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

Esakkiammal, M.; Selvarani, V.; Neelakantan, M.A.; Silambarasan, V.; Velmurugan, D.

doi:10.1107/S1600536812031637

organic compounds

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ISSN: 2056-9890

Volume 68| Part 8| August 2012| Page o2465

https://doi.org/10.1107/S1600536812031637

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

M. Esakkiammal,^a V. Selvarani,^a M. A. Neelakantan,^a ^* V. Silambarasan ^b and D. Velmurugan ^b

^aChemistry Research Centre, National Engineering College, K. R. Nagar, Kovilpatti 628 503, India, and ^bCAS in Crystallography and Biophysics, University of Madras, Guindy Campus, Chennai 25, India
^*Correspondence e-mail: drmaneelakantan@gmail.com

(Received 29 June 2012; accepted 11 July 2012; online 18 July 2012)

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, P 2₁ /n
a = 4.9219 (2) Å
b = 16.8705 (7) Å
c = 13.4326 (6) Å
β = 98.236 (3)°
V = 1103.87 (8) Å³
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[F² > 2σ(F²)] = 0.039
wR(F²) = 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

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) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

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 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536812031637/bt5961sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812031637/bt5961Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536812031637/bt5961Isup3.cml

checkCIF report

Comment top

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).

Related literature top

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 top

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.

Structure description top

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).

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: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top

	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.

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

Crystal data top

C₁₃H₁₀O₃	F(000) = 448
M_r = 214.21	D_x = 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 top

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

Refinement top

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(F_o²) + (0.0546P)² + 0.1741P] where P = (F_o² + 2F_c²)/3
S = 1.04	(Δ/σ)_max < 0.001
2754 reflections	Δρ_max = 0.25 e Å⁻³
154 parameters	Δρ_min = −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)

Crystal data top

C₁₃H₁₀O₃	V = 1103.87 (8) Å³
M_r = 214.21	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 4.9219 (2) Å	µ = 0.09 mm⁻¹
b = 16.8705 (7) Å	T = 293 K
c = 13.4326 (6) Å	0.20 × 0.20 × 0.20 mm
β = 98.236 (3)°

Data collection top

Bruker SMART APEXII area-detector diffractometer	2754 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2008)	2177 reflections with I > 2σ(I)
T_min = 0.982, T_max = 0.982	R_int = 0.025
10446 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.039	0 restraints
wR(F²) = 0.113	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	Δρ_max = 0.25 e Å⁻³
2754 reflections	Δρ_min = −0.16 e Å⁻³
154 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
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 (Å²) top

	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) top

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) top

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.

Experimental details

Crystal data
Chemical formula	C₁₃H₁₀O₃
M_r	214.21
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	293
a, b, c (Å)	4.9219 (2), 16.8705 (7), 13.4326 (6)
β (°)	98.236 (3)
V (Å³)	1103.87 (8)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.20 × 0.20 × 0.20

Data collection
Diffractometer	Bruker SMART APEXII area-detector
Absorption correction	Multi-scan (SADABS; Bruker, 2008)
T_min, T_max	0.982, 0.982
No. of measured, independent and observed [I > 2σ(I)] reflections	10446, 2754, 2177
R_int	0.025
(sin θ/λ)_max (Å⁻¹)	0.670

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.113, 1.04
No. of reflections	2754
No. of parameters	154
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.25, −0.16

Computer programs: APEX2 (Bruker, 2008), SAINT (Bruker, 2008), SHELXS97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6···O1ⁱ	0.93	2.48	3.3616 (14)	158.5

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

Acknowledgements

The authors thank TBI Consultancy, University of Madras, India, for the data collection.

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