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

Abstract

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,

• a = 8.6576 (16) Å

• b = 6.6685 (12) Å

• c = 9.6162 (18) Å

• β = 97.682 (4)°

• V = 550.19 (18) ų

• 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[F ² > 2σ(F ²)] = 0.038

• wR(F ²) = 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

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.

Supplementary Material

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

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) ; (ii) .

supplementary crystallographic information

Comment

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.

Experimental

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

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 U_iso(H) = 1.2 U_eq(C).

Figures

Fig. 1.

Structure of the title compound with 30% displacement ellipsoids. [Symmetry code: (A) 2-x, -1-y, -z.]

Crystal data

C10H10N8	F(000) = 252
Mr = 242.26	Dx = 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

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

Refinement

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(Fo2) + (0.0659P)2 + 0.0834P] where P = (Fo2 + 2Fc2)/3
946 reflections	(Δ/σ)max < 0.001
90 parameters	Δρmax = 0.20 e Å−3
0 restraints	Δρmin = −0.13 e Å−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	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, °)

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 codes: (i) −x+2, −y−1, −z.

Hydrogen-bond geometry (Å, °)

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.