2-Hydroxy­amino-2-oxoacetohydrazide

Trofymchuk, O.S.; Pavlova, S.V.; Bon, V.; Boyko, A.N.; Pekhnyo, V.

doi:10.1107/S1600536810012341

organic compounds

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ISSN: 2056-9890

Volume 66| Part 5| May 2010| Page o1058

https://doi.org/10.1107/S1600536810012341

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2-Hydroxyamino-2-oxoacetohydrazide

Oleksandra S. Trofymchuk,^a ^* Svetlana V. Pavlova,^a Vladimir Bon,^b Alexander N. Boyko ^b and Vasily Pekhnyo ^b

^aDepartment of Chemistry, National Taras Shevchenko University, Volodymyrska Str. 64, 01601 Kyiv, Ukraine, and ^bInstitute of General and Inorganic Chemistry, NAS Ukraine, prosp. Palladina 32/34, 03680 Kyiv, Ukraine
^*Correspondence e-mail: trofymch@gmail.com

(Received 25 March 2010; accepted 1 April 2010; online 14 April 2010)

In the title compound, C₂H₅N₃O₃, the hydroxamic group adopts an anti orientation with respect to the hydrazide group. In the crystal, molecules are connected by N—H⋯O and O—H⋯N hydrogen bonds into zigzag chains along the c axis.

Related literature

For hydroxamic acids in biological chemistry, see: Kaczka et al. (1962 ); Komatsu et al. (2001 ). For the use of hydroxamic acids as strong chelating agents, see: Dobosz et al. (1999 ); Świątek-Kozłowska et al. (2000 ). For hydroxamic acids as the basis for the synthesis of metallacrowns compounds, see: Bodwin et al. (2001 ); Gumienna-Kontecka et al. (2007 ). For related structures, see: Sliva et al. (1997a ,b ); Mokhir et al. (2002 ); Fritsky et al. (2006 ); Moroz et al. (2008 ).

Experimental

Crystal data

C₂H₅N₃O₃
M_r = 119.09
Monoclinic, C c
a = 9.3968 (7) Å
b = 3.6728 (2) Å
c = 12.7510 (8) Å
β = 95.598 (5)°
V = 437.97 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.17 mm⁻¹
T = 77 K
0.12 × 0.10 × 0.07 mm

Data collection

Bruker APEXII diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2008 ) T_min = 0.980, T_max = 0.988
1149 measured reflections
445 independent reflections
404 reflections with I > 2σ(I)
R_int = 0.021

Refinement

R[F² > 2σ(F²)] = 0.032
wR(F²) = 0.077
S = 1.06
445 reflections
74 parameters
3 restraints
H-atom parameters constrained
Δρ_max = 0.19 e Å⁻³
Δρ_min = −0.20 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H1N2⋯O3ⁱ	0.88	2.02	2.813 (5)	149
O1—H1O1⋯N3ⁱⁱ	0.95	1.83	2.740 (4)	161
O1—H1O1⋯N3ⁱⁱ	0.95	1.83	2.740 (4)	161
N3—H1N3⋯O1ⁱⁱⁱ	0.90	2.29	3.013 (3)	137
N3—H2N3⋯O1^iv	0.93	2.44	3.024 (4)	121
Symmetry codes: (i) $[x+{\script{1\over 2}}, y-{\script{1\over 2}}, z]$ ; (ii) $[x, -y+2, z+{\script{1\over 2}}]$ ; (iii) $[x+{\script{1\over 2}}, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ ; (iv) $[x, -y+1, z-{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1999 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536810012341/jh2142sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810012341/jh2142Isup2.hkl

checkCIF report

Comment top

Hydroxamic acids represent an important class of chelating agents and recently have been used for synthesis of metallocrown compounds (Dobosz et al., 1999; Świątek-Kozłowska et al., 2000; Bodwin et al., 2001; Gumienna-Kontecka et al., 2007). Besides, it is known that hydroxamic acids can act as inhibitors of enzymes as well as promising antitumor agents (Kaczka et al.,1962; Komatsu et al., 2001). Therefore, study of new hydroxamic acids is timely and important research topic. As a part of our on-going work, we report the structure of the title compound (1), which comprises several groups capable to form hydrogen bond interactions.

The molecular structure of (1) is shown in Fig. 1. The hydroxamic group is in anti-position with respect to the hydrazide group. The carbonyl groups are in trans-position with respect to each other, and the NH₂ group is cis with respect to the hydrazide carbonyl and the OH group is cis with respect to the hydroxamic carbonyl. The C1—N1 , N1—O1 , C1—O2, C2—O3, C2—N2, N2—N3 bond lengths are 1.319 (5) Å, 1.381 (5) Å, 1.242 (6) Å, 1.220 (5) Å, 1.321 (4) Å and 1.422 (6) Å respectively, adopt typical values to the hydroxamic and hydrazide groups (Sliva et al., 1997a, b); Mokhir et al., 2002; Fritsky et al., 2006; Moroz et al., 2008).

In the crystal the molecules are connected by N—H···O, O—H···N hydrogen bonds (Table 1, Fig. 2) into supramolecular zig-zag chains along the c-axis.

Related literature top

For hydroxamic acids in biological chemistry, see: Kaczka et al. (1962); Komatsu et al. (2001). For the use of hydroxamic acids as strong chelating agents, see: Dobosz et al. (1999); Świątek-Kozłowska et al. (2000). For hydroxamic acids as the basis for the synthesis of metallacrowns compounds, see: Bodwin et al. (2001); Gumienna-Kontecka et al. (2007). For related structures, see: Sliva et al. (1997a,b); Mokhir et al. (2002); Fritsky et al. (2006); Moroz et al. (2008).

Experimental top

Compound (1) was synthesized as a white powder precipitate by addition of 1 equiv. of N₂H₄^.H₂O to cooled ethanol solution of ethyl- 2-(hydroxyamino)-2-oxoacetate (250 mmol) following by recrystallization of the resulting product from water. Single crystals suitable for X-ray structure analysis were obtained by slow evaporation of aqueous solution at room temperature. ¹H NMR (400 MHz, DMSO-d₆, δ): 4.482 (s, 2H, NH₂); 9.193 (br s, 1H, NH); 9.991(s, 1H, NH); 11.435 (br s, 1H, OH) ppm. ¹³C NMR (CDCl₃, 100 MHz, δ): 162.07, 163.219 ppm.

Structure description top

In the crystal the molecules are connected by N—H···O, O—H···N hydrogen bonds (Table 1, Fig. 2) into supramolecular zig-zag chains along the c-axis.

For hydroxamic acids in biological chemistry, see: Kaczka et al. (1962); Komatsu et al. (2001). For the use of hydroxamic acids as strong chelating agents, see: Dobosz et al. (1999); Świątek-Kozłowska et al. (2000). For hydroxamic acids as the basis for the synthesis of metallacrowns compounds, see: Bodwin et al. (2001); Gumienna-Kontecka et al. (2007). For related structures, see: Sliva et al. (1997a,b); Mokhir et al. (2002); Fritsky et al. (2006); Moroz et al. (2008).

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1999); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of (1), with 40% probability displacement ellipsoids showing the atom-numbering scheme employed.
	Fig. 2. A packing diagram for (1) compound. Hydrogen bonds are indicated by dashed lines.

2-Hydroxyamino-2-oxoacetohydrazide top

Crystal data top

C₂H₅N₃O₃	F(000) = 248
M_r = 119.09	D_x = 1.806 Mg m⁻³
Monoclinic, Cc	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: C -2yc	Cell parameters from 1149 reflections
a = 9.3968 (7) Å	θ = 3.2–26.5°
b = 3.6728 (2) Å	µ = 0.17 mm⁻¹
c = 12.7510 (8) Å	T = 77 K
β = 95.598 (5)°	Block, colourless
V = 437.97 (5) Å³	0.12 × 0.10 × 0.07 mm
Z = 4

Data collection top

Bruker APEXII diffractometer	445 independent reflections
Radiation source: fine-focus sealed tube	404 reflections with I > 2σ(I)
Horizontally mounted graphite crystal monochromator	R_int = 0.021
Detector resolution: 9 pixels mm^-1	θ_max = 26.5°, θ_min = 3.2°
φ scans and ω scans with κ offset	h = −10→11
Absorption correction: multi-scan (SADABS; Sheldrick, 2008)	k = −4→4
T_min = 0.980, T_max = 0.988	l = −15→15
1149 measured reflections

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)] = 0.032	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.077	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.0363P)² + 0.3945P] where P = (F_o² + 2F_c²)/3
445 reflections	(Δ/σ)_max < 0.001
74 parameters	Δρ_max = 0.19 e Å⁻³
3 restraints	Δρ_min = −0.20 e Å⁻³

Crystal data top

C₂H₅N₃O₃	V = 437.97 (5) Å³
M_r = 119.09	Z = 4
Monoclinic, Cc	Mo Kα radiation
a = 9.3968 (7) Å	µ = 0.17 mm⁻¹
b = 3.6728 (2) Å	T = 77 K
c = 12.7510 (8) Å	0.12 × 0.10 × 0.07 mm
β = 95.598 (5)°

Data collection top

Bruker APEXII diffractometer	445 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2008)	404 reflections with I > 2σ(I)
T_min = 0.980, T_max = 0.988	R_int = 0.021
1149 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.032	3 restraints
wR(F²) = 0.077	H-atom parameters constrained
S = 1.06	Δρ_max = 0.19 e Å⁻³
445 reflections	Δρ_min = −0.20 e Å⁻³
74 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 > 2σ(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	0.4570 (5)	0.6710 (10)	0.8492 (3)	0.0187 (10)
C2	0.4385 (4)	0.8528 (9)	0.7408 (3)	0.0149 (9)
N1	0.3439 (4)	0.7171 (8)	0.9018 (3)	0.0185 (8)
H1N1	0.2695	0.8396	0.8732	0.022*
N2	0.5546 (4)	0.8238 (9)	0.6907 (3)	0.0199 (8)
H1N2	0.6295	0.7036	0.7194	0.024*
N3	0.5578 (4)	0.9881 (9)	0.5899 (3)	0.0215 (9)
H1N3	0.6479	1.0696	0.5880	0.032*
H2N3	0.5534	0.8113	0.5371	0.032*
O1	0.3428 (3)	0.5725 (8)	1.0016 (2)	0.0249 (8)
H1O1	0.4139	0.6969	1.0456	0.037*
O2	0.5674 (3)	0.5033 (7)	0.8820 (2)	0.0236 (8)
O3	0.3288 (3)	1.0094 (7)	0.7077 (2)	0.0248 (9)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.016 (3)	0.0199 (18)	0.020 (2)	0.0004 (15)	0.0007 (17)	−0.0040 (15)
C2	0.016 (2)	0.0162 (16)	0.013 (2)	0.0003 (14)	0.0037 (17)	−0.0026 (14)
N1	0.0142 (17)	0.0252 (17)	0.0162 (19)	0.0030 (13)	0.0019 (14)	0.0015 (14)
N2	0.0194 (19)	0.0256 (16)	0.015 (2)	0.0059 (14)	0.0050 (14)	0.0019 (14)
N3	0.020 (2)	0.0287 (16)	0.017 (2)	0.0034 (13)	0.0093 (15)	0.0020 (14)
O1	0.0266 (19)	0.0337 (15)	0.0150 (17)	−0.0005 (13)	0.0048 (13)	0.0048 (14)
O2	0.018 (2)	0.0294 (17)	0.024 (2)	0.0081 (12)	0.0057 (16)	0.0060 (12)
O3	0.020 (2)	0.0373 (18)	0.0173 (19)	0.0095 (12)	0.0025 (16)	0.0031 (12)

Geometric parameters (Å, º) top

C1—O2	1.243 (6)	N1—H1N1	0.8800
C1—N1	1.322 (4)	N2—N3	1.422 (6)
C1—C2	1.530 (4)	N2—H1N2	0.8800
C2—O3	1.220 (5)	N3—H1N3	0.9009
C2—N2	1.321 (4)	N3—H2N3	0.9332
N1—O1	1.380 (5)	O1—H1O1	0.9468

O2—C1—N1	125.4 (4)	O1—N1—H1N1	120.1
O2—C1—C2	122.5 (3)	C2—N2—N3	119.6 (4)
N1—C1—C2	112.1 (3)	C2—N2—H1N2	120.2
O3—C2—N2	125.5 (4)	N3—N2—H1N2	120.2
O3—C2—C1	122.4 (3)	N2—N3—H1N3	105.5
N2—C2—C1	112.1 (3)	N2—N3—H2N3	110.6
C1—N1—O1	119.8 (4)	H1N3—N3—H2N3	100.8
C1—N1—H1N1	120.1	N1—O1—H1O1	107.0

O2—C1—C2—O3	178.1 (5)	O2—C1—N1—O1	0.0 (6)
N1—C1—C2—O3	−2.3 (4)	C2—C1—N1—O1	−179.6 (3)
O2—C1—C2—N2	−3.1 (4)	O3—C2—N2—N3	0.8 (6)
N1—C1—C2—N2	176.5 (4)	C1—C2—N2—N3	−178.0 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H1N2···O3ⁱ	0.88	2.02	2.813 (5)	149
O1—H1O1···N3ⁱⁱ	0.95	1.83	2.740 (4)	161
O1—H1O1···N3ⁱⁱ	0.95	1.83	2.740 (4)	161
N3—H1N3···O1ⁱⁱⁱ	0.90	2.29	3.013 (3)	137
N3—H2N3···O1^iv	0.93	2.44	3.024 (4)	121

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

Experimental details

Crystal data
Chemical formula	C₂H₅N₃O₃
M_r	119.09
Crystal system, space group	Monoclinic, Cc
Temperature (K)	77
a, b, c (Å)	9.3968 (7), 3.6728 (2), 12.7510 (8)
β (°)	95.598 (5)
V (Å³)	437.97 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.17
Crystal size (mm)	0.12 × 0.10 × 0.07

Data collection
Diffractometer	Bruker APEXII
Absorption correction	Multi-scan (SADABS; Sheldrick, 2008)
T_min, T_max	0.980, 0.988
No. of measured, independent and observed [I > 2σ(I)] reflections	1149, 445, 404
R_int	0.021
(sin θ/λ)_max (Å⁻¹)	0.628

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.032, 0.077, 1.06
No. of reflections	445
No. of parameters	74
No. of restraints	3
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.19, −0.20

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H1N2···O3ⁱ	0.88	2.02	2.813 (5)	148.7
O1—H1O1···N3ⁱⁱ	0.95	1.83	2.740 (4)	161.3
O1—H1O1···N3ⁱⁱ	0.95	1.83	2.740 (4)	161.3
N3—H1N3···O1ⁱⁱⁱ	0.90	2.29	3.013 (3)	137.4
N3—H2N3···O1^iv	0.93	2.44	3.024 (4)	121.0

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

Acknowledgements

The authors thank the Ministry of Education and Science of Ukraine for financial support (grant No. F28/241–2009). We are grateful to Professor Igor O. Fritsky and Dr Yurii S. Moroz for helpful discussions.

References

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