(E)-2-Acetyl­pyrazine 4-nitro­phenyl­hydrazone

Shan, S.; Tian, Y.-L.; Wang, S.-H.; Wang, W.-L.; Xu, Y.-L.

doi:10.1107/S1600536808017479

organic compounds

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ISSN: 2056-9890

Volume 64| Part 7| July 2008| Page o1265

doi:10.1107/S1600536808017479

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(E)-2-Acetylpyrazine 4-nitrophenylhydrazone

Shang Shan,^a ^* Yu-Liang Tian,^a Shan-Heng Wang,^a Wen-Long Wang ^a and Ying-Li Xu ^a

^aCollege of Chemical Engineering and Materials Science, Zhejiang University of Technology, People's Republic of China
^*Correspondence e-mail: shanshang@mail.hz.zj.cn

(Received 7 June 2008; accepted 10 June 2008; online 13 June 2008)

In the title compound, C₁₂H₁₁N₅O₂, the molecule adopts an E configuration, with the benzene and pyrazine rings located on opposite sides of the N=C double bond. The face-to-face separations of 3.413 (14) and 3.430 (8) Å, respectively between parallel benzene rings and between pyrazine rings indicate the existence of π–π stacking between adjacent molecules. The crystal structure also contains N—H⋯N and C—H⋯O hydrogen bonding.

Related literature

For general background, see: Okabe et al. (1993 ); Hu et al. (2001 ); Chen et al. (2007 ). For a related structure, see: Shan et al. (2008 ).

Experimental

Crystal data

C₁₂H₁₁N₅O₂
M_r = 257.26
Monoclinic, P 2₁ /n
a = 8.0101 (6) Å
b = 12.5154 (11) Å
c = 12.1506 (12) Å
β = 98.564 (2)°
V = 1204.51 (18) Å³
Z = 4
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 295 (2) K
0.40 × 0.38 × 0.26 mm

Data collection

Rigaku R-AXIS RAPID IP diffractometer
Absorption correction: none
11633 measured reflections
2747 independent reflections
1446 reflections with I > 2σ(I)
R_int = 0.033

Refinement

R[F² > 2σ(F²)] = 0.042
wR(F²) = 0.149
S = 1.08
2747 reflections
174 parameters
H-atom parameters constrained
Δρ_max = 0.20 e Å⁻³
Δρ_min = −0.19 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2N⋯N5ⁱ	0.91	2.30	3.185 (2)	164
C11—H11⋯O1ⁱⁱ	0.93	2.60	3.300 (3)	133
Symmetry codes: (i) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (ii) x-1, y-1, z.

Data collection: PROCESS-AUTO (Rigaku, 1998 ); cell refinement: PROCESS-AUTO; data reduction: CrystalStructure (Rigaku, 2002 ); program(s) used to solve structure: SIR92 (Altomare et al., 1993 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808017479/sg2248sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808017479/sg2248Isup2.hkl

checkCIF report

Comment top

Hydrazone and its derivatives have attracted much attention because of their potential application in biology (Okabe et al., 1993; Hu et al., 2001). As part of an ongoing investigation into anti-cancer compounds (Chen et al., 2007), the title compound has recently been prepared in our laboratory and its crystal structure is presented here.

The molecular structure of the title compound is shown in Fig. 1. The molecule adopts an E-configuration, with the benzene and pyrazine rings located on the opposite positions of the N3=C7 double bond, similar to that found in a related structure, (E)-2-Furyl methyl ketone 2,4-dinitrophenylhydrazone (Shan et al., 2008). The pyrazine plane is twisted with respect to the benzene ring by a smaller dihedral angle of 14.25 (10)°.

The partially overlapped arrangement is observed between parallel benzene rings and between parallel pyrazine rings (Fig. 2), face-to-face separations of 3.413 (14) [for benzene rings] and 3.430 (8) Å [for pyrazine rings] are significantly shorter than van der Waals thickness of the aromatic ring (3.70 Å), and indicate the existence of π-π stacking between the adjacent molecules. Intermolecular N—H···N and weak C—H···O hydrogen bondings are present in the crystal structure (Table 1).

Related literature top

For general background, see: Okabe et al. (1993); Hu et al. (2001); Chen et al. (2007). For a related structure, see: Shan et al. (2008).

Experimental top

4-Nitrophenylhydrazine (0.31 g, 2 mmol) was dissolved in ethanol (10 ml), then H₂SO₄ solution (98%, 0.5 ml) was added slowly to the ethanol solution with stirring. The solution was heated at about 333 K for several minutes until the solution cleared. An ethanol solution (5 ml) of acetylpyrazine (0.24 g, 2 mmol) was dropped slowly into the above solution with continuous stirring, and the mixture solution was kept at about 333 K for 0.5 h. When the solution had cooled to room temperature, yellow microcrystals appeared. They were separated and washed with cold water three times to get the product 0.40 g. Single crystals of the title compound were obtained by recrystallization from an absolute ethanol solution.

Computing details top

Data collection: PROCESS-AUTO (Rigaku, 1998); cell refinement: PROCESS-AUTO (Rigaku, 1998); data reduction: CrystalStructure (Rigaku, 2002); program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

	Fig. 1. The molecular structure of (I) with 30% probability displacement ellipsoids (arbitrary spheres for H atoms), dashed line indicates hydrogen bonding.
	Fig. 2. A diagram showing π-π stacking [symmetry codes: (i) 2 - x,1 - y,1 - z; (ii) 1 - x,-y,1 - z].

(E)-2-Acetylpyrazine 4-nitrophenylhydrazone top

Crystal data top

C₁₂H₁₁N₅O₂	F(000) = 536
M_r = 257.26	D_x = 1.419 Mg m⁻³
Monoclinic, P2₁/n	Melting point: 498 K
Hall symbol: -P 2yn	Mo Kα radiation, λ = 0.71069 Å
a = 8.0101 (6) Å	Cell parameters from 4236 reflections
b = 12.5154 (11) Å	θ = 3.2–25.0°
c = 12.1506 (12) Å	µ = 0.10 mm⁻¹
β = 98.564 (2)°	T = 295 K
V = 1204.51 (18) Å³	Prism, yellow
Z = 4	0.40 × 0.38 × 0.26 mm

Data collection top

Rigaku R-AXIS RAPID IP diffractometer	1446 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.033
Graphite monochromator	θ_max = 27.4°, θ_min = 3.0°
Detector resolution: 10.00 pixels mm^-1	h = −10→10
ω scans	k = −16→16
11633 measured reflections	l = −15→15
2747 independent reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.042	H-atom parameters constrained
wR(F²) = 0.149	w = 1/[σ²(F_o²) + (0.0615P)² + 0.2787P] where P = (F_o² + 2F_c²)/3
S = 1.09	(Δ/σ)_max = 0.001
2747 reflections	Δρ_max = 0.20 e Å⁻³
174 parameters	Δρ_min = −0.19 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.024 (3)

Crystal data top

C₁₂H₁₁N₅O₂	V = 1204.51 (18) Å³
M_r = 257.26	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 8.0101 (6) Å	µ = 0.10 mm⁻¹
b = 12.5154 (11) Å	T = 295 K
c = 12.1506 (12) Å	0.40 × 0.38 × 0.26 mm
β = 98.564 (2)°

Data collection top

Rigaku R-AXIS RAPID IP diffractometer	1446 reflections with I > 2σ(I)
11633 measured reflections	R_int = 0.033
2747 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.042	0 restraints
wR(F²) = 0.149	H-atom parameters constrained
S = 1.09	Δρ_max = 0.20 e Å⁻³
2747 reflections	Δρ_min = −0.19 e Å⁻³
174 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.

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
N1	0.9003 (3)	0.68785 (16)	0.3418 (2)	0.0684 (6)
N2	0.6332 (2)	0.36085 (12)	0.57394 (13)	0.0448 (4)
H2N	0.6470	0.3652	0.6496	0.054*
N3	0.5365 (2)	0.28334 (12)	0.51838 (13)	0.0425 (4)
N4	0.3197 (2)	0.04376 (14)	0.55830 (14)	0.0518 (5)
N5	0.2175 (2)	0.07812 (15)	0.33069 (14)	0.0571 (5)
O1	0.9806 (3)	0.75846 (16)	0.3955 (2)	0.1041 (8)
O2	0.8729 (3)	0.68826 (16)	0.2397 (2)	0.1012 (8)
C1	0.6976 (2)	0.43994 (15)	0.51344 (16)	0.0412 (5)
C2	0.7855 (3)	0.52394 (16)	0.57162 (17)	0.0490 (5)
H2	0.7989	0.5251	0.6490	0.059*
C3	0.8519 (3)	0.60439 (16)	0.51558 (18)	0.0521 (5)
H3	0.9109	0.6601	0.5544	0.062*
C4	0.8306 (3)	0.60198 (15)	0.40117 (18)	0.0488 (5)
C5	0.7461 (3)	0.51920 (17)	0.34168 (17)	0.0513 (5)
H5	0.7339	0.5187	0.2644	0.062*
C6	0.6803 (3)	0.43744 (17)	0.39758 (16)	0.0482 (5)
H6	0.6246	0.3809	0.3583	0.058*
C7	0.4778 (2)	0.20837 (14)	0.57459 (15)	0.0408 (5)
C8	0.5120 (3)	0.19727 (18)	0.69835 (17)	0.0593 (6)
H8A	0.6317	0.1939	0.7222	0.089*
H8B	0.4602	0.1331	0.7202	0.089*
H8C	0.4663	0.2578	0.7322	0.089*
C9	0.3700 (2)	0.13023 (15)	0.50718 (15)	0.0408 (5)
C10	0.3179 (3)	0.14575 (16)	0.39353 (16)	0.0496 (5)
H10	0.3553	0.2063	0.3602	0.059*
C11	0.1699 (3)	−0.00860 (18)	0.38283 (19)	0.0569 (6)
H11	0.1002	−0.0587	0.3424	0.068*
C12	0.2214 (3)	−0.02519 (17)	0.49398 (19)	0.0554 (6)
H12	0.1865	−0.0871	0.5263	0.067*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0742 (15)	0.0486 (11)	0.0895 (17)	0.0037 (10)	0.0352 (12)	0.0135 (11)
N2	0.0566 (11)	0.0430 (9)	0.0341 (8)	−0.0036 (8)	0.0039 (7)	−0.0005 (7)
N3	0.0478 (10)	0.0391 (8)	0.0397 (9)	0.0001 (7)	0.0036 (7)	−0.0009 (7)
N4	0.0623 (12)	0.0469 (10)	0.0465 (10)	−0.0033 (8)	0.0094 (8)	0.0044 (8)
N5	0.0678 (13)	0.0578 (11)	0.0435 (10)	−0.0075 (9)	0.0012 (9)	−0.0042 (9)
O1	0.1140 (18)	0.0645 (12)	0.137 (2)	−0.0350 (12)	0.0270 (15)	0.0119 (13)
O2	0.146 (2)	0.0841 (14)	0.0860 (15)	−0.0086 (13)	0.0569 (14)	0.0232 (12)
C1	0.0454 (11)	0.0388 (10)	0.0393 (10)	0.0033 (8)	0.0064 (8)	−0.0002 (8)
C2	0.0588 (13)	0.0456 (11)	0.0419 (11)	−0.0015 (10)	0.0050 (9)	−0.0038 (9)
C3	0.0542 (13)	0.0412 (11)	0.0609 (14)	−0.0029 (9)	0.0087 (10)	−0.0062 (10)
C4	0.0517 (12)	0.0405 (10)	0.0577 (13)	0.0055 (9)	0.0198 (10)	0.0075 (10)
C5	0.0610 (14)	0.0527 (12)	0.0414 (11)	0.0029 (10)	0.0117 (10)	0.0022 (10)
C6	0.0569 (13)	0.0471 (11)	0.0411 (11)	−0.0013 (10)	0.0088 (9)	−0.0023 (9)
C7	0.0469 (12)	0.0381 (10)	0.0370 (10)	0.0050 (8)	0.0046 (8)	0.0027 (8)
C8	0.0780 (17)	0.0573 (13)	0.0396 (12)	−0.0086 (12)	−0.0009 (11)	0.0065 (10)
C9	0.0459 (11)	0.0391 (10)	0.0379 (10)	0.0036 (8)	0.0079 (8)	0.0035 (8)
C10	0.0605 (14)	0.0483 (11)	0.0394 (11)	−0.0045 (10)	0.0060 (10)	0.0024 (9)
C11	0.0619 (15)	0.0520 (13)	0.0561 (13)	−0.0091 (11)	0.0064 (11)	−0.0063 (11)
C12	0.0634 (14)	0.0473 (12)	0.0568 (13)	−0.0107 (10)	0.0127 (11)	0.0019 (11)

Geometric parameters (Å, º) top

N1—O1	1.223 (3)	C3—H3	0.9300
N1—O2	1.226 (3)	C4—C5	1.381 (3)
N1—C4	1.452 (3)	C5—C6	1.376 (3)
N2—N3	1.357 (2)	C5—H5	0.9300
N2—C1	1.378 (2)	C6—H6	0.9300
N2—H2N	0.9106	C7—C9	1.470 (3)
N3—C7	1.290 (2)	C7—C8	1.494 (3)
N4—C12	1.339 (3)	C8—H8A	0.9600
N4—C9	1.339 (2)	C8—H8B	0.9600
N5—C10	1.328 (3)	C8—H8C	0.9600
N5—C11	1.340 (3)	C9—C10	1.395 (3)
C1—C6	1.394 (3)	C10—H10	0.9300
C1—C2	1.397 (3)	C11—C12	1.368 (3)
C2—C3	1.367 (3)	C11—H11	0.9300
C2—H2	0.9300	C12—H12	0.9300
C3—C4	1.375 (3)

O1—N1—O2	122.5 (2)	C5—C6—C1	119.6 (2)
O1—N1—C4	118.7 (2)	C5—C6—H6	120.2
O2—N1—C4	118.8 (2)	C1—C6—H6	120.2
N3—N2—C1	118.65 (15)	N3—C7—C9	114.78 (16)
N3—N2—H2N	121.3	N3—C7—C8	125.00 (18)
C1—N2—H2N	119.8	C9—C7—C8	120.23 (17)
C7—N3—N2	118.88 (16)	C7—C8—H8A	109.5
C12—N4—C9	116.19 (18)	C7—C8—H8B	109.5
C10—N5—C11	115.78 (18)	H8A—C8—H8B	109.5
N2—C1—C6	122.25 (18)	C7—C8—H8C	109.5
N2—C1—C2	118.10 (17)	H8A—C8—H8C	109.5
C6—C1—C2	119.64 (19)	H8B—C8—H8C	109.5
C3—C2—C1	120.42 (19)	N4—C9—C10	120.35 (18)
C3—C2—H2	119.8	N4—C9—C7	118.11 (16)
C1—C2—H2	119.8	C10—C9—C7	121.53 (17)
C2—C3—C4	119.2 (2)	N5—C10—C9	123.13 (19)
C2—C3—H3	120.4	N5—C10—H10	118.4
C4—C3—H3	120.4	C9—C10—H10	118.4
C3—C4—C5	121.53 (19)	N5—C11—C12	121.6 (2)
C3—C4—N1	119.1 (2)	N5—C11—H11	119.2
C5—C4—N1	119.3 (2)	C12—C11—H11	119.2
C6—C5—C4	119.56 (19)	N4—C12—C11	122.9 (2)
C6—C5—H5	120.2	N4—C12—H12	118.6
C4—C5—H5	120.2	C11—C12—H12	118.6

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2N···N5ⁱ	0.91	2.30	3.185 (2)	164
C11—H11···O1ⁱⁱ	0.93	2.60	3.300 (3)	133

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

Experimental details

Crystal data
Chemical formula	C₁₂H₁₁N₅O₂
M_r	257.26
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	295
a, b, c (Å)	8.0101 (6), 12.5154 (11), 12.1506 (12)
β (°)	98.564 (2)
V (Å³)	1204.51 (18)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.40 × 0.38 × 0.26

Data collection
Diffractometer	Rigaku R-AXIS RAPID IP diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	11633, 2747, 1446
R_int	0.033
(sin θ/λ)_max (Å⁻¹)	0.648

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.042, 0.149, 1.09
No. of reflections	2747
No. of parameters	174
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.20, −0.19

Computer programs: PROCESS-AUTO (Rigaku, 1998), CrystalStructure (Rigaku, 2002), SIR92 (Altomare et al., 1993), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2N···N5ⁱ	0.91	2.30	3.185 (2)	164
C11—H11···O1ⁱⁱ	0.93	2.60	3.300 (3)	133

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

Acknowledgements

The work was supported by the Natural Science Foundation of Zhejiang Province of China (No. M203027).

References

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