Acta Cryst. (2010). E66, o1403 [ doi:10.1107/S1600536810018076 ]
The crystal structure of the title compound, C8H9N2+·Cl-, is stabilized by N-H
Cl hydrogen bonds.
Single crystals (average size: 0.7×0.8×1.0 mm) of 4-(cyanomethyl)anilinium chloride were prepared by slowevaporation at room temperature of an ethanol solution of equal molar for 4 days.
Positional parameters of all the H atoms were calculated geometrically and were allowed to ride on the C and N atoms to which they are bonded, with Uiso(H) = 1.2Ueq(C),Uiso(H) = 1.5Ueq(N).
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: PRPKAPPA (Ferguson, 1999).
![[Figure 1]](./jh2157fig1thm.gif)
| Fig. 1. The molecular structure of the title compound, showing the atomic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. |
![[Figure 2]](./jh2157fig2thm.gif)
| Fig. 2. A view of the packing of the title compound, stacking along the a axis. Dashed lines indicate hydrogen bonds. |
| C8H9N2+·Cl− | F(000) = 352 |
| Mr = 168.62 | Dx = 1.340 Mg m−3 |
| Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: -P 2yn | Cell parameters from 2330 reflections |
| a = 5.4348 (12) Å | θ = 3.2–27.6° |
| b = 8.5630 (18) Å | µ = 0.39 mm−1 |
| c = 18.000 (4) Å | T = 293 K |
| β = 93.734 (16)° | Prism, orange |
| V = 835.9 (3) Å3 | 0.45 × 0.28 × 0.25 mm |
| Z = 4 |
| Rigaku SCXmini diffractometer | 1890 independent reflections |
| Radiation source: fine-focus sealed tube | 1593 reflections with I > 2σ(I) |
| graphite | Rint = 0.036 |
| Detector resolution: 13.6612 pixels mm-1 | θmax = 27.5°, θmin = 2.3° |
| CCD_Profile_fitting scans | h = −7→7 |
| Absorption correction: multi-scan (CrystalClear; Rigaku, 2005) | k = −11→11 |
| Tmin = 0.5, Tmax = 0.5 | l = −23→23 |
| 8241 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)] = 0.039 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.139 | H-atom parameters constrained |
| S = 1.18 | w = 1/[σ2(Fo2) + (0.0842P)2] where P = (Fo2 + 2Fc2)/3 |
| 1890 reflections | (Δ/σ)max < 0.001 |
| 101 parameters | Δρmax = 0.50 e Å−3 |
| 0 restraints | Δρmin = −0.54 e Å−3 |
| C8H9N2+·Cl− | V = 835.9 (3) Å3 |
| Mr = 168.62 | Z = 4 |
| Monoclinic, P21/n | Mo Kα radiation |
| a = 5.4348 (12) Å | µ = 0.39 mm−1 |
| b = 8.5630 (18) Å | T = 293 K |
| c = 18.000 (4) Å | 0.45 × 0.28 × 0.25 mm |
| β = 93.734 (16)° |
| Rigaku SCXmini diffractometer | 1890 independent reflections |
| Absorption correction: multi-scan (CrystalClear; Rigaku, 2005) | 1593 reflections with I > 2σ(I) |
| Tmin = 0.5, Tmax = 0.5 | Rint = 0.036 |
| 8241 measured reflections | θmax = 27.5° |
| R[F2 > 2σ(F2)] = 0.039 | H-atom parameters constrained |
| wR(F2) = 0.139 | Δρmax = 0.50 e Å−3 |
| S = 1.18 | Δρmin = −0.54 e Å−3 |
| 1890 reflections | Absolute structure: ? |
| 101 parameters | Flack parameter: ? |
| 0 restraints | Rogers parameter: ? |
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 > 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. |
| x | y | z | Uiso*/Ueq | ||
| C1 | 0.4618 (3) | 0.31846 (19) | 0.11664 (9) | 0.0300 (4) | |
| C2 | 0.2846 (3) | 0.3656 (2) | 0.06362 (11) | 0.0392 (4) | |
| H2 | 0.1527 | 0.4266 | 0.0768 | 0.047* | |
| C3 | 0.3045 (3) | 0.3213 (2) | −0.00980 (11) | 0.0399 (5) | |
| H3 | 0.1846 | 0.3524 | −0.0460 | 0.048* | |
| C4 | 0.5017 (3) | 0.2308 (2) | −0.02981 (9) | 0.0318 (4) | |
| C5 | 0.6768 (3) | 0.1847 (2) | 0.02470 (10) | 0.0381 (4) | |
| H5 | 0.8087 | 0.1233 | 0.0119 | 0.046* | |
| C6 | 0.6587 (3) | 0.2288 (2) | 0.09839 (10) | 0.0375 (4) | |
| H6 | 0.7780 | 0.1981 | 0.1348 | 0.045* | |
| C7 | 0.5134 (4) | 0.1847 (3) | −0.11122 (11) | 0.0424 (5) | |
| H7A | 0.3717 | 0.1201 | −0.1257 | 0.051* | |
| H7B | 0.5031 | 0.2784 | −0.1416 | 0.051* | |
| C8 | 0.7369 (4) | 0.1002 (2) | −0.12648 (10) | 0.0380 (4) | |
| N1 | 0.4471 (3) | 0.36295 (19) | 0.19498 (8) | 0.0339 (4) | |
| H1A | 0.3056 | 0.4126 | 0.2005 | 0.051* | |
| H1B | 0.5727 | 0.4256 | 0.2087 | 0.051* | |
| H1C | 0.4541 | 0.2776 | 0.2233 | 0.051* | |
| N2 | 0.9120 (4) | 0.0349 (3) | −0.13867 (12) | 0.0593 (6) | |
| Cl1 | 0.94611 (8) | 0.55382 (5) | 0.21151 (3) | 0.0395 (2) |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| C1 | 0.0310 (9) | 0.0303 (8) | 0.0290 (8) | −0.0016 (7) | 0.0037 (7) | 0.0014 (7) |
| C2 | 0.0324 (9) | 0.0462 (11) | 0.0391 (10) | 0.0129 (8) | 0.0023 (7) | −0.0008 (8) |
| C3 | 0.0344 (10) | 0.0505 (11) | 0.0339 (10) | 0.0123 (8) | −0.0045 (7) | 0.0023 (8) |
| C4 | 0.0309 (9) | 0.0335 (9) | 0.0310 (9) | 0.0017 (7) | 0.0011 (7) | 0.0010 (7) |
| C5 | 0.0318 (9) | 0.0460 (11) | 0.0362 (10) | 0.0116 (8) | 0.0005 (7) | −0.0027 (8) |
| C6 | 0.0324 (9) | 0.0471 (10) | 0.0322 (9) | 0.0095 (8) | −0.0030 (7) | 0.0022 (8) |
| C7 | 0.0409 (11) | 0.0528 (12) | 0.0327 (10) | 0.0119 (9) | −0.0024 (8) | −0.0024 (8) |
| C8 | 0.0395 (11) | 0.0464 (10) | 0.0279 (9) | 0.0031 (9) | 0.0011 (7) | 0.0002 (8) |
| N1 | 0.0347 (8) | 0.0367 (8) | 0.0305 (8) | 0.0031 (6) | 0.0034 (6) | 0.0007 (6) |
| N2 | 0.0484 (12) | 0.0836 (15) | 0.0463 (11) | 0.0210 (10) | 0.0059 (9) | −0.0014 (10) |
| Cl1 | 0.0360 (3) | 0.0418 (3) | 0.0404 (3) | 0.00352 (17) | −0.0006 (2) | −0.00759 (18) |
| C1—C2 | 1.372 (3) | C5—H5 | 0.9300 |
| C1—C6 | 1.374 (2) | C6—H6 | 0.9300 |
| C1—N1 | 1.468 (2) | C7—C8 | 1.455 (3) |
| C2—C3 | 1.386 (3) | C7—H7A | 0.9700 |
| C2—H2 | 0.9300 | C7—H7B | 0.9700 |
| C3—C4 | 1.389 (2) | C8—N2 | 1.137 (3) |
| C3—H3 | 0.9300 | N1—H1A | 0.8900 |
| C4—C5 | 1.380 (3) | N1—H1B | 0.8900 |
| C4—C7 | 1.523 (3) | N1—H1C | 0.8900 |
| C5—C6 | 1.389 (3) | ||
| C2—C1—C6 | 121.37 (16) | C1—C6—H6 | 120.5 |
| C2—C1—N1 | 120.80 (16) | C5—C6—H6 | 120.5 |
| C6—C1—N1 | 117.82 (16) | C8—C7—C4 | 113.47 (16) |
| C1—C2—C3 | 119.20 (16) | C8—C7—H7A | 108.9 |
| C1—C2—H2 | 120.4 | C4—C7—H7A | 108.9 |
| C3—C2—H2 | 120.4 | C8—C7—H7B | 108.9 |
| C2—C3—C4 | 120.63 (17) | C4—C7—H7B | 108.9 |
| C2—C3—H3 | 119.7 | H7A—C7—H7B | 107.7 |
| C4—C3—H3 | 119.7 | N2—C8—C7 | 179.6 (3) |
| C5—C4—C3 | 118.92 (16) | C1—N1—H1A | 109.5 |
| C5—C4—C7 | 122.68 (16) | C1—N1—H1B | 109.5 |
| C3—C4—C7 | 118.39 (16) | H1A—N1—H1B | 109.5 |
| C4—C5—C6 | 120.85 (17) | C1—N1—H1C | 109.5 |
| C4—C5—H5 | 119.6 | H1A—N1—H1C | 109.5 |
| C6—C5—H5 | 119.6 | H1B—N1—H1C | 109.5 |
| C1—C6—C5 | 119.02 (17) | ||
| C6—C1—C2—C3 | 0.2 (3) | C2—C1—C6—C5 | −0.3 (3) |
| N1—C1—C2—C3 | −179.95 (17) | N1—C1—C6—C5 | 179.84 (17) |
| C1—C2—C3—C4 | −0.3 (3) | C4—C5—C6—C1 | 0.5 (3) |
| C2—C3—C4—C5 | 0.5 (3) | C5—C4—C7—C8 | −5.2 (3) |
| C2—C3—C4—C7 | 179.66 (19) | C3—C4—C7—C8 | 175.67 (19) |
| C3—C4—C5—C6 | −0.6 (3) | C4—C7—C8—N2 | −114 (37) |
| C7—C4—C5—C6 | −179.74 (18) |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N1—H1B···Cl1 | 0.89 | 2.31 | 3.1638 (17) | 162 |
| N1—H1A···Cl1i | 0.89 | 2.32 | 3.2061 (16) | 177 |
| N1—H1C···Cl1ii | 0.89 | 2.29 | 3.1700 (17) | 168 |
| Symmetry codes: (i) x−1, y, z; (ii) −x+3/2, y−1/2, −z+1/2. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N1—H1B···Cl1 | 0.89 | 2.31 | 3.1638 (17) | 162 |
| N1—H1A···Cl1i | 0.89 | 2.32 | 3.2061 (16) | 177 |
| N1—H1C···Cl1ii | 0.89 | 2.29 | 3.1700 (17) | 168 |
| Symmetry codes: (i) x−1, y, z; (ii) −x+3/2, y−1/2, −z+1/2. |
The author is are grateful to the starter fund of Southeast University for financial support to buy the X-ray diffractometer.
Ferguson, G. (1999). PRPKAPPA. University of Guelph, Canada.
Li, X. Z., Qu, Z. R. & Xiong, R. G. (2008). Chin. J. Chem. 11, 1959–1962
Rigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
Zhang, W., Chen, L. Z., Xiong, R. G., Nakamura, T. & Huang, S. D. (2009). J. Am. Chem. Soc. 131, 12544–12545
Most non-hydrogen atoms of the 4-(cyanomethyl)anilinium were coplanar, with the mean deviation from plane of 0.0320 and N2—C8—C7—C4 torsion angle of 114 (37)°. The strong π-π packing interactions of benzene rings with Cg(1)···Cg(1) of 3.487 Å (Cg(1) is the centroid of benzene ring) stabilized the crystal structure. The N—H···Cl hydrogen bonding with the N···Cl distances from 3.1638 (17) Å to 3.2061 (17) Å link the molecules into infinite two-dimensional plane.
As a continuation of our study of phase transition materials, including organic ligands (Li et al., 2008), metal-organic coordination compounds (Zhang et al., 2009 ),the dielectric constant of 4-(cyanomethyl)anilinium chloride compound as a function of temperature indicates that the permittivity is basically temperature-independent (dielectric constant equaling to 5.3 to 21.1), suggesting that this compound should be not a real ferroelectrics or there may be no distinct phase transition occurred within the measured temperature range.