Bis[(diamino­methyl­idene)aza­nium] 5-(1-oxido-1H-1,2,3,4-tetra­zol-5-yl)-1H-1,2,3,4-tetra­zol-1-olate

Fan, R.; Li, P.; Ng, S.W.

doi:10.1107/S1600536812014456

organic compounds

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Bis[(diaminomethylidene)azanium] 5-(1-oxido-1H-1,2,3,4-tetrazol-5-yl)-1H-1,2,3,4-tetrazol-1-olate

Rong Fan,^a Ping Li ^b and Seik Weng Ng ^c,^d ^*

^aShanghai Institute of Materia Medica, Chinese Academy of Sciences, Shanghai 201203, People's Republic of China, ^bJining Teachers College, Department of Chemistry, 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 2 April 2012; accepted 3 April 2012; online 13 April 2012)

The anion of the title salt, 2[C(NH₂)₃]⁺·C₂N₈O₂²⁻, lies on a center of inversion and its two five-membered rings are coplanar. The guanidinium cation forms N—H⋯O and N—H⋯N hydrogen bonds to the anion, generating an eight-membered ring. Other hydrogen bonds lead to the formation of a three-dimensional network.

Related literature

For the synthesis of 1,1′-dihydroxy-5,5′-bistetrazole, see: Tselinskii et al. (2001 ).

Experimental

Crystal data

2CH₆N₃⁺·C₂N₈O₂²⁻
M_r = 288.28
Monoclinic, P 2₁ /c
a = 3.6477 (3) Å
b = 16.9661 (12) Å
c = 9.5465 (7) Å
β = 97.465 (1)°
V = 585.80 (8) Å³
Z = 2
Mo Kα radiation
μ = 0.13 mm⁻¹
T = 293 K
0.12 × 0.11 × 0.08 mm

Data collection

Bruker SMART APEX diffractometer
3402 measured reflections
1328 independent reflections
1229 reflections with I > 2σ(I)
R_int = 0.021

Refinement

R[F² > 2σ(F²)] = 0.039
wR(F²) = 0.107
S = 1.02
1328 reflections
115 parameters
6 restraints
All H-atom parameters refined
Δρ_max = 0.24 e Å⁻³
Δρ_min = −0.25 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N5—H1⋯O1	0.89 (1)	1.94 (1)	2.821 (2)	173 (2)
N5—H2⋯N3ⁱ	0.88 (1)	2.40 (1)	3.196 (2)	152 (2)
N6—H3⋯N3ⁱ	0.88 (1)	2.34 (1)	3.126 (2)	149 (2)
N6—H4⋯N4ⁱⁱ	0.88 (1)	2.12 (1)	2.975 (2)	164 (2)
N7—H5⋯O1ⁱⁱⁱ	0.87 (1)	1.97 (1)	2.754 (2)	150 (2)
N7—H6⋯N2	0.88 (1)	2.23 (1)	3.104 (2)	177 (2)
Symmetry codes: (i) $[x+1, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ ; (ii) $[-x, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iii) $[x, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ .

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/S1600536812014456/bt5870sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812014456/bt5870Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812014456/bt5870Isup3.cml

checkCIF report

Comment top

The depronated ion of 1,1'-dihydroxy-5,5'-bistetrazole is an example of an organic compound having no hydrogen atoms, and is an appropriate building block for the synthesis of coordination polymers that require metal–nitrogen linkages. To date, no crystal structure of the metal derivatives have been reported. The ion is obtained by the reaction of 1,1'-dihydroxy-5,5'-bistetrazole with guanidine. In the salt (Scheme I), the anion lies on a center of inversion; its two five-membered rings are necessarily coplanar. The guanidinium cation forms N–H···O and N–H···N hydrogen bonds to the anion to generate an eight-membered ring (Fig. 1). Other hydrogen bonds lead to the formation of a three-dimensional network (Table 1).

Related literature top

For the synthesis of 1,1'-dihydroxy-5,5'-bistetrazole, see: Tselinskii et al. (2001).

Experimental top

Guanidine carbonate (180 mg, 1 mmol) was added to a methanol solution (10 ml) of 1,1'-dihydroxy-5,5'-bistetrazole (206 mg, 1 mmol). The mixture was stirred for 2 h. The white precipitate that formed was filtered and washed with methanol; yield 0.245 g (90%). CH&N Elemental analysis for C₄H₈N₁₄O₂: Calc. C 16.90, H 2.84, N 69.00%. Found C 16.74, H 2.87, N 68.23%. Diethyl ether was used to recrystallize the compound.

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 2[C(NH₂)₃]⁺ (C₂N₈O₂)^2- at the 50% probability level; hydrogen atoms are drawn as spheres of arbitrary radius. The dianion lies on a center of inversion; symmetry-related atoms are not labeled.

Bis[(diaminomethylidene)azanium] 5-(1-oxido-1H-1,2,3,4-tetrazol-5-yl)- 1H-1,2,3,4-tetrazol-1-olate top

Crystal data top

2CH₆N₃⁺·C₂N₈O₂²⁻	F(000) = 300
M_r = 288.28	D_x = 1.634 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2581 reflections
a = 3.6477 (3) Å	θ = 2.5–28.5°
b = 16.9661 (12) Å	µ = 0.13 mm⁻¹
c = 9.5465 (7) Å	T = 293 K
β = 97.465 (1)°	Prism, colorless
V = 585.80 (8) Å³	0.12 × 0.11 × 0.08 mm
Z = 2

Data collection top

Bruker SMART APEX diffractometer	1229 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.021
Graphite monochromator	θ_max = 27.5°, θ_min = 2.5°
ω scans	h = −4→4
3402 measured reflections	k = −20→21
1328 independent reflections	l = −7→12

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)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.107	All H-atom parameters refined
S = 1.02	w = 1/[σ²(F_o²) + (0.0648P)² + 0.1424P] where P = (F_o² + 2F_c²)/3
1328 reflections	(Δ/σ)_max = 0.001
115 parameters	Δρ_max = 0.24 e Å⁻³
6 restraints	Δρ_min = −0.25 e Å⁻³

Crystal data top

2CH₆N₃⁺·C₂N₈O₂²⁻	V = 585.80 (8) Å³
M_r = 288.28	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 3.6477 (3) Å	µ = 0.13 mm⁻¹
b = 16.9661 (12) Å	T = 293 K
c = 9.5465 (7) Å	0.12 × 0.11 × 0.08 mm
β = 97.465 (1)°

Data collection top

Bruker SMART APEX diffractometer	1229 reflections with I > 2σ(I)
3402 measured reflections	R_int = 0.021
1328 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.039	6 restraints
wR(F²) = 0.107	All H-atom parameters refined
S = 1.02	Δρ_max = 0.24 e Å⁻³
1328 reflections	Δρ_min = −0.25 e Å⁻³
115 parameters

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

	x	y	z	U_iso*/U_eq
O1	0.3597 (3)	0.63225 (6)	0.54252 (10)	0.0478 (3)
N1	0.1684 (3)	0.59470 (6)	0.43882 (10)	0.0326 (3)
N2	0.1200 (3)	0.62317 (6)	0.30734 (11)	0.0409 (3)
N3	−0.0687 (3)	0.56977 (7)	0.22907 (12)	0.0431 (3)
N4	−0.1457 (3)	0.50828 (6)	0.30661 (11)	0.0377 (3)
N5	0.5844 (4)	0.79085 (7)	0.52906 (12)	0.0447 (3)
N6	0.5689 (4)	0.90966 (7)	0.41611 (13)	0.0441 (3)
N7	0.2983 (4)	0.80194 (7)	0.30217 (12)	0.0427 (3)
C1	0.0040 (3)	0.52416 (6)	0.43820 (11)	0.0283 (3)
C2	0.4842 (3)	0.83418 (7)	0.41568 (12)	0.0324 (3)
H1	0.525 (5)	0.7400 (6)	0.528 (2)	0.056 (5)*
H2	0.703 (5)	0.8143 (11)	0.6033 (15)	0.064 (5)*
H3	0.699 (5)	0.9327 (11)	0.4888 (16)	0.065 (5)*
H4	0.485 (5)	0.9392 (9)	0.3427 (15)	0.061 (5)*
H5	0.242 (5)	0.8300 (10)	0.2262 (15)	0.061 (5)*
H6	0.248 (5)	0.7514 (6)	0.3000 (19)	0.057 (5)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0689 (7)	0.0371 (5)	0.0365 (5)	−0.0201 (4)	0.0028 (4)	−0.0089 (4)
N1	0.0422 (5)	0.0260 (5)	0.0292 (5)	−0.0022 (4)	0.0034 (4)	−0.0017 (4)
N2	0.0550 (7)	0.0330 (5)	0.0343 (6)	−0.0011 (4)	0.0043 (5)	0.0064 (4)
N3	0.0527 (7)	0.0423 (6)	0.0321 (6)	−0.0019 (5)	−0.0028 (5)	0.0072 (4)
N4	0.0456 (6)	0.0365 (5)	0.0285 (5)	−0.0041 (4)	−0.0049 (4)	0.0021 (4)
N5	0.0657 (8)	0.0332 (6)	0.0318 (6)	−0.0096 (5)	−0.0073 (5)	0.0051 (4)
N6	0.0572 (7)	0.0303 (5)	0.0422 (6)	−0.0014 (5)	−0.0037 (5)	0.0048 (4)
N7	0.0584 (7)	0.0391 (6)	0.0287 (5)	−0.0054 (5)	−0.0021 (5)	0.0004 (4)
C1	0.0324 (5)	0.0244 (5)	0.0270 (5)	0.0011 (4)	−0.0004 (4)	−0.0007 (4)
C2	0.0360 (6)	0.0315 (5)	0.0294 (6)	−0.0006 (4)	0.0032 (4)	0.0016 (4)

Geometric parameters (Å, º) top

O1—N1	1.3013 (13)	N5—H2	0.877 (9)
N1—N2	1.3350 (14)	N6—C2	1.3172 (16)
N1—C1	1.3383 (14)	N6—H3	0.879 (10)
N2—N3	1.3112 (16)	N6—H4	0.883 (9)
N3—N4	1.3301 (15)	N7—C2	1.3200 (16)
N4—C1	1.3305 (14)	N7—H5	0.869 (9)
N5—C2	1.3201 (16)	N7—H6	0.876 (9)
N5—H1	0.889 (9)	C1—C1ⁱ	1.440 (2)

O1—N1—N2	122.03 (10)	H3—N6—H4	117.9 (18)
O1—N1—C1	129.56 (10)	C2—N7—H5	119.9 (13)
N2—N1—C1	108.36 (10)	C2—N7—H6	120.5 (12)
N3—N2—N1	106.34 (10)	H5—N7—H6	119.3 (18)
N2—N3—N4	110.97 (10)	N4—C1—N1	108.29 (10)
N3—N4—C1	106.04 (10)	N4—C1—C1ⁱ	127.50 (13)
C2—N5—H1	119.3 (12)	N1—C1—C1ⁱ	124.20 (13)
C2—N5—H2	117.7 (13)	N6—C2—N7	120.04 (11)
H1—N5—H2	123.0 (18)	N6—C2—N5	119.94 (11)
C2—N6—H3	122.5 (14)	N7—C2—N5	120.01 (11)
C2—N6—H4	119.5 (12)

O1—N1—N2—N3	177.18 (11)	N3—N4—C1—C1ⁱ	179.84 (15)
C1—N1—N2—N3	−0.51 (14)	O1—N1—C1—N4	−177.19 (12)
N1—N2—N3—N4	0.58 (15)	N2—N1—C1—N4	0.26 (14)
N2—N3—N4—C1	−0.42 (14)	O1—N1—C1—C1ⁱ	3.0 (2)
N3—N4—C1—N1	0.09 (13)	N2—N1—C1—C1ⁱ	−179.50 (13)

Symmetry code: (i) −x, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N5—H1···O1	0.89 (1)	1.94 (1)	2.821 (2)	173 (2)
N5—H2···N3ⁱⁱ	0.88 (1)	2.40 (1)	3.196 (2)	152 (2)
N6—H3···N3ⁱⁱ	0.88 (1)	2.34 (1)	3.126 (2)	149 (2)
N6—H4···N4ⁱⁱⁱ	0.88 (1)	2.12 (1)	2.975 (2)	164 (2)
N7—H5···O1^iv	0.87 (1)	1.97 (1)	2.754 (2)	150 (2)
N7—H6···N2	0.88 (1)	2.23 (1)	3.104 (2)	177 (2)

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

Experimental details

Crystal data
Chemical formula	2CH₆N₃⁺·C₂N₈O₂²⁻
M_r	288.28
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	3.6477 (3), 16.9661 (12), 9.5465 (7)
β (°)	97.465 (1)
V (Å³)	585.80 (8)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.13
Crystal size (mm)	0.12 × 0.11 × 0.08

Data collection
Diffractometer	Bruker SMART APEX diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	3402, 1328, 1229
R_int	0.021
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.107, 1.02
No. of reflections	1328
No. of parameters	115
No. of restraints	6
H-atom treatment	All H-atom parameters refined
Δρ_max, Δρ_min (e Å⁻³)	0.24, −0.25

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
N5—H1···O1	0.89 (1)	1.94 (1)	2.821 (2)	173 (2)
N5—H2···N3ⁱ	0.88 (1)	2.40 (1)	3.196 (2)	152 (2)
N6—H3···N3ⁱ	0.88 (1)	2.34 (1)	3.126 (2)	149 (2)
N6—H4···N4ⁱⁱ	0.88 (1)	2.12 (1)	2.975 (2)	164 (2)
N7—H5···O1ⁱⁱⁱ	0.87 (1)	1.97 (1)	2.754 (2)	150 (2)
N7—H6···N2	0.88 (1)	2.23 (1)	3.104 (2)	177 (2)

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

Acknowledgements

We acknowledge the Scientific Research Project of Higher Education of Inner Mongolia (grant No. NJ09204) and the Ministry of Higher Education of Malaysia (grant No. UM.C/HIR/MOHE/SC/12) for supporting this study.

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
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Tselinskii, I. V., Mel'nikova, S. F. & Romanova, T. V. (2001). Russ. J. Org. Chem. (Engl. Transl.), 37, 455–461. 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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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 68| Part 5| May 2012| Page o1376

doi:10.1107/S1600536812014456

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

Bis[(di­amino­methyl­­idene)aza­nium] 5-(1-oxido-1H-1,2,3,4-tetra­zol-5-yl)-1H-1,2,3,4-tetra­zol-1-olate

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

Bis[(diaminomethylidene)azanium] 5-(1-oxido-1H-1,2,3,4-tetrazol-5-yl)-1H-1,2,3,4-tetrazol-1-olate