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The structure of the title compound, C2H4N4O, was determined and found to be almost planar, excluding H atoms. The N-N bond lengths of 1.130 (2) and 1.231 (2) Å in the azide group exhibited a resonance effect and the characteristic organic azide structure.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S160053680001850X/cf6003sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S160053680001850X/cf6003Isup2.hkl
Contains datablock I

CCDC reference: 155854

Key indicators

  • Single-crystal X-ray study
  • T = 100 K
  • Mean [sigma](C-C) = 0.001 Å
  • R factor = 0.050
  • wR factor = 0.095
  • Data-to-parameter ratio = 10.6

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry
Red Alert Alert Level A:
DIFF_020 Alert A _diffrn_standards_interval_count and _diffrn_standards_interval_time are missing. Number of measurements between standards or time (min) between standards.
Amber Alert Alert Level B:
ABSMU_01 Alert B The ratio of given/expected absorption coefficient lies outside the range 0.95 <> 1.05 Calculated value of mu = 0.124 Value of mu given = 0.130
Yellow Alert Alert Level C:
REFLT_03 From the CIF: _diffrn_reflns_theta_max 26.40 From the CIF: _reflns_number_total 848 TEST2: Reflns within _diffrn_reflns_theta_max Count of symmetry unique reflns 910 Completeness (_total/calc) 93.19% Alert C: < 95% complete
1 Alert Level A = Potentially serious problem
1 Alert Level B = Potential problem
1 Alert Level C = Please check

Comment top

Azide compounds constitute a category of energetic materials. Since their properties are of great interest, much effort has been devoted to clarify their decomposition processes, conformation and molecular structures with molecular orbital calculations. However, there have been few experimental studies of the molecular structures in crystals, since azide compounds are potentially explosive and it is difficult to safely treat crystals. In this study, the structure determination of the title compound, azidoacetamide, (I), was carried out to obtain more knowledge about azide compounds.

Azidoacetamide is the smallest compound of the neutral organic azides whose crystal structures have been determined. In this study, it was revealed that non-H atoms were close to planar as the maximum deviation from the least-squares plane was <0.184 Å.

Azideacetamide easily releases the N6—N7 part as a nitrogen molecule. However, the N6—N7 bond length of 1.130 (2) Å is longer than the NN bond length of 1.0977 Å (Sasada, 1984). The N5—N6 bond length of 1.231 (2) Å is slightly shorter than the NN bond length of 1.247 Å in azomethane (CH3NNCH3) (Sasada, 1984). Therefore, the bond lengths are influenced by the resonance effect.

Table 4 summarizes the bond lengths and angles of the azide groups in organic azide compounds whose structures have already been determined. In C3N3(N3)3 (Knaggs, 1935) and [(H2N)2CN3]Cl (Henke & Bärnighausen, 1972), the conjugated systems were extended over the molecules. CH3N3 (Livingston & Rao, 1960) is the archetypical alkyl azide. Since the table indicates that the bond lengths in azide groups are almost the same, it could be said that these parameters would be characteristic of organic azide compounds.

The molecular arrangement indicates that two acetamide groups are favourably located so that the H atoms form hydrogen bonds in the bc plane. The O···HN distances are typical hydrogen-bond distances. The same interactions can be found in the intramolecular N5···H3B—N3 arrangement. However, H3B is not in an effective position to form a hydrogen bond. Therefore, H3B—N3 is shorter than H3A—N3.

Experimental top

Chloroacetamide and sodium azide were mixed in water and stirred until the water evaporated. The residue was dissolved in acetone and the solution filtered and allowed to evaporate. Azidoacetamide was obtained as colourless crystals. Single crystals were prepared by recrystallization from benzene.

Refinement top

The H atoms were refined and the C—H and N—H distances are in the range 0.89 (2)–1.01 (1) Å. The H–atom Uiso values are <0.038 Å2.

Structure description top

Azide compounds constitute a category of energetic materials. Since their properties are of great interest, much effort has been devoted to clarify their decomposition processes, conformation and molecular structures with molecular orbital calculations. However, there have been few experimental studies of the molecular structures in crystals, since azide compounds are potentially explosive and it is difficult to safely treat crystals. In this study, the structure determination of the title compound, azidoacetamide, (I), was carried out to obtain more knowledge about azide compounds.

Azidoacetamide is the smallest compound of the neutral organic azides whose crystal structures have been determined. In this study, it was revealed that non-H atoms were close to planar as the maximum deviation from the least-squares plane was <0.184 Å.

Azideacetamide easily releases the N6—N7 part as a nitrogen molecule. However, the N6—N7 bond length of 1.130 (2) Å is longer than the NN bond length of 1.0977 Å (Sasada, 1984). The N5—N6 bond length of 1.231 (2) Å is slightly shorter than the NN bond length of 1.247 Å in azomethane (CH3NNCH3) (Sasada, 1984). Therefore, the bond lengths are influenced by the resonance effect.

Table 4 summarizes the bond lengths and angles of the azide groups in organic azide compounds whose structures have already been determined. In C3N3(N3)3 (Knaggs, 1935) and [(H2N)2CN3]Cl (Henke & Bärnighausen, 1972), the conjugated systems were extended over the molecules. CH3N3 (Livingston & Rao, 1960) is the archetypical alkyl azide. Since the table indicates that the bond lengths in azide groups are almost the same, it could be said that these parameters would be characteristic of organic azide compounds.

The molecular arrangement indicates that two acetamide groups are favourably located so that the H atoms form hydrogen bonds in the bc plane. The O···HN distances are typical hydrogen-bond distances. The same interactions can be found in the intramolecular N5···H3B—N3 arrangement. However, H3B is not in an effective position to form a hydrogen bond. Therefore, H3B—N3 is shorter than H3A—N3.

Computing details top

Data collection: DIP Image Plate Control Software (MacScience, 1992); cell refinement: MAC-DENZO (Otwinowski & Minor, 1996); data reduction: maXus (Mackay et al., 1997); program(s) used to solve structure: maXus; program(s) used to refine structure: maXus; molecular graphics: maXus; software used to prepare material for publication: maXus.

Figures top
[Figure 1]
[Figure 2]
Azidoacetamide top
Crystal data top
C2H4N4ODx = 1.509 Mg m3
Mr = 100.08Mo Kα radiation, λ = 0.71073 Å
Monoclinic, P21/nCell parameters from 192 reflections
a = 6.648 (4) Åθ = 1.0–26.4°
b = 5.1190 (9) ŵ = 0.13 mm1
c = 13.124 (5) ÅT = 100 K
β = 99.36 (2)°Prism, colourless
V = 440.7 (5) Å30.2 × 0.2 × 0.2 mm
Z = 4
Data collection top
DIP Image Plate
diffractometer
Rint = 0.029
φ scansθmax = 26.4°
1544 measured reflectionsh = 08
848 independent reflectionsk = 66
848 reflections with I > 0l = 1616
Refinement top
Refinement on F2All H-atom parameters refined
R[F2 > 2σ(F2)] = 0.050Weighting scheme based on measured s.u.'s w = 1/[σ2(Fo) + 0.03Fo2]
wR(F2) = 0.095(Δ/σ)max < 0.001
S = 1.14Δρmax = 0.22 e Å3
848 reflectionsΔρmin = 0.29 e Å3
80 parameters
Crystal data top
C2H4N4OV = 440.7 (5) Å3
Mr = 100.08Z = 4
Monoclinic, P21/nMo Kα radiation
a = 6.648 (4) ŵ = 0.13 mm1
b = 5.1190 (9) ÅT = 100 K
c = 13.124 (5) Å0.2 × 0.2 × 0.2 mm
β = 99.36 (2)°
Data collection top
DIP Image Plate
diffractometer
848 reflections with I > 0
1544 measured reflectionsRint = 0.029
848 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.05080 parameters
wR(F2) = 0.095All H-atom parameters refined
S = 1.14Δρmax = 0.22 e Å3
848 reflectionsΔρmin = 0.29 e Å3
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
O10.7318 (1)0.0469 (1)0.13075 (4)0.0258 (3)
N30.7744 (1)0.4839 (1)0.14557 (6)0.0169 (3)
N50.7519 (1)0.5552 (1)0.05640 (5)0.0231 (4)
N60.6982 (1)0.5954 (1)0.14931 (6)0.0206 (3)
N70.6518 (1)0.6566 (2)0.23253 (6)0.0368 (4)
C20.7489 (1)0.2646 (1)0.09127 (6)0.0135 (3)
C40.7399 (2)0.2802 (1)0.02374 (6)0.0165 (4)
H3A0.772 (2)0.482 (2)0.2186 (8)0.028 (3)*
H3B0.777 (2)0.635 (2)0.1125 (8)0.038 (3)*
H4A0.610 (2)0.196 (2)0.0601 (7)0.028 (2)*
H4B0.857 (2)0.181 (2)0.0425 (8)0.036 (3)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0551 (5)0.0086 (2)0.0121 (3)0.0008 (3)0.0015 (3)0.0025 (2)
N30.0321 (5)0.0089 (3)0.0088 (4)0.0024 (3)0.0023 (3)0.0016 (2)
N50.0421 (5)0.0162 (3)0.0099 (4)0.0035 (3)0.0024 (3)0.0036 (3)
N60.0266 (5)0.0173 (3)0.0179 (4)0.0022 (3)0.0075 (3)0.0048 (3)
N70.0508 (7)0.0381 (4)0.0203 (5)0.0041 (4)0.0039 (4)0.0149 (3)
C20.0194 (5)0.0112 (3)0.0091 (4)0.0012 (3)0.0007 (3)0.0005 (3)
C40.0281 (5)0.0102 (3)0.0104 (4)0.0008 (3)0.0020 (3)0.0007 (3)
Geometric parameters (Å, º) top
O1—C21.242 (1)C2—C41.503 (2)
N3—C21.326 (1)N3—H3A0.96 (2)
N5—N61.231 (2)N3—H3B0.89 (2)
N5—C41.478 (1)C4—H4A1.01 (1)
N6—N71.130 (2)C4—H4B0.99 (2)
O1···N3i2.899 (1)N7···H4Bv2.946 (9)
O1···N3ii2.960 (1)C2···H3Aii2.906 (9)
O1···H3Aii2.01 (1)H3A···H3Aii2.72 (1)
O1···H3Bi2.15 (1)H3A···H3Avii2.72 (1)
O1···H4Aiii2.626 (9)H3A···H3Bii2.90 (1)
N6···N7iv2.991 (1)H3B···H4Avi2.70 (1)
N7···N7iv2.943 (1)H3B···H4Bviii2.90 (1)
N7···N7v2.943 (1)H4B···H4Bix2.76 (1)
N7···H3Avi2.94 (1)
N6—N5—C4115.2 (1)C2—N3—H3B119.1 (7)
N5—N6—N7173.5 (1)H3A—N3—H3B119.9 (9)
O1—C2—N3123.2 (1)N5—C4—H4A110.6 (5)
O1—C2—C4118.4 (1)N5—C4—H4B109.6 (6)
N3—C2—C4118.4 (1)C2—C4—H4A110.1 (6)
N5—C4—C2110.3 (1)C2—C4—H4B108.5 (6)
C2—N3—H3A120.5 (5)H4A—C4—H4B107.8 (8)
N6—N5—C4—C2163.6 (1)N6—N5—C4—H4A41.6 (6)
O1—C2—C4—N5176.9 (1)N6—N5—C4—H4B77.1 (7)
N3—C2—C4—N52.9 (1)O1—C2—C4—H4A54.7 (6)
H3A—N3—C2—O14.1 (7)O1—C2—C4—H4B63.0 (7)
H3A—N3—C2—C4175.8 (7)N3—C2—C4—H4A125.2 (6)
H3B—N3—C2—O1175.6 (8)N3—C2—C4—H4B117.1 (7)
H3B—N3—C2—C44.3 (8)
Symmetry codes: (i) x, y1, z; (ii) x+3/2, y1/2, z+1/2; (iii) x+1, y, z; (iv) x+3/2, y1/2, z1/2; (v) x+3/2, y+1/2, z1/2; (vi) x+1, y+1, z; (vii) x+3/2, y+1/2, z+1/2; (viii) x+2, y+1, z; (ix) x+2, y, z.
Hydrogen-bond geometry (Å) top
D—H···AD—HH···AD···A
N3ii—H3Aii···O10.96 (2)2.01 (1)2.960 (1)
N3i—H3Bi···O10.89 (2)2.15 (1)2.899 (1)
N3—H3B···N50.89 (2)2.23 (1)2.656 (1)
Symmetry codes: (i) x, y1, z; (ii) x+3/2, y1/2, z+1/2.

Experimental details

Crystal data
Chemical formulaC2H4N4O
Mr100.08
Crystal system, space groupMonoclinic, P21/n
Temperature (K)100
a, b, c (Å)6.648 (4), 5.1190 (9), 13.124 (5)
β (°) 99.36 (2)
V3)440.7 (5)
Z4
Radiation typeMo Kα
µ (mm1)0.13
Crystal size (mm)0.2 × 0.2 × 0.2
Data collection
DiffractometerDIP Image Plate
Absorption correction
No. of measured, independent and
observed (I > 0) reflections
1544, 848, 848
Rint0.029
(sin θ/λ)max1)0.626
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.050, 0.095, 1.14
No. of reflections848
No. of parameters80
No. of restraints?
H-atom treatmentAll H-atom parameters refined
Δρmax, Δρmin (e Å3)0.22, 0.29

Computer programs: DIP Image Plate Control Software (MacScience, 1992), MAC-DENZO (Otwinowski & Minor, 1996), maXus (Mackay et al., 1997), maXus.

Selected geometric parameters (Å, º) top
O1—C21.242 (1)N5—C41.478 (1)
N3—C21.326 (1)N6—N71.130 (2)
N5—N61.231 (2)C2—C41.503 (2)
O1···N3i2.899 (1)N7···H4Bv2.946 (9)
O1···N3ii2.960 (1)C2···H3Aii2.906 (9)
O1···H3Aii2.01 (1)H3A···H3Aii2.72 (1)
O1···H3Bi2.15 (1)H3A···H3Avii2.72 (1)
O1···H4Aiii2.626 (9)H3A···H3Bii2.90 (1)
N6···N7iv2.991 (1)H3B···H4Avi2.70 (1)
N7···N7iv2.943 (1)H3B···H4Bviii2.90 (1)
N7···N7v2.943 (1)H4B···H4Bix2.76 (1)
N7···H3Avi2.94 (1)
N6—N5—C4115.2 (1)O1—C2—C4118.4 (1)
N5—N6—N7173.5 (1)N3—C2—C4118.4 (1)
O1—C2—N3123.2 (1)N5—C4—C2110.3 (1)
N6—N5—C4—C2163.6 (1)N3—C2—C4—N52.9 (1)
O1—C2—C4—N5176.9 (1)
Symmetry codes: (i) x, y1, z; (ii) x+3/2, y1/2, z+1/2; (iii) x+1, y, z; (iv) x+3/2, y1/2, z1/2; (v) x+3/2, y+1/2, z1/2; (vi) x+1, y+1, z; (vii) x+3/2, y+1/2, z+1/2; (viii) x+2, y+1, z; (ix) x+2, y, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···A
N3ii—H3Aii···O10.96 (2)2.01 (1)2.960 (1)
N3i—H3Bi···O10.89 (2)2.15 (1)2.899 (1)
N3—H3B···N50.89 (2)2.23 (1)2.656 (1)
Symmetry codes: (i) x, y1, z; (ii) x+3/2, y1/2, z+1/2.
Summary of bond lengths and angles (Å, °) of azide group in organic azide compounds top
C—NN—NN—NC—N—NN—N—N
CH3N31.47 (2)1.24 (1)1.12 (1)120 (2)180
C3N3(N3)31.381.261.11114180
[(H2N)2CN3]Cl1.393 (4)1.265 (4)1.110 (4)114.2 (3)170.8 (3)
This work1.478 (1)1.231 (2)1.130 (2)115.2 (1)173.5 (1)
 

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