1,4-Bis(3-chloro­prop­­oxy)benzene

The mol­ecule of the title compound, C₁₂H₁₆Cl₂O₂, has a center of inversion at the centroid of the benzene ring and the asymmetric unit contains one half-mol­ecule. Inter­molecular C—H⋯π inter­actions stabilize the crystal structure.

Related literature

For general background to the use of alk­oxy­benzene derivatives as inter­mediates in organic synthesis, see: Dudones & Pearson et al. (2000); Chen & Chao (1996); Jin et al. (2010; Rabindranath et al. (2006); Zhang & Tieke (2008); Zhu et al. (2007). For bond-length data, see: Allen et al. (1987).

Experimental

Crystal data

• C₁₂H₁₆Cl₂O₂

• M_r = 263.15

• Monoclinic, P 2₁ /c

• a = 4.9813 (8) Å

• b = 8.3200 (14) Å

• c = 15.273 (2) Å

• β = 93.156 (6)°

• V = 632.02 (17) ų

• Z = 2

• Mo Kα radiation

• μ = 0.50 mm⁻¹

• T = 113 K

• 0.22 × 0.20 × 0.18 mm

Data collection

• Rigaku Saturn diffractometer

• Absorption correction: multi-scan (CrystalClear; Rigaku, 2000) T_min = 0.899, T_max = 0.916

• 5847 measured reflections

• 1502 independent reflections

• 1273 reflections with I > 2σ(I)

• R_int = 0.033

Refinement

• R[F² > 2σ(F²)] = 0.031

• wR(F²) = 0.078

• S = 1.07

• 1502 reflections

• 73 parameters

• H-atom parameters constrained

• Δρ_max = 0.37 e Å⁻³

• Δρ_min = −0.16 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the phenyl ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C4—H4A⋯Cg1^i	0.99	2.74	3.577 (2)	143
Symmetry code: (i) .

Data collection: CrystalClear (Rigaku, 2000); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: CrystalStructure (Rigaku, 2000); software used to prepare material for publication: CrystalStructure.

Supporting information

S1. Comment

Alkoxybenzene derivatives are useful intermediates in organic synthesis (Dudones & Pearson, 2000; Chen et al., 1996). Especially, halogenoalkoxybenzenes are used to synthesize diketopyrrolopyrrole derivatives which are a class of strongly fluorescent heterocyclic pigments and their structures could be easily optimized through variations of substituents at the 2,5- and 3,6-positions (Jin et al., 2010; Rabindranath et al., 2006; Zhang et al., 2008; Zhu et al., 2007). In this paper, the structure of the title compound synthesized, (I), and we report herein its crystal structure. In the molecule of (I) (Fig. 1) the bond lengths and angles are within normal ranges (Allen et al., 1987). The asymmetric unit of the title compound contains a half of the molecule situated on a two-fold rotational axis. Intermolecular C4-H4···Cg1 interactions (Cg1 is the centroid of the phenyl ring ring) stabilize the crystal structure.

Related literature

For general background to the use of alkoxybenzene derivatives as intermediates in organic synthesis, see: Dudones & Pearson et al. (2000); Chen et al. (1996); Jin et al. (2010; Rabindranath et al. (2006); Zhang et al. (2008); Zhu et al. (2007). For bond-length data, see: Allen et al. (1987).

S2. Experimental

For the preparation of the title compound, p-dihydroxybenzene (11.0 g, 0.1 mol) was dissolved in dry acetone (100 ml). 1-Bromo-3-chloropropane (31.5 g, 0.2 mol) and potassium carbonate (138 g, 1mol) were added to this solution, the reaction was stirred under reflux for 11 h, The reaction mixture was filtered, the filtrate was concentrated, then washed with sodium hydroxide solution and extracted with ethyl acetate. After concentration, the residue was purified by recrystallization from chloroform (yield; 20.1 g, 76%, m.p. 339 K). Spectroscopic analysis: IR (KBr, ν, cm^-1): 3085, 2957, 1541, 1351, 1032, 814. ¹HNMR (400 MHz, CDCl₃, ppm): 2.21 (m, 4H), 3.75 (t, 4H), 4.06 (t, 4H), 6.84 (d, 4H).

S3. Refinement

All H atoms were positioned geometrically and refined as riding (C-H = 0.95-0.99Å) and allowed to ride on their parent atoms, with U_iso(H) =1.2U_eq(parent).

Computing details

Data collection: CrystalClear (Rigaku, 2000); cell refinement: CrystalClear (Rigaku, 2000); data reduction: CrystalClear (Rigaku, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: CrystalStructure (Rigaku, 2000); software used to prepare material for publication: CrystalStructure (Rigaku, 2000).

Figures

	Fig. 1. The molecular structure of the title molecule, with the atom-numbering scheme, symmetry code: -x+1, -y, -z+1. Displacement ellipsoids are drawn at the 75% probability level.
	Fig. 2. Part of the crystal structure of the title compound showing molecules being stacked along the c-axis.

1,4-Bis(3-chloropropoxy)benzene

Crystal data

C12H16Cl2O2	F(000) = 276
Mr = 263.15	Dx = 1.383 Mg m^−3
Monoclinic, P21/c	Melting point: 339 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71075 Å
a = 4.9813 (8) Å	Cell parameters from 2060 reflections
b = 8.3200 (14) Å	θ = 2.7–27.9°
c = 15.273 (2) Å	µ = 0.50 mm^−1
β = 93.156 (6)°	T = 113 K
V = 632.02 (17) Å^3	Prism, colorless
Z = 2	0.22 × 0.20 × 0.18 mm

Data collection

Rigaku Saturn diffractometer	1502 independent reflections
Radiation source: rotating anode	1273 reflections with I > 2σ(I)
Multilayer monochromator	Rint = 0.033
Detector resolution: 14.222 pixels mm^-1	θmax = 27.9°, θmin = 2.7°
ω scans	h = −4→6
Absorption correction: multi-scan (CrystalClear; Rigaku, 2000)	k = −10→9
Tmin = 0.899, Tmax = 0.916	l = −20→20
5847 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.031	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.078	H-atom parameters constrained
S = 1.07	w = 1/[σ^2(Fo^2) + (0.0407P)^2 + ] where P = (Fo^2 + 2Fc^2)/3
1502 reflections	(Δ/σ)max < 0.001
73 parameters	Δρmax = 0.37 e Å^−3
0 restraints	Δρmin = −0.16 e Å^−3

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Cl1	0.22691 (7)	0.61216 (4)	0.66618 (2)	0.02618 (13)
O1	0.16835 (18)	0.17363 (11)	0.60468 (6)	0.0199 (2)
C1	0.5063 (2)	−0.01858 (15)	0.59005 (8)	0.0186 (3)
H1	0.5102	−0.0314	0.6519	0.022*
C2	0.3281 (3)	0.09041 (14)	0.54960 (8)	0.0167 (3)
C3	0.3213 (3)	0.10898 (15)	0.45872 (9)	0.0185 (3)
H3	0.1997	0.1829	0.4304	0.022*
C4	−0.0045 (3)	0.29417 (15)	0.56500 (9)	0.0194 (3)
H4A	−0.1349	0.2444	0.5218	0.023*
H4B	0.1027	0.3745	0.5342	0.023*
C5	−0.1508 (3)	0.37389 (16)	0.63743 (9)	0.0226 (3)
H5A	−0.2664	0.2930	0.6644	0.027*
H5B	−0.2697	0.4587	0.6114	0.027*
C6	0.0331 (3)	0.44827 (16)	0.70864 (9)	0.0250 (3)
H6A	0.1569	0.3651	0.7337	0.030*
H6B	−0.0759	0.4887	0.7562	0.030*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.0298 (2)	0.0224 (2)	0.0265 (2)	−0.00092 (14)	0.00272 (15)	−0.00187 (14)
O1	0.0221 (5)	0.0210 (5)	0.0167 (5)	0.0060 (4)	0.0016 (4)	0.0003 (4)
C1	0.0212 (7)	0.0210 (7)	0.0135 (6)	−0.0013 (5)	0.0005 (5)	0.0011 (5)
C2	0.0159 (7)	0.0165 (6)	0.0178 (7)	−0.0012 (5)	0.0015 (5)	−0.0018 (5)
C3	0.0184 (7)	0.0174 (6)	0.0193 (7)	0.0010 (5)	−0.0021 (5)	0.0016 (5)
C4	0.0199 (7)	0.0191 (6)	0.0190 (7)	0.0029 (5)	−0.0014 (5)	0.0003 (5)
C5	0.0224 (7)	0.0224 (7)	0.0234 (8)	0.0019 (5)	0.0043 (6)	0.0004 (6)
C6	0.0318 (8)	0.0227 (7)	0.0210 (7)	−0.0005 (6)	0.0056 (6)	−0.0005 (6)

Geometric parameters (Å, º)

Cl1—C6	1.8113 (14)	C4—C5	1.5111 (17)
O1—C2	1.3762 (14)	C4—H4A	0.9900
O1—C4	1.4342 (15)	C4—H4B	0.9900
C1—C3^i	1.3887 (17)	C5—C6	1.5151 (19)
C1—C2	1.3897 (17)	C5—H5A	0.9900
C1—H1	0.9500	C5—H5B	0.9900
C2—C3	1.3951 (18)	C6—H6A	0.9900
C3—C1^i	1.3886 (17)	C6—H6B	0.9900
C3—H3	0.9500
C2—O1—C4	116.58 (10)	C5—C4—H4B	110.2
C3^i—C1—C2	120.91 (12)	H4A—C4—H4B	108.5
C3^i—C1—H1	119.5	C4—C5—C6	114.07 (11)
C2—C1—H1	119.5	C4—C5—H5A	108.7
O1—C2—C1	115.67 (11)	C6—C5—H5A	108.7
O1—C2—C3	124.69 (12)	C4—C5—H5B	108.7
C1—C2—C3	119.63 (11)	C6—C5—H5B	108.7
C1^i—C3—C2	119.46 (12)	H5A—C5—H5B	107.6
C1^i—C3—H3	120.3	C5—C6—Cl1	111.33 (9)
C2—C3—H3	120.3	C5—C6—H6A	109.4
O1—C4—C5	107.47 (11)	Cl1—C6—H6A	109.4
O1—C4—H4A	110.2	C5—C6—H6B	109.4
C5—C4—H4A	110.2	Cl1—C6—H6B	109.4
O1—C4—H4B	110.2	H6A—C6—H6B	108.0
C4—O1—C2—C1	176.07 (11)	C1—C2—C3—C1^i	−0.2 (2)
C4—O1—C2—C3	−3.86 (18)	C2—O1—C4—C5	−177.69 (10)
C3^i—C1—C2—O1	−179.68 (10)	O1—C4—C5—C6	57.71 (14)
C3^i—C1—C2—C3	0.2 (2)	C4—C5—C6—Cl1	64.36 (13)
O1—C2—C3—C1^i	179.68 (11)

Symmetry code: (i) −x+1, −y, −z+1.

Hydrogen-bond geometry (Å, º)

Cg1 is the centroid of the phenyl ring.

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4A···Cg1^ii	0.99	2.74	3.577 (2)	143

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