Acta Cryst. (2009). E65, o2378 [ doi:10.1107/S1600536809035429 ]
The crystal structure of the title compound, C7H10NO+·Cl-, was synthesized by the reaction of 4-methoxyaniline and hydrochloric acid. In the crystal structure, the ions are involved in intermolecular N-H
Cl hydrogen bonds.
Single crystals of 4-methoxy-anilinium chloride are prepared by slow evaporation at room temperature of 20 mL of an ethanolic solution of 4-methoxyphenylamine and an excess of hydrogen chloride (6 mol/L).
All hydrogen atoms were calculated geometrically with C—H distances of 0.93 Å for aromatic C–H functions, 0.96 Å for the methyl group and 0.89 Å for the ammonium substituent. All hydrogen atoms were allowed to ride on the C and N atoms to which they are bonded with thermal parameters of Uiso(H) = 1.2Ueq(parent atom).
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]](./im2133fig1thm.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]](./im2133fig2thm.gif)
| Fig. 2. View of the packing of the title compound, stacking along the a axis. Dashed lines indicate hydrogen bonds. |
| C7H10NO+·Cl− | F(000) = 672 |
| Mr = 159.61 | Dx = 1.286 Mg m−3 |
| Orthorhombic, Pbca | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: -P 2ac 2ab | Cell parameters from 6458 reflections |
| a = 8.905 (2) Å | θ = 3.0–27.6° |
| b = 8.489 (2) Å | µ = 0.40 mm−1 |
| c = 21.817 (4) Å | T = 298 K |
| V = 1649.3 (6) Å3 | Prism, colourless |
| Z = 8 | 0.20 × 0.20 × 0.20 mm |
| Rigaku SCXmini diffractometer | 1886 independent reflections |
| Radiation source: fine-focus sealed tube | 1452 reflections with I > 2σ(I) |
| graphite | Rint = 0.058 |
| Detector resolution: 13.6612 pixels mm-1 | θmax = 27.5°, θmin = 3.4° |
| ω scans | h = −11→11 |
| Absorption correction: multi-scan (CrystalClear; Rigaku, 2005) | k = −10→11 |
| Tmin = 0.924, Tmax = 0.924 | l = −27→28 |
| 15436 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)] = 0.062 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.165 | H-atom parameters constrained |
| S = 1.12 | w = 1/[σ2(Fo2) + (0.0824P)2 + 0.5018P] where P = (Fo2 + 2Fc2)/3 |
| 1886 reflections | (Δ/σ)max < 0.001 |
| 91 parameters | Δρmax = 0.25 e Å−3 |
| 0 restraints | Δρmin = −0.53 e Å−3 |
| C7H10NO+·Cl− | V = 1649.3 (6) Å3 |
| Mr = 159.61 | Z = 8 |
| Orthorhombic, Pbca | Mo Kα radiation |
| a = 8.905 (2) Å | µ = 0.40 mm−1 |
| b = 8.489 (2) Å | T = 298 K |
| c = 21.817 (4) Å | 0.20 × 0.20 × 0.20 mm |
| Rigaku SCXmini diffractometer | 1886 independent reflections |
| Absorption correction: multi-scan (CrystalClear; Rigaku, 2005) | 1452 reflections with I > 2σ(I) |
| Tmin = 0.924, Tmax = 0.924 | Rint = 0.058 |
| 15436 measured reflections | θmax = 27.5° |
| R[F2 > 2σ(F2)] = 0.062 | H-atom parameters constrained |
| wR(F2) = 0.165 | Δρmax = 0.25 e Å−3 |
| S = 1.12 | Δρmin = −0.53 e Å−3 |
| 1886 reflections | Absolute structure: ? |
| 91 parameters | Flack parameter: ? |
| 0 restraints | Rogers parameter: ? |
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. |
| x | y | z | Uiso*/Ueq | ||
| Cl1 | 0.75138 (6) | 0.98509 (7) | 0.52111 (3) | 0.0470 (3) | |
| O1 | 0.1534 (2) | 0.1996 (2) | 0.29469 (8) | 0.0623 (6) | |
| N1 | 0.0252 (3) | 0.2494 (3) | 0.04478 (10) | 0.0617 (7) | |
| H1D | −0.0468 | 0.3203 | 0.0383 | 0.093* | |
| H1E | −0.0059 | 0.1553 | 0.0320 | 0.093* | |
| H1F | 0.1073 | 0.2770 | 0.0242 | 0.093* | |
| C2 | 0.1175 (3) | 0.2222 (3) | 0.23454 (10) | 0.0438 (6) | |
| C5 | 0.0595 (3) | 0.2423 (3) | 0.11049 (11) | 0.0441 (6) | |
| C4 | 0.1677 (3) | 0.1392 (3) | 0.13138 (12) | 0.0561 (7) | |
| H4A | 0.2203 | 0.0762 | 0.1039 | 0.067* | |
| C6 | −0.0179 (3) | 0.3363 (3) | 0.15081 (12) | 0.0492 (6) | |
| H6A | −0.0895 | 0.4069 | 0.1363 | 0.059* | |
| C7 | 0.0108 (3) | 0.3259 (3) | 0.21326 (11) | 0.0472 (6) | |
| H7A | −0.0420 | 0.3890 | 0.2407 | 0.057* | |
| C3 | 0.1970 (3) | 0.1303 (4) | 0.19295 (13) | 0.0575 (7) | |
| H3A | 0.2710 | 0.0621 | 0.2071 | 0.069* | |
| C1 | 0.0870 (4) | 0.3025 (4) | 0.33900 (13) | 0.0761 (10) | |
| H1A | 0.1211 | 0.2740 | 0.3792 | 0.114* | |
| H1B | −0.0203 | 0.2934 | 0.3371 | 0.114* | |
| H1C | 0.1157 | 0.4092 | 0.3304 | 0.114* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Cl1 | 0.0461 (4) | 0.0472 (4) | 0.0478 (4) | −0.0017 (2) | 0.0013 (3) | −0.0042 (2) |
| O1 | 0.0691 (13) | 0.0735 (13) | 0.0442 (10) | −0.0047 (11) | −0.0113 (9) | 0.0042 (9) |
| N1 | 0.0690 (16) | 0.0723 (16) | 0.0439 (12) | −0.0200 (12) | −0.0091 (11) | 0.0082 (11) |
| C2 | 0.0435 (14) | 0.0466 (12) | 0.0414 (13) | −0.0109 (11) | −0.0051 (10) | 0.0065 (10) |
| C5 | 0.0440 (13) | 0.0496 (13) | 0.0388 (12) | −0.0143 (11) | −0.0040 (10) | 0.0055 (10) |
| C4 | 0.0598 (16) | 0.0597 (16) | 0.0488 (15) | 0.0083 (13) | 0.0060 (12) | −0.0031 (12) |
| C6 | 0.0421 (13) | 0.0499 (14) | 0.0554 (14) | 0.0024 (11) | −0.0056 (11) | 0.0060 (12) |
| C7 | 0.0404 (13) | 0.0526 (15) | 0.0486 (13) | −0.0008 (11) | 0.0000 (11) | −0.0056 (11) |
| C3 | 0.0570 (16) | 0.0592 (16) | 0.0564 (16) | 0.0167 (14) | −0.0053 (13) | 0.0062 (13) |
| C1 | 0.075 (2) | 0.109 (3) | 0.0448 (15) | −0.011 (2) | −0.0045 (14) | −0.0147 (16) |
| O1—C2 | 1.364 (3) | C4—C3 | 1.370 (4) |
| O1—C1 | 1.431 (4) | C4—H4A | 0.9300 |
| N1—C5 | 1.467 (3) | C6—C7 | 1.389 (4) |
| N1—H1D | 0.8900 | C6—H6A | 0.9300 |
| N1—H1E | 0.8900 | C7—H7A | 0.9300 |
| N1—H1F | 0.8900 | C3—H3A | 0.9300 |
| C2—C7 | 1.376 (4) | C1—H1A | 0.9600 |
| C2—C3 | 1.390 (4) | C1—H1B | 0.9600 |
| C5—C6 | 1.373 (4) | C1—H1C | 0.9600 |
| C5—C4 | 1.380 (4) | ||
| C2—O1—C1 | 117.9 (2) | C5—C6—C7 | 119.9 (2) |
| C5—N1—H1D | 109.5 | C5—C6—H6A | 120.0 |
| C5—N1—H1E | 109.5 | C7—C6—H6A | 120.0 |
| H1D—N1—H1E | 109.5 | C2—C7—C6 | 119.9 (2) |
| C5—N1—H1F | 109.5 | C2—C7—H7A | 120.0 |
| H1D—N1—H1F | 109.5 | C6—C7—H7A | 120.0 |
| H1E—N1—H1F | 109.5 | C4—C3—C2 | 120.8 (2) |
| O1—C2—C7 | 125.2 (2) | C4—C3—H3A | 119.6 |
| O1—C2—C3 | 115.4 (2) | C2—C3—H3A | 119.6 |
| C7—C2—C3 | 119.4 (2) | O1—C1—H1A | 109.5 |
| C6—C5—C4 | 120.5 (2) | O1—C1—H1B | 109.5 |
| C6—C5—N1 | 119.8 (2) | H1A—C1—H1B | 109.5 |
| C4—C5—N1 | 119.6 (2) | O1—C1—H1C | 109.5 |
| C3—C4—C5 | 119.5 (2) | H1A—C1—H1C | 109.5 |
| C3—C4—H4A | 120.3 | H1B—C1—H1C | 109.5 |
| C5—C4—H4A | 120.3 | ||
| C1—O1—C2—C7 | −6.9 (4) | O1—C2—C7—C6 | −178.8 (2) |
| C1—O1—C2—C3 | 173.4 (3) | C3—C2—C7—C6 | 0.9 (4) |
| C6—C5—C4—C3 | 0.4 (4) | C5—C6—C7—C2 | 0.4 (4) |
| N1—C5—C4—C3 | −178.5 (2) | C5—C4—C3—C2 | 1.0 (4) |
| C4—C5—C6—C7 | −1.1 (4) | O1—C2—C3—C4 | 178.1 (3) |
| N1—C5—C6—C7 | 177.8 (2) | C7—C2—C3—C4 | −1.6 (4) |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N1—H1D···Cl1i | 0.89 | 2.47 | 3.360 (3) | 179 |
| N1—H1E···Cl1ii | 0.89 | 2.50 | 3.209 (2) | 137 |
| N1—H1F···Cl1iii | 0.89 | 2.38 | 3.167 (2) | 147 |
| Symmetry codes: (i) x−1, −y+3/2, z−1/2; (ii) −x+1/2, −y+1, z−1/2; (iii) −x+1, y−1/2, −z+1/2. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N1—H1D···Cl1i | 0.89 | 2.47 | 3.360 (3) | 179 |
| N1—H1E···Cl1ii | 0.89 | 2.50 | 3.209 (2) | 137 |
| N1—H1F···Cl1iii | 0.89 | 2.38 | 3.167 (2) | 147 |
| Symmetry codes: (i) x−1, −y+3/2, z−1/2; (ii) −x+1/2, −y+1, z−1/2; (iii) −x+1, y−1/2, −z+1/2. |
The authors are grateful to the starter fund of Southeast University for financial support to buy the X-ray diffractometer.
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Rigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan.
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Wu, B.-C., Dai, X.-Y., Xiao, F.-P. & Jin, L.-F. (2006). Acta Cryst. E62, o4327–o4328.
Acid-base reactions of organic reactands were already widely researched by ancient chemists (Wu et al., 2006). This study is a part of a systematic investigation of dielectric-ferroelectric materials, including organic ligands, metal-organic coordination compounds and organic-inorganic hybrid materials (Li et al., 2008; Hang et al., 2009). Nevertheless, 4-methoxy-anilinium chloride shows no dielectric irregularity in the temperature range of 80 K to 400 K, (m.p. 401 K).
The asymmetric unit of the title compound is composed of cationic (CH3O–C6H4–NH3+) and chloride anions (Fig 1). Intramolecular hydrogen bonds between the ammonium groups of the organic cations and the chloride anions are observed in the crystal structure.