Buy article online - an online subscription or single-article purchase is required to access this article.
Download citation
Download citation
link to html
The mol­ecule of title compound, C2H7N3O2, has a zwitterionic structure. All non-H atoms, apart from the terminal N atom of the NH3 group, lie in the same plane, with a maximum deviation of 0.056 (1) Å for the amine N atom of the nitr­amine group, whereas the deviation of the terminal N atom of the NH3 group from the same plane is 1.222 (2) Å. Intermolecular hydrogen bonds within the crystal form a three-dimensional network.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270101011404/av1081sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270101011404/av1081Isup2.hkl
Contains datablock I

CCDC reference: 174835

Comment top

Aminonitramines are of interest as biologically active non-protein amino acids (Alston et al., 1981; Nilsson et al., 1983) and as a new class of energetic compounds (Astachov et al., 2000a). The zwitterionic nature of aminonitramines was established on the basis of indirect physical and chemical investigations (McKay et al., 1954). Here, we present an X-ray structure determination of 1-amino-2-nitraminoethane, (I), which belongs to the same class of compounds. \sch

The present study unambiguously confirms the zwitterionic structure of (I). Fig. 1 provides a view of the crystal packing with the numbering scheme; selected molecular bond lengths and angles are given in Table 1. The C2—N3 bond length is in accord with that of various salts of organic amines (1.474–1.480 Å; Allen & Kennard, 1993; Georg et al., 1991; Burgess et al., 1991). The N—N bond length of the molecular nitramine part is shorter, and N—O bond lengths are longer, than the corresponding values in primary nitramines (N—N 1.301, and N—O 1.236 and 1.240 Å in 1,2-dinitraminoethane; Turley, 1968). As a whole, the nitramine fragment and bond lengths in (I) are close to the values characteristic of onium salts of primary nitramines (N—N 1.273 and N—O 1.283 Å in the dihydrazinium salt of 1,2-dinitraminoethane; Allen & Kennard, 1993; Bircher et al., 1996).

In the structure of (I), atom O1 forms two short hydrogen bonds with atoms H6 and H7 of two neighbouring molecules. The second oxygen, O2, is not involved in any hydrogen-bonding contacts. As a consequence, there is a significant difference in N—O bond lengths in (I) compared with both 1,2-dinitraminoethane (Turley, 1968) and its dihydrazine salt (Bircher et al., 1996). An intermolecular N3—H5···N2 hydrogen bond (Table 2) completes the picture of molecular packing.

From the established bond length values, it is difficult to fix the negative charge unambiguously on any atom of the nitramine part of the molecule. By analogy with salts of primary nitramines (Avakyan, 1971), the anion charge is rather delocalized over the whole nitramine fragment, but the electron density is distributed unevenly: the negative charge on atom O1 exceeds that on atoms N2 and O2.

In conclusion, the zwitterionic structure of aminonitramines, and of (I) in particular, leads to an increase in intermolecular interaction (crystal lattice energy) and, as a consequence, to an increase in thermal stability and the density of the compounds in comparison with the primary nitramines (Astachov et al., 2000a; Astachov, 1999).

Experimental top

Compound (I) was synthesized as described by Astachov et al. (2000b).

Refinement top

H atoms were located on a difference Fourier map and refined as riding, with a common isotropic displacement parameter of 0.032 Å2 for CH2 groups and 0.039 Å2 for the NH3 group. C—H distances were constrained to 0.97 Å and N—H distances to 0.935 Å.

Computing details top

Data collection: KM-4 Software (Kuma, 1991); cell refinement: KM-4 Software; data reduction: DATARED in KM-4 Software; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Sheldrick, 1995); software used to prepare material for publication: SHELXL97.

Figures top
[Figure 1] Fig. 1. The molecular arrangement of (I) in the crystal, with the atomic numbering scheme and 50% probability displacement ellipsoids. H atoms are shown as small spheres of arbitrary radii and dashed lines indicate intermolecular hydrogen bonds.
1-Amino-2-nitraminoethane top
Crystal data top
C2H7N3O2Z = 2
Mr = 105.11F(000) = 112
Triclinic, P1Dx = 1.563 Mg m3
a = 4.3449 (2) ÅCu Kα radiation, λ = 1.5418 Å
b = 6.2955 (3) ÅCell parameters from 25 reflections
c = 8.5432 (5) Åθ = 27–35°
α = 105.240 (5)°µ = 1.17 mm1
β = 92.743 (4)°T = 293 K
γ = 96.356 (4)°Lump, colourless
V = 223.36 (2) Å30.36 × 0.32 × 0.27 mm
Data collection top
Kuma KM-4
diffractometer
Rint = 0.029
Radiation source: fine-focus sealed tubeθmax = 64.8°, θmin = 5.4°
Graphite monochromatorh = 55
θ/2θ scansk = 77
814 measured reflectionsl = 09
756 independent reflections2 standard reflections every 40 reflections
685 reflections with I > 2σ(I) intensity decay: no decay, variation 0.4%
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.029H-atom parameters constrained
wR(F2) = 0.082 w = 1/[σ2(Fo2) + (0.0534P)2 + 0.0467P]
where P = (Fo2 + 2Fc2)/3
S = 1.02(Δ/σ)max = 0.002
756 reflectionsΔρmax = 0.21 e Å3
67 parametersΔρmin = 0.14 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.135 (10)
Crystal data top
C2H7N3O2γ = 96.356 (4)°
Mr = 105.11V = 223.36 (2) Å3
Triclinic, P1Z = 2
a = 4.3449 (2) ÅCu Kα radiation
b = 6.2955 (3) ŵ = 1.17 mm1
c = 8.5432 (5) ÅT = 293 K
α = 105.240 (5)°0.36 × 0.32 × 0.27 mm
β = 92.743 (4)°
Data collection top
Kuma KM-4
diffractometer
Rint = 0.029
814 measured reflections2 standard reflections every 40 reflections
756 independent reflections intensity decay: no decay, variation 0.4%
685 reflections with I > 2σ(I)
Refinement top
R[F2 > 2σ(F2)] = 0.0290 restraints
wR(F2) = 0.082H-atom parameters constrained
S = 1.02Δρmax = 0.21 e Å3
756 reflectionsΔρmin = 0.14 e Å3
67 parameters
Special details top

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 (Å2) top
xyzUiso*/Ueq
N10.0237 (2)0.32208 (17)0.21151 (12)0.0220 (3)
O10.1902 (2)0.21586 (15)0.09892 (11)0.0333 (3)
O20.0966 (2)0.23165 (16)0.32042 (12)0.0359 (3)
N20.1460 (2)0.51362 (17)0.20486 (12)0.0240 (3)
C10.3897 (3)0.6137 (2)0.33447 (15)0.0250 (3)
H10.54170.51210.33520.032*
H20.30150.64570.43910.032*
C20.5438 (3)0.8261 (2)0.30539 (16)0.0264 (4)
H30.39490.93200.31610.032*
H40.71450.88970.38770.032*
N30.6629 (2)0.78806 (17)0.14224 (13)0.0241 (3)
H50.81180.68990.13280.039*
H60.75330.92300.12820.039*
H70.49890.72720.06250.039*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.0224 (6)0.0211 (5)0.0250 (6)0.0040 (4)0.0037 (4)0.0100 (4)
O10.0337 (6)0.0291 (5)0.0350 (6)0.0072 (4)0.0085 (4)0.0116 (4)
O20.0423 (6)0.0316 (6)0.0395 (6)0.0009 (4)0.0047 (4)0.0235 (5)
N20.0259 (6)0.0210 (6)0.0272 (6)0.0011 (4)0.0012 (4)0.0109 (4)
C10.0272 (7)0.0264 (7)0.0226 (7)0.0030 (5)0.0018 (5)0.0089 (5)
C20.0292 (7)0.0220 (6)0.0254 (7)0.0005 (5)0.0029 (5)0.0031 (5)
N30.0248 (6)0.0210 (6)0.0270 (6)0.0003 (4)0.0012 (4)0.0088 (4)
Geometric parameters (Å, º) top
N1—O21.2571 (14)C2—N31.4794 (16)
N1—N21.2794 (15)C2—H30.9700
N1—O11.2942 (14)C2—H40.9700
N2—C11.4551 (16)N3—H50.9350
C1—C21.5136 (17)N3—H60.9350
C1—H10.9700N3—H70.9350
C1—H20.9700
O2—N1—N2124.29 (10)N3—C2—H3109.2
O2—N1—O1118.17 (10)C1—C2—H3109.2
N2—N1—O1117.53 (10)N3—C2—H4109.2
N1—N2—C1112.56 (10)C1—C2—H4109.2
N2—C1—C2108.58 (10)H3—C2—H4107.9
N2—C1—H1110.0C2—N3—H5109.5
C2—C1—H1110.0C2—N3—H6109.5
N2—C1—H2110.0H5—N3—H6109.5
C2—C1—H2110.0C2—N3—H7109.5
H1—C1—H2108.4H5—N3—H7109.5
N3—C2—C1112.00 (10)H6—N3—H7109.5
O2—N1—N2—C12.25 (16)N1—N2—C1—C2173.66 (10)
O1—N1—N2—C1178.19 (9)N2—C1—C2—N355.64 (13)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N3—H5···N2i0.942.092.976 (2)159
N3—H6···O1ii0.941.922.822 (2)163
N3—H7···O1iii0.942.002.832 (2)147
Symmetry codes: (i) x+1, y, z; (ii) x+1, y+1, z; (iii) x, y+1, z.

Experimental details

Crystal data
Chemical formulaC2H7N3O2
Mr105.11
Crystal system, space groupTriclinic, P1
Temperature (K)293
a, b, c (Å)4.3449 (2), 6.2955 (3), 8.5432 (5)
α, β, γ (°)105.240 (5), 92.743 (4), 96.356 (4)
V3)223.36 (2)
Z2
Radiation typeCu Kα
µ (mm1)1.17
Crystal size (mm)0.36 × 0.32 × 0.27
Data collection
DiffractometerKuma KM-4
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
814, 756, 685
Rint0.029
(sin θ/λ)max1)0.587
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.029, 0.082, 1.02
No. of reflections756
No. of parameters67
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.21, 0.14

Computer programs: KM-4 Software (Kuma, 1991), DATARED in KM-4 Software, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Sheldrick, 1995), SHELXL97.

Selected geometric parameters (Å, º) top
N1—O21.2571 (14)N2—C11.4551 (16)
N1—N21.2794 (15)C1—C21.5136 (17)
N1—O11.2942 (14)C2—N31.4794 (16)
O2—N1—N2124.29 (10)N1—N2—C1112.56 (10)
O2—N1—O1118.17 (10)N2—C1—C2108.58 (10)
N2—N1—O1117.53 (10)N3—C2—C1112.00 (10)
O2—N1—N2—C12.25 (16)N1—N2—C1—C2173.66 (10)
O1—N1—N2—C1178.19 (9)N2—C1—C2—N355.64 (13)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N3—H5···N2i0.9352.092.976 (2)159
N3—H6···O1ii0.9351.922.822 (2)163
N3—H7···O1iii0.9352.002.832 (2)147
Symmetry codes: (i) x+1, y, z; (ii) x+1, y+1, z; (iii) x, y+1, z.
 

Subscribe to Acta Crystallographica Section C: Structural Chemistry

The full text of this article is available to subscribers to the journal.

If you have already registered and are using a computer listed in your registration details, please email support@iucr.org for assistance.

Buy online

You may purchase this article in PDF and/or HTML formats. For purchasers in the European Community who do not have a VAT number, VAT will be added at the local rate. Payments to the IUCr are handled by WorldPay, who will accept payment by credit card in several currencies. To purchase the article, please complete the form below (fields marked * are required), and then click on `Continue'.
E-mail address* 
Repeat e-mail address* 
(for error checking) 

Format*   PDF (US $40)
   HTML (US $40)
   PDF+HTML (US $50)
In order for VAT to be shown for your country javascript needs to be enabled.

VAT number 
(non-UK EC countries only) 
Country* 
 

Terms and conditions of use
Contact us

Follow Acta Cryst. C
Sign up for e-alerts
Follow Acta Cryst. on Twitter
Follow us on facebook
Sign up for RSS feeds