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

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

doi:10.1107/S1600536811007513

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 67| Part 4| April 2011| Page o784

doi:10.1107/S1600536811007513

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

Abel M. Maharramov,^a Ali N. Khalilov,^a Atash V. Gurbanov,^a Mirze A. Allahverdiyev ^a and Seik Weng Ng ^b ^*

^aDepartment of Organic Chemistry, Baku State University, Baku, Azerbaijan, and ^bDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: seikweng@um.edu.my

(Received 27 February 2011; accepted 28 February 2011; online 5 March 2011)

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.

Related literature

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

Crystal data

C₁₃H₂₁NO
M_r = 207.31
Monoclinic, P 2₁ /c
a = 14.408 (1) Å
b = 5.8150 (4) Å
c = 14.4503 (10) Å
β = 91.371 (1)°
V = 1210.34 (14) Å³
Z = 4
Mo Kα radiation
μ = 0.07 mm⁻¹
T = 100 K
0.30 × 0.20 × 0.20 mm

Data collection

Bruker APEXII diffractometer
9964 measured reflections
2775 independent reflections
2384 reflections with I > 2σ(I)
R_int = 0.019

Refinement

R[F² > 2σ(F²)] = 0.038
wR(F²) = 0.111
S = 1.04
2775 reflections
148 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.29 e Å⁻³
Δρ_min = −0.15 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯N1ⁱ	0.87 (1)	1.93 (1)	2.789 (1)	173 (2)
Symmetry code: (i) $[-x+1, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Data collection: APEX2 (Bruker, 2005 ); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT; 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 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811007513/bt5484sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811007513/bt5484Isup2.hkl

checkCIF report

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%.

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

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

C₁₃H₂₁NO	F(000) = 456
M_r = 207.31	D_x = 1.138 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 4648 reflections
a = 14.408 (1) Å	θ = 2.8–28.3°
b = 5.8150 (4) Å	µ = 0.07 mm⁻¹
c = 14.4503 (10) Å	T = 100 K
β = 91.371 (1)°	Block, colorless
V = 1210.34 (14) Å³	0.30 × 0.20 × 0.20 mm
Z = 4

Data collection top

Bruker APEXII diffractometer	2384 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.019
Graphite monochromator	θ_max = 27.5°, θ_min = 2.8°
ϕ and ω scans	h = −18→18
9964 measured reflections	k = −7→7
2775 independent reflections	l = −18→18

Refinement top

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)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.111	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ²(F_o²) + (0.0562P)² + 0.3427P] where P = (F_o² + 2F_c²)/3
2775 reflections	(Δ/σ)_max = 0.001
148 parameters	Δρ_max = 0.29 e Å⁻³
2 restraints	Δρ_min = −0.15 e Å⁻³

Crystal data top

C₁₃H₂₁NO	V = 1210.34 (14) Å³
M_r = 207.31	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 14.408 (1) Å	µ = 0.07 mm⁻¹
b = 5.8150 (4) Å	T = 100 K
c = 14.4503 (10) Å	0.30 × 0.20 × 0.20 mm
β = 91.371 (1)°

Data collection top

Bruker APEXII diffractometer	2384 reflections with I > 2σ(I)
9964 measured reflections	R_int = 0.019
2775 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.038	2 restraints
wR(F²) = 0.111	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	Δρ_max = 0.29 e Å⁻³
2775 reflections	Δρ_min = −0.15 e Å⁻³
148 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
O1	0.40834 (5)	0.62853 (13)	0.68021 (5)	0.02485 (19)
H1	0.4176 (12)	0.690 (3)	0.7345 (8)	0.054 (5)*
N1	0.54856 (6)	0.29883 (16)	0.64351 (6)	0.0236 (2)
H2	0.5558 (9)	0.4495 (15)	0.6437 (9)	0.032 (4)*
C1	0.60577 (8)	0.1994 (2)	0.57080 (8)	0.0292 (3)
H1A	0.6715	0.2278	0.5856	0.044*
H1B	0.5893	0.2709	0.5112	0.044*
H1C	0.5947	0.0334	0.5671	0.044*
C2	0.44967 (7)	0.25622 (18)	0.62563 (7)	0.0240 (2)
H2A	0.4369	0.0898	0.6320	0.029*
H2B	0.4332	0.3018	0.5613	0.029*
C3	0.39001 (7)	0.38978 (18)	0.69225 (7)	0.0222 (2)
H3	0.4073	0.3446	0.7572	0.027*
C4	0.28756 (7)	0.3311 (2)	0.67318 (8)	0.0265 (2)
H4A	0.2725	0.3660	0.6075	0.032*
H4B	0.2792	0.1636	0.6820	0.032*
C5	0.21865 (7)	0.45598 (19)	0.73277 (7)	0.0233 (2)
C6	0.19897 (7)	0.37481 (19)	0.82164 (7)	0.0246 (2)
C7	0.13219 (7)	0.4868 (2)	0.87371 (7)	0.0260 (2)
H7	0.1190	0.4302	0.9337	0.031*
C8	0.08455 (7)	0.6778 (2)	0.84056 (8)	0.0261 (2)
C9	0.10519 (8)	0.75788 (19)	0.75269 (8)	0.0266 (2)
H9	0.0734	0.8891	0.7289	0.032*
C10	0.17130 (7)	0.65081 (19)	0.69854 (7)	0.0246 (2)
C11	0.18859 (9)	0.7448 (2)	0.60308 (8)	0.0316 (3)
H11A	0.1554	0.8907	0.5949	0.047*
H11B	0.1664	0.6344	0.5564	0.047*
H11C	0.2553	0.7704	0.5960	0.047*
C12	0.01217 (8)	0.7968 (2)	0.89726 (9)	0.0340 (3)
H12A	0.0111	0.7277	0.9591	0.051*
H12B	−0.0489	0.7795	0.8668	0.051*
H12C	0.0274	0.9606	0.9028	0.051*
C13	0.24826 (8)	0.1699 (2)	0.86386 (8)	0.0303 (3)
H13A	0.2144	0.1166	0.9179	0.045*
H13B	0.3115	0.2139	0.8831	0.045*
H13C	0.2509	0.0459	0.8180	0.045*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0301 (4)	0.0223 (4)	0.0221 (4)	−0.0012 (3)	−0.0007 (3)	−0.0008 (3)
N1	0.0252 (5)	0.0231 (5)	0.0225 (4)	0.0006 (4)	0.0033 (3)	−0.0003 (3)
C1	0.0308 (6)	0.0302 (6)	0.0268 (5)	0.0043 (5)	0.0060 (4)	−0.0012 (4)
C2	0.0263 (5)	0.0241 (5)	0.0217 (5)	0.0004 (4)	0.0004 (4)	−0.0024 (4)
C3	0.0242 (5)	0.0218 (5)	0.0206 (5)	−0.0002 (4)	0.0000 (4)	−0.0008 (4)
C4	0.0254 (5)	0.0274 (5)	0.0267 (5)	−0.0013 (4)	−0.0003 (4)	−0.0061 (4)
C5	0.0199 (5)	0.0254 (5)	0.0245 (5)	−0.0033 (4)	−0.0018 (4)	−0.0045 (4)
C6	0.0211 (5)	0.0252 (5)	0.0273 (5)	−0.0039 (4)	−0.0028 (4)	−0.0009 (4)
C7	0.0222 (5)	0.0323 (6)	0.0235 (5)	−0.0045 (4)	−0.0001 (4)	0.0000 (4)
C8	0.0197 (5)	0.0316 (6)	0.0270 (5)	−0.0020 (4)	−0.0011 (4)	−0.0060 (4)
C9	0.0237 (5)	0.0278 (5)	0.0282 (5)	0.0013 (4)	−0.0045 (4)	−0.0011 (4)
C10	0.0236 (5)	0.0280 (5)	0.0221 (5)	−0.0029 (4)	−0.0033 (4)	−0.0027 (4)
C11	0.0339 (6)	0.0369 (6)	0.0240 (5)	0.0013 (5)	−0.0023 (4)	0.0015 (5)
C12	0.0267 (6)	0.0412 (7)	0.0342 (6)	0.0045 (5)	0.0030 (5)	−0.0061 (5)
C13	0.0285 (6)	0.0284 (6)	0.0339 (6)	−0.0016 (4)	−0.0003 (5)	0.0047 (5)

Geometric parameters (Å, º) top

O1—C3	1.4247 (13)	C6—C7	1.3966 (15)
O1—H1	0.870 (9)	C6—C13	1.5087 (16)
N1—C2	1.4632 (14)	C7—C8	1.3854 (16)
N1—C1	1.4693 (14)	C7—H7	0.9500
N1—H2	0.882 (9)	C8—C9	1.3912 (16)
C1—H1A	0.9800	C8—C12	1.5094 (15)
C1—H1B	0.9800	C9—C10	1.3939 (15)
C1—H1C	0.9800	C9—H9	0.9500
C2—C3	1.5193 (14)	C10—C11	1.5100 (15)
C2—H2A	0.9900	C11—H11A	0.9800
C2—H2B	0.9900	C11—H11B	0.9800
C3—C4	1.5334 (14)	C11—H11C	0.9800
C3—H3	1.0000	C12—H12A	0.9800
C4—C5	1.5149 (15)	C12—H12B	0.9800
C4—H4A	0.9900	C12—H12C	0.9800
C4—H4B	0.9900	C13—H13A	0.9800
C5—C6	1.4036 (15)	C13—H13B	0.9800
C5—C10	1.4062 (15)	C13—H13C	0.9800

C3—O1—H1	108.4 (11)	C7—C6—C13	118.31 (10)
C2—N1—C1	111.57 (9)	C5—C6—C13	122.15 (10)
C2—N1—H2	106.4 (9)	C8—C7—C6	121.98 (10)
C1—N1—H2	109.0 (9)	C8—C7—H7	119.0
N1—C1—H1A	109.5	C6—C7—H7	119.0
N1—C1—H1B	109.5	C7—C8—C9	117.96 (10)
H1A—C1—H1B	109.5	C7—C8—C12	121.53 (10)
N1—C1—H1C	109.5	C9—C8—C12	120.51 (11)
H1A—C1—H1C	109.5	C8—C9—C10	121.79 (10)
H1B—C1—H1C	109.5	C8—C9—H9	119.1
N1—C2—C3	111.40 (8)	C10—C9—H9	119.1
N1—C2—H2A	109.3	C9—C10—C5	119.65 (10)
C3—C2—H2A	109.3	C9—C10—C11	118.75 (10)
N1—C2—H2B	109.3	C5—C10—C11	121.59 (10)
C3—C2—H2B	109.3	C10—C11—H11A	109.5
H2A—C2—H2B	108.0	C10—C11—H11B	109.5
O1—C3—C2	108.14 (8)	H11A—C11—H11B	109.5
O1—C3—C4	112.04 (9)	C10—C11—H11C	109.5
C2—C3—C4	109.23 (8)	H11A—C11—H11C	109.5
O1—C3—H3	109.1	H11B—C11—H11C	109.5
C2—C3—H3	109.1	C8—C12—H12A	109.5
C4—C3—H3	109.1	C8—C12—H12B	109.5
C5—C4—C3	115.63 (9)	H12A—C12—H12B	109.5
C5—C4—H4A	108.4	C8—C12—H12C	109.5
C3—C4—H4A	108.4	H12A—C12—H12C	109.5
C5—C4—H4B	108.4	H12B—C12—H12C	109.5
C3—C4—H4B	108.4	C6—C13—H13A	109.5
H4A—C4—H4B	107.4	C6—C13—H13B	109.5
C6—C5—C10	119.07 (10)	H13A—C13—H13B	109.5
C6—C5—C4	120.56 (10)	C6—C13—H13C	109.5
C10—C5—C4	120.34 (10)	H13A—C13—H13C	109.5
C7—C6—C5	119.54 (10)	H13B—C13—H13C	109.5

C1—N1—C2—C3	−171.17 (9)	C13—C6—C7—C8	179.21 (10)
N1—C2—C3—O1	60.20 (11)	C6—C7—C8—C9	−0.18 (16)
N1—C2—C3—C4	−177.63 (9)	C6—C7—C8—C12	179.70 (10)
O1—C3—C4—C5	−58.72 (12)	C7—C8—C9—C10	0.23 (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—C5	0.23 (16)
C3—C4—C5—C10	99.05 (12)	C8—C9—C10—C11	178.81 (10)
C10—C5—C6—C7	0.81 (15)	C6—C5—C10—C9	−0.75 (15)
C4—C5—C6—C7	−177.18 (9)	C4—C5—C10—C9	177.24 (9)
C10—C5—C6—C13	−178.73 (10)	C6—C5—C10—C11	−179.29 (10)
C4—C5—C6—C13	3.28 (15)	C4—C5—C10—C11	−1.30 (15)
C5—C6—C7—C8	−0.35 (16)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1ⁱ	0.87 (1)	1.93 (1)	2.789 (1)	173 (2)

Symmetry code: (i) −x+1, y+1/2, −z+3/2.

Experimental details

Crystal data
Chemical formula	C₁₃H₂₁NO
M_r	207.31
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	100
a, b, c (Å)	14.408 (1), 5.8150 (4), 14.4503 (10)
β (°)	91.371 (1)
V (Å³)	1210.34 (14)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.07
Crystal size (mm)	0.30 × 0.20 × 0.20

Data collection
Diffractometer	Bruker APEXII diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	9964, 2775, 2384
R_int	0.019
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.038, 0.111, 1.04
No. of reflections	2775
No. of parameters	148
No. of restraints	2
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.29, −0.15

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1ⁱ	0.87 (1)	1.925 (9)	2.789 (1)	173 (2)

Symmetry code: (i) −x+1, y+1/2, −z+3/2.

Acknowledgements

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

References

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