N′-[1-(Pyrazin-2-yl)ethyl­idene]pyrazine-2-carbo­hydrazide

Wang, Z.

doi:10.1107/S241431461801146X

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 3| Part 8| August 2018| x181146

https://doi.org/10.1107/S241431461801146X

Open

access

N′-[1-(Pyrazin-2-yl)ethylidene]pyrazine-2-carbohydrazide

Zhaodong Wang ^a ^*

^aChongqing Key Laboratory of Environmental, Materials & Remediation Technologies, Chongqing University of Arts and Sciences, Yongchuan, Chongqing, 402160, People's Republic of China
^*Correspondence e-mail: ouwzdong@qq.com

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 10 August 2018; accepted 12 August 2018; online 21 August 2018)

The title compoud, C₁₁H₁₀N₆O, was synthesized by the condensation reaction of pyrazine-2-carbohydrazide with 2-acetylpyrazine in ethanol. The dihedral angle between the pyrazine rings is 4.7 (3)°. In the crystal, aromatic π–π stacking [centroid–centroid separations = 3.606 (5) and 3.671 (5) Å] connect the molecules into stacks propagating in the [010] direction. A weak C—H⋯N interaction is also observed. The crystal studied was refined as a two-component twin.

Keywords: crystal structure; pyrazine; acylhydrazone.

CCDC reference: 1852715

Structure description

The Schiff base acylhydrazone ligand has been well studied and used in supramolecular chemistry (Stadler & Harrowfield, 2009 ). Its applications have focused on molecular switches (Coskun et al., 2012 ), sensors (Albelda et al., 2012 ) and single molecular magnets (SMMs) (Anwar et al., 2018 ). 2-Acetylpyrazine-based hydrazone ligands and their transition metal chemistry have also been reported (Hou et al., 2018 ; Li et al., 2015 ). As part of our studies in this area, we synthesized the title 2-acetylpyrazine-based hydrazone ligand with two pyrazine rings as a possible new ligand.

The dihedral angle between the pyrazine rings is 4.7 (3)° (Fig. 1). The C2—N2 bond length is 1.291 (7) Å, which is shorter than C1—N1 [1.362 (7) Å], showing that C2—N2 has strong double-bond character. The N—H grouping is sterically hindered from forming hydrogen bonds but a short intramolecular N—H⋯N contact occurs (Table 1). In the crystal, aromatic π–π stacking [centroid–centroid separations = 3.606 (5) and 3.671 (5) Å] connect the molecules into stacks propagating in the [010] direction (Fig. 2). A weak C—H⋯N interaction is also observed (Table 1).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯N5	0.86	2.28	2.671 (7)	108
C7—H7C⋯N4ⁱ	0.96	2.57	3.247 (8)	127
Symmetry code: (i) x, y-1, z.

Figure 1
The title compound showing displacement ellipsoids drawn at the 50% probability level.

Figure 2
Crystal packing viewed along the b-axis direction.

Synthesis and crystallization

The title molecule was prepared by the condensation reaction of pyrazine-2-carbohydrazide (1.38 g, 10 mmol) with 2-acetylpyrazine (1.22 g, 10 mmol) in 50 ml of refluxing ethanol for 16 h, resulting in a transparent light-yellow solution. After one night, colourless crystals suitable for X-ray analysis had formed.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	C₁₁H₁₀N₆O
M_r	242.25
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	296
a, b, c (Å)	7.247 (8), 8.066 (9), 9.77 (1)
α, β, γ (°)	79.706 (14), 79.526 (15), 89.518 (14)
V (Å³)	552.4 (10)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	0.10
Crystal size (mm)	0.2 × 0.17 × 0.12

Data collection
Diffractometer	Bruker P4
Absorption correction	Multi-scan (SADABS; Bruker, 2014 )
T_min, T_max	0.598, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	1918, 1918, 1155
R_int	0.037
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.087, 0.268, 1.08
No. of reflections	1918
No. of parameters	165
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.36, −0.33
Computer programs: APEX2 and SAINT (Bruker, 2014), SHELXT (Sheldrick, 2015a ), SHELXL2018 (Sheldrick, 2015b ) and OLEX2 (Dolomanov et al., 2009 ).

Structural data

CCDC reference: 1852715

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S241431461801146X/hb4253sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S241431461801146X/hb4253Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S241431461801146X/hb4253Isup3.cml

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2014); cell refinement: SAINT (Bruker, 2014); data reduction: SAINT (Bruker, 2013); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018 (Sheldrick, 2015b); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

N'-[1-(Pyrazin-2-yl)ethylidene]pyrazine-2-carbohydrazide top

Crystal data top

C₁₁H₁₀N₆O	Z = 2
M_r = 242.25	F(000) = 252
Triclinic, P1	D_x = 1.456 Mg m⁻³
a = 7.247 (8) Å	Mo Kα radiation, λ = 0.71073 Å
b = 8.066 (9) Å	Cell parameters from 1331 reflections
c = 9.77 (1) Å	θ = 2.6–27.8°
α = 79.706 (14)°	µ = 0.10 mm⁻¹
β = 79.526 (15)°	T = 296 K
γ = 89.518 (14)°	Block, colourless
V = 552.4 (10) Å³	0.2 × 0.17 × 0.12 mm

Data collection top

Bruker P4 diffractometer	R_int = 0.037
ω scan	θ_max = 25.0°, θ_min = 2.6°
Absorption correction: multi-scan (SADABS; Bruker, 2014)	h = −8→8
T_min = 0.598, T_max = 0.746	k = −9→9
1918 measured reflections	l = −11→11
1918 independent reflections	1 standard reflections every 20 reflections
1155 reflections with I > 2σ(I)	intensity decay: 1%

Refinement top

Refinement on F²	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.087	H-atom parameters constrained
wR(F²) = 0.268	w = 1/[σ²(F_o²) + (0.1018P)² + 1.0907P] where P = (F_o² + 2F_c²)/3
S = 1.08	(Δ/σ)_max < 0.001
1918 reflections	Δρ_max = 0.36 e Å⁻³
165 parameters	Δρ_min = −0.33 e Å⁻³
0 restraints

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.

Refinement. Refined as a 2-component twin.

The U_iso values of all C(H) groups and all N(H) groups were set to 1.2U_eq(C). The U_iso values of all C(H,H,H)groups were set to 1.5U_eq(C) Aromatic/amide H refined with riding coordinates: N1(H1), C6(H6), C4(H4), C11(H11), C9(H9), C10(H10), C5(H5) Idealized Me refined as rotating group: C7(H7A,H7B,H7C)

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

	x	y	z	U_iso*/U_eq
O1	0.6785 (7)	1.0992 (5)	−0.2460 (4)	0.0522 (13)
N1	0.7251 (7)	0.9311 (5)	−0.0408 (4)	0.0346 (12)
H1	0.727205	0.829179	0.003733	0.042*
N2	0.7598 (6)	1.0627 (5)	0.0231 (4)	0.0315 (11)
N3	0.8448 (8)	1.1337 (6)	0.3525 (5)	0.0436 (14)
N4	0.8932 (8)	1.4608 (6)	0.1988 (5)	0.0454 (14)
N5	0.6503 (7)	0.6541 (6)	−0.1374 (5)	0.0375 (12)
N6	0.6035 (8)	0.6692 (7)	−0.4173 (5)	0.0510 (15)
C1	0.6874 (8)	0.9607 (7)	−0.1745 (6)	0.0329 (14)
C2	0.7991 (7)	1.0232 (6)	0.1484 (5)	0.0278 (13)
C3	0.8373 (8)	1.1694 (6)	0.2138 (6)	0.0320 (13)
C4	0.8768 (10)	1.2648 (7)	0.4115 (6)	0.0479 (17)
H4	0.885694	1.246186	0.506743	0.057*
C5	0.8969 (9)	1.4251 (8)	0.3369 (7)	0.0469 (17)
H5	0.913865	1.512815	0.383846	0.056*
C6	0.8640 (9)	1.3318 (6)	0.1381 (6)	0.0381 (15)
H6	0.861439	1.351038	0.041703	0.046*
C7	0.8116 (10)	0.8504 (7)	0.2285 (6)	0.0473 (17)
H7A	0.688201	0.799464	0.257749	0.071*
H7B	0.865746	0.855539	0.310357	0.071*
H7C	0.888978	0.784256	0.169222	0.071*
C8	0.6552 (8)	0.8001 (6)	−0.2275 (6)	0.0325 (13)
C9	0.6244 (9)	0.5172 (7)	−0.1905 (6)	0.0439 (16)
H9	0.623360	0.412256	−0.132576	0.053*
C10	0.5992 (9)	0.5243 (8)	−0.3272 (6)	0.0455 (16)
H10	0.578353	0.424432	−0.357767	0.055*
C11	0.6329 (9)	0.8077 (8)	−0.3658 (6)	0.0435 (16)
H11	0.638494	0.912245	−0.424953	0.052*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.082 (4)	0.032 (2)	0.043 (3)	0.001 (2)	−0.016 (2)	0.0002 (19)
N1	0.045 (3)	0.026 (2)	0.032 (3)	−0.006 (2)	−0.006 (2)	−0.006 (2)
N2	0.036 (3)	0.026 (2)	0.032 (3)	−0.002 (2)	−0.003 (2)	−0.008 (2)
N3	0.057 (4)	0.040 (3)	0.034 (3)	−0.006 (2)	−0.008 (3)	−0.007 (2)
N4	0.065 (4)	0.026 (2)	0.046 (3)	−0.005 (2)	−0.008 (3)	−0.009 (2)
N5	0.046 (3)	0.033 (3)	0.032 (3)	−0.004 (2)	−0.006 (2)	−0.005 (2)
N6	0.064 (4)	0.054 (3)	0.037 (3)	−0.011 (3)	−0.010 (3)	−0.015 (3)
C1	0.038 (4)	0.028 (3)	0.032 (3)	−0.001 (2)	−0.005 (3)	−0.005 (2)
C2	0.030 (3)	0.020 (2)	0.031 (3)	0.000 (2)	−0.003 (3)	−0.001 (2)
C3	0.035 (3)	0.030 (3)	0.030 (3)	0.001 (2)	−0.004 (3)	−0.005 (2)
C4	0.066 (5)	0.045 (4)	0.034 (3)	−0.009 (3)	−0.011 (3)	−0.009 (3)
C5	0.060 (4)	0.044 (4)	0.042 (4)	−0.006 (3)	−0.011 (3)	−0.020 (3)
C6	0.058 (4)	0.021 (3)	0.035 (3)	−0.002 (3)	−0.010 (3)	−0.002 (2)
C7	0.072 (5)	0.027 (3)	0.039 (3)	−0.007 (3)	−0.009 (3)	0.003 (3)
C8	0.030 (3)	0.030 (3)	0.036 (3)	−0.003 (2)	−0.002 (3)	−0.006 (2)
C9	0.056 (4)	0.033 (3)	0.041 (3)	−0.014 (3)	−0.004 (3)	−0.005 (3)
C10	0.054 (4)	0.040 (3)	0.045 (4)	−0.009 (3)	−0.009 (3)	−0.014 (3)
C11	0.055 (4)	0.043 (3)	0.031 (3)	−0.005 (3)	−0.006 (3)	−0.004 (3)

Geometric parameters (Å, º) top

O1—C1	1.215 (6)	C2—C7	1.482 (7)
N1—H1	0.8600	C3—C6	1.381 (7)
N1—N2	1.371 (6)	C4—H4	0.9300
N1—C1	1.362 (7)	C4—C5	1.361 (8)
N2—C2	1.291 (7)	C5—H5	0.9300
N3—C3	1.345 (7)	C6—H6	0.9300
N3—C4	1.332 (7)	C7—H7A	0.9600
N4—C5	1.333 (8)	C7—H7B	0.9600
N4—C6	1.323 (7)	C7—H7C	0.9600
N5—C8	1.335 (7)	C8—C11	1.380 (8)
N5—C9	1.329 (7)	C9—H9	0.9300
N6—C10	1.329 (8)	C9—C10	1.372 (8)
N6—C11	1.339 (7)	C10—H10	0.9300
C1—C8	1.514 (7)	C11—H11	0.9300
C2—C3	1.487 (7)

N2—N1—H1	119.8	C4—C5—H5	118.8
C1—N1—H1	119.8	N4—C6—C3	121.8 (5)
C1—N1—N2	120.4 (4)	N4—C6—H6	119.1
C2—N2—N1	116.3 (4)	C3—C6—H6	119.1
C4—N3—C3	115.7 (5)	C2—C7—H7A	109.5
C6—N4—C5	116.3 (5)	C2—C7—H7B	109.5
C9—N5—C8	115.4 (5)	C2—C7—H7C	109.5
C10—N6—C11	115.6 (5)	H7A—C7—H7B	109.5
O1—C1—N1	125.2 (5)	H7A—C7—H7C	109.5
O1—C1—C8	122.1 (5)	H7B—C7—H7C	109.5
N1—C1—C8	112.7 (5)	N5—C8—C1	118.1 (5)
N2—C2—C3	114.7 (4)	N5—C8—C11	122.1 (5)
N2—C2—C7	126.4 (5)	C11—C8—C1	119.8 (5)
C7—C2—C3	118.9 (5)	N5—C9—H9	118.6
N3—C3—C2	115.7 (5)	N5—C9—C10	122.8 (6)
N3—C3—C6	121.6 (5)	C10—C9—H9	118.6
C6—C3—C2	122.7 (5)	N6—C10—C9	122.1 (5)
N3—C4—H4	118.9	N6—C10—H10	118.9
N3—C4—C5	122.2 (6)	C9—C10—H10	118.9
C5—C4—H4	118.9	N6—C11—C8	122.0 (5)
N4—C5—C4	122.3 (5)	N6—C11—H11	119.0
N4—C5—H5	118.8	C8—C11—H11	119.0

O1—C1—C8—N5	−173.8 (5)	C1—C8—C11—N6	−179.8 (6)
O1—C1—C8—C11	6.5 (9)	C2—C3—C6—N4	178.3 (6)
N1—N2—C2—C3	179.5 (5)	C3—N3—C4—C5	1.3 (9)
N1—N2—C2—C7	0.5 (8)	C4—N3—C3—C2	−179.3 (6)
N1—C1—C8—N5	5.8 (7)	C4—N3—C3—C6	0.9 (9)
N1—C1—C8—C11	−173.9 (5)	C5—N4—C6—C3	0.5 (9)
N2—N1—C1—O1	−1.1 (9)	C6—N4—C5—C4	1.7 (10)
N2—N1—C1—C8	179.4 (5)	C7—C2—C3—N3	−12.5 (8)
N2—C2—C3—N3	168.4 (5)	C7—C2—C3—C6	167.4 (6)
N2—C2—C3—C6	−11.8 (8)	C8—N5—C9—C10	−1.7 (9)
N3—C3—C6—N4	−1.8 (10)	C9—N5—C8—C1	−179.0 (5)
N3—C4—C5—N4	−2.7 (11)	C9—N5—C8—C11	0.6 (8)
N5—C8—C11—N6	0.6 (10)	C10—N6—C11—C8	−0.7 (9)
N5—C9—C10—N6	1.7 (10)	C11—N6—C10—C9	−0.4 (10)
C1—N1—N2—C2	−178.2 (5)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···N5	0.86	2.28	2.671 (7)	108
C7—H7C···N4ⁱ	0.96	2.57	3.247 (8)	127

Symmetry code: (i) x, y−1, z.

Funding information

The author would like to thank the major cultivation project of Chongqing University of Arts and Sciences (No. P2017CH10) for financial support.

References

Albelda, M. T., Frias, J. C., Garcia-Espana, E. & Schneider, H. J. (2012). Chem. Soc. Rev. 41, 3859–3877. Google Scholar
Anwar, M. U., Al-Harrasi, A., Gavey, E. L., Pilkington, M., Rawson, J. M. & Thompson, L. K. (2018). Dalton Trans. 47, 2511–2521. CrossRef Google Scholar
Bruker (2014). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Coskun, A., Banaszak, M., Astumian, R. D., Stoddart, J. F. & Grzybowski, B. A. (2012). Chem. Soc. Rev. 41, 19–30. CrossRef Google Scholar
Dolomanov, O. V., Bourhis, L. J., Gildea, R. J., Howard, J. A. K. & Puschmann, H. (2009). J. Appl. Cryst. 42, 339–341. Web of Science CrossRef CAS IUCr Journals Google Scholar
Hou, X.-F., Zhao, X.-L., Zhang, L., Wu, W.-N. & Wang, Y. (2018). Chin. J. Inorg. Chem. 34, 201–205. Google Scholar
Li, C.-R., Liao, Z.-C., Qin, J.-C., Wang, B.-D. & Yang, Z.-Y. (2015). J. Lumin. 168, 330–333. CrossRef Google Scholar
Sheldrick, G. M. (2015a). Acta Cryst. A71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2015b). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Stadler, A. M. & Harrowfield, J. (2009). Inorg. Chim. Acta, 362, 4298–4314. CrossRef Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.