3)
H20A	0.4158	0.2532	0.4737	0.039*
H20B	0.5953	0.2886	0.4801	0.039*
H20C	0.5462	0.2332	0.3989	0.039*
H4	0.2754 (19)	0.6750 (8)	0.1757 (11)	0.023 (4)*
H6	0.328 (2)	0.2611 (8)	0.2589 (12)	0.028 (4)*
H5	0.121 (2)	0.4641 (8)	0.4594 (12)	0.026 (4)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.03026 (19)	0.01401 (16)	0.02806 (18)	0.00117 (12)	0.01467 (14)	−0.00363 (12)
N1	0.0180 (5)	0.0129 (5)	0.0204 (5)	0.0004 (4)	0.0057 (4)	−0.0004 (4)
N2	0.0212 (5)	0.0138 (5)	0.0183 (5)	0.0006 (4)	0.0073 (4)	−0.0011 (4)
N3	0.0178 (5)	0.0128 (5)	0.0167 (5)	0.0009 (4)	0.0051 (4)	0.0011 (4)
N4	0.0208 (5)	0.0124 (5)	0.0186 (5)	0.0018 (4)	0.0060 (4)	0.0022 (4)
N5	0.0312 (6)	0.0139 (5)	0.0188 (5)	0.0035 (5)	0.0135 (5)	0.0016 (4)
N6	0.0214 (6)	0.0127 (5)	0.0185 (5)	0.0032 (4)	0.0036 (4)	−0.0010 (4)
C1	0.0132 (6)	0.0148 (6)	0.0169 (6)	0.0001 (5)	0.0022 (5)	0.0000 (5)
C2	0.0164 (6)	0.0144 (6)	0.0184 (6)	0.0001 (5)	0.0040 (5)	−0.0029 (5)
C3	0.0173 (6)	0.0138 (6)	0.0171 (6)	0.0000 (5)	0.0037 (5)	−0.0006 (4)
C4	0.0195 (6)	0.0188 (6)	0.0143 (6)	0.0019 (5)	0.0044 (5)	0.0008 (5)
C5	0.0178 (6)	0.0161 (6)	0.0161 (6)	0.0010 (5)	0.0045 (5)	−0.0003 (5)
C6	0.0179 (6)	0.0200 (6)	0.0214 (6)	−0.0005 (5)	0.0039 (5)	−0.0004 (5)
C7	0.0284 (7)	0.0280 (7)	0.0192 (6)	0.0055 (6)	0.0074 (5)	0.0071 (5)
C8	0.0198 (6)	0.0284 (7)	0.0196 (6)	0.0013 (5)	0.0005 (5)	−0.0031 (5)
C9	0.0218 (7)	0.0440 (9)	0.0281 (8)	0.0038 (6)	−0.0022 (6)	−0.0143 (7)
C10	0.0205 (7)	0.0291 (8)	0.0307 (7)	0.0056 (6)	−0.0004 (6)	−0.0020 (6)
C11	0.0247 (8)	0.0372 (9)	0.0492 (10)	−0.0104 (7)	−0.0008 (7)	0.0141 (7)
C12	0.0276 (7)	0.0120 (6)	0.0183 (6)	0.0031 (5)	0.0100 (5)	−0.0003 (5)
C13	0.0250 (7)	0.0171 (6)	0.0184 (6)	0.0066 (5)	0.0041 (5)	0.0020 (5)
C14	0.0267 (7)	0.0156 (6)	0.0161 (6)	0.0043 (5)	0.0028 (5)	0.0012 (5)
C15	0.0187 (6)	0.0143 (6)	0.0236 (6)	0.0015 (5)	0.0048 (5)	−0.0004 (5)
C16	0.0212 (6)	0.0156 (6)	0.0210 (6)	−0.0008 (5)	0.0044 (5)	−0.0016 (5)
C17	0.0453 (9)	0.0215 (7)	0.0179 (6)	0.0063 (6)	0.0084 (6)	0.0019 (5)
C18	0.0296 (8)	0.0247 (7)	0.0245 (7)	0.0015 (6)	−0.0030 (6)	−0.0013 (6)
C19	0.0251 (7)	0.0248 (7)	0.0407 (8)	0.0007 (6)	0.0148 (6)	−0.0015 (6)
C20	0.0243 (7)	0.0201 (7)	0.0317 (7)	0.0037 (5)	−0.0012 (6)	0.0015 (6)

Geometric parameters (Å, º)

Cl1—C2	1.7420 (12)	C9—H9C	0.9800
N1—C2	1.3171 (16)	C10—H10A	0.9800
N1—C1	1.3679 (16)	C10—H10B	0.9800
N2—C2	1.3185 (16)	C10—H10C	0.9800
N2—C3	1.3695 (16)	C11—H11A	0.9800
N3—C1	1.3358 (16)	C11—H11B	0.9800
N3—C3	1.3386 (15)	C11—H11C	0.9800
N4—C1	1.3389 (16)	C12—C16	1.5198 (18)
N4—C4	1.4789 (16)	C12—C13	1.5212 (19)
N4—H4	0.880 (17)	C12—H12	1.0000
N5—C3	1.3351 (16)	C13—C14	1.5305 (17)
N5—C12	1.4658 (16)	C13—H13A	0.9900
N5—H5	0.866 (17)	C13—H13B	0.9900
N6—C15	1.4819 (17)	C14—C18	1.5310 (19)
N6—C14	1.4832 (16)	C14—C17	1.5387 (18)
N6—H6	0.893 (17)	C15—C20	1.5307 (18)
C4—C7	1.5331 (17)	C15—C16	1.5323 (17)
C4—C8	1.5343 (18)	C15—C19	1.5400 (18)
C4—C5	1.5487 (17)	C16—H16A	0.9900
C5—C6	1.5471 (18)	C16—H16B	0.9900
C5—H5A	0.9900	C17—H17A	0.9800
C5—H5B	0.9900	C17—H17B	0.9800
C6—C11	1.525 (2)	C17—H17C	0.9800
C6—C9	1.5312 (19)	C18—H18A	0.9800
C6—C10	1.5312 (19)	C18—H18B	0.9800
C7—H7A	0.9800	C18—H18C	0.9800
C7—H7B	0.9800	C19—H19A	0.9800
C7—H7C	0.9800	C19—H19B	0.9800
C8—H8A	0.9800	C19—H19C	0.9800
C8—H8B	0.9800	C20—H20A	0.9800
C8—H8C	0.9800	C20—H20B	0.9800
C9—H9A	0.9800	C20—H20C	0.9800
C9—H9B	0.9800
C2—N1—C1	112.33 (10)	H10B—C10—H10C	109.5
C2—N2—C3	111.59 (10)	C6—C11—H11A	109.5
C1—N3—C3	115.68 (10)	C6—C11—H11B	109.5
C1—N4—C4	126.45 (11)	H11A—C11—H11B	109.5
C1—N4—H4	116.0 (10)	C6—C11—H11C	109.5
C4—N4—H4	117.1 (10)	H11A—C11—H11C	109.5
C3—N5—C12	122.77 (11)	H11B—C11—H11C	109.5
C3—N5—H5	116.8 (11)	N5—C12—C16	110.90 (10)
C12—N5—H5	118.7 (11)	N5—C12—C13	110.48 (10)
C15—N6—C14	120.26 (10)	C16—C12—C13	109.95 (10)
C15—N6—H6	108.5 (10)	N5—C12—H12	108.5
C14—N6—H6	105.6 (10)	C16—C12—H12	108.5
N3—C1—N4	119.83 (11)	C13—C12—H12	108.5
N3—C1—N1	124.57 (11)	C12—C13—C14	113.09 (11)
N4—C1—N1	115.60 (11)	C12—C13—H13A	109.0
N1—C2—N2	130.58 (11)	C14—C13—H13A	109.0
N1—C2—Cl1	113.76 (9)	C12—C13—H13B	109.0
N2—C2—Cl1	115.66 (9)	C14—C13—H13B	109.0
N5—C3—N3	117.67 (11)	H13A—C13—H13B	107.8
N5—C3—N2	117.18 (11)	N6—C14—C13	109.20 (10)
N3—C3—N2	125.15 (11)	N6—C14—C18	106.08 (10)
N4—C4—C7	105.68 (10)	C13—C14—C18	108.54 (11)
N4—C4—C8	109.35 (10)	N6—C14—C17	114.12 (11)
C7—C4—C8	107.80 (11)	C13—C14—C17	110.72 (11)
N4—C4—C5	113.75 (10)	C18—C14—C17	107.94 (11)
C7—C4—C5	112.47 (10)	N6—C15—C20	105.88 (10)
C8—C4—C5	107.63 (10)	N6—C15—C16	109.11 (10)
C6—C5—C4	124.50 (11)	C20—C15—C16	108.55 (11)
C6—C5—H5A	106.2	N6—C15—C19	114.11 (11)
C4—C5—H5A	106.2	C20—C15—C19	107.89 (11)
C6—C5—H5B	106.2	C16—C15—C19	111.03 (11)
C4—C5—H5B	106.2	C12—C16—C15	112.19 (10)
H5A—C5—H5B	106.4	C12—C16—H16A	109.2
C11—C6—C9	109.06 (13)	C15—C16—H16A	109.2
C11—C6—C10	108.07 (12)	C12—C16—H16B	109.2
C9—C6—C10	106.83 (12)	C15—C16—H16B	109.2
C11—C6—C5	113.76 (11)	H16A—C16—H16B	107.9
C9—C6—C5	112.89 (11)	C14—C17—H17A	109.5
C10—C6—C5	105.84 (11)	C14—C17—H17B	109.5
C4—C7—H7A	109.5	H17A—C17—H17B	109.5
C4—C7—H7B	109.5	C14—C17—H17C	109.5
H7A—C7—H7B	109.5	H17A—C17—H17C	109.5
C4—C7—H7C	109.5	H17B—C17—H17C	109.5
H7A—C7—H7C	109.5	C14—C18—H18A	109.5
H7B—C7—H7C	109.5	C14—C18—H18B	109.5
C4—C8—H8A	109.5	H18A—C18—H18B	109.5
C4—C8—H8B	109.5	C14—C18—H18C	109.5
H8A—C8—H8B	109.5	H18A—C18—H18C	109.5
C4—C8—H8C	109.5	H18B—C18—H18C	109.5
H8A—C8—H8C	109.5	C15—C19—H19A	109.5
H8B—C8—H8C	109.5	C15—C19—H19B	109.5
C6—C9—H9A	109.5	H19A—C19—H19B	109.5
C6—C9—H9B	109.5	C15—C19—H19C	109.5
H9A—C9—H9B	109.5	H19A—C19—H19C	109.5
C6—C9—H9C	109.5	H19B—C19—H19C	109.5
H9A—C9—H9C	109.5	C15—C20—H20A	109.5
H9B—C9—H9C	109.5	C15—C20—H20B	109.5
C6—C10—H10A	109.5	H20A—C20—H20B	109.5
C6—C10—H10B	109.5	C15—C20—H20C	109.5
H10A—C10—H10B	109.5	H20A—C20—H20C	109.5
C6—C10—H10C	109.5	H20B—C20—H20C	109.5
H10A—C10—H10C	109.5
C3—N3—C1—N4	−179.70 (11)	C4—C5—C6—C11	−55.96 (17)
C3—N3—C1—N1	0.73 (18)	C4—C5—C6—C9	69.01 (16)
C4—N4—C1—N3	8.97 (19)	C4—C5—C6—C10	−174.47 (11)
C4—N4—C1—N1	−171.43 (11)	C3—N5—C12—C16	138.28 (13)
C2—N1—C1—N3	−2.54 (17)	C3—N5—C12—C13	−99.54 (14)
C2—N1—C1—N4	177.87 (11)	N5—C12—C13—C14	−179.25 (10)
C1—N1—C2—N2	1.44 (19)	C16—C12—C13—C14	−56.51 (14)
C1—N1—C2—Cl1	−177.96 (8)	C15—N6—C14—C13	−48.00 (15)
C3—N2—C2—N1	1.3 (2)	C15—N6—C14—C18	−164.79 (11)
C3—N2—C2—Cl1	−179.28 (9)	C15—N6—C14—C17	76.50 (15)
C12—N5—C3—N3	−4.09 (19)	C12—C13—C14—N6	49.64 (14)
C12—N5—C3—N2	175.73 (11)	C12—C13—C14—C18	164.86 (11)
C1—N3—C3—N5	−177.61 (11)	C12—C13—C14—C17	−76.83 (14)
C1—N3—C3—N2	2.58 (18)	C14—N6—C15—C20	165.88 (11)
C2—N2—C3—N5	176.71 (12)	C14—N6—C15—C16	49.23 (15)
C2—N2—C3—N3	−3.48 (18)	C14—N6—C15—C19	−75.61 (14)
C1—N4—C4—C7	173.46 (12)	N5—C12—C16—C15	179.88 (10)
C1—N4—C4—C8	57.68 (16)	C13—C12—C16—C15	57.39 (14)
C1—N4—C4—C5	−62.67 (16)	N6—C15—C16—C12	−51.79 (14)
N4—C4—C5—C6	−49.78 (16)	C20—C15—C16—C12	−166.74 (11)
C7—C4—C5—C6	70.32 (15)	C19—C15—C16—C12	74.83 (14)
C8—C4—C5—C6	−171.09 (11)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N5—H5···N2^i	0.866 (17)	2.510 (17)	3.3531 (15)	164.7 (14)
N6—H6···N1^ii	0.893 (17)	2.337 (17)	3.1653 (15)	154.2 (14)
N4—H4···N6^iii	0.880 (17)	2.415 (17)	3.2470 (15)	157.9 (14)

Symmetry codes: (i) −x, −y+1, −z+1; (ii) −x+1/2, y−1/2, −z+1/2; (iii) −x+1/2, y+1/2, −z+1/2.