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ISSN: 2056-9890
Volume 68| Part 5| May 2012| Page o1573

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

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[Kulikov, A. S. & Kakhova, N. N. (1994). Russ. Chem. Bull. 43, 630-632.]); Zhou et al. (2007[Zhou, Y.-S., Li, J.-K. & Huang, X.-P. (2007). Chin. J. Explosives Propellants, 30, 454-556.]).

[Scheme 1]

Experimental

Crystal data
  • C6H4N8O3

  • Mr = 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)

  • Rint = 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

  • Δρmax = 0.28 e Å−3

  • Δρmin = −0.17 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA 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[Bruker (2009). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2009[Bruker (2009). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: X-SEED (Barbour, 2001[Barbour, L. J. (2001). J. Supramol. Chem. 1, 189-191.]); software used to prepare material for publication: publCIF (Westrip, 2010[Westrip, S. P. (2010). J. Appl. Cryst. 43, 920-925.]).

Supporting information


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.

Refinement top

The H-atoms were located in a difference Fourier map, and were refined freely.

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
[Figure 1] 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.
[Figure 2] 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
C6H4N8O3F(000) = 480
Mr = 236.17Dx = 1.683 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 1575 reflections
a = 7.1681 (9) Åθ = 3.4–27.7°
b = 10.8147 (13) ŵ = 0.14 mm1
c = 12.3448 (18) ÅT = 293 K
β = 103.155 (1)°Prism, colorless
V = 931.9 (2) Å30.33 × 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 tubeRint = 0.014
Graphite monochromatorθmax = 27.5°, θmin = 3.4°
ω scansh = 99
2675 measured reflectionsk = 1413
1047 independent reflectionsl = 158
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.031All H-atom parameters refined
wR(F2) = 0.096 w = 1/[σ2(Fo2) + (0.0566P)2 + 0.219P]
where P = (Fo2 + 2Fc2)/3
S = 1.08(Δ/σ)max < 0.001
1047 reflectionsΔρmax = 0.28 e Å3
87 parametersΔρmin = 0.17 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.020 (3)
Crystal data top
C6H4N8O3V = 931.9 (2) Å3
Mr = 236.17Z = 4
Monoclinic, C2/cMo Kα radiation
a = 7.1681 (9) ŵ = 0.14 mm1
b = 10.8147 (13) ÅT = 293 K
c = 12.3448 (18) Å0.33 × 0.26 × 0.17 mm
β = 103.155 (1)°
Data collection top
Bruker SMART APEX
diffractometer
933 reflections with I > 2σ(I)
2675 measured reflectionsRint = 0.014
1047 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0310 restraints
wR(F2) = 0.096All H-atom parameters refined
S = 1.08Δρmax = 0.28 e Å3
1047 reflectionsΔρmin = 0.17 e Å3
87 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
O10.00000.80892 (10)0.75000.0471 (3)
O20.16242 (12)0.35531 (8)0.56878 (8)0.0482 (3)
N10.09563 (14)0.73719 (9)0.68904 (8)0.0431 (3)
N20.06415 (14)0.41475 (9)0.63634 (9)0.0446 (3)
N30.29963 (15)0.43342 (9)0.54042 (9)0.0453 (3)
N40.3974 (2)0.63687 (11)0.58898 (12)0.0626 (4)
H10.372 (2)0.7101 (14)0.6165 (12)0.059 (4)*
H20.480 (3)0.6342 (15)0.5474 (15)0.064 (5)*
C10.06039 (15)0.62259 (9)0.71097 (9)0.0349 (3)
C20.13553 (15)0.52528 (10)0.65104 (9)0.0358 (3)
C30.28563 (16)0.53785 (10)0.59138 (10)0.0393 (3)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0644 (8)0.0324 (6)0.0520 (7)0.0000.0291 (6)0.000
O20.0540 (5)0.0385 (5)0.0600 (6)0.0051 (4)0.0291 (4)0.0103 (4)
N10.0529 (6)0.0356 (5)0.0471 (6)0.0024 (4)0.0248 (5)0.0011 (4)
N20.0460 (5)0.0397 (5)0.0549 (6)0.0046 (4)0.0255 (5)0.0068 (4)
N30.0513 (6)0.0401 (5)0.0526 (6)0.0004 (4)0.0287 (5)0.0004 (4)
N40.0745 (8)0.0423 (6)0.0915 (10)0.0118 (5)0.0614 (8)0.0088 (6)
C10.0364 (5)0.0344 (5)0.0373 (5)0.0010 (4)0.0151 (4)0.0007 (4)
C20.0374 (5)0.0349 (6)0.0390 (6)0.0004 (4)0.0166 (4)0.0010 (4)
C30.0435 (6)0.0366 (6)0.0436 (6)0.0017 (4)0.0223 (5)0.0022 (4)
Geometric parameters (Å, º) top
O1—N1i1.3685 (11)N4—C31.3419 (16)
O1—N11.3686 (11)N4—H10.896 (16)
O2—N21.3684 (12)N4—H20.871 (19)
O2—N31.4001 (13)C1—C1i1.434 (2)
N1—C11.3055 (14)C1—C21.4582 (15)
N2—C21.2967 (15)C2—C31.4419 (15)
N3—C31.3077 (15)
N1i—O1—N1110.94 (11)N1—C1—C2117.95 (9)
N2—O2—N3110.93 (8)C1i—C1—C2133.62 (6)
C1—N1—O1106.22 (9)N2—C2—C3109.39 (10)
C2—N2—O2106.07 (9)N2—C2—C1123.83 (9)
C3—N3—O2105.40 (9)C3—C2—C1126.57 (10)
C3—N4—H1121.5 (10)N3—C3—N4124.54 (11)
C3—N4—H2118.5 (11)N3—C3—C2108.19 (10)
H1—N4—H2118.6 (15)N4—C3—C2127.25 (11)
N1—C1—C1i108.31 (6)
N1i—O1—N1—C10.18 (6)N1—C1—C2—C317.47 (17)
N3—O2—N2—C20.32 (13)C1i—C1—C2—C3167.05 (15)
N2—O2—N3—C30.77 (13)O2—N3—C3—N4177.65 (12)
O1—N1—C1—C1i0.43 (14)O2—N3—C3—C20.87 (13)
O1—N1—C1—C2176.12 (8)N2—C2—C3—N30.73 (14)
O2—N2—C2—C30.23 (13)C1—C2—C3—N3174.16 (11)
O2—N2—C2—C1174.83 (10)N2—C2—C3—N4177.73 (13)
N1—C1—C2—N2156.72 (11)C1—C2—C3—N47.4 (2)
C1i—C1—C2—N218.8 (2)
Symmetry code: (i) x, y, z+3/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N4—H1···N10.90 (2)2.37 (2)2.932 (2)121 (1)
N4—H2···N3ii0.87 (2)2.23 (2)3.070 (2)162 (2)
Symmetry code: (ii) x+1, y+1, z+1.

Experimental details

Crystal data
Chemical formulaC6H4N8O3
Mr236.17
Crystal system, space groupMonoclinic, C2/c
Temperature (K)293
a, b, c (Å)7.1681 (9), 10.8147 (13), 12.3448 (18)
β (°) 103.155 (1)
V3)931.9 (2)
Z4
Radiation typeMo Kα
µ (mm1)0.14
Crystal size (mm)0.33 × 0.26 × 0.17
Data collection
DiffractometerBruker SMART APEX
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
2675, 1047, 933
Rint0.014
(sin θ/λ)max1)0.649
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.031, 0.096, 1.08
No. of reflections1047
No. of parameters87
H-atom treatmentAll H-atom parameters refined
Δρmax, Δρmin (e Å3)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···AD—HH···AD···AD—H···A
N4—H1···N10.90 (2)2.37 (2)2.932 (2)121 (1)
N4—H2···N3i0.87 (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

First citationBarbour, L. J. (2001). J. Supramol. Chem. 1, 189–191.  CrossRef CAS Google Scholar
First citationBruker (2009). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
First citationKulikov, A. S. & Kakhova, N. N. (1994). Russ. Chem. Bull. 43, 630–632.  CrossRef Web of Science Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationWestrip, S. P. (2010). J. Appl. Cryst. 43, 920–925.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationZhou, Y.-S., Li, J.-K. & Huang, X.-P. (2007). Chin. J. Explosives Propellants, 30, 454–556.  Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 68| Part 5| May 2012| Page o1573
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