Carbamo­yl(di­amino­methyl­idene)aza­nium 3-nitro-5-oxo-4,5-di­hydro-1H-1,2,4-triazol-4-ide

Huang, X.-P.; Wang, B.-Z.; Li, D.-P.; Ng, S.W.

doi:10.1107/S1600536813015699

organic compounds

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Carbamoyl(diaminomethylidene)azanium 3-nitro-5-oxo-4,5-dihydro-1H-1,2,4-triazol-4-ide

Xin-Ping Huang,^a Bo-Zhou Wang,^a Dong-Ping Li ^b and Seik Weng Ng ^c,^d ^*

^aXi'an Modern Chemistry Research Institute, Xi'an 710065, People's Republic of China, ^bDepartment of Mathematics, Jining Teachers College, Wulanchabu 012000, People's Republic of China, ^cDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia, and ^dChemistry Department, King Abdulaziz University, PO Box 80203 Jeddah, Saudi Arabia
^*Correspondence e-mail: seikweng@um.edu.my

(Received 7 May 2013; accepted 5 June 2013; online 12 June 2013)

In the anion of the title salt, C₂H₇N₄O⁺·C₂HN₄O₃⁻, the negative charge resides formally on the N³ atom of the triazole ring. In the crystal, the N³ and exocyclic O atoms are hydrogen-bond acceptors with respect to the formally double-bond iminium and amido N atoms of the cation. The cation and anion are almost planar (r.m.s. deviations = 0.012 and 0.051 Å, respectively), but they are slightly bent with respect to each other [dihedral angle = 12.6 (1)°]. In the crystal, adjacent anions and cations are linked by extensive N—H⋯N and N—H⋯O hydrogen bonds, generating a ribbon running along the b-axis direction.

Related literature

For background to applications of similar compounds as propellants and explosives, see: Liu et al. (2006 ); Östmark et al. (2002 ).

Experimental

Crystal data

C₂H₇N₄O⁺·C₂HN₄O₃⁻
M_r = 232.18
Monoclinic, P 2₁ /n
a = 3.7100 (5) Å
b = 13.4195 (19) Å
c = 18.033 (3) Å
β = 94.143 (3)°
V = 895.5 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.15 mm⁻¹
T = 293 K
0.30 × 0.30 × 0.20 mm

Data collection

Bruker SMART APEX diffractometer
5217 measured reflections
2032 independent reflections
1297 reflections with I > 2σ(I)
R_int = 0.035

Refinement

R[F² > 2σ(F²)] = 0.044
wR(F²) = 0.116
S = 1.00
2032 reflections
177 parameters
All H-atom parameters refined
Δρ_max = 0.17 e Å⁻³
Δρ_min = −0.23 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O4ⁱ	0.87 (2)	1.97 (2)	2.819 (2)	166 (2)
N5—H2⋯N3	0.94 (2)	1.99 (3)	2.926 (3)	173 (2)
N5—H3⋯O1ⁱⁱ	0.90 (3)	2.13 (3)	3.005 (2)	164 (2)
N6—H4⋯O1	0.89 (2)	1.96 (2)	2.824 (2)	163 (2)
N8—H5⋯O1	0.95 (3)	2.15 (3)	2.966 (3)	142 (2)
N8—H6⋯O3ⁱⁱⁱ	0.87 (2)	2.32 (3)	3.183 (3)	173 (2)
N7—H7⋯N2ⁱⁱⁱ	0.90 (2)	2.03 (3)	2.913 (2)	166 (2)
N7—H8⋯O4	0.85 (2)	2.02 (2)	2.645 (2)	129 (2)
Symmetry codes: (i) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (ii) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (iii) $[x-{\script{3\over 2}}, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536813015699/xu5702sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536813015699/xu5702Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536813015699/xu5702Isup3.cml

checkCIF report

Comment top

We have reported organic compounds that do not possess carbon-bound hydrogen atoms; N-guanylurea dinitramide, NH₂C(NH)NHC(O)NH₂^.NH(NO₂)₂ (Liu et al., 2006), exemplifies such a compound that has been evaluated for use as a propellant and an insensitive-munitions explosive (Östmark et al., 2002). The title salt (Scheme I, Fig. 1) features an (NH₂)₂C(NH)C(O)NH₂ cation that has been protonated by 3-nitro-1,2,4-triazol-5-one, which is acidic owing to the electron-withdrawing nitro group. The N³ and exocyclic O atoms are hydrogen bond acceptors with respect to the formally double-bond iminium and amido N atoms of the cation. The cation and anion are planar but they are slightly bent with respect to each other. Adjacent ion-pairs are linked by extensive N···N and N···O hydrogen bonds to generate a ribbon structure (Table 1).

Related literature top

For background to applications of similar compounds as propellants and explosives, see: Liu et al. (2006); Östmark et al. (2002).

Experimental top

3-Nitro-1,2,4-triazol-5-one (26.0 g, 0.2 mol) was suspended in water (150 ml) kept at 303–313 K. Sodium hydroxide (8.2 g, 0.2 mol) dissolved in water (50 ml) was added. Guanylurea hydrochloride (27.8 g, 0.2 mol) dissolved in water (175 ml) was aded. The mixture was warmed to 323–333 K for 1.5 h. This was then cooled to 275–278 K. The solid material was collected and recrystallized from water (yield 35.0 g, 85% yield).

Structure description top

For background to applications of similar compounds as propellants and explosives, see: Liu et al. (2006); Östmark et al. (2002).

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

	Fig. 1. Thermal ellipsoid plot (Barbour, 2001) of C₂H₇N₄O^.C₂HN₄O₃ at the 70% probability level; hydrogen atoms are drawn as spheres of arbitrary radius.
	Fig. 2. Packing diagram.

Carbamoyl(diaminomethylidene)azanium 3-nitro-5-oxo-4,5-dihydro-1H-1,2,4-triazol-4-ide top

Crystal data top

C₂H₇N₄O⁺·C₂HN₄O₃⁻	F(000) = 480
M_r = 232.18	D_x = 1.722 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 976 reflections
a = 3.7100 (5) Å	θ = 2.3–24.8°
b = 13.4195 (19) Å	µ = 0.15 mm⁻¹
c = 18.033 (3) Å	T = 293 K
β = 94.143 (3)°	Prism, yellow
V = 895.5 (2) Å³	0.30 × 0.30 × 0.20 mm
Z = 4

Data collection top

Bruker SMART APEX diffractometer	1297 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.035
Graphite monochromator	θ_max = 27.5°, θ_min = 1.9°
ω scans	h = −4→4
5217 measured reflections	k = −14→17
2032 independent reflections	l = −22→21

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.116	All H-atom parameters refined
S = 1.00	w = 1/[σ²(F_o²) + (0.0564P)²] where P = (F_o² + 2F_c²)/3
2032 reflections	(Δ/σ)_max = 0.001
177 parameters	Δρ_max = 0.17 e Å⁻³
0 restraints	Δρ_min = −0.23 e Å⁻³

Crystal data top

C₂H₇N₄O⁺·C₂HN₄O₃⁻	V = 895.5 (2) Å³
M_r = 232.18	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 3.7100 (5) Å	µ = 0.15 mm⁻¹
b = 13.4195 (19) Å	T = 293 K
c = 18.033 (3) Å	0.30 × 0.30 × 0.20 mm
β = 94.143 (3)°

Data collection top

Bruker SMART APEX diffractometer	1297 reflections with I > 2σ(I)
5217 measured reflections	R_int = 0.035
2032 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.044	0 restraints
wR(F²) = 0.116	All H-atom parameters refined
S = 1.00	Δρ_max = 0.17 e Å⁻³
2032 reflections	Δρ_min = −0.23 e Å⁻³
177 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
O1	0.3898 (4)	0.79686 (10)	0.74934 (8)	0.0387 (4)
O2	0.9393 (5)	0.48678 (10)	0.86971 (9)	0.0526 (5)
O3	1.2361 (4)	0.56912 (12)	0.95758 (9)	0.0502 (5)
O4	0.0042 (5)	0.49420 (10)	0.59852 (8)	0.0429 (4)
N1	0.7380 (5)	0.80376 (12)	0.86167 (9)	0.0309 (4)
N2	0.9228 (5)	0.73874 (11)	0.90892 (8)	0.0301 (4)
N3	0.6699 (5)	0.65784 (11)	0.80734 (9)	0.0288 (4)
N4	1.0257 (5)	0.56440 (12)	0.90216 (9)	0.0343 (4)
N5	0.3102 (5)	0.50638 (14)	0.71153 (9)	0.0356 (5)
N6	0.1708 (5)	0.64808 (12)	0.64482 (9)	0.0304 (4)
N7	−0.1373 (5)	0.66445 (15)	0.52843 (10)	0.0364 (5)
N8	0.0601 (6)	0.80164 (14)	0.59459 (12)	0.0465 (6)
C1	0.8697 (5)	0.65588 (13)	0.87193 (10)	0.0257 (4)
C2	0.5814 (5)	0.75613 (14)	0.80084 (10)	0.0281 (5)
C3	0.1543 (6)	0.54422 (14)	0.64972 (10)	0.0291 (5)
C4	0.0251 (6)	0.70408 (14)	0.58795 (10)	0.0283 (4)
H1	0.703 (6)	0.8651 (17)	0.8753 (12)	0.042 (6)*
H2	0.434 (6)	0.5511 (18)	0.7446 (12)	0.046 (7)*
H3	0.290 (7)	0.440 (2)	0.7190 (14)	0.064 (8)*
H4	0.257 (7)	0.6841 (19)	0.6834 (13)	0.053 (7)*
H5	0.177 (8)	0.8310 (19)	0.6379 (16)	0.076 (9)*
H6	−0.034 (7)	0.8406 (18)	0.5601 (13)	0.052 (7)*
H7	−0.248 (6)	0.7032 (18)	0.4929 (13)	0.051 (7)*
H8	−0.162 (6)	0.6015 (18)	0.5248 (13)	0.046 (7)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0502 (10)	0.0337 (8)	0.0302 (8)	0.0054 (7)	−0.0120 (7)	0.0002 (6)
O2	0.0776 (13)	0.0250 (8)	0.0544 (10)	0.0059 (8)	−0.0017 (9)	−0.0022 (7)
O3	0.0493 (10)	0.0527 (10)	0.0459 (10)	0.0033 (8)	−0.0145 (8)	0.0133 (8)
O4	0.0670 (11)	0.0287 (8)	0.0307 (8)	−0.0121 (7)	−0.0130 (7)	0.0012 (6)
N1	0.0418 (11)	0.0222 (8)	0.0274 (9)	0.0024 (8)	−0.0054 (8)	−0.0039 (7)
N2	0.0362 (11)	0.0268 (8)	0.0262 (9)	0.0003 (7)	−0.0050 (7)	−0.0025 (7)
N3	0.0338 (10)	0.0244 (9)	0.0272 (9)	0.0000 (7)	−0.0036 (7)	−0.0030 (7)
N4	0.0375 (11)	0.0305 (9)	0.0348 (10)	0.0012 (8)	0.0027 (8)	0.0045 (8)
N5	0.0521 (12)	0.0251 (9)	0.0276 (10)	−0.0028 (9)	−0.0099 (9)	0.0016 (8)
N6	0.0434 (11)	0.0234 (8)	0.0231 (9)	−0.0028 (8)	−0.0071 (8)	−0.0013 (7)
N7	0.0484 (12)	0.0306 (10)	0.0283 (10)	−0.0027 (9)	−0.0103 (9)	0.0033 (8)
N8	0.0717 (16)	0.0240 (10)	0.0413 (12)	0.0037 (10)	−0.0129 (11)	0.0019 (9)
C1	0.0271 (11)	0.0260 (10)	0.0238 (10)	0.0004 (8)	0.0004 (8)	−0.0009 (8)
C2	0.0341 (12)	0.0246 (10)	0.0252 (10)	−0.0009 (8)	−0.0014 (9)	−0.0020 (8)
C3	0.0362 (12)	0.0263 (10)	0.0244 (10)	−0.0025 (9)	−0.0002 (9)	−0.0013 (8)
C4	0.0313 (11)	0.0275 (10)	0.0263 (10)	−0.0003 (9)	0.0024 (8)	0.0003 (8)

Geometric parameters (Å, º) top

O1—C2	1.253 (2)	N5—H2	0.94 (2)
O2—N4	1.226 (2)	N5—H3	0.90 (3)
O3—N4	1.224 (2)	N6—C4	1.352 (2)
O4—C3	1.240 (2)	N6—C3	1.398 (2)
N1—C2	1.363 (2)	N6—H4	0.89 (2)
N1—N2	1.369 (2)	N7—C4	1.306 (3)
N1—H1	0.87 (2)	N7—H7	0.90 (2)
N2—C1	1.304 (2)	N7—H8	0.85 (2)
N3—C1	1.335 (2)	N8—C4	1.320 (3)
N3—C2	1.362 (2)	N8—H5	0.95 (3)
N4—C1	1.447 (2)	N8—H6	0.87 (2)
N5—C3	1.320 (2)

C2—N1—N2	111.56 (15)	H7—N7—H8	119 (2)
C2—N1—H1	127.4 (15)	C4—N8—H5	121.4 (16)
N2—N1—H1	120.3 (15)	C4—N8—H6	120.0 (16)
C1—N2—N1	100.07 (14)	H5—N8—H6	118 (2)
C1—N3—C2	102.08 (15)	N2—C1—N3	118.90 (16)
O3—N4—O2	124.25 (18)	N2—C1—N4	119.28 (17)
O3—N4—C1	118.53 (17)	N3—C1—N4	121.82 (16)
O2—N4—C1	117.21 (17)	O1—C2—N3	127.31 (18)
C3—N5—H2	117.0 (14)	O1—C2—N1	125.30 (18)
C3—N5—H3	118.0 (17)	N3—C2—N1	107.39 (16)
H2—N5—H3	125 (2)	O4—C3—N5	124.49 (19)
C4—N6—C3	125.80 (17)	O4—C3—N6	120.77 (18)
C4—N6—H4	113.2 (16)	N5—C3—N6	114.74 (18)
C3—N6—H4	120.6 (16)	N7—C4—N8	121.0 (2)
C4—N7—H7	120.5 (15)	N7—C4—N6	122.19 (18)
C4—N7—H8	120.5 (16)	N8—C4—N6	116.81 (19)

C2—N1—N2—C1	1.2 (2)	C1—N3—C2—O1	−179.1 (2)
N1—N2—C1—N3	−1.0 (2)	C1—N3—C2—N1	0.4 (2)
N1—N2—C1—N4	179.47 (16)	N2—N1—C2—O1	178.41 (19)
C2—N3—C1—N2	0.4 (2)	N2—N1—C2—N3	−1.1 (2)
C2—N3—C1—N4	179.90 (17)	C4—N6—C3—O4	1.9 (3)
O3—N4—C1—N2	−7.9 (3)	C4—N6—C3—N5	−178.53 (19)
O2—N4—C1—N2	172.69 (18)	C3—N6—C4—N7	−3.2 (3)
O3—N4—C1—N3	172.61 (18)	C3—N6—C4—N8	178.0 (2)
O2—N4—C1—N3	−6.8 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O4ⁱ	0.87 (2)	1.97 (2)	2.819 (2)	166 (2)
N5—H2···N3	0.94 (2)	1.99 (3)	2.926 (3)	173 (2)
N5—H3···O1ⁱⁱ	0.90 (3)	2.13 (3)	3.005 (2)	164 (2)
N6—H4···O1	0.89 (2)	1.96 (2)	2.824 (2)	163 (2)
N8—H5···O1	0.95 (3)	2.15 (3)	2.966 (3)	142 (2)
N8—H6···O3ⁱⁱⁱ	0.87 (2)	2.32 (3)	3.183 (3)	173 (2)
N7—H7···N2ⁱⁱⁱ	0.90 (2)	2.03 (3)	2.913 (2)	166 (2)
N7—H8···O4	0.85 (2)	2.02 (2)	2.645 (2)	129 (2)

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

Experimental details

Crystal data
Chemical formula	C₂H₇N₄O⁺·C₂HN₄O₃⁻
M_r	232.18
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	293
a, b, c (Å)	3.7100 (5), 13.4195 (19), 18.033 (3)
β (°)	94.143 (3)
V (Å³)	895.5 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.15
Crystal size (mm)	0.30 × 0.30 × 0.20

Data collection
Diffractometer	Bruker SMART APEX
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	5217, 2032, 1297
R_int	0.035
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.044, 0.116, 1.00
No. of reflections	2032
No. of parameters	177
H-atom treatment	All H-atom parameters refined
Δρ_max, Δρ_min (e Å⁻³)	0.17, −0.23

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O4ⁱ	0.87 (2)	1.97 (2)	2.819 (2)	166 (2)
N5—H2···N3	0.94 (2)	1.99 (3)	2.926 (3)	173 (2)
N5—H3···O1ⁱⁱ	0.90 (3)	2.13 (3)	3.005 (2)	164 (2)
N6—H4···O1	0.89 (2)	1.96 (2)	2.824 (2)	163 (2)
N8—H5···O1	0.95 (3)	2.15 (3)	2.966 (3)	142 (2)
N8—H6···O3ⁱⁱⁱ	0.87 (2)	2.32 (3)	3.183 (3)	173 (2)
N7—H7···N2ⁱⁱⁱ	0.90 (2)	2.03 (3)	2.913 (2)	166 (2)
N7—H8···O4	0.85 (2)	2.02 (2)	2.645 (2)	129 (2)

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

Acknowledgements

We thank the Scientific Research Project of Higher Education of Inner Mongolia (No. NJZY13284 and No. NJZC13283), the Inner Mongolia Science & Technology Plan and the Ministry of Higher Education of Malaysia (grant No. UM.C/HIR-MOHE/SC/03) for supporting this study.

References

Barbour, L. J. (2001). J. Supramol. Chem. 1, 189–191. CrossRef CAS Google Scholar
Bruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Liu, Q., Wang, B.-Z., Zhang, Z.-Z., Zhu, Z.-H. & Lian, P. (2006). Chin. J. Explosives Propellants, 29, 29–31. Google Scholar
Östmark, H., Bemm, U., Bergman, H. & Langlet, A. (2002). Thermochim. Acta, 384, 253–259. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar

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Carbamo­yl(di­amino­methyl­­idene)aza­nium 3-nitro-5-oxo-4,5-di­hydro-1H-1,2,4-triazol-4-ide

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

Carbamoyl(diaminomethylidene)azanium 3-nitro-5-oxo-4,5-dihydro-1H-1,2,4-triazol-4-ide