5-[(9H-Fluoren-9-yl­idene)meth­yl]furan-2-carbonitrile

Perašínová, L.; Andicsová, A.; Végh, D.; Kožíšek, J.

doi:10.1107/S1600536807065798

5-[(9H-Fluoren-9-ylidene)methyl]furan-2-carbonitrile

L. Perašínová, A. Andicsová, D. Végh and J. Kožíšek

The title compound, C₁₉H₁₁NO, is stabilized by one intramolecular C—H

O hydrogen bond. The compound can be synthesized in good yield (49%), by transformation of functional groups [starting with 5-(fluoren-9-ylidenemethyl)furan-2-carbaldehyde]. The flourene and furan ring systems are nearly coplanar, with a dihedral angle of 6.36 (7)°.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807065798/bx2120sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536807065798/bx2120Isup2.hkl Contains datablock I

CCDC reference: 674569

checkCIF report

Key indicators

Single-crystal X-ray study
T = 293 K
Mean (C-C) = 0.003 Å
R factor = 0.062
wR factor = 0.179
Data-to-parameter ratio = 14.5

checkCIF/PLATON results

No syntax errors found



Alert level G
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature .        293 K

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   0 ALERT level C = Check and explain
   2 ALERT level G = General alerts; check

   2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 ALERT type 2 Indicator that the structure model may be wrong or deficient
   0 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

Comment top

Our synthetic research efforts have been focused to a set of multi-ring monomer systems based on furan and fluorene. Fluorene containing oligomeres are an important class of electroactive and photoactive materials. These compounds possesses exceptional electrooptical properties for applications in polymer light emitting diodes (PLEDs) and nanocomposite materials with advanced anticorrosive properties (Leclerc, 2001).

In the title compound the O1—C15 [1.359 (2) Å] and O1—C18 [1.381 (2) Å] bond lengths, are in a quite good agreement with similar furan compounds in the Cambridge Structural Database (CSD; Version 5.27, 2006 release; Allen, 2002)2-(1,2,3,5-Diselenadiazol-4-yl)-5-cyanofuran (Britten et al., 2001; CSD refcode YIFHUQ) as representative example. The flourene moiety is almost planar with maximun deviation of 0.030 (2)Å for C13. The flourene and furan rings are nearly coplanar with a dihedral angle of 6.36 (7)°. In the crystal structure the molecular packing is stabilized by intramolecular hydrogen bond (Fig. 1).

Related literature top

For a related structure, see: Britten et al. (2001).

For related literature, see: Allen (2002); Leclerc (2001).

Experimental top

A solution of 5-fluoren-9-ylidenemethyl-furan-2-carbaldehyde (0.0033 mol, 0.91 g), NH₂OH.HCl (0.0039 mol, 0.3 g, 1.12 eq.) in N-Methyl-pyrrolidinone (5.5 ml) was heated at 110 - 115°C. Progress of the reaction was followed by TLC and after 8 h the mixture was poured into H₂O (100 ml) and extracted with EtOAc (2 x 50 ml). The combined layers EtOAc were dried (Na₂SO₄) and the solvent was evaporated in vacuo. Crude product could be purified by collumn chromatography using silikagel Merck 60 in toluene as eluent (40% yield) R_f = 0,51 (toluen). M.p.: 167–169°C.

¹H NMR (300 MHz, DMSO – d₆, p.p.m.): δ= 6.78 (d, 1H, J = 3.6 Hz), 7.15 (s, 1H), 7.31 - 7.29 (m, 1H), 7.45 - 7.33 (m, 4H), 7.72 - 7.66 (m, 3H), 8.51 (d, 1H, J = 7.65 Hz).

¹³C-NMR (75 MHz, DMSO – d₆, p.p.m.) δ= 109.99, 111.77, 114.62, 119.80, 119.87, 120.33, 123.91, 125.74, 125.82, 127.20, 127.69, 129.69, 129.23, 129.88, 135.25, 138.06, 139.37, 139.62, 141.75, 156.19.

IR (KBr, cm^-1): 3136 (w), 3120 (vw), 3053(w), 2221(s, νC≡N), 1716(s, ν(C=C)), 1633(m), 1611(m), 1600(m, ν(C=C) aromatic), 1494(s, ν(C=C) aromatic), 1469(w), 1448(s), 1354(m), 1297(m), 1290(m), 1274(m, ν_as (C—O—C)), 1263(m), 1198(w), 1180(m), 1152(m), 1138(w), 1111(m), 1098(w), 1029(s, ν_s (C—O—C)), 975(m), 966(m), 941(m), 917(m), 882(m), 871(m), 793(νs, γ(CCH)), 781(νs, γ(CCH)), 772(m, γ(CCH)), 737(m, γ(CCH)), 728(νs, γ(CCH)), 724(νs, γ(CCH)), 668(m), 645(m), 625(m), 580(w), 561(w), 524(w), 511(w), 473(m), 455(m), 442(vw), 432(vw), 401(m)

Structure description top

For a related structure, see: Britten et al. (2001).

For related literature, see: Allen (2002); Leclerc (2001).

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2007); cell refinement: CrysAlis CCD (Oxford Diffraction, 2007); data reduction: CrysAlis RED (Oxford Diffraction, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: DIAMOND (Brandenburg, 1998); software used to prepare material for publication: enCIFer (Allen et al., 2004).

Figures top

Fig. 1.

The numbering scheme of 5-((9H-fluoren-9-ylidene) methyl) furan-2-carbonitrile. Displacement ellipsoids are drawn at the 50% probability level. Hydrogen-bond interactions are indicated by dashed lines.

5-[(9H-Fluoren-9-ylidene)methyl]furan-2-carbonitrile top

Crystal data top

C₁₉H₁₁NO	F(000) = 560
M_r = 269.29	D_x = 1.317 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 7057 reflections
a = 15.899 (3) Å	θ = 3.1–29.1°
b = 5.6109 (11) Å	µ = 0.08 mm⁻¹
c = 15.664 (3) Å	T = 293 K
β = 103.69 (3)°	Block, yellow
V = 1357.6 (5) Å³	0.32 × 0.07 × 0.05 mm
Z = 4

Data collection top

Oxford Diffraction Gemini R CCD diffractometer	2746 independent reflections
Radiation source: fine-focus sealed tube	1524 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.043
Rotation method data acquisition using ω and phi scans	θ_max = 26.4°, θ_min = 4.2°
Absorption correction: analytical (Clark & Reid, 1995)	h = −19→19
T_min = 0.921, T_max = 0.987	k = −7→7
27628 measured reflections	l = −19→19

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)] = 0.062	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.179	H-atom parameters constrained
S = 0.94	w = 1/[σ²(F_o²) + (0.121P)²] where P = (F_o² + 2F_c²)/3
2746 reflections	(Δ/σ)_max < 0.001
190 parameters	Δρ_max = 0.24 e Å⁻³
0 restraints	Δρ_min = −0.21 e Å⁻³

Crystal data top

C₁₉H₁₁NO	V = 1357.6 (5) Å³
M_r = 269.29	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 15.899 (3) Å	µ = 0.08 mm⁻¹
b = 5.6109 (11) Å	T = 293 K
c = 15.664 (3) Å	0.32 × 0.07 × 0.05 mm
β = 103.69 (3)°

Data collection top

Oxford Diffraction Gemini R CCD diffractometer	2746 independent reflections
Absorption correction: analytical (Clark & Reid, 1995)	1524 reflections with I > 2σ(I)
T_min = 0.921, T_max = 0.987	R_int = 0.043
27628 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.062	0 restraints
wR(F²) = 0.179	H-atom parameters constrained
S = 0.94	Δρ_max = 0.24 e Å⁻³
2746 reflections	Δρ_min = −0.21 e Å⁻³
190 parameters

Special details top

Experimental. face-indexed (CrysAlis RED; Oxford Diffraction, 2007)

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
C1	0.17033 (14)	0.6172 (3)	0.88196 (13)	0.0544 (5)
C2	0.23065 (15)	0.6471 (4)	0.96102 (15)	0.0680 (6)
H2A	0.2259	0.7739	0.9978	0.082*
C3	0.29834 (16)	0.4852 (4)	0.98462 (15)	0.0737 (7)
H3A	0.3385	0.5046	1.0380	0.088*
C4	0.30765 (16)	0.2974 (4)	0.93141 (16)	0.0741 (7)
H4A	0.3537	0.1919	0.9484	0.089*
C5	0.24829 (15)	0.2672 (4)	0.85303 (15)	0.0651 (6)
H5A	0.2536	0.1400	0.8166	0.078*
C6	0.17991 (13)	0.4280 (3)	0.82809 (13)	0.0538 (5)
C7	0.10829 (13)	0.4398 (3)	0.75032 (13)	0.0521 (5)
C8	0.08974 (15)	0.2931 (4)	0.67850 (14)	0.0602 (6)
H8A	0.1248	0.1626	0.6747	0.072*
C9	0.01799 (15)	0.3426 (4)	0.61169 (14)	0.0660 (6)
H9A	0.0044	0.2436	0.5627	0.079*
C10	−0.03397 (15)	0.5382 (4)	0.61677 (14)	0.0686 (6)
H10A	−0.0818	0.5685	0.5709	0.082*
C11	−0.01619 (14)	0.6875 (4)	0.68787 (13)	0.0605 (6)
H11A	−0.0512	0.8188	0.6904	0.073*
C12	0.05522 (13)	0.6391 (3)	0.75621 (12)	0.0518 (5)
C13	0.09090 (13)	0.7573 (3)	0.84099 (13)	0.0532 (5)
C14	0.06414 (15)	0.9425 (3)	0.88210 (14)	0.0599 (6)
H14A	0.1013	0.9725	0.9365	0.072*
C15	−0.00743 (14)	1.1057 (3)	0.86312 (14)	0.0577 (6)
C16	−0.02863 (18)	1.2789 (4)	0.91496 (15)	0.0737 (7)
H16A	0.0017	1.3139	0.9720	0.088*
C17	−0.10323 (17)	1.3964 (4)	0.86887 (16)	0.0732 (7)
H17A	−0.1314	1.5227	0.8886	0.088*
C18	−0.12551 (15)	1.2896 (4)	0.79073 (16)	0.0647 (6)
C19	−0.19420 (18)	1.3303 (4)	0.7165 (2)	0.0743 (7)
N1	−0.25096 (16)	1.3660 (4)	0.65689 (17)	0.0953 (7)
O1	−0.06784 (9)	1.1091 (2)	0.78554 (9)	0.0624 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0575 (13)	0.0541 (11)	0.0489 (12)	−0.0072 (10)	0.0075 (10)	0.0027 (9)
C2	0.0730 (15)	0.0716 (13)	0.0545 (13)	−0.0084 (12)	0.0054 (12)	−0.0022 (11)
C3	0.0701 (15)	0.0820 (15)	0.0601 (14)	−0.0014 (13)	−0.0021 (12)	0.0087 (13)
C4	0.0673 (16)	0.0750 (15)	0.0735 (16)	0.0064 (12)	0.0036 (13)	0.0144 (13)
C5	0.0609 (14)	0.0672 (13)	0.0650 (14)	0.0063 (11)	0.0102 (12)	0.0039 (10)
C6	0.0540 (12)	0.0550 (11)	0.0524 (12)	−0.0026 (9)	0.0126 (10)	0.0015 (9)
C7	0.0565 (12)	0.0515 (11)	0.0487 (11)	−0.0040 (9)	0.0130 (10)	0.0011 (9)
C8	0.0649 (14)	0.0590 (12)	0.0572 (13)	−0.0001 (10)	0.0156 (11)	−0.0064 (10)
C9	0.0745 (15)	0.0676 (13)	0.0534 (13)	−0.0045 (12)	0.0101 (12)	−0.0116 (10)
C10	0.0710 (15)	0.0762 (14)	0.0521 (13)	0.0013 (12)	0.0015 (11)	−0.0044 (11)
C11	0.0613 (14)	0.0601 (12)	0.0542 (13)	0.0058 (10)	0.0020 (11)	−0.0042 (10)
C12	0.0540 (12)	0.0518 (11)	0.0485 (11)	−0.0052 (9)	0.0099 (10)	0.0009 (9)
C13	0.0578 (13)	0.0519 (10)	0.0478 (11)	−0.0054 (9)	0.0083 (10)	−0.0021 (9)
C14	0.0685 (14)	0.0564 (12)	0.0536 (12)	−0.0046 (10)	0.0119 (11)	−0.0030 (9)
C15	0.0656 (14)	0.0555 (11)	0.0526 (12)	−0.0046 (10)	0.0154 (11)	−0.0029 (9)
C16	0.0938 (19)	0.0651 (13)	0.0619 (14)	0.0079 (13)	0.0179 (13)	−0.0055 (11)
C17	0.0869 (18)	0.0621 (13)	0.0746 (16)	0.0074 (12)	0.0272 (14)	−0.0099 (11)
C18	0.0620 (14)	0.0586 (12)	0.0759 (16)	0.0016 (10)	0.0211 (13)	−0.0007 (11)
C19	0.0684 (17)	0.0674 (14)	0.0895 (19)	0.0048 (12)	0.0233 (15)	−0.0074 (13)
N1	0.0808 (16)	0.0981 (16)	0.0986 (18)	0.0118 (13)	0.0047 (15)	−0.0131 (13)
O1	0.0625 (10)	0.0616 (9)	0.0637 (10)	0.0017 (7)	0.0162 (8)	−0.0079 (7)

Geometric parameters (Å, º) top

C1—C2	1.386 (3)	C10—C11	1.368 (3)
C1—C6	1.386 (3)	C10—H10A	0.9300
C1—C13	1.497 (3)	C11—C12	1.390 (3)
C2—C3	1.390 (3)	C11—H11A	0.9300
C2—H2A	0.9300	C12—C13	1.473 (3)
C3—C4	1.373 (3)	C13—C14	1.344 (3)
C3—H3A	0.9300	C14—C15	1.436 (3)
C4—C5	1.370 (3)	C14—H14A	0.9300
C4—H4A	0.9300	C15—O1	1.359 (2)
C5—C6	1.396 (3)	C15—C16	1.359 (3)
C5—H5A	0.9300	C16—C17	1.399 (3)
C6—C7	1.459 (3)	C16—H16A	0.9300
C7—C8	1.369 (3)	C17—C18	1.333 (3)
C7—C12	1.417 (3)	C17—H17A	0.9300
C8—C9	1.381 (3)	C18—O1	1.381 (2)
C8—H8A	0.9300	C18—C19	1.413 (4)
C9—C10	1.387 (3)	C19—N1	1.152 (3)
C9—H9A	0.9300

C2—C1—C6	119.0 (2)	C11—C10—H10A	119.3
C2—C1—C13	130.90 (19)	C9—C10—H10A	119.3
C6—C1—C13	110.13 (18)	C10—C11—C12	118.7 (2)
C1—C2—C3	119.1 (2)	C10—C11—H11A	120.6
C1—C2—H2A	120.4	C12—C11—H11A	120.6
C3—C2—H2A	120.4	C11—C12—C7	119.62 (18)
C4—C3—C2	121.9 (2)	C11—C12—C13	132.57 (18)
C4—C3—H3A	119.1	C7—C12—C13	107.81 (17)
C2—C3—H3A	119.1	C14—C13—C12	133.0 (2)
C5—C4—C3	119.2 (2)	C14—C13—C1	122.10 (19)
C5—C4—H4A	120.4	C12—C13—C1	104.83 (17)
C3—C4—H4A	120.4	C13—C14—C15	136.0 (2)
C4—C5—C6	119.8 (2)	C13—C14—H14A	112.0
C4—C5—H5A	120.1	C15—C14—H14A	112.0
C6—C5—H5A	120.1	O1—C15—C16	107.54 (19)
C1—C6—C5	121.0 (2)	O1—C15—C14	123.50 (18)
C1—C6—C7	107.29 (17)	C16—C15—C14	129.0 (2)
C5—C6—C7	131.70 (19)	C15—C16—C17	109.2 (2)
C8—C7—C12	120.82 (19)	C15—C16—H16A	125.4
C8—C7—C6	129.27 (19)	C17—C16—H16A	125.4
C12—C7—C6	109.90 (17)	C18—C17—C16	105.7 (2)
C7—C8—C9	118.7 (2)	C18—C17—H17A	127.1
C7—C8—H8A	120.6	C16—C17—H17A	127.1
C9—C8—H8A	120.6	C17—C18—O1	110.3 (2)
C8—C9—C10	120.78 (19)	C17—C18—C19	132.0 (2)
C8—C9—H9A	119.6	O1—C18—C19	117.7 (2)
C10—C9—H9A	119.6	N1—C19—C18	178.7 (3)
C11—C10—C9	121.3 (2)	C15—O1—C18	107.23 (16)

C6—C1—C2—C3	−0.8 (3)	C8—C7—C12—C13	178.99 (18)
C13—C1—C2—C3	178.4 (2)	C6—C7—C12—C13	−1.8 (2)
C1—C2—C3—C4	0.6 (3)	C11—C12—C13—C14	3.9 (4)
C2—C3—C4—C5	−0.5 (4)	C7—C12—C13—C14	−175.5 (2)
C3—C4—C5—C6	0.5 (3)	C11—C12—C13—C1	−178.4 (2)
C2—C1—C6—C5	0.9 (3)	C7—C12—C13—C1	2.1 (2)
C13—C1—C6—C5	−178.45 (18)	C2—C1—C13—C14	−3.0 (3)
C2—C1—C6—C7	−179.96 (18)	C6—C1—C13—C14	176.26 (18)
C13—C1—C6—C7	0.7 (2)	C2—C1—C13—C12	179.0 (2)
C4—C5—C6—C1	−0.8 (3)	C6—C1—C13—C12	−1.7 (2)
C4—C5—C6—C7	−179.6 (2)	C12—C13—C14—C15	−1.0 (4)
C1—C6—C7—C8	179.8 (2)	C1—C13—C14—C15	−178.4 (2)
C5—C6—C7—C8	−1.2 (4)	C13—C14—C15—O1	−4.3 (4)
C1—C6—C7—C12	0.7 (2)	C13—C14—C15—C16	175.6 (2)
C5—C6—C7—C12	179.7 (2)	O1—C15—C16—C17	−0.8 (3)
C12—C7—C8—C9	−0.1 (3)	C14—C15—C16—C17	179.3 (2)
C6—C7—C8—C9	−179.15 (19)	C15—C16—C17—C18	0.5 (3)
C7—C8—C9—C10	0.5 (3)	C16—C17—C18—O1	0.0 (3)
C8—C9—C10—C11	−0.2 (3)	C16—C17—C18—C19	−179.5 (2)
C9—C10—C11—C12	−0.5 (3)	C16—C15—O1—C18	0.8 (2)
C10—C11—C12—C7	0.8 (3)	C14—C15—O1—C18	−179.31 (19)
C10—C11—C12—C13	−178.6 (2)	C17—C18—O1—C15	−0.5 (2)
C8—C7—C12—C11	−0.5 (3)	C19—C18—O1—C15	179.08 (19)
C6—C7—C12—C11	178.63 (17)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C11—H11A···O1	0.93	2.27	3.034 (3)	140

Experimental details

Crystal data
Chemical formula	C₁₉H₁₁NO
M_r	269.29
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	293
a, b, c (Å)	15.899 (3), 5.6109 (11), 15.664 (3)
β (°)	103.69 (3)
V (Å³)	1357.6 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.08
Crystal size (mm)	0.32 × 0.07 × 0.05

Data collection
Diffractometer	Oxford Diffraction Gemini R CCD
Absorption correction	Analytical (Clark & Reid, 1995)
T_min, T_max	0.921, 0.987
No. of measured, independent and observed [I > 2σ(I)] reflections	27628, 2746, 1524
R_int	0.043
(sin θ/λ)_max (Å⁻¹)	0.625

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.062, 0.179, 0.94
No. of reflections	2746
No. of parameters	190
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.24, −0.21

Computer programs: CrysAlis CCD (Oxford Diffraction, 2007), CrysAlis RED (Oxford Diffraction, 2007), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), DIAMOND (Brandenburg, 1998), enCIFer (Allen et al., 2004).

Selected geometric parameters (Å, º) top

C15—O1	1.359 (2)	C18—O1	1.381 (2)

O1—C18—C19	117.7 (2)	C15—O1—C18	107.23 (16)