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ISSN: 2056-9890

(Z,Z)-N′′-[Amino­(pyrazin-2-yl)methyl­ene]pyrazine-2-carbohydrazonamide

aSchool of Chemistry and Chemical Engineering, Southeast University, Nanjing 211189, People's Republic of China
*Correspondence e-mail: cep02chl@yahoo.com.cn

(Received 15 July 2009; accepted 15 July 2009; online 22 July 2009)

The title compound, C10H10N8, resides on a crystallographic symmetry center and features an essentially planar mol­ecule [r.m.s. deviation = 0.278 (1) Å]. In the C=N—N=C fragment, the C=N distance is 1.3017 (18) Å and the N—N distance is 1.403 (2) Å. In the crystal, adjacent mol­ecules are linked by N—H⋯N hydrogen bonds into a three-dimensional network.

Related literature

For related structures, see: Armstrong et al. (1998[Armstrong, J. A., Barnes, J. C. & Weakley, T. J. R. (1998). Acta Cryst. C54, 1923-1925.]), Xu et al. (2006[Xu, R.-H., Zhou, J., Xu, Y., Qi, L., Shen, X. & Zhu, D.-R. (2006). Acta Cryst. E62, o5234-o5235.]), Shi et al. (2008[Shi, S., Yao, T., Geng, X., Chen, L. & Ji, L. (2008). Acta Cryst. E64, o272.]).

[Scheme 1]

Experimental

Crystal data
  • C10H10N8

  • Mr = 242.26

  • Monoclinic, P 21 /c

  • a = 8.6576 (16) Å

  • b = 6.6685 (12) Å

  • c = 9.6162 (18) Å

  • β = 97.682 (4)°

  • V = 550.19 (18) Å3

  • Z = 2

  • Mo Kα radiation

  • μ = 0.10 mm−1

  • T = 295 K

  • 0.30 × 0.19 × 0.16 mm

Data collection
  • Bruker SMART CCD diffractometer

  • Absorption correction: multi-scan (SADABS; Sheldrick, 2000[Sheldrick, G. M. (2000). SADABS. University of Göttingen, Germany.]) Tmin = 0.970, Tmax = 0.984

  • 1946 measured reflections

  • 946 independent reflections

  • 844 reflections with I > 2σ(I)

  • Rint = 0.013

Refinement
  • R[F2 > 2σ(F2)] = 0.038

  • wR(F2) = 0.108

  • S = 1.05

  • 946 reflections

  • 90 parameters

  • H atoms treated by a mixture of independent and constrained refinement

  • Δρmax = 0.20 e Å−3

  • Δρmin = −0.13 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
N3—H3B⋯N2i 0.906 (18) 2.280 (18) 3.0539 (18) 143.2 (14)
N3—H3C⋯N4ii 0.892 (19) 2.405 (18) 3.1587 (18) 142.3 (16)
Symmetry codes: (i) [-x+2, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]; (ii) [x, -y-{\script{1\over 2}}, z+{\script{1\over 2}}].

Data collection: SMART (Bruker, 2000[Bruker (2000). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2000[Bruker (2000). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); software used to prepare material for publication: SHELXL97.

Supporting information


Comment top

The title compound can be regarded as a dihydrazidine with all atoms essentially coplanar and has now been shown to have trans geometry because of steric repulsion effect. In the C=N—N=C fragment, the C=N distance is 1.302 (2) Å, which is much shorter than the N—N distance of 1.403 (2) Å. All other C—N distances are 1.341 (2) Å, which are considered to have full double-bond character. Adjacent molecules are linked into a two-dimensional sheet by intermolecular N—H···N hydrogen bonds with the N···N distance of 3.054 (2) Å. Each molecule acts as double hydrogen-bond acceptors with the 2-positon N atoms of pyrazine rings and donors with the two amino groups.

Related literature top

For related structures, see: Armstrong et al. (1998), Xu et al. (2006), Shi et al. (2008).

Experimental top

A mixture of pyrazine-2-carbonitrile (0.210 g, 2 mmol), MnSO4.H2O (0.169 g, 1 mmol), hydrazine hydrate (80%, 2 ml) and anhydrous ethanol (6 ml) was heated in a 15 ml Teflon-lined autoclave at 393 K for 3 days, followed by slow cooling (5 K h-1) to room temperature. The resulting mixture was filtered and washed with 95% ethanol, and yellow block crystals were collected and dried in vacuum. Yield (0.32 g) 26.4%.

Refinement top

The H atom bonded to N were located in a difference map and freely refined. Other H atoms were positioned geometrically and refined using a riding model with C—H = 0.93 Å and with Uiso(H) = 1.2 Ueq(C).

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL97 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. Structure of the title compound with 30% displacement ellipsoids. [Symmetry code: (A) 2-x, -1-y, -z.]
(Z,Z)-N''-[Amino(pyrazin-2-yl)methylene]pyrazine-2-carbohydrazonamide top
Crystal data top
C10H10N8F(000) = 252
Mr = 242.26Dx = 1.462 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 651 reflections
a = 8.6576 (16) Åθ = 3.9–26.5°
b = 6.6685 (12) ŵ = 0.10 mm1
c = 9.6162 (18) ÅT = 295 K
β = 97.682 (4)°Block, yellow
V = 550.19 (18) Å30.30 × 0.19 × 0.16 mm
Z = 2
Data collection top
Bruker SMART CCD
diffractometer
946 independent reflections
Radiation source: fine-focus sealed tube844 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.013
ϕ and ω scansθmax = 25.0°, θmin = 2.4°
Absorption correction: multi-scan
(SADABS; Sheldrick, 2000)
h = 104
Tmin = 0.970, Tmax = 0.984k = 77
1946 measured reflectionsl = 1111
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.038Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.108H atoms treated by a mixture of independent and constrained refinement
S = 1.05 w = 1/[σ2(Fo2) + (0.0659P)2 + 0.0834P]
where P = (Fo2 + 2Fc2)/3
946 reflections(Δ/σ)max < 0.001
90 parametersΔρmax = 0.20 e Å3
0 restraintsΔρmin = 0.13 e Å3
Crystal data top
C10H10N8V = 550.19 (18) Å3
Mr = 242.26Z = 2
Monoclinic, P21/cMo Kα radiation
a = 8.6576 (16) ŵ = 0.10 mm1
b = 6.6685 (12) ÅT = 295 K
c = 9.6162 (18) Å0.30 × 0.19 × 0.16 mm
β = 97.682 (4)°
Data collection top
Bruker SMART CCD
diffractometer
946 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2000)
844 reflections with I > 2σ(I)
Tmin = 0.970, Tmax = 0.984Rint = 0.013
1946 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0380 restraints
wR(F2) = 0.108H atoms treated by a mixture of independent and constrained refinement
S = 1.05Δρmax = 0.20 e Å3
946 reflectionsΔρmin = 0.13 e Å3
90 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
xyzUiso*/Ueq
C10.71263 (17)0.1470 (2)0.12888 (15)0.0400 (4)
H1A0.71770.26410.18060.048*
C20.61260 (19)0.1595 (2)0.10119 (17)0.0459 (4)
H2A0.55020.26690.13530.055*
C30.69636 (18)0.1731 (2)0.03029 (16)0.0421 (4)
H3A0.68510.28660.08420.050*
C40.80524 (15)0.1312 (2)0.00078 (14)0.0326 (4)
C50.92285 (16)0.2845 (2)0.05271 (14)0.0322 (4)
N10.61789 (15)0.0024 (2)0.18134 (13)0.0462 (4)
N20.79325 (14)0.02862 (18)0.08288 (12)0.0372 (4)
N31.00358 (16)0.2540 (2)0.17988 (13)0.0431 (4)
H3B1.071 (2)0.351 (3)0.2148 (18)0.045 (4)*
H3C0.974 (2)0.154 (3)0.2320 (19)0.050 (5)*
N40.94266 (14)0.43331 (17)0.03069 (11)0.0356 (4)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0420 (8)0.0408 (8)0.0350 (8)0.0018 (6)0.0029 (6)0.0042 (7)
C20.0441 (9)0.0435 (9)0.0475 (9)0.0069 (7)0.0038 (7)0.0066 (7)
C30.0468 (9)0.0355 (8)0.0426 (9)0.0047 (6)0.0013 (7)0.0023 (7)
C40.0353 (8)0.0329 (8)0.0295 (7)0.0030 (6)0.0039 (6)0.0006 (6)
C50.0363 (8)0.0316 (7)0.0280 (7)0.0025 (6)0.0017 (6)0.0015 (6)
N10.0459 (8)0.0486 (8)0.0405 (8)0.0040 (6)0.0078 (6)0.0010 (6)
N20.0429 (7)0.0339 (7)0.0335 (7)0.0024 (5)0.0002 (5)0.0018 (5)
N30.0534 (9)0.0409 (8)0.0317 (7)0.0145 (6)0.0068 (6)0.0050 (6)
N40.0425 (7)0.0312 (7)0.0313 (7)0.0042 (5)0.0016 (5)0.0001 (5)
Geometric parameters (Å, º) top
C1—N11.3219 (19)C4—N21.3386 (18)
C1—C41.393 (2)C4—C51.4815 (19)
C1—H1A0.9300C5—N41.3017 (18)
C2—N11.331 (2)C5—N31.3405 (18)
C2—C31.374 (2)N3—H3B0.906 (18)
C2—H2A0.9300N3—H3C0.893 (19)
C3—N21.3318 (19)N4—N4i1.403 (2)
C3—H3A0.9300
N1—C1—C4122.66 (14)C1—C4—C5122.46 (13)
N1—C1—H1A118.7N4—C5—N3125.59 (13)
C4—C1—H1A118.7N4—C5—C4117.36 (12)
N1—C2—C3122.11 (14)N3—C5—C4117.01 (13)
N1—C2—H2A118.9C1—N1—C2116.02 (13)
C3—C2—H2A118.9C3—N2—C4116.52 (12)
N2—C3—C2122.01 (14)C5—N3—H3B117.6 (10)
N2—C3—H3A119.0C5—N3—H3C118.3 (11)
C2—C3—H3A119.0H3B—N3—H3C123.0 (15)
N2—C4—C1120.49 (13)C5—N4—N4i111.61 (13)
N2—C4—C5117.03 (12)
Symmetry code: (i) x+2, y1, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N3—H3B···N2ii0.906 (18)2.280 (18)3.0539 (18)143.2 (14)
N3—H3C···N4iii0.892 (19)2.405 (18)3.1587 (18)142.3 (16)
Symmetry codes: (ii) x+2, y1/2, z+1/2; (iii) x, y1/2, z+1/2.

Experimental details

Crystal data
Chemical formulaC10H10N8
Mr242.26
Crystal system, space groupMonoclinic, P21/c
Temperature (K)295
a, b, c (Å)8.6576 (16), 6.6685 (12), 9.6162 (18)
β (°) 97.682 (4)
V3)550.19 (18)
Z2
Radiation typeMo Kα
µ (mm1)0.10
Crystal size (mm)0.30 × 0.19 × 0.16
Data collection
DiffractometerBruker SMART CCD
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 2000)
Tmin, Tmax0.970, 0.984
No. of measured, independent and
observed [I > 2σ(I)] reflections
1946, 946, 844
Rint0.013
(sin θ/λ)max1)0.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.038, 0.108, 1.05
No. of reflections946
No. of parameters90
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.20, 0.13

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), SHELXTL97 (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N3—H3B···N2i0.906 (18)2.280 (18)3.0539 (18)143.2 (14)
N3—H3C···N4ii0.892 (19)2.405 (18)3.1587 (18)142.3 (16)
Symmetry codes: (i) x+2, y1/2, z+1/2; (ii) x, y1/2, z+1/2.
 

Acknowledgements

The authors thank the Program for Young Excellent Talents in Southeast University for financial support.

References

First citationArmstrong, J. A., Barnes, J. C. & Weakley, T. J. R. (1998). Acta Cryst. C54, 1923–1925.  Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
First citationBruker (2000). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
First citationSheldrick, G. M. (2000). SADABS. University of Göttingen, Germany.  Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationShi, S., Yao, T., Geng, X., Chen, L. & Ji, L. (2008). Acta Cryst. E64, o272.  Web of Science CSD CrossRef IUCr Journals Google Scholar
First citationXu, R.-H., Zhou, J., Xu, Y., Qi, L., Shen, X. & Zhu, D.-R. (2006). Acta Cryst. E62, o5234–o5235.  Web of Science CSD CrossRef IUCr Journals Google Scholar

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ISSN: 2056-9890
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