2-(2H-Tetra­zol-5-yl)pyridinium nitrate

Cui, L.-J.; Yu, M.-J.

doi:10.1107/S1600536809018078

organic compounds

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ISSN: 2056-9890

Volume 65| Part 6| June 2009| Page o1318

doi:10.1107/S1600536809018078

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2-(2H-Tetrazol-5-yl)pyridinium nitrate

Li-Jing Cui ^a ^* and Miao-Jia Yu ^a

^aOrdered Matter Science Research Center, College of Chemistry and Chemical Engineering, Southeast University, Nanjing 210096, People's Republic of China
^*Correspondence e-mail: fudavid88@yahoo.com.cn

(Received 10 April 2009; accepted 13 May 2009; online 20 May 2009)

In the cation of the title compound, C₆H₆N₅⁺·NO₃⁻, the dihedral angle between the pyridinium and tetrazole rings is 8.2 (2)°. The constituent ions of the compound are linked via N—H⋯O hydrogen bonds, forming helical chains running along the b axis. C—H⋯N and C—H⋯O hydrogen bonds are also observed.

Related literature

For the use of tetrazole derivatives in coordination chemistry, see: Xiong et al. (2002 ); Fu et al. (2008 ); Wang et al. (2005 ). For the crystal structures of related compounds, see: Dai & Fu (2008 ); Wen (2008 ).

Experimental

Crystal data

C₆H₆N₅⁺·NO₃⁻
M_r = 210.17
Monoclinic, C 2/c
a = 20.400 (4) Å
b = 4.8981 (10) Å
c = 19.135 (4) Å
β = 114.77 (3)°
V = 1736.1 (7) Å³
Z = 8
Mo Kα radiation
μ = 0.13 mm⁻¹
T = 298 K
0.20 × 0.15 × 0.15 mm

Data collection

Rigaku Mercury2 diffractometer
Absorption correction: multi-scan (CrystalClear, Rigaku, 2005 ) T_min = 0.976, T_max = 0.980
8427 measured reflections
1999 independent reflections
1033 reflections with I > 2σ(I)
R_int = 0.123

Refinement

R[F² > 2σ(F²)] = 0.081
wR(F²) = 0.209
S = 1.04
1999 reflections
136 parameters
H-atom parameters constrained
Δρ_max = 0.34 e Å⁻³
Δρ_min = −0.36 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O3ⁱ	0.86	1.92	2.772 (4)	172
N4—H4A⋯O3	0.86	1.87	2.717 (4)	170
C2—H2⋯N2ⁱⁱ	0.93	2.58	3.507 (5)	173
C3—H3⋯O1ⁱⁱⁱ	0.93	2.52	3.435 (5)	171
C5—H5⋯O2ⁱ	0.93	2.54	3.218 (5)	130
C5—H5⋯O2^iv	0.93	2.36	3.223 (5)	155
Symmetry codes: (i) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (ii) $[-x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+1]$ ; (iii) $[-x+{\script{1\over 2}}, -y+{\script{3\over 2}}, -z+1]$ ; (iv) $[x-{\script{1\over 2}}, -y+{\script{5\over 2}}, z-{\script{1\over 2}}]$ .

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809018078/ci2780sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809018078/ci2780Isup2.hkl

checkCIF report

Comment top

In the past few years, more and more people have focused on the chemistry of tetrazole derivatives because of their multiple coordination modes as ligands to metal ions and for the construction of novel metal-organic frameworks (Fu et al., 2008; Wang, et al. 2005; Xiong, et al. 2002; Wen 2008). We report here the crystal structure of the title compound, 2-(2H-tetrazol-5-yl)pyridinium nitrate.

In the title compound (Fig.1), the N atom (N1) of the pyridine ring is protonated. The pyridine and tetrazole rings are nearly coplanar and are twisted from each other by a dihedral angle of 8.2 (2)°. The geometric parameters of the tetrazole ring are comparable to those observed in related structures (Wang et al. 2005; Dai & Fu 2008).

The crystal packing is stabilized by N—H···O hydrogen bonds which link the molecules into a helical chain running along the b axis (Table 1 and Fig.2). In addition, C—H···N and C—H···O hydrogen bonds are observed.

Related literature top

For the use of tetrazole derivatives in coordination chemistry, see: Xiong et al. (2002); Fu et al. (2008); Wang et al. (2005). For the crystal structures of related compounds, see: Dai & Fu (2008); Wen (2008).

Experimental top

Picolinonitrile (30 mmol), NaN₃ (45 mmol), NH₄Cl (33 mmol) and DMF (50 ml) were added in a flask under nitrogen atmosphere. The mixture stirred at 110°C for 20 h. The resulting solution was then poured into ice-water (100 ml), and a white solid was obtained after adding HCl (6 M) at pH = 6. The precipitate was filtered and washed with distilled water. Colourless block-shaped crystals suitable for X-ray analysis were obtained from the crude product by slow evaporation of an ethanol-HNO₃ (50:1 v/v) solution.

Computing details top

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. A view of the title compound with the atomic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. Partial packing view of the title compound showing the formation of chains along the b axis. H atoms not involved in hydrogen bonding (dashed lines) have been omitted for clarity.

2-(2H-Tetrazol-5-yl)pyridinium nitrate top

Crystal data top

C₆H₆N₅⁺·NO₃⁻	F(000) = 864
M_r = 210.17	D_x = 1.608 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 1999 reflections
a = 20.400 (4) Å	θ = 3.8–27.5°
b = 4.8981 (10) Å	µ = 0.13 mm⁻¹
c = 19.135 (4) Å	T = 298 K
β = 114.77 (3)°	Block, colourless
V = 1736.1 (7) Å³	0.20 × 0.15 × 0.15 mm
Z = 8

Data collection top

Rigaku Mercury2 diffractometer	1999 independent reflections
Radiation source: fine-focus sealed tube	1033 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.123
Detector resolution: 13.6612 pixels mm^-1	θ_max = 27.5°, θ_min = 3.8°
ω scans	h = −26→26
Absorption correction: multi-scan (CrystalClear, Rigaku, 2005)	k = −6→6
T_min = 0.976, T_max = 0.980	l = −24→24
8427 measured reflections

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)] = 0.081	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.209	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0838P)²] where P = (F_o² + 2F_c²)/3
1999 reflections	(Δ/σ)_max = 0.001
136 parameters	Δρ_max = 0.34 e Å⁻³
0 restraints	Δρ_min = −0.36 e Å⁻³

Crystal data top

C₆H₆N₅⁺·NO₃⁻	V = 1736.1 (7) Å³
M_r = 210.17	Z = 8
Monoclinic, C2/c	Mo Kα radiation
a = 20.400 (4) Å	µ = 0.13 mm⁻¹
b = 4.8981 (10) Å	T = 298 K
c = 19.135 (4) Å	0.20 × 0.15 × 0.15 mm
β = 114.77 (3)°

Data collection top

Rigaku Mercury2 diffractometer	1999 independent reflections
Absorption correction: multi-scan (CrystalClear, Rigaku, 2005)	1033 reflections with I > 2σ(I)
T_min = 0.976, T_max = 0.980	R_int = 0.123
8427 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.081	0 restraints
wR(F²) = 0.209	H-atom parameters constrained
S = 1.04	Δρ_max = 0.34 e Å⁻³
1999 reflections	Δρ_min = −0.36 e Å⁻³
136 parameters

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	U_iso*/U_eq
N1	0.11658 (15)	0.9420 (6)	0.51774 (16)	0.0383 (7)
H1	0.1239	1.0055	0.5623	0.046*
C6	0.21176 (18)	0.6182 (7)	0.58420 (19)	0.0362 (8)
N2	0.24979 (17)	0.3908 (6)	0.58539 (17)	0.0485 (8)
C1	0.15732 (18)	0.7297 (7)	0.51387 (19)	0.0364 (8)
N5	0.23230 (16)	0.7307 (6)	0.65302 (17)	0.0447 (8)
C3	0.0917 (2)	0.7442 (8)	0.3768 (2)	0.0506 (10)
H3	0.0831	0.6771	0.3283	0.061*
N4	0.28398 (16)	0.5624 (6)	0.69580 (17)	0.0463 (8)
H4A	0.3082	0.5846	0.7445	0.056*
N3	0.29538 (17)	0.3572 (7)	0.65769 (18)	0.0518 (9)
C4	0.0518 (2)	0.9615 (9)	0.3841 (2)	0.0520 (11)
H4	0.0161	1.0411	0.3408	0.062*
C2	0.14442 (19)	0.6270 (8)	0.4418 (2)	0.0436 (9)
H2	0.1711	0.4798	0.4371	0.052*
C5	0.0657 (2)	1.0571 (8)	0.4558 (2)	0.0446 (9)
H5	0.0395	1.2039	0.4615	0.053*
N6	0.41263 (16)	0.8821 (6)	0.85439 (18)	0.0434 (8)
O3	0.37035 (14)	0.6773 (5)	0.84530 (13)	0.0533 (8)
O2	0.44457 (14)	0.9758 (6)	0.91958 (15)	0.0570 (8)
O1	0.41958 (16)	0.9759 (6)	0.79835 (16)	0.0672 (9)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0387 (17)	0.0438 (18)	0.0341 (16)	−0.0043 (14)	0.0169 (14)	−0.0018 (14)
C6	0.0362 (19)	0.037 (2)	0.038 (2)	−0.0036 (17)	0.0179 (16)	−0.0003 (16)
N2	0.0487 (19)	0.054 (2)	0.0364 (18)	0.0079 (16)	0.0115 (15)	−0.0008 (15)
C1	0.0372 (19)	0.039 (2)	0.036 (2)	−0.0052 (16)	0.0181 (17)	−0.0005 (16)
N5	0.0421 (18)	0.0480 (19)	0.0379 (18)	0.0021 (15)	0.0108 (14)	−0.0026 (15)
C3	0.057 (3)	0.058 (3)	0.038 (2)	−0.015 (2)	0.020 (2)	−0.0046 (19)
N4	0.0434 (18)	0.0510 (19)	0.0352 (17)	−0.0010 (16)	0.0073 (14)	−0.0014 (16)
N3	0.047 (2)	0.055 (2)	0.049 (2)	0.0072 (17)	0.0154 (17)	−0.0032 (16)
C4	0.041 (2)	0.068 (3)	0.038 (2)	−0.009 (2)	0.0078 (18)	0.009 (2)
C2	0.042 (2)	0.049 (2)	0.043 (2)	−0.0064 (18)	0.0212 (18)	−0.0027 (18)
C5	0.040 (2)	0.046 (2)	0.045 (2)	−0.0021 (17)	0.0155 (19)	0.0074 (18)
N6	0.0382 (18)	0.049 (2)	0.0414 (19)	0.0006 (15)	0.0156 (15)	−0.0023 (16)
O3	0.0543 (17)	0.0578 (17)	0.0413 (16)	−0.0174 (14)	0.0136 (13)	−0.0034 (13)
O2	0.0527 (18)	0.070 (2)	0.0460 (17)	−0.0192 (14)	0.0180 (14)	−0.0189 (14)
O1	0.077 (2)	0.080 (2)	0.0499 (17)	−0.0107 (17)	0.0314 (16)	0.0090 (16)

Geometric parameters (Å, º) top

N1—C5	1.329 (4)	C3—H3	0.93
N1—C1	1.352 (4)	N4—N3	1.318 (4)
N1—H1	0.86	N4—H4A	0.86
C6—N5	1.323 (4)	C4—C5	1.363 (5)
C6—N2	1.352 (4)	C4—H4	0.93
C6—C1	1.446 (5)	C2—H2	0.93
N2—N3	1.314 (4)	C5—H5	0.93
C1—C2	1.386 (5)	N6—O1	1.228 (3)
N5—N4	1.318 (4)	N6—O2	1.229 (4)
C3—C4	1.382 (5)	N6—O3	1.286 (4)
C3—C2	1.383 (5)

C5—N1—C1	123.0 (3)	N5—N4—H4A	122.8
C5—N1—H1	118.5	N3—N4—H4A	122.8
C1—N1—H1	118.5	N2—N3—N4	106.0 (3)
N5—C6—N2	112.7 (3)	C5—C4—C3	118.9 (4)
N5—C6—C1	124.7 (3)	C5—C4—H4	120.5
N2—C6—C1	122.6 (3)	C3—C4—H4	120.5
N3—N2—C6	105.6 (3)	C3—C2—C1	119.8 (4)
N1—C1—C2	117.9 (3)	C3—C2—H2	120.1
N1—C1—C6	119.3 (3)	C1—C2—H2	120.1
C2—C1—C6	122.8 (3)	N1—C5—C4	120.5 (4)
N4—N5—C6	101.3 (3)	N1—C5—H5	119.8
C4—C3—C2	119.8 (4)	C4—C5—H5	119.8
C4—C3—H3	120.1	O1—N6—O2	122.7 (3)
C2—C3—H3	120.1	O1—N6—O3	119.3 (3)
N5—N4—N3	114.4 (3)	O2—N6—O3	118.0 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O3ⁱ	0.86	1.92	2.772 (4)	172
N4—H4A···O3	0.86	1.87	2.717 (4)	170
C2—H2···N2ⁱⁱ	0.93	2.58	3.507 (5)	173
C3—H3···O1ⁱⁱⁱ	0.93	2.52	3.435 (5)	171
C5—H5···O2ⁱ	0.93	2.54	3.218 (5)	130
C5—H5···O2^iv	0.93	2.36	3.223 (5)	155

Symmetry codes: (i) −x+1/2, y+1/2, −z+3/2; (ii) −x+1/2, −y+1/2, −z+1; (iii) −x+1/2, −y+3/2, −z+1; (iv) x−1/2, −y+5/2, z−1/2.

Experimental details

Crystal data
Chemical formula	C₆H₆N₅⁺·NO₃⁻
M_r	210.17
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	298
a, b, c (Å)	20.400 (4), 4.8981 (10), 19.135 (4)
β (°)	114.77 (3)
V (Å³)	1736.1 (7)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.13
Crystal size (mm)	0.20 × 0.15 × 0.15

Data collection
Diffractometer	Rigaku Mercury2 diffractometer
Absorption correction	Multi-scan (CrystalClear, Rigaku, 2005)
T_min, T_max	0.976, 0.980
No. of measured, independent and observed [I > 2σ(I)] reflections	8427, 1999, 1033
R_int	0.123
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.081, 0.209, 1.04
No. of reflections	1999
No. of parameters	136
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.34, −0.36

Computer programs: CrystalClear (Rigaku, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O3ⁱ	0.86	1.92	2.772 (4)	172
N4—H4A···O3	0.86	1.87	2.717 (4)	170
C2—H2···N2ⁱⁱ	0.93	2.58	3.507 (5)	173
C3—H3···O1ⁱⁱⁱ	0.93	2.52	3.435 (5)	171
C5—H5···O2ⁱ	0.93	2.54	3.218 (5)	130
C5—H5···O2^iv	0.93	2.36	3.223 (5)	155

Symmetry codes: (i) −x+1/2, y+1/2, −z+3/2; (ii) −x+1/2, −y+1/2, −z+1; (iii) −x+1/2, −y+3/2, −z+1; (iv) x−1/2, −y+5/2, z−1/2.

Acknowledgements

This work was supported by a start-up grant from Southeast University to Professor Ren-Gen Xiong.

References

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