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

Abstract

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)°.

Related literature

For a related structure, see: Britten et al. (2001 ▶). For related literature, see: Allen (2002 ▶); Leclerc (2001 ▶).

Experimental

Crystal data

• C₁₉H₁₁NO

• M _r = 269.29

• Monoclinic,

• a = 15.899 (3) Å

• b = 5.6109 (11) Å

• c = 15.664 (3) Å

• β = 103.69 (3)°

• V = 1357.6 (5) ų

• Z = 4

• Mo Kα radiation

• μ = 0.08 mm⁻¹

• T = 293 K

• 0.32 × 0.07 × 0.05 mm

Data collection

• Oxford Diffraction Gemini R CCD diffractometer

• Absorption correction: analytical (Clark & Reid, 1995 ▶) T _min = 0.921, T _max = 0.987

• 27628 measured reflections

• 2746 independent reflections

• 1524 reflections with I > 2σ(I)

• R _int = 0.043

Refinement

• R[F ² > 2σ(F ²)] = 0.062

• wR(F ²) = 0.179

• S = 0.94

• 2746 reflections

• 190 parameters

• H-atom parameters constrained

• Δρ_max = 0.24 e Å⁻³

• Δρ_min = −0.21 e Å⁻³

Data collection: CrysAlis CCD (Oxford Diffraction, 2007 ▶); cell refinement: CrysAlis CCD; 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 ▶).

Supplementary Material

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
C11—H11A⋯O1	0.93	2.27	3.034 (3)	140

supplementary crystallographic information

Comment

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).

Experimental

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)

Refinement

H atoms were placed in calculated positions and refined using a riding model, with C—H = 0.93 Å and U_iso(H) = 1.2 U_eq(C).

Figures

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.

Crystal data

C19H11NO	F000 = 560
Mr = 269.29	Dx = 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 = 3.1–29.1º
b = 5.6109 (11) Å	µ = 0.08 mm−1
c = 15.664 (3) Å	T = 293 K
β = 103.69 (3)º	Block, yellow
V = 1357.6 (5) Å3	0.32 × 0.07 × 0.05 mm
Z = 4

Data collection

Oxford Diffraction Gemini R CCD diffractometer	2746 independent reflections
Radiation source: fine-focus sealed tube	1524 reflections with I > 2σ(I)
Monochromator: graphite	Rint = 0.043
T = 293 K	θmax = 26.4º
Rotation method data acquisition using ω and phi scans	θmin = 4.2º
Absorption correction: analytical(Clark & Reid, 1995)	h = −19→19
Tmin = 0.921, Tmax = 0.987	k = −7→7
27628 measured reflections	l = −19→19

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)] = 0.062	H-atom parameters constrained
wR(F2) = 0.179	w = 1/[σ2(Fo2) + (0.121P)2] where P = (Fo2 + 2Fc2)/3
S = 0.94	(Δ/σ)max < 0.001
2746 reflections	Δρmax = 0.24 e Å−3
190 parameters	Δρmin = −0.21 e Å−3
Primary atom site location: structure-invariant direct methods	Extinction correction: none

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	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, °)

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, °)

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