4-Chloro-3-ethyl-phenol.

The title compound, C8H9ClO, packs with two independent mol-ecules in the asymmetric unit, without significant differences in corresponding bond lengths and angles, with the ethyl group in each oriented nearly perpendicular to the aromatic ring having ring-to-side chain torsion angles of 81.14 (18) and -81.06 (19)°. In the crystal, mol-ecules form an O-H⋯O hydrogen-bonded chain extending along the b-axis direction, through the phenol groups in which the H atoms are disordered. These chains pack together in the solid state, giving a sheet lying parallel to (001), via an offset face-to-face π-stacking inter-action characterized by a centroid-centroid distance of 3.580 (1) Å, together with a short inter-molecular Cl⋯Cl contact [3.412 (1) Å].

Related literature

For information regarding the synthesis of 4-chloro-3-ethyl­phenol, see the following patents: Awano et al. (1987 ▶) or Schroetter et al. (1977 ▶). For applications in biological systems, see: Gerbershagen et al. (2005 ▶); Low et al. (1997 ▶). For similar chlorinated phenols, see: Cox (1995 ▶, 2003 ▶); Oswald et al. (2005 ▶). For more information on π-stacking, see: Lueckheide et al. (2013 ▶) and on halogen–halogen inter­actions, see: Pedireddi et al. (1994 ▶).

Experimental

Crystal data

C8H9ClO

M = 156.60

Triclinic,

a = 7.5580 (7) Å

b = 8.6854 (8) Å

c = 12.2520 (11) Å

α = 78.363 (1)°

β = 78.762 (1)°

γ = 80.355 (1)°

V = 765.72 (12) Å3

Z = 4

Mo Kα radiation

μ = 0.42 mm−1

T = 125 K

0.20 × 0.15 × 0.10 mm

Data collection

Bruker APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2007 ▶) T min = 0.910, T max = 0.949

17904 measured reflections

4656 independent reflections

4176 reflections with I > 2σ(I)

R int = 0.019

Refinement

R[F 2 > 2σ(F 2)] = 0.037

wR(F 2) = 0.107

S = 1.13

4656 reflections

183 parameters

4 restraints

H-atom parameters constrained

Δρmax = 0.48 e Å−3

Δρmin = −0.26 e Å−3

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL, OLEX2 (Dolomanov et al., 2009 ▶) and Mercury (Macrae et al., 2006 ▶).

Crystal structure: contains datablock(s) I, New_Global_Publ_Block. DOI: 10.1107/S1600536814013919/zs2303sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814013919/zs2303Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S1600536814013919/zs2303Isup3.cml

CCDC reference: 1008296

Additional supporting information: crystallographic information; 3D view; checkCIF report

C8H9ClO	Z = 4
Mr = 156.60	F(000) = 328
Triclinic, P1	Dx = 1.358 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.5580 (7) Å	Cell parameters from 9958 reflections
b = 8.6854 (8) Å	θ = 2.7–30.5°
c = 12.2520 (11) Å	µ = 0.42 mm−1
α = 78.363 (1)°	T = 125 K
β = 78.762 (1)°	Block, colourless
γ = 80.355 (1)°	0.20 × 0.15 × 0.10 mm
V = 765.72 (12) Å3

Bruker APEXII CCD diffractometer	4656 independent reflections
Radiation source: fine-focus sealed tube	4176 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.019
φ and ω scans	θmax = 30.5°, θmin = 1.7°
Absorption correction: multi-scan (SADABS; Bruker, 2007)	h = −10→10
Tmin = 0.910, Tmax = 0.949	k = −12→12
17904 measured reflections	l = −17→17

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)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.107	H-atom parameters constrained
S = 1.13	w = 1/[σ2(Fo2) + (0.0336P)2 + 0.751P] where P = (Fo2 + 2Fc2)/3
4656 reflections	(Δ/σ)max < 0.001
183 parameters	Δρmax = 0.48 e Å−3
4 restraints	Δρmin = −0.26 e Å−3

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	Occ. (<1)
Cl1	−0.28100 (5)	0.74811 (5)	0.30473 (4)	0.02708 (10)
O1	0.36924 (19)	0.62233 (15)	0.52135 (12)	0.0328 (3)
H1	0.4258	0.5340	0.5280	0.039*	0.50
H1A	0.4024	0.7019	0.5320	0.039*	0.50
C1	0.2194 (2)	0.65320 (17)	0.46838 (13)	0.0186 (3)
C2	0.20646 (19)	0.56371 (16)	0.38898 (12)	0.0173 (3)
H2B	0.3035	0.4836	0.3702	0.021*
C3	0.05376 (19)	0.58914 (16)	0.33626 (11)	0.0157 (2)
C4	−0.08454 (19)	0.70975 (17)	0.36563 (12)	0.0171 (3)
C5	−0.0719 (2)	0.80067 (17)	0.44421 (13)	0.0192 (3)
H5A	−0.1676	0.8822	0.4622	0.023*
C6	0.0802 (2)	0.77258 (17)	0.49633 (12)	0.0197 (3)
H6A	0.0894	0.8340	0.5505	0.024*
C7	0.0464 (2)	0.49276 (18)	0.24819 (13)	0.0207 (3)
H7A	−0.0793	0.4686	0.2557	0.025*
H7B	0.1272	0.3910	0.2611	0.025*
C8	0.1054 (3)	0.5813 (2)	0.12819 (13)	0.0276 (3)
H8A	0.1021	0.5144	0.0733	0.041*
H8B	0.2294	0.6062	0.1207	0.041*
H8C	0.0223	0.6799	0.1140	0.041*
Cl2	0.36637 (6)	0.24774 (5)	−0.04071 (3)	0.02827 (10)
O2	0.53688 (18)	0.12745 (14)	0.41968 (10)	0.0271 (3)
H2	0.5511	0.2054	0.4427	0.033*	0.50
H2A	0.5219	0.0420	0.4598	0.033*	0.50
C9	0.4935 (2)	0.15527 (17)	0.31266 (12)	0.0171 (3)
C10	0.37918 (19)	0.06378 (16)	0.28560 (12)	0.0172 (3)
H10A	0.3293	−0.0170	0.3419	0.021*
C11	0.33641 (19)	0.08887 (17)	0.17674 (12)	0.0172 (3)
C12	0.4129 (2)	0.20931 (18)	0.09713 (12)	0.0188 (3)
C13	0.5254 (2)	0.30228 (18)	0.12387 (13)	0.0204 (3)
H13A	0.5744	0.3839	0.0679	0.024*
C14	0.5662 (2)	0.27599 (18)	0.23228 (13)	0.0195 (3)
H14A	0.6426	0.3394	0.2513	0.023*
C15	0.2080 (2)	−0.00900 (19)	0.15052 (14)	0.0233 (3)
H15A	0.2089	−0.1105	0.2046	0.028*
H15B	0.2514	−0.0339	0.0736	0.028*
C16	0.0132 (2)	0.0767 (2)	0.15729 (16)	0.0292 (3)
H16A	−0.0649	0.0098	0.1385	0.044*
H16B	0.0116	0.1770	0.1036	0.044*
H16C	−0.0320	0.0981	0.2341	0.044*

	U11	U22	U33	U12	U13	U23
Cl1	0.01775 (17)	0.0333 (2)	0.0317 (2)	0.00267 (14)	−0.00926 (14)	−0.00914 (16)
O1	0.0381 (7)	0.0216 (5)	0.0469 (8)	−0.0047 (5)	−0.0307 (6)	−0.0013 (5)
C1	0.0229 (7)	0.0145 (6)	0.0204 (6)	−0.0042 (5)	−0.0092 (5)	−0.0007 (5)
C2	0.0173 (6)	0.0147 (6)	0.0199 (6)	−0.0004 (5)	−0.0041 (5)	−0.0032 (5)
C3	0.0172 (6)	0.0154 (6)	0.0147 (6)	−0.0028 (5)	−0.0022 (5)	−0.0027 (5)
C4	0.0152 (6)	0.0188 (6)	0.0172 (6)	−0.0018 (5)	−0.0030 (5)	−0.0029 (5)
C5	0.0201 (6)	0.0165 (6)	0.0199 (6)	−0.0011 (5)	−0.0007 (5)	−0.0042 (5)
C6	0.0262 (7)	0.0162 (6)	0.0180 (6)	−0.0039 (5)	−0.0045 (5)	−0.0044 (5)
C7	0.0224 (7)	0.0223 (7)	0.0195 (6)	−0.0016 (5)	−0.0051 (5)	−0.0084 (5)
C8	0.0329 (8)	0.0333 (8)	0.0170 (7)	0.0006 (7)	−0.0055 (6)	−0.0085 (6)
Cl2	0.0300 (2)	0.0399 (2)	0.01504 (16)	−0.00312 (16)	−0.00605 (13)	−0.00440 (14)
O2	0.0433 (7)	0.0205 (5)	0.0222 (5)	−0.0027 (5)	−0.0190 (5)	−0.0029 (4)
C9	0.0188 (6)	0.0160 (6)	0.0173 (6)	0.0007 (5)	−0.0071 (5)	−0.0035 (5)
C10	0.0184 (6)	0.0152 (6)	0.0180 (6)	−0.0014 (5)	−0.0048 (5)	−0.0022 (5)
C11	0.0161 (6)	0.0174 (6)	0.0194 (6)	0.0012 (5)	−0.0054 (5)	−0.0063 (5)
C12	0.0182 (6)	0.0240 (7)	0.0140 (6)	0.0010 (5)	−0.0042 (5)	−0.0045 (5)
C13	0.0185 (6)	0.0232 (7)	0.0183 (6)	−0.0040 (5)	−0.0016 (5)	−0.0011 (5)
C14	0.0178 (6)	0.0200 (6)	0.0220 (7)	−0.0036 (5)	−0.0052 (5)	−0.0039 (5)
C15	0.0236 (7)	0.0223 (7)	0.0280 (8)	−0.0042 (6)	−0.0098 (6)	−0.0075 (6)
C16	0.0220 (7)	0.0332 (9)	0.0340 (9)	−0.0055 (6)	−0.0099 (6)	−0.0031 (7)

Cl1—C4	1.7430 (15)	Cl2—C12	1.7469 (15)
O1—C1	1.3751 (18)	O2—C9	1.3778 (17)
O1—H1	0.8098	O2—H2	0.8144
O1—H1A	0.8145	O2—H2A	0.8150
C1—C2	1.388 (2)	C9—C10	1.391 (2)
C1—C6	1.391 (2)	C9—C14	1.392 (2)
C2—C3	1.395 (2)	C10—C11	1.399 (2)
C2—H2B	0.9500	C10—H10A	0.9500
C3—C4	1.3993 (19)	C11—C12	1.397 (2)
C3—C7	1.5072 (19)	C11—C15	1.508 (2)
C4—C5	1.388 (2)	C12—C13	1.388 (2)
C5—C6	1.385 (2)	C13—C14	1.388 (2)
C5—H5A	0.9500	C13—H13A	0.9500
C6—H6A	0.9500	C14—H14A	0.9500
C7—C8	1.535 (2)	C15—C16	1.529 (2)
C7—H7A	0.9900	C15—H15A	0.9900
C7—H7B	0.9900	C15—H15B	0.9900
C8—H8A	0.9800	C16—H16A	0.9800
C8—H8B	0.9800	C16—H16B	0.9800
C8—H8C	0.9800	C16—H16C	0.9800
C1—O1—H1	119.3	C9—O2—H2	115.6
C1—O1—H1A	113.5	C9—O2—H2A	118.3
H1—O1—H1A	126.1	H2—O2—H2A	124.2
O1—C1—C2	119.94 (14)	O2—C9—C10	120.42 (13)
O1—C1—C6	119.55 (14)	O2—C9—C14	118.89 (13)
C2—C1—C6	120.51 (13)	C10—C9—C14	120.69 (13)
C1—C2—C3	121.26 (13)	C9—C10—C11	121.06 (13)
C1—C2—H2B	119.4	C9—C10—H10A	119.5
C3—C2—H2B	119.4	C11—C10—H10A	119.5
C2—C3—C4	117.27 (13)	C12—C11—C10	117.20 (13)
C2—C3—C7	119.86 (13)	C12—C11—C15	122.80 (13)
C4—C3—C7	122.82 (13)	C10—C11—C15	119.97 (13)
C5—C4—C3	121.79 (13)	C13—C12—C11	122.05 (13)
C5—C4—Cl1	117.97 (11)	C13—C12—Cl2	117.98 (12)
C3—C4—Cl1	120.23 (11)	C11—C12—Cl2	119.97 (11)
C6—C5—C4	120.02 (13)	C14—C13—C12	120.01 (14)
C6—C5—H5A	120.0	C14—C13—H13A	120.0
C4—C5—H5A	120.0	C12—C13—H13A	120.0
C5—C6—C1	119.14 (13)	C13—C14—C9	118.97 (14)
C5—C6—H6A	120.4	C13—C14—H14A	120.5
C1—C6—H6A	120.4	C9—C14—H14A	120.5
C3—C7—C8	111.60 (13)	C11—C15—C16	112.21 (13)
C3—C7—H7A	109.3	C11—C15—H15A	109.2
C8—C7—H7A	109.3	C16—C15—H15A	109.2
C3—C7—H7B	109.3	C11—C15—H15B	109.2
C8—C7—H7B	109.3	C16—C15—H15B	109.2
H7A—C7—H7B	108.0	H15A—C15—H15B	107.9
C7—C8—H8A	109.5	C15—C16—H16A	109.5
C7—C8—H8B	109.5	C15—C16—H16B	109.5
H8A—C8—H8B	109.5	H16A—C16—H16B	109.5
C7—C8—H8C	109.5	C15—C16—H16C	109.5
H8A—C8—H8C	109.5	H16A—C16—H16C	109.5
H8B—C8—H8C	109.5	H16B—C16—H16C	109.5
O1—C1—C2—C3	178.12 (13)	O2—C9—C10—C11	−178.90 (13)
C6—C1—C2—C3	−0.8 (2)	C14—C9—C10—C11	1.0 (2)
C1—C2—C3—C4	0.8 (2)	C9—C10—C11—C12	−0.1 (2)
C1—C2—C3—C7	178.38 (13)	C9—C10—C11—C15	−178.34 (13)
C2—C3—C4—C5	−0.2 (2)	C10—C11—C12—C13	−0.6 (2)
C7—C3—C4—C5	−177.72 (14)	C15—C11—C12—C13	177.52 (14)
C2—C3—C4—Cl1	−179.38 (11)	C10—C11—C12—Cl2	179.89 (11)
C7—C3—C4—Cl1	3.11 (19)	C15—C11—C12—Cl2	−2.0 (2)
C3—C4—C5—C6	−0.3 (2)	C11—C12—C13—C14	0.5 (2)
Cl1—C4—C5—C6	178.84 (11)	Cl2—C12—C13—C14	−179.95 (12)
C4—C5—C6—C1	0.3 (2)	C12—C13—C14—C9	0.3 (2)
O1—C1—C6—C5	−178.70 (14)	O2—C9—C14—C13	178.84 (13)
C2—C1—C6—C5	0.2 (2)	C10—C9—C14—C13	−1.1 (2)
C2—C3—C7—C8	−96.30 (16)	C12—C11—C15—C16	−81.06 (19)
C4—C3—C7—C8	81.14 (18)	C10—C11—C15—C16	97.03 (17)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O1i	0.81	1.97	2.708 (3)	152
O1—H1A···O2i	0.81	1.86	2.6642 (17)	171
O2—H2···O1i	0.81	1.86	2.6642 (17)	168
O2—H2A···O2ii	0.82	1.91	2.704 (2)	166

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯O1i	0.81	1.97	2.708 (3)	152
O1—H1A⋯O2i	0.81	1.86	2.6642 (17)	171
O2—H2⋯O1i	0.81	1.86	2.6642 (17)	168
O2—H2A⋯O2ii	0.82	1.91	2.704 (2)	166

Symmetry codes: (i) ; (ii) .