4-(Furan-2-ylmeth­oxy)benzene-1,2-dicarbonitrile

Tuncer, H.; Görgülü, A.O.; Hökelek, T.

doi:10.1107/S1600536811053669

organic compounds

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Volume 68| Part 1| January 2012| Page o153

doi:10.1107/S1600536811053669

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4-(Furan-2-ylmethoxy)benzene-1,2-dicarbonitrile

Hülya Tuncer,^a Ahmet Orhan Görgülü ^a and Tuncer Hökelek ^b ^*

^aFırat University, Department of Chemistry, 23169 Elazığ, Turkey, and ^bHacettepe University, Department of Physics, 06800 Beytepe, Ankara, Turkey
^*Correspondence e-mail: merzifon@hacettepe.edu.tr

(Received 9 December 2011; accepted 13 December 2011; online 17 December 2011)

In the title compound, C₁₃H₈N₂O₂, prepared from furfuryl alcohol and 4-nitrophthalonitrile in the presence of potassium carbonate in dimethylformamide, the furan and benzene rings are oriented at a dihedral angle of 53.45 (9)°. In the crystal, weak C—H⋯O and C—H⋯N hydrogen bonds link the molecules into a three-dimensional network.

Related literature

For the use of phthalonitriles in the preparation of symmetrically and unsymmetrically substituted phthalocyanine complexes, see: Leznoff & Lever (1996 ). For the fundamental optical and electronic properties of phthalocyanines and their applications, see: McKeown (1998 ). For bond-length data, see: Allen et al. (1987 ).

Experimental

Crystal data

C₁₃H₈N₂O₂
M_r = 224.21
Orthorhombic, P 2₁ 2₁ 2₁
a = 3.9681 (2) Å
b = 14.3029 (3) Å
c = 19.2100 (5) Å
V = 1090.27 (7) Å³
Z = 4
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 100 K
0.15 × 0.08 × 0.06 mm

Data collection

Bruker Kappa APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2007 ) T_min = 0.986, T_max = 0.994
6208 measured reflections
2615 independent reflections
1709 reflections with I > 2σ(I)
R_int = 0.047

Refinement

R[F² > 2σ(F²)] = 0.048
wR(F²) = 0.141
S = 1.06
2615 reflections
154 parameters
H-atom parameters constrained
Δρ_max = 0.21 e Å⁻³
Δρ_min = −0.23 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C7—H7⋯N1ⁱ	0.95	2.45	3.369 (4)	162
C10—H10⋯O2ⁱⁱ	0.95	2.42	3.233 (3)	144
Symmetry codes: (i) $[-x+1, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (ii) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+1]$ .

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; 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, 1997 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ) and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811053669/bq2327sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811053669/bq2327Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811053669/bq2327Isup3.cml

checkCIF report

Comment top

Phthalonitriles are used for preparing symmetrically and unsymmetrically substituted phthalocyanine complexes (Leznoff & Lever, 1996). Phthalocyanines have currently been the topic of research because of their wide application fields, such as thin film fabrication, organic pigments, chemical sensors, electrochromic display devices, molecular epitaxic deposition and composites, liquid crystals, photovoltaic cells self-assembled materials. The fundamental optical and electronic properties of these materials are explained and their potential in non-linear optics, optical data storage, electronic sensors, xerography, solar energy conversion, nuclear chemistry, molecular magnetism, electrochromic displays and heterogeneous catalysis is evaluated by McKeown (1998). The title compound was synthesized and its crystal structure is reported herein.

In the title compound, (Fig. 1), the bond lengths are close to standard values (Allen et al., 1987). The furan [A (O2/C1—C4)] and the benzene [B (C6—C11)] rings are oriented at a dihedral angle of 53.45 (9)°. Atoms O1 and C5 are 1.094 (2) and -0.089 (3) Å away from the plane of ring A, while atoms O1, N1, N2, C5, C12 and C13 are -0.023 (2), -0.007 (3), 0.075 (3), 0.193 (3), 0.029 (3) and -0.003 (3) Å away from the plane of ring B, respectively. So, they are almost co-planar with the adjacent benzene ring.

In the crystal, weak intermolecular C—H···O and C—H···N hydrogen bonds (Table 1) link the molecules into a three-dimensional network (Fig. 2).

Related literature top

For the use of phthalonitriles in the preparation of symmetrically and unsymmetrically substituted phthalocyanine complexes, see: Leznoff & Lever (1996). For the fundamental optical and electronic properties of phthalocyanines and their applications, see: McKeown (1998). For bond-length data, see: Allen et al. (1987).

Experimental top

For the preparation of the title compound, furfuryl alcohol (1.49 g, 15.2 mmol) and 4-nitrophthalonitrile (2.64 g, 15.2 mmol) were heated at 358 K in dry DMF (15 ml) with stirring under argon atmosphere. Then, dry fine powdered potassium carbonate (6.00 g, 43.47 mmol) was added in portions (14 × 3.1 mmol) every 10 min. The mixture was heated for a further 24 h. After cooling, the mixture was added into ice-water (200 g). The product was filtered off and washed with NaOH solution (10%) and water until the filtrate was neutral. Recrystallization from ethanol gave a white product (yield: 1.25 g, 55.85%). Single crystals suitable for X-ray diffraction mesurement was obtained by slow evaporation of the solution in ethanol (m.p. 385-387 K).

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); 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, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999) and PLATON (Spek, 2009).

Figures top

	Fig. 1. The molecular structure of the title molecule with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. A partial packing diagram. Hydrogen bonds are shown as dashed lines.

4-(Furan-2-ylmethoxy)benzene-1,2-dicarbonitrile top

Crystal data top

C₁₃H₈N₂O₂	F(000) = 464
M_r = 224.21	D_x = 1.366 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 1088 reflections
a = 3.9681 (2) Å	θ = 3.0–23.3°
b = 14.3029 (3) Å	µ = 0.10 mm⁻¹
c = 19.2100 (5) Å	T = 100 K
V = 1090.27 (7) Å³	Rod-shaped, colorless
Z = 4	0.15 × 0.08 × 0.06 mm

Data collection top

Bruker Kappa APEXII CCD area-detector diffractometer	2615 independent reflections
Radiation source: fine-focus sealed tube	1709 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.047
ϕ and ω scans	θ_max = 28.2°, θ_min = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 2007)	h = −4→5
T_min = 0.986, T_max = 0.994	k = −18→18
6208 measured reflections	l = −21→24

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)] = 0.048	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.141	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.0634P)²] where P = (F_o² + 2F_c²)/3
2615 reflections	(Δ/σ)_max < 0.001
154 parameters	Δρ_max = 0.21 e Å⁻³
0 restraints	Δρ_min = −0.23 e Å⁻³

Crystal data top

C₁₃H₈N₂O₂	V = 1090.27 (7) Å³
M_r = 224.21	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 3.9681 (2) Å	µ = 0.10 mm⁻¹
b = 14.3029 (3) Å	T = 100 K
c = 19.2100 (5) Å	0.15 × 0.08 × 0.06 mm

Data collection top

Bruker Kappa APEXII CCD area-detector diffractometer	2615 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2007)	1709 reflections with I > 2σ(I)
T_min = 0.986, T_max = 0.994	R_int = 0.047
6208 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.048	0 restraints
wR(F²) = 0.141	H-atom parameters constrained
S = 1.06	Δρ_max = 0.21 e Å⁻³
2615 reflections	Δρ_min = −0.23 e Å⁻³
154 parameters

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. 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 > 2sigma(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
O1	−0.0385 (5)	0.13224 (11)	0.56836 (9)	0.0273 (5)
O2	0.0884 (5)	−0.01570 (12)	0.46812 (10)	0.0298 (5)
N1	0.3842 (7)	0.51178 (17)	0.75462 (12)	0.0422 (7)
N2	0.6574 (7)	0.26606 (17)	0.82143 (14)	0.0400 (7)
C1	−0.0302 (8)	−0.09143 (17)	0.43144 (15)	0.0309 (7)
H1	0.0059	−0.1016	0.3831	0.037*
C2	−0.2035 (8)	−0.14879 (19)	0.47319 (15)	0.0311 (7)
H2	−0.3107	−0.2056	0.4602	0.037*
C3	−0.1961 (8)	−0.10832 (18)	0.54078 (15)	0.0303 (7)
H3	−0.2976	−0.1328	0.5817	0.036*
C4	−0.0165 (7)	−0.02822 (17)	0.53552 (14)	0.0236 (6)
C5	0.0991 (8)	0.04146 (16)	0.58672 (14)	0.0269 (6)
H5A	0.0227	0.0235	0.6339	0.032*
H5B	0.3483	0.0443	0.5868	0.032*
C6	0.0587 (7)	0.20592 (17)	0.60840 (14)	0.0230 (6)
C7	0.2357 (7)	0.19683 (18)	0.67054 (14)	0.0236 (6)
H7	0.2995	0.1369	0.6873	0.028*
C8	0.3172 (7)	0.27691 (18)	0.70750 (14)	0.0234 (6)
C9	0.2258 (7)	0.36548 (18)	0.68341 (13)	0.0239 (6)
C10	0.0516 (7)	0.37317 (18)	0.62082 (13)	0.0264 (6)
H10	−0.0107	0.4331	0.6037	0.032*
C11	−0.0306 (7)	0.29413 (17)	0.58357 (14)	0.0262 (6)
H11	−0.1487	0.2997	0.5408	0.031*
C12	0.5042 (8)	0.26926 (18)	0.77133 (15)	0.0272 (7)
C13	0.3132 (8)	0.4472 (2)	0.72251 (15)	0.0303 (7)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0331 (11)	0.0226 (9)	0.0264 (10)	0.0029 (9)	−0.0048 (9)	−0.0034 (8)
O2	0.0384 (12)	0.0241 (9)	0.0268 (10)	−0.0047 (9)	0.0026 (10)	−0.0003 (8)
N1	0.0552 (19)	0.0336 (13)	0.0378 (16)	−0.0074 (14)	−0.0024 (14)	−0.0029 (13)
N2	0.0422 (16)	0.0472 (16)	0.0304 (16)	0.0012 (13)	−0.0040 (14)	0.0020 (13)
C1	0.0389 (18)	0.0255 (14)	0.0282 (16)	−0.0005 (14)	−0.0043 (15)	−0.0053 (12)
C2	0.0318 (17)	0.0240 (14)	0.0374 (18)	−0.0012 (13)	−0.0028 (14)	−0.0039 (13)
C3	0.0314 (16)	0.0274 (14)	0.0321 (17)	−0.0040 (13)	0.0049 (14)	0.0055 (13)
C4	0.0241 (14)	0.0261 (13)	0.0206 (14)	0.0008 (13)	0.0029 (12)	0.0018 (11)
C5	0.0299 (16)	0.0225 (13)	0.0282 (15)	0.0041 (12)	−0.0014 (13)	0.0017 (12)
C6	0.0220 (14)	0.0243 (13)	0.0228 (14)	−0.0008 (12)	0.0024 (11)	−0.0032 (11)
C7	0.0236 (14)	0.0241 (13)	0.0231 (15)	−0.0008 (12)	0.0011 (12)	0.0041 (11)
C8	0.0221 (14)	0.0289 (15)	0.0194 (14)	−0.0014 (12)	0.0015 (12)	0.0010 (12)
C9	0.0258 (15)	0.0245 (13)	0.0216 (15)	−0.0023 (12)	0.0041 (12)	−0.0023 (12)
C10	0.0276 (16)	0.0250 (13)	0.0267 (15)	0.0026 (13)	0.0019 (13)	0.0030 (12)
C11	0.0227 (14)	0.0323 (14)	0.0237 (14)	0.0011 (13)	−0.0015 (13)	0.0028 (12)
C12	0.0299 (16)	0.0277 (15)	0.0239 (16)	−0.0015 (13)	−0.0016 (14)	−0.0007 (12)
C13	0.0358 (17)	0.0275 (15)	0.0277 (17)	0.0004 (14)	0.0001 (14)	0.0002 (13)

Geometric parameters (Å, º) top

O1—C5	1.452 (3)	C5—H5A	0.9900
O1—C6	1.360 (3)	C5—H5B	0.9900
O2—C1	1.375 (3)	C6—C7	1.391 (4)
O2—C4	1.372 (3)	C7—H7	0.9500
N1—C13	1.146 (3)	C8—C7	1.386 (4)
N2—C12	1.139 (4)	C8—C12	1.437 (4)
C1—H1	0.9500	C9—C8	1.397 (4)
C2—C1	1.338 (4)	C9—C10	1.391 (4)
C2—H2	0.9500	C10—C11	1.377 (3)
C3—C2	1.422 (4)	C10—H10	0.9500
C3—H3	0.9500	C11—C6	1.395 (3)
C4—C3	1.353 (4)	C11—H11	0.9500
C5—C4	1.473 (4)	C13—C9	1.432 (4)

C6—O1—C5	116.7 (2)	O1—C6—C7	123.8 (2)
C4—O2—C1	106.1 (2)	O1—C6—C11	115.8 (2)
O2—C1—H1	124.7	C7—C6—C11	120.4 (2)
C2—C1—O2	110.6 (2)	C6—C7—H7	120.6
C2—C1—H1	124.7	C8—C7—C6	118.7 (2)
C1—C2—C3	106.7 (2)	C8—C7—H7	120.6
C1—C2—H2	126.7	C7—C8—C9	121.3 (2)
C3—C2—H2	126.7	C7—C8—C12	119.6 (2)
C2—C3—H3	126.6	C9—C8—C12	119.1 (2)
C4—C3—C2	106.7 (3)	C8—C9—C13	120.2 (2)
C4—C3—H3	126.6	C10—C9—C8	119.1 (2)
O2—C4—C5	116.6 (2)	C10—C9—C13	120.6 (2)
C3—C4—O2	109.9 (2)	C9—C10—H10	119.9
C3—C4—C5	133.4 (2)	C11—C10—C9	120.1 (2)
O1—C5—C4	109.0 (2)	C11—C10—H10	119.9
O1—C5—H5A	109.9	C6—C11—H11	119.8
O1—C5—H5B	109.9	C10—C11—C6	120.3 (2)
C4—C5—H5A	109.9	C10—C11—H11	119.8
C4—C5—H5B	109.9	N2—C12—C8	177.7 (3)
H5A—C5—H5B	108.3	N1—C13—C9	179.0 (3)

C8—C9—C10—C11	0.4 (4)	C5—C4—C3—C2	−175.4 (3)
C13—C9—C10—C11	179.9 (3)	C4—C3—C2—C1	−0.1 (3)
C9—C10—C11—C6	0.3 (4)	C3—C2—C1—O2	−0.2 (3)
C5—O1—C6—C7	−10.1 (4)	C4—O2—C1—C2	0.4 (3)
C5—O1—C6—C11	170.0 (2)	C10—C9—C8—C7	−0.5 (4)
C10—C11—C6—O1	179.0 (3)	C13—C9—C8—C7	−179.9 (3)
C10—C11—C6—C7	−0.9 (4)	C10—C9—C8—C12	178.5 (3)
C6—O1—C5—C4	−176.6 (2)	C13—C9—C8—C12	−1.0 (4)
C1—O2—C4—C3	−0.4 (3)	C9—C8—C7—C6	−0.2 (4)
C1—O2—C4—C5	176.1 (2)	C12—C8—C7—C6	−179.1 (2)
O1—C5—C4—C3	−121.0 (3)	O1—C6—C7—C8	−179.1 (3)
O1—C5—C4—O2	63.5 (3)	C11—C6—C7—C8	0.8 (4)
O2—C4—C3—C2	0.3 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7···N1ⁱ	0.95	2.45	3.369 (4)	162
C10—H10···O2ⁱⁱ	0.95	2.42	3.233 (3)	144

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

Experimental details

Crystal data
Chemical formula	C₁₃H₈N₂O₂
M_r	224.21
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	100
a, b, c (Å)	3.9681 (2), 14.3029 (3), 19.2100 (5)
V (Å³)	1090.27 (7)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.15 × 0.08 × 0.06

Data collection
Diffractometer	Bruker Kappa APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2007)
T_min, T_max	0.986, 0.994
No. of measured, independent and observed [I > 2σ(I)] reflections	6208, 2615, 1709
R_int	0.047
(sin θ/λ)_max (Å⁻¹)	0.665

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.048, 0.141, 1.06
No. of reflections	2615
No. of parameters	154
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.21, −0.23

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7···N1ⁱ	0.95	2.45	3.369 (4)	162
C10—H10···O2ⁱⁱ	0.95	2.42	3.233 (3)	144

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

Acknowledgements

The authors are indebted to Anadolu University and the Medicinal Plants and Medicine Research Centre of Anadolu University, Eskişehir, Turkey, for the use of the diffractometer.

References

Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19. CrossRef Web of Science Google Scholar
Bruker (2007). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838. CrossRef CAS IUCr Journals Google Scholar
Leznoff, C. C. & Lever, A. B. P. (1996). Editors. Phthalocyanines: Properties and Applications, Vols. 1-4. Weinheim: VHC. Google Scholar
McKeown, N. B. (1998). Phthalocyanine Materials: Synthesis, Structure and Function. Cambridge University Press. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar