2,6-Bis(prop-2-yn­yloxy)naphthalene

Abstract

The title compound, C₁₆H₁₂O₂, crystallizes with one half-mol­ecule in the asymmetric unit. The mol­ecule lies on an inversion centre, located at the mid-point of the naphthyl group. All non-H atoms are almost coplanar, with a mean deviation from the least-squares plane of 0.0536 (11) Å. Mol­ecules are linked into a three-dimensional framework by a combination of C—H⋯O and C—H⋯π(arene) hydrogen bonds.

Related literature

For compound preparation, see: Burchell et al. (2006 ▶). For related structures, see: Zhang et al. (2008 ▶); Ghosh et al. (2007 ▶).

Experimental

Crystal data

• C₁₆H₁₂O₂

• M _r = 236.26

• Orthorhombic,

• a = 7.5783 (11) Å

• b = 8.0295 (12) Å

• c = 20.972 (3) Å

• V = 1276.1 (3) ų

• Z = 4

• Mo Kα radiation

• μ = 0.08 mm⁻¹

• T = 293 (2) K

• 0.20 × 0.19 × 0.17 mm

Data collection

• Bruker SMART APEXII CCD area-detector diffractometer

• Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T _min = 0.98, T _max = 0.99

• 6824 measured reflections

• 1250 independent reflections

• 952 reflections with I > 2σ(I)

• R _int = 0.029

Refinement

• R[F ² > 2σ(F ²)] = 0.039

• wR(F ²) = 0.099

• S = 1.04

• 1250 reflections

• 82 parameters

• H-atom parameters constrained

• Δρ_max = 0.11 e Å⁻³

• Δρ_min = −0.10 e Å⁻³

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: APEX2; 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: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

Cg1 and Cg2 are the centroids of the C4–C7/C7ⁱ/C8 and C4ⁱ–C7ⁱ/C7/C8ⁱ rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1⋯O1i	0.93	2.56	3.385 (2)	148
C3—H3A⋯Cg1ii	0.97	2.76	3.579 (2)	143
C3—H3A⋯Cg2iii	0.97	2.76	3.579 (2)	143

Symmetry codes: (i) ; (ii) ; (iii) .

supplementary crystallographic information

Comment

The molecule of the title compound (Fig. 1) lies on an inversion center, placed at the midpoint of the naphthyl group. Except for H atoms of the methylenes, all the remaining atoms are almost coplanar, with a mean deviation from the least-square plane to be 0.0675 (11) Å. The bond lengths and angles are normal.

No classical hydrogen bonds or π—π interactions are observed. The molecules of the title complex are linked into a three-dimensional framework by a combination of C—H···O and C—H···π(arene) hydrogen bonds (Fig. 2, Table 1). [Cg1 and Cg2 are the centroids of the C4—C7, C7ⁱ, C8 and C4ⁱ—C7ⁱ, C7, C8ⁱ rings, respectively. Symmetry code: (i) -x + 2,-y + 1,-z.]

Experimental

The title compound was obtaind unintentionally as the product of an attempted synthesis of a network complex (Burchell et al., 2006) based on Co^II and 2,6-bis(prop-2-ynyloxy)naphthalene, by evaporation of a methyl alcohol and acetone solution of CoCl₂, NaN₃ and the title molecule, at 298 K. All chemical reagents were obtained commercially from Alfa Aesar Company and used without further purification.

Refinement

All the H atoms could be detected in the difference electron density maps. Nevertheless, they were situated into the idealized position and refined using a riding model. C—H = 0.97 Å for the methylene groups and C—H = 0.93 Å for the remaining H atoms. U_iso(H) = 1.2 U_eq (carrier C) for all the H atoms.

Figures

Fig. 1.

A view of the title compound, showing the atom-labeling scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbritary radii. 'A' labeled atoms are generated by symmetry code -x + 2,-y + 1,-z.

Fig. 2.

The three-dimensional supramolecular framework of the title complound formed by C—H···O and C—H···π(arene) hydrogen bonds.

Crystal data

C16H12O2	F(000) = 496
Mr = 236.26	Dx = 1.230 Mg m−3
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 1948 reflections
a = 7.5783 (11) Å	θ = 2.7–26.2°
b = 8.0295 (12) Å	µ = 0.08 mm−1
c = 20.972 (3) Å	T = 293 K
V = 1276.1 (3) Å3	Block, colourless
Z = 4	0.20 × 0.19 × 0.17 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer	1250 independent reflections
Radiation source: fine-focus sealed tube	952 reflections with I > 2σ(I)
graphite	Rint = 0.029
φ and ω scans	θmax = 26.0°, θmin = 1.9°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −9→9
Tmin = 0.98, Tmax = 0.99	k = −9→9
6824 measured reflections	l = −12→25

Refinement

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)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.099	H-atom parameters constrained
S = 1.04	w = 1/[σ2(Fo2) + (0.0447P)2 + 0.1717P] where P = (Fo2 + 2Fc2)/3
1250 reflections	(Δ/σ)max < 0.001
82 parameters	Δρmax = 0.11 e Å−3
0 restraints	Δρmin = −0.10 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
O1	0.99206 (12)	0.82529 (11)	0.13702 (4)	0.0551 (3)
C1	0.9300 (3)	1.1886 (2)	0.21293 (9)	0.0939 (7)
H1	0.9416	1.2665	0.2455	0.113*
C2	0.9155 (2)	1.09120 (19)	0.17226 (8)	0.0662 (5)
C3	0.8995 (2)	0.97311 (17)	0.12002 (7)	0.0600 (4)
H3A	0.7762	0.9479	0.1123	0.072*
H3B	0.9492	1.0202	0.0814	0.072*
C4	1.00020 (16)	0.70096 (16)	0.09247 (7)	0.0473 (3)
C5	1.09064 (17)	0.55721 (17)	0.11300 (7)	0.0532 (4)
H5	1.1365	0.5528	0.1541	0.064*
C6	1.11120 (18)	0.42548 (16)	0.07337 (7)	0.0525 (4)
H6	1.1699	0.3313	0.0881	0.063*
C7	1.04565 (15)	0.42735 (15)	0.01009 (7)	0.0458 (3)
C8	0.93214 (16)	0.70846 (16)	0.03204 (6)	0.0481 (4)
H8	0.8713	0.8029	0.0187	0.058*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
O1	0.0576 (6)	0.0521 (6)	0.0555 (6)	0.0050 (5)	−0.0035 (5)	0.0030 (5)
C1	0.145 (2)	0.0720 (11)	0.0651 (12)	0.0012 (12)	0.0035 (12)	−0.0069 (10)
C2	0.0822 (11)	0.0563 (9)	0.0601 (10)	0.0052 (8)	0.0045 (8)	0.0045 (8)
C3	0.0666 (10)	0.0526 (8)	0.0609 (9)	0.0060 (7)	−0.0028 (7)	0.0032 (7)
C4	0.0400 (7)	0.0467 (7)	0.0553 (8)	−0.0026 (6)	0.0014 (6)	0.0045 (6)
C5	0.0497 (8)	0.0572 (8)	0.0525 (8)	0.0020 (7)	−0.0072 (6)	0.0088 (7)
C6	0.0476 (7)	0.0494 (7)	0.0603 (9)	0.0081 (6)	−0.0066 (6)	0.0109 (7)
C7	0.0364 (6)	0.0465 (7)	0.0546 (8)	−0.0008 (5)	−0.0014 (6)	0.0103 (6)
C8	0.0424 (7)	0.0446 (7)	0.0575 (9)	0.0042 (6)	−0.0021 (6)	0.0095 (6)

Geometric parameters (Å, °)

O1—C4	1.3687 (16)	C5—C6	1.3541 (18)
O1—C3	1.4240 (16)	C5—H5	0.9300
C1—C2	1.162 (2)	C6—C7	1.417 (2)
C1—H1	0.9300	C6—H6	0.9300
C2—C3	1.454 (2)	C7—C8i	1.4136 (18)
C3—H3A	0.9700	C7—C7i	1.421 (2)
C3—H3B	0.9700	C8—C7i	1.4136 (18)
C4—C8	1.3695 (19)	C8—H8	0.9300
C4—C5	1.4098 (18)
C4—O1—C3	117.34 (10)	C6—C5—C4	120.54 (13)
C2—C1—H1	180.0	C6—C5—H5	119.7
C1—C2—C3	178.25 (18)	C4—C5—H5	119.7
O1—C3—C2	108.28 (12)	C5—C6—C7	121.74 (12)
O1—C3—H3A	110.0	C5—C6—H6	119.1
C2—C3—H3A	110.0	C7—C6—H6	119.1
O1—C3—H3B	110.0	C8i—C7—C6	122.38 (12)
C2—C3—H3B	110.0	C8i—C7—C7i	120.34 (15)
H3A—C3—H3B	108.4	C6—C7—C7i	117.28 (16)
O1—C4—C8	125.63 (12)	C4—C8—C7i	119.98 (12)
O1—C4—C5	114.25 (12)	C4—C8—H8	120.0
C8—C4—C5	120.11 (13)	C7i—C8—H8	120.0
C4—O1—C3—C2	−176.80 (12)	C4—C5—C6—C7	0.9 (2)
C3—O1—C4—C8	2.36 (19)	C5—C6—C7—C8i	179.27 (12)
C3—O1—C4—C5	−178.77 (11)	C5—C6—C7—C7i	−1.0 (2)
O1—C4—C5—C6	−178.91 (12)	O1—C4—C8—C7i	178.05 (12)
C8—C4—C5—C6	0.02 (19)	C5—C4—C8—C7i	−0.75 (19)

Symmetry codes: (i) −x+2, −y+1, −z.

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···O1ii	0.93	2.56	3.385 (2)	148
C3—H3A···Cg1iii	0.97	2.76	3.579 (2)	143
C3—H3A···Cg2iv	0.97	2.76	3.579 (2)	143

Symmetry codes: (ii) −x+2, y+1/2, −z+1/2; (iii) −x+1/2, y−1/2, z; (iv) x−1/2, −y+3/2, −z.