1-(Piperidin-1-yl)-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/S1600536811006568

organic compounds

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ISSN: 2056-9890

Volume 67| Part 3| March 2011| Page o739

doi:10.1107/S1600536811006568

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1-(Piperidin-1-yl)-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 20 February 2011; accepted 21 February 2011; online 26 February 2011)

The title compound, C₁₇H₂₇NO, features a bufferfly-shaped substituted 2-propanol having an aromatic ring on the 1-carbon and a piperidine ring on the 3-carbon. The piperidine ring adopts a chair conformation and its N atom shows a trigonal coordination. In the crystal, the hydroxy group interacts with the N atom of an inversion-related molecule, generating an O—H⋯N hydrogen-bonded dimer.

Related literature

For background to the synthesis: see: Yadigarov et al. (2010 ). For the structure of tolperisone hydrochloride, see: Tanaka & Hirayama (2007 ). For a related structure, see: Maharramov et al. (2011 ).

Experimental

Crystal data

C₁₇H₂₇NO
M_r = 261.40
Monoclinic, P 2₁ /c
a = 11.7992 (12) Å
b = 8.0940 (8) Å
c = 17.0196 (17) Å
β = 107.489 (1)°
V = 1550.3 (3) 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
6615 measured reflections
3537 independent reflections
2964 reflections with I > 2σ(I)
R_int = 0.016

Refinement

R[F² > 2σ(F²)] = 0.040
wR(F²) = 0.110
S = 1.02
3537 reflections
179 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.36 e Å⁻³
Δρ_min = −0.19 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯N1ⁱ	0.85 (1)	2.07 (1)	2.880 (1)	158 (2)
Symmetry code: (i) -x+1, -y+1, -z+1.

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/S1600536811006568/bt5478sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811006568/bt5478Isup2.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 thiourea as the amino reactant (Maharramov et al., 2011). The present study employs a 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), which has been characterized as a hydrochloride (Tanaka & Hirayama, 2007). The title compound, C₁₇H₂₇NO, (Scheme I) is a bufferfly-shaped substituted 2-propanol having an aromatic ring on one carbon end and a piperidinyl ring on the other. The hydroxy group interacts with the N atom of an inversion-related molecule to generate a hydrogen-bonded dimer (Fig. 1).

Related literature top

For background to the synthesis: see: Yadigarov et al. (2010). For the structure of tolperisone hydrochloride, see: Tanaka & Hirayama (2007). For a related structure, 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 distallate 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 the hydrogen-bonded dimeric structure of C₁₇H₂₇NO at the 70% probability level; hydrogen atoms are drawn as spheres of arbitrary radius.

1-(Piperidin-1-yl)-3-(2,4,6-trimethylphenyl)propan-2-ol top

Crystal data top

C₁₇H₂₇NO	F(000) = 576
M_r = 261.40	D_x = 1.120 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1896 reflections
a = 11.7992 (12) Å	θ = 2.8–29.2°
b = 8.0940 (8) Å	µ = 0.07 mm⁻¹
c = 17.0196 (17) Å	T = 100 K
β = 107.489 (1)°	Prism, colorless
V = 1550.3 (3) Å³	0.30 × 0.20 × 0.20 mm
Z = 4

Data collection top

Bruker APEXII diffractometer	2964 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.016
Graphite monochromator	θ_max = 27.5°, θ_min = 2.5°
ϕ and ω scans	h = −13→15
6615 measured reflections	k = −8→10
3537 independent reflections	l = −15→22

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)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.110	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ²(F_o²) + (0.0565P)² + 0.4799P] where P = (F_o² + 2F_c²)/3
3537 reflections	(Δ/σ)_max = 0.001
179 parameters	Δρ_max = 0.36 e Å⁻³
1 restraint	Δρ_min = −0.19 e Å⁻³

Crystal data top

C₁₇H₂₇NO	V = 1550.3 (3) Å³
M_r = 261.40	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 11.7992 (12) Å	µ = 0.07 mm⁻¹
b = 8.0940 (8) Å	T = 100 K
c = 17.0196 (17) Å	0.30 × 0.20 × 0.20 mm
β = 107.489 (1)°

Data collection top

Bruker APEXII diffractometer	2964 reflections with I > 2σ(I)
6615 measured reflections	R_int = 0.016
3537 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.040	1 restraint
wR(F²) = 0.110	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	Δρ_max = 0.36 e Å⁻³
3537 reflections	Δρ_min = −0.19 e Å⁻³
179 parameters

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

	x	y	z	U_iso*/U_eq
O1	0.42350 (7)	0.36548 (10)	0.53159 (5)	0.0213 (2)
H1	0.4165 (15)	0.373 (2)	0.4804 (6)	0.042 (5)*
N1	0.54620 (8)	0.67399 (12)	0.62908 (6)	0.0164 (2)
C1	0.64459 (10)	0.66941 (15)	0.70653 (7)	0.0196 (2)
H1A	0.6716	0.5539	0.7190	0.023*
H1B	0.6161	0.7100	0.7522	0.023*
C2	0.74826 (10)	0.77528 (15)	0.70081 (7)	0.0219 (3)
H2A	0.7807	0.7296	0.6580	0.026*
H2B	0.8121	0.7723	0.7541	0.026*
C3	0.70960 (11)	0.95379 (15)	0.67944 (7)	0.0229 (3)
H3A	0.7759	1.0172	0.6697	0.027*
H3B	0.6890	1.0054	0.7261	0.027*
C4	0.60210 (11)	0.95923 (15)	0.60243 (7)	0.0225 (3)
H4A	0.5717	1.0738	0.5930	0.027*
H4B	0.6263	0.9249	0.5540	0.027*
C5	0.50422 (10)	0.84561 (14)	0.61153 (7)	0.0196 (2)
H5A	0.4751	0.8863	0.6568	0.024*
H5B	0.4369	0.8481	0.5601	0.024*
C6	0.44843 (10)	0.56903 (15)	0.63656 (7)	0.0194 (2)
H6A	0.4001	0.6329	0.6644	0.023*
H6B	0.4825	0.4734	0.6721	0.023*
C7	0.36711 (10)	0.50483 (14)	0.55465 (7)	0.0173 (2)
H7	0.3549	0.5928	0.5116	0.021*
C8	0.24722 (10)	0.45733 (15)	0.56663 (7)	0.0186 (2)
H8A	0.2625	0.3806	0.6140	0.022*
H8B	0.2107	0.5583	0.5813	0.022*
C9	0.15852 (10)	0.37740 (14)	0.49344 (7)	0.0162 (2)
C10	0.08491 (10)	0.47543 (14)	0.43015 (7)	0.0170 (2)
C11	−0.00046 (10)	0.40041 (14)	0.36511 (7)	0.0177 (2)
H11	−0.0496	0.4676	0.3226	0.021*
C12	−0.01591 (10)	0.22964 (14)	0.36054 (7)	0.0175 (2)
C13	0.05775 (10)	0.13441 (14)	0.42312 (7)	0.0178 (2)
H13	0.0488	0.0177	0.4209	0.021*
C14	0.14458 (10)	0.20477 (14)	0.48924 (7)	0.0172 (2)
C15	0.21904 (11)	0.09380 (15)	0.55627 (7)	0.0229 (3)
H15A	0.2038	−0.0219	0.5394	0.034*
H15B	0.1984	0.1125	0.6072	0.034*
H15C	0.3034	0.1187	0.5657	0.034*
C16	−0.11163 (11)	0.15251 (15)	0.29073 (7)	0.0245 (3)
H16A	−0.0934	0.0354	0.2861	0.037*
H16B	−0.1153	0.2092	0.2391	0.037*
H16C	−0.1884	0.1627	0.3015	0.037*
C17	0.09396 (11)	0.66162 (14)	0.43230 (8)	0.0213 (3)
H17A	0.0326	0.7081	0.3851	0.032*
H17B	0.1726	0.6948	0.4297	0.032*
H17C	0.0825	0.7028	0.4835	0.032*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0219 (4)	0.0226 (4)	0.0206 (4)	0.0023 (3)	0.0080 (4)	−0.0009 (3)
N1	0.0141 (4)	0.0170 (5)	0.0163 (5)	−0.0008 (4)	0.0017 (4)	0.0007 (4)
C1	0.0176 (5)	0.0214 (6)	0.0169 (5)	−0.0004 (4)	0.0010 (4)	0.0011 (4)
C2	0.0172 (6)	0.0247 (6)	0.0214 (6)	−0.0025 (5)	0.0022 (4)	−0.0019 (5)
C3	0.0249 (6)	0.0212 (6)	0.0227 (6)	−0.0065 (5)	0.0074 (5)	−0.0038 (5)
C4	0.0275 (6)	0.0180 (5)	0.0216 (6)	−0.0005 (5)	0.0066 (5)	0.0007 (5)
C5	0.0189 (6)	0.0187 (5)	0.0194 (6)	0.0029 (4)	0.0028 (4)	0.0000 (4)
C6	0.0185 (6)	0.0233 (6)	0.0164 (5)	−0.0042 (4)	0.0050 (4)	−0.0009 (4)
C7	0.0161 (5)	0.0185 (5)	0.0169 (5)	−0.0018 (4)	0.0045 (4)	−0.0011 (4)
C8	0.0175 (5)	0.0210 (5)	0.0179 (5)	−0.0027 (4)	0.0064 (4)	−0.0035 (4)
C9	0.0142 (5)	0.0177 (5)	0.0180 (5)	−0.0015 (4)	0.0067 (4)	−0.0027 (4)
C10	0.0167 (5)	0.0156 (5)	0.0205 (6)	−0.0002 (4)	0.0083 (4)	−0.0012 (4)
C11	0.0157 (5)	0.0185 (5)	0.0186 (5)	0.0011 (4)	0.0048 (4)	0.0012 (4)
C12	0.0158 (5)	0.0193 (5)	0.0181 (5)	−0.0018 (4)	0.0059 (4)	−0.0024 (4)
C13	0.0192 (6)	0.0140 (5)	0.0214 (6)	−0.0017 (4)	0.0079 (5)	−0.0014 (4)
C14	0.0164 (5)	0.0174 (5)	0.0187 (5)	0.0009 (4)	0.0068 (4)	0.0015 (4)
C15	0.0227 (6)	0.0204 (6)	0.0236 (6)	0.0005 (5)	0.0040 (5)	0.0033 (5)
C16	0.0256 (6)	0.0236 (6)	0.0209 (6)	−0.0052 (5)	0.0017 (5)	−0.0025 (5)
C17	0.0226 (6)	0.0152 (5)	0.0261 (6)	−0.0010 (4)	0.0072 (5)	−0.0009 (4)

Geometric parameters (Å, º) top

O1—C7	1.4233 (14)	C8—C9	1.5106 (15)
O1—H1	0.852 (9)	C8—H8A	0.9900
N1—C6	1.4687 (14)	C8—H8B	0.9900
N1—C1	1.4720 (14)	C9—C14	1.4062 (15)
N1—C5	1.4749 (14)	C9—C10	1.4079 (16)
C1—C2	1.5205 (16)	C10—C11	1.3923 (15)
C1—H1A	0.9900	C10—C17	1.5104 (15)
C1—H1B	0.9900	C11—C12	1.3933 (16)
C2—C3	1.5258 (17)	C11—H11	0.9500
C2—H2A	0.9900	C12—C13	1.3883 (16)
C2—H2B	0.9900	C12—C16	1.5068 (15)
C3—C4	1.5262 (17)	C13—C14	1.3955 (16)
C3—H3A	0.9900	C13—H13	0.9500
C3—H3B	0.9900	C14—C15	1.5092 (16)
C4—C5	1.5203 (17)	C15—H15A	0.9800
C4—H4A	0.9900	C15—H15B	0.9800
C4—H4B	0.9900	C15—H15C	0.9800
C5—H5A	0.9900	C16—H16A	0.9800
C5—H5B	0.9900	C16—H16B	0.9800
C6—C7	1.5265 (15)	C16—H16C	0.9800
C6—H6A	0.9900	C17—H17A	0.9800
C6—H6B	0.9900	C17—H17B	0.9800
C7—C8	1.5375 (15)	C17—H17C	0.9800
C7—H7	1.0000

C7—O1—H1	108.5 (12)	C6—C7—H7	109.8
C6—N1—C1	109.65 (9)	C8—C7—H7	109.8
C6—N1—C5	109.73 (9)	C9—C8—C7	115.77 (9)
C1—N1—C5	109.36 (9)	C9—C8—H8A	108.3
N1—C1—C2	111.20 (9)	C7—C8—H8A	108.3
N1—C1—H1A	109.4	C9—C8—H8B	108.3
C2—C1—H1A	109.4	C7—C8—H8B	108.3
N1—C1—H1B	109.4	H8A—C8—H8B	107.4
C2—C1—H1B	109.4	C14—C9—C10	119.03 (10)
H1A—C1—H1B	108.0	C14—C9—C8	120.59 (10)
C1—C2—C3	111.12 (10)	C10—C9—C8	120.32 (10)
C1—C2—H2A	109.4	C11—C10—C9	119.67 (10)
C3—C2—H2A	109.4	C11—C10—C17	118.91 (10)
C1—C2—H2B	109.4	C9—C10—C17	121.40 (10)
C3—C2—H2B	109.4	C10—C11—C12	121.89 (11)
H2A—C2—H2B	108.0	C10—C11—H11	119.1
C2—C3—C4	110.11 (10)	C12—C11—H11	119.1
C2—C3—H3A	109.6	C13—C12—C11	117.82 (10)
C4—C3—H3A	109.6	C13—C12—C16	121.53 (10)
C2—C3—H3B	109.6	C11—C12—C16	120.64 (10)
C4—C3—H3B	109.6	C12—C13—C14	122.05 (10)
H3A—C3—H3B	108.2	C12—C13—H13	119.0
C5—C4—C3	110.84 (10)	C14—C13—H13	119.0
C5—C4—H4A	109.5	C13—C14—C9	119.52 (10)
C3—C4—H4A	109.5	C13—C14—C15	119.10 (10)
C5—C4—H4B	109.5	C9—C14—C15	121.35 (10)
C3—C4—H4B	109.5	C14—C15—H15A	109.5
H4A—C4—H4B	108.1	C14—C15—H15B	109.5
N1—C5—C4	111.78 (9)	H15A—C15—H15B	109.5
N1—C5—H5A	109.3	C14—C15—H15C	109.5
C4—C5—H5A	109.3	H15A—C15—H15C	109.5
N1—C5—H5B	109.3	H15B—C15—H15C	109.5
C4—C5—H5B	109.3	C12—C16—H16A	109.5
H5A—C5—H5B	107.9	C12—C16—H16B	109.5
N1—C6—C7	114.35 (9)	H16A—C16—H16B	109.5
N1—C6—H6A	108.7	C12—C16—H16C	109.5
C7—C6—H6A	108.7	H16A—C16—H16C	109.5
N1—C6—H6B	108.7	H16B—C16—H16C	109.5
C7—C6—H6B	108.7	C10—C17—H17A	109.5
H6A—C6—H6B	107.6	C10—C17—H17B	109.5
O1—C7—C6	107.70 (9)	H17A—C17—H17B	109.5
O1—C7—C8	111.31 (9)	C10—C17—H17C	109.5
C6—C7—C8	108.36 (9)	H17A—C17—H17C	109.5
O1—C7—H7	109.8	H17B—C17—H17C	109.5

C6—N1—C1—C2	179.35 (9)	C14—C9—C10—C11	0.41 (16)
C5—N1—C1—C2	−60.29 (12)	C8—C9—C10—C11	−176.83 (10)
N1—C1—C2—C3	57.57 (13)	C14—C9—C10—C17	178.63 (10)
C1—C2—C3—C4	−52.80 (13)	C8—C9—C10—C17	1.39 (16)
C2—C3—C4—C5	52.23 (13)	C9—C10—C11—C12	0.14 (17)
C6—N1—C5—C4	−179.48 (9)	C17—C10—C11—C12	−178.12 (11)
C1—N1—C5—C4	60.20 (12)	C10—C11—C12—C13	−0.52 (17)
C3—C4—C5—N1	−56.81 (13)	C10—C11—C12—C16	178.08 (10)
C1—N1—C6—C7	−155.49 (10)	C11—C12—C13—C14	0.34 (16)
C5—N1—C6—C7	84.37 (12)	C16—C12—C13—C14	−178.24 (11)
N1—C6—C7—O1	81.03 (12)	C12—C13—C14—C9	0.20 (17)
N1—C6—C7—C8	−158.46 (9)	C12—C13—C14—C15	178.26 (10)
O1—C7—C8—C9	−56.80 (13)	C10—C9—C14—C13	−0.57 (16)
C6—C7—C8—C9	−175.04 (10)	C8—C9—C14—C13	176.66 (10)
C7—C8—C9—C14	98.81 (13)	C10—C9—C14—C15	−178.59 (10)
C7—C8—C9—C10	−84.00 (13)	C8—C9—C14—C15	−1.36 (16)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1ⁱ	0.85 (1)	2.07 (1)	2.880 (1)	158 (2)

Symmetry code: (i) −x+1, −y+1, −z+1.

Experimental details

Crystal data
Chemical formula	C₁₇H₂₇NO
M_r	261.40
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	100
a, b, c (Å)	11.7992 (12), 8.0940 (8), 17.0196 (17)
β (°)	107.489 (1)
V (Å³)	1550.3 (3)
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	6615, 3537, 2964
R_int	0.016
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.110, 1.02
No. of reflections	3537
No. of parameters	179
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.36, −0.19

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	0.85 (1)	2.07 (1)	2.880 (1)	157.6 (16)

Symmetry code: (i) −x+1, −y+1, −z+1.

Acknowledgements

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

References

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