1,4-Bis[(oxan-2-yl)­oxy]benzene

Raj, R.M.; Lekha, L.; Viswanathan, V.; Velmurugan, D.; Easwaramoorthy, D.

doi:10.1107/S2414314617007179

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 2| Part 5| May 2017| x170717

https://doi.org/10.1107/S2414314617007179

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1,4-Bis[(oxan-2-yl)oxy]benzene

Radhakrishnan Mohan Raj,^a Logu Lekha,^b Vijayan Viswanathan,^c Devadasan Velmurugan ^c and Deivanayagam Easwaramoorthy ^a ^*

^aDepartment of Chemistry, B.S. Abdur Rahman University, Chennai, Tamil Nadu, India, ^bDepartment of Chemistry, Saveetha School of Engineering, Thandalam, Chennai 602 105, Tamil Nadu, India, and ^cCentre of Advanced Study in Crystallography and Biophysics, University of Madras, Guindy Campus, Chennai 600 025, India
^*Correspondence e-mail: easwar@bsauniv.ac.in

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 14 March 2017; accepted 15 May 2017; online 23 May 2017)

The complete molecule of the title compound, C₁₆H₂₂O₄, is generated by crystallographic inversion symmetry. The oxane ring system adopts a chair conformation with the exocyclic C—C bond in an axial orientation; the dihedral angle between the oxane ring (all non-H atoms) and the benzene ring is 73.45 (1)°. A short intramolecular C—H⋯O contact occcurs. In the crystal, a very weak C—H⋯π interaction generates [010] chains.

Keywords: crystal structure; oxane; 4H-pyran nucleus; intramolecular C—H⋯O contact.

Structure description

The 4H-pyran nucleus occurs in molecules possessing a wide spectrum of biological and pharmacological activities (Shehab & Ghoneim, 2016 ). As part of our studies in this area, we have undertaken the X-ray crystal structure analysis of the title compound (Fig. 1).

Figure 1
The molecular structure of the title compound, showing displacement ellipsoids drawn at the 50% probability level. The intramolecular C—H⋯O contact is shown as a dashed line.

The title compound contains a half of the molecule in an asymmetric unit; the complete molecule is generated by crystallographic inversion symmetry with the inversion point at (1, 0, 1) for the asymmetric molecule. The oxane ring (C1–C5/O1) adopts a chair conformation: the mean plane of the oxane ring makes a dihedral angle of 73.45 (1)° with the benzene ring. A short intramolecular C—H⋯O contact occurs. In the crystal, a very weak C—H⋯π interaction (Table 1) generates [010] chains (Fig. 2).

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the benzene ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C7—H7⋯O1	0.93	2.41	2.966 (2)	119
C5—H5A⋯Cg1ⁱ	0.93	2.94	3.621 (3)	129
Symmetry code: (i) x, y-1, z.

Figure 2
The partial packing of the title compound viewed down the c axis showing the C—H⋯π interaction as a dashed line. H atoms not involved in this interaction have been excluded for clarity.

Synthesis and crystallization

A solution of p-quinone (2.0 mmol), 3,4-dihydro-2H-pyran (5.0 mmol) and pTsOH (1.0 mmol) in 1,2-dichloroethane (5 ml) was stirred at 83°C under an oxygen atmosphere. The progress of the reaction was monitored by TLC (20% ethyl acetate/hexane). After completion, it was concentrated and the residue was subjected for separation of the respective products by column chromatography using silica gel (elutant: hexane and ethyl acetate): yield: 28%. Colourless blocks were recrystallized from acetonitrile solution.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	C₁₆H₂₂O₄
M_r	278.33
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	293
a, b, c (Å)	6.767 (5), 6.817 (5), 15.864 (5)
β (°)	99.391 (5)
V (Å³)	722.0 (8)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	0.09
Crystal size (mm)	0.30 × 0.20 × 0.20

Data collection
Diffractometer	Bruker SMART APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2008 )
T_min, T_max	0.756, 0.853
No. of measured, independent and observed [I > 2σ(I)] reflections	5817, 1175, 976
R_int	0.024
(sin θ/λ)_max (Å⁻¹)	0.580

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.033, 0.084, 1.09
No. of reflections	1175
No. of parameters	91
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.14, −0.14
Computer programs: APEX2 and SAINT (Bruker, 2008), SHELXS97 (Sheldrick, 2008 ), SHELXL2016 (Sheldrick, 2015 ), ORTEP-3 for Windows (Farrugia, 2012 ) and PLATON (Spek, 2009 ).

Structural data

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S2414314617007179/hb4130sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314617007179/hb4130Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314617007179/hb4130Isup3.cml

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2008); cell refinement: APEX2 (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2016 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: PLATON (Spek, 2009).

1,4-Bis[(oxan-2-yl)oxy]benzene top

Crystal data top

C₁₆H₂₂O₄	F(000) = 300
M_r = 278.33	D_x = 1.280 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 6.767 (5) Å	Cell parameters from 1175 reflections
b = 6.817 (5) Å	θ = 2.6–24.4°
c = 15.864 (5) Å	µ = 0.09 mm⁻¹
β = 99.391 (5)°	T = 293 K
V = 722.0 (8) Å³	Block, colourless
Z = 2	0.30 × 0.20 × 0.20 mm

Data collection top

Bruker SMART APEXII CCD diffractometer	976 reflections with I > 2σ(I)
ω and φ scans	R_int = 0.024
Absorption correction: multi-scan (SADABS; Bruker, 2008)	θ_max = 24.4°, θ_min = 2.6°
T_min = 0.756, T_max = 0.853	h = −7→7
5817 measured reflections	k = −7→7
1175 independent reflections	l = −17→18

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.033	H-atom parameters constrained
wR(F²) = 0.084	w = 1/[σ²(F_o²) + (0.0356P)² + 0.1292P] where P = (F_o² + 2F_c²)/3
S = 1.09	(Δ/σ)_max < 0.001
1175 reflections	Δρ_max = 0.14 e Å⁻³
91 parameters	Δρ_min = −0.14 e Å⁻³

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Refinement. The hydrogen atoms were placed in calculated positions with C—H = 0.93 Å to 0.98 Å, refined in the riding model with fixed isotropic displacement parameters:U_iso(H) = 1.5U_eq(C) for methyl group and U_iso(H) = 1.2U_eq(C) for other groups.

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

	x	y	z	U_iso*/U_eq
C1	0.6512 (2)	0.2718 (2)	0.83666 (9)	0.0426 (4)
H1	0.683390	0.166073	0.799310	0.051*
C2	0.4358 (2)	0.3315 (2)	0.80928 (10)	0.0526 (4)
H2A	0.348919	0.222001	0.816930	0.063*
H2B	0.413944	0.365739	0.749130	0.063*
C3	0.3834 (2)	0.5052 (3)	0.86102 (10)	0.0582 (5)
H3A	0.249437	0.550953	0.838501	0.070*
H3B	0.386157	0.466188	0.920008	0.070*
C4	0.5329 (3)	0.6680 (3)	0.85653 (13)	0.0660 (5)
H4A	0.517002	0.718745	0.798690	0.079*
H4B	0.507999	0.774275	0.894067	0.079*
C5	0.7431 (2)	0.5937 (2)	0.88259 (11)	0.0565 (4)
H5A	0.837039	0.697816	0.876008	0.068*
H5B	0.762908	0.556370	0.942381	0.068*
C6	0.83603 (19)	0.10172 (19)	0.95814 (9)	0.0377 (3)
C7	1.0155 (2)	0.1063 (2)	0.92723 (9)	0.0431 (4)
H7	1.026663	0.177577	0.878240	0.052*
C8	0.8222 (2)	−0.0044 (2)	1.03046 (9)	0.0425 (4)
H8	0.701375	−0.007568	1.051230	0.051*
O1	0.78259 (13)	0.42824 (14)	0.83219 (6)	0.0445 (3)
O2	0.66348 (13)	0.19763 (15)	0.92132 (6)	0.0456 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0471 (8)	0.0427 (8)	0.0385 (8)	−0.0007 (7)	0.0088 (6)	−0.0002 (6)
C2	0.0457 (8)	0.0616 (11)	0.0477 (9)	−0.0040 (8)	−0.0006 (7)	0.0095 (8)
C3	0.0439 (9)	0.0719 (12)	0.0602 (10)	0.0161 (8)	0.0130 (7)	0.0142 (9)
C4	0.0698 (11)	0.0512 (10)	0.0811 (13)	0.0138 (9)	0.0244 (9)	−0.0040 (9)
C5	0.0593 (10)	0.0461 (10)	0.0658 (11)	−0.0048 (8)	0.0153 (8)	−0.0094 (8)
C6	0.0356 (7)	0.0364 (8)	0.0419 (8)	0.0027 (6)	0.0091 (6)	0.0020 (6)
C7	0.0425 (8)	0.0465 (9)	0.0430 (8)	0.0039 (7)	0.0152 (6)	0.0106 (7)
C8	0.0368 (7)	0.0460 (8)	0.0483 (8)	0.0036 (6)	0.0171 (6)	0.0058 (7)
O1	0.0438 (5)	0.0432 (6)	0.0495 (6)	0.0004 (5)	0.0168 (4)	0.0033 (5)
O2	0.0378 (5)	0.0532 (7)	0.0475 (6)	0.0086 (5)	0.0122 (4)	0.0146 (5)

Geometric parameters (Å, º) top

C1—O1	1.3977 (18)	C4—H4B	0.9700
C1—O2	1.4247 (17)	C5—O1	1.4324 (19)
C1—C2	1.507 (2)	C5—H5A	0.9700
C1—H1	0.9800	C5—H5B	0.9700
C2—C3	1.515 (2)	C6—C8	1.372 (2)
C2—H2A	0.9700	C6—O2	1.3818 (17)
C2—H2B	0.9700	C6—C7	1.383 (2)
C3—C4	1.511 (3)	C7—C8ⁱ	1.378 (2)
C3—H3A	0.9700	C7—H7	0.9300
C3—H3B	0.9700	C8—C7ⁱ	1.378 (2)
C4—C5	1.503 (2)	C8—H8	0.9300
C4—H4A	0.9700

O1—C1—O2	112.26 (11)	C5—C4—H4B	109.5
O1—C1—C2	111.88 (13)	C3—C4—H4B	109.5
O2—C1—C2	105.81 (11)	H4A—C4—H4B	108.1
O1—C1—H1	108.9	O1—C5—C4	111.49 (13)
O2—C1—H1	108.9	O1—C5—H5A	109.3
C2—C1—H1	108.9	C4—C5—H5A	109.3
C1—C2—C3	110.83 (12)	O1—C5—H5B	109.3
C1—C2—H2A	109.5	C4—C5—H5B	109.3
C3—C2—H2A	109.5	H5A—C5—H5B	108.0
C1—C2—H2B	109.5	C8—C6—O2	115.75 (12)
C3—C2—H2B	109.5	C8—C6—C7	119.49 (12)
H2A—C2—H2B	108.1	O2—C6—C7	124.76 (13)
C4—C3—C2	109.30 (13)	C8ⁱ—C7—C6	119.50 (13)
C4—C3—H3A	109.8	C8ⁱ—C7—H7	120.2
C2—C3—H3A	109.8	C6—C7—H7	120.2
C4—C3—H3B	109.8	C6—C8—C7ⁱ	121.01 (13)
C2—C3—H3B	109.8	C6—C8—H8	119.5
H3A—C3—H3B	108.3	C7ⁱ—C8—H8	119.5
C5—C4—C3	110.50 (15)	C1—O1—C5	113.21 (11)
C5—C4—H4A	109.5	C6—O2—C1	118.80 (10)
C3—C4—H4A	109.5

O1—C1—C2—C3	−55.28 (16)	C7—C6—C8—C7ⁱ	0.1 (2)
O2—C1—C2—C3	67.28 (16)	O2—C1—O1—C5	−61.30 (15)
C1—C2—C3—C4	53.15 (18)	C2—C1—O1—C5	57.50 (16)
C2—C3—C4—C5	−53.58 (19)	C4—C5—O1—C1	−57.90 (17)
C3—C4—C5—O1	55.58 (19)	C8—C6—O2—C1	−165.57 (12)
C8—C6—C7—C8ⁱ	−0.1 (2)	C7—C6—O2—C1	14.3 (2)
O2—C6—C7—C8ⁱ	−179.97 (13)	O1—C1—O2—C6	−68.23 (16)
O2—C6—C8—C7ⁱ	179.98 (13)	C2—C1—O2—C6	169.46 (12)

Symmetry code: (i) −x+2, −y, −z+2.

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of the benzene ring.

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7···O1	0.93	2.41	2.966 (2)	119
C5—H5A···Cg1ⁱⁱ	0.93	2.94	3.621 (3)	129

Symmetry code: (ii) x, y−1, z.

Acknowledgements

RMR thanks the B. S. Abdur Rahman University for support. The authors thank the TBI X-ray facility, CAS in Crystallography and Biophysics, University of Madras, India, for the data collection.

References

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