4-[4-(4-Amino-1,2,5-oxadiazol-3-yl)-1,2,5-oxadiazol-3-yl]-1,2,5-oxadiazol-3-amine

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

doi:10.1107/S1600536812017825

organic compounds

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ISSN: 2056-9890

Volume 68| Part 5| May 2012| Page o1573

doi:10.1107/S1600536812017825

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4-[4-(4-Amino-1,2,5-oxadiazol-3-yl)-1,2,5-oxadiazol-3-yl]-1,2,5-oxadiazol-3-amine

Si-Yuan Jia,^a Bo-Zhou Wang,^a Xue-Zhong Fan,^a 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 Chemistry, Jining Teachers College, Wulanchabu 012000, Inner Mongolia, 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 19 April 2012; accepted 21 April 2012; online 28 April 2012)

The complete molecule of the compound, C₆H₄N₈O₃, is generated by a crystallographic twofold rotation axis that runs through the central ring. The flanking ring is twisted by 20.2 (1)° with respect to the central ring. One of the amino H atoms forms an intramolecular N—H⋯N hydrogen bond; adjacent molecules are linked by N—H⋯N hydrogen bonds forming a chain running along [10-2].

Related literature

For the synthesis, see: Kulikov & Kakhova (1994 ); Zhou et al. (2007 ).

Experimental

Crystal data

C₆H₄N₈O₃
M_r = 236.17
Monoclinic, C 2/c
a = 7.1681 (9) Å
b = 10.8147 (13) Å
c = 12.3448 (18) Å
β = 103.155 (1)°
V = 931.9 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.14 mm⁻¹
T = 293 K
0.33 × 0.26 × 0.17 mm

Data collection

Bruker SMART APEX diffractometer
2675 measured reflections
1047 independent reflections
933 reflections with I > 2σ(I)
R_int = 0.014

Refinement

R[F² > 2σ(F²)] = 0.031
wR(F²) = 0.096
S = 1.08
1047 reflections
87 parameters
All H-atom parameters refined
Δρ_max = 0.28 e Å⁻³
Δρ_min = −0.17 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N4—H1⋯N1	0.90 (2)	2.37 (2)	2.932 (2)	121 (1)
N4—H2⋯N3ⁱ	0.87 (2)	2.23 (2)	3.070 (2)	162 (2)
Symmetry code: (i) -x+1, -y+1, -z+1.

Data collection: APEX2 (Bruker, 2009 ); cell refinement: SAINT (Bruker, 2009); 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: 10.1107/S1600536812017825/bt5881sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812017825/bt5881Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812017825/bt5881Isup3.cml

checkCIF report

Comment top

We are interested in N-heterocyclic compounds having few hydrogen atoms as these compounds are a source of explosives. In the title compound (Scheme I), the hydrogen atoms constitute an amino group. In NH₂–C₂N₂O–C₂N₂O–C₂N₂O–NH₂, two amino-subsituted 1,2,5-oxadiazole rings flanking a central 1,2,5-oxadiazole ring; the molecule lies on a twofold rotation axis that relates one flanking ring to the other (Fig. 1). The flanking ring is twisted by 20.2 (1) ° with respect to the central ring. One of the amino H atoms forms an intramolecular hydrogen bond; adjacent molecules are linked by an N–H···N hydrogen bond (Table 1, Fig. 2). to form a chain running along [1 0 -2].

Related literature top

For the synthesis, see: Kulikov & Kakhova (1994); Zhou et al. (2007).

Experimental top

3,4-Bis(4'-aminofurazano-3')furoxan was synthesized by using a literature procedure (Zhou et al., 2007). The compound (7.5 g) was dissolved in acetic acid (30 ml). The solution was added to a reducing agent prepared from stannous chloride dihydrate (22.6 g. 100 mm mol) dissolved in acetic anhydride (20 ml), acetic acid (100 ml) and concentrated hydrochloric acid (20 ml). The reduction was performed according to an literature procedure (Kulikov & Kakhova, 1994). The mixture was heated atto 348 K for 8 h. The cool mixture was then poured into water (150 ml). The white precipitate that separated was collected and recrystallized from an ethyl acetate/ether mixture; yield 70%, m.pt. 456–457 K. The purity was established by HPLC to be 99.6%. CH&N elemental analysis. Calculated for C₆H₄N₈O₃ (%): C 30.51, N 47.46, H1.69. Found: C 30.41, N 47.58,H 1.61.

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); 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. Anisotropic displacement ellipsoid plot (Barbour, 2001) of C₆H₄N₈O₃ at the 50% probability level; hydrogen atoms are drawn as spheres of arbitrary radius. The molecule is located on a twofold rotation axis; symmetry-related atoms are not labeled.
	Fig. 2. Hydrogen-bonded chain structure. The intermolecular H bond is drawn as a dashed line, the intramolecular H bond is not shown.

4-[4-(4-Amino-1,2,5-oxadiazol-3-yl)-1,2,5-oxadiazol-3-yl]-1,2,5-oxadiazol-3- amine top

Crystal data top

C₆H₄N₈O₃	F(000) = 480
M_r = 236.17	D_x = 1.683 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 1575 reflections
a = 7.1681 (9) Å	θ = 3.4–27.7°
b = 10.8147 (13) Å	µ = 0.14 mm⁻¹
c = 12.3448 (18) Å	T = 293 K
β = 103.155 (1)°	Prism, colorless
V = 931.9 (2) Å³	0.33 × 0.26 × 0.17 mm
Z = 4

Data collection top

Bruker SMART APEX diffractometer	933 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.014
Graphite monochromator	θ_max = 27.5°, θ_min = 3.4°
ω scans	h = −9→9
2675 measured reflections	k = −14→13
1047 independent reflections	l = −15→8

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.031	All H-atom parameters refined
wR(F²) = 0.096	w = 1/[σ²(F_o²) + (0.0566P)² + 0.219P] where P = (F_o² + 2F_c²)/3
S = 1.08	(Δ/σ)_max < 0.001
1047 reflections	Δρ_max = 0.28 e Å⁻³
87 parameters	Δρ_min = −0.17 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.020 (3)

Crystal data top

C₆H₄N₈O₃	V = 931.9 (2) Å³
M_r = 236.17	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 7.1681 (9) Å	µ = 0.14 mm⁻¹
b = 10.8147 (13) Å	T = 293 K
c = 12.3448 (18) Å	0.33 × 0.26 × 0.17 mm
β = 103.155 (1)°

Data collection top

Bruker SMART APEX diffractometer	933 reflections with I > 2σ(I)
2675 measured reflections	R_int = 0.014
1047 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.031	0 restraints
wR(F²) = 0.096	All H-atom parameters refined
S = 1.08	Δρ_max = 0.28 e Å⁻³
1047 reflections	Δρ_min = −0.17 e Å⁻³
87 parameters

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

	x	y	z	U_iso*/U_eq
O1	0.0000	0.80892 (10)	0.7500	0.0471 (3)
O2	0.16242 (12)	0.35531 (8)	0.56878 (8)	0.0482 (3)
N1	0.09563 (14)	0.73719 (9)	0.68904 (8)	0.0431 (3)
N2	0.06415 (14)	0.41475 (9)	0.63634 (9)	0.0446 (3)
N3	0.29963 (15)	0.43342 (9)	0.54042 (9)	0.0453 (3)
N4	0.3974 (2)	0.63687 (11)	0.58898 (12)	0.0626 (4)
H1	0.372 (2)	0.7101 (14)	0.6165 (12)	0.059 (4)*
H2	0.480 (3)	0.6342 (15)	0.5474 (15)	0.064 (5)*
C1	0.06039 (15)	0.62259 (9)	0.71097 (9)	0.0349 (3)
C2	0.13553 (15)	0.52528 (10)	0.65104 (9)	0.0358 (3)
C3	0.28563 (16)	0.53785 (10)	0.59138 (10)	0.0393 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0644 (8)	0.0324 (6)	0.0520 (7)	0.000	0.0291 (6)	0.000
O2	0.0540 (5)	0.0385 (5)	0.0600 (6)	−0.0051 (4)	0.0291 (4)	−0.0103 (4)
N1	0.0529 (6)	0.0356 (5)	0.0471 (6)	−0.0024 (4)	0.0248 (5)	−0.0011 (4)
N2	0.0460 (5)	0.0397 (5)	0.0549 (6)	−0.0046 (4)	0.0255 (5)	−0.0068 (4)
N3	0.0513 (6)	0.0401 (5)	0.0526 (6)	0.0004 (4)	0.0287 (5)	−0.0004 (4)
N4	0.0745 (8)	0.0423 (6)	0.0915 (10)	−0.0118 (5)	0.0614 (8)	−0.0088 (6)
C1	0.0364 (5)	0.0344 (5)	0.0373 (5)	−0.0010 (4)	0.0151 (4)	0.0007 (4)
C2	0.0374 (5)	0.0349 (6)	0.0390 (6)	−0.0004 (4)	0.0166 (4)	0.0010 (4)
C3	0.0435 (6)	0.0366 (6)	0.0436 (6)	0.0017 (4)	0.0223 (5)	0.0022 (4)

Geometric parameters (Å, º) top

O1—N1ⁱ	1.3685 (11)	N4—C3	1.3419 (16)
O1—N1	1.3686 (11)	N4—H1	0.896 (16)
O2—N2	1.3684 (12)	N4—H2	0.871 (19)
O2—N3	1.4001 (13)	C1—C1ⁱ	1.434 (2)
N1—C1	1.3055 (14)	C1—C2	1.4582 (15)
N2—C2	1.2967 (15)	C2—C3	1.4419 (15)
N3—C3	1.3077 (15)

N1ⁱ—O1—N1	110.94 (11)	N1—C1—C2	117.95 (9)
N2—O2—N3	110.93 (8)	C1ⁱ—C1—C2	133.62 (6)
C1—N1—O1	106.22 (9)	N2—C2—C3	109.39 (10)
C2—N2—O2	106.07 (9)	N2—C2—C1	123.83 (9)
C3—N3—O2	105.40 (9)	C3—C2—C1	126.57 (10)
C3—N4—H1	121.5 (10)	N3—C3—N4	124.54 (11)
C3—N4—H2	118.5 (11)	N3—C3—C2	108.19 (10)
H1—N4—H2	118.6 (15)	N4—C3—C2	127.25 (11)
N1—C1—C1ⁱ	108.31 (6)

N1ⁱ—O1—N1—C1	0.18 (6)	N1—C1—C2—C3	17.47 (17)
N3—O2—N2—C2	−0.32 (13)	C1ⁱ—C1—C2—C3	−167.05 (15)
N2—O2—N3—C3	0.77 (13)	O2—N3—C3—N4	177.65 (12)
O1—N1—C1—C1ⁱ	−0.43 (14)	O2—N3—C3—C2	−0.87 (13)
O1—N1—C1—C2	176.12 (8)	N2—C2—C3—N3	0.73 (14)
O2—N2—C2—C3	−0.23 (13)	C1—C2—C3—N3	−174.16 (11)
O2—N2—C2—C1	174.83 (10)	N2—C2—C3—N4	−177.73 (13)
N1—C1—C2—N2	−156.72 (11)	C1—C2—C3—N4	7.4 (2)
C1ⁱ—C1—C2—N2	18.8 (2)

Symmetry code: (i) −x, y, −z+3/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N4—H1···N1	0.90 (2)	2.37 (2)	2.932 (2)	121 (1)
N4—H2···N3ⁱⁱ	0.87 (2)	2.23 (2)	3.070 (2)	162 (2)

Symmetry code: (ii) −x+1, −y+1, −z+1.

Experimental details

Crystal data
Chemical formula	C₆H₄N₈O₃
M_r	236.17
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	293
a, b, c (Å)	7.1681 (9), 10.8147 (13), 12.3448 (18)
β (°)	103.155 (1)
V (Å³)	931.9 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.14
Crystal size (mm)	0.33 × 0.26 × 0.17

Data collection
Diffractometer	Bruker SMART APEX diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	2675, 1047, 933
R_int	0.014
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.031, 0.096, 1.08
No. of reflections	1047
No. of parameters	87
H-atom treatment	All H-atom parameters refined
Δρ_max, Δρ_min (e Å⁻³)	0.28, −0.17

Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), 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
N4—H1···N1	0.90 (2)	2.37 (2)	2.932 (2)	121 (1)
N4—H2···N3ⁱ	0.87 (2)	2.23 (2)	3.070 (2)	162 (2)

Symmetry code: (i) −x+1, −y+1, −z+1.

Acknowledgements

We acknowledge support from the Equipment Department Preselected Project (grant No. 404060020502) and the Ministry of Higher Education of Malaysia (grant No. UM.C/HIR/MOHE/SC/12).

References

Barbour, L. J. (2001). J. Supramol. Chem. 1, 189–191. CrossRef CAS Google Scholar
Bruker (2009). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Kulikov, A. S. & Kakhova, N. N. (1994). Russ. Chem. Bull. 43, 630–632. CrossRef Web of Science 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
Zhou, Y.-S., Li, J.-K. & Huang, X.-P. (2007). Chin. J. Explosives Propellants, 30, 454–556. Google Scholar

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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 68| Part 5| May 2012| Page o1573

doi:10.1107/S1600536812017825

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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

4-[4-(4-Amino-1,2,5-oxa­diazol-3-yl)-1,2,5-oxa­diazol-3-yl]-1,2,5-oxa­diazol-3-amine

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

4-[4-(4-Amino-1,2,5-oxadiazol-3-yl)-1,2,5-oxadiazol-3-yl]-1,2,5-oxadiazol-3-amine