4-(2H-Tetra­zol-5-yl)pyridinium perchlorate

Dai, J.

doi:10.1107/S1600536809018200

organic compounds

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Volume 65| Part 6| June 2009| Page o1349

doi:10.1107/S1600536809018200

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4-(2H-Tetrazol-5-yl)pyridinium perchlorate

Jing Dai ^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 3 April 2009; accepted 14 May 2009; online 20 May 2009)

In the cation of the title compound, C₆H₆N₅⁺·ClO₄⁻, the pyridinium and tetrazole rings form a dihedral angle of 23.6 (1)°. In the crystal structure, weak intermolecular N—H⋯O and N—H⋯N hydrogen bonds link cations and anions into chains extending along the b axis.

Related literature

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

Experimental

Crystal data

C₆H₆N₅⁺·ClO₄⁻
M_r = 247.61
Monoclinic, P 2₁ /n
a = 5.2033 (10) Å
b = 14.764 (3) Å
c = 12.244 (2) Å
β = 101.78 (3)°
V = 920.8 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.43 mm⁻¹
T = 298 K
0.30 × 0.25 × 0.20 mm

Data collection

Rigaku Mercury2 diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ) T_min = 0.872, T_max = 1.000 (expected range = 0.801–0.919)
9546 measured reflections
2108 independent reflections
1849 reflections with I > 2σ(I)
R_int = 0.036

Refinement

R[F² > 2σ(F²)] = 0.035
wR(F²) = 0.093
S = 1.09
2108 reflections
146 parameters
H-atom parameters constrained
Δρ_max = 0.29 e Å⁻³
Δρ_min = −0.37 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N5—H5A⋯O3ⁱ	0.86	2.28	2.964 (2)	136
N5—H5A⋯N2ⁱⁱ	0.86	2.38	3.059 (2)	136
N3—H3A⋯O4ⁱⁱⁱ	0.86	2.21	2.884 (2)	135
Symmetry codes: (i) -x, -y+1, -z+1; (ii) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (iii) $[x+{\script{1\over 2}}, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ .

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/S1600536809018200/cv2545sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809018200/cv2545Isup2.hkl

checkCIF report

Comment top

In the past few years, more and more people have focused their attention 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 (Wang et al. 2005; Xiong et al. 2002; Wen, 2008). We report here the crystal structure of the title compound, 4-(2H-tetrazol-5-yl)pyridinium perchlorate).

In the title compound (Fig.1), the pyridine N atom is protonated. The pyridine ring makes a dihedral angle of 23.62 (1)° with the tetrazole ring. The geometric parameters of the tetrazole rings are comparable to those in related molecules (Wang et al. 2005; Dai & Fu, 2008).

The crystal packing is stabilized by N—H···O and N—H···N hydrogen bonds (Table 1) with the formation of zig-zag chains parallel to b axis.

Related literature top

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

Experimental top

Isonicotinonitrile (30 mmol), NaN ₃ (45 mmol), NH₄Cl (33 mmol) and DMF (50 ml) were added in a flask under nitrogen atmosphere and 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) till 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/HClO₄ (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 were drawn at the 30% probability level.

4-(2H-Tetrazol-5-yl)pyridinium perchlorate top

Crystal data top

C₆H₆N₅⁺·ClO₄⁻	F(000) = 504
M_r = 247.61	D_x = 1.786 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2108 reflections
a = 5.2033 (10) Å	θ = 3.2–27.5°
b = 14.764 (3) Å	µ = 0.43 mm⁻¹
c = 12.244 (2) Å	T = 298 K
β = 101.78 (3)°	Block, colourless
V = 920.8 (3) Å³	0.30 × 0.25 × 0.20 mm
Z = 4

Data collection top

Rigaku Mercury2 diffractometer	2108 independent reflections
Radiation source: fine-focus sealed tube	1849 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.036
Detector resolution: 13.6612 pixels mm^-1	θ_max = 27.5°, θ_min = 3.2°
CCD profile fitting scans	h = −6→6
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −19→19
T_min = 0.872, T_max = 1.000	l = −15→15
9546 measured reflections

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)] = 0.035	H-atom parameters constrained
wR(F²) = 0.093	w = 1/[σ²(F_o²) + (0.0391P)² + 0.4636P] where P = (F_o² + 2F_c²)/3
S = 1.09	(Δ/σ)_max < 0.001
2108 reflections	Δρ_max = 0.29 e Å⁻³
146 parameters	Δρ_min = −0.37 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: 0.032 (3)

Crystal data top

C₆H₆N₅⁺·ClO₄⁻	V = 920.8 (3) Å³
M_r = 247.61	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 5.2033 (10) Å	µ = 0.43 mm⁻¹
b = 14.764 (3) Å	T = 298 K
c = 12.244 (2) Å	0.30 × 0.25 × 0.20 mm
β = 101.78 (3)°

Data collection top

Rigaku Mercury2 diffractometer	2108 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	1849 reflections with I > 2σ(I)
T_min = 0.872, T_max = 1.000	R_int = 0.036
9546 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.035	0 restraints
wR(F²) = 0.093	H-atom parameters constrained
S = 1.09	Δρ_max = 0.29 e Å⁻³
2108 reflections	Δρ_min = −0.37 e Å⁻³
146 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
Cl1	0.54774 (8)	0.68556 (3)	0.60933 (3)	0.02861 (15)
O4	0.6154 (3)	0.76134 (10)	0.54624 (12)	0.0425 (4)
O3	0.2704 (3)	0.68626 (10)	0.60633 (13)	0.0433 (4)
O2	0.6150 (3)	0.60331 (10)	0.55912 (15)	0.0524 (4)
N1	0.3679 (3)	0.59831 (10)	0.88383 (13)	0.0307 (3)
N5	0.0708 (3)	0.33991 (11)	0.61681 (12)	0.0317 (3)
H5A	−0.0101	0.3029	0.5673	0.038*
N4	0.7318 (3)	0.51759 (10)	0.89177 (13)	0.0325 (4)
C3	0.3301 (3)	0.45759 (11)	0.77061 (13)	0.0247 (3)
C6	0.4761 (3)	0.52315 (11)	0.85006 (13)	0.0246 (3)
N2	0.5614 (3)	0.64262 (10)	0.94760 (13)	0.0327 (4)
C5	0.2877 (4)	0.31159 (12)	0.68590 (16)	0.0337 (4)
H5	0.3471	0.2526	0.6810	0.040*
N3	0.7722 (3)	0.59329 (10)	0.95023 (13)	0.0325 (4)
H3A	0.9246	0.6090	0.9871	0.039*
O1	0.6915 (3)	0.69193 (12)	0.72169 (12)	0.0516 (4)
C2	0.0996 (3)	0.48426 (12)	0.69840 (15)	0.0298 (4)
H2	0.0327	0.5423	0.7026	0.036*
C4	0.4234 (4)	0.37000 (12)	0.76447 (15)	0.0308 (4)
H4	0.5756	0.3511	0.8129	0.037*
C1	−0.0268 (4)	0.42336 (13)	0.62097 (15)	0.0334 (4)
H1	−0.1799	0.4401	0.5716	0.040*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0264 (2)	0.0283 (2)	0.0283 (2)	−0.00122 (15)	−0.00104 (16)	0.00377 (16)
O4	0.0439 (8)	0.0389 (8)	0.0435 (8)	−0.0015 (6)	0.0060 (6)	0.0151 (6)
O3	0.0268 (7)	0.0536 (9)	0.0482 (8)	−0.0018 (6)	0.0044 (6)	−0.0002 (7)
O2	0.0510 (9)	0.0366 (8)	0.0687 (11)	0.0080 (7)	0.0098 (8)	−0.0074 (7)
N1	0.0302 (8)	0.0249 (8)	0.0349 (8)	−0.0011 (6)	0.0013 (6)	−0.0052 (6)
N5	0.0349 (8)	0.0290 (8)	0.0287 (8)	−0.0066 (6)	0.0006 (6)	−0.0077 (6)
N4	0.0284 (8)	0.0285 (8)	0.0371 (8)	0.0002 (6)	−0.0016 (6)	−0.0049 (6)
C3	0.0260 (8)	0.0227 (8)	0.0247 (8)	−0.0023 (6)	0.0036 (6)	−0.0002 (6)
C6	0.0262 (8)	0.0215 (8)	0.0244 (8)	0.0000 (6)	0.0012 (6)	0.0007 (6)
N2	0.0346 (8)	0.0266 (8)	0.0344 (8)	−0.0041 (6)	0.0014 (6)	−0.0049 (6)
C5	0.0423 (11)	0.0224 (9)	0.0348 (10)	0.0007 (7)	0.0037 (8)	−0.0026 (7)
N3	0.0289 (8)	0.0293 (8)	0.0348 (8)	−0.0038 (6)	−0.0038 (6)	−0.0047 (6)
O1	0.0471 (9)	0.0699 (11)	0.0306 (8)	−0.0147 (7)	−0.0092 (6)	0.0103 (7)
C2	0.0291 (9)	0.0249 (9)	0.0328 (9)	0.0015 (7)	0.0003 (7)	−0.0014 (7)
C4	0.0331 (9)	0.0247 (9)	0.0304 (9)	0.0024 (7)	−0.0030 (7)	−0.0009 (7)
C1	0.0294 (9)	0.0345 (10)	0.0325 (9)	−0.0008 (7)	−0.0027 (7)	−0.0011 (8)

Geometric parameters (Å, º) top

Cl1—O1	1.4285 (15)	C3—C4	1.389 (2)
Cl1—O2	1.4363 (15)	C3—C2	1.394 (2)
Cl1—O3	1.4363 (15)	C3—C6	1.469 (2)
Cl1—O4	1.4433 (14)	N2—N3	1.312 (2)
N1—N2	1.315 (2)	C5—C4	1.375 (2)
N1—C6	1.347 (2)	C5—H5	0.9300
N5—C5	1.332 (2)	N3—H3A	0.8600
N5—C1	1.338 (2)	C2—C1	1.373 (2)
N5—H5A	0.8600	C2—H2	0.9300
N4—N3	1.321 (2)	C4—H4	0.9300
N4—C6	1.327 (2)	C1—H1	0.9300

O1—Cl1—O2	110.02 (11)	N3—N2—N1	105.86 (15)
O1—Cl1—O3	110.48 (10)	N5—C5—C4	119.66 (17)
O2—Cl1—O3	109.06 (9)	N5—C5—H5	120.2
O1—Cl1—O4	109.12 (9)	C4—C5—H5	120.2
O2—Cl1—O4	108.60 (10)	N2—N3—N4	114.64 (14)
O3—Cl1—O4	109.53 (9)	N2—N3—H3A	122.7
N2—N1—C6	105.96 (15)	N4—N3—H3A	122.7
C5—N5—C1	122.96 (15)	C1—C2—C3	118.82 (16)
C5—N5—H5A	118.5	C1—C2—H2	120.6
C1—N5—H5A	118.5	C3—C2—H2	120.6
N3—N4—C6	101.09 (14)	C5—C4—C3	119.14 (16)
C4—C3—C2	119.59 (15)	C5—C4—H4	120.4
C4—C3—C6	120.69 (15)	C3—C4—H4	120.4
C2—C3—C6	119.70 (15)	N5—C1—C2	119.82 (16)
N4—C6—N1	112.45 (15)	N5—C1—H1	120.1
N4—C6—C3	123.79 (15)	C2—C1—H1	120.1
N1—C6—C3	123.66 (15)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N5—H5A···O3ⁱ	0.86	2.28	2.964 (2)	136
N5—H5A···N2ⁱⁱ	0.86	2.38	3.059 (2)	136
N3—H3A···O4ⁱⁱⁱ	0.86	2.21	2.884 (2)	135

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

Experimental details

Crystal data
Chemical formula	C₆H₆N₅⁺·ClO₄⁻
M_r	247.61
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	298
a, b, c (Å)	5.2033 (10), 14.764 (3), 12.244 (2)
β (°)	101.78 (3)
V (Å³)	920.8 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.43
Crystal size (mm)	0.30 × 0.25 × 0.20

Data collection
Diffractometer	Rigaku Mercury2 diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.872, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	9546, 2108, 1849
R_int	0.036
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.093, 1.09
No. of reflections	2108
No. of parameters	146
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.29, −0.37

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
N5—H5A···O3ⁱ	0.86	2.28	2.964 (2)	136.4
N5—H5A···N2ⁱⁱ	0.86	2.38	3.059 (2)	135.7
N3—H3A···O4ⁱⁱⁱ	0.86	2.21	2.884 (2)	135.2

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