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ISSN: 2056-9890

Different cation-protonation patterns in mol­ecular salts of unsymmetrical dimethyhydrazine: C2H9N2·Br and C2H9N2·H2PO3

aDepartment of Chemistry, University of Aberdeen, Meston Walk, Aberdeen AB24 3UE, Scotland
*Correspondence e-mail: w.harrison@abdn.ac.uk

Edited by H. Stoeckli-Evans, University of Neuchâtel, Switzerland (Received 19 July 2016; accepted 22 July 2016; online 29 July 2016)

We describe the syntheses and crystal structures of two mol­ecular salts containing the 1,1-di­methyl­hydrazinium cation, namely 1,1-di­methyl­hydrazin-1-ium bromide, C2H9N2+·Br, (I), and 2,2-di­methyl­hydrazin-1-ium di­hydrogen phosphite, C2H9N2+·H2PO3, (II). In (I), the cation is protonated at the methyl­ated N atom and N—H⋯Br hydrogen bonds generate [010] chains in the crystal. In (II), the cation is protonated at the terminal N atom and cation-to-anion N—H⋯O and anion-to-anion O—H⋯O hydrogen bonds generate (001) sheets.

1. Chemical context

Unsymmetrical di­methyl­hydrazine (1,1-di­methyl­hydrazine; C2H8N2; UDMH) is a colourless liquid at room temperature and pressure with a strong and unpleasant ammonia-like or fishy smell. The best known application of this compound is the fuel (reducing agent) in hypergolic rocket fuels (Edwards, 2003[Edwards, T. (2003). J. Propul. Power, 19, 1089-1107.]), where it can be used alone or mixed with hydrazine: the latter formulation (trade name `Aerozine 50') was used by the Apollo lunar modules to begin their homeward journeys from the moon.

Chemically, both nitro­gen atoms in UDMH bear lone pairs of electrons, which can act as weak bases to accept protons and therefore result in the formation of mol­ecular salts when reacted with acids. The first crystal structure of a UDMH salt was reported by Klapötke et al. (1999[Klapötke, T. M., Nöth, H., Schwenk-Kircher, H., Walther, W. H. & Holl, G. (1999). Polyhedron, 18, 717-719.]), who prepared 1,1-dimetylhydrazinium azide as a possible high-energy-density material with military applications; the methyl­ated UDMH nitro­gen atom is protonated and the components are linked by strong N—H⋯N hydrogen bonds in the crystal. However, this salt exhibited pronounced hygroscopic behaviour and had a low melting point of 311 K, which deemed it unsuitable for such uses. The nitrate salt of UDMH, which may be a decomposition product of hypergolic fuels, was prepared soon afterwards by the same workers (De Bonn et al., 2001[Bonn, O. de, Hammerl, A., Klapötke, T. M., Mayer, P., Piotrowski, H. & Zewen, H. (2001). Z. Anorg. Allg. Chem. 627, 2011-2015.]) by a low-temperature, non-aqueous synthesis: anhydrous nitric acid and UDMH were separately dissolved in di­chloro­methane at 195 K and the solutions mixed at the same temperature. The resulting hygroscopic salt, 1,1-di­methyl­hydrazinium nitrate, is protonated at the methyl­ated nitro­gen atom and features N—H⋯O hydrogen bonds in its crystal structure.

Merkoulov et al. (2005[Merkoulov, A., Harms, K. & Sundermeyer, J. (2005). Acta Cryst. E61, o1800-o1801.]) synthesized 1,1-di­methyl­hydrazinium chloride by reacting liquid UDMH with HCl dissolved in diethyl ether: its crystal structure consists of two independent cations and two chloride anions in the asymmetric unit. The cation is protonated at the methyl­ated nitro­gen atom and a dense network of strong N—H⋯Cl and weak C—H⋯Cl hydrogen bonds helps to consolidate the packing in the crystal. A salt with a more complicated counter-ion was synthesised by Mu et al. (2011[Mu, X.-G., Wang, X.-J., Liu, X.-X., Cui, H. & Wang, H. (2011). Acta Cryst. E67, o2749.]): the addition of liquid UDMH to a solution of picric acid in ethanol at room temperature yielded 1,1-di­methyl­hydrazinium picrate. As before, the UDMH protonates at the methyl­ated nitro­gen atom and cation-to-anion N—H⋯O hydrogen bonds help to establish the packing.

[Scheme 1]

As an extension of these studies, we now describe the syntheses and crystal structures of 1,1-di­methyl­hydrazin-1-ium bromide, C2H9N2+·Br (I)[link] and 2,2-di­methyl­hydrazin-1-ium di­hydrogen phosphite, C2H9N2+·H2PO3 (II)[link].

2. Structural commentary

Compound (I)[link] crystallizes in space group I2/a (non-standard setting of C2/c) with one cation and one bromide anion in the asymmetric unit (Fig. 1[link]). The cation is protonated at the central N2 atom, as seen in previous UDMH salts referred to above. The N1—N2 bond length [1.4478 (19) Å] is slightly shorter than the C—N bond lengths [1.482 (2) and 1.485 (2) Å]. N2 is displaced from N1, C1 and C2 by 0.4834 (16) Å and the C—N—C bond angle [111.38 (14)°] is slightly greater than the C—N—N angles [108.93 (12) and 108.97 (14)°]. The H atoms attached to N1 point away from the carbon atoms [C1—N2—N1—H2n = −175.7 (2); C2—N2—N1—H1n = 178.0 (2)°] and the N2—H3n bond bis­ects the N1H2 group [H3n—N2—N1—H1n = 61 (2)°].

[Figure 1]
Figure 1
The mol­ecular structure of (I)[link], showing 50% displacement ellipsoids. The N—H⋯Br hydrogen bond is indicated by a double-dashed line (Table 1[link]).

Compound (II)[link] crystallizes in space group Pna21 with one cation and one di­hydrogen phosphite anion in the asymmetric unit (Fig. 2[link]). In this case, the cation is protonated at the terminal N atom rather than the central N atom, which has not been seen previously in UDMH salts. The N1—N2 bond length is 1.454 (3) Å and the C—N bond lengths are 1.462 (3) and 1.463 (3) Å. The geometry about N2 is pyramidal and this atom is displaced from N1, C1 and C2 by 0.504 (2) Å. The bond angles about N2 show the same trend as those in (I)[link]: C—N—C = 110.69 (18); C—N—N = 107.62 (17) and 107.94 (18)°. Two of the H atoms attached to N1 have almost the same locations as the corresponding atoms in (I)[link], whereas the third bis­ects the C1—N2—C2 grouping [C1—N2—N1—H3n = −62°]. In the anion, the P1—O3 bond length of 1.5638 (16) Å is typical (Harrison, 2003[Harrison, W. T. A. (2003). Acta Cryst. E59, o1351-o1353.]) for the protonated O atom in a di­hydrogen phosphite group whereas P1—O1 [1.4982 (15) Å] and P1—O2 [1.5003 (16) Å] are almost the same length, indicating the expected delocalization (resonance) of the negative charge over these two O atoms. The O—P—O bond angle for the unprotonated oxygen atoms [116.76 (9)°] is significantly larger than the O—P—OH angles [106.37 (9) and 111.46 (9)°], as seen previously for similar species (Harrison, 2003[Harrison, W. T. A. (2003). Acta Cryst. E59, o1351-o1353.]). P1 is displaced from its attached O atoms by 0.4510 (13) Å.

[Figure 2]
Figure 2
The mol­ecular structure of (II)[link], showing 50% displacement ellipsoids. The N—H⋯O hydrogen bond is indicated by a double-dashed line (Table 2[link]).

3. Supra­molecular features

In the crystal of (I)[link], N—H⋯Br hydrogen bonds (Table 1[link]) link the components into [010] chains (Fig. 3[link]): each Br ion accepts three N—H⋯Br bonds and alternating, centrosymmetric R42(8) and R42(10) loops occur within the chain. The N2 bond is significantly shorter than the N1 bonds, which may be due to the positive charge residing on N2: this was also observed in the structure of the nitrate salt (de Bonn et al., 2001[Bonn, O. de, Hammerl, A., Klapötke, T. M., Mayer, P., Piotrowski, H. & Zewen, H. (2001). Z. Anorg. Allg. Chem. 627, 2011-2015.]). There are also several weak C—H⋯Br contacts (Table 1[link]) in (I)[link]; the weak and strong inter­actions result in each bromide ion accepting a total of seven hydrogen bonds (Fig. 4[link]).

Table 1
Hydrogen-bond geometry (Å, °) for (I)[link]

D—H⋯A D—H H⋯A DA D—H⋯A
N1—H1n⋯Br1i 0.89 (2) 2.68 (3) 3.5666 (15) 170.7 (18)
N1—H2n⋯Br1 0.89 (2) 2.62 (2) 3.5117 (14) 175.0 (19)
N2—H3n⋯Br1ii 0.87 (2) 2.39 (2) 3.2490 (13) 173.3 (17)
C1—H1a⋯Br1i 0.98 3.11 3.9690 (18) 148
C1—H1b⋯Br1iii 0.98 3.09 4.0175 (19) 158
C1—H1c⋯Br1iv 0.98 2.90 3.8682 (17) 168
C2—H2c⋯Br1iii 0.98 3.07 3.9843 (18) 156
Symmetry codes: (i) [-x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+{\script{1\over 2}}]; (ii) [-x+{\script{1\over 2}}, -y+{\script{3\over 2}}, -z+{\script{1\over 2}}]; (iii) [-x, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]; (iv) [x, -y+{\script{3\over 2}}, z+{\script{1\over 2}}].
[Figure 3]
Figure 3
Partial packing diagram for (I)[link], showing the formation of [010] chains linked by N—H⋯Br hydrogen bonds. C-bound H atoms are omitted for clarity. Symmetry codes as in Table 1[link].
[Figure 4]
Figure 4
The environment of the bromide ion in the crystal of (I)[link]. [Symmetry codes: (i) [{1\over 2}] − x, [{3\over 2}] − y, [{1\over 2}] − z; (ii) [{1\over 2}] − x, [{1\over 2}] − y, [{1\over 2}] − z; (iii) −x, [{1\over 2}] + y, [{1\over 2}] − y; (iv) x, [{3\over 2}] − y, z − [{1\over 2}].] Note that each of the five cations has a different bonding mode: η1 N1, N2 and C1 and η2 N1 + C1 and C1 + C2.

The crystal structure of (II)[link] appears to correlate with the novel protonation pattern of the C2H9N2+ cation: the three H atoms attached to N1 each partake in a strong, near-linear N—H⋯O hydrogen bond to nearby H2PO3 anions (Table 2[link]). The anions are linked into [100] chains by O—H⋯O hydrogen bonds with adjacent anions in the chain related by a-glide symmetry. Together, these inter­actions generate (001) sheets (Fig. 5[link]) As usual (Harrison, 2001[Harrison, W. T. A. (2001). J. Solid State Chem. 160, 4-7.]), the P—H grouping of the anion does not participate in hydrogen bonds and the H atom points into the inter-layer region.

Table 2
Hydrogen-bond geometry (Å, °) for (II)[link]

D—H⋯A D—H H⋯A DA D—H⋯A
N1—H1n⋯O1i 0.91 1.83 2.736 (2) 176
N1—H2n⋯O1ii 0.91 1.85 2.762 (2) 176
N1—H3n⋯O2 0.91 1.91 2.814 (2) 175
O3—H1o⋯O2i 0.87 1.74 2.568 (2) 159
Symmetry codes: (i) [x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z]; (ii) x, y+1, z.
[Figure 5]
Figure 5
Partial packing diagram for (II)[link], showing part of an (001) sheet. Symmetry codes as in Table 2[link].

4. Database survey

A search of the Cambridge Structural Database (CSD; Groom et al., 2016[Groom, C. R., Bruno, I. J., Lightfoot, M. P. & Ward, S. C. (2016). Acta Cryst. B72, 171-179.]) revealed the crystal structures of the four UDMH derivatives cited above: refcodes for the azide, nitrate, chloride and picrate salts are CORRUW, IBOLOA, FOHLUK and AZUXID, respectively.

5. Synthesis and crystallization

Caution! UDMH is toxic, potentially carcinogenic and may form explosive mixtures with oxidizing agents: all appropriate safety measures must be put in place when handling this compound.

To prepare (I)[link], aqueous solutions of UDMH (10 ml, 1.0 M) and hydro­bromic acid (10 ml, 1.0 M) were mixed at room temperature to yield a colourless solution and colourless rods (to ∼1 mm in length) of (I)[link] grew as the solvent evaporated in a watch glass. These crystals are extremely hygroscopic and should be immediately transferred to a desiccator for storage: if left in air, they absorb enough water to completely dissolve within an hour or two.

To prepare (II)[link], aqueous solutions of UDMH (10 ml, 1.0 M) and phospho­rus acid (10 ml, 1.0 M) were mixed at room temperature to yield a colourless solution and yellowish slabs of (II)[link] grew as the increasingly viscous solvent slowly evaporated over several days in a watch glass. These crystals are hygroscopic and should be stored in a desiccator. IR: 2383 cm−1 (P—H stretch).

The IR spectra of UDMH, (I)[link] and (II)[link] are available as supporting information.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3[link]. The N-bound H atoms in (I)[link] were located in difference maps and their positions freely refined; those in (II)[link] were relocated to idealized locations and refined as riding atoms. The O-bound H atom in (II)[link] was located in a difference map and refined as riding, in its as-found relative position. The methyl H atoms were geometrically placed (C—H = 0.98 Å): the –CH3 groups were allowed to rotate, but not to tip, to best fit the electron density. The constraint Uiso(H) = 1.2Ueq(carrier) or 1.5Ueq(methyl carrier) was applied in all cases.

Table 3
Experimental details

  (I) (II)
Crystal data
Chemical formula C2H9N2+·Br C2H9N2+·H2PO3
Mr 141.02 142.10
Crystal system, space group Monoclinic, I2/a Orthorhombic, Pna21
Temperature (K) 100 100
a, b, c (Å) 13.2423 (2), 5.1239 (1), 16.1839 (3) 8.0690 (2), 6.9970 (2), 11.7001 (6)
α, β, γ (°) 90, 94.838 (2), 90 90, 90, 90
V3) 1094.20 (3) 660.57 (4)
Z 8 4
Radiation type Mo Kα Mo Kα
μ (mm−1) 7.36 0.35
Crystal size (mm) 0.23 × 0.09 × 0.09 0.18 × 0.18 × 0.02
 
Data collection
Diffractometer Rigaku Mercury CCD Rigaku Mercury CCD
Absorption correction Multi-scan (CrystalClear; Rigaku, 2012[Rigaku (2012). CrystalClear. Rigaku Corporation, Tokyo, Japan.])
Tmin, Tmax 0.282, 0.557
No. of measured, independent and observed [I > 2σ(I)] reflections 6485, 1258, 1224 5347, 1395, 1365
Rint 0.029 0.023
(sin θ/λ)max−1) 0.649 0.649
 
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.020, 0.051, 1.12 0.025, 0.065, 1.09
No. of reflections 1258 1395
No. of parameters 58 77
No. of restraints 0 1
H-atom treatment H atoms treated by a mixture of independent and constrained refinement H-atom parameters constrained
Δρmax, Δρmin (e Å−3) 0.50, −0.48 0.24, −0.28
Absolute structure Refined as an inversion twin.
Absolute structure parameter 0.15 (14)
Computer programs: CrystalClear (Rigaku, 2012[Rigaku (2012). CrystalClear. Rigaku Corporation, Tokyo, Japan.]), SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]), SHELXL2014 (Sheldrick, 2015[Sheldrick, G. M. (2015). Acta Cryst. C71, 3-8.]), ORTEP-3 for Windows (Farrugia, 2012[Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849-854.]) and publCIF (Westrip, 2010[Westrip, S. P. (2010). J. Appl. Cryst. 43, 920-925.]).

Supporting information


Computing details top

For both compounds, data collection: CrystalClear (Rigaku, 2012); cell refinement: CrystalClear (Rigaku, 2012); data reduction: CrystalClear (Rigaku, 2012); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: publCIF (Westrip, 2010).

(I) 1,1-Dimethylhydrazin-1-ium bromide top
Crystal data top
C2H9N2+·BrF(000) = 560
Mr = 141.02Dx = 1.712 Mg m3
Monoclinic, I2/aMo Kα radiation, λ = 0.71073 Å
a = 13.2423 (2) ÅCell parameters from 5743 reflections
b = 5.1239 (1) Åθ = 2.5–27.5°
c = 16.1839 (3) ŵ = 7.36 mm1
β = 94.838 (2)°T = 100 K
V = 1094.20 (3) Å3Rod, colourless
Z = 80.23 × 0.09 × 0.09 mm
Data collection top
Rigaku Mercury CCD
diffractometer
1224 reflections with I > 2σ(I)
ω scansRint = 0.029
Absorption correction: multi-scan
(CrystalClear; Rigaku, 2012)
θmax = 27.5°, θmin = 2.5°
Tmin = 0.282, Tmax = 0.557h = 1717
6485 measured reflectionsk = 65
1258 independent reflectionsl = 2019
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: mixed
R[F2 > 2σ(F2)] = 0.020H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.051 w = 1/[σ2(Fo2) + (0.0349P)2 + 0.3874P]
where P = (Fo2 + 2Fc2)/3
S = 1.12(Δ/σ)max = 0.001
1258 reflectionsΔρmax = 0.50 e Å3
58 parametersΔρmin = 0.48 e Å3
0 restraintsExtinction correction: SHELXL2014 (Sheldrick, 2015), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0151 (6)
Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
N10.13506 (11)0.3029 (3)0.30499 (9)0.0197 (3)
H1n0.1888 (17)0.204 (4)0.3204 (13)0.024*
H2n0.1477 (17)0.393 (3)0.2599 (15)0.024*
N20.13068 (10)0.4851 (2)0.37297 (8)0.0170 (3)
H3n0.1867 (17)0.574 (4)0.3765 (12)0.020*
C10.11750 (14)0.3372 (3)0.45000 (11)0.0191 (3)
H1a0.17080.20470.45820.029*
H1b0.05100.25190.44540.029*
H1c0.12200.45710.49730.029*
C20.04544 (15)0.6693 (3)0.35325 (15)0.0278 (4)
H2a0.05670.76560.30250.042*
H2b0.04160.79250.39920.042*
H2c0.01820.57150.34500.042*
Br10.17057 (2)0.64136 (3)0.12100 (2)0.01501 (11)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.0198 (7)0.0244 (6)0.0150 (7)0.0014 (6)0.0030 (5)0.0027 (5)
N20.0120 (6)0.0147 (6)0.0240 (7)0.0019 (5)0.0004 (5)0.0017 (5)
C10.0195 (8)0.0226 (8)0.0151 (8)0.0015 (5)0.0010 (6)0.0008 (5)
C20.0175 (9)0.0173 (8)0.0479 (12)0.0030 (6)0.0014 (8)0.0067 (7)
Br10.01199 (13)0.01558 (14)0.01745 (14)0.00069 (4)0.00116 (7)0.00263 (4)
Geometric parameters (Å, º) top
N1—N21.4478 (19)C1—H1a0.98
N1—H1n0.89 (2)C1—H1b0.98
N1—H2n0.89 (2)C1—H1c0.98
N2—C11.482 (2)C2—H2a0.98
N2—C21.485 (2)C2—H2b0.98
N2—H3n0.87 (2)C2—H2c0.98
N2—N1—H1n103.6 (14)H1a—C1—H1b109.5
N2—N1—H2n108.0 (12)N2—C1—H1c109.5
H1n—N1—H2n108.8 (19)H1a—C1—H1c109.5
N1—N2—C1108.93 (12)H1b—C1—H1c109.5
N1—N2—C2108.97 (14)N2—C2—H2a109.5
C1—N2—C2111.38 (14)N2—C2—H2b109.5
N1—N2—H3n107.4 (13)H2a—C2—H2b109.5
C1—N2—H3n111.9 (13)N2—C2—H2c109.5
C2—N2—H3n108.1 (13)H2a—C2—H2c109.5
N2—C1—H1a109.5H2b—C2—H2c109.5
N2—C1—H1b109.5
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1n···Br1i0.89 (2)2.68 (3)3.5666 (15)170.7 (18)
N1—H2n···Br10.89 (2)2.62 (2)3.5117 (14)175.0 (19)
N2—H3n···Br1ii0.87 (2)2.39 (2)3.2490 (13)173.3 (17)
C1—H1a···Br1i0.983.113.9690 (18)148
C1—H1b···Br1iii0.983.094.0175 (19)158
C1—H1c···Br1iv0.982.903.8682 (17)168
C2—H2c···Br1iii0.983.073.9843 (18)156
Symmetry codes: (i) x+1/2, y+1/2, z+1/2; (ii) x+1/2, y+3/2, z+1/2; (iii) x, y1/2, z+1/2; (iv) x, y+3/2, z+1/2.
(II) 2,2-Dimethylhydrazin-1-ium dihydrogen phosphite top
Crystal data top
C2H9N2+·H2PO3Dx = 1.429 Mg m3
Mr = 142.10Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pna21Cell parameters from 4031 reflections
a = 8.0690 (2) Åθ = 3.4–27.5°
b = 6.9970 (2) ŵ = 0.35 mm1
c = 11.7001 (6) ÅT = 100 K
V = 660.57 (4) Å3Plate, yellow
Z = 40.18 × 0.18 × 0.02 mm
F(000) = 304
Data collection top
Rigaku Mercury CCD
diffractometer
Rint = 0.023
ω scansθmax = 27.5°, θmin = 3.4°
5347 measured reflectionsh = 810
1395 independent reflectionsk = 89
1365 reflections with I > 2σ(I)l = 1513
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: mixed
R[F2 > 2σ(F2)] = 0.025H-atom parameters constrained
wR(F2) = 0.065 w = 1/[σ2(Fo2) + (0.0374P)2 + 0.203P]
where P = (Fo2 + 2Fc2)/3
S = 1.09(Δ/σ)max < 0.001
1395 reflectionsΔρmax = 0.24 e Å3
77 parametersΔρmin = 0.28 e Å3
1 restraintAbsolute structure: Refined as an inversion twin.
Primary atom site location: structure-invariant direct methodsAbsolute structure parameter: 0.15 (14)
Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Refinement. Refined as a 2-component inversion twin.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
N10.5416 (2)0.5852 (2)0.22552 (17)0.0132 (4)
H1n0.64550.59720.19620.016*
H2n0.47790.68480.20160.016*
H3n0.49600.47350.20110.016*
N20.5499 (2)0.5853 (3)0.34964 (17)0.0145 (4)
C10.3807 (3)0.5724 (3)0.3936 (3)0.0189 (5)
H1a0.31690.68340.36770.028*
H1b0.38320.56990.47730.028*
H1c0.32860.45510.36520.028*
C20.6471 (3)0.4186 (3)0.3845 (2)0.0206 (5)
H2a0.75750.42550.34990.031*
H2b0.59120.30180.35900.031*
H2c0.65760.41690.46790.031*
P10.45797 (6)0.05934 (7)0.10615 (6)0.01209 (15)
H10.46660.05290.00640.015*
O10.35870 (18)0.1101 (2)0.14409 (14)0.0153 (3)
O20.39202 (17)0.2526 (2)0.13797 (14)0.0165 (4)
O30.63746 (19)0.0285 (2)0.15307 (17)0.0196 (4)
H1o0.70590.12240.14170.024*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.0099 (8)0.0108 (8)0.0189 (10)0.0002 (6)0.0001 (7)0.0003 (7)
N20.0114 (9)0.0142 (9)0.0180 (11)0.0005 (6)0.0007 (7)0.0007 (8)
C10.0124 (10)0.0206 (11)0.0236 (13)0.0007 (8)0.0021 (10)0.0016 (9)
C20.0172 (11)0.0209 (12)0.0237 (13)0.0050 (8)0.0028 (10)0.0023 (10)
P10.0074 (2)0.0095 (2)0.0194 (3)0.00031 (18)0.0003 (3)0.0004 (2)
O10.0097 (6)0.0100 (7)0.0263 (9)0.0005 (6)0.0011 (6)0.0013 (6)
O20.0097 (6)0.0112 (7)0.0286 (10)0.0017 (6)0.0011 (6)0.0023 (6)
O30.0075 (6)0.0127 (7)0.0386 (10)0.0009 (6)0.0030 (7)0.0040 (7)
Geometric parameters (Å, º) top
N1—N21.454 (3)C2—H2a0.98
N1—H1n0.91C2—H2b0.98
N1—H2n0.91C2—H2c0.98
N1—H3n0.91P1—O11.4982 (15)
N2—C11.462 (3)P1—O21.5003 (16)
N2—C21.463 (3)P1—O31.5638 (16)
C1—H1a0.98P1—H11.32
C1—H1b0.98O3—H1o0.8689
C1—H1c0.98
N2—N1—H1n109.5H1b—C1—H1c109.5
N2—N1—H2n109.5N2—C2—H2a109.5
H1n—N1—H2n109.5N2—C2—H2b109.5
N2—N1—H3n109.5H2a—C2—H2b109.5
H1n—N1—H3n109.5N2—C2—H2c109.5
H2n—N1—H3n109.5H2a—C2—H2c109.5
N1—N2—C1107.94 (18)H2b—C2—H2c109.5
N1—N2—C2107.62 (17)O1—P1—O2116.76 (9)
C1—N2—C2110.69 (18)O1—P1—O3106.37 (9)
N2—C1—H1a109.5O2—P1—O3111.46 (9)
N2—C1—H1b109.5O1—P1—H1107.3
H1a—C1—H1b109.5O2—P1—H1107.3
N2—C1—H1c109.5O3—P1—H1107.3
H1a—C1—H1c109.5P1—O3—H1o115.5
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1n···O1i0.911.832.736 (2)176
N1—H2n···O1ii0.911.852.762 (2)176
N1—H3n···O20.911.912.814 (2)175
O3—H1o···O2i0.871.742.568 (2)159
Symmetry codes: (i) x+1/2, y+1/2, z; (ii) x, y+1, z.
 

Acknowledgements

We thank the EPSRC National Crystallography Service (University of Southampton) for the data collections.

References

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