2,5-Bis[(E)-2-phenyl­ethen­yl]-3,6-bis­(pyridin-2-yl)pyrazine

Heiner Detert; Matthias Jochem; Dieter Schollmeyer

doi:10.1107/S2414314620003727

. 2020 Mar 17;5(Pt 3):x200372. doi: 10.1107/S2414314620003727

2,5-Bis[(E)-2-phenylethenyl]-3,6-bis(pyridin-2-yl)pyrazine

Heiner Detert ^a,^*, Matthias Jochem ^a, Dieter Schollmeyer ^a

Editor: M Bolte^b

PMCID: PMC9462200 PMID: 36339482

The title molecule has inversion symmetry, adopting the shape of a St Andrew’s cross. It shows dihedral angles between adjacent aryl units of around 50° whereas torsion angles of ca 10° are found along the arylene vinylene path.

Keywords: crystal structure, heterocycles, conjugated oligomers

Abstract

The molecule of the title compound, C₃₀H₂₂N₄, exhibits inversion symmetry adopting the shape of a St Andrew’s Cross. It shows dihedral angles between adjacent aryl units of around 50° whereas torsion angles of ca 10° are found along the arylene vinylene path.

Structure description

The title compound 2,5-(E,E)-distyryl-3,6-di-(2-pyridyl)pyrazine, C₃₀H₂₂N₄, was prepared as a reference chromophore in a project on pyrazine-centered materials, solvatochromic dyes (Schmitt et al., 2008 ▸, Wink & Detert, 2013 ▸) and liquid crystals (Röder et al., 2019 ▸; Schmitt et al., 2011 ▸).

The molecule has the shape of a centrosymmetrical St Andrew’s cross (Fig. 1 ▸). The central pyrazine ring as well as the vinylene groups and the peripheral pyridine and phenyl rings are totally planar. A dihedral angle of 48.07 (6)° at the teraryl axis is nearly identical to those in a related compound with phenyl rings (50.8, 48.6°, Schmitt et al., 2013 ▸). Torsion angles along the distyryl axis are −170.21 (15)°, (phenyl-vinyl) and −169.56 (14)° (vinyl-pyrazine). The packing is shown in Fig. 2 ▸.

Perspective view of the title compound. Displacement ellipsoids are drawn at the 50% probability level. The second part of the molecule is generated by the symmetry operation 1 − x, 1 − y, 1 − z.

Partial packing diagram of the title compound. View along the a axis.

Synthesis and crystallization

The title compound was prepared from 2,5-dimethyl-3,6-di(2-pyridyl)pyrazine (Kolb, 1896 ▸) (0.08 g) and benzaldehyde (0.13 g) in 35 ml of DMF by the action of 0.34 g potassium t-butylate. The base was added in portions to the stirred and cooled (30 min at 273 K) solution. After 4 h at ambient temperature, the mixture was poured into water, extracted with ethyl acetate and the organic layers were washed, dried (Na₂SO₄) and concentrated. Purification by chromatography on solica gel with toluene/ethyl acetate (20/1) as eluent, R _f = 0.33. Yield: 40 mg, 30%.

¹H NMR (CDCl₃, 400 MHz): 8.83 (dd, J = 4.9 Hz, J = 1.5 Hz, 2 H), 8.23 (d, J = 7.8 Hz, 2 H), 8.03 (s = 2d, J = 16.1 Hz, 4 H), 7.95 (dt, J = 7.8 Hz, J = 1.9 Hz, 2 H), 7.58 (d, 4 H), 7.43 (ddd, J = 7.8 Hz, J = 4.9 Hz, J = 1.5 Hz, 2H), 7.36 (t, J = 7.3 Hz, 4 H), 7.29 (dt, J = 7.3 Hz, J = 1.4 Hz, 2H); ¹³C NMR (CDCl₃, 100 MHz): 157.1, 148.9, 148.3, 145.9, 137.3, 137.0, 135.2, 128.7, 127.6, 125.4, 124.7, 123.6; IR (ATR): 3009, 2988, 2926, 2853, 2688, 1473, 1448, 1276, 1254, 1135, 1086, 1040, 962, 901, 89, 752, 699, 621; MS (APCI): calculated for C₃₀H₂₂N₄+H⁺): 439.1917, found 439.1908.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1 ▸.

Table 1. Experimental details.

Crystal data
Chemical formula	C₃₀H₂₂N₄
M _r	438.51
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	193
a, b, c (Å)	7.0953 (8), 8.9310 (8), 18.219 (2)
β (°)	95.490 (9)
V (Å³)	1149.2 (2)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	0.08
Crystal size (mm)	0.53 × 0.32 × 0.06

Data collection
Diffractometer	STOE IPDS 2T
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	5878, 2718, 1622
R _int	0.029
(sin θ/λ)_max (Å⁻¹)	0.659

Refinement
R[F ² > 2σ(F ²)], wR(F ²), S	0.043, 0.110, 0.99
No. of reflections	2718
No. of parameters	154
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.17, −0.14

Open in a new tab

Computer programs: X-AREA and X-RED (Stoe & Cie, 1996 ▸), SIR2004 (Burla et al., 2005 ▸), SHELXL2018 (Sheldrick, 2015 ▸) and PLATON (Spek, 2020 ▸).

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S2414314620003727/bt4090sup1.cif

x-05-x200372-sup1.cif^{(219KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S2414314620003727/bt4090Isup2.hkl

x-05-x200372-Isup2.hkl^{(217.5KB, hkl)}

Click here for additional data file.^{(8.8KB, cml)}

Supporting information file. DOI: 10.1107/S2414314620003727/bt4090Isup3.cml

CCDC reference: 1989990

Additional supporting information: crystallographic information; 3D view; checkCIF report

full crystallographic data

Crystal data

C₃₀H₂₂N₄	F(000) = 460
M_r = 438.51	D_x = 1.267 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 7.0953 (8) Å	Cell parameters from 3402 reflections
b = 8.9310 (8) Å	θ = 2.5–28.2°
c = 18.219 (2) Å	µ = 0.08 mm⁻¹
β = 95.490 (9)°	T = 193 K
V = 1149.2 (2) Å³	Plate, yellow
Z = 2	0.53 × 0.32 × 0.06 mm

Open in a new tab

Data collection

STOE IPDS 2T diffractometer	1622 reflections with I > 2σ(I)
Radiation source: sealed X-ray tube, 12 x 0.4 mm long-fine focus	R_int = 0.029
Detector resolution: 6.67 pixels mm^-1	θ_max = 27.9°, θ_min = 2.5°
rotation method scans	h = −9→9
5878 measured reflections	k = −10→11
2718 independent reflections	l = −23→21

Open in a new tab

Refinement

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.043	H-atom parameters constrained
wR(F²) = 0.110	w = 1/[σ²(F_o²) + (0.0551P)²] where P = (F_o² + 2F_c²)/3
S = 0.99	(Δ/σ)_max < 0.001
2718 reflections	Δρ_max = 0.17 e Å⁻³
154 parameters	Δρ_min = −0.14 e Å⁻³
0 restraints

Open in a new tab

Special details

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. Hydrogen atoms attached to carbons were placed at calculated positions and were refined in the riding-model approximation with C–H = 0.95 Å, and with U_iso(H) = 1.2 U_eq(C).

Open in a new tab

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

	x	y	z	U_iso*/U_eq
N1	0.56710 (15)	0.38847 (13)	0.45640 (6)	0.0371 (3)
C2	0.65303 (18)	0.52229 (16)	0.46177 (7)	0.0356 (3)
C3	0.58305 (19)	0.63537 (16)	0.50618 (7)	0.0349 (3)
C4	0.82169 (19)	0.54154 (17)	0.42232 (8)	0.0377 (3)
H4	0.898305	0.627307	0.433494	0.045*
C5	0.8747 (2)	0.44665 (17)	0.37180 (8)	0.0394 (3)
H5	0.796135	0.361702	0.361337	0.047*
C6	1.04162 (19)	0.45956 (17)	0.33065 (8)	0.0385 (4)
C7	1.0601 (2)	0.3624 (2)	0.27172 (8)	0.0524 (4)
H7	0.965446	0.288996	0.259487	0.063*
C8	1.2135 (3)	0.3716 (2)	0.23111 (10)	0.0691 (6)
H8	1.223164	0.305063	0.190953	0.083*
C9	1.3524 (3)	0.4758 (3)	0.24812 (10)	0.0697 (6)
H9	1.458129	0.481619	0.219953	0.084*
C10	1.3377 (2)	0.5724 (2)	0.30648 (10)	0.0585 (5)
H10	1.433770	0.644817	0.318544	0.070*
C11	1.1840 (2)	0.56400 (19)	0.34735 (8)	0.0444 (4)
H11	1.175609	0.630726	0.387515	0.053*
C12	0.66436 (18)	0.78758 (17)	0.51362 (8)	0.0364 (3)
N13	0.69586 (16)	0.85842 (14)	0.45085 (7)	0.0415 (3)
C14	0.7551 (2)	1.00017 (19)	0.45675 (10)	0.0487 (4)
H14	0.774730	1.052537	0.412735	0.058*
C15	0.7892 (2)	1.0746 (2)	0.52227 (11)	0.0545 (5)
H15	0.831478	1.175580	0.523436	0.065*
C16	0.7610 (2)	1.0003 (2)	0.58648 (10)	0.0555 (5)
H16	0.786532	1.048282	0.632899	0.067*
C17	0.6949 (2)	0.85434 (19)	0.58234 (9)	0.0467 (4)
H17	0.671004	0.801209	0.625662	0.056*

Open in a new tab

Atomic displacement parameters (Å²)

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0403 (6)	0.0387 (7)	0.0329 (6)	0.0050 (5)	0.0070 (5)	0.0027 (5)
C2	0.0356 (7)	0.0408 (9)	0.0310 (7)	0.0055 (6)	0.0066 (6)	0.0059 (6)
C3	0.0365 (7)	0.0376 (8)	0.0312 (7)	0.0064 (6)	0.0056 (5)	0.0055 (6)
C4	0.0389 (7)	0.0382 (8)	0.0371 (7)	0.0031 (6)	0.0087 (6)	0.0026 (7)
C5	0.0414 (7)	0.0412 (8)	0.0362 (8)	0.0023 (7)	0.0069 (6)	0.0029 (7)
C6	0.0382 (7)	0.0472 (9)	0.0306 (7)	0.0095 (6)	0.0054 (5)	0.0028 (7)
C7	0.0546 (10)	0.0671 (12)	0.0359 (8)	0.0094 (8)	0.0072 (7)	−0.0088 (8)
C8	0.0652 (12)	0.1046 (17)	0.0397 (9)	0.0236 (12)	0.0156 (8)	−0.0111 (10)
C9	0.0503 (10)	0.1129 (18)	0.0494 (10)	0.0206 (12)	0.0227 (8)	0.0132 (12)
C10	0.0414 (8)	0.0791 (13)	0.0562 (10)	0.0031 (9)	0.0107 (7)	0.0166 (10)
C11	0.0429 (8)	0.0512 (10)	0.0400 (8)	0.0060 (7)	0.0079 (6)	0.0034 (7)
C12	0.0312 (7)	0.0392 (8)	0.0391 (8)	0.0059 (6)	0.0057 (6)	0.0000 (7)
N13	0.0395 (7)	0.0396 (7)	0.0462 (7)	−0.0004 (6)	0.0073 (5)	0.0044 (6)
C14	0.0401 (8)	0.0426 (10)	0.0644 (11)	0.0005 (7)	0.0093 (7)	0.0066 (8)
C15	0.0393 (8)	0.0422 (10)	0.0820 (13)	0.0020 (7)	0.0065 (8)	−0.0087 (10)
C16	0.0446 (9)	0.0606 (11)	0.0602 (11)	0.0061 (8)	0.0001 (8)	−0.0226 (9)
C17	0.0437 (8)	0.0532 (10)	0.0433 (9)	0.0070 (7)	0.0049 (6)	−0.0042 (8)

Open in a new tab

Geometric parameters (Å, º)

N1—C3ⁱ	1.3356 (17)	C9—C10	1.381 (3)
N1—C2	1.3410 (18)	C9—H9	0.9500
C2—C3	1.4136 (19)	C10—C11	1.380 (2)
C2—C4	1.4638 (19)	C10—H10	0.9500
C3—C12	1.478 (2)	C11—H11	0.9500
C4—C5	1.332 (2)	C12—N13	1.3442 (18)
C4—H4	0.9500	C12—C17	1.385 (2)
C5—C6	1.4655 (19)	N13—C14	1.335 (2)
C5—H5	0.9500	C14—C15	1.368 (2)
C6—C11	1.387 (2)	C14—H14	0.9500
C6—C7	1.396 (2)	C15—C16	1.376 (3)
C7—C8	1.376 (2)	C15—H15	0.9500
C7—H7	0.9500	C16—C17	1.385 (2)
C8—C9	1.369 (3)	C16—H16	0.9500
C8—H8	0.9500	C17—H17	0.9500

C3ⁱ—N1—C2	118.95 (12)	C10—C9—H9	120.2
N1—C2—C3	119.76 (12)	C11—C10—C9	120.21 (17)
N1—C2—C4	117.14 (13)	C11—C10—H10	119.9
C3—C2—C4	123.06 (13)	C9—C10—H10	119.9
N1ⁱ—C3—C2	121.29 (13)	C10—C11—C6	120.97 (16)
N1ⁱ—C3—C12	115.04 (12)	C10—C11—H11	119.5
C2—C3—C12	123.65 (12)	C6—C11—H11	119.5
C5—C4—C2	124.26 (14)	N13—C12—C17	122.83 (15)
C5—C4—H4	117.9	N13—C12—C3	116.76 (13)
C2—C4—H4	117.9	C17—C12—C3	120.31 (14)
C4—C5—C6	126.81 (14)	C14—N13—C12	117.03 (14)
C4—C5—H5	116.6	N13—C14—C15	124.01 (16)
C6—C5—H5	116.6	N13—C14—H14	118.0
C11—C6—C7	117.79 (14)	C15—C14—H14	118.0
C11—C6—C5	123.22 (13)	C14—C15—C16	118.66 (17)
C7—C6—C5	118.99 (14)	C14—C15—H15	120.7
C8—C7—C6	120.94 (17)	C16—C15—H15	120.7
C8—C7—H7	119.5	C15—C16—C17	118.92 (16)
C6—C7—H7	119.5	C15—C16—H16	120.5
C9—C8—C7	120.52 (17)	C17—C16—H16	120.5
C9—C8—H8	119.7	C16—C17—C12	118.51 (16)
C7—C8—H8	119.7	C16—C17—H17	120.7
C8—C9—C10	119.56 (16)	C12—C17—H17	120.7
C8—C9—H9	120.2

C3ⁱ—N1—C2—C3	−0.4 (2)	C9—C10—C11—C6	−0.2 (2)
C3ⁱ—N1—C2—C4	177.52 (12)	C7—C6—C11—C10	0.7 (2)
N1—C2—C3—N1ⁱ	0.4 (2)	C5—C6—C11—C10	−179.48 (14)
C4—C2—C3—N1ⁱ	−177.38 (12)	N1ⁱ—C3—C12—N13	−130.40 (13)
N1—C2—C3—C12	−177.97 (12)	C2—C3—C12—N13	48.11 (17)
C4—C2—C3—C12	4.2 (2)	N1ⁱ—C3—C12—C17	46.03 (17)
N1—C2—C4—C5	12.6 (2)	C2—C3—C12—C17	−135.47 (14)
C3—C2—C4—C5	−169.56 (13)	C17—C12—N13—C14	−1.5 (2)
C2—C4—C5—C6	−179.88 (13)	C3—C12—N13—C14	174.83 (12)
C4—C5—C6—C11	9.9 (2)	C12—N13—C14—C15	1.6 (2)
C4—C5—C6—C7	−170.21 (15)	N13—C14—C15—C16	−0.1 (2)
C11—C6—C7—C8	−0.8 (2)	C14—C15—C16—C17	−1.6 (2)
C5—C6—C7—C8	179.34 (15)	C15—C16—C17—C12	1.7 (2)
C6—C7—C8—C9	0.5 (3)	N13—C12—C17—C16	−0.1 (2)
C7—C8—C9—C10	−0.1 (3)	C3—C12—C17—C16	−176.32 (13)
C8—C9—C10—C11	−0.1 (3)

Open in a new tab

Symmetry code: (i) −x+1, −y+1, −z+1.

References

Burla, M. C., Caliandro, R., Camalli, M., Carrozzini, B., Cascarano, G. L., De Caro, L., Giacovazzo, C., Polidori, G. & Spagna, R. (2005). J. Appl. Cryst. 38, 381–388.
Kolb, A. (1896). Justus Liebigs Ann. Chem. 291, 253–297.
Röder, N., Marszalek, T., Limbach, D., Pisula, W. & Detert, H. (2019). ChemPhysChem, 20, 463–469. [DOI] [PubMed]
Schmitt, V., Glang, S., Preis, J. & Detert, H. (2008). Sen Lett, 6, 524–530.
Schmitt, V., Moschel, S. & Detert, H. (2013). Eur. J. Org. Chem. pp. 5655–5669.
Schmitt, V., Schollmeyer, D. & Detert, H. (2011). Acta Cryst. E67, o1553. [DOI] [PMC free article] [PubMed]
Sheldrick, G. M. (2015). Acta Cryst. C71, 3–8.
Spek, A. L. (2020). Acta Cryst. E76, 1–11. [DOI] [PMC free article] [PubMed]
Stoe & Cie (1996). X-RED and X-AREA. Stoe & Cie, Darmstadt, Germany.
Wink, C. & Detert, H. (2013). J. Phys. Org. Chem. 26, 137–143.

Associated Data

This section collects any data citations, data availability statements, or supplementary materials included in this article.

Supplementary Materials

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S2414314620003727/bt4090sup1.cif

x-05-x200372-sup1.cif^{(219KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S2414314620003727/bt4090Isup2.hkl

x-05-x200372-Isup2.hkl^{(217.5KB, hkl)}

Click here for additional data file.^{(8.8KB, cml)}

Supporting information file. DOI: 10.1107/S2414314620003727/bt4090Isup3.cml

CCDC reference: 1989990

Additional supporting information: crystallographic information; 3D view; checkCIF report

[bb1] Burla, M. C., Caliandro, R., Camalli, M., Carrozzini, B., Cascarano, G. L., De Caro, L., Giacovazzo, C., Polidori, G. & Spagna, R. (2005). J. Appl. Cryst. 38, 381–388.

[bb2] Kolb, A. (1896). Justus Liebigs Ann. Chem. 291, 253–297.

[bb3] Röder, N., Marszalek, T., Limbach, D., Pisula, W. & Detert, H. (2019). ChemPhysChem, 20, 463–469. [DOI] [PubMed]

[bb4] Schmitt, V., Glang, S., Preis, J. & Detert, H. (2008). Sen Lett, 6, 524–530.

[bb5] Schmitt, V., Moschel, S. & Detert, H. (2013). Eur. J. Org. Chem. pp. 5655–5669.

[bb6] Schmitt, V., Schollmeyer, D. & Detert, H. (2011). Acta Cryst. E67, o1553. [DOI] [PMC free article] [PubMed]

[bb7] Sheldrick, G. M. (2015). Acta Cryst. C71, 3–8.

[bb8] Spek, A. L. (2020). Acta Cryst. E76, 1–11. [DOI] [PMC free article] [PubMed]

[bb9] Stoe & Cie (1996). X-RED and X-AREA. Stoe & Cie, Darmstadt, Germany.

[bb10] Wink, C. & Detert, H. (2013). J. Phys. Org. Chem. 26, 137–143.

PERMALINK

2,5-Bis[(E)-2-phenylethenyl]-3,6-bis(pyridin-2-yl)pyrazine

Heiner Detert

Matthias Jochem

Dieter Schollmeyer

Roles

Abstract

Structure description

Figure 1.

Figure 2.

Synthesis and crystallization

Refinement

Table 1. Experimental details.

Supplementary Material

full crystallographic data

Crystal data

Data collection

Refinement

Special details

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

Atomic displacement parameters (Å²)

Geometric parameters (Å, º)

References

Associated Data

Supplementary Materials

ACTIONS

PERMALINK

RESOURCES

Cite

Add to Collections

PERMALINK

2,5-Bis[(E)-2-phenyl­ethen­yl]-3,6-bis­(pyridin-2-yl)pyrazine

Heiner Detert

Matthias Jochem

Dieter Schollmeyer

Roles

Abstract

Structure description

Figure 1.

Figure 2.

Synthesis and crystallization

Refinement

Table 1. Experimental details.

Supplementary Material

full crystallographic data

Crystal data

Data collection

Refinement

Special details

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

Atomic displacement parameters (Å2)

Geometric parameters (Å, º)

References

Associated Data

Supplementary Materials

ACTIONS

PERMALINK

RESOURCES

Similar articles

Cited by other articles

Links to NCBI Databases

2,5-Bis[(E)-2-phenylethenyl]-3,6-bis(pyridin-2-yl)pyrazine

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

Atomic displacement parameters (Å²)