1,6-Bis(p-tol­yloxy)hexa­ne

Zhang, X.Q.; Xiao, J.; Xue, W.-W.; Chen, Q.; Wang, K.

doi:10.1107/S1600536814009222

organic compounds

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doi:10.1107/S1600536814009222

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1,6-Bis(p-tolyloxy)hexane

XiuQin Zhang,^a Jian Xiao,^b Wei-Wei Xue,^b Qiang Chen ^a and Kai Wang ^a ^*

^aHigh Technology Research Institute of Nanjing University, Changzhou 213162, Jiangsu, People's Republic of China, and ^bSchool of Petrochemical Engineering, Changzhou University, Changzhou 213164, Jiangsu, People's Republic of China
^*Correspondence e-mail: wkcoool@163.com

(Received 10 April 2014; accepted 24 April 2014; online 30 April 2014)

The title compound, C₂₀H₂₆O₂, crystallized with one half-molecule in the asymmetric unit. The whole molecule is generated by inversion symmetry, with the center of inversion being situated at the mid-point of the central –CH₂—CH₂- bond of the bridging hexane chain. In the crystal, molecules stack in columns along the b axis. C—H⋯π interactions are present within the columns.

CCDC reference: 999158

Related literature

For the properties and synthesis of the title compound, see: Saito et al. (1988 ). For bond-length data, see: Allen et al. (1987 ).

Experimental

Crystal data

C₂₀H₂₆O₂
M_r = 298.41
Monoclinic, P 2₁ /c
a = 18.932 (12) Å
b = 7.327 (4) Å
c = 6.352 (4) Å
β = 91.000 (13)°
V = 881.0 (9) Å³
Z = 2
Mo Kα radiation
μ = 0.07 mm⁻¹
T = 293 K
0.25 × 0.20 × 0.18 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ) T_min = 0.983, T_max = 0.987
4572 measured reflections
1544 independent reflections
963 reflections with I > 2σ(I)
R_int = 0.117
3 standard reflections every 200 reflections intensity decay: 1%

Refinement

R[F² > 2σ(F²)] = 0.077
wR(F²) = 0.316
S = 1.10
1544 reflections
101 parameters
H-atom parameters constrained
Δρ_max = 0.36 e Å⁻³
Δρ_min = −0.32 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

Cg is the centroid of the C2–C7 benzene ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C4—H4⋯Cgⁱ	0.93	2.95	3.696 (4)	138
C7—H7⋯Cgⁱⁱ	0.93	2.84	3.572 (4)	137
Symmetry codes: (i) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (ii) $[x, -y-{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

Data collection: CAD-4 Software (Enraf–Nonius, 1985 ); cell refinement: CAD-4 Software; data reduction: XCAD4 (Harms & Wocadlo,1995 ); 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.

Supporting information

CCDC reference: 999158

Crystal structure: contains datablocks I, zxq. DOI: 10.1107/S1600536814009222/su2725sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536814009222/su2725Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536814009222/su2725Isup3.cml

checkCIF report

Comment top

The title compound is used as a sensitizer for thermal recording materials, polyester-resin monomers and fire-resistant materials (Saito et al., 1988).

The molecular structure of the title compound is shown in Fig. 1. The bond lengths (Allen et al. (1987) and angles are within normal ranges. It crystallized with half a molecule in the asymmetric unit. The whole molecule is generated by inversion symmetry with the center of inversion being situated at the center of the C10—C10ⁱ bond of the bridging hexane chain [symmetry code: (i) -x, -y, -z + 2].

In the crystal, there are no intermolecular hydrogen bonds present (Fig. 2). The molecules stack in columns along the b axis and within the columns there are C—H···π interactions present (Table 1).

Related literature top

For the properties and synthesis of the title compound, see: Saito et al. (1988). For bond-length data, see: Allen et al. (1987).

Experimental top

The title compound was prepared by the reported procedure (Saito et al., 1988). Anhydrous potassium carbonate (6.2 g, 45 mmol) was added to a solution of 1,6-dibromohexane (2.5 g, 10.25 mmol) and 4-methoxyphenol (3.18 g, 25.6 mmol) in acetonitrile (100 ml). The mixture was stirred overnight at 338 K, and then filtered and the filtrate evaporated under reduced pressure. The residue was subjected to flash chromatography on silica gel, eluting with (10:1/petroleum ether:ethyl acetate) to give the title compound (Yield 2.13 g). Colourless block-like crystals of the title compound were obtained by slow evaporation of a solution in ethanol (20 ml), after ca. 7 days.

Computing details top

Data collection: CAD-4 Software (Enraf–Nonius, 1985); cell refinement: CAD-4 Software (Enraf–Nonius, 1985); data reduction: XCAD4 (Harms & Wocadlo,1995); 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 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title molecule, with atom labelling. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. A view along the b axis of the crystal packing of the title compound.

1,6-Bis(p-tolyloxy)hexane top

Crystal data top

C₂₀H₂₆O₂	F(000) = 324
M_r = 298.41	D_x = 1.125 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1071 reflections
a = 18.932 (12) Å	θ = 2.2–23.2°
b = 7.327 (4) Å	µ = 0.07 mm⁻¹
c = 6.352 (4) Å	T = 293 K
β = 91.000 (13)°	Block, colourless
V = 881.0 (9) Å³	0.25 × 0.20 × 0.18 mm
Z = 2

Data collection top

Enraf–Nonius CAD-4 diffractometer	963 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.117
Graphite monochromator	θ_max = 25.0°, θ_min = 1.1°
ω/2θ scans	h = −22→21
Absorption correction: ψ scan (North et al., 1968)	k = −5→8
T_min = 0.983, T_max = 0.987	l = −7→7
4572 measured reflections	3 standard reflections every 200 reflections
1544 independent reflections	intensity decay: 1%

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)] = 0.077	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.316	H-atom parameters constrained
S = 1.10	w = 1/[σ²(F_o²) + (0.2P)²] where P = (F_o² + 2F_c²)/3
1544 reflections	(Δ/σ)_max < 0.001
101 parameters	Δρ_max = 0.36 e Å⁻³
0 restraints	Δρ_min = −0.32 e Å⁻³

Crystal data top

C₂₀H₂₆O₂	V = 881.0 (9) Å³
M_r = 298.41	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 18.932 (12) Å	µ = 0.07 mm⁻¹
b = 7.327 (4) Å	T = 293 K
c = 6.352 (4) Å	0.25 × 0.20 × 0.18 mm
β = 91.000 (13)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	963 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.117
T_min = 0.983, T_max = 0.987	3 standard reflections every 200 reflections
4572 measured reflections	intensity decay: 1%
1544 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.077	0 restraints
wR(F²) = 0.316	H-atom parameters constrained
S = 1.10	Δρ_max = 0.36 e Å⁻³
1544 reflections	Δρ_min = −0.32 e Å⁻³
101 parameters

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq
O1	0.15451 (11)	−0.0150 (4)	0.5211 (3)	0.0524 (8)
C1	0.4342 (2)	−0.0202 (7)	0.2221 (7)	0.0812 (15)
H1A	0.4508	−0.1439	0.2302	0.122*
H1B	0.4644	0.0567	0.3067	0.122*
H1C	0.4349	0.0203	0.0784	0.122*
C2	0.36013 (17)	−0.0103 (5)	0.3018 (6)	0.0535 (10)
C3	0.34523 (17)	0.0740 (5)	0.4910 (6)	0.0555 (10)
H3	0.3819	0.1277	0.5682	0.067*
C4	0.27798 (16)	0.0806 (5)	0.5681 (5)	0.0497 (10)
H4	0.2691	0.1409	0.6937	0.060*
C5	0.22302 (16)	−0.0041 (4)	0.4560 (5)	0.0400 (9)
C6	0.23675 (16)	−0.0871 (5)	0.2660 (4)	0.0439 (9)
H6	0.2002	−0.1416	0.1892	0.053*
C7	0.30380 (17)	−0.0892 (5)	0.1906 (5)	0.0502 (10)
H7	0.3121	−0.1448	0.0618	0.060*
C8	0.13751 (15)	0.0427 (5)	0.7259 (5)	0.0456 (9)
H8A	0.1378	0.1749	0.7336	0.055*
H8B	0.1719	−0.0042	0.8273	0.055*
C9	0.06519 (15)	−0.0294 (5)	0.7732 (4)	0.0449 (9)
H9A	0.0669	−0.1617	0.7745	0.054*
H9B	0.0327	0.0074	0.6612	0.054*
C10	0.03691 (14)	0.0366 (5)	0.9817 (4)	0.0403 (9)
H10A	0.0358	0.1690	0.9826	0.048*
H10B	0.0682	−0.0032	1.0951	0.048*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0479 (16)	0.0683 (18)	0.0413 (14)	−0.0032 (10)	0.0101 (10)	−0.0063 (11)
C1	0.064 (3)	0.093 (4)	0.088 (3)	0.002 (2)	0.034 (2)	−0.005 (3)
C2	0.053 (2)	0.043 (2)	0.065 (2)	0.0025 (15)	0.0202 (17)	0.0055 (17)
C3	0.051 (2)	0.051 (2)	0.065 (2)	−0.0086 (16)	0.0069 (16)	−0.0079 (18)
C4	0.055 (2)	0.049 (2)	0.0456 (18)	−0.0020 (15)	0.0089 (15)	−0.0109 (16)
C5	0.0429 (18)	0.0390 (19)	0.0385 (18)	0.0012 (13)	0.0136 (13)	0.0055 (13)
C6	0.0538 (19)	0.043 (2)	0.0346 (16)	−0.0022 (14)	0.0030 (13)	0.0022 (14)
C7	0.065 (2)	0.043 (2)	0.0433 (18)	0.0040 (16)	0.0137 (15)	−0.0009 (15)
C8	0.0469 (19)	0.049 (2)	0.0411 (18)	0.0042 (14)	0.0062 (14)	−0.0022 (14)
C9	0.0475 (19)	0.053 (2)	0.0341 (17)	−0.0005 (14)	0.0093 (13)	−0.0078 (14)
C10	0.0457 (19)	0.046 (2)	0.0297 (16)	0.0024 (13)	0.0059 (13)	−0.0025 (12)

Geometric parameters (Å, º) top

O1—C5	1.371 (3)	C6—C7	1.365 (4)
O1—C8	1.410 (4)	C6—H6	0.9300
C1—C2	1.502 (4)	C7—H7	0.9300
C1—H1A	0.9600	C8—C9	1.503 (4)
C1—H1B	0.9600	C8—H8A	0.9700
C1—H1C	0.9600	C8—H8B	0.9700
C2—C3	1.385 (5)	C9—C10	1.516 (4)
C2—C7	1.394 (5)	C9—H9A	0.9700
C3—C4	1.373 (4)	C9—H9B	0.9700
C3—H3	0.9300	C10—C10ⁱ	1.519 (5)
C4—C5	1.396 (5)	C10—H10A	0.9700
C4—H4	0.9300	C10—H10B	0.9700
C5—C6	1.380 (4)

C5—O1—C8	119.6 (2)	C6—C7—C2	121.7 (3)
C2—C1—H1A	109.5	C6—C7—H7	119.2
C2—C1—H1B	109.5	C2—C7—H7	119.2
H1A—C1—H1B	109.5	O1—C8—C9	107.6 (3)
C2—C1—H1C	109.5	O1—C8—H8A	110.2
H1A—C1—H1C	109.5	C9—C8—H8A	110.2
H1B—C1—H1C	109.5	O1—C8—H8B	110.2
C3—C2—C7	117.3 (3)	C9—C8—H8B	110.2
C3—C2—C1	121.3 (4)	H8A—C8—H8B	108.5
C7—C2—C1	121.3 (3)	C8—C9—C10	113.5 (3)
C4—C3—C2	122.0 (3)	C8—C9—H9A	108.9
C4—C3—H3	119.0	C10—C9—H9A	108.9
C2—C3—H3	119.0	C8—C9—H9B	108.9
C3—C4—C5	119.3 (3)	C10—C9—H9B	108.9
C3—C4—H4	120.3	H9A—C9—H9B	107.7
C5—C4—H4	120.3	C9—C10—C10ⁱ	111.2 (3)
O1—C5—C6	115.6 (3)	C9—C10—H10A	109.4
O1—C5—C4	124.9 (3)	C10ⁱ—C10—H10A	109.4
C6—C5—C4	119.5 (3)	C9—C10—H10B	109.4
C7—C6—C5	120.2 (3)	C10ⁱ—C10—H10B	109.4
C7—C6—H6	119.9	H10A—C10—H10B	108.0
C5—C6—H6	119.9

C7—C2—C3—C4	0.0 (5)	C4—C5—C6—C7	1.3 (5)
C1—C2—C3—C4	−178.6 (4)	C5—C6—C7—C2	0.6 (5)
C2—C3—C4—C5	1.8 (5)	C3—C2—C7—C6	−1.2 (5)
C8—O1—C5—C6	171.1 (3)	C1—C2—C7—C6	177.4 (4)
C8—O1—C5—C4	−7.9 (5)	C5—O1—C8—C9	−165.3 (3)
C3—C4—C5—O1	176.6 (3)	O1—C8—C9—C10	−174.7 (3)
C3—C4—C5—C6	−2.4 (5)	C8—C9—C10—C10ⁱ	178.6 (3)
O1—C5—C6—C7	−177.8 (3)

Symmetry code: (i) −x, −y, −z+2.

Hydrogen-bond geometry (Å, º) top

Cg is the centroid of the C2–C7 benzene ring.

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4···Cgⁱⁱ	0.93	2.95	3.696 (4)	138
C7—H7···Cgⁱⁱⁱ	0.93	2.84	3.572 (4)	137

Symmetry codes: (ii) x, −y+1/2, z+1/2; (iii) x, −y−1/2, z−1/2.

Hydrogen-bond geometry (Å, º) top

Cg is the centroid of the C2–C7 benzene ring.

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4···Cgⁱ	0.93	2.95	3.696 (4)	138
C7—H7···Cgⁱⁱ	0.93	2.84	3.572 (4)	137

Symmetry codes: (i) x, −y+1/2, z+1/2; (ii) x, −y−1/2, z−1/2.

Acknowledgements

The authors thank the Center of Testing and Analysis, Nanjing University, for the data collection.

References

Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19. CrossRef Web of Science Google Scholar
Enraf–Nonius (1985). CAD-4 Software. Enraf–Nonius, Delft, The Netherlands. Google Scholar
Harms, K. & Wocadlo, S. (1995). XCAD4. University of Marburg, Germany. Google Scholar
North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351–359. CrossRef IUCr Journals Web of Science Google Scholar
Saito, T., Kitani, M. & Ishibashi, T. (1988). Patent No. JP 63156731. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar

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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 70| Part 5| May 2014| Page o617

doi:10.1107/S1600536814009222

Open

access