2,6-Di-tert-butyl-4-(3-chloro-2-hy­droxy­prop­yl)phenol

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

doi:10.1107/S1600536811008592

organic compounds

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ISSN: 2056-9890

Volume 67| Part 4| April 2011| Page o852

doi:10.1107/S1600536811008592

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2,6-Di-tert-butyl-4-(3-chloro-2-hydroxypropyl)phenol

Ayten R. Asgarova,^a Abel M. Maharramov,^a Ali N. Khalilov,^a Atash V. Gurbanov ^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 25 February 2011; accepted 7 March 2011; online 12 March 2011)

In the title 2-propanol derivative, C₁₇H₂₇ClO₂, the two tert-butyl groups both have one methyl C atom lying in the plane of the aromatic ring. In the crystal, the phenol group forms a hydrogen bond to the hydroxy O atom belonging to the alkyl substituent of an adjacent molecule, forming a chain along the ac diagonal. The Cl atom is disordered over two positions in a 0.73 (4):0.27 (4) ratio.

Related literature

For the synthesis: see: Krysin et al. (2010 ).

Experimental

Crystal data

C₁₇H₂₇ClO₂
M_r = 298.84
Monoclinic, P 2₁ /c
a = 5.9536 (3) Å
b = 19.4819 (9) Å
c = 14.4310 (7) Å
β = 96.798 (1)°
V = 1662.05 (14) Å³
Z = 4
Mo Kα radiation
μ = 0.23 mm⁻¹
T = 100 K
0.30 × 0.30 × 0.30 mm

Data collection

Bruker APEXII diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.934, T_max = 0.934
17600 measured reflections
3819 independent reflections
3374 reflections with I > 2σ(I)
R_int = 0.035

Refinement

R[F² > 2σ(F²)] = 0.049
wR(F²) = 0.131
S = 1.12
3819 reflections
193 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.59 e Å⁻³
Δρ_min = −0.36 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2⋯O1ⁱ	0.84	2.31	2.956 (2)	134
Symmetry code: (i) $[x-1, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

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/S1600536811008592/xu5167sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811008592/xu5167Isup2.hkl

checkCIF report

Comment top

The chlorohydrin unit (i.e., an alkyl chain having a chlorine atom and a hydroxy group on adjacent carbons) is an important unit in compounds used for the treatment of protozoal and bacterial infections; and chlorohydrin-based compounds are important intermediates in the synthesis of some HIV protease inhibitors. The di-tert-butyl phenol unit is also an important component of medicinal compounds. The two units are assembled in the title compound (Scheme I).

The compound can be further transformed; in fact, replacing the chlorine atom by a diisopropylamino group furnishes a 2:1 co-crystal with succinic acid that has been patented for its antiarrhythmic and antihypertensive activities (Krysin et al., 2010).

The two tert-butyl groups of C₁₇H₂₇ClO₂ both have one methyl C lying in the plane of the aromatic ring (Fig. 1). The phenolic group forms a hydrogen bond to the hydroxy O atom belonging to the alkyl substituent of an adjacent molecule to form a chain along the a–c diagonal of the monoclinic unit cell (Fig. 2).

Related literature top

For the synthesis: see: Krysin et al. (2010).

Experimental top

The compound was prepared by using a procedure reported in the patent literature (Krysin et al., 2010), and colorless crystals was obtained upon recrystallization from ethanol.

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. Thermal ellipsoid plot (Barbour, 2001) of C₁₇H₂₇ClO₂ at the 70% probability level; hydrogen atoms are drawn as spheres of arbitrary radius. The disorder in the chlorine atom is not shown.
	Fig. 2. Hydrogen-bonded chain motif.

2,6-Di-tert-butyl-4-(3-chloro-2-hydroxypropyl)phenol top

Crystal data top

C₁₇H₂₇ClO₂	F(000) = 648
M_r = 298.84	D_x = 1.194 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 6280 reflections
a = 5.9536 (3) Å	θ = 2.5–28.3°
b = 19.4819 (9) Å	µ = 0.23 mm⁻¹
c = 14.4310 (7) Å	T = 100 K
β = 96.798 (1)°	Prism, colorless
V = 1662.05 (14) Å³	0.30 × 0.30 × 0.30 mm
Z = 4

Data collection top

Bruker APEXII diffractometer	3819 independent reflections
Radiation source: fine-focus sealed tube	3374 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.035
ϕ and ω scans	θ_max = 27.5°, θ_min = 1.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −7→7
T_min = 0.934, T_max = 0.934	k = −25→25
17600 measured 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)] = 0.049	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.131	H-atom parameters constrained
S = 1.12	w = 1/[σ²(F_o²) + (0.057P)² + 1.2061P] where P = (F_o² + 2F_c²)/3
3819 reflections	(Δ/σ)_max = 0.001
193 parameters	Δρ_max = 0.59 e Å⁻³
1 restraint	Δρ_min = −0.36 e Å⁻³

Crystal data top

C₁₇H₂₇ClO₂	V = 1662.05 (14) Å³
M_r = 298.84	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 5.9536 (3) Å	µ = 0.23 mm⁻¹
b = 19.4819 (9) Å	T = 100 K
c = 14.4310 (7) Å	0.30 × 0.30 × 0.30 mm
β = 96.798 (1)°

Data collection top

Bruker APEXII diffractometer	3819 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	3374 reflections with I > 2σ(I)
T_min = 0.934, T_max = 0.934	R_int = 0.035
17600 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.049	1 restraint
wR(F²) = 0.131	H-atom parameters constrained
S = 1.12	Δρ_max = 0.59 e Å⁻³
3819 reflections	Δρ_min = −0.36 e Å⁻³
193 parameters

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
Cl1	1.2917 (5)	0.47575 (14)	0.5791 (3)	0.0266 (6)	0.73 (4)
Cl1'	1.311 (2)	0.4728 (6)	0.5926 (16)	0.048 (2)	0.27 (4)
O1	1.1454 (2)	0.31683 (6)	0.56395 (9)	0.0212 (3)
H1	1.2420	0.3195	0.5261	0.032*
O2	0.3696 (2)	0.18279 (6)	0.25797 (9)	0.0199 (3)
H2	0.3138	0.2071	0.2130	0.030*
C1	1.0528 (3)	0.43104 (10)	0.61378 (14)	0.0235 (4)
H1A	1.0903	0.4130	0.6779	0.028*	0.73 (4)
H1B	0.9240	0.4631	0.6139	0.028*	0.73 (4)
H1'A	1.0701	0.4134	0.6786	0.028*	0.27 (4)
H1'B	0.9292	0.4653	0.6082	0.028*	0.27 (4)
C2	0.9867 (3)	0.37230 (9)	0.54759 (13)	0.0202 (4)
H2A	0.9834	0.3886	0.4817	0.024*
C3	0.7524 (3)	0.34483 (9)	0.56317 (12)	0.0190 (4)
H3A	0.7664	0.3169	0.6209	0.023*
H3B	0.6514	0.3840	0.5721	0.023*
C4	0.6473 (3)	0.30175 (9)	0.48281 (12)	0.0159 (3)
C5	0.5064 (3)	0.33223 (9)	0.41043 (12)	0.0159 (3)
H5	0.4776	0.3801	0.4134	0.019*
C6	0.4059 (3)	0.29514 (8)	0.33367 (11)	0.0144 (3)
C7	0.4559 (3)	0.22451 (9)	0.33061 (11)	0.0146 (3)
C8	0.5969 (3)	0.19141 (8)	0.40264 (11)	0.0145 (3)
C9	0.6889 (3)	0.23165 (9)	0.47749 (12)	0.0155 (3)
H9	0.7837	0.2104	0.5268	0.019*
C10	0.2464 (3)	0.33124 (9)	0.25678 (12)	0.0169 (3)
C11	0.2100 (3)	0.40719 (9)	0.27950 (14)	0.0244 (4)
H11A	0.3558	0.4311	0.2862	0.037*
H11B	0.1420	0.4107	0.3379	0.037*
H11C	0.1089	0.4282	0.2289	0.037*
C12	0.3501 (3)	0.33046 (10)	0.16400 (13)	0.0225 (4)
H12A	0.4996	0.3522	0.1729	0.034*
H12B	0.2516	0.3558	0.1166	0.034*
H12C	0.3653	0.2829	0.1434	0.034*
C13	0.0101 (3)	0.29757 (10)	0.24768 (13)	0.0211 (4)
H13A	−0.0494	0.2991	0.3081	0.032*
H13B	0.0218	0.2497	0.2279	0.032*
H13C	−0.0922	0.3226	0.2013	0.032*
C14	0.6512 (3)	0.11431 (8)	0.39914 (12)	0.0158 (3)
C15	0.8079 (3)	0.09121 (9)	0.48583 (13)	0.0215 (4)
H15A	0.9483	0.1179	0.4907	0.032*
H15B	0.8430	0.0423	0.4803	0.032*
H15C	0.7324	0.0986	0.5417	0.032*
C16	0.4356 (3)	0.07064 (9)	0.39586 (14)	0.0234 (4)
H16A	0.3307	0.0835	0.3411	0.035*
H16B	0.3637	0.0785	0.4526	0.035*
H16C	0.4749	0.0220	0.3917	0.035*
C17	0.7752 (3)	0.09881 (9)	0.31401 (13)	0.0216 (4)
H17A	0.6804	0.1128	0.2570	0.032*
H17B	0.8062	0.0495	0.3114	0.032*
H17C	0.9182	0.1242	0.3193	0.032*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0251 (8)	0.0174 (9)	0.0380 (11)	−0.0002 (7)	0.0068 (6)	0.0062 (11)
Cl1'	0.022 (2)	0.042 (4)	0.078 (5)	−0.016 (2)	0.001 (3)	−0.034 (3)
O1	0.0165 (6)	0.0191 (6)	0.0277 (7)	0.0035 (5)	0.0020 (5)	−0.0010 (5)
O2	0.0264 (7)	0.0159 (6)	0.0154 (6)	0.0009 (5)	−0.0061 (5)	−0.0014 (5)
C1	0.0196 (9)	0.0227 (9)	0.0280 (10)	−0.0023 (7)	0.0022 (7)	−0.0025 (7)
C2	0.0180 (8)	0.0182 (8)	0.0238 (9)	0.0019 (7)	−0.0002 (7)	−0.0011 (7)
C3	0.0171 (8)	0.0202 (8)	0.0186 (8)	0.0021 (7)	−0.0020 (6)	−0.0044 (7)
C4	0.0122 (7)	0.0189 (8)	0.0167 (8)	−0.0006 (6)	0.0022 (6)	−0.0027 (6)
C5	0.0154 (8)	0.0137 (7)	0.0189 (8)	0.0005 (6)	0.0029 (6)	−0.0001 (6)
C6	0.0128 (7)	0.0158 (8)	0.0145 (8)	0.0002 (6)	0.0017 (6)	0.0022 (6)
C7	0.0139 (7)	0.0165 (8)	0.0133 (8)	−0.0011 (6)	0.0015 (6)	−0.0016 (6)
C8	0.0132 (7)	0.0146 (8)	0.0160 (8)	0.0012 (6)	0.0030 (6)	0.0009 (6)
C9	0.0132 (7)	0.0189 (8)	0.0141 (8)	0.0013 (6)	0.0008 (6)	0.0012 (6)
C10	0.0157 (8)	0.0163 (8)	0.0180 (8)	0.0003 (6)	−0.0011 (6)	0.0022 (6)
C11	0.0277 (10)	0.0159 (8)	0.0276 (10)	0.0041 (7)	−0.0051 (8)	0.0024 (7)
C12	0.0237 (9)	0.0257 (9)	0.0176 (9)	−0.0010 (7)	0.0007 (7)	0.0059 (7)
C13	0.0142 (8)	0.0238 (9)	0.0242 (9)	0.0003 (7)	−0.0018 (7)	0.0020 (7)
C14	0.0171 (8)	0.0138 (8)	0.0162 (8)	0.0014 (6)	0.0006 (6)	0.0013 (6)
C15	0.0228 (9)	0.0182 (8)	0.0222 (9)	0.0051 (7)	−0.0023 (7)	0.0027 (7)
C16	0.0205 (9)	0.0191 (9)	0.0298 (10)	−0.0025 (7)	0.0001 (7)	0.0053 (7)
C17	0.0256 (9)	0.0173 (8)	0.0226 (9)	0.0044 (7)	0.0058 (7)	−0.0006 (7)

Geometric parameters (Å, º) top

Cl1—C1	1.788 (3)	C9—H9	0.9500
Cl1'—C1	1.795 (6)	C10—C11	1.537 (2)
O1—C2	1.437 (2)	C10—C12	1.539 (3)
O1—H1	0.8400	C10—C13	1.544 (2)
O2—C7	1.377 (2)	C11—H11A	0.9800
O2—H2	0.8400	C11—H11B	0.9800
C1—C2	1.513 (3)	C11—H11C	0.9800
C1—H1A	0.9900	C12—H12A	0.9800
C1—H1B	0.9900	C12—H12B	0.9800
C1—H1'A	0.9900	C12—H12C	0.9800
C1—H1'B	0.9900	C13—H13A	0.9800
C2—C3	1.535 (2)	C13—H13B	0.9800
C2—H2A	1.0000	C13—H13C	0.9800
C3—C4	1.506 (2)	C14—C17	1.536 (2)
C3—H3A	0.9900	C14—C16	1.536 (2)
C3—H3B	0.9900	C14—C15	1.537 (2)
C4—C9	1.392 (2)	C15—H15A	0.9800
C4—C5	1.393 (2)	C15—H15B	0.9800
C5—C6	1.396 (2)	C15—H15C	0.9800
C5—H5	0.9500	C16—H16A	0.9800
C6—C7	1.410 (2)	C16—H16B	0.9800
C6—C10	1.542 (2)	C16—H16C	0.9800
C7—C8	1.412 (2)	C17—H17A	0.9800
C8—C9	1.393 (2)	C17—H17B	0.9800
C8—C14	1.539 (2)	C17—H17C	0.9800

C2—O1—H1	109.5	C11—C10—C6	112.10 (14)
C7—O2—H2	109.5	C12—C10—C6	110.19 (14)
C2—C1—Cl1	110.38 (18)	C11—C10—C13	106.08 (14)
C2—C1—Cl1'	113.5 (5)	C12—C10—C13	112.16 (15)
C2—C1—H1A	109.6	C6—C10—C13	110.17 (14)
Cl1—C1—H1A	109.6	C10—C11—H11A	109.5
Cl1'—C1—H1A	102.5	C10—C11—H11B	109.5
C2—C1—H1B	109.6	H11A—C11—H11B	109.5
Cl1—C1—H1B	109.6	C10—C11—H11C	109.5
Cl1'—C1—H1B	113.1	H11A—C11—H11C	109.5
H1A—C1—H1B	108.1	H11B—C11—H11C	109.5
C2—C1—H1'A	108.9	C10—C12—H12A	109.5
Cl1—C1—H1'A	115.9	C10—C12—H12B	109.5
Cl1'—C1—H1'A	108.9	H12A—C12—H12B	109.5
C2—C1—H1'B	108.9	C10—C12—H12C	109.5
Cl1'—C1—H1'B	108.9	H12A—C12—H12C	109.5
H1'A—C1—H1'B	107.7	H12B—C12—H12C	109.5
O1—C2—C1	110.37 (15)	C10—C13—H13A	109.5
O1—C2—C3	107.78 (14)	C10—C13—H13B	109.5
C1—C2—C3	110.14 (15)	H13A—C13—H13B	109.5
O1—C2—H2A	109.5	C10—C13—H13C	109.5
C1—C2—H2A	109.5	H13A—C13—H13C	109.5
C3—C2—H2A	109.5	H13B—C13—H13C	109.5
C4—C3—C2	112.54 (14)	C17—C14—C16	110.21 (15)
C4—C3—H3A	109.1	C17—C14—C8	109.93 (13)
C2—C3—H3A	109.1	C16—C14—C8	111.33 (14)
C4—C3—H3B	109.1	C17—C14—C15	106.87 (14)
C2—C3—H3B	109.1	C16—C14—C15	106.72 (14)
H3A—C3—H3B	107.8	C8—C14—C15	111.65 (14)
C9—C4—C5	118.18 (15)	C14—C15—H15A	109.5
C9—C4—C3	121.94 (15)	C14—C15—H15B	109.5
C5—C4—C3	119.88 (15)	H15A—C15—H15B	109.5
C6—C5—C4	122.53 (15)	C14—C15—H15C	109.5
C6—C5—H5	118.7	H15A—C15—H15C	109.5
C4—C5—H5	118.7	H15B—C15—H15C	109.5
C5—C6—C7	117.23 (15)	C14—C16—H16A	109.5
C5—C6—C10	120.29 (15)	C14—C16—H16B	109.5
C7—C6—C10	122.48 (15)	H16A—C16—H16B	109.5
O2—C7—C6	122.59 (15)	C14—C16—H16C	109.5
O2—C7—C8	115.26 (14)	H16A—C16—H16C	109.5
C6—C7—C8	122.14 (15)	H16B—C16—H16C	109.5
C9—C8—C7	117.30 (15)	C14—C17—H17A	109.5
C9—C8—C14	120.65 (14)	C14—C17—H17B	109.5
C7—C8—C14	122.04 (15)	H17A—C17—H17B	109.5
C4—C9—C8	122.60 (15)	C14—C17—H17C	109.5
C4—C9—H9	118.7	H17A—C17—H17C	109.5
C8—C9—H9	118.7	H17B—C17—H17C	109.5
C11—C10—C12	106.04 (15)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O1ⁱ	0.84	2.31	2.956 (2)	134

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

Experimental details

Crystal data
Chemical formula	C₁₇H₂₇ClO₂
M_r	298.84
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	100
a, b, c (Å)	5.9536 (3), 19.4819 (9), 14.4310 (7)
β (°)	96.798 (1)
V (Å³)	1662.05 (14)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.23
Crystal size (mm)	0.30 × 0.30 × 0.30

Data collection
Diffractometer	Bruker APEXII diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.934, 0.934
No. of measured, independent and observed [I > 2σ(I)] reflections	17600, 3819, 3374
R_int	0.035
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.049, 0.131, 1.12
No. of reflections	3819
No. of parameters	193
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.59, −0.36

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
O2—H2···O1ⁱ	0.84	2.31	2.956 (2)	134

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

Acknowledgements

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

References

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