2-tert-Butyl-1-(4-nitro­amino-1,2,5-oxadiazol-3-yl)diazene 1-oxide

Li, X.-Z.; Wang, B.-Z.; Fan, X.-Z.; Ng, S.W.

doi:10.1107/S1600536812027353

organic compounds

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Volume 68| Part 7| July 2012| Page o2171

https://doi.org/10.1107/S1600536812027353

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2-tert-Butyl-1-(4-nitroamino-1,2,5-oxadiazol-3-yl)diazene 1-oxide

Xiang-Zhi Li,^a Bo-Zhou Wang,^a Xue-Zhong Fan ^a and Seik Weng Ng ^b,^c ^*

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

(Received 15 June 2012; accepted 16 June 2012; online 23 June 2012)

In the title compound, C₆H₁₀N₆O₄, the nitroamine –NHNO₂ substituent and the C–N=N(→ O) unit of the other substituent of the oxadiazole ring are nearly coplanar with the five-membered ring [dihedral angles = 5.7 (1) and 3.0 (1)°]. The amino group of the –NHNO₂ substituent is a hydrogen-bond donor to the two-coordinate N atom of the C—N=N(→ O) unit.

Related literature

The synthesis required several steps; see: Churakov et al. (1995 ); Li et al. (2008 ); Mel'nikova et al. (2001 ).

Experimental

Crystal data

C₆H₁₀N₆O₄
M_r = 230.20
Monoclinic, P 2₁ /n
a = 6.2509 (5) Å
b = 9.1327 (8) Å
c = 18.6566 (16) Å
β = 92.134 (2)°
V = 1064.32 (16) Å³
Z = 4
Mo Kα radiation
μ = 0.12 mm⁻¹
T = 293 K
0.32 × 0.22 × 0.18 mm

Data collection

Bruker SMART APEX diffractometer
6176 measured reflections
2402 independent reflections
1711 reflections with I > 2σ(I)
R_int = 0.023

Refinement

R[F² > 2σ(F²)] = 0.050
wR(F²) = 0.166
S = 1.05
2402 reflections
149 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.21 e Å⁻³
Δρ_min = −0.21 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N5—H1⋯N1	0.87 (1)	2.18 (2)	2.758 (2)	124 (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/S1600536812027353/xu5568sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812027353/xu5568Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536812027353/xu5568Isup3.cml

checkCIF report

Comment top

The title compound (Scheme I) as well as the precusor compounds (Churakov et al., 1995; Li et al., 2008; Mel'nikova et al., 2001) represent a class of high energy materials that has a low hydrogen content in the molecular formula. The nitroamine –NHNO₂ substituent and the C–N═ N(→O) unit of the second substituent of the oxadiazole ring of C₆H₁₀N₆O₄ are nearly coplanar with the five-membered ring [dihedral angles 5.7 (1), 3.0 (1) °] (Fig. 1). The amino group of the –NHNO₂ substituent is hydrogen bond donor to the two-coordinate N atom of C–N═ N(→O) (Table 1).

Related literature top

The synthesis required several steps; see: Churakov et al. (1995); Li et al. (2008); Mel'nikova et al. (2001).

Experimental top

The steps given below were adapted from published procedures (Churakov et al., 1995; Li et al., 2008; Mel'nikova et al., 2001)..

Synthesis of 3-amino-4-nitrosofurazan

To a mixture of benzene (200 ml), 30% hydrogen peroxide (145 ml, 1.29 mol) and sodium tungstate dihydrate (16.5 g, 0.05 mol), concentrated sulfuric acid (10 ml, 180 mmol) was added dropwise at 278–283 K followed by diaminofurazan (10.8 g, 0.10 mmol). The mixture was kept stirred at 288 K for 1.5 h. The organic layer was separated, washed with water and dried over magnesium sulfate. The solvent was removed to yield a yellow solid (5.19 g, 90% yield). CH&N elemental analysis. Calc. for C₂H₂N₄O₂: C 21.06, H 1.77, N 49.12%. Found: C 20.82, H 1.77, N 48.95%.

Synthesis of 3-amino-4-(tert-butyl-NNO-azoxy)furazan

A suspension solution of N,N-dibromo-tert-butylamine (11.5 g, 50 mmol), cuprous chloride (10 g, 0.1 mol), and the above compound (50 mmol) in dichloromethane (500 ml) was stirred at 288–298 K for 15 h. The reaction mixture was poured into ice-water (500 ml). Sodium thiosulfate was then added. The organic layer was separated, washed with water and dried over magnesium sulfate. The solvent was removed to give a yellow solid (6.8 g, 70%). CH&N elemental analysis. Calc. for C₆H₁₁N₅O₂: C 38.92, H 5.99, N37.82%. Found: C 39.36, H 5.96, N 35.60%.

Synthesis of 3-nitramino-4-(tert-butyl-NNO-azoxy)furazan

To a stirred and cooled (273 K) solution of the above compound (2 g, 10.8 mmol) in carbon tetrachloride, concentrated nitric acid (2.72 g, 21.6 mmol) was added. Thesolution was stirred for 2 h after after which the temperature was raised to room temperature. The solvent was removed. Dichloromethane (100 ml) was added and the organic phase was washed with cold water (20 ml). The aqueous layer was extracted with more dichloromethyane (2×50 ml). The combined organic layer was dried over magnesium sulfate, filtered and the solvent was removed to give the title compound as a yellow solid (2.47 g, 100% yield). CH&N elemental analysis. Calc. for C₆H₁N₆O₃: C31.30, H 4.35, N 36.52%. Found: C 31.73, H 4.41, N 36.12%. Crystals were obtained upon recrystallization from dichloromethane.

Structure description top

The synthesis required several steps; see: Churakov et al. (1995); Li et al. (2008); Mel'nikova et al. (2001).

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 C₆H₁₀N₆O₄ at the 50% probability level; hydrogen atoms are drawn as spheres of arbitrary radius.

2-tert-Butyl-1-(4-nitroamino-1,2,5-oxadiazol-3-yl)diazene 1-oxide top

Crystal data top

C₆H₁₀N₆O₄	F(000) = 480
M_r = 230.20	D_x = 1.437 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2279 reflections
a = 6.2509 (5) Å	θ = 2.2–26.2°
b = 9.1327 (8) Å	µ = 0.12 mm⁻¹
c = 18.6566 (16) Å	T = 293 K
β = 92.134 (2)°	Prism, yellow
V = 1064.32 (16) Å³	0.32 × 0.22 × 0.18 mm
Z = 4

Data collection top

Bruker SMART APEX diffractometer	1711 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.023
Graphite monochromator	θ_max = 27.5°, θ_min = 2.2°
ω scans	h = −8→7
6176 measured reflections	k = −11→11
2402 independent reflections	l = −14→24

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)] = 0.050	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.166	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ²(F_o²) + (0.0903P)² + 0.1496P] where P = (F_o² + 2F_c²)/3
2402 reflections	(Δ/σ)_max = 0.001
149 parameters	Δρ_max = 0.21 e Å⁻³
1 restraint	Δρ_min = −0.21 e Å⁻³

Crystal data top

C₆H₁₀N₆O₄	V = 1064.32 (16) Å³
M_r = 230.20	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 6.2509 (5) Å	µ = 0.12 mm⁻¹
b = 9.1327 (8) Å	T = 293 K
c = 18.6566 (16) Å	0.32 × 0.22 × 0.18 mm
β = 92.134 (2)°

Data collection top

Bruker SMART APEX diffractometer	1711 reflections with I > 2σ(I)
6176 measured reflections	R_int = 0.023
2402 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.050	1 restraint
wR(F²) = 0.166	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	Δρ_max = 0.21 e Å⁻³
2402 reflections	Δρ_min = −0.21 e Å⁻³
149 parameters

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

	x	y	z	U_iso*/U_eq
O1	0.0322 (3)	0.3824 (2)	0.18681 (9)	0.0936 (6)
O2	0.2815 (3)	0.3201 (2)	0.38149 (7)	0.0895 (5)
O4	0.8233 (3)	0.0997 (2)	0.34861 (9)	0.0993 (6)
O5	0.9040 (3)	0.04877 (19)	0.24053 (10)	0.0906 (5)
N1	0.3219 (2)	0.25696 (16)	0.15264 (7)	0.0506 (4)
N2	0.2040 (2)	0.31596 (16)	0.19716 (7)	0.0541 (4)
N3	0.1665 (3)	0.3517 (2)	0.32062 (9)	0.0761 (5)
N4	0.4710 (3)	0.2504 (2)	0.36761 (8)	0.0782 (5)
N5	0.6222 (2)	0.17780 (19)	0.25756 (8)	0.0630 (4)
N6	0.7946 (3)	0.10260 (19)	0.28501 (10)	0.0678 (5)
C1	0.4246 (5)	0.1849 (4)	0.03862 (11)	0.1183 (12)
H1A	0.4277	0.0852	0.0549	0.177*
H1B	0.5609	0.2299	0.0493	0.177*
H1C	0.3948	0.1871	−0.0122	0.177*
C2	0.0397 (4)	0.1911 (4)	0.06269 (13)	0.1051 (9)
H2A	−0.0692	0.2447	0.0864	0.158*
H2B	0.0471	0.0932	0.0813	0.158*
H2C	0.0056	0.1880	0.0121	0.158*
C3	0.2466 (4)	0.4235 (3)	0.05127 (11)	0.0851 (7)
H3A	0.1365	0.4744	0.0758	0.128*
H3B	0.2158	0.4270	0.0005	0.128*
H3C	0.3822	0.4694	0.0619	0.128*
C4	0.2546 (3)	0.2664 (2)	0.07571 (9)	0.0600 (5)
C5	0.2791 (3)	0.30095 (19)	0.27008 (9)	0.0525 (4)
C6	0.4692 (3)	0.23759 (19)	0.29834 (9)	0.0536 (4)
H1	0.602 (3)	0.170 (2)	0.2114 (5)	0.056 (5)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0717 (9)	0.1239 (14)	0.0855 (11)	0.0512 (9)	0.0053 (8)	0.0056 (9)
O2	0.1138 (13)	0.1042 (12)	0.0515 (8)	0.0024 (10)	0.0179 (8)	−0.0145 (8)
O4	0.0878 (11)	0.1234 (14)	0.0836 (11)	0.0008 (10)	−0.0391 (9)	0.0258 (10)
O5	0.0688 (10)	0.0861 (11)	0.1168 (13)	0.0227 (8)	0.0031 (10)	0.0077 (10)
N1	0.0488 (7)	0.0592 (8)	0.0438 (7)	0.0092 (6)	−0.0008 (6)	−0.0007 (6)
N2	0.0491 (8)	0.0583 (8)	0.0549 (8)	0.0101 (6)	0.0022 (6)	0.0009 (6)
N3	0.0848 (12)	0.0828 (12)	0.0617 (10)	0.0064 (10)	0.0172 (9)	−0.0119 (9)
N4	0.1005 (14)	0.0881 (13)	0.0456 (8)	−0.0036 (11)	−0.0042 (9)	−0.0002 (8)
N5	0.0591 (9)	0.0774 (11)	0.0520 (8)	0.0157 (8)	−0.0053 (7)	0.0085 (8)
N6	0.0552 (9)	0.0646 (10)	0.0825 (12)	−0.0009 (8)	−0.0130 (8)	0.0146 (9)
C1	0.136 (2)	0.167 (3)	0.0522 (12)	0.068 (2)	0.0072 (14)	−0.0082 (15)
C2	0.110 (2)	0.131 (2)	0.0727 (14)	−0.0425 (18)	−0.0282 (14)	0.0022 (15)
C3	0.1064 (18)	0.0854 (15)	0.0623 (12)	−0.0030 (13)	−0.0119 (12)	0.0188 (11)
C4	0.0629 (11)	0.0721 (12)	0.0443 (9)	0.0054 (9)	−0.0068 (7)	0.0025 (8)
C5	0.0587 (10)	0.0507 (9)	0.0485 (9)	−0.0033 (7)	0.0088 (7)	−0.0030 (7)
C6	0.0646 (10)	0.0516 (9)	0.0442 (8)	−0.0055 (8)	−0.0017 (7)	0.0036 (7)

Geometric parameters (Å, º) top

O1—N2	1.2417 (19)	C1—C4	1.489 (3)
O2—N3	1.352 (2)	C1—H1A	0.9600
O2—N4	1.378 (3)	C1—H1B	0.9600
O4—N6	1.194 (2)	C1—H1C	0.9600
O5—N6	1.200 (2)	C2—C4	1.520 (3)
N1—N2	1.2527 (18)	C2—H2A	0.9600
N1—C4	1.483 (2)	C2—H2B	0.9600
N2—C5	1.429 (2)	C2—H2C	0.9600
N3—C5	1.284 (2)	C3—C4	1.506 (3)
N4—C6	1.297 (2)	C3—H3A	0.9600
N5—C6	1.358 (2)	C3—H3B	0.9600
N5—N6	1.362 (2)	C3—H3C	0.9600
N5—H1	0.869 (9)	C5—C6	1.407 (2)

N3—O2—N4	112.00 (13)	C4—C2—H2C	109.5
N2—N1—C4	117.65 (13)	H2A—C2—H2C	109.5
O1—N2—N1	129.32 (15)	H2B—C2—H2C	109.5
O1—N2—C5	116.51 (15)	C4—C3—H3A	109.5
N1—N2—C5	114.15 (13)	C4—C3—H3B	109.5
C5—N3—O2	104.54 (17)	H3A—C3—H3B	109.5
C6—N4—O2	104.67 (17)	C4—C3—H3C	109.5
C6—N5—N6	123.77 (16)	H3A—C3—H3C	109.5
C6—N5—H1	120.6 (12)	H3B—C3—H3C	109.5
N6—N5—H1	114.5 (13)	C1—C4—N1	103.85 (15)
O4—N6—O5	127.57 (19)	C1—C4—C3	110.6 (2)
O4—N6—N5	118.2 (2)	N1—C4—C3	110.69 (16)
O5—N6—N5	114.21 (17)	C1—C4—C2	110.0 (2)
C4—C1—H1A	109.5	N1—C4—C2	110.20 (16)
C4—C1—H1B	109.5	C3—C4—C2	111.28 (19)
H1A—C1—H1B	109.5	N3—C5—C6	110.60 (16)
C4—C1—H1C	109.5	N3—C5—N2	119.65 (17)
H1A—C1—H1C	109.5	C6—C5—N2	129.75 (15)
H1B—C1—H1C	109.5	N4—C6—N5	127.89 (18)
C4—C2—H2A	109.5	N4—C6—C5	108.18 (17)
C4—C2—H2B	109.5	N5—C6—C5	123.90 (15)
H2A—C2—H2B	109.5

C4—N1—N2—O1	0.8 (3)	N1—N2—C5—N3	−177.04 (17)
C4—N1—N2—C5	179.52 (14)	O1—N2—C5—C6	−177.20 (18)
N4—O2—N3—C5	1.0 (2)	N1—N2—C5—C6	3.9 (3)
N3—O2—N4—C6	−1.0 (2)	O2—N4—C6—N5	179.06 (18)
C6—N5—N6—O4	−6.7 (3)	O2—N4—C6—C5	0.6 (2)
C6—N5—N6—O5	174.83 (19)	N6—N5—C6—N4	9.1 (3)
N2—N1—C4—C1	−179.1 (2)	N6—N5—C6—C5	−172.60 (17)
N2—N1—C4—C3	62.2 (2)	N3—C5—C6—N4	0.0 (2)
N2—N1—C4—C2	−61.4 (2)	N2—C5—C6—N4	179.17 (17)
O2—N3—C5—C6	−0.7 (2)	N3—C5—C6—N5	−178.51 (18)
O2—N3—C5—N2	−179.88 (15)	N2—C5—C6—N5	0.6 (3)
O1—N2—C5—N3	1.8 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N5—H1···N1	0.87 (1)	2.18 (2)	2.758 (2)	124 (2)

Experimental details

Crystal data
Chemical formula	C₆H₁₀N₆O₄
M_r	230.20
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	293
a, b, c (Å)	6.2509 (5), 9.1327 (8), 18.6566 (16)
β (°)	92.134 (2)
V (Å³)	1064.32 (16)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.12
Crystal size (mm)	0.32 × 0.22 × 0.18

Data collection
Diffractometer	Bruker SMART APEX
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	6176, 2402, 1711
R_int	0.023
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.050, 0.166, 1.05
No. of reflections	2402
No. of parameters	149
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.21, −0.21

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
N5—H1···N1	0.87 (1)	2.18 (2)	2.758 (2)	124 (2)

Acknowledgements

We thank the Equipment Department Preselected Projects (404060020502) and the Ministry of Higher Education of Malaysia (grant No. UM·C/HIR/MOHE/SC/12) for supporting this study.

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