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

Abstract

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,

• a = 20.400 (4) Å

• b = 4.8981 (10) Å

• c = 19.135 (4) Å

• β = 114.77 (3)°

• V = 1736.1 (7) ų

• 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[F ² > 2σ(F ²)] = 0.081

• wR(F ²) = 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

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.

Supplementary Material

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

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⋯O2iv	0.93	2.36	3.223 (5)	155

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) .

supplementary crystallographic information

Comment

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.

Experimental

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.

Refinement

All H atoms attached to C and N atoms were fixed geometrically and treated as riding, with C–H = 0.93 Å, N–H = 0.86 Å and U_iso(H) =1.2U_eq(C or N).

Figures

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.

Crystal data

C6H6N5+·NO3−	F(000) = 864
Mr = 210.17	Dx = 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

Rigaku Mercury2 diffractometer	1999 independent reflections
Radiation source: fine-focus sealed tube	1033 reflections with I > 2σ(I)
graphite	Rint = 0.123
Detector resolution: 13.6612 pixels mm-1	θmax = 27.5°, θmin = 3.8°
ω scans	h = −26→26
Absorption correction: multi-scan (CrystalClear, Rigaku, 2005)	k = −6→6
Tmin = 0.976, Tmax = 0.980	l = −24→24
8427 measured reflections

Refinement

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(Fo2) + (0.0838P)2] where P = (Fo2 + 2Fc2)/3
1999 reflections	(Δ/σ)max = 0.001
136 parameters	Δρmax = 0.34 e Å−3
0 restraints	Δρmin = −0.36 e Å−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	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, °)

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, °)

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···O2iv	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.