2,4-Bis[(prop-2-yn­yl)­oxy]benzaldehyde

Abstract

In the title compound, C₁₃H₁₀O₃, two prop-2-yn­yloxy groups are attached to the benzaldehyde ring at positions 2 and 6. The crystal packing features C—H⋯O inter­actions.

Related literature  

For the biological activity of benzaldehyde derivatives, see: Zhao et al. (2007 ▶). For related literature, see: Delogu et al. (2010 ▶); Ley & Bertram (2001 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶).

Experimental  

Crystal data  

• C₁₃H₁₀O₃

• M _r = 214.21

• Monoclinic,

• a = 4.9219 (2) Å

• b = 16.8705 (7) Å

• c = 13.4326 (6) Å

• β = 98.236 (3)°

• V = 1103.87 (8) ų

• Z = 4

• Mo Kα radiation

• μ = 0.09 mm⁻¹

• T = 293 K

• 0.20 × 0.20 × 0.20 mm

Data collection  

• Bruker SMART APEXII area-detector diffractometer

• Absorption correction: multi-scan (SADABS; Bruker, 2008 ▶) T _min = 0.982, T _max = 0.982

• 10446 measured reflections

• 2754 independent reflections

• 2177 reflections with I > 2σ(I)

• R _int = 0.025

Refinement  

• R[F ² > 2σ(F ²)] = 0.039

• wR(F ²) = 0.113

• S = 1.04

• 2754 reflections

• 154 parameters

• H atoms treated by a mixture of independent and constrained refinement

• Δρ_max = 0.25 e Å⁻³

• Δρ_min = −0.16 e Å⁻³

Data collection: APEX2 (Bruker, 2008 ▶); cell refinement: APEX2; data reduction: SAINT (Bruker, 2008 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ▶).

Supplementary Material

Supplementary material file. DOI: 10.1107/S1600536812031637/bt5961Isup3.cml

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

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C6—H6⋯O1i	0.93	2.48	3.3616 (14)	159

Symmetry code: (i) .

supplementary crystallographic information

Comment

The Schiff base derived from amines and substitued benzaldehydes exhibit antibacterial, anticancer and antitumour activities (Zhao et al. (2007)). Several benzaldoximes, benzaldehyde-O-ethyloximes, and acetophenonoximes were synthesized and evaluated as tyrosinase inhibitors (Ley & Bertram (2001)). The bis-salicylaldehydes exhibited greater inhibitory activity than salicylaldehyde (Delogu et al.(2010)).

The ORTEP plot of the molecule is shown in Fig. 1. The dihedral angles of phenyl ring (C2—C7) attached to prop-2-yn-1-yloxy group at 2, 6-positions (O2/C8/C9/C10) & (O3/C11/C12/C13) are 82.3 (1)° & 71.4 (1)°, respectively. The prop-2-yn-1-yloxy group is in an extended conformation which can be seen from torsion angles O2/C8/C9/C10= -177.0 (10)° and O3/C11/C12/C13= 166 (6)°, respectively.

The crystal packing includes an inter-molecular interaction between a terminal ethynyl H atom and an ethynyl group on a glide-related molecule and another interaction between an O-atom-linked methylene H and an ethynyl group of a different glide-related molecule.

The packing of the molecules viewed down a axis is shown in Fig. 2. The molecules are stabilized by C—H···π and bifurcated C—H···O types of intra and intermolecular interactions, which form a dimer C8 chain running along the a axis (Bernstein et al., 1995).

Experimental

2,4-dihydroxybenzaldehyde (10 mmol), 3-bromopropyne (20 mmol) and potassium carbonate (15 mmol) were suspended in acetonitrile (40 ml) and refluxed for 30 h in presence of KI (0.1 g) as catalyst. The reaction mixture was filtered while hot to remove insoluble impurities, neutralized with dil.HCl (3 N) and extracted with chloroform and dried with Na₂SO₄. The extracts were concentrated to obtain a brown solid which was then purified by column chromatography over SiO₂ by eluting a mixture of 4% ethyl acetate with n-hexane. Evaporation of the purified extract yielded 2, 4-dipropynoxybenzaldehyde in the form of pure white solid. Yield: 85%. Crystals suitable for X-ray analysis were obtained by slow evaporation method.

Refinement

H atoms were positioned geometrically (C–H = 0.93–0.97 Å) and allowed to ride on their parent atoms, with U_iso(H) = 1.2U_eq(C).

Figures

Fig. 1.

The molecular structure of the title compound, showing the atomic numbering and displacement ellipsoids drawn at 30% probability level.

Fig. 2.

The crystal packing of the molecules viewed down a axis.

Crystal data

C13H10O3	F(000) = 448
Mr = 214.21	Dx = 1.289 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2754 reflections
a = 4.9219 (2) Å	θ = 2.0–28.4°
b = 16.8705 (7) Å	µ = 0.09 mm−1
c = 13.4326 (6) Å	T = 293 K
β = 98.236 (3)°	Block, colourless
V = 1103.87 (8) Å3	0.20 × 0.20 × 0.20 mm
Z = 4

Data collection

Bruker SMART APEXII area-detector diffractometer	2754 independent reflections
Radiation source: fine-focus sealed tube	2177 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.025
ω and φ scans	θmax = 28.4°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −6→6
Tmin = 0.982, Tmax = 0.982	k = −22→22
10446 measured reflections	l = −16→17

Refinement

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.039	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.113	w = 1/[σ2(Fo2) + (0.0546P)2 + 0.1741P] where P = (Fo2 + 2Fc2)/3
S = 1.04	(Δ/σ)max < 0.001
2754 reflections	Δρmax = 0.25 e Å−3
154 parameters	Δρmin = −0.16 e Å−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.035 (4)

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
O2	0.05286 (17)	0.31557 (5)	0.65108 (6)	0.0445 (2)
O3	0.68295 (18)	0.16361 (5)	0.49674 (7)	0.0501 (3)
O1	0.0285 (2)	0.15987 (5)	0.87280 (7)	0.0554 (3)
C6	0.3759 (2)	0.23786 (7)	0.57231 (9)	0.0396 (3)
H6	0.3799	0.2751	0.5214	0.047*
C2	0.2097 (2)	0.19456 (6)	0.72497 (8)	0.0376 (3)
C3	0.3673 (2)	0.12642 (7)	0.72331 (9)	0.0430 (3)
H3	0.3642	0.0890	0.7739	0.052*
C4	0.5284 (2)	0.11234 (7)	0.64902 (9)	0.0447 (3)
H4	0.6320	0.0662	0.6492	0.054*
C9	−0.1318 (3)	0.43691 (7)	0.59180 (9)	0.0447 (3)
C7	0.2148 (2)	0.25048 (6)	0.64716 (8)	0.0361 (2)
C5	0.5317 (2)	0.16901 (7)	0.57387 (9)	0.0398 (3)
C12	0.9705 (3)	0.09766 (8)	0.40030 (11)	0.0554 (3)
C1	0.0455 (3)	0.20717 (7)	0.80598 (9)	0.0459 (3)
H1	−0.0521	0.2544	0.8063	0.055*
C10	−0.2730 (3)	0.49054 (8)	0.60585 (11)	0.0539 (3)
C11	0.8314 (3)	0.09202 (8)	0.48871 (10)	0.0495 (3)
H11A	0.7066	0.0472	0.4822	0.059*
H11B	0.9646	0.0844	0.5485	0.059*
C8	0.0455 (3)	0.37140 (7)	0.57073 (9)	0.0453 (3)
H8A	−0.0264	0.3465	0.5073	0.054*
H8B	0.2290	0.3907	0.5663	0.054*
C13	1.0861 (4)	0.10046 (11)	0.33041 (14)	0.0791 (5)
H10	−0.379 (4)	0.5352 (11)	0.6156 (14)	0.087 (6)*
H13	1.176 (5)	0.1042 (13)	0.2780 (18)	0.114 (7)*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
O2	0.0548 (5)	0.0381 (4)	0.0443 (5)	0.0099 (4)	0.0197 (4)	0.0088 (3)
O3	0.0517 (5)	0.0511 (5)	0.0520 (5)	0.0140 (4)	0.0224 (4)	0.0074 (4)
O1	0.0824 (7)	0.0460 (5)	0.0421 (5)	−0.0069 (4)	0.0231 (5)	0.0041 (4)
C6	0.0420 (6)	0.0392 (6)	0.0391 (6)	0.0024 (5)	0.0107 (5)	0.0070 (5)
C2	0.0419 (6)	0.0363 (6)	0.0351 (5)	−0.0024 (4)	0.0070 (4)	0.0019 (4)
C3	0.0493 (7)	0.0398 (6)	0.0400 (6)	0.0020 (5)	0.0068 (5)	0.0085 (5)
C4	0.0453 (6)	0.0406 (6)	0.0484 (7)	0.0091 (5)	0.0081 (5)	0.0052 (5)
C9	0.0512 (7)	0.0403 (6)	0.0432 (6)	0.0027 (5)	0.0090 (5)	0.0061 (5)
C7	0.0376 (5)	0.0335 (5)	0.0377 (6)	0.0004 (4)	0.0072 (4)	0.0020 (4)
C5	0.0361 (5)	0.0439 (6)	0.0402 (6)	0.0021 (4)	0.0089 (4)	0.0009 (5)
C12	0.0588 (8)	0.0540 (8)	0.0555 (8)	0.0105 (6)	0.0152 (6)	−0.0073 (6)
C1	0.0597 (7)	0.0398 (6)	0.0409 (6)	−0.0003 (5)	0.0158 (5)	0.0017 (5)
C10	0.0645 (8)	0.0434 (7)	0.0551 (8)	0.0106 (6)	0.0129 (6)	0.0036 (6)
C11	0.0487 (7)	0.0486 (7)	0.0533 (7)	0.0094 (5)	0.0146 (6)	−0.0023 (6)
C8	0.0520 (7)	0.0425 (6)	0.0437 (6)	0.0085 (5)	0.0147 (5)	0.0105 (5)
C13	0.0998 (13)	0.0800 (12)	0.0659 (10)	0.0122 (10)	0.0402 (10)	−0.0076 (9)

Geometric parameters (Å, º)

O2—C7	1.3622 (13)	C4—C5	1.3922 (16)
O2—C8	1.4292 (14)	C4—H4	0.9300
O3—C5	1.3626 (13)	C9—C10	1.1722 (18)
O3—C11	1.4235 (14)	C9—C8	1.4608 (16)
O1—C1	1.2127 (14)	C12—C13	1.166 (2)
C6—C7	1.3832 (15)	C12—C11	1.4565 (18)
C6—C5	1.3905 (15)	C1—H1	0.9300
C6—H6	0.9300	C10—H10	0.935 (19)
C2—C3	1.3886 (16)	C11—H11A	0.9700
C2—C7	1.4109 (15)	C11—H11B	0.9700
C2—C1	1.4611 (15)	C8—H8A	0.9700
C3—C4	1.3814 (17)	C8—H8B	0.9700
C3—H3	0.9300	C13—H13	0.89 (2)
C7—O2—C8	116.99 (8)	C6—C5—C4	121.39 (10)
C5—O3—C11	117.16 (9)	C13—C12—C11	178.21 (17)
C7—C6—C5	119.35 (10)	O1—C1—C2	124.02 (11)
C7—C6—H6	120.3	O1—C1—H1	118.0
C5—C6—H6	120.3	C2—C1—H1	118.0
C3—C2—C7	118.20 (10)	C9—C10—H10	176.8 (12)
C3—C2—C1	120.16 (10)	O3—C11—C12	108.22 (11)
C7—C2—C1	121.65 (10)	O3—C11—H11A	110.1
C4—C3—C2	122.26 (11)	C12—C11—H11A	110.1
C4—C3—H3	118.9	O3—C11—H11B	110.1
C2—C3—H3	118.9	C12—C11—H11B	110.1
C3—C4—C5	118.25 (11)	H11A—C11—H11B	108.4
C3—C4—H4	120.9	O2—C8—C9	107.67 (9)
C5—C4—H4	120.9	O2—C8—H8A	110.2
C10—C9—C8	177.88 (13)	C9—C8—H8A	110.2
O2—C7—C6	123.48 (9)	O2—C8—H8B	110.2
O2—C7—C2	115.97 (9)	C9—C8—H8B	110.2
C6—C7—C2	120.55 (10)	H8A—C8—H8B	108.5
O3—C5—C6	113.87 (10)	C12—C13—H13	178.1 (16)
O3—C5—C4	124.74 (10)
C7—C2—C3—C4	0.52 (18)	C11—O3—C5—C4	4.98 (17)
C1—C2—C3—C4	−179.18 (11)	C7—C6—C5—O3	−179.57 (10)
C2—C3—C4—C5	0.20 (19)	C7—C6—C5—C4	0.22 (18)
C8—O2—C7—C6	2.28 (16)	C3—C4—C5—O3	179.19 (11)
C8—O2—C7—C2	−177.39 (10)	C3—C4—C5—C6	−0.58 (18)
C5—C6—C7—O2	−179.13 (10)	C3—C2—C1—O1	−2.48 (19)
C5—C6—C7—C2	0.53 (17)	C7—C2—C1—O1	177.83 (12)
C3—C2—C7—O2	178.80 (10)	C5—O3—C11—C12	178.25 (10)
C1—C2—C7—O2	−1.51 (16)	C13—C12—C11—O3	166 (6)
C3—C2—C7—C6	−0.89 (16)	C7—O2—C8—C9	−178.20 (10)
C1—C2—C7—C6	178.81 (11)	C10—C9—C8—O2	−177 (100)
C11—O3—C5—C6	−175.24 (11)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6···O1i	0.93	2.48	3.3616 (14)	159

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