Acetohydrazide

Abstract

In the title compound, C₂H₆N₂O, a hydrazine derivative, the asymmetric unit contains two mol­ecules with similar geom­etries. The crystal structure is stabilized by inter­molecular N—H⋯O hydrogen bonds.

Related literature

For general background to hydrazine and its derivatives, see: Gagnon et al. (1951 ▶); Hermanson (1996 ▶); Lumley-Woodyear et al. (1996 ▶); Raddatz et al. (2002 ▶).

Experimental

Crystal data

• C₂H₆N₂O

• M _r = 74.09

• Monoclinic,

• a = 9.5636 (7) Å

• b = 8.7642 (6) Å

• c = 10.4282 (7) Å

• β = 110.886 (1)°

• V = 816.63 (10) ų

• Z = 8

• Mo Kα radiation

• μ = 0.10 mm⁻¹

• T = 298 K

• 0.20 × 0.15 × 0.10 mm

Data collection

• Bruker SMART 4K CCD diffractometer

• Absorption correction: multi-scan (SADABS; Bruker, 2001 ▶) T _min = 0.971, T _max = 0.990

• 4189 measured reflections

• 1762 independent reflections

• 1604 reflections with I > 2σ(I)

• R _int = 0.097

Refinement

• R[F ² > 2σ(F ²)] = 0.056

• wR(F ²) = 0.151

• S = 1.15

• 1762 reflections

• 112 parameters

• 6 restraints

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

• Δρ_max = 0.19 e Å⁻³

• Δρ_min = −0.19 e Å⁻³

Data collection: SMART (Bruker, 2001 ▶); cell refinement: SAINT-Plus (Bruker, 2001 ▶); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: PLATON (Spek, 2009 ▶); 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
N1—H1D⋯O2	0.863 (9)	2.052 (10)	2.8971 (17)	166.0 (19)
N4—H4B⋯N2i	0.865 (9)	2.342 (12)	3.160 (2)	157.9 (19)
N4—H4A⋯O1ii	0.868 (9)	2.216 (11)	3.061 (2)	164.2 (19)
N3—H3D⋯O1iii	0.857 (9)	2.018 (10)	2.8599 (17)	167.1 (19)
N2—H2B⋯O2iv	0.867 (10)	2.255 (13)	3.065 (2)	155 (2)
N2—H2A⋯O2v	0.863 (10)	2.400 (15)	3.152 (2)	145.7 (19)

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) .

supplementary crystallographic information

Comment

Hydrazide and its derivatives were used as versatile synthons. For example, substituted pyrazolones can be prepared by treatment of corresponding hydrazide with strong alkalies (Gagnon et al., 1951). What's more, hydrazides are reactive functional groups routinely used in protein and carbohydrate chemistry (Raddatz et al., 2002; Hermanson, 1996). It is reported that oligonucleotides can be modified with hydrazide (Lumley-Woodyear et al., 1996). Acethydrazide is an important organic intermediate mainly for synthesis of nifuratrone in the pharmaceutical industry. Here we report the structure of the title compound (Fig. 1). Asymmetric unit contains two molecules with the same geometry. The crystal packing is stabilized by intermolecular classical N—H···O hydrogen bonds (Table 1).

Experimental

Acethydrazide, prepared from ethyl acetate and 85% hydrazine was synthesized in 40% isolated yield. Crystals of acethydrazide suitable for X–ray data collection were obtained by cooled the reaction solution from 353 K to 293 K for overnight.

Refinement

All H atoms of methyl groups were positioned geometrically with C—H = 0.96Å and U_iso(H) = 1.5U_iso(C). H atoms of amino–groups were found from the difference maps and refined with U_iso(H) = 1.2U_iso(N).

Figures

Fig. 1.

View of the asymmetric unit showing the atom–labelling scheme. Displacement ellipsoids are drawn at the 30% probability level. H atoms are presented as a small spheres of arbitrary radius.

Crystal data

C2H6N2O	F(000) = 320
Mr = 74.09	Dx = 1.205 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2153 reflections
a = 9.5636 (7) Å	θ = 2.5–28.0°
b = 8.7642 (6) Å	µ = 0.10 mm−1
c = 10.4282 (7) Å	T = 298 K
β = 110.886 (1)°	Block, colourless
V = 816.63 (10) Å3	0.20 × 0.15 × 0.10 mm
Z = 8

Data collection

Bruker SMART 4K CCD diffractometer	1762 independent reflections
Radiation source: fine-focus sealed tube	1604 reflections with I > 2σ(I)
graphite	Rint = 0.097
φ and ω scans	θmax = 27.0°, θmin = 2.5°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −10→12
Tmin = 0.971, Tmax = 0.990	k = −11→9
4189 measured reflections	l = −13→10

Refinement

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)] = 0.056	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.151	w = 1/[σ2(Fo2) + (0.061P)2 + 0.1265P] where P = (Fo2 + 2Fc2)/3
S = 1.15	(Δ/σ)max < 0.001
1762 reflections	Δρmax = 0.19 e Å−3
112 parameters	Δρmin = −0.18 e Å−3
6 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: 0.17 (2)

Special details

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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	0.8855 (2)	0.2274 (2)	0.0022 (2)	0.0608 (5)
H1A	0.9481	0.3141	0.0057	0.091*
H1B	0.7835	0.2603	−0.0227	0.091*
H1C	0.8932	0.1562	−0.0649	0.091*
C2	0.93450 (16)	0.15234 (18)	0.13942 (17)	0.0434 (4)
C3	0.4604 (2)	0.0155 (2)	0.1911 (2)	0.0646 (5)
H3A	0.4598	−0.0526	0.1188	0.097*
H3B	0.3836	−0.0142	0.2254	0.097*
H3C	0.5561	0.0111	0.2640	0.097*
C4	0.43160 (16)	0.17510 (19)	0.13651 (16)	0.0443 (4)
N1	0.83138 (14)	0.13848 (17)	0.19703 (16)	0.0501 (4)
H1D	0.7430 (14)	0.176 (2)	0.1567 (19)	0.060*
N2	0.86280 (16)	0.0740 (2)	0.32791 (17)	0.0575 (5)
H2A	0.9337 (19)	0.128 (2)	0.3837 (19)	0.069*
H2B	0.893 (2)	−0.0180 (14)	0.321 (2)	0.069*
N3	0.30038 (14)	0.23464 (17)	0.12609 (15)	0.0490 (4)
H3D	0.2363 (18)	0.182 (2)	0.148 (2)	0.059*
N4	0.25433 (16)	0.38388 (19)	0.07867 (18)	0.0550 (4)
H4B	0.257 (2)	0.398 (2)	−0.0025 (13)	0.066*
H4A	0.3202 (19)	0.443 (2)	0.1362 (18)	0.066*
O1	1.06315 (12)	0.10511 (15)	0.19701 (13)	0.0578 (4)
O2	0.52482 (11)	0.24591 (14)	0.10257 (13)	0.0560 (4)

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
C1	0.0487 (9)	0.0676 (12)	0.0619 (11)	−0.0009 (8)	0.0147 (8)	0.0087 (9)
C2	0.0331 (7)	0.0403 (8)	0.0566 (9)	−0.0026 (6)	0.0158 (6)	−0.0024 (7)
C3	0.0511 (10)	0.0578 (11)	0.0859 (14)	−0.0015 (9)	0.0256 (10)	0.0131 (10)
C4	0.0338 (7)	0.0516 (9)	0.0478 (8)	−0.0028 (6)	0.0149 (6)	−0.0019 (7)
N1	0.0330 (7)	0.0591 (9)	0.0590 (9)	0.0061 (6)	0.0174 (6)	0.0051 (7)
N2	0.0446 (8)	0.0717 (11)	0.0612 (10)	0.0017 (7)	0.0252 (7)	0.0019 (8)
N3	0.0350 (7)	0.0567 (9)	0.0605 (9)	−0.0027 (6)	0.0234 (6)	0.0018 (7)
N4	0.0385 (7)	0.0613 (10)	0.0690 (10)	0.0052 (6)	0.0237 (7)	0.0025 (8)
O1	0.0343 (6)	0.0723 (9)	0.0706 (8)	0.0085 (5)	0.0233 (6)	0.0194 (6)
O2	0.0369 (6)	0.0574 (7)	0.0806 (9)	0.0047 (5)	0.0292 (6)	0.0124 (6)

Geometric parameters (Å, °)

C1—C2	1.491 (2)	C4—O2	1.2370 (18)
C1—H1A	0.9600	C4—N3	1.327 (2)
C1—H1B	0.9600	N1—N2	1.407 (2)
C1—H1C	0.9600	N1—H1D	0.863 (9)
C2—O1	1.2324 (18)	N2—H2A	0.863 (10)
C2—N1	1.331 (2)	N2—H2B	0.867 (10)
C3—C4	1.498 (3)	N3—N4	1.412 (2)
C3—H3A	0.9600	N3—H3D	0.857 (9)
C3—H3B	0.9600	N4—H4B	0.865 (9)
C3—H3C	0.9600	N4—H4A	0.868 (9)
C2—C1—H1A	109.5	O2—C4—N3	122.42 (16)
C2—C1—H1B	109.5	O2—C4—C3	121.57 (14)
H1A—C1—H1B	109.5	N3—C4—C3	116.01 (14)
C2—C1—H1C	109.5	C2—N1—N2	122.56 (13)
H1A—C1—H1C	109.5	C2—N1—H1D	120.0 (14)
H1B—C1—H1C	109.5	N2—N1—H1D	117.3 (14)
O1—C2—N1	121.40 (16)	N1—N2—H2A	106.0 (15)
O1—C2—C1	122.26 (15)	N1—N2—H2B	104.9 (16)
N1—C2—C1	116.34 (14)	H2A—N2—H2B	111 (2)
C4—C3—H3A	109.5	C4—N3—N4	124.09 (14)
C4—C3—H3B	109.5	C4—N3—H3D	120.8 (14)
H3A—C3—H3B	109.5	N4—N3—H3D	115.1 (14)
C4—C3—H3C	109.5	N3—N4—H4B	110.9 (14)
H3A—C3—H3C	109.5	N3—N4—H4A	104.5 (14)
H3B—C3—H3C	109.5	H4B—N4—H4A	109 (2)
O1—C2—N1—N2	2.0 (3)	O2—C4—N3—N4	−1.3 (3)
C1—C2—N1—N2	−178.17 (16)	C3—C4—N3—N4	179.13 (16)

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1D···O2	0.86 (1)	2.05 (1)	2.8971 (17)	166 (2)
N4—H4B···N2i	0.87 (1)	2.34 (1)	3.160 (2)	158 (2)
N4—H4A···O1ii	0.87 (1)	2.22 (1)	3.061 (2)	164 (2)
N3—H3D···O1iii	0.86 (1)	2.02 (1)	2.8599 (17)	167 (2)
N2—H2B···O2iv	0.87 (1)	2.26 (1)	3.065 (2)	155 (2)
N2—H2A···O2v	0.86 (1)	2.40 (2)	3.152 (2)	146 (2)

Symmetry codes: (i) x−1/2, −y+1/2, z−1/2; (ii) −x+3/2, y+1/2, −z+1/2; (iii) x−1, y, z; (iv) −x+3/2, y−1/2, −z+1/2; (v) x+1/2, −y+1/2, z+1/2.