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

Zhang, Y.-W.; Wang, J.-Q.; Cheng, L.

doi:10.1107/S1600536809027834

organic compounds

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ISSN: 2056-9890

Volume 65| Part 8| August 2009| Page o1941

doi:10.1107/S1600536809027834

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

Ya-Wen Zhang,^a Jian-Quan Wang ^a and Lin Cheng ^a ^*

^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 ), Xu et al. (2006 ), Shi et al. (2008 ).

Experimental

Crystal data

C₁₀H₁₀N₈
M_r = 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 ) T_min = 0.970, T_max = 0.984
1946 measured reflections
946 independent reflections
844 reflections with I > 2σ(I)
R_int = 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
Δρ_max = 0.20 e Å⁻³
Δρ_min = −0.13 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	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 ); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; 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: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809027834/bt5007sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809027834/bt5007Isup2.hkl

checkCIF report

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%.

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

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

C₁₀H₁₀N₈	F(000) = 252
M_r = 242.26	D_x = 1.462 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 651 reflections
a = 8.6576 (16) Å	θ = 3.9–26.5°
b = 6.6685 (12) Å	µ = 0.10 mm⁻¹
c = 9.6162 (18) Å	T = 295 K
β = 97.682 (4)°	Block, yellow
V = 550.19 (18) Å³	0.30 × 0.19 × 0.16 mm
Z = 2

Data collection top

Bruker SMART CCD diffractometer	946 independent reflections
Radiation source: fine-focus sealed tube	844 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.013
ϕ and ω scans	θ_max = 25.0°, θ_min = 2.4°
Absorption correction: multi-scan (SADABS; Sheldrick, 2000)	h = −10→4
T_min = 0.970, T_max = 0.984	k = −7→7
1946 measured reflections	l = −11→11

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.108	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ²(F_o²) + (0.0659P)² + 0.0834P] where P = (F_o² + 2F_c²)/3
946 reflections	(Δ/σ)_max < 0.001
90 parameters	Δρ_max = 0.20 e Å⁻³
0 restraints	Δρ_min = −0.13 e Å⁻³

Crystal data top

C₁₀H₁₀N₈	V = 550.19 (18) Å³
M_r = 242.26	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 8.6576 (16) Å	µ = 0.10 mm⁻¹
b = 6.6685 (12) Å	T = 295 K
c = 9.6162 (18) Å	0.30 × 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)
T_min = 0.970, T_max = 0.984	R_int = 0.013
1946 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.038	0 restraints
wR(F²) = 0.108	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	Δρ_max = 0.20 e Å⁻³
946 reflections	Δρ_min = −0.13 e Å⁻³
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

	x	y	z	U_iso*/U_eq
C1	0.71263 (17)	−0.1470 (2)	−0.12888 (15)	0.0400 (4)
H1A	0.7177	−0.2641	−0.1806	0.048*
C2	0.61260 (19)	0.1595 (2)	−0.10119 (17)	0.0459 (4)
H2A	0.5502	0.2669	−0.1353	0.055*
C3	0.69636 (18)	0.1731 (2)	0.03029 (16)	0.0421 (4)
H3A	0.6851	0.2866	0.0842	0.050*
C4	0.80524 (15)	−0.1312 (2)	0.00078 (14)	0.0326 (4)
C5	0.92285 (16)	−0.2845 (2)	0.05271 (14)	0.0322 (4)
N1	0.61789 (15)	−0.0024 (2)	−0.18134 (13)	0.0462 (4)
N2	0.79325 (14)	0.02862 (18)	0.08288 (12)	0.0372 (4)
N3	1.00358 (16)	−0.2540 (2)	0.17988 (13)	0.0431 (4)
H3B	1.071 (2)	−0.351 (3)	0.2148 (18)	0.045 (4)*
H3C	0.974 (2)	−0.154 (3)	0.2320 (19)	0.050 (5)*
N4	0.94266 (14)	−0.43331 (17)	−0.03069 (11)	0.0356 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0420 (8)	0.0408 (8)	0.0350 (8)	0.0018 (6)	−0.0029 (6)	−0.0042 (7)
C2	0.0441 (9)	0.0435 (9)	0.0475 (9)	0.0069 (7)	−0.0038 (7)	0.0066 (7)
C3	0.0468 (9)	0.0355 (8)	0.0426 (9)	0.0047 (6)	0.0013 (7)	−0.0023 (7)
C4	0.0353 (8)	0.0329 (8)	0.0295 (7)	−0.0030 (6)	0.0039 (6)	0.0006 (6)
C5	0.0363 (8)	0.0316 (7)	0.0280 (7)	−0.0025 (6)	0.0017 (6)	0.0015 (6)
N1	0.0459 (8)	0.0486 (8)	0.0405 (8)	0.0040 (6)	−0.0078 (6)	0.0010 (6)
N2	0.0429 (7)	0.0339 (7)	0.0335 (7)	0.0024 (5)	−0.0002 (5)	−0.0018 (5)
N3	0.0534 (9)	0.0409 (8)	0.0317 (7)	0.0145 (6)	−0.0068 (6)	−0.0050 (6)
N4	0.0425 (7)	0.0312 (7)	0.0313 (7)	0.0042 (5)	−0.0016 (5)	−0.0001 (5)

Geometric parameters (Å, º) top

C1—N1	1.3219 (19)	C4—N2	1.3386 (18)
C1—C4	1.393 (2)	C4—C5	1.4815 (19)
C1—H1A	0.9300	C5—N4	1.3017 (18)
C2—N1	1.331 (2)	C5—N3	1.3405 (18)
C2—C3	1.374 (2)	N3—H3B	0.906 (18)
C2—H2A	0.9300	N3—H3C	0.893 (19)
C3—N2	1.3318 (19)	N4—N4ⁱ	1.403 (2)
C3—H3A	0.9300

N1—C1—C4	122.66 (14)	C1—C4—C5	122.46 (13)
N1—C1—H1A	118.7	N4—C5—N3	125.59 (13)
C4—C1—H1A	118.7	N4—C5—C4	117.36 (12)
N1—C2—C3	122.11 (14)	N3—C5—C4	117.01 (13)
N1—C2—H2A	118.9	C1—N1—C2	116.02 (13)
C3—C2—H2A	118.9	C3—N2—C4	116.52 (12)
N2—C3—C2	122.01 (14)	C5—N3—H3B	117.6 (10)
N2—C3—H3A	119.0	C5—N3—H3C	118.3 (11)
C2—C3—H3A	119.0	H3B—N3—H3C	123.0 (15)
N2—C4—C1	120.49 (13)	C5—N4—N4ⁱ	111.61 (13)
N2—C4—C5	117.03 (12)

Symmetry code: (i) −x+2, −y−1, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3B···N2ⁱⁱ	0.906 (18)	2.280 (18)	3.0539 (18)	143.2 (14)
N3—H3C···N4ⁱⁱⁱ	0.892 (19)	2.405 (18)	3.1587 (18)	142.3 (16)

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

Experimental details

Crystal data
Chemical formula	C₁₀H₁₀N₈
M_r	242.26
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	295
a, b, c (Å)	8.6576 (16), 6.6685 (12), 9.6162 (18)
β (°)	97.682 (4)
V (Å³)	550.19 (18)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.30 × 0.19 × 0.16

Data collection
Diffractometer	Bruker SMART CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2000)
T_min, T_max	0.970, 0.984
No. of measured, independent and observed [I > 2σ(I)] reflections	1946, 946, 844
R_int	0.013
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.038, 0.108, 1.05
No. of reflections	946
No. of parameters	90
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	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···A	D—H	H···A	D···A	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−1/2, −z+1/2; (ii) x, −y−1/2, z+1/2.

Acknowledgements

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

References

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Sheldrick, G. M. (2000). SADABS. University of Göttingen, Germany. Google Scholar
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