Energetic propane-1,3-diaminium and butane-1,4-diaminium salts of N,N′-di­nitro­ethyl­enedi­aza­nide: syntheses, crystal structures and thermal properties

The acidity of the amine H atoms and the consequent salt formation ability of ethyl­enedinitramine (EDNA) were analyzed in an attempt to improve the thermal stability of EDNA. Two short-chain alkanedi­amine bases, namely propane-1,3-di­amine and butane-1,4-di­amine, were chosen for this purpose. The resulting salts, namely propane-1,3-diaminium N,N′-di­nitro­ethyl­enedi­aza­nide, C₃H₁₂N₂²⁺·C₂H₄N₄O₄²⁻, and butane-1,4-diaminium N,N′-di­nitro­ethyl­enedi­aza­nide, C₄H₁₄N₂²⁺·C₂H₄N₄O₄²⁻, crystallize in the ortho­rhom­bic space group Pbca and the monoclinic space group P2₁/n, respectively. The resulting salts display extensive hydrogen-bonding networks because of the presence of ammonium and diazenide ions in the crystal lattice. This results in an enhanced thermal stability and raises the thermal decomposition temperatures to 202 and 221 °C compared to 180 °C for EDNA. The extensive hydrogen bonding present also plays a crucial role in lowering the sensitivity to impact of these energetic salts.

Computing details

Data collection: APEX2 (Bruker, 2016) for mo_17ca_grcc5a_0ma; APEX2 (Bruker, 2015) for mo_17ca_grcc6_0m. Cell refinement: SAINT (Bruker, 2016) for mo_17ca_grcc5a_0ma; SAINT (Bruker, 2015) for mo_17ca_grcc6_0m. Data reduction: SAINT (Bruker, 2016) for mo_17ca_grcc5a_0ma; SAINT (Bruker, 2015) for mo_17ca_grcc6_0m. For both structures, program(s) used to solve structure: SHELXT2014 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018 (Sheldrick, 2015b); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

Propane-1,3-diaminium (ethane-1,2-diyl)bis(nitroazanide) (mo_17ca_grcc5a_0ma)

Crystal data

C3H12N2^2+·C2H4N4O4^2^−	Dx = 1.428 Mg m^−3
Mr = 224.24	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pbca	Cell parameters from 2241 reflections
a = 12.3448 (14) Å	θ = 2.4–24.2°
b = 9.9435 (13) Å	µ = 0.12 mm^−1
c = 16.9904 (19) Å	T = 100 K
V = 2085.6 (4) Å^3	Block, clear colourless
Z = 8	0.26 × 0.17 × 0.08 mm
F(000) = 960

Data collection

Bruker APEXII CCD diffractometer	1827 reflections with I > 2σ(I)
φ and ω scans	Rint = 0.077
Absorption correction: multi-scan (SADABS; Bruker, 2016)	θmax = 28.3°, θmin = 2.4°
Tmin = 0.656, Tmax = 0.746	h = −16→16
18809 measured reflections	k = −9→13
2591 independent reflections	l = −22→22

Refinement

Refinement on F^2	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.046	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.115	w = 1/[σ^2(Fo^2) + (0.0437P)^2 + 0.6333P] where P = (Fo^2 + 2Fc^2)/3
S = 1.02	(Δ/σ)max < 0.001
2591 reflections	Δρmax = 0.24 e Å^−3
160 parameters	Δρmin = −0.25 e Å^−3
6 restraints

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
O1	0.52445 (10)	0.84025 (13)	0.72260 (7)	0.0297 (3)
O2	0.62676 (11)	0.85073 (13)	0.61563 (7)	0.0370 (4)
O3	0.56105 (9)	0.18981 (13)	0.55971 (6)	0.0261 (3)
O4	0.67822 (10)	0.19857 (13)	0.46112 (7)	0.0297 (3)
N1	0.56838 (11)	0.78109 (16)	0.66152 (8)	0.0256 (3)
N2	0.55013 (11)	0.65589 (15)	0.65373 (8)	0.0239 (3)
N3	0.64024 (11)	0.38529 (15)	0.52363 (7)	0.0230 (3)
N4	0.62552 (11)	0.25971 (15)	0.51576 (7)	0.0232 (3)
N5	0.64848 (11)	−0.07170 (16)	0.44556 (8)	0.0218 (3)
H5A	0.7032 (13)	−0.111 (2)	0.4714 (10)	0.035 (5)*
H5B	0.5844 (12)	−0.1040 (19)	0.4607 (10)	0.031 (5)*
H5C	0.6522 (16)	0.0172 (14)	0.4549 (11)	0.035 (6)*
N6	0.89704 (11)	−0.10009 (17)	0.21727 (8)	0.0224 (3)
H6A	0.9411 (15)	−0.149 (2)	0.2470 (11)	0.041 (6)*
H6B	0.9196 (16)	−0.0147 (14)	0.2187 (11)	0.035 (6)*
H6C	0.9024 (16)	−0.129 (2)	0.1678 (8)	0.035 (5)*
C1	0.60335 (14)	0.59631 (18)	0.58573 (9)	0.0232 (4)
H1A	0.682372	0.612859	0.587960	0.028*
H1B	0.574704	0.636047	0.536522	0.028*
C2	0.58044 (13)	0.44706 (18)	0.58800 (9)	0.0242 (4)
H2A	0.604022	0.408707	0.638970	0.029*
H2B	0.501852	0.430337	0.581751	0.029*
C3	0.65865 (12)	−0.09557 (18)	0.35959 (9)	0.0223 (4)
H3A	0.607638	−0.036108	0.331128	0.027*
H3B	0.638830	−0.189875	0.347697	0.027*
C4	0.77355 (12)	−0.06866 (18)	0.33093 (9)	0.0215 (4)
H4A	0.790641	0.028115	0.336666	0.026*
H4B	0.825733	−0.120459	0.363156	0.026*
C5	0.78367 (13)	−0.10960 (19)	0.24521 (9)	0.0246 (4)
H5D	0.757743	−0.203187	0.238837	0.030*
H5E	0.737193	−0.050622	0.212600	0.030*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0322 (7)	0.0338 (8)	0.0232 (6)	0.0002 (6)	0.0068 (5)	0.0004 (5)
O2	0.0510 (8)	0.0317 (8)	0.0282 (7)	−0.0132 (6)	0.0154 (6)	0.0016 (5)
O3	0.0217 (6)	0.0323 (8)	0.0243 (6)	−0.0079 (5)	0.0001 (5)	0.0081 (5)
O4	0.0286 (7)	0.0291 (7)	0.0315 (6)	0.0004 (5)	0.0067 (5)	0.0016 (5)
N1	0.0232 (7)	0.0334 (9)	0.0202 (7)	−0.0021 (6)	0.0000 (5)	0.0041 (6)
N2	0.0204 (7)	0.0291 (9)	0.0223 (7)	−0.0039 (6)	−0.0004 (5)	0.0028 (6)
N3	0.0209 (7)	0.0270 (8)	0.0211 (7)	−0.0052 (6)	−0.0002 (5)	0.0013 (6)
N4	0.0182 (7)	0.0298 (9)	0.0217 (7)	−0.0040 (6)	−0.0017 (5)	0.0050 (6)
N5	0.0163 (7)	0.0264 (9)	0.0225 (7)	0.0010 (6)	0.0019 (5)	0.0036 (6)
N6	0.0192 (7)	0.0305 (9)	0.0175 (6)	0.0014 (6)	0.0006 (6)	0.0028 (6)
C1	0.0209 (8)	0.0309 (10)	0.0179 (7)	−0.0047 (7)	−0.0015 (6)	0.0028 (7)
C2	0.0215 (8)	0.0322 (10)	0.0189 (7)	−0.0074 (7)	−0.0007 (6)	0.0010 (7)
C3	0.0172 (8)	0.0285 (10)	0.0213 (7)	−0.0013 (7)	0.0004 (6)	−0.0027 (7)
C4	0.0170 (8)	0.0293 (10)	0.0183 (7)	−0.0019 (7)	−0.0006 (6)	0.0023 (6)
C5	0.0186 (8)	0.0317 (10)	0.0236 (8)	−0.0022 (7)	0.0001 (6)	−0.0030 (7)

Geometric parameters (Å, º)

O1—N1	1.3103 (18)	N6—C5	1.481 (2)
O2—N1	1.2676 (18)	C1—H1A	0.9900
O3—N4	1.2939 (17)	C1—H1B	0.9900
O4—N4	1.2863 (18)	C1—C2	1.511 (2)
N1—N2	1.272 (2)	C2—H2A	0.9900
N2—C1	1.455 (2)	C2—H2B	0.9900
N3—N4	1.269 (2)	C3—H3A	0.9900
N3—C2	1.455 (2)	C3—H3B	0.9900
N5—H5A	0.894 (13)	C3—C4	1.523 (2)
N5—H5B	0.892 (12)	C4—H4A	0.9900
N5—H5C	0.899 (13)	C4—H4B	0.9900
N5—C3	1.485 (2)	C4—C5	1.517 (2)
N6—H6A	0.887 (13)	C5—H5D	0.9900
N6—H6B	0.894 (13)	C5—H5E	0.9900
N6—H6C	0.889 (12)
O2—N1—O1	118.50 (15)	C2—C1—H1B	110.3
O2—N1—N2	124.85 (14)	N3—C2—C1	107.47 (13)
N2—N1—O1	116.64 (13)	N3—C2—H2A	110.2
N1—N2—C1	113.65 (13)	N3—C2—H2B	110.2
N4—N3—C2	114.95 (13)	C1—C2—H2A	110.2
O4—N4—O3	118.28 (14)	C1—C2—H2B	110.2
N3—N4—O3	123.77 (14)	H2A—C2—H2B	108.5
N3—N4—O4	117.95 (13)	N5—C3—H3A	109.3
H5A—N5—H5B	111.8 (18)	N5—C3—H3B	109.3
H5A—N5—H5C	107.6 (18)	N5—C3—C4	111.42 (13)
H5B—N5—H5C	110.4 (18)	H3A—C3—H3B	108.0
C3—N5—H5A	110.4 (12)	C4—C3—H3A	109.3
C3—N5—H5B	107.5 (12)	C4—C3—H3B	109.3
C3—N5—H5C	109.1 (12)	C3—C4—H4A	109.7
H6A—N6—H6B	108.2 (19)	C3—C4—H4B	109.7
H6A—N6—H6C	108.6 (19)	H4A—C4—H4B	108.2
H6B—N6—H6C	107.8 (18)	C5—C4—C3	109.66 (13)
C5—N6—H6A	111.2 (14)	C5—C4—H4A	109.7
C5—N6—H6B	110.3 (13)	C5—C4—H4B	109.7
C5—N6—H6C	110.7 (13)	N6—C5—C4	111.62 (13)
N2—C1—H1A	110.3	N6—C5—H5D	109.3
N2—C1—H1B	110.3	N6—C5—H5E	109.3
N2—C1—C2	107.16 (13)	C4—C5—H5D	109.3
H1A—C1—H1B	108.5	C4—C5—H5E	109.3
C2—C1—H1A	110.3	H5D—C5—H5E	108.0
O1—N1—N2—C1	−178.69 (13)	N5—C3—C4—C5	173.46 (14)
O2—N1—N2—C1	0.1 (2)	C2—N3—N4—O3	1.4 (2)
N1—N2—C1—C2	176.08 (13)	C2—N3—N4—O4	−178.29 (13)
N2—C1—C2—N3	−175.71 (12)	C3—C4—C5—N6	−173.42 (15)
N4—N3—C2—C1	−177.19 (13)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N5—H5B···O3^i	0.89 (1)	2.02 (1)	2.8421 (18)	153 (2)
N5—H5C···O4	0.90 (1)	1.84 (1)	2.725 (2)	170 (2)
N6—H6B···O1^ii	0.89 (1)	1.87 (1)	2.761 (2)	177 (2)
N6—H6C···O3^iii	0.89 (1)	1.99 (1)	2.8687 (18)	171 (2)

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

Butane-1,4-diaminium (ethane-1,2-diyl)bis(nitroazanide) (mo_17ca_grcc6_0m)

Crystal data

C4H14N2^2+·C2H4N4O4^2^−	F(000) = 256
Mr = 238.26	Dx = 1.436 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 5.408 (3) Å	Cell parameters from 6899 reflections
b = 7.203 (4) Å	θ = 2.9–28.6°
c = 14.288 (8) Å	µ = 0.12 mm^−1
β = 98.03 (3)°	T = 100 K
V = 551.0 (5) Å^3	Block, colourless
Z = 2	0.44 × 0.41 × 0.26 mm

Data collection

Bruker APEXII CCD diffractometer	1258 reflections with I > 2σ(I)
φ and ω scans	Rint = 0.044
Absorption correction: multi-scan (SADABS; Bruker, 2016)	θmax = 28.3°, θmin = 2.9°
Tmin = 0.697, Tmax = 0.746	h = −7→7
11975 measured reflections	k = −9→9
1371 independent reflections	l = −18→19

Refinement

Refinement on F^2	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.031	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.086	w = 1/[σ^2(Fo^2) + (0.0442P)^2 + 0.1942P] where P = (Fo^2 + 2Fc^2)/3
S = 1.07	(Δ/σ)max < 0.001
1371 reflections	Δρmax = 0.42 e Å^−3
85 parameters	Δρmin = −0.22 e Å^−3
3 restraints

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
O1	0.57312 (12)	0.50962 (10)	0.36574 (5)	0.01429 (17)
O2	0.69613 (12)	0.32306 (10)	0.25666 (5)	0.01567 (18)
N2	0.98232 (14)	0.42748 (11)	0.37090 (5)	0.01234 (19)
N3	0.75026 (14)	0.42316 (10)	0.33261 (5)	0.01133 (18)
C3	1.03227 (16)	0.54830 (13)	0.45476 (6)	0.0120 (2)
H3A	0.932325	0.663346	0.443575	0.014*
H3B	1.210935	0.583655	0.464369	0.014*
N1	0.26171 (14)	0.13317 (11)	0.29615 (5)	0.01154 (18)
H1A	0.406 (2)	0.1838 (18)	0.2778 (10)	0.023 (3)*
H1B	0.174 (2)	0.2286 (17)	0.3205 (9)	0.019 (3)*
H1C	0.164 (2)	0.0814 (19)	0.2444 (9)	0.026 (4)*
C1	0.32151 (18)	−0.01024 (13)	0.37207 (6)	0.0145 (2)
H1D	0.411205	−0.114988	0.347103	0.017*
H1E	0.164198	−0.058994	0.390608	0.017*
C2	0.48284 (17)	0.07085 (12)	0.45915 (6)	0.0130 (2)
H2A	0.402580	0.184428	0.479772	0.016*
H2B	0.648300	0.105825	0.442502	0.016*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0104 (3)	0.0184 (4)	0.0143 (3)	0.0033 (2)	0.0024 (2)	0.0007 (2)
O2	0.0150 (3)	0.0199 (4)	0.0115 (3)	−0.0031 (3)	−0.0001 (2)	−0.0043 (3)
N2	0.0094 (3)	0.0152 (4)	0.0119 (4)	−0.0003 (3)	−0.0003 (3)	−0.0013 (3)
N3	0.0108 (3)	0.0123 (4)	0.0109 (3)	−0.0008 (3)	0.0015 (3)	0.0012 (3)
C3	0.0113 (4)	0.0132 (4)	0.0114 (4)	−0.0021 (3)	0.0011 (3)	−0.0015 (3)
N1	0.0111 (3)	0.0123 (4)	0.0107 (4)	0.0000 (3)	−0.0004 (3)	0.0006 (3)
C1	0.0182 (4)	0.0121 (4)	0.0117 (4)	−0.0011 (3)	−0.0032 (3)	0.0017 (3)
C2	0.0148 (4)	0.0121 (4)	0.0111 (4)	−0.0009 (3)	−0.0015 (3)	0.0005 (3)

Geometric parameters (Å, º)

O1—N3	1.2869 (11)	N1—H1C	0.924 (11)
O2—N3	1.3017 (11)	N1—C1	1.5000 (12)
N2—N3	1.2974 (12)	C1—H1D	0.9900
N2—C3	1.4749 (12)	C1—H1E	0.9900
C3—C3^i	1.5503 (18)	C1—C2	1.5320 (13)
C3—H3A	0.9900	C2—C2^ii	1.5420 (18)
C3—H3B	0.9900	C2—H2A	0.9900
N1—H1A	0.931 (11)	C2—H2B	0.9900
N1—H1B	0.931 (10)
N3—N2—C3	114.41 (8)	C1—N1—H1B	107.9 (8)
O1—N3—O2	118.84 (8)	C1—N1—H1C	110.0 (9)
O1—N3—N2	124.00 (8)	N1—C1—H1D	109.3
N2—N3—O2	117.16 (8)	N1—C1—H1E	109.3
N2—C3—C3^i	112.06 (10)	N1—C1—C2	111.44 (8)
N2—C3—H3A	109.2	H1D—C1—H1E	108.0
N2—C3—H3B	109.2	C2—C1—H1D	109.3
C3^i—C3—H3A	109.2	C2—C1—H1E	109.3
C3^i—C3—H3B	109.2	C1—C2—C2^ii	110.92 (10)
H3A—C3—H3B	107.9	C1—C2—H2A	109.5
H1A—N1—H1B	108.0 (12)	C1—C2—H2B	109.5
H1A—N1—H1C	109.8 (13)	C2^ii—C2—H2A	109.5
H1B—N1—H1C	109.5 (12)	C2^ii—C2—H2B	109.5
C1—N1—H1A	111.6 (8)	H2A—C2—H2B	108.0
N3—N2—C3—C3^i	81.04 (11)	C3—N2—N3—O2	178.03 (7)
C3—N2—N3—O1	−2.72 (12)	N1—C1—C2—C2^ii	173.34 (9)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O2	0.93 (1)	1.92 (1)	2.8422 (15)	170 (1)
N1—H1B···N2^iii	0.93 (1)	1.96 (1)	2.8927 (15)	179 (1)
N1—H1C···O1^iv	0.92 (1)	1.96 (1)	2.8723 (16)	171 (1)

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