2-[(3-Oxo-1-benzofuran-6-yl)­oxy]aceto­nitrile

Kinfe, H.H.; Belay, Y.H.; Phasha, Z.H.

doi:10.1107/S1600536812048441

organic compounds

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Volume 69| Part 1| January 2013| Page o74

https://doi.org/10.1107/S1600536812048441

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2-[(3-Oxo-1-benzofuran-6-yl)oxy]acetonitrile

Henok H. Kinfe,^a Yonas H. Belay ^a and Zanele H Phasha ^a ^*

^aResearch Center for Synthesis and Catalysis, Department of Chemistry, University of Johannesburg (APK Campus), PO Box 524, Auckland Park, Johannesburg, 2006, South Africa
^*Correspondence e-mail: zhphasha@uj.ac.za

(Received 31 October 2012; accepted 26 November 2012; online 12 December 2012)

The molecule of the title compound, C₁₁H₈O₃, is essentially planar [r.m.s. deviation = 0.025 (2) Å]. In the crystal, molecules are stacked along [110] but no short π–π contacts are observed. Weak C—H⋯O interactions link the molecules into chains along [101].

Related literature

For background to the development of hybrid drug candidates against tuberculosis, malaria and cancer, see: Morphy et al. (2004 ). For the synthesis of the title compound, see: Hoogendoorn et al. (2011 ).

Experimental

Crystal data

C₁₁H₈O₃
M_r = 188.17
Monoclinic, C 2/c
a = 16.8785 (5) Å
b = 5.4202 (2) Å
c = 19.6107 (6) Å
β = 91.469 (2)°
V = 1793.49 (10) Å³
Z = 8
Cu Kα radiation
μ = 0.85 mm⁻¹
T = 100 K
0.19 × 0.15 × 0.11 mm

Data collection

Bruker APEX DUO 4K CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2008 ) T_min = 0.855, T_max = 0.912
10685 measured reflections
1545 independent reflections
1451 reflections with I > 2σ(I)
R_int = 0.026

Refinement

R[F² > 2σ(F²)] = 0.030
wR(F²) = 0.076
S = 1.04
1545 reflections
127 parameters
H-atom parameters constrained
Δρ_max = 0.18 e Å⁻³
Δρ_min = −0.13 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C11—H11⋯O1ⁱ	0.95	2.24	3.1676 (15)	165
Symmetry code: (i) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2011 ); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT and XPREP (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ); software used to prepare material for publication: WinGX (Farrugia, 2012).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536812048441/ld2084sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812048441/ld2084Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536812048441/ld2084Isup3.cml

checkCIF report

Comment top

As a continuation of our progress in the development of hybrid drug candidates against tuberculosis, malaria and cancer (Morphy et al., 2004), the title compound was identified as a promising starting material. The compound was synthesized by reaction of 6–Hydroxy–benzofuran–3–one with propargyl bromide at comparatively low temperature in the presence of potassium carbonate (Hoogendoorn et al., 2011). To confirm the effect of temperature on the reaction, herein we report the single-crystal structure of the title Compound.

The molecular structure of the compound is shown in Figure 1. The molecule is essentially planar (r.m.s. deviation = 0.025 (2) Å). In the crystal the molecules are linked by infinite one-dimensional C–H···O hydrogen bonding into chains that propagate in the [101] direction (Table 1, Figure 2).

Related literature top

For background to the development of hybrid drug candidates against tuberculosis, malaria and cancer, see: Morphy et al. (2004). For the synthesis of the title compound, see: Hoogendoorn et al. (2011).

Experimental top

A solution of 6–Hydroxy–benzofuran–3–one (1 g, 6.66 mm) in dry acetone was treated with potassium carbonate (1.3 g, 9.32 mm). The reaction mixture was heated at a temperature of 40 – 50 °C for about 30 minutes and then propargyl bromide (1.6 ml, 14.65 mm) was added to it. The combined solution was stirred for about 2.5 h and concentrated under vacuum. The residue was diluted with water and extracted three times with ethyl acetate. The combined organic layer was washed with brine and water and dried over anhydrous magnesium sulfate. After that filtered and the filtrate solid product was recrystalized from ethyl acetate and hexane to afford 80% of the target compound as yellow crystal.

Analytical data: m.p: 112 – 114 oC; ¹H NMR (CDCl3, 400 MHZ): d 7.56 (d, 1H), 6.69 – 6.64 (m, 2H), 4.74 (s, 2H), 4.60 (s, 2H), 2.57(s, 1H); ¹³C NMR (CDCl3, 400 MHZ): d 197.6, 176.1, 165.8, 125.2, 115.0, 111.9, 97.7, 75.2, 56.2.

Structure description top

For background to the development of hybrid drug candidates against tuberculosis, malaria and cancer, see: Morphy et al. (2004). For the synthesis of the title compound, see: Hoogendoorn et al. (2011).

Computing details top

Data collection: APEX2 (Bruker, 2011); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT and XPREP (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: WinGX (Farrugia, 2012).

Figures top

	Fig. 1. Crystal structure of the title compound with labeling and displacement ellipsoids drawn at the 50% probability level.
	Fig. 2. A portion of the crystal packing viewed approximately down the b axis. Dotted lines show intermolecular C–H···O interactions.

2-[(3-Oxo-1-benzofuran-6-yl)oxy]acetonitrile top

Crystal data top

C₁₁H₈O₃	F(000) = 784
M_r = 188.17	D_x = 1.394 Mg m⁻³
Monoclinic, C2/c	Cu Kα radiation, λ = 1.54178 Å
Hall symbol: -C 2yc	Cell parameters from 6173 reflections
a = 16.8785 (5) Å	θ = 6.8–65.7°
b = 5.4202 (2) Å	µ = 0.85 mm⁻¹
c = 19.6107 (6) Å	T = 100 K
β = 91.469 (2)°	Cube, yellow
V = 1793.49 (10) Å³	0.19 × 0.15 × 0.11 mm
Z = 8

Data collection top

Bruker APEX DUO 4K CCD diffractometer	1545 independent reflections
Incoatec Quazar Multilayer Mirror monochromator	1451 reflections with I > 2σ(I)
Detector resolution: 8.4 pixels mm^-1	R_int = 0.026
φ and ω scans	θ_max = 66.2°, θ_min = 6.8°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −19→18
T_min = 0.855, T_max = 0.912	k = −6→6
10685 measured reflections	l = −22→23

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)] = 0.030	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.076	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0326P)² + 1.2605P] where P = (F_o² + 2F_c²)/3
1545 reflections	(Δ/σ)_max < 0.001
127 parameters	Δρ_max = 0.18 e Å⁻³
0 restraints	Δρ_min = −0.13 e Å⁻³

Crystal data top

C₁₁H₈O₃	V = 1793.49 (10) Å³
M_r = 188.17	Z = 8
Monoclinic, C2/c	Cu Kα radiation
a = 16.8785 (5) Å	µ = 0.85 mm⁻¹
b = 5.4202 (2) Å	T = 100 K
c = 19.6107 (6) Å	0.19 × 0.15 × 0.11 mm
β = 91.469 (2)°

Data collection top

Bruker APEX DUO 4K CCD diffractometer	1545 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2008)	1451 reflections with I > 2σ(I)
T_min = 0.855, T_max = 0.912	R_int = 0.026
10685 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.030	0 restraints
wR(F²) = 0.076	H-atom parameters constrained
S = 1.04	Δρ_max = 0.18 e Å⁻³
1545 reflections	Δρ_min = −0.13 e Å⁻³
127 parameters

Special details top

Experimental. The intensity data was collected on a Bruker Apex DUO 4 K CCD diffractometer using an exposure time of 5 s/frame. A total of 2405 frames were collected with a frame width of 1° covering up to θ = 66.21° with 98.0% completeness accomplished.

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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
C1	0.33402 (7)	−0.0134 (2)	0.16647 (6)	0.0301 (3)
H1A	0.3908	0.0177	0.1582	0.036*
H1B	0.33	−0.1366	0.2035	0.036*
C2	0.29260 (7)	0.2247 (2)	0.18581 (6)	0.0275 (3)
C3	0.22985 (7)	0.2558 (2)	0.13478 (6)	0.0258 (3)
C4	0.23445 (6)	0.0603 (2)	0.08957 (6)	0.0252 (3)
C5	0.18383 (6)	0.0313 (2)	0.03363 (6)	0.0256 (3)
H5	0.188	−0.1042	0.0032	0.031*
C6	0.12641 (6)	0.2130 (2)	0.02471 (6)	0.0253 (3)
C7	0.12021 (7)	0.4147 (2)	0.06963 (6)	0.0275 (3)
H7	0.0802	0.5354	0.0618	0.033*
C8	0.17159 (7)	0.4373 (2)	0.12444 (6)	0.0277 (3)
H8A	0.1678	0.5731	0.1548	0.033*
C9	0.07331 (7)	0.0050 (2)	−0.07344 (6)	0.0281 (3)
H9A	0.0623	−0.1496	−0.0485	0.034*
H9B	0.1263	−0.009	−0.0936	0.034*
C10	0.01328 (7)	0.0443 (2)	−0.12691 (6)	0.0295 (3)
C11	−0.03534 (7)	0.0700 (2)	−0.17094 (6)	0.0340 (3)
H11	−0.0744	0.0906	−0.2063	0.041*
O1	0.31189 (5)	0.35618 (16)	0.23405 (4)	0.0328 (2)
O2	0.29422 (5)	−0.10199 (15)	0.10488 (4)	0.0296 (2)
O3	0.07151 (5)	0.21196 (15)	−0.02749 (4)	0.0289 (2)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0269 (6)	0.0336 (7)	0.0295 (6)	0.0015 (5)	−0.0041 (5)	0.0012 (5)
C2	0.0270 (6)	0.0289 (6)	0.0265 (6)	−0.0038 (5)	0.0012 (5)	0.0022 (5)
C3	0.0264 (6)	0.0253 (6)	0.0257 (6)	−0.0028 (5)	0.0015 (4)	0.0019 (5)
C4	0.0226 (5)	0.0245 (6)	0.0285 (6)	0.0000 (4)	0.0032 (4)	0.0043 (5)
C5	0.0262 (6)	0.0246 (6)	0.0261 (6)	−0.0008 (5)	0.0029 (4)	−0.0001 (5)
C6	0.0243 (6)	0.0269 (6)	0.0248 (6)	−0.0023 (5)	0.0010 (4)	0.0040 (5)
C7	0.0288 (6)	0.0236 (6)	0.0303 (6)	0.0022 (5)	−0.0001 (5)	0.0025 (5)
C8	0.0313 (6)	0.0232 (6)	0.0288 (6)	−0.0003 (5)	0.0018 (5)	−0.0001 (5)
C9	0.0276 (6)	0.0295 (6)	0.0273 (6)	0.0010 (5)	0.0016 (5)	−0.0016 (5)
C10	0.0279 (6)	0.0311 (6)	0.0296 (6)	−0.0003 (5)	0.0047 (5)	−0.0010 (5)
C11	0.0297 (6)	0.0418 (7)	0.0304 (6)	0.0012 (5)	−0.0018 (5)	−0.0021 (5)
O1	0.0324 (5)	0.0349 (5)	0.0307 (5)	−0.0012 (4)	−0.0048 (3)	−0.0026 (4)
O2	0.0273 (4)	0.0297 (5)	0.0316 (4)	0.0052 (3)	−0.0036 (3)	−0.0019 (3)
O3	0.0288 (4)	0.0298 (4)	0.0278 (4)	0.0034 (3)	−0.0046 (3)	−0.0026 (3)

Geometric parameters (Å, º) top

C1—O2	1.4489 (14)	C6—O3	1.3631 (13)
C1—C2	1.5206 (17)	C6—C7	1.4095 (16)
C1—H1A	0.99	C7—C8	1.3691 (17)
C1—H1B	0.99	C7—H7	0.95
C2—O1	1.2220 (14)	C8—H8A	0.95
C2—C3	1.4481 (16)	C9—O3	1.4396 (14)
C3—C4	1.3851 (16)	C9—C10	1.4551 (16)
C3—C8	1.4021 (17)	C9—H9A	0.99
C4—O2	1.3661 (14)	C9—H9B	0.99
C4—C5	1.3822 (16)	C10—C11	1.1840 (17)
C5—C6	1.3896 (16)	C11—H11	0.95
C5—H5	0.95

O2—C1—C2	106.42 (9)	O3—C6—C7	114.37 (10)
O2—C1—H1A	110.4	C5—C6—C7	122.25 (10)
C2—C1—H1A	110.4	C8—C7—C6	120.30 (11)
O2—C1—H1B	110.4	C8—C7—H7	119.8
C2—C1—H1B	110.4	C6—C7—H7	119.8
H1A—C1—H1B	108.6	C7—C8—C3	118.58 (11)
O1—C2—C3	129.99 (11)	C7—C8—H8A	120.7
O1—C2—C1	124.96 (11)	C3—C8—H8A	120.7
C3—C2—C1	105.04 (9)	O3—C9—C10	108.15 (9)
C4—C3—C8	119.66 (10)	O3—C9—H9A	110.1
C4—C3—C2	107.53 (10)	C10—C9—H9A	110.1
C8—C3—C2	132.81 (11)	O3—C9—H9B	110.1
O2—C4—C5	122.62 (10)	C10—C9—H9B	110.1
O2—C4—C3	113.91 (10)	H9A—C9—H9B	108.4
C5—C4—C3	123.47 (11)	C11—C10—C9	178.27 (13)
C4—C5—C6	115.74 (11)	C10—C11—H11	180
C4—C5—H5	122.1	C4—O2—C1	107.09 (9)
C6—C5—H5	122.1	C6—O3—C9	116.64 (9)
O3—C6—C5	123.37 (10)

O2—C1—C2—O1	−177.45 (10)	C4—C5—C6—C7	0.20 (16)
O2—C1—C2—C3	1.34 (12)	O3—C6—C7—C8	179.74 (10)
O1—C2—C3—C4	177.78 (12)	C5—C6—C7—C8	−0.07 (17)
C1—C2—C3—C4	−0.93 (12)	C6—C7—C8—C3	−0.23 (17)
O1—C2—C3—C8	−1.2 (2)	C4—C3—C8—C7	0.40 (16)
C1—C2—C3—C8	−179.91 (12)	C2—C3—C8—C7	179.28 (11)
C8—C3—C4—O2	179.30 (10)	C5—C4—O2—C1	−179.70 (10)
C2—C3—C4—O2	0.16 (13)	C3—C4—O2—C1	0.73 (12)
C8—C3—C4—C5	−0.27 (17)	C2—C1—O2—C4	−1.26 (12)
C2—C3—C4—C5	−179.41 (10)	C5—C6—O3—C9	2.07 (15)
O2—C4—C5—C6	−179.56 (10)	C7—C6—O3—C9	−177.74 (9)
C3—C4—C5—C6	−0.03 (16)	C10—C9—O3—C6	−177.25 (9)
C4—C5—C6—O3	−179.59 (10)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C11—H11···O1ⁱ	0.95	2.24	3.1676 (15)	165

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

Experimental details

Crystal data
Chemical formula	C₁₁H₈O₃
M_r	188.17
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	100
a, b, c (Å)	16.8785 (5), 5.4202 (2), 19.6107 (6)
β (°)	91.469 (2)
V (Å³)	1793.49 (10)
Z	8
Radiation type	Cu Kα
µ (mm⁻¹)	0.85
Crystal size (mm)	0.19 × 0.15 × 0.11

Data collection
Diffractometer	Bruker APEX DUO 4K CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2008)
T_min, T_max	0.855, 0.912
No. of measured, independent and observed [I > 2σ(I)] reflections	10685, 1545, 1451
R_int	0.026
(sin θ/λ)_max (Å⁻¹)	0.593

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.030, 0.076, 1.04
No. of reflections	1545
No. of parameters	127
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.18, −0.13

Computer programs: APEX2 (Bruker, 2011), SAINT (Bruker, 2008), SAINT and XPREP (Bruker, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 2012), WinGX (Farrugia, 2012).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C11—H11···O1ⁱ	0.95	2.24	3.1676 (15)	164.6

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

Acknowledgements

Support by the research funds of the University of Johannesburg is gratefully acknowledged.

References

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