(E)-N,N′-(1,2-Di­cyano­ethene-1,2-di­yl)dipicolin­amide

Posel, M.; Stoeckli-Evans, H.

doi:10.1107/S2414314616014644

organic compounds

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ISSN: 2414-3146

Volume 1| Part 9| September 2016| x161464

doi:10.1107/S2414314616014644

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(E)-N,N′-(1,2-Dicyanoethene-1,2-diyl)dipicolinamide

Maciej Posel ^a and Helen Stoeckli-Evans ^b ^*

^aInstitute of Chemistry, University of Neuchâtel, Av de Bellevaux 51, CH-2000 Neuchâtel, Switzerland, and ^bInstitute of Physics, University of Neuchâtel, rue Emile-Argand 11, CH-2000 Neuchâtel, Switzerland
^*Correspondence e-mail: helen.stoeckli-evans@unine.ch

Edited by P. C. Healy, Griffith University, Australia (Received 14 September 2016; accepted 15 September 2016; online 23 September 2016)

The whole molecule of the title dicyanoethene derivative, C₁₆H₁₀N₆O₂, is generated by inversion symmetry. The conformation about the central C=C bond, which is situated about the inversion center, is E. There are short intramolecular N—H⋯N contacts present and the molecule is slightly twisted, with the plane of the amide C(=O)N group being inclined to the pyridine ring by 10.6 (4)°, and by 20.2 (4)° to the plane of the dicyanoethene unit (N≡C—C=C—C≡N). In the crystal, molecules are linked by C—H⋯O and C—H⋯N hydrogen bonds, forming sheets parallel to (1-21), enclosing R²₂(10), R²₂(22) and R⁴₄(22) ring motifs.

Keywords: crystal structure; picolinamide; dicyanoethene; hydrogen bonding.

CCDC reference: 1504520

Structure description

When synthesizing 2,3-bis(2-pyridyl)-5,6-dicyanopyrazine, whose structure and an alternative synthesis have been described (Du et al., 2001 ), an orange–brown precipitate was formed. This precipitate was recrystallized from a mixture of solvents (see below) and found to be the title compound. From the filtrate, colourless crystals of 2,3-bis(2-pyridyl)-5,6-dicyanopyrazine were obtained.

The whole molecule of the title dicyanoethene derivative, Fig. 1, is generated by inversion symmetry. The conformation about the central C7=C7ⁱ bond [symmetry code: (i) −x + 1, −y + 1, −z + 1], situated about the inversion center, is E. There are short intramolecular N—H⋯N contacts present and the molecule is slightly twisted, with the plane of the amide C(=O)N group being inclined to the pyridine ring by 10.6 (4)°, and by 20.2 (4)° to the plane of the dicyanoethene unit (N≡C—C=C—C≡ N).

Figure 1
A view of the molecular structure of the title compound, with atom labelling. Displacement ellipsoids are drawn at the 50% probability level. Unlabelled atoms are related to the labelled atoms by the inversion-symmetry operation −x + 1, −y + 1, −z + 1.

In the crystal, molecules are linked by C—H⋯O and C—H⋯N hydrogen bonds, forming sheets parallel to (1 $[\overline{2}]$ 1), enclosing $[R_{2}^{2}]$ (10), $[R_{2}^{2}]$ (22) and $[R_{4}^{4}]$ (22) ring motifs (Table 1 and Fig. 2).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2N⋯N1	0.86 (3)	2.23 (3)	2.671 (3)	111 (3)
C2—H2⋯N3ⁱ	0.93	2.61	3.354 (4)	138
C4—H4⋯O1ⁱⁱ	0.93	2.51	3.274 (4)	140
Symmetry codes: (i) x-1, y-1, z-1; (ii) -x+2, -y+1, -z.

Figure 2
A view along the normal to (1 $[\overline{2}]$ 1) of the crystal packing of the title compound. Hydrogen bonds are shown as dashed lines (see Table 1

Synthesis and crystallization

In a round-bottomed flask outfitted with a reflux condenser, 9.3663 g (0.0 3 mol) of 2,2′-pyridyl were dissolved in 15 ml of dry n-butanol. A solution of 2.7026 g (0.025 mol) of diaminomaleonitrile in 15 ml of dry n-butanol was then added at 333 K with stirring. The mixture was refluxed for 3 h. After stopping the reaction, the mixture was filtered to remove the orange–brown precipitate that had formed. This orange–brown precipitate was recrystallized from a mixture of methanol/acetonitrile/acetylacetone (3/3/1), which resulted in the formation of yellow needle-like crystals of the title compound on slow evaporation of the solvents (yield 2.5 g, 32%; m.p. > 360 K). From the filtrate, colourless crystals of 2,3-bis(2-pyridyl)-5,6-dicyanopyrazine were obtained on slow evaporation of the solvent n-butanol.

The mechanism for the synthesis of the title compound is unknown. However, Du et al. (2001) did note that 2,3-bis(2-pyridyl)-5,6-dicyanopyrazine is not stable when exposed to air for several months. Hence, we may postulate that the title compound may be formed by oxidation of 2,3-bis(2-pyridyl)-5,6-dicyanopyrazine.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. The NH H atom was located in a difference Fourier map and freely refined. Only one equivalent of data was measured, hence R_int = 0.

Table 2
Experimental details

Crystal data
Chemical formula	C₁₆H₁₀N₆O₂
M_r	318.30
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	293
a, b, c (Å)	5.1939 (11), 8.0697 (17), 9.1482 (15)
α, β, γ (°)	106.819 (19), 96.077 (18), 92.804 (18)
V (Å³)	363.69 (13)
Z	1
Radiation type	Mo Kα
μ (mm⁻¹)	0.10
Crystal size (mm)	0.72 × 0.30 × 0.30

Data collection
Diffractometer	STOE–Siemens AED2, 4-circle
No. of measured, independent and observed [I > 2σ(I)] reflections	1281, 1281, 1196
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.073, 0.155, 1.40
No. of reflections	1281
No. of parameters	114
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.17, −0.17
Computer programs: STADI4 and X-RED (Stoe & Cie, 1997 ), SHELXS97 (Sheldrick, 2008 ), SHELXL2014/6 (Sheldrick, 2015 ), PLATON (Spek, 2009 ), Mercury (Macrae et al., 2008 ) and publCIF (Westrip, 2010 ).

Structural data

CCDC reference: 1504520

Crystal structure: contains datablocks I, Global. DOI: 10.1107/S2414314616014644/hg4014sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S2414314616014644/hg4014Isup2.hkl

Supporting information file. DOI: 10.1107/S2414314616014644/hg4014Isup3.cml

checkCIF report

Computing details top

Data collection: STADI4 (Stoe & Cie, 1997); cell refinement: STADI4 (Stoe & Cie, 1997); data reduction: X-RED (Stoe & Cie, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014/6 (Sheldrick, 2015); molecular graphics: PLATON (Spek, 2009) and Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL2014/6 (Sheldrick, 2015), PLATON (Spek, 2009) and publCIF (Westrip, 2010).

(E)-N,N'-(1,2-Dicyanoethene-1,2-diyl)dipicolinamide top

Crystal data top

C₁₆H₁₀N₆O₂	Z = 1
M_r = 318.30	F(000) = 164
Triclinic, P1	D_x = 1.444 Mg m⁻³
a = 5.1939 (11) Å	Mo Kα radiation, λ = 0.71073 Å
b = 8.0697 (17) Å	Cell parameters from 18 reflections
c = 9.1482 (15) Å	θ = 12.5–19.5°
α = 106.819 (19)°	µ = 0.10 mm⁻¹
β = 96.077 (18)°	T = 293 K
γ = 92.804 (18)°	Needle, yellow
V = 363.69 (13) Å³	0.72 × 0.30 × 0.30 mm

Data collection top

STOE–Siemens AED2, 4-circle diffractometer	R_int = 0.0
Radiation source: fine-focus sealed tube	θ_max = 25.0°, θ_min = 2.7°
Plane graphite monochromator	h = −6→6
ω/2θ scans	k = −9→9
1281 measured reflections	l = 0→10
1281 independent reflections	3 standard reflections every 60 min
1196 reflections with I > 2σ(I)	intensity decay: 4%

Refinement top

Refinement on F²	Hydrogen site location: mixed
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F² > 2σ(F²)] = 0.073	w = 1/[σ²(F_o²) + (0.0451P)² + 0.1443P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.155	(Δ/σ)_max < 0.001
S = 1.40	Δρ_max = 0.17 e Å⁻³
1281 reflections	Δρ_min = −0.17 e Å⁻³
114 parameters	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.063 (14)

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
O1	0.8969 (4)	0.4716 (3)	0.2158 (2)	0.0663 (7)
N1	0.3495 (4)	0.1893 (3)	0.0137 (3)	0.0459 (6)
N2	0.5113 (4)	0.4118 (3)	0.2910 (3)	0.0440 (6)
H2N	0.359 (7)	0.360 (4)	0.255 (4)	0.069 (10)*
N3	0.9259 (6)	0.7628 (4)	0.5384 (3)	0.0728 (9)
C1	0.2632 (5)	0.0829 (4)	−0.1254 (3)	0.0524 (8)
H1	0.1094	0.0137	−0.1371	0.063*
C2	0.3889 (6)	0.0691 (4)	−0.2533 (3)	0.0573 (8)
H2	0.3210	−0.0075	−0.3483	0.069*
C3	0.6154 (6)	0.1702 (4)	−0.2379 (3)	0.0573 (8)
H3	0.7030	0.1644	−0.3226	0.069*
C4	0.7115 (6)	0.2807 (4)	−0.0949 (3)	0.0492 (7)
H4	0.8652	0.3506	−0.0807	0.059*
C5	0.5737 (5)	0.2848 (3)	0.0266 (3)	0.0405 (6)
C6	0.6791 (5)	0.3986 (4)	0.1837 (3)	0.0441 (7)
C7	0.5678 (5)	0.5119 (3)	0.4442 (3)	0.0396 (6)
C8	0.7738 (5)	0.6490 (4)	0.4874 (3)	0.0473 (7)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0450 (12)	0.0910 (17)	0.0489 (13)	−0.0214 (11)	0.0134 (9)	0.0003 (11)
N1	0.0381 (12)	0.0477 (13)	0.0495 (14)	−0.0021 (10)	0.0072 (10)	0.0110 (11)
N2	0.0359 (12)	0.0535 (14)	0.0370 (13)	−0.0098 (10)	0.0077 (10)	0.0059 (10)
N3	0.0664 (18)	0.0739 (19)	0.0645 (18)	−0.0321 (16)	0.0050 (14)	0.0064 (15)
C1	0.0429 (16)	0.0514 (17)	0.0549 (19)	−0.0035 (13)	−0.0033 (13)	0.0077 (14)
C2	0.0615 (19)	0.0557 (18)	0.0441 (17)	0.0014 (15)	−0.0043 (14)	0.0027 (14)
C3	0.0638 (19)	0.067 (2)	0.0387 (16)	0.0033 (16)	0.0120 (14)	0.0109 (14)
C4	0.0456 (16)	0.0547 (17)	0.0454 (17)	−0.0026 (13)	0.0110 (12)	0.0110 (13)
C5	0.0391 (14)	0.0423 (14)	0.0387 (15)	0.0025 (11)	0.0071 (11)	0.0093 (11)
C6	0.0383 (14)	0.0499 (16)	0.0437 (16)	−0.0027 (12)	0.0097 (12)	0.0127 (12)
C7	0.0335 (13)	0.0436 (15)	0.0394 (15)	−0.0050 (11)	0.0071 (10)	0.0094 (11)
C8	0.0426 (15)	0.0563 (17)	0.0391 (15)	−0.0094 (13)	0.0082 (12)	0.0093 (13)

Geometric parameters (Å, º) top

O1—C6	1.215 (3)	C2—C3	1.369 (4)
N1—C1	1.329 (3)	C2—H2	0.9300
N1—C5	1.339 (3)	C3—C4	1.378 (4)
N2—C6	1.365 (3)	C3—H3	0.9300
N2—C7	1.392 (3)	C4—C5	1.378 (4)
N2—H2N	0.86 (3)	C4—H4	0.9300
N3—C8	1.135 (4)	C5—C6	1.493 (4)
C1—C2	1.379 (4)	C7—C7ⁱ	1.352 (5)
C1—H1	0.9300	C7—C8	1.438 (4)

C1—N1—C5	116.4 (2)	C5—C4—C3	118.2 (3)
C6—N2—C7	124.1 (2)	C5—C4—H4	120.9
C6—N2—H2N	115 (2)	C3—C4—H4	120.9
C7—N2—H2N	121 (2)	N1—C5—C4	123.9 (3)
N1—C1—C2	123.7 (3)	N1—C5—C6	116.9 (2)
N1—C1—H1	118.1	C4—C5—C6	119.2 (2)
C2—C1—H1	118.1	O1—C6—N2	122.1 (3)
C3—C2—C1	118.8 (3)	O1—C6—C5	123.5 (2)
C3—C2—H2	120.6	N2—C6—C5	114.3 (2)
C1—C2—H2	120.6	C7ⁱ—C7—N2	122.5 (3)
C2—C3—C4	118.9 (3)	C7ⁱ—C7—C8	117.8 (3)
C2—C3—H3	120.5	N2—C7—C8	119.7 (2)
C4—C3—H3	120.5	N3—C8—C7	171.7 (3)

C5—N1—C1—C2	−1.0 (4)	C7—N2—C6—O1	1.8 (5)
N1—C1—C2—C3	−0.1 (5)	C7—N2—C6—C5	−179.4 (2)
C1—C2—C3—C4	0.7 (5)	N1—C5—C6—O1	168.8 (3)
C2—C3—C4—C5	−0.2 (4)	C4—C5—C6—O1	−10.0 (4)
C1—N1—C5—C4	1.6 (4)	N1—C5—C6—N2	−10.0 (4)
C1—N1—C5—C6	−177.1 (2)	C4—C5—C6—N2	171.2 (3)
C3—C4—C5—N1	−1.0 (4)	C6—N2—C7—C7ⁱ	−161.8 (3)
C3—C4—C5—C6	177.7 (3)	C6—N2—C7—C8	19.5 (4)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2N···N1	0.86 (3)	2.23 (3)	2.671 (3)	111 (3)
C2—H2···N3ⁱⁱ	0.93	2.61	3.354 (4)	138
C4—H4···O1ⁱⁱⁱ	0.93	2.51	3.274 (4)	140

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

Acknowledgements

We are grateful to the Swiss National Science Foundation and the University of Neuchâtel for financial support.

References

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