Acta Cryst. (2007). E63, i179 [ doi:10.1107/S1600536807042523 ]
The crystal structure of the title compound, N2H62+·2Cl-, previously determined by photographic methods [Wyckoff (1923). Am. J. Sci. 5, 15-22; Donohue & Lipscomb (1947). J. Chem. Phys. 15, 115-119], has been redetermined from single-crystal data. The N and Cl atoms are located on threefold rotation axes, whereas the H atom lies in a general position. The [H6N2]2+ cations and the Cl- anions are connected via N-H
Cl hydrogen bonds forming a three-dimensional net, whereby R63(14) rings are generated.
Commercially available hydrogenhydrazinium dichloride (pure, Merck, CAS 5341–61-7) was recrystallized from a saturated solution of 0.2 mol/dm3 hydrochloric acid (about 2.7 g of the title compound in 1 cm3 of acid).
The H atom was found from a difference Fourier synthesis after four cycles of anisotropic refinement for the N and Cl atoms, and was refined freely.
Data collection: CrysAlis CCD (UNIL IC & Kuma, 2000); cell refinement: CrysAlis RED (UNIL IC & Kuma, 2000); data reduction: CrysAlis RED (UNIL IC & Kuma, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP in SHELXTL (Sheldrick, 1990) and ORTEP-3 (Farrugia 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997) and PLATON (Spek, 2003).
![[Figure 1]](./wm2141fig1thm.gif)
| Fig. 1. The molecular structure of the title compound. Displacement ellipsoids are drawn at the 50% probability level. [Symmetry code: (i) −x + 1, −y + 1, −z.] |
![[Figure 2]](./wm2141fig2thm.gif)
| Fig. 2. The packing of the structure units in a view approximately along [111]. Hydrogen bonds are indicated by dashed lines. |
| N2H62+·2Cl– | Z = 4 |
| Mr = 104.97 | F000 = 216 |
| Cubic, Pa3 | Dx = 1.429 Mg m−3 Dm = 1.43 Mg m−3 Dm measured by Berman density torsion balance |
| Hall symbol: -P 2ac 2ab | Mo Kα radiation λ = 0.71073 Å |
| a = 7.8731 (1) Å | Cell parameters from 1003 reflections |
| b = 7.8731 (1) Å | θ = 4.0–25.0º |
| c = 7.8731 (1) Å | µ = 1.15 mm−1 |
| α = 90º | T = 291.0 (3) K |
| β = 90º | Needle, colourless |
| γ = 90º | 0.37 × 0.11 × 0.11 mm |
| V = 488.020 (11) Å3 |
| Kuma KM4 CCD diffractometer | 146 independent reflections |
| Radiation source: fine-focus sealed tube | 146 reflections with I > 2σ(I) |
| Monochromator: graphite | Rint = 0.015 |
| Detector resolution: 1048576 pixels mm-1 | θmax = 25.1º |
| T = 291.0(3) K | θmin = 4.5º |
| ω scans | h = −9→9 |
| Absorption correction: numerical (X-RED; Stoe & Cie, 1999) | k = −9→9 |
| Tmin = 0.837, Tmax = 0.880 | l = −9→9 |
| 4076 measured reflections |
| Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
| Least-squares matrix: full | All H-atom parameters refined |
| R[F2 > 2σ(F2)] = 0.017 | w = 1/[σ2(Fo2) + (0.0276P)2 + 0.0263P] where P = (Fo2 + 2Fc2)/3 |
| wR(F2) = 0.044 | (Δ/σ)max < 0.001 |
| S = 1.34 | Δρmax = 0.16 e Å−3 |
| 146 reflections | Δρmin = −0.42 e Å−3 |
| 12 parameters | Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
| Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.46 (3) |
| Secondary atom site location: difference Fourier map |
| N2H62+·2Cl– | γ = 90º |
| Mr = 104.97 | V = 488.020 (11) Å3 |
| Cubic, Pa3 | Z = 4 |
| a = 7.8731 (1) Å | Mo Kα |
| b = 7.8731 (1) Å | µ = 1.15 mm−1 |
| c = 7.8731 (1) Å | T = 291.0 (3) K |
| α = 90º | 0.37 × 0.11 × 0.11 mm |
| β = 90º |
| Kuma KM4 CCD diffractometer | 146 independent reflections |
| Absorption correction: numerical (X-RED; Stoe & Cie, 1999) | 146 reflections with I > 2σ(I) |
| Tmin = 0.837, Tmax = 0.880 | Rint = 0.015 |
| 4076 measured reflections |
| R[F2 > 2σ(F2)] = 0.017 | 12 parameters |
| wR(F2) = 0.044 | All H-atom parameters refined |
| S = 1.34 | Δρmax = 0.16 e Å−3 |
| 146 reflections | Δρmin = −0.42 e Å−3 |
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 > 2sigma(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. |
| x | y | z | Uiso*/Ueq | ||
| Cl1 | 0.77910 (3) | 0.27910 (3) | 0.22090 (3) | 0.0283 (4) | |
| N1 | 0.55244 (9) | 0.44756 (9) | −0.05244 (9) | 0.0254 (4) | |
| H1 | 0.6227 (17) | 0.3953 (15) | 0.0133 (16) | 0.042 (3)* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Cl1 | 0.0283 (4) | 0.0283 (4) | 0.0283 (4) | 0.00117 (8) | −0.00117 (8) | −0.00117 (8) |
| N1 | 0.0254 (4) | 0.0254 (4) | 0.0254 (4) | 0.0005 (3) | 0.0005 (3) | −0.0005 (3) |
| N1—N1i | 1.4302 (10) | N1—H1 | 0.862 (13) |
| N1i—N1—H1 | 107.5 (9) |
| Symmetry codes: (i) −x+1, −y+1, −z. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N1—H1···Cl1 | 0.862 (13) | 2.242 (13) | 3.0944 (3) | 170.0 (12) |
| N1—N1i | 1.4302 (10) | N1—H1 | 0.862 (13) |
| N1i—N1—H1 | 107.5 (9) |
| Symmetry codes: (i) −x+1, −y+1, −z. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N1—H1···Cl1 | 0.862 (13) | 2.242 (13) | 3.0944 (3) | 170.0 (12) |
This work was supported by funds allocated by the Ministry of Science and Higher Education to the Institute of General and Ecological Chemistry, Technical University of Łódź, Poland.
Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555–1573.
Chekhlov, A. N. & Martynov, I. V. (1988). Kristallografiya, 33, 1010–1011.
Collin, R. L. & Lipscomb, W. N. (1951). Acta Cryst. 4, 10–14.
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Spek, A. L. (2003). J. Appl. Cryst. 36, 7–13.
Stoe & Cie (1999). X-RED. Version 1.18. Stoe & Cie GmbH, Darmstadt, Germany.
UNIL IC & Kuma (2000). CrysAlis CCD and CrysAlis RED. Versions 1.163. Kuma Diffraction Instruments GmbH, Wrocław, Poland.
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Hydrogenhydrazinium dichloride, or commonly hydrazine dihydrochloride, is the most excellent source of dry hydrazine for organic syntheses. It is commonly used as a reducing agent for the recovery of precious metals or in soldering fluxes for aluminium and magnesium alloys. It is also used as a polymerization catalyst and a chain extender, and is a source of a large number of derivatives, for example used in agrochemicals, pharmaceuticals, photographics, heat stabilizers, polymerization catalysts, flame-retardants, blowing agents for plastics, explosives, and dyes.
The crystal structure of the title compound has been previously determined by photographic methods (Wyckoff, 1923; Donohue & Lipscomb, 1947). The results of the present re-determination show a much higher precision and accuracy. The nitrogen and chlorine atoms are located on threefold rotation axis, whereas the hydrogen atom lies in a general position. The [H6N2]2+ cations and Cl− anions are connected via N—H···Cl hydrogen bonds (Table) to a 3-D net, generating R63(14) rings (Bernstein et al., 1995). The bond lengths in the title compound (Table) are comparable to those observed for hydrazinium chloride (Sakurai & Tomiie, 1952; Chekhlov & Martynov, 1988) and hydrazine (Collin & Lipscomb, 1951), respectively.