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

In the title compound, C₆H₆N₅⁺·Cl⁻, the pyridinium and tetra­zole rings are essentially coplanar. The pyridine N atoms are protonated. In the crystal structure, mol­ecules are connected via N—H...Cl, C—H...Cl, C—H...N and N—H...N hydrogen bonds into layers that are parallel to the (001) plane. There are two crystallographically independent mol­ecules in the asymmetric unit which are located on mirror planes.

Key indicators

• Single-crystal X-ray study
• T = 298 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.062
• wR factor = 0.148
• Data-to-parameter ratio = 14.1

checkCIF/PLATON results

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Alert level C
            Value of measurement temperature given =   298.000
            Value of melting point given =     0.000
PLAT340_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ...          5

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   1 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 ALERT type 2 Indicator that the structure model may be wrong or deficient
   1 ALERT type 3 Indicator that the structure quality may be low
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   0 ALERT type 5 Informative message, check

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S1. Comment

Tetrazole derivatives have found wide range of applications in coordination chemistry 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). In our ongoing investigations in this field we report here the crystal of 2-(2H-tetrazol-5-yl)pyridine-1-ium chloride (Fig.1).

In the crystal structure there are two crystallographically independent molecules, both of them located on mirror planes. Therefore, the benzene and tetrazole rings in both independent molecules are essentially planar. The geometric parameters of the tetrazole rings are comparable to those in related molecules (Wang et al., 2005; Dai & Fu, 2008).

The crystal structure is stabilized by N—H···Cl, C—H···Cl, C—H···N and N—H···N hydrogen bonding. The different H bonding interactions connect the molecules into layers, that are parallel to the (0 0 1) plane (Table 1, Fig. 2).

Related literature

For related literature on tetrazole derivatives, see: Dai & Fu (2008); Wang et al. (2005); Wen (2008); Xiong et al. (2002).

S2. Experimental

Picolinonitrile (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 the solvent from an ethanol/HCl (50:1 v/v) solution.

S3. Refinement

All H atoms were located in difference map but were positioned with idealized geometry with C—H = 0.93 Å and N—H = 0.86 Å and were refined isotropic with U_iso(H) = 1.2Ueq(C or N) using a riding model.

Computing details

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

	Fig. 1. A view of the title compound with the atomic numbering scheme. Displacement ellipsoids were drawn at the 30% probability level.
	Fig. 2. The crystal packing of the title compound viewed along the c axis showing the two-dimensionnal hydrogen bondings network.

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

Crystal data

C6H6N5^+·Cl^−	F(000) = 752
Mr = 183.61	Dx = 1.492 Mg m^−3
Orthorhombic, Pbcm	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2c 2b	Cell parameters from 2986 reflections
a = 16.375 (3) Å	θ = 2.5–27.5°
b = 15.313 (3) Å	µ = 0.42 mm^−1
c = 6.5176 (13) Å	T = 298 K
V = 1634.3 (5) Å^3	Block, colourless
Z = 8	0.25 × 0.20 × 0.18 mm

Data collection

Rigaku Mercury2 diffractometer	2041 independent reflections
Radiation source: fine-focus sealed tube	1511 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.077
Detector resolution: 13.6612 pixels mm^-1	θmax = 27.5°, θmin = 2.5°
ω scans	h = −21→21
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −19→19
Tmin = 0.910, Tmax = 0.938	l = −8→8
16127 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.062	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.148	H-atom parameters constrained
S = 1.14	w = 1/[σ^2(Fo^2) + (0.0616P)^2 + 0.4596P] where P = (Fo^2 + 2Fc^2)/3
2041 reflections	(Δ/σ)max < 0.001
145 parameters	Δρmax = 0.32 e Å^−3
0 restraints	Δρmin = −0.23 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
C9	0.0640 (2)	0.4651 (2)	0.2500	0.0494 (10)
H9	0.0803	0.5232	0.2500	0.059*
N6	0.26721 (19)	0.3543 (2)	0.2500	0.0476 (8)
N7	0.33865 (17)	0.3973 (2)	0.2500	0.0466 (8)
N8	0.3269 (2)	0.4819 (3)	0.2500	0.0568 (9)
N9	0.24511 (18)	0.4938 (2)	0.2500	0.0480 (8)
H9A	0.2202	0.5432	0.2500	0.058*
C7	0.2096 (2)	0.4149 (2)	0.2500	0.0399 (8)
C8	0.1215 (2)	0.3988 (2)	0.2500	0.0373 (8)
N10	0.09641 (17)	0.31585 (19)	0.2500	0.0422 (8)
H10A	0.1325	0.2750	0.2500	0.051*
C12	0.0174 (2)	0.2938 (3)	0.2500	0.0516 (10)
H12	0.0025	0.2352	0.2500	0.062*
C11	−0.0412 (3)	0.3566 (3)	0.2500	0.0619 (12)
H11	−0.0962	0.3414	0.2500	0.074*
C10	−0.0181 (2)	0.4434 (3)	0.2500	0.0566 (11)
H10	−0.0575	0.4871	0.2500	0.068*
N4	0.4116 (2)	0.8572 (2)	0.2500	0.0671 (11)
N3	0.3635 (2)	0.7880 (2)	0.2500	0.0663 (10)
N2	0.2886 (2)	0.8188 (2)	0.2500	0.0615 (10)
H2	0.2462	0.7856	0.2500	0.074*
N1	0.2836 (2)	0.9048 (2)	0.2500	0.0591 (10)
N5	0.33937 (17)	1.0833 (2)	0.2500	0.0414 (7)
H5A	0.2880	1.0714	0.2500	0.050*
C1	0.3619 (2)	0.9270 (2)	0.2500	0.0422 (9)
C2	0.3931 (2)	1.0162 (2)	0.2500	0.0373 (8)
C3	0.4760 (2)	1.0352 (2)	0.2500	0.0475 (9)
H3	0.5145	0.9905	0.2500	0.057*
C4	0.5005 (2)	1.1221 (3)	0.2500	0.0533 (10)
H4	0.5559	1.1355	0.2500	0.064*
C5	0.4444 (3)	1.1881 (3)	0.2500	0.0546 (11)
H5	0.4611	1.2461	0.2500	0.066*
C6	0.3620 (2)	1.1670 (3)	0.2500	0.0486 (9)
H6	0.3228	1.2110	0.2500	0.058*
Cl1	0.15729 (5)	0.12495 (6)	0.2500	0.0456 (3)
Cl2	0.16485 (7)	0.66996 (7)	0.2500	0.0764 (4)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C9	0.048 (2)	0.0309 (19)	0.070 (3)	0.0017 (17)	0.000	0.000
N6	0.0410 (18)	0.0434 (19)	0.059 (2)	0.0073 (14)	0.000	0.000
N7	0.0324 (16)	0.052 (2)	0.055 (2)	0.0076 (14)	0.000	0.000
N8	0.0363 (17)	0.061 (2)	0.073 (3)	−0.0044 (15)	0.000	0.000
N9	0.0340 (16)	0.0395 (18)	0.070 (2)	−0.0027 (13)	0.000	0.000
C7	0.041 (2)	0.0356 (19)	0.043 (2)	−0.0021 (16)	0.000	0.000
C8	0.0345 (18)	0.0339 (18)	0.044 (2)	−0.0007 (14)	0.000	0.000
N10	0.0408 (17)	0.0346 (16)	0.051 (2)	0.0027 (13)	0.000	0.000
C12	0.043 (2)	0.043 (2)	0.069 (3)	−0.0116 (18)	0.000	0.000
C11	0.036 (2)	0.059 (3)	0.091 (4)	−0.0024 (19)	0.000	0.000
C10	0.044 (2)	0.047 (2)	0.078 (3)	0.0132 (19)	0.000	0.000
N4	0.047 (2)	0.040 (2)	0.114 (3)	0.0033 (16)	0.000	0.000
N3	0.053 (2)	0.0384 (18)	0.107 (3)	0.0054 (17)	0.000	0.000
N2	0.046 (2)	0.0358 (18)	0.103 (3)	−0.0036 (16)	0.000	0.000
N1	0.0431 (19)	0.0336 (18)	0.100 (3)	0.0011 (14)	0.000	0.000
N5	0.0351 (16)	0.0371 (16)	0.0520 (19)	0.0015 (13)	0.000	0.000
C1	0.0372 (19)	0.0374 (19)	0.052 (2)	0.0022 (16)	0.000	0.000
C2	0.0327 (18)	0.0386 (19)	0.041 (2)	0.0023 (15)	0.000	0.000
C3	0.038 (2)	0.047 (2)	0.058 (3)	0.0049 (17)	0.000	0.000
C4	0.043 (2)	0.053 (2)	0.064 (3)	−0.0091 (19)	0.000	0.000
C5	0.055 (3)	0.039 (2)	0.071 (3)	−0.0112 (19)	0.000	0.000
C6	0.052 (2)	0.035 (2)	0.059 (3)	0.0049 (17)	0.000	0.000
Cl1	0.0394 (5)	0.0403 (5)	0.0572 (6)	−0.0005 (4)	0.000	0.000
Cl2	0.0564 (7)	0.0340 (5)	0.1387 (12)	−0.0022 (5)	0.000	0.000

Geometric parameters (Å, º)

C9—C8	1.384 (5)	N4—N3	1.320 (5)
C9—C10	1.385 (5)	N4—C1	1.343 (5)
C9—H9	0.9300	N3—N2	1.315 (4)
N6—C7	1.324 (5)	N2—N1	1.320 (4)
N6—N7	1.343 (4)	N2—H2	0.8600
N7—N8	1.309 (5)	N1—C1	1.326 (5)
N8—N9	1.352 (4)	N5—C6	1.335 (5)
N9—C7	1.340 (4)	N5—C2	1.351 (4)
N9—H9A	0.8600	N5—H5A	0.8600
C7—C8	1.464 (5)	C1—C2	1.459 (5)
C8—N10	1.334 (4)	C2—C3	1.389 (5)
N10—C12	1.337 (4)	C3—C4	1.390 (5)
N10—H10A	0.8600	C3—H3	0.9300
C12—C11	1.359 (6)	C4—C5	1.365 (5)
C12—H12	0.9300	C4—H4	0.9300
C11—C10	1.382 (6)	C5—C6	1.387 (5)
C11—H11	0.9300	C5—H5	0.9300
C10—H10	0.9300	C6—H6	0.9300
C8—C9—C10	119.0 (4)	N3—N4—C1	106.1 (3)
C8—C9—H9	120.5	N2—N3—N4	105.5 (3)
C10—C9—H9	120.5	N3—N2—N1	114.6 (3)
C7—N6—N7	106.0 (3)	N3—N2—H2	122.7
N8—N7—N6	111.0 (3)	N1—N2—H2	122.7
N7—N8—N9	106.2 (3)	N2—N1—C1	101.2 (3)
C7—N9—N8	108.0 (3)	C6—N5—C2	123.3 (3)
C7—N9—H9A	126.0	C6—N5—H5A	118.4
N8—N9—H9A	126.0	C2—N5—H5A	118.4
N6—C7—N9	108.9 (3)	N1—C1—N4	112.5 (3)
N6—C7—C8	125.7 (3)	N1—C1—C2	125.3 (3)
N9—C7—C8	125.4 (3)	N4—C1—C2	122.2 (3)
N10—C8—C9	119.3 (3)	N5—C2—C3	118.5 (3)
N10—C8—C7	117.6 (3)	N5—C2—C1	118.9 (3)
C9—C8—C7	123.1 (3)	C3—C2—C1	122.5 (3)
C8—N10—C12	122.6 (3)	C2—C3—C4	118.8 (3)
C8—N10—H10A	118.7	C2—C3—H3	120.6
C12—N10—H10A	118.7	C4—C3—H3	120.6
N10—C12—C11	120.3 (4)	C5—C4—C3	121.0 (4)
N10—C12—H12	119.8	C5—C4—H4	119.5
C11—C12—H12	119.8	C3—C4—H4	119.5
C12—C11—C10	119.1 (4)	C4—C5—C6	118.8 (4)
C12—C11—H11	120.4	C4—C5—H5	120.6
C10—C11—H11	120.4	C6—C5—H5	120.6
C11—C10—C9	119.8 (4)	N5—C6—C5	119.6 (4)
C11—C10—H10	120.1	N5—C6—H6	120.2
C9—C10—H10	120.1	C5—C6—H6	120.2

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N9—H9A···Cl2	0.86	2.14	3.001 (3)	177
N10—H10A···Cl1	0.86	2.33	3.088 (3)	147
N2—H2···Cl2	0.86	2.22	3.050 (4)	163
N5—H5A···Cl1^i	0.86	2.29	3.049 (3)	147
N5—H5A···N1	0.86	2.55	2.881 (4)	104
N10—H10A···N6	0.86	2.52	2.858 (4)	105
C9—H9···Cl2	0.93	2.64	3.545 (4)	165
C3—H3···N8^ii	0.93	2.60	3.329 (5)	136
C6—H6···N6^i	0.93	2.38	3.260 (5)	159
C10—H10···Cl1^iii	0.93	2.67	3.596 (4)	174

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