3-(Di­cyano­methyl­ene)-1,5-di­phenyl­penta-1,4-diyne

Jones, P.G.; Hopf, H.; Kreutzer, M.

doi:10.1107/S1600536802002490

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3-(Dicyanomethylene)-1,5-diphenylpenta-1,4-diyne

P. G. Jones, H. Hopf and M. Kreutzer

The molecule of the title compound, C₂₀H₁₀N₂, displays no imposed symmetry, but is largely planar [one phenyl ring is twisted by 10.4 (1)° out of the plane of the rest of the molecule]. The central C=C bond length is 1.371 (3) Å. The molecules are linked by a weak hydrogen bond of the form C—H

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536802002490/na6140sup1.cif Contains datablocks I, global
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536802002490/na6140Isup2.hkl Contains datablock I

CCDC reference: 182614

checkCIF report

Key indicators

Single-crystal X-ray study
T = 178 K
Mean (C-C) = 0.003 Å
R factor = 0.047
wR factor = 0.138
Data-to-parameter ratio = 13.7

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


 Alert Level C:



PLAT_371  Alert C Long   C(sp2)-C(sp1) Bond  C(1)   -   C(9)   =       1.43 Ang.

PLAT_371  Alert C Long   C(sp2)-C(sp1) Bond  C(2)   -   C(3)   =       1.42 Ang.

PLAT_371  Alert C Long   C(sp2)-C(sp1) Bond  C(3)   -   C(4)   =       1.42 Ang.

PLAT_371  Alert C Long   C(sp2)-C(sp1) Bond  C(5)   -   C(15)  =       1.43 Ang.

PLAT_371  Alert C Long   C(sp2)-C(sp1) Bond  C(6)   -   C(7)   =       1.43 Ang.

PLAT_371  Alert C Long   C(sp2)-C(sp1) Bond  C(6)   -   C(8)   =       1.42 Ang.


 0 Alert Level A = Potentially serious problem

 0 Alert Level B = Potential problem

 6 Alert Level C = Please check

Comment top

Cross-conjugated endiynes are attracting increasing attention, since they can be used for the preparation of extended π-systems with novel electronic properties (Zhao et al., 2002). We are interested in the synthesis of derivatives of 1,1-diethynylethene that bear polarizing functional groups (Hopf et al., 1991). As a reference compound, we prepared the title compound, (I), by the condensation of 1,5-diphenylpenta-1,4-diyn-4-one with malonitrile in acetic acid/ethanol in the presence of β-alanine as catalyst (Kreutzer, 1993); we report here its crystal structure.

The molecule (Fig. 1) displays no imposed crystallographic symmetry. It is approximately planar; a closer analysis shows that the ring C9–14 is rotated by 10.4 (1)° from the rest of the molecule (mean deviations 0.004/0.033 Å, respectively). The molecular dimensions may be regarded as normal; the central double bond C3═C6 has a length of 1.371 (3) Å, and the angles subtended by each pair of substituents at this bond are slightly less than the ideal 120° [118.6 (2)° for the phenylethynyl and 117.4 (2)° for the cyano groups]. These values may be compared with the values of 1.378 (3)/1.373 (3) Å and 116.8 (1)/118.2 (2)° observed in two independent centrosymmetric molecules of tetrakis(phenylethynyl)ethene (Hopf et al., 1991).

The molecules are connected by a weak C19—H19···N1 hydrogen bond by the 2₁ operator parallel to the y axis, forming a flattened herring-bone pattern (Fig. 2).

Experimental top

Crystals of (I) were grown by diffusion of pentane into a solution in chloroform.

Computing details top

Data collection: P3 (Nicolet, 1987); cell refinement: P3; data reduction: XDISK (Nicolet, 1987); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP (Siemens, 1994); software used to prepare material for publication: SHELXL97.

Figures top

	Fig. 1. The molecule of the title compound in the crystal. Ellipsoids represent 50% probability levels.
	Fig. 2. Packing diagram of the title compound with view direction slightly rotated from the x axis. The hydrogen bond is indicated by a dashed line. Radii are arbitrary.

(I) top

Crystal data top

C₂₀H₁₀N₂	F(000) = 576
M_r = 278.30	D_x = 1.191 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 12.138 (4) Å	Cell parameters from 50 reflections
b = 15.279 (4) Å	θ = 10–12.5°
c = 8.763 (3) Å	µ = 0.07 mm⁻¹
β = 107.24 (3)°	T = 178 K
V = 1552.1 (8) Å³	Prism, yellow
Z = 4	0.7 × 0.2 × 0.15 mm

Data collection top

Siemens R3 diffractometer	R_int = 0.050
Radiation source: fine-focus sealed tube	θ_max = 25.0°, θ_min = 3.2°
Graphite monochromator	h = −13→14
ω scans	k = −18→0
2909 measured reflections	l = −10→0
2722 independent reflections	3 standard reflections every 147 reflections
1498 reflections with I > 2σ(I)	intensity decay: none

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) = 0.138	H-atom parameters constrained
S = 0.90	w = 1/[σ²(F_o²) + (0.0783P)²] where P = (F_o² + 2F_c²)/3
2722 reflections	(Δ/σ)_max < 0.001
199 parameters	Δρ_max = 0.15 e Å⁻³
0 restraints	Δρ_min = −0.18 e Å⁻³

Crystal data top

C₂₀H₁₀N₂	V = 1552.1 (8) Å³
M_r = 278.30	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 12.138 (4) Å	µ = 0.07 mm⁻¹
b = 15.279 (4) Å	T = 178 K
c = 8.763 (3) Å	0.7 × 0.2 × 0.15 mm
β = 107.24 (3)°

Data collection top

Siemens R3 diffractometer	R_int = 0.050
2909 measured reflections	3 standard reflections every 147 reflections
2722 independent reflections	intensity decay: none
1498 reflections with I > 2σ(I)

Refinement top

R[F² > 2σ(F²)] = 0.048	0 restraints
wR(F²) = 0.138	H-atom parameters constrained
S = 0.90	Δρ_max = 0.15 e Å⁻³
2722 reflections	Δρ_min = −0.18 e Å⁻³
199 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.

Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane)

2.8515 (0.0028) x + 6.0879 (0.0063) y + 6.8101 (0.0040) z = 6.1884 (0.0045)

* 0.0591 (0.0017) C1 * 0.0221 (0.0019) C2 * -0.0037 (0.0020) C3 * -0.0307 (0.0021) C4 * -0.0580 (0.0020) C5 * 0.0018 (0.0021) C6 * -0.0046 (0.0024) C7 * 0.0103 (0.0022) C8 * -0.0425 (0.0019) C15 * -0.0166 (0.0020) C16 * 0.0419 (0.0021) C17 * 0.0484 (0.0022) C18 * 0.0045 (0.0021) C19 * -0.0354 (0.0021) C20 * -0.0222 (0.0024) N1 * 0.0258 (0.0019) N2

Rms deviation of fitted atoms = 0.0326

1.4180 (0.0111) x + 8.0575 (0.0125) y + 6.7400 (0.0061) z = 6.6724 (0.0040)

Angle to previous plane (with approximate e.s.d.) = 10.36 (0.10)

* 0.0002 (0.0015) C9 * 0.0042 (0.0016) C10 * -0.0046 (0.0017) C11 * 0.0004 (0.0017) C12 * 0.0041 (0.0016) C13 * -0.0044 (0.0015) C14

Rms deviation of fitted atoms = 0.0035

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	0.28762 (18)	0.44530 (14)	0.3989 (2)	0.0388 (5)
C2	0.33034 (18)	0.49656 (15)	0.3297 (3)	0.0395 (5)
C3	0.38344 (18)	0.55699 (14)	0.2497 (2)	0.0382 (5)
C4	0.48916 (19)	0.53310 (14)	0.2228 (3)	0.0401 (5)
C5	0.57830 (18)	0.51400 (14)	0.1986 (2)	0.0395 (5)
C6	0.33413 (18)	0.63674 (15)	0.1999 (3)	0.0428 (6)
C7	0.2260 (2)	0.66089 (15)	0.2226 (3)	0.0558 (7)
C8	0.3878 (2)	0.69866 (16)	0.1233 (3)	0.0493 (6)
C9	0.23571 (18)	0.38470 (14)	0.4805 (2)	0.0386 (5)
C10	0.12400 (18)	0.39891 (16)	0.4876 (3)	0.0447 (6)
H10	0.0821	0.4490	0.4379	0.052*
C11	0.0741 (2)	0.34003 (18)	0.5672 (3)	0.0575 (7)
H11	−0.0024	0.3493	0.5709	0.066*
C12	0.1354 (2)	0.26789 (18)	0.6413 (3)	0.0592 (7)
H12	0.1010	0.2279	0.6965	0.068*
C13	0.2463 (2)	0.25348 (15)	0.6357 (3)	0.0524 (6)
H13	0.2879	0.2038	0.6876	0.061*
C14	0.2971 (2)	0.31104 (14)	0.5550 (3)	0.0443 (6)
H14	0.3732	0.3006	0.5501	0.049*
C15	0.68660 (17)	0.49547 (14)	0.1721 (2)	0.0376 (5)
C16	0.73691 (18)	0.55803 (14)	0.0989 (3)	0.0417 (6)
H16	0.6980	0.6116	0.0639	0.049*
C17	0.84309 (19)	0.54268 (16)	0.0767 (3)	0.0488 (6)
H17	0.8779	0.5861	0.0286	0.055*
C18	0.8986 (2)	0.46398 (17)	0.1248 (3)	0.0533 (7)
H18	0.9716	0.4532	0.1090	0.061*
C19	0.84869 (19)	0.40125 (16)	0.1953 (3)	0.0538 (7)
H19	0.8872	0.3471	0.2271	0.062*
C20	0.74349 (18)	0.41595 (15)	0.2204 (3)	0.0472 (6)
H20	0.7098	0.3725	0.2700	0.055*
N1	0.1390 (2)	0.67914 (15)	0.2401 (3)	0.0818 (8)
N2	0.43116 (18)	0.74921 (15)	0.0622 (3)	0.0699 (7)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0405 (12)	0.0429 (13)	0.0331 (12)	−0.0021 (10)	0.0111 (10)	−0.0039 (10)
C2	0.0411 (12)	0.0426 (13)	0.0374 (12)	0.0001 (10)	0.0154 (10)	−0.0026 (11)
C3	0.0406 (12)	0.0426 (13)	0.0337 (12)	−0.0052 (10)	0.0145 (10)	−0.0039 (10)
C4	0.0399 (13)	0.0426 (13)	0.0368 (13)	−0.0027 (10)	0.0097 (10)	0.0003 (10)
C5	0.0404 (13)	0.0443 (13)	0.0316 (12)	−0.0046 (10)	0.0075 (10)	−0.0026 (10)
C6	0.0415 (13)	0.0447 (14)	0.0478 (14)	−0.0056 (11)	0.0222 (11)	−0.0044 (11)
C7	0.0591 (16)	0.0439 (14)	0.0752 (18)	−0.0015 (12)	0.0365 (14)	−0.0009 (13)
C8	0.0477 (14)	0.0435 (14)	0.0601 (15)	−0.0007 (11)	0.0212 (13)	0.0040 (13)
C9	0.0439 (13)	0.0418 (13)	0.0314 (12)	−0.0083 (10)	0.0129 (10)	−0.0045 (10)
C10	0.0401 (13)	0.0534 (14)	0.0412 (13)	−0.0051 (11)	0.0128 (11)	−0.0006 (12)
C11	0.0464 (14)	0.0735 (18)	0.0558 (16)	−0.0134 (13)	0.0200 (13)	−0.0025 (15)
C12	0.0704 (18)	0.0616 (17)	0.0512 (16)	−0.0240 (14)	0.0264 (14)	−0.0014 (14)
C13	0.0745 (17)	0.0403 (13)	0.0439 (14)	−0.0052 (13)	0.0199 (13)	−0.0007 (11)
C14	0.0504 (14)	0.0443 (13)	0.0384 (13)	−0.0017 (11)	0.0136 (11)	−0.0046 (11)
C15	0.0341 (12)	0.0439 (13)	0.0337 (12)	−0.0026 (10)	0.0087 (10)	−0.0034 (11)
C16	0.0442 (13)	0.0389 (12)	0.0435 (13)	0.0022 (10)	0.0153 (11)	0.0001 (11)
C17	0.0464 (14)	0.0521 (15)	0.0534 (15)	−0.0030 (12)	0.0233 (12)	0.0038 (12)
C18	0.0387 (13)	0.0628 (17)	0.0620 (16)	0.0042 (12)	0.0204 (12)	0.0029 (14)
C19	0.0440 (14)	0.0516 (15)	0.0653 (17)	0.0096 (12)	0.0153 (13)	0.0097 (13)
C20	0.0411 (13)	0.0470 (14)	0.0521 (14)	−0.0035 (11)	0.0116 (11)	0.0060 (12)
N1	0.0709 (16)	0.0622 (15)	0.134 (2)	0.0077 (13)	0.0637 (17)	0.0012 (15)
N2	0.0654 (15)	0.0631 (14)	0.0883 (17)	−0.0050 (12)	0.0339 (13)	0.0160 (13)

Geometric parameters (Å, º) top

C1—C2	1.198 (3)	C12—C13	1.378 (3)
C1—C9	1.426 (3)	C12—H12	0.9500
C2—C3	1.424 (3)	C13—C14	1.384 (3)
C3—C6	1.371 (3)	C13—H13	0.9500
C3—C4	1.419 (3)	C14—H14	0.9500
C4—C5	1.199 (3)	C15—C16	1.389 (3)
C5—C15	1.429 (3)	C15—C20	1.400 (3)
C6—C8	1.425 (3)	C16—C17	1.379 (3)
C6—C7	1.433 (3)	C16—H16	0.9500
C7—N1	1.145 (3)	C17—C18	1.382 (3)
C8—N2	1.152 (3)	C17—H17	0.9500
C9—C10	1.393 (3)	C18—C19	1.375 (3)
C9—C14	1.400 (3)	C18—H18	0.9500
C10—C11	1.383 (3)	C19—C20	1.377 (3)
C10—H10	0.9500	C19—H19	0.9500
C11—C12	1.380 (4)	C20—H20	0.9500
C11—H11	0.9500

C2—C1—C9	179.4 (2)	C12—C13—C14	120.3 (2)
C1—C2—C3	178.8 (3)	C12—C13—H13	119.8
C6—C3—C4	120.44 (19)	C14—C13—H13	119.8
C6—C3—C2	120.98 (19)	C13—C14—C9	119.5 (2)
C4—C3—C2	118.6 (2)	C13—C14—H14	120.2
C5—C4—C3	179.0 (2)	C9—C14—H14	120.2
C4—C5—C15	177.2 (2)	C16—C15—C20	119.5 (2)
C3—C6—C8	121.53 (19)	C16—C15—C5	119.3 (2)
C3—C6—C7	121.1 (2)	C20—C15—C5	121.2 (2)
C8—C6—C7	117.4 (2)	C17—C16—C15	120.3 (2)
N1—C7—C6	179.1 (3)	C17—C16—H16	119.8
N2—C8—C6	179.5 (3)	C15—C16—H16	119.8
C10—C9—C14	119.7 (2)	C16—C17—C18	119.8 (2)
C10—C9—C1	120.1 (2)	C16—C17—H17	120.1
C14—C9—C1	120.2 (2)	C18—C17—H17	120.1
C11—C10—C9	119.9 (2)	C19—C18—C17	120.2 (2)
C11—C10—H10	120.0	C19—C18—H18	119.9
C9—C10—H10	120.0	C17—C18—H18	119.9
C12—C11—C10	120.1 (2)	C18—C19—C20	120.7 (2)
C12—C11—H11	120.0	C18—C19—H19	119.6
C10—C11—H11	120.0	C20—C19—H19	119.6
C13—C12—C11	120.5 (2)	C19—C20—C15	119.4 (2)
C13—C12—H12	119.8	C19—C20—H20	120.3
C11—C12—H12	119.8	C15—C20—H20	120.3

C4—C3—C6—C8	−1.4 (3)	C10—C9—C14—C13	−0.4 (3)
C2—C3—C6—C8	178.4 (2)	C1—C9—C14—C13	179.05 (19)
C4—C3—C6—C7	178.4 (2)	C20—C15—C16—C17	−1.2 (3)
C2—C3—C6—C7	−1.8 (3)	C5—C15—C16—C17	177.92 (19)
C14—C9—C10—C11	−0.4 (3)	C15—C16—C17—C18	1.3 (3)
C1—C9—C10—C11	−179.9 (2)	C16—C17—C18—C19	−0.4 (4)
C9—C10—C11—C12	0.8 (3)	C17—C18—C19—C20	−0.5 (4)
C10—C11—C12—C13	−0.5 (4)	C18—C19—C20—C15	0.5 (4)
C11—C12—C13—C14	−0.3 (4)	C16—C15—C20—C19	0.3 (3)
C12—C13—C14—C9	0.8 (3)	C5—C15—C20—C19	−178.8 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C19—H19···N1ⁱ	0.95	2.61	3.436 (3)	145

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

Experimental details

Crystal data
Chemical formula	C₂₀H₁₀N₂
M_r	278.30
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	178
a, b, c (Å)	12.138 (4), 15.279 (4), 8.763 (3)
β (°)	107.24 (3)
V (Å³)	1552.1 (8)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.07
Crystal size (mm)	0.7 × 0.2 × 0.15

Data collection
Diffractometer	Siemens R3 diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	2909, 2722, 1498
R_int	0.050
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.048, 0.138, 0.90
No. of reflections	2722
No. of parameters	199
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.15, −0.18

Computer programs: P3 (Nicolet, 1987), P3, XDISK (Nicolet, 1987), SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), XP (Siemens, 1994), SHELXL97.

Selected geometric parameters (Å, º) top

C1—C2	1.198 (3)	C5—C15	1.429 (3)
C1—C9	1.426 (3)	C6—C8	1.425 (3)
C2—C3	1.424 (3)	C6—C7	1.433 (3)
C3—C6	1.371 (3)	C7—N1	1.145 (3)
C3—C4	1.419 (3)	C8—N2	1.152 (3)
C4—C5	1.199 (3)

C2—C1—C9	179.4 (2)	C4—C5—C15	177.2 (2)
C1—C2—C3	178.8 (3)	C3—C6—C8	121.53 (19)
C6—C3—C4	120.44 (19)	C3—C6—C7	121.1 (2)
C6—C3—C2	120.98 (19)	C8—C6—C7	117.4 (2)
C4—C3—C2	118.6 (2)	N1—C7—C6	179.1 (3)
C5—C4—C3	179.0 (2)	N2—C8—C6	179.5 (3)

C4—C3—C6—C8	−1.4 (3)	C2—C3—C6—C7	−1.8 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C19—H19···N1ⁱ	0.95	2.61	3.436 (3)	145.3

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

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