Hydrazinium nitrate

The monoprotonated hydrazinium cation in the title compound, N₂H₅⁺·NO₃^-, forms several types of hydrogen bonds. Stronger ones, in which the H atoms attached to the protonated N atom take part, link cations and anions into layers. Less strong hydrogen bonds, with participation of H atoms attached to the non-protonated N atom, link the layers into a three-dimensional structure. In addition to hydrogen bonds, short contacts of 2.8607 (10) Å have been found between O and N atoms of neighbouring nitrate anions. Such contacts can correspond to a weak inter­molecular inter­action similar to that in organic compounds containing nitro groups.

Key indicators

• Single-crystal X-ray study
• T = 120 K
• Mean [sigma](O-N) = 0.001 Å
• R factor = 0.028
• wR factor = 0.072
• Data-to-parameter ratio = 11.0

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT432_ALERT_2_C Short Inter X...Y Contact  O2     ..  N3      ..       2.86 Ang.

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   2 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 ALERT type 2 Indicator that the structure model may be wrong or deficient
   0 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion

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S1. Comment

Hydrazine and its derivatives are widely used in various chemical technologies. X-ray structural data available for several inorganic salts of mono- and biprotonated hydrazine (Conant & Roof, 1970; Jönsson & Hamilton, 1970; Jönsson & Liminga, 1971; Klapötke et al., 1996; Kvick et al., 1972; Liminga, 1966; Liminga & Lundgren, 1965; Nitta et al., 1951) show the importance of hydrogen bonding in the formation of their crystal structures. We present here the structure of hydrazinium nitrate, (I), having a three-dimensional system of hydrogen bonds.

The principal bond lengths and bond angles in the title compound, (I), are given in Table 1. Fig. 1 shows a molecular view of the structure. Each H atom of the monoprotonated hydrazinium cation takes part in hydrogen bonding (Table 2). H atoms attached to the protonated N atom give strong hydrogen bonds in which the acceptors are two O atoms of nitrate anions and the non-protonated N atom of a neighbouring cation. These hydrogen bonds link cations and anions into layers parallel to (101) (Fig. 2). Each shortest cycle in these layers contains two nitrate anions and four hydrazinium cations. Less strong hydrogen bonds with participation of H atoms attached to the non-protonated N atom and O atoms of nitrate anions link the layers into a three-dimensional structure. In addition to hydrogen bonds, short contacts of 2.86 Å have been found between O and N atoms of neighbouring nitrate anions. Such contacts can correspond to a weak intermolecular interaction similar to that in organic compounds containing nitro groups (Platts et al., 1995).

S2. Experimental

For the preparation of (I), a stoichiometric amount of 14.7 M HNO₃ was added dropwise to pure hydrazine (5 ml) at 278 K. The pH of the resulting solution was about 4.5–5.0. The solution was kept at room temperature under a hood for slow evaporation of water. After two months, bulky colourless crystals were formed.

Computing details

Data collection: COLLECT (Nonius, 1998); cell refinement: HKL (Otwinowski & Minor, 1997); data reduction: HKL; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b); software used to prepare material for publication: SHELXTL.

Figures

	Fig. 1. A view of N2H5NO3, showing the atom-labelling scheme. Displacement ellipsoids (spheres for H atoms) are drawn at the 50% probability level. A dashed line indicates the hydrogen-bonding interaction.
	Fig. 2. A ne t of stronger hydogen bonds (dashed lines) in N2H5NO3.

Hydrazinium nitrate

Crystal data

N2H5^+·NO3^−	F(000) = 200
Mr = 95.07	Dx = 1.726 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2616 reflections
a = 7.9649 (4) Å	θ = 3.5–27.4°
b = 5.6569 (3) Å	µ = 0.17 mm^−1
c = 8.1221 (3) Å	T = 120 K
β = 91.340 (3)°	Fragment, colourless
V = 365.85 (3) Å^3	0.30 × 0.20 × 0.15 mm
Z = 4

Data collection

Nonius KappaCCD area-detector diffractometer	772 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.043
Graphite monochromator	θmax = 27.4°, θmin = 3.5°
ϕ and ω scans	h = −10→9
2616 measured reflections	k = −7→6
824 independent reflections	l = −10→10

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.028	Hydrogen site location: difference Fourier map
wR(F^2) = 0.072	All H-atom parameters refined
S = 1.10	w = 1/[σ^2(Fo^2) + (0.0338P)^2 + 0.0639P] where P = (Fo^2 + 2Fc^2)/3
824 reflections	(Δ/σ)max < 0.001
75 parameters	Δρmax = 0.19 e Å^−3
0 restraints	Δρmin = −0.26 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
O1	0.96785 (8)	0.23386 (12)	0.58479 (8)	0.0186 (2)
O2	0.81207 (8)	0.10354 (12)	0.78062 (8)	0.0189 (2)
O3	0.70853 (8)	0.13309 (12)	0.53166 (8)	0.0178 (2)
N1	0.35432 (10)	0.34749 (14)	0.65521 (10)	0.0154 (2)
H1	0.3322 (16)	0.295 (2)	0.5512 (18)	0.022 (3)*
H2	0.4440 (16)	0.444 (3)	0.6482 (16)	0.024 (3)*
N2	0.41983 (10)	0.14757 (14)	0.74737 (10)	0.0149 (2)
H3	0.4431 (15)	0.190 (2)	0.8492 (17)	0.019 (3)*
H4	0.5070 (16)	0.091 (2)	0.7017 (15)	0.019 (3)*
H5	0.3395 (17)	0.038 (3)	0.7542 (16)	0.024 (3)*
N3	0.82928 (9)	0.15701 (13)	0.63245 (9)	0.0137 (2)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0148 (3)	0.0208 (4)	0.0201 (4)	−0.0039 (3)	−0.0003 (3)	−0.0009 (3)
O2	0.0241 (4)	0.0189 (4)	0.0136 (3)	0.0001 (3)	−0.0008 (3)	0.0023 (2)
O3	0.0152 (3)	0.0219 (4)	0.0162 (4)	−0.0008 (2)	−0.0044 (3)	−0.0031 (2)
N1	0.0163 (4)	0.0153 (4)	0.0145 (4)	−0.0007 (3)	−0.0027 (3)	0.0015 (3)
N2	0.0144 (4)	0.0151 (4)	0.0151 (4)	0.0008 (3)	−0.0011 (3)	0.0007 (3)
N3	0.0151 (4)	0.0114 (4)	0.0145 (4)	0.0010 (3)	−0.0018 (3)	−0.0017 (3)

Geometric parameters (Å, º)

O1—N3	1.2558 (10)	N1—H2	0.903 (14)
O2—N3	1.2516 (10)	N2—H3	0.878 (14)
O3—N3	1.2556 (10)	N2—H4	0.856 (13)
N1—N2	1.4468 (11)	N2—H5	0.893 (15)
N1—H1	0.909 (15)
N2—N1—H1	106.5 (8)	N1—N2—H5	108.9 (9)
N2—N1—H2	103.3 (9)	H3—N2—H5	105.6 (12)
H1—N1—H2	106.1 (11)	H4—N2—H5	111.1 (12)
N1—N2—H3	109.7 (9)	O2—N3—O3	120.10 (7)
N1—N2—H4	110.6 (9)	O2—N3—O1	119.79 (7)
H3—N2—H4	110.8 (12)	O3—N3—O1	120.11 (7)
H1—N1—N2—H3	180.0 (12)	H2—N1—N2—H3	68.5 (12)
H1—N1—N2—H4	57.5 (12)	H2—N1—N2—H4	−54.1 (13)
H1—N1—N2—H5	−64.8 (12)	H2—N1—N2—H5	−176.4 (12)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O2^i	0.909 (15)	2.274 (14)	3.0657 (10)	145.4 (11)
N1—H2···O2^ii	0.903 (14)	2.206 (14)	3.0603 (11)	157.5 (12)
N2—H3···O1^iii	0.878 (14)	1.966 (14)	2.8386 (11)	172.6 (12)
N2—H4···O3	0.856 (13)	2.155 (13)	2.9245 (10)	149.5 (12)
N2—H5···N1^iv	0.893 (15)	2.035 (15)	2.8908 (11)	160.1 (12)

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