organic compounds
N′-[1-(Pyrazin-2-yl)ethylidene]pyrazine-2-carbohydrazide
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
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).
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 .
details are summarized in Table 2Structural data
CCDC reference: 1852715
https://doi.org/10.1107/S241431461801146X/hb4253sup1.cif
contains datablock I. DOI: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
Data collection: APEX2 (Bruker, 2014); cell
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).C11H10N6O | Z = 2 |
Mr = 242.25 | F(000) = 252 |
Triclinic, P1 | Dx = 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 |
Bruker P4 diffractometer | Rint = 0.037 |
ω scan | θmax = 25.0°, θmin = 2.6° |
Absorption correction: multi-scan (SADABS; Bruker, 2014) | h = −8→8 |
Tmin = 0.598, Tmax = 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 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(Fo2) + (0.1018P)2 + 1.0907P] where P = (Fo2 + 2Fc2)/3 |
S = 1.08 | (Δ/σ)max < 0.001 |
1918 reflections | Δρmax = 0.36 e Å−3 |
165 parameters | Δρmin = −0.33 e Å−3 |
0 restraints |
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 Uiso values of all C(H) groups and all N(H) groups were set to 1.2Ueq(C). The Uiso values of all C(H,H,H)groups were set to 1.5Ueq(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) |
x | y | z | Uiso*/Ueq | ||
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* |
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) |
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) |
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.