Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807031637/bt2407sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807031637/bt2407Isup2.hkl |
CCDC reference: 658980
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.
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).
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.
For general background, see: Borzatta & Carrozza (1991). For related structures, see: Deng et al. (2006). For related literature, see: Kaiser & Thurston (1951).
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.
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. |
C15H28ClN5 | Dx = 1.146 Mg m−3 |
Mr = 313.87 | Melting point = 156–158 K |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
a = 19.411 (4) Å | Cell parameters from 2586 reflections |
b = 8.2182 (17) Å | θ = 2.5–23.1° |
c = 23.245 (5) Å | µ = 0.21 mm−1 |
β = 101.091 (4)° | T = 294 K |
V = 3638.9 (13) Å3 | Block, colourless |
Z = 8 | 0.22 × 0.20 × 0.18 mm |
F(000) = 1360 |
Bruker SMART CCD area-detector diffractometer | 3213 independent reflections |
Radiation source: fine-focus sealed tube | 2283 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.032 |
φ and ω scans | θmax = 25.0°, θmin = 1.8° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −22→22 |
Tmin = 0.955, Tmax = 0.963 | k = −9→9 |
8608 measured reflections | l = −27→11 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.054 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.161 | H 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 parameters | Δρmax = 0.57 e Å−3 |
0 restraints | Δρmin = −0.30 e Å−3 |
C15H28ClN5 | V = 3638.9 (13) Å3 |
Mr = 313.87 | Z = 8 |
Monoclinic, C2/c | Mo Kα radiation |
a = 19.411 (4) Å | µ = 0.21 mm−1 |
b = 8.2182 (17) Å | T = 294 K |
c = 23.245 (5) Å | 0.22 × 0.20 × 0.18 mm |
β = 101.091 (4)° |
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 = 0.963 | Rint = 0.032 |
8608 measured reflections |
R[F2 > 2σ(F2)] = 0.054 | 0 restraints |
wR(F2) = 0.161 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.04 | Δρmax = 0.57 e Å−3 |
3213 reflections | Δρmin = −0.30 e Å−3 |
200 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
Cl1 | 1.11711 (4) | −0.02496 (10) | 0.15825 (3) | 0.0586 (3) | |
N1 | 1.00664 (10) | 0.0414 (3) | 0.08007 (9) | 0.0376 (5) | |
N2 | 1.00846 (10) | 0.1316 (3) | 0.17761 (8) | 0.0375 (5) | |
N3 | 0.90867 (10) | 0.1911 (3) | 0.10248 (8) | 0.0367 (5) | |
N4 | 0.91215 (12) | 0.1087 (3) | 0.00839 (9) | 0.0441 (6) | |
H4 | 0.9338 (16) | 0.063 (4) | −0.0112 (14) | 0.053* | |
N5 | 0.91392 (11) | 0.2638 (3) | 0.19970 (9) | 0.0406 (6) | |
H5 | 0.9351 (15) | 0.245 (4) | 0.2334 (13) | 0.049* | |
C1 | 1.03346 (12) | 0.0595 (3) | 0.13587 (11) | 0.0358 (6) | |
C2 | 0.94263 (12) | 0.1942 (3) | 0.15820 (10) | 0.0338 (6) | |
C3 | 0.94272 (12) | 0.1153 (3) | 0.06501 (10) | 0.0344 (6) | |
C8 | 0.84288 (13) | 0.3361 (3) | 0.19418 (11) | 0.0420 (7) | |
C9 | 0.78787 (14) | 0.2044 (4) | 0.17388 (15) | 0.0580 (8) | |
H9A | 0.7902 | 0.1716 | 0.1347 | 0.087* | |
H9B | 0.7420 | 0.2466 | 0.1746 | 0.087* | |
H9C | 0.7969 | 0.1122 | 0.1996 | 0.087* | |
C10 | 0.83748 (17) | 0.3866 (4) | 0.25678 (13) | 0.0659 (9) | |
H10A | 0.8719 | 0.4688 | 0.2704 | 0.099* | |
H10B | 0.8458 | 0.2936 | 0.2822 | 0.099* | |
H10C | 0.7914 | 0.4290 | 0.2569 | 0.099* | |
C11 | 0.82914 (15) | 0.4783 (3) | 0.15022 (13) | 0.0478 (7) | |
H11A | 0.7811 | 0.5125 | 0.1494 | 0.057* | |
H11B | 0.8299 | 0.4316 | 0.1120 | 0.057* | |
C12 | 0.87304 (19) | 0.6361 (4) | 0.15384 (16) | 0.0684 (10) | |
C13 | 0.9485 (2) | 0.6015 (5) | 0.1488 (3) | 0.124 (2) | |
H13A | 0.9491 | 0.5404 | 0.1138 | 0.185* | |
H13B | 0.9710 | 0.5399 | 0.1823 | 0.185* | |
H13C | 0.9730 | 0.7024 | 0.1473 | 0.185* | |
C14 | 0.8716 (3) | 0.7385 (5) | 0.2077 (2) | 0.131 (2) | |
H14A | 0.8970 | 0.6839 | 0.2418 | 0.196* | |
H14B | 0.8238 | 0.7545 | 0.2120 | 0.196* | |
H14C | 0.8929 | 0.8421 | 0.2036 | 0.196* | |
C15 | 0.8392 (3) | 0.7383 (5) | 0.1007 (2) | 0.1218 (18) | |
H15A | 0.8644 | 0.8388 | 0.1007 | 0.183* | |
H15B | 0.7912 | 0.7607 | 0.1029 | 0.183* | |
H15C | 0.8409 | 0.6793 | 0.0654 | 0.183* | |
C4 | 0.84612 (15) | 0.1883 (4) | −0.01574 (12) | 0.0559 (8) | |
H4A | 0.8134 | 0.1688 | 0.0102 | 0.067* | |
H4B | 0.8267 | 0.1389 | −0.0533 | 0.067* | |
C5 | 0.8518 (2) | 0.3659 (5) | −0.02418 (16) | 0.0793 (11) | |
H5A | 0.8051 | 0.4089 | −0.0384 | 0.095* | |
H5B | 0.8694 | 0.4154 | 0.0137 | 0.095* | |
C6 | 0.8958 (2) | 0.4149 (5) | −0.0636 (2) | 0.0987 (14) | |
H6A | 0.8782 | 0.3671 | −0.1017 | 0.118* | |
H6B | 0.9427 | 0.3730 | −0.0496 | 0.118* | |
C7 | 0.8997 (3) | 0.6042 (6) | −0.0704 (2) | 0.149 (2) | |
H7A | 0.9226 | 0.6297 | −0.1023 | 0.223* | |
H7B | 0.9258 | 0.6503 | −0.0348 | 0.223* | |
H7C | 0.8531 | 0.6485 | −0.0781 | 0.223* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl1 | 0.0456 (4) | 0.0801 (6) | 0.0485 (4) | 0.0282 (4) | 0.0048 (3) | −0.0040 (4) |
N1 | 0.0381 (12) | 0.0436 (13) | 0.0323 (11) | 0.0069 (9) | 0.0096 (9) | −0.0024 (10) |
N2 | 0.0337 (11) | 0.0484 (13) | 0.0314 (11) | 0.0066 (9) | 0.0089 (9) | −0.0011 (10) |
N3 | 0.0357 (11) | 0.0443 (12) | 0.0312 (11) | 0.0055 (9) | 0.0089 (9) | −0.0029 (10) |
N4 | 0.0415 (13) | 0.0603 (16) | 0.0312 (12) | 0.0123 (11) | 0.0087 (9) | −0.0062 (11) |
N5 | 0.0383 (12) | 0.0559 (14) | 0.0287 (11) | 0.0112 (10) | 0.0092 (9) | −0.0030 (11) |
C1 | 0.0332 (13) | 0.0395 (14) | 0.0359 (14) | 0.0056 (11) | 0.0097 (11) | 0.0013 (11) |
C2 | 0.0349 (13) | 0.0365 (14) | 0.0314 (13) | 0.0008 (10) | 0.0103 (10) | −0.0003 (11) |
C3 | 0.0372 (13) | 0.0365 (14) | 0.0307 (13) | 0.0010 (11) | 0.0098 (10) | 0.0005 (11) |
C8 | 0.0371 (14) | 0.0516 (17) | 0.0409 (15) | 0.0100 (12) | 0.0163 (11) | −0.0002 (13) |
C9 | 0.0413 (16) | 0.0580 (19) | 0.079 (2) | 0.0018 (14) | 0.0215 (15) | 0.0076 (17) |
C10 | 0.072 (2) | 0.081 (2) | 0.0524 (18) | 0.0291 (18) | 0.0321 (16) | 0.0016 (17) |
C11 | 0.0474 (16) | 0.0467 (16) | 0.0521 (17) | 0.0094 (13) | 0.0168 (13) | 0.0014 (14) |
C12 | 0.083 (2) | 0.0458 (18) | 0.084 (2) | 0.0018 (17) | 0.036 (2) | −0.0050 (18) |
C13 | 0.090 (3) | 0.069 (3) | 0.229 (6) | −0.028 (2) | 0.073 (4) | −0.005 (3) |
C14 | 0.216 (6) | 0.061 (3) | 0.131 (4) | −0.027 (3) | 0.071 (4) | −0.039 (3) |
C15 | 0.180 (5) | 0.061 (3) | 0.132 (4) | −0.001 (3) | 0.048 (4) | 0.034 (3) |
C4 | 0.0498 (17) | 0.079 (2) | 0.0374 (15) | 0.0144 (16) | 0.0053 (13) | −0.0014 (15) |
C5 | 0.083 (3) | 0.090 (3) | 0.062 (2) | 0.020 (2) | 0.0057 (19) | 0.010 (2) |
C6 | 0.091 (3) | 0.095 (3) | 0.112 (3) | −0.015 (3) | 0.024 (3) | −0.002 (3) |
C7 | 0.202 (7) | 0.114 (4) | 0.128 (5) | −0.052 (4) | 0.028 (4) | 0.032 (4) |
Cl1—C1 | 1.750 (2) | C12—C14 | 1.514 (5) |
N1—C1 | 1.310 (3) | C12—C13 | 1.518 (5) |
N1—C3 | 1.365 (3) | C12—C15 | 1.532 (5) |
N2—C1 | 1.307 (3) | C13—H13A | 0.9600 |
N2—C2 | 1.371 (3) | C13—H13B | 0.9600 |
N3—C2 | 1.336 (3) | C13—H13C | 0.9600 |
N3—C3 | 1.344 (3) | C14—H14A | 0.9600 |
N4—C3 | 1.337 (3) | C14—H14B | 0.9600 |
N4—C4 | 1.452 (3) | C14—H14C | 0.9600 |
N4—H4 | 0.77 (3) | C15—H15A | 0.9600 |
N5—C2 | 1.333 (3) | C15—H15B | 0.9600 |
N5—C8 | 1.484 (3) | C15—H15C | 0.9600 |
N5—H5 | 0.83 (3) | C4—C5 | 1.480 (5) |
C8—C9 | 1.530 (4) | C4—H4A | 0.9700 |
C8—C10 | 1.536 (4) | C4—H4B | 0.9700 |
C8—C11 | 1.541 (4) | C5—C6 | 1.425 (5) |
C9—H9A | 0.9600 | C5—H5A | 0.9700 |
C9—H9B | 0.9600 | C5—H5B | 0.9700 |
C9—H9C | 0.9600 | C6—C7 | 1.567 (6) |
C10—H10A | 0.9600 | C6—H6A | 0.9700 |
C10—H10B | 0.9600 | C6—H6B | 0.9700 |
C10—H10C | 0.9600 | C7—H7A | 0.9600 |
C11—C12 | 1.545 (4) | C7—H7B | 0.9600 |
C11—H11A | 0.9700 | C7—H7C | 0.9600 |
C11—H11B | 0.9700 | ||
C1—N1—C3 | 111.8 (2) | C14—C12—C11 | 114.4 (3) |
C1—N2—C2 | 112.4 (2) | C13—C12—C11 | 111.6 (3) |
C2—N3—C3 | 115.1 (2) | C15—C12—C11 | 105.6 (3) |
C3—N4—C4 | 123.6 (2) | C12—C13—H13A | 109.5 |
C3—N4—H4 | 114 (2) | C12—C13—H13B | 109.5 |
C4—N4—H4 | 122 (2) | H13A—C13—H13B | 109.5 |
C2—N5—C8 | 128.3 (2) | C12—C13—H13C | 109.5 |
C2—N5—H5 | 114 (2) | H13A—C13—H13C | 109.5 |
C8—N5—H5 | 116 (2) | H13B—C13—H13C | 109.5 |
N2—C1—N1 | 130.8 (2) | C12—C14—H14A | 109.5 |
N2—C1—Cl1 | 114.49 (18) | C12—C14—H14B | 109.5 |
N1—C1—Cl1 | 114.74 (18) | H14A—C14—H14B | 109.5 |
N5—C2—N3 | 120.8 (2) | C12—C14—H14C | 109.5 |
N5—C2—N2 | 114.6 (2) | H14A—C14—H14C | 109.5 |
N3—C2—N2 | 124.6 (2) | H14B—C14—H14C | 109.5 |
N4—C3—N3 | 118.5 (2) | C12—C15—H15A | 109.5 |
N4—C3—N1 | 116.3 (2) | C12—C15—H15B | 109.5 |
N3—C3—N1 | 125.2 (2) | H15A—C15—H15B | 109.5 |
N5—C8—C9 | 109.0 (2) | C12—C15—H15C | 109.5 |
N5—C8—C10 | 104.9 (2) | H15A—C15—H15C | 109.5 |
C9—C8—C10 | 108.2 (2) | H15B—C15—H15C | 109.5 |
N5—C8—C11 | 113.6 (2) | N4—C4—C5 | 114.4 (3) |
C9—C8—C11 | 108.1 (2) | N4—C4—H4A | 108.7 |
C10—C8—C11 | 112.9 (2) | C5—C4—H4A | 108.7 |
C8—C9—H9A | 109.5 | N4—C4—H4B | 108.7 |
C8—C9—H9B | 109.5 | C5—C4—H4B | 108.7 |
H9A—C9—H9B | 109.5 | H4A—C4—H4B | 107.6 |
C8—C9—H9C | 109.5 | C6—C5—C4 | 115.6 (3) |
H9A—C9—H9C | 109.5 | C6—C5—H5A | 108.4 |
H9B—C9—H9C | 109.5 | C4—C5—H5A | 108.4 |
C8—C10—H10A | 109.5 | C6—C5—H5B | 108.4 |
C8—C10—H10B | 109.5 | C4—C5—H5B | 108.4 |
H10A—C10—H10B | 109.5 | H5A—C5—H5B | 107.4 |
C8—C10—H10C | 109.5 | C5—C6—C7 | 113.1 (4) |
H10A—C10—H10C | 109.5 | C5—C6—H6A | 109.0 |
H10B—C10—H10C | 109.5 | C7—C6—H6A | 109.0 |
C8—C11—C12 | 125.2 (3) | C5—C6—H6B | 109.0 |
C8—C11—H11A | 106.0 | C7—C6—H6B | 109.0 |
C12—C11—H11A | 106.0 | H6A—C6—H6B | 107.8 |
C8—C11—H11B | 106.0 | C6—C7—H7A | 109.5 |
C12—C11—H11B | 106.0 | C6—C7—H7B | 109.5 |
H11A—C11—H11B | 106.3 | H7A—C7—H7B | 109.5 |
C14—C12—C13 | 109.9 (4) | C6—C7—H7C | 109.5 |
C14—C12—C15 | 106.8 (3) | H7A—C7—H7C | 109.5 |
C13—C12—C15 | 108.1 (4) | H7B—C7—H7C | 109.5 |
C2—N2—C1—N1 | 1.4 (4) | C1—N1—C3—N4 | 177.6 (2) |
C2—N2—C1—Cl1 | −179.32 (17) | C1—N1—C3—N3 | −3.2 (4) |
C3—N1—C1—N2 | 1.7 (4) | C2—N5—C8—C9 | 60.6 (3) |
C3—N1—C1—Cl1 | −177.58 (17) | C2—N5—C8—C10 | 176.3 (3) |
C8—N5—C2—N3 | 4.2 (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—N2 | 2.3 (4) | C10—C8—C11—C12 | 61.0 (3) |
C1—N2—C2—N5 | 177.7 (2) | C8—C11—C12—C14 | −63.0 (4) |
C1—N2—C2—N3 | −3.6 (4) | C8—C11—C12—C13 | 62.5 (4) |
C4—N4—C3—N3 | 4.2 (4) | C8—C11—C12—C15 | 179.8 (3) |
C4—N4—C3—N1 | −176.5 (3) | C3—N4—C4—C5 | 77.2 (4) |
C2—N3—C3—N4 | −179.5 (2) | N4—C4—C5—C6 | 61.1 (4) |
C2—N3—C3—N1 | 1.4 (4) | C4—C5—C6—C7 | −179.8 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
N4—H4···N1i | 0.77 (3) | 2.31 (3) | 3.079 (3) | 171 (3) |
N5—H5···N2ii | 0.83 (3) | 2.34 (3) | 3.151 (3) | 167 (3) |
Symmetry codes: (i) −x+2, −y, −z; (ii) −x+2, y, −z+1/2. |
Experimental details
Crystal data | |
Chemical formula | C15H28ClN5 |
Mr | 313.87 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 294 |
a, b, c (Å) | 19.411 (4), 8.2182 (17), 23.245 (5) |
β (°) | 101.091 (4) |
V (Å3) | 3638.9 (13) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 0.21 |
Crystal size (mm) | 0.22 × 0.20 × 0.18 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.955, 0.963 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 8608, 3213, 2283 |
Rint | 0.032 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.054, 0.161, 1.04 |
No. of reflections | 3213 |
No. of parameters | 200 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.57, −0.30 |
Computer programs: SMART (Bruker, 1997), SMART, SAINT (Bruker, 1997), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1997), SHELXTL.
D—H···A | D—H | H···A | D···A | D—H···A |
N4—H4···N1i | 0.77 (3) | 2.31 (3) | 3.079 (3) | 171 (3) |
N5—H5···N2ii | 0.83 (3) | 2.34 (3) | 3.151 (3) | 167 (3) |
Symmetry codes: (i) −x+2, −y, −z; (ii) −x+2, y, −z+1/2. |
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.