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access4-Cyanopyridinium chloride
aCollege of Chemistry and Chemical Engineering, Southeast University, Nanjing 210096, People's Republic of China
*Correspondence e-mail: chenxinyuanseu@yahoo.com.cn
In the of the title salt, C6H5N2+·Cl−, the pyridinium cation links to the Cl− anion via an N—H⋯Cl hydrogen bond. Weak C—H⋯Cl interactions also occur.
Related literature
For the structures and properties of related compounds, see: Chen et al. (2000![[Chen, Z.-F., Xiong, R.-G., Zhang, J., Zuo, J.-L., You, X.-Z., Che, C.-M. & Fun, H.-K. (2000). J. Chem. Soc. Dalton Trans. pp. 4010-4012.]](../../../../../../logos/arrows/e_arr.gif "Chen, Z.-F., Xiong, R.-G., Zhang, J., Zuo, J.-L., You, X.-Z., Che, C.-M. & Fun, H.-K. (2000). J. Chem. Soc. Dalton Trans. pp. 4010-4012.")
); Dai & Chen (2011); Xu et al. (2011); Liu et al. (1999); Zhao et al. (2003); Zheng (2011).
![[Scheme 1]](xu5524scheme1.gif)
Experimental
Crystal data
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![[P \overline 1]](teximages/xu5524fi1.gif)
Refinement
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Data collection: CrystalClear (Rigaku, 2005); cell CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
Supporting information
contains datablocks I, global. DOI: 10.1107/S1600536812018648/xu5524sup1.cif
Structure factors: contains datablock I. DOI: 10.1107/S1600536812018648/xu5524Isup2.hkl
Supporting information file. DOI: 10.1107/S1600536812018648/xu5524Isup3.cml
The HCl (5 mL), isonicotinonitrile (20 mmol) and ethanol (50 mL) were added into a 100 mL flask. The mixture was stirred at 333 K for 2 h, and then the precipitate was filtrated out. Colourless crystals suitable for X-ray diffraction were obtained by slow evaporation of the solution.
All the H atoms were situated into the idealized positions and treated as riding with C–H = 0.95 and N—H = 0.90 Å, Uiso(H) = 1.2Ueq(C,N).
Data collection: CrystalClear (Rigaku, 2005); cell CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
![[Figure 1]](./xu5524fig1thm.gif) | Fig. 1. A view of the asymmetric unit with the atomic numbering scheme. The displacement ellipsoids were drawn at the 30% probability level. |
| C6H5N2+·Cl− | Z = 2 |
| Mr = 140.57 | F(000) = 144 |
| Triclinic, P1 | Dx = 1.322 Mg m−3 |
| Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
| a = 6.6166 (2) Å | Cell parameters from 1231 reflections |
| b = 7.6552 (3) Å | θ = 2.8–27.5° |
| c = 8.3495 (5) Å | µ = 0.45 mm−1 |
| α = 63.957 (5)° | T = 123 K |
| β = 69.830 (2)° | Block, colorless |
| γ = 74.367 (4)° | 0.10 × 0.05 × 0.05 mm |
| V = 353.16 (3) Å3 |
| Rigaku Mercury2 diffractometer | 1231 independent reflections |
| Radiation source: fine-focus sealed tube | 1078 reflections with I > 2σ(I) |
| Graphite monochromator | Rint = 0.042 |
| Detector resolution: 13.6612 pixels mm-1 | θmax = 25.0°, θmin = 2.8° |
| CCD profile fitting scans | h = −7→7 |
| Absorption correction: multi-scan (CrystalClear; Rigaku, 2005) | k = −9→9 |
| Tmin = 0.910, Tmax = 1.000 | l = −9→9 |
| 3077 measured reflections |
| 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)] = 0.086 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.234 | H-atom parameters constrained |
| S = 1.32 | w = 1/[σ2(Fo2) + (0.0002P)2 + 3.2997P] where P = (Fo2 + 2Fc2)/3 |
| 1231 reflections | (Δ/σ)max < 0.001 |
| 82 parameters | Δρmax = 0.97 e Å−3 |
| 1 restraint | Δρmin = −0.62 e Å−3 |
| C6H5N2+·Cl− | γ = 74.367 (4)° |
| Mr = 140.57 | V = 353.16 (3) Å3 |
| Triclinic, P1 | Z = 2 |
| a = 6.6166 (2) Å | Mo Kα radiation |
| b = 7.6552 (3) Å | µ = 0.45 mm−1 |
| c = 8.3495 (5) Å | T = 123 K |
| α = 63.957 (5)° | 0.10 × 0.05 × 0.05 mm |
| β = 69.830 (2)° |
| Rigaku Mercury2 diffractometer | 1231 independent reflections |
| Absorption correction: multi-scan (CrystalClear; Rigaku, 2005) | 1078 reflections with I > 2σ(I) |
| Tmin = 0.910, Tmax = 1.000 | Rint = 0.042 |
| 3077 measured reflections |
| R[F2 > 2σ(F2)] = 0.086 | 1 restraint |
| wR(F2) = 0.234 | H-atom parameters constrained |
| S = 1.32 | Δρmax = 0.97 e Å−3 |
| 1231 reflections | Δρmin = −0.62 e Å−3 |
| 82 parameters |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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. |
| x | y | z | Uiso*/Ueq | ||
| N2 | 0.8017 (7) | 0.1582 (6) | 0.6278 (6) | 0.0267 (11) | |
| N1 | 0.4202 (7) | 0.2736 (6) | 0.0960 (6) | 0.0234 (10) | |
| H1 | 0.3576 | 0.2900 | 0.0094 | 0.028* | |
| C1 | 0.6318 (8) | 0.1817 (7) | 0.0856 (7) | 0.0238 (12) | |
| H1A | 0.7092 | 0.1377 | −0.0122 | 0.029* | |
| C3 | 0.6118 (8) | 0.2221 (7) | 0.3646 (6) | 0.0192 (11) | |
| C4 | 0.3919 (8) | 0.3182 (7) | 0.3713 (7) | 0.0238 (13) | |
| H4A | 0.3103 | 0.3648 | 0.4667 | 0.029* | |
| C6 | 0.7156 (8) | 0.1908 (7) | 0.5071 (7) | 0.0258 (13) | |
| C5 | 0.3016 (8) | 0.3411 (7) | 0.2334 (7) | 0.0251 (13) | |
| H5A | 0.1565 | 0.4042 | 0.2349 | 0.030* | |
| C2 | 0.7328 (8) | 0.1531 (7) | 0.2198 (7) | 0.0222 (12) | |
| H2A | 0.8783 | 0.0894 | 0.2146 | 0.027* | |
| Cl1 | 0.1808 (2) | 0.31778 (18) | 0.82634 (17) | 0.0249 (3) |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| N2 | 0.031 (2) | 0.021 (2) | 0.0189 (19) | −0.0006 (18) | −0.0026 (17) | −0.0048 (16) |
| N1 | 0.031 (2) | 0.0187 (18) | 0.0204 (18) | −0.0053 (17) | −0.0098 (16) | −0.0034 (15) |
| C1 | 0.028 (2) | 0.017 (2) | 0.020 (2) | −0.001 (2) | −0.0027 (19) | −0.0056 (18) |
| C3 | 0.024 (2) | 0.0126 (19) | 0.015 (2) | −0.0054 (18) | −0.0029 (18) | −0.0008 (16) |
| C4 | 0.023 (2) | 0.017 (2) | 0.022 (2) | 0.0001 (19) | 0.0000 (19) | −0.0059 (18) |
| C6 | 0.025 (2) | 0.023 (2) | 0.025 (2) | −0.002 (2) | −0.003 (2) | −0.0097 (19) |
| C5 | 0.022 (2) | 0.018 (2) | 0.029 (2) | −0.0011 (19) | −0.008 (2) | −0.0029 (19) |
| C2 | 0.023 (2) | 0.016 (2) | 0.022 (2) | 0.0010 (19) | −0.0046 (18) | −0.0052 (18) |
| Cl1 | 0.0244 (6) | 0.0273 (6) | 0.0235 (5) | 0.0001 (5) | −0.0081 (4) | −0.0108 (4) |
| N2—C6 | 1.225 (7) | C3—C4 | 1.437 (7) |
| N1—C5 | 1.371 (7) | C3—C6 | 1.473 (8) |
| N1—C1 | 1.379 (6) | C4—C5 | 1.398 (8) |
| N1—H1 | 0.8999 | C4—H4A | 0.9500 |
| C1—C2 | 1.404 (8) | C5—H5A | 0.9500 |
| C1—H1A | 0.9500 | C2—H2A | 0.9500 |
| C3—C2 | 1.430 (7) | ||
| C5—N1—C1 | 122.5 (5) | C5—C4—H4A | 121.0 |
| C5—N1—H1 | 118.8 | C3—C4—H4A | 121.0 |
| C1—N1—H1 | 118.8 | N2—C6—C3 | 177.9 (5) |
| N1—C1—C2 | 119.9 (5) | N1—C5—C4 | 120.7 (4) |
| N1—C1—H1A | 120.0 | N1—C5—H5A | 119.6 |
| C2—C1—H1A | 120.0 | C4—C5—H5A | 119.6 |
| C2—C3—C4 | 120.3 (5) | C1—C2—C3 | 118.5 (4) |
| C2—C3—C6 | 118.9 (4) | C1—C2—H2A | 120.7 |
| C4—C3—C6 | 120.8 (5) | C3—C2—H2A | 120.7 |
| C5—C4—C3 | 118.1 (5) |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N1—H1···Cl1i | 0.90 | 2.14 | 3.033 (5) | 174 |
| C4—H4A···Cl1 | 0.95 | 2.71 | 3.566 (5) | 151 |
| C5—H5A···Cl1ii | 0.95 | 2.65 | 3.566 (6) | 161 |
| Symmetry codes: (i) x, y, z−1; (ii) −x, −y+1, −z+1. |
Experimental details
| Crystal data | |
| Chemical formula | C6H5N2+·Cl− |
| Mr | 140.57 |
| Crystal system, space group | Triclinic, P1 |
| Temperature (K) | 123 |
| a, b, c (Å) | 6.6166 (2), 7.6552 (3), 8.3495 (5) |
| α, β, γ (°) | 63.957 (5), 69.830 (2), 74.367 (4) |
| V (Å3) | 353.16 (3) |
| Z | 2 |
| Radiation type | Mo Kα |
| µ (mm−1) | 0.45 |
| Crystal size (mm) | 0.10 × 0.05 × 0.05 |
| Data collection | |
| Diffractometer | Rigaku Mercury2 diffractometer |
| Absorption correction | Multi-scan (CrystalClear; Rigaku, 2005) |
| Tmin, Tmax | 0.910, 1.000 |
| No. of measured, independent and observed [I > 2σ(I)] reflections | 3077, 1231, 1078 |
| Rint | 0.042 |
| (sin θ/λ)max (Å−1) | 0.595 |
| Refinement | |
| R[F2 > 2σ(F2)], wR(F2), S | 0.086, 0.234, 1.32 |
| No. of reflections | 1231 |
| No. of parameters | 82 |
| No. of restraints | 1 |
| H-atom treatment | H-atom parameters constrained |
| Δρmax, Δρmin (e Å−3) | 0.97, −0.62 |
Computer programs: CrystalClear (Rigaku, 2005), SHELXTL (Sheldrick, 2008).
| D—H···A | D—H | H···A | D···A | D—H···A |
| N1—H1···Cl1i | 0.90 | 2.14 | 3.033 (5) | 174.1 |
| C4—H4A···Cl1 | 0.95 | 2.71 | 3.566 (5) | 151 |
| C5—H5A···Cl1ii | 0.95 | 2.65 | 3.566 (6) | 161 |
| Symmetry codes: (i) x, y, z−1; (ii) −x, −y+1, −z+1. |
Acknowledgements
This work was supported by a start-up grant from Southeast University, China.
References
Chen, Z.-F., Xiong, R.-G., Zhang, J., Zuo, J.-L., You, X.-Z., Che, C.-M. & Fun, H.-K. (2000). J. Chem. Soc. Dalton Trans. pp. 4010–4012. Web of Science CrossRef Google Scholar
Dai, J. & Chen, X.-Y. (2011). Acta Cryst. E67, o287. Web of Science CSD CrossRef IUCr Journals Google Scholar
Liu, C.-M., Yu, Z., Xiong, R.-G., Liu, K. & You, X.-Z. (1999). Inorg. Chem. Commun. 2, 31–34. Web of Science CSD CrossRef CAS Google Scholar
Rigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Xu, R.-J., Fu, D.-W., Dai, J., Zhang, Y., Ge, J.-Z. & Ye, H.-Y. (2011). Inorg. Chem. Commun. 14, 1093–1096. Web of Science CSD CrossRef CAS Google Scholar
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| CRYSTALLOGRAPHIC COMMUNICATIONS |
Simple organic salts containing strong intrermolecular H-bonds have attracted an attention as materials which display ferroelectric-paraelectric phase transitions (Chen et al., 2000; Liu et al., 1999; Zhao et al., 2003). With the purpose of obtaining phase transition crystals of organic salts, various organic molecules have been studied and a series of new materials have been elaborated (Dai & Chen, 2011; Xu et al., 2011; Zheng, 2011). Herewith we present the synthesis and crystal structure of the title compound.
In the title compound (Fig. 1), the bond lengths and angles have normal values. The asymmetric unit was composed of one 4-cyanopyridinium cation and one Cl- anion. The protonated N atom was involved in strong intramolecular N—H···Cl hydrogen bonds with the N···Cl distance of 3.033 (5)Å. The weak intermolecular C4—H4A···Cl1 and C5—H45···Cl1 interactions were presented in the crystal structure with C5···Cl1 = 3.566 (5)Å and C5···Cl1 = 3.566 (6)Å, respectively. The crystal packing is further stabilized by aromatic π···π interactions between the pyridine rings of the neighbouring 4-cyanopyridinium cations with the Cg···Cg distances of 4.416 (5) Å and 4.102 (5) Å (Cg is the centroide of the pyridine ring) (Fig. 2 and Table 1).