Acetohydrazide

Zhou, B.-H.

doi:10.1107/S1600536809042469

organic compounds

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ISSN: 2056-9890

Volume 65| Part 11| November 2009| Page o2821

https://doi.org/10.1107/S1600536809042469

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Acetohydrazide

Bao-Han Zhou ^a ^*

^aChemical and Environmental Engineering Department, Hu Bei University of Technology, Wuhan 430068, People's Republic of China
^*Correspondence e-mail: zhoubaohan@126.com

(Received 7 July 2009; accepted 15 October 2009; online 23 October 2009)

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, P 2₁ /n
a = 9.5636 (7) Å
b = 8.7642 (6) Å
c = 10.4282 (7) Å
β = 110.886 (1)°
V = 816.63 (10) Å³
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[F² > 2σ(F²)] = 0.056
wR(F²) = 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

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⋯O2^iv	0.867 (10)	2.255 (13)	3.065 (2)	155 (2)
N2—H2A⋯O2^v	0.863 (10)	2.400 (15)	3.152 (2)	145.7 (19)
Symmetry codes: (i) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (ii) $[-x+{\script{3\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iii) x-1, y, z; (iv) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (v) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

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.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536809042469/rk2154sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536809042469/rk2154Isup2.hkl

checkCIF report

Comment top

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).

Related literature top

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

Experimental top

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.

Structure description top

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

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus (Bruker, 2001); 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 (Sheldrick, 2008).

Figures top

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.

Acetohydrazide top

Crystal data top

C₂H₆N₂O	F(000) = 320
M_r = 74.09	D_x = 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 top

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

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)] = 0.056	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.151	w = 1/[σ²(F_o²) + (0.061P)² + 0.1265P] where P = (F_o² + 2F_c²)/3
S = 1.15	(Δ/σ)_max < 0.001
1762 reflections	Δρ_max = 0.19 e Å⁻³
112 parameters	Δρ_min = −0.19 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)

Crystal data top

C₂H₆N₂O	V = 816.63 (10) Å³
M_r = 74.09	Z = 8
Monoclinic, P2₁/n	Mo Kα radiation
a = 9.5636 (7) Å	µ = 0.10 mm⁻¹
b = 8.7642 (6) Å	T = 298 K
c = 10.4282 (7) Å	0.20 × 0.15 × 0.10 mm
β = 110.886 (1)°

Data collection top

Bruker SMART 4K CCD diffractometer	1762 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2001)	1604 reflections with I > 2σ(I)
T_min = 0.971, T_max = 0.990	R_int = 0.097
4189 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.056	6 restraints
wR(F²) = 0.151	H atoms treated by a mixture of independent and constrained refinement
S = 1.15	Δρ_max = 0.19 e Å⁻³
1762 reflections	Δρ_min = −0.19 e Å⁻³
112 parameters

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq
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 (Å²) top

	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, º) top

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, º) top

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···O2^iv	0.87 (1)	2.26 (1)	3.065 (2)	155 (2)
N2—H2A···O2^v	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.

Experimental details

Crystal data
Chemical formula	C₂H₆N₂O
M_r	74.09
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	298
a, b, c (Å)	9.5636 (7), 8.7642 (6), 10.4282 (7)
β (°)	110.886 (1)
V (Å³)	816.63 (10)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.20 × 0.15 × 0.10

Data collection
Diffractometer	Bruker SMART 4K CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2001)
T_min, T_max	0.971, 0.990
No. of measured, independent and observed [I > 2σ(I)] reflections	4189, 1762, 1604
R_int	0.097
(sin θ/λ)_max (Å⁻¹)	0.639

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.056, 0.151, 1.15
No. of reflections	1762
No. of parameters	112
No. of restraints	6
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.19, −0.19

Computer programs: SMART (Bruker, 2001), SAINT-Plus (Bruker, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

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···O2^iv	0.867 (10)	2.255 (13)	3.065 (2)	155 (2)
N2—H2A···O2^v	0.863 (10)	2.400 (15)	3.152 (2)	145.7 (19)

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.

Acknowledgements

The author thanks Professor An–Xin Wu (Central China Normal University, Wuhan, China) for helpful discussions, and Dr Xiang–Gao Meng (Central China Normal University, Wuhan, China) for the X–ray data collection.

References

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