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In the title compound, C16H28ClN5, the piperidine ring has a classical chair conformation. In the crystal structure, weak inter­molecular N—H...N hydrogen bonds link two mol­ecules, related by a twofold axis of symmetry, into dimers.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807027341/cv2257sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807027341/cv2257Isup2.hkl
Contains datablock I

CCDC reference: 655605

Key indicators

  • Single-crystal X-ray study
  • T = 113 K
  • Mean [sigma](C-C) = 0.003 Å
  • R factor = 0.052
  • wR factor = 0.116
  • Data-to-parameter ratio = 21.0

checkCIF/PLATON results

No syntax errors found



Alert level C PLAT125_ALERT_4_C No _symmetry_space_group_name_Hall Given ....... ? PLAT220_ALERT_2_C Large Non-Solvent C Ueq(max)/Ueq(min) ... 2.91 Ratio PLAT222_ALERT_3_C Large Non-Solvent H Ueq(max)/Ueq(min) ... 3.12 Ratio
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 3 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 1 ALERT type 3 Indicator that the structure quality may be low 1 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check

Comment top

The title compound (I), has attracted much attention as an important intermediate of hindered light stabilizers (Borzatta & Carrozza, 1991). These compounds containing triazine ring are widely used (Deng et al., 2006). Herein we reported the crystal structure of the title compound, (I) (Fig. 1).

The triazine ring in (I) is essentially planar with an r.m.s. deviation from the mean plane of 0.0133 Å. In the crystal, the molecules are linked into dimers by intermolecular N—H···N hydrogen bonds (Table 1).

Related literature top

For a related crystal structure, see: Deng et al. (2006).

For related literature, see: Borzatta & Carrozza (1991); 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 added dropwise for 0.5 h. The mixture was stirred at 273–278 K for a further 3 h. Piperidine (18.46 g, 0.217 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 (54.50 g) was obtained in powder form in a yield of 82.1%. Crystals of (I) were obtained by slow evaporation of a solution of methanol (m.p. 427–429 K).

Refinement top

The atom H5 (attached to N5) was located from difference map and refined isotropically. The rest H atoms were positioned geometrically (C—H = 0.98–0.99 Å), and refined as riding with Uiso(H) = 1.2–1.5Ueq(C).

Structure description top

The title compound (I), has attracted much attention as an important intermediate of hindered light stabilizers (Borzatta & Carrozza, 1991). These compounds containing triazine ring are widely used (Deng et al., 2006). Herein we reported the crystal structure of the title compound, (I) (Fig. 1).

The triazine ring in (I) is essentially planar with an r.m.s. deviation from the mean plane of 0.0133 Å. In the crystal, the molecules are linked into dimers by intermolecular N—H···N hydrogen bonds (Table 1).

For a related crystal structure, see: Deng et al. (2006).

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

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: SHELXL97.

Figures top
[Figure 1] Fig. 1. A view of the molecule of (I). Displacement ellopsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii.
4-Chloro-6-(piperidin-1-yl)-N2-(2,4,4-trimethylpentan-2-yl)- 1,3,5-triazin-2-amine top
Crystal data top
C16H28ClN5Dx = 1.180 Mg m3
Mr = 325.88Melting point = 103–106 K
Monoclinic, C2/cMo Kα radiation, λ = 0.71070 Å
a = 23.603 (3) ÅCell parameters from 3587 reflections
b = 7.9486 (12) Åθ = 2.7–25.0°
c = 19.659 (3) ŵ = 0.21 mm1
β = 95.818 (13)°T = 113 K
V = 3669.3 (9) Å3Prism, colourless
Z = 80.34 × 0.24 × 0.20 mm
F(000) = 1408
Data collection top
Rigaku Saturn
diffractometer
4366 independent reflections
Radiation source: rotating anode3747 reflections with I > 2σ(I)
Confocal monochromatorRint = 0.045
Detector resolution: 7.31 pixels mm-1θmax = 27.9°, θmin = 1.7°
ω scansh = 3030
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
k = 1010
Tmin = 0.920, Tmax = 0.959l = 2525
16244 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)] = 0.052Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.116H atoms treated by a mixture of independent and constrained refinement
S = 1.11 w = 1/[σ2(Fo2) + (0.0479P)2 + 1.7404P]
where P = (Fo2 + 2Fc2)/3
4366 reflections(Δ/σ)max < 0.001
208 parametersΔρmax = 0.20 e Å3
0 restraintsΔρmin = 0.30 e Å3
Crystal data top
C16H28ClN5V = 3669.3 (9) Å3
Mr = 325.88Z = 8
Monoclinic, C2/cMo Kα radiation
a = 23.603 (3) ŵ = 0.21 mm1
b = 7.9486 (12) ÅT = 113 K
c = 19.659 (3) Å0.34 × 0.24 × 0.20 mm
β = 95.818 (13)°
Data collection top
Rigaku Saturn
diffractometer
4366 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
3747 reflections with I > 2σ(I)
Tmin = 0.920, Tmax = 0.959Rint = 0.045
16244 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0520 restraints
wR(F2) = 0.116H atoms treated by a mixture of independent and constrained refinement
S = 1.11Δρmax = 0.20 e Å3
4366 reflectionsΔρmin = 0.30 e Å3
208 parameters
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
Cl10.100756 (18)0.56099 (6)0.13014 (2)0.02726 (13)
N10.16998 (6)0.47978 (17)0.23565 (6)0.0196 (3)
N20.13973 (5)0.33320 (17)0.33276 (6)0.0187 (3)
N30.07186 (6)0.40830 (17)0.23796 (6)0.0185 (3)
N40.23465 (6)0.3886 (2)0.32432 (7)0.0286 (4)
N50.04278 (6)0.27903 (17)0.33219 (6)0.0182 (3)
C10.11603 (7)0.4726 (2)0.21150 (8)0.0180 (3)
C20.18014 (7)0.4003 (2)0.29723 (8)0.0191 (3)
C30.08661 (6)0.34137 (19)0.30201 (8)0.0171 (3)
C40.28234 (7)0.4602 (2)0.29193 (9)0.0273 (4)
H4A0.26810.51160.24760.033*
H4B0.30950.37000.28300.033*
C50.31245 (8)0.5928 (2)0.33808 (9)0.0281 (4)
H5A0.28650.68940.34230.034*
H5B0.34630.63410.31730.034*
C60.33093 (8)0.5218 (3)0.40907 (10)0.0369 (5)
H6A0.36110.43660.40580.044*
H6B0.34680.61340.43940.044*
C70.28043 (9)0.4416 (3)0.43953 (10)0.0452 (6)
H7A0.25280.53010.44890.054*
H7B0.29390.38670.48340.054*
C80.25106 (8)0.3113 (3)0.39086 (10)0.0389 (5)
H8A0.27720.21600.38550.047*
H8B0.21680.26720.41010.047*
C90.04368 (7)0.1958 (2)0.39985 (7)0.0185 (3)
C100.08715 (7)0.0497 (2)0.41039 (8)0.0202 (3)
H10A0.08600.01060.45800.024*
H10B0.12520.10060.40820.024*
C110.08562 (8)0.1109 (2)0.36542 (9)0.0258 (4)
C120.05982 (8)0.3252 (2)0.45668 (8)0.0260 (4)
H12A0.09900.36350.45390.039*
H12B0.05690.27300.50140.039*
H12C0.03380.42150.45100.039*
C130.01778 (7)0.1390 (2)0.40468 (9)0.0256 (4)
H13A0.04220.23790.40720.038*
H13B0.01950.07010.44580.038*
H13C0.03100.07250.36420.038*
C140.08364 (9)0.0723 (2)0.28890 (9)0.0329 (4)
H14A0.08660.17750.26350.049*
H14B0.11550.00170.28070.049*
H14C0.04760.01640.27350.049*
C150.03606 (10)0.2286 (3)0.37689 (12)0.0483 (6)
H15A0.00000.17530.35950.072*
H15B0.03600.25110.42590.072*
H15C0.04050.33470.35260.072*
C160.14161 (10)0.2037 (3)0.38666 (12)0.0498 (6)
H16A0.14290.30770.36010.075*
H16B0.14390.23110.43550.075*
H16C0.17380.13170.37800.075*
H50.0088 (8)0.308 (2)0.3122 (10)0.030 (5)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.0267 (2)0.0337 (3)0.0210 (2)0.00372 (18)0.00062 (16)0.00908 (16)
N10.0193 (7)0.0206 (7)0.0192 (6)0.0013 (6)0.0037 (5)0.0017 (5)
N20.0149 (7)0.0208 (7)0.0203 (6)0.0010 (5)0.0015 (5)0.0028 (5)
N30.0177 (7)0.0202 (7)0.0177 (6)0.0004 (5)0.0021 (5)0.0023 (5)
N40.0162 (7)0.0402 (9)0.0293 (8)0.0037 (6)0.0012 (6)0.0138 (7)
N50.0151 (7)0.0219 (7)0.0175 (6)0.0005 (5)0.0017 (5)0.0033 (5)
C10.0200 (8)0.0166 (8)0.0178 (7)0.0000 (6)0.0031 (6)0.0014 (6)
C20.0186 (8)0.0182 (8)0.0207 (8)0.0010 (6)0.0023 (6)0.0011 (6)
C30.0167 (8)0.0154 (7)0.0195 (7)0.0009 (6)0.0030 (6)0.0006 (6)
C40.0172 (9)0.0372 (10)0.0281 (9)0.0030 (7)0.0056 (7)0.0056 (7)
C50.0242 (9)0.0298 (10)0.0311 (9)0.0006 (7)0.0059 (7)0.0054 (7)
C60.0308 (11)0.0475 (12)0.0311 (10)0.0103 (9)0.0030 (8)0.0081 (9)
C70.0320 (11)0.0757 (16)0.0270 (10)0.0091 (11)0.0019 (8)0.0178 (10)
C80.0199 (9)0.0534 (13)0.0419 (11)0.0070 (9)0.0042 (8)0.0288 (10)
C90.0193 (8)0.0200 (8)0.0166 (7)0.0001 (6)0.0042 (6)0.0028 (6)
C100.0212 (8)0.0202 (8)0.0190 (7)0.0004 (6)0.0011 (6)0.0021 (6)
C110.0321 (10)0.0182 (8)0.0285 (9)0.0032 (7)0.0089 (7)0.0005 (7)
C120.0335 (10)0.0245 (9)0.0207 (8)0.0012 (7)0.0054 (7)0.0033 (7)
C130.0221 (9)0.0298 (9)0.0257 (8)0.0009 (7)0.0069 (7)0.0075 (7)
C140.0436 (12)0.0287 (10)0.0277 (9)0.0005 (8)0.0094 (8)0.0086 (7)
C150.0667 (16)0.0258 (11)0.0573 (14)0.0143 (10)0.0303 (12)0.0109 (10)
C160.0594 (15)0.0381 (12)0.0510 (13)0.0258 (11)0.0006 (11)0.0073 (10)
Geometric parameters (Å, º) top
Cl1—C11.7506 (15)C8—H8B0.9900
N1—C11.314 (2)C9—C131.531 (2)
N1—C21.3650 (19)C9—C121.538 (2)
N2—C31.3371 (19)C9—C101.549 (2)
N2—C21.348 (2)C10—C111.551 (2)
N3—C11.315 (2)C10—H10A0.9900
N3—C31.3787 (19)C10—H10B0.9900
N4—C21.345 (2)C11—C141.531 (2)
N4—C81.461 (2)C11—C151.532 (3)
N4—C41.464 (2)C11—C161.534 (3)
N5—C31.339 (2)C12—H12A0.9800
N5—C91.4839 (19)C12—H12B0.9800
N5—H50.886 (19)C12—H12C0.9800
C4—C51.519 (2)C13—H13A0.9800
C4—H4A0.9900C13—H13B0.9800
C4—H4B0.9900C13—H13C0.9800
C5—C61.527 (2)C14—H14A0.9800
C5—H5A0.9900C14—H14B0.9800
C5—H5B0.9900C14—H14C0.9800
C6—C71.527 (3)C15—H15A0.9800
C6—H6A0.9900C15—H15B0.9800
C6—H6B0.9900C15—H15C0.9800
C7—C81.528 (3)C16—H16A0.9800
C7—H7A0.9900C16—H16B0.9800
C7—H7B0.9900C16—H16C0.9800
C8—H8A0.9900
C1—N1—C2112.15 (13)N5—C9—C13105.04 (12)
C3—N2—C2115.26 (13)N5—C9—C12109.45 (13)
C1—N3—C3111.98 (13)C13—C9—C12108.58 (13)
C2—N4—C8122.67 (14)N5—C9—C10113.77 (13)
C2—N4—C4123.21 (14)C13—C9—C10112.92 (13)
C8—N4—C4114.03 (13)C12—C9—C10106.99 (12)
C3—N5—C9128.38 (13)C9—C10—C11124.32 (13)
C3—N5—H5114.4 (12)C9—C10—H10A106.2
C9—N5—H5116.2 (13)C11—C10—H10A106.2
N1—C1—N3130.69 (14)C9—C10—H10B106.2
N1—C1—Cl1114.51 (12)C11—C10—H10B106.2
N3—C1—Cl1114.79 (11)H10A—C10—H10B106.4
N4—C2—N2117.78 (14)C14—C11—C15108.62 (16)
N4—C2—N1117.28 (14)C14—C11—C16107.66 (16)
N2—C2—N1124.94 (14)C15—C11—C16108.39 (17)
N2—C3—N5120.86 (14)C14—C11—C10113.06 (14)
N2—C3—N3124.76 (14)C15—C11—C10113.11 (15)
N5—C3—N3114.37 (13)C16—C11—C10105.74 (15)
N4—C4—C5110.12 (15)C9—C12—H12A109.5
N4—C4—H4A109.6C9—C12—H12B109.5
C5—C4—H4A109.6H12A—C12—H12B109.5
N4—C4—H4B109.6C9—C12—H12C109.5
C5—C4—H4B109.6H12A—C12—H12C109.5
H4A—C4—H4B108.2H12B—C12—H12C109.5
C4—C5—C6111.24 (15)C9—C13—H13A109.5
C4—C5—H5A109.4C9—C13—H13B109.5
C6—C5—H5A109.4H13A—C13—H13B109.5
C4—C5—H5B109.4C9—C13—H13C109.5
C6—C5—H5B109.4H13A—C13—H13C109.5
H5A—C5—H5B108.0H13B—C13—H13C109.5
C7—C6—C5110.53 (15)C11—C14—H14A109.5
C7—C6—H6A109.5C11—C14—H14B109.5
C5—C6—H6A109.5H14A—C14—H14B109.5
C7—C6—H6B109.5C11—C14—H14C109.5
C5—C6—H6B109.5H14A—C14—H14C109.5
H6A—C6—H6B108.1H14B—C14—H14C109.5
C6—C7—C8111.12 (18)C11—C15—H15A109.5
C6—C7—H7A109.4C11—C15—H15B109.5
C8—C7—H7A109.4H15A—C15—H15B109.5
C6—C7—H7B109.4C11—C15—H15C109.5
C8—C7—H7B109.4H15A—C15—H15C109.5
H7A—C7—H7B108.0H15B—C15—H15C109.5
N4—C8—C7109.77 (16)C11—C16—H16A109.5
N4—C8—H8A109.7C11—C16—H16B109.5
C7—C8—H8A109.7H16A—C16—H16B109.5
N4—C8—H8B109.7C11—C16—H16C109.5
C7—C8—H8B109.7H16A—C16—H16C109.5
H8A—C8—H8B108.2H16B—C16—H16C109.5
C2—N1—C1—N32.7 (2)C2—N4—C4—C5118.14 (18)
C2—N1—C1—Cl1176.28 (11)C8—N4—C4—C558.5 (2)
C3—N3—C1—N11.2 (2)N4—C4—C5—C654.8 (2)
C3—N3—C1—Cl1179.80 (11)C4—C5—C6—C753.5 (2)
C8—N4—C2—N21.9 (3)C5—C6—C7—C853.7 (2)
C4—N4—C2—N2178.23 (15)C2—N4—C8—C7118.13 (19)
C8—N4—C2—N1178.03 (17)C4—N4—C8—C758.5 (2)
C4—N4—C2—N11.7 (2)C6—C7—C8—N455.1 (2)
C3—N2—C2—N4176.96 (15)C3—N5—C9—C13175.67 (15)
C3—N2—C2—N13.1 (2)C3—N5—C9—C1267.9 (2)
C1—N1—C2—N4175.05 (15)C3—N5—C9—C1051.7 (2)
C1—N1—C2—N25.0 (2)N5—C9—C10—C1160.8 (2)
C2—N2—C3—N5179.97 (14)C13—C9—C10—C1158.8 (2)
C2—N2—C3—N31.6 (2)C12—C9—C10—C11178.18 (15)
C9—N5—C3—N20.1 (2)C9—C10—C11—C1453.1 (2)
C9—N5—C3—N3178.72 (14)C9—C10—C11—C1570.9 (2)
C1—N3—C3—N23.5 (2)C9—C10—C11—C16170.68 (16)
C1—N3—C3—N5177.93 (13)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N5—H5···N3i0.886 (19)2.20 (2)3.0860 (19)173.5 (17)
Symmetry code: (i) x, y, z+1/2.

Experimental details

Crystal data
Chemical formulaC16H28ClN5
Mr325.88
Crystal system, space groupMonoclinic, C2/c
Temperature (K)113
a, b, c (Å)23.603 (3), 7.9486 (12), 19.659 (3)
β (°) 95.818 (13)
V3)3669.3 (9)
Z8
Radiation typeMo Kα
µ (mm1)0.21
Crystal size (mm)0.34 × 0.24 × 0.20
Data collection
DiffractometerRigaku Saturn
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.920, 0.959
No. of measured, independent and
observed [I > 2σ(I)] reflections
16244, 4366, 3747
Rint0.045
(sin θ/λ)max1)0.658
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.052, 0.116, 1.11
No. of reflections4366
No. of parameters208
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.20, 0.30

Computer programs: SMART (Bruker, 1997), SMART, SAINT (Bruker, 1997), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1997), SHELXL97.

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N5—H5···N3i0.886 (19)2.20 (2)3.0860 (19)173.5 (17)
Symmetry code: (i) x, y, z+1/2.
 

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