supplementary materials


HTML versionpdf versioncif file3d viewstructure factorssupplementary materialsCIF check reportcited insimilar papers Open access

bt5484 scheme

Acta Cryst. (2011). E67, o784    [ doi:10.1107/S1600536811007513 ]

1-Methylamino-3-(2,4,6-trimethylphenyl)propan-2-ol

A. M. Maharramov, A. N. Khalilov, A. V. Gurbanov, M. A. Allahverdiyev and S. W. Ng

Abstract top

The methylaminopropyl chain in the title compound, C13H21NO, adopts an extended zigzag conformation and the N atom shows a trigonal coordination. The N atom acts as hydrogen-bond acceptor to the hydroxy group of an adjacent molecule, generating a helical chain running along the b axis. The amino H atom is not involved in hydrogen bonding.

Comment top

A recent study reported the reaction of 1-chloro-3-(2,4,6-trimethylphenyl)propan-2-one and primary amines. The chlorine atom in the α-chloro ketone is not replaced directly by the amino RNH– group; the intermediate product undergoes a Favorskii rearrangement that furnishes a compound having two methylene groups between the aromatic system and the amido unit (Yadigarov et al., 2010). A recent study used cyclic secondary amine as the amino reactant in the synthesis of a compound having a formulation similar to that of tolperisone (a piperidine derivative that is commercially used as a muscle relaxant) (Maharramov et al. 2011). The present study uses the methylamine to yield the C13H21NO molecule (Scheme I). The methylaminopropyl chain of C13H27NO adopts an extended zigzag conformation and the N atom shows trigonal coordination (Fig. 1). The N atom acts as hydrogen-bond acceptor to the hydroxy group of an adjacent molecule to generate a helical chain running along the b-axis of the monoclinic unit cell.

Related literature top

For background to the synthesis: see: Yadigarov et al. (2010). For the structure of 1-(piperidin-1-yl)-3-(2,4,6-trimethylphenyl)propan-2-ol, see: Maharramov et al. (2011).

Experimental top

1-Chloro-3-(2,4,6-trimethylphenyl)propan-2-one (1 mol) and piperidine (1 mmol) were stirred in water for 18 h at 53 K. The water was decanted and the oil was distilled in vacuum. The distillate was a liquid; the liquid crystallized after 6 months; yield 70%.

Refinement top

Carbon-bound H-atoms were placed in calculated positions [C–H 0.95 to 1.00 Å; U(H) 1.2 to 1.5U(C)] and were included in the refinement in the riding model approximation.

The hydroxy and amino H-atoms were located in a difference Fourier map, and were refined with distance restraints of O–H 0.84±0.01 and N–H 0.88±0.01 Å.

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top
[Figure 1] Fig. 1. Anisotropic displacement ellipsoid plot (Barbour, 2001) of C13H21NO at the 70% probability level; hydrogen atoms are drawn as spheres of arbitrary radius.
1-Methylamino-3-(2,4,6-trimethylphenyl)propan-2-ol top
Crystal data top
C13H21NOF(000) = 456
Mr = 207.31Dx = 1.138 Mg m−3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 4648 reflections
a = 14.408 (1) Åθ = 2.8–28.3°
b = 5.8150 (4) ŵ = 0.07 mm−1
c = 14.4503 (10) ÅT = 100 K
β = 91.371 (1)°Block, colorless
V = 1210.34 (14) Å30.30 × 0.20 × 0.20 mm
Z = 4
Data collection top
Bruker APEXII
diffractometer		2384 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.019
graphiteθmax = 27.5°, θmin = 2.8°
φ and ω scansh = −18→18
9964 measured reflectionsk = −7→7
2775 independent reflectionsl = −18→18
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)] = 0.038Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.111H atoms treated by a mixture of independent and constrained refinement
S = 1.04 w = 1/[σ2(Fo2) + (0.0562P)2 + 0.3427P]
where P = (Fo2 + 2Fc2)/3
2775 reflections(Δ/σ)max = 0.001
148 parametersΔρmax = 0.29 e Å−3
2 restraintsΔρmin = −0.15 e Å−3
Crystal data top
C13H21NOV = 1210.34 (14) Å3
Mr = 207.31Z = 4
Monoclinic, P21/cMo Kα radiation
a = 14.408 (1) ŵ = 0.07 mm−1
b = 5.8150 (4) ÅT = 100 K
c = 14.4503 (10) Å0.30 × 0.20 × 0.20 mm
β = 91.371 (1)°
Data collection top
Bruker APEXII
diffractometer		Rint = 0.019
9964 measured reflectionsθmax = 27.5°
2775 independent reflectionsStandard reflections: 0
2384 reflections with I > 2σ(I)
Refinement top
R[F2 > 2σ(F2)] = 0.038H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.111Δρmax = 0.29 e Å−3
S = 1.04Δρmin = −0.15 e Å−3
2775 reflectionsAbsolute structure: ?
148 parametersFlack parameter: ?
2 restraintsRogers parameter: ?
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
O10.40834 (5)0.62853 (13)0.68021 (5)0.02485 (19)
H10.4176 (12)0.690 (3)0.7345 (8)0.054 (5)*
N10.54856 (6)0.29883 (16)0.64351 (6)0.0236 (2)
H20.5558 (9)0.4495 (15)0.6437 (9)0.032 (4)*
C10.60577 (8)0.1994 (2)0.57080 (8)0.0292 (3)
H1A0.67150.22780.58560.044*
H1B0.58930.27090.51120.044*
H1C0.59470.03340.56710.044*
C20.44967 (7)0.25622 (18)0.62563 (7)0.0240 (2)
H2A0.43690.08980.63200.029*
H2B0.43320.30180.56130.029*
C30.39001 (7)0.38978 (18)0.69225 (7)0.0222 (2)
H30.40730.34460.75720.027*
C40.28756 (7)0.3311 (2)0.67318 (8)0.0265 (2)
H4A0.27250.36600.60750.032*
H4B0.27920.16360.68200.032*
C50.21865 (7)0.45598 (19)0.73277 (7)0.0233 (2)
C60.19897 (7)0.37481 (19)0.82164 (7)0.0246 (2)
C70.13219 (7)0.4868 (2)0.87371 (7)0.0260 (2)
H70.11900.43020.93370.031*
C80.08455 (7)0.6778 (2)0.84056 (8)0.0261 (2)
C90.10519 (8)0.75788 (19)0.75269 (8)0.0266 (2)
H90.07340.88910.72890.032*
C100.17130 (7)0.65081 (19)0.69854 (7)0.0246 (2)
C110.18859 (9)0.7448 (2)0.60308 (8)0.0316 (3)
H11A0.15540.89070.59490.047*
H11B0.16640.63440.55640.047*
H11C0.25530.77040.59600.047*
C120.01217 (8)0.7968 (2)0.89726 (9)0.0340 (3)
H12A0.01110.72770.95910.051*
H12B−0.04890.77950.86680.051*
H12C0.02740.96060.90280.051*
C130.24826 (8)0.1699 (2)0.86386 (8)0.0303 (3)
H13A0.21440.11660.91790.045*
H13B0.31150.21390.88310.045*
H13C0.25090.04590.81800.045*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0301 (4)0.0223 (4)0.0221 (4)−0.0012 (3)−0.0007 (3)−0.0008 (3)
N10.0252 (5)0.0231 (5)0.0225 (4)0.0006 (4)0.0033 (3)−0.0003 (3)
C10.0308 (6)0.0302 (6)0.0268 (5)0.0043 (5)0.0060 (4)−0.0012 (4)
C20.0263 (5)0.0241 (5)0.0217 (5)0.0004 (4)0.0004 (4)−0.0024 (4)
C30.0242 (5)0.0218 (5)0.0206 (5)−0.0002 (4)0.0000 (4)−0.0008 (4)
C40.0254 (5)0.0274 (5)0.0267 (5)−0.0013 (4)−0.0003 (4)−0.0061 (4)
C50.0199 (5)0.0254 (5)0.0245 (5)−0.0033 (4)−0.0018 (4)−0.0045 (4)
C60.0211 (5)0.0252 (5)0.0273 (5)−0.0039 (4)−0.0028 (4)−0.0009 (4)
C70.0222 (5)0.0323 (6)0.0235 (5)−0.0045 (4)−0.0001 (4)0.0000 (4)
C80.0197 (5)0.0316 (6)0.0270 (5)−0.0020 (4)−0.0011 (4)−0.0060 (4)
C90.0237 (5)0.0278 (5)0.0282 (5)0.0013 (4)−0.0045 (4)−0.0011 (4)
C100.0236 (5)0.0280 (5)0.0221 (5)−0.0029 (4)−0.0033 (4)−0.0027 (4)
C110.0339 (6)0.0369 (6)0.0240 (5)0.0013 (5)−0.0023 (4)0.0015 (5)
C120.0267 (6)0.0412 (7)0.0342 (6)0.0045 (5)0.0030 (5)−0.0061 (5)
C130.0285 (6)0.0284 (6)0.0339 (6)−0.0016 (4)−0.0003 (5)0.0047 (5)
Geometric parameters (Å, °) top
O1—C31.4247 (13)C6—C71.3966 (15)
O1—H10.870 (9)C6—C131.5087 (16)
N1—C21.4632 (14)C7—C81.3854 (16)
N1—C11.4693 (14)C7—H70.9500
N1—H20.882 (9)C8—C91.3912 (16)
C1—H1A0.9800C8—C121.5094 (15)
C1—H1B0.9800C9—C101.3939 (15)
C1—H1C0.9800C9—H90.9500
C2—C31.5193 (14)C10—C111.5100 (15)
C2—H2A0.9900C11—H11A0.9800
C2—H2B0.9900C11—H11B0.9800
C3—C41.5334 (14)C11—H11C0.9800
C3—H31.0000C12—H12A0.9800
C4—C51.5149 (15)C12—H12B0.9800
C4—H4A0.9900C12—H12C0.9800
C4—H4B0.9900C13—H13A0.9800
C5—C61.4036 (15)C13—H13B0.9800
C5—C101.4062 (15)C13—H13C0.9800
C3—O1—H1108.4 (11)C7—C6—C13118.31 (10)
C2—N1—C1111.57 (9)C5—C6—C13122.15 (10)
C2—N1—H2106.4 (9)C8—C7—C6121.98 (10)
C1—N1—H2109.0 (9)C8—C7—H7119.0
N1—C1—H1A109.5C6—C7—H7119.0
N1—C1—H1B109.5C7—C8—C9117.96 (10)
H1A—C1—H1B109.5C7—C8—C12121.53 (10)
N1—C1—H1C109.5C9—C8—C12120.51 (11)
H1A—C1—H1C109.5C8—C9—C10121.79 (10)
H1B—C1—H1C109.5C8—C9—H9119.1
N1—C2—C3111.40 (8)C10—C9—H9119.1
N1—C2—H2A109.3C9—C10—C5119.65 (10)
C3—C2—H2A109.3C9—C10—C11118.75 (10)
N1—C2—H2B109.3C5—C10—C11121.59 (10)
C3—C2—H2B109.3C10—C11—H11A109.5
H2A—C2—H2B108.0C10—C11—H11B109.5
O1—C3—C2108.14 (8)H11A—C11—H11B109.5
O1—C3—C4112.04 (9)C10—C11—H11C109.5
C2—C3—C4109.23 (8)H11A—C11—H11C109.5
O1—C3—H3109.1H11B—C11—H11C109.5
C2—C3—H3109.1C8—C12—H12A109.5
C4—C3—H3109.1C8—C12—H12B109.5
C5—C4—C3115.63 (9)H12A—C12—H12B109.5
C5—C4—H4A108.4C8—C12—H12C109.5
C3—C4—H4A108.4H12A—C12—H12C109.5
C5—C4—H4B108.4H12B—C12—H12C109.5
C3—C4—H4B108.4C6—C13—H13A109.5
H4A—C4—H4B107.4C6—C13—H13B109.5
C6—C5—C10119.07 (10)H13A—C13—H13B109.5
C6—C5—C4120.56 (10)C6—C13—H13C109.5
C10—C5—C4120.34 (10)H13A—C13—H13C109.5
C7—C6—C5119.54 (10)H13B—C13—H13C109.5
C1—N1—C2—C3−171.17 (9)C13—C6—C7—C8179.21 (10)
N1—C2—C3—O160.20 (11)C6—C7—C8—C9−0.18 (16)
N1—C2—C3—C4−177.63 (9)C6—C7—C8—C12179.70 (10)
O1—C3—C4—C5−58.72 (12)C7—C8—C9—C100.23 (16)
C2—C3—C4—C5−178.53 (9)C12—C8—C9—C10−179.64 (10)
C3—C4—C5—C6−82.99 (12)C8—C9—C10—C50.23 (16)
C3—C4—C5—C1099.05 (12)C8—C9—C10—C11178.81 (10)
C10—C5—C6—C70.81 (15)C6—C5—C10—C9−0.75 (15)
C4—C5—C6—C7−177.18 (9)C4—C5—C10—C9177.24 (9)
C10—C5—C6—C13−178.73 (10)C6—C5—C10—C11−179.29 (10)
C4—C5—C6—C133.28 (15)C4—C5—C10—C11−1.30 (15)
C5—C6—C7—C8−0.35 (16)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1—H1···N1i0.87 (1)1.93 (1)2.789 (1)173 (2)
Symmetry codes: (i) −x+1, y+1/2, −z+3/2.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1—H1···N1i0.87 (1)1.93 (1)2.789 (1)173 (2)
Symmetry codes: (i) −x+1, y+1/2, −z+3/2.
Acknowledgements top

We thank Baku State University and the University of Malaya for supporting this study.

references
References top

Barbour, L. J. (2001). J. Supramol. Chem. 1, 189–191.

Bruker (2005). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.

Maharramov, A. M., Khalilov, A. N., Gurbanov, A. V., Allahverdiyev, M. A. & Ng, S. W. (2011). Acta Cryst. E67, o739.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925.

Yadigarov, R. R., Khalilov, A. N., Mamedov, I. G., Nagiev, F. N., Magerramov, A. M. & Allakhverdiev, M. A. (2010). Russ. J. Org. Chem. 45, 1856–1858.