Acta Cryst. (2009). E65, o2344 [ doi:10.1107/S160053680903503X ]
The title compound, C7H10NO+·Br-, consists of almost planar 4-methoxyanilinium cations, wherein the O atom lies 0.049 (3) Å out of the plane formed by the non-H atoms, and a Br- anion. Strong N-H
Br and N-H(Br,Br) hydrogen bonding contributes to the stability of the crystal structure and links the cations and anions into a three-dimensional network.
Single crystals of 4-methoxyanilinium bromide were prepared by slow evaporation at room temperature of an ethanol solution of 4-methoxybenzenamine and hydrobromic acid.
Positional parameters of all the H atoms were calculated geometrically and were allowed to ride on the C atoms to which they are bonded, with Uiso(H) = 1.2Ueq(C).
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]](./pv2194fig1thm.gif)
| Fig. 1. The molecular structure of the title compound, with the atomic numbering scheme. Displacement ellipsoids are drawn at 30% probability level. |
![[Figure 2]](./pv2194fig2thm.gif)
| Fig. 2. A view of the packing of the title compound; dashed lines indicate hydrogen bonds. |
| C7H10NO+·Br− | F(000) = 816 |
| Mr = 204.07 | Dx = 1.569 Mg m−3 |
| Orthorhombic, Pbca | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: -P 2ac 2ab | Cell parameters from 6139 reflections |
| a = 8.9779 (18) Å | θ = 3.3–27.7° |
| b = 8.6978 (17) Å | µ = 4.69 mm−1 |
| c = 22.132 (4) Å | T = 298 K |
| V = 1728.2 (6) Å3 | Prism, colourless |
| Z = 8 | 0.20 × 0.20 × 0.20 mm |
| Rigaku SCXmini diffractometer | 1985 independent reflections |
| Radiation source: fine-focus sealed tube | 1276 reflections with I > 2σ(I) |
| graphite | Rint = 0.075 |
| 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 = −11→11 |
| Tmin = 0.391, Tmax = 0.391 | l = −28→28 |
| 16334 measured reflections |
| 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)] = 0.043 | H-atom parameters constrained |
| wR(F2) = 0.100 | w = 1/[σ2(Fo2) + (0.0263P)2 + 1.3429P] where P = (Fo2 + 2Fc2)/3 |
| S = 1.12 | (Δ/σ)max = 0.001 |
| 1985 reflections | Δρmax = 0.39 e Å−3 |
| 93 parameters | Δρmin = −0.33 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: 0.0232 (9) |
| C7H10NO+·Br− | V = 1728.2 (6) Å3 |
| Mr = 204.07 | Z = 8 |
| Orthorhombic, Pbca | Mo Kα radiation |
| a = 8.9779 (18) Å | µ = 4.69 mm−1 |
| b = 8.6978 (17) Å | T = 298 K |
| c = 22.132 (4) Å | 0.20 × 0.20 × 0.20 mm |
| Rigaku SCXmini diffractometer | 1985 independent reflections |
| Absorption correction: multi-scan (CrystalClear; Rigaku, 2005) | 1276 reflections with I > 2σ(I) |
| Tmin = 0.391, Tmax = 0.391 | Rint = 0.075 |
| 16334 measured reflections | θmax = 27.5° |
| R[F2 > 2σ(F2)] = 0.043 | H-atom parameters constrained |
| wR(F2) = 0.100 | Δρmax = 0.39 e Å−3 |
| S = 1.12 | Δρmin = −0.33 e Å−3 |
| 1985 reflections | Absolute structure: ? |
| 93 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 | ||
| O1 | 0.1517 (3) | 0.3060 (4) | 0.29591 (13) | 0.0721 (9) | |
| N1 | 0.0282 (4) | 0.2527 (4) | 0.05037 (14) | 0.0548 (9) | |
| H1A | 0.0842 | 0.3201 | 0.0305 | 0.066* | |
| H1B | −0.0676 | 0.2748 | 0.0447 | 0.066* | |
| H1C | 0.0469 | 0.1583 | 0.0369 | 0.066* | |
| C1 | 0.1170 (5) | 0.2823 (5) | 0.23712 (18) | 0.0497 (10) | |
| C2 | 0.1934 (5) | 0.3727 (5) | 0.1965 (2) | 0.0650 (12) | |
| H2A | 0.2650 | 0.4412 | 0.2105 | 0.078* | |
| C3 | 0.1653 (5) | 0.3630 (5) | 0.13576 (18) | 0.0596 (11) | |
| H3A | 0.2166 | 0.4258 | 0.1088 | 0.071* | |
| C4 | 0.0621 (4) | 0.2612 (4) | 0.11502 (17) | 0.0427 (9) | |
| C5 | −0.0123 (4) | 0.1673 (5) | 0.15443 (17) | 0.0538 (10) | |
| H5A | −0.0808 | 0.0958 | 0.1401 | 0.065* | |
| C6 | 0.0153 (5) | 0.1797 (5) | 0.21591 (17) | 0.0533 (11) | |
| H6A | −0.0363 | 0.1173 | 0.2429 | 0.064* | |
| C7 | 0.0851 (7) | 0.2069 (6) | 0.3394 (2) | 0.0914 (17) | |
| H7A | 0.1184 | 0.2351 | 0.3791 | 0.137* | |
| H7B | 0.1134 | 0.1025 | 0.3312 | 0.137* | |
| H7C | −0.0213 | 0.2162 | 0.3373 | 0.137* | |
| Br1 | 0.25218 (4) | 0.51025 (4) | −0.021898 (16) | 0.0495 (2) |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| O1 | 0.084 (2) | 0.088 (2) | 0.0449 (17) | 0.0026 (19) | −0.0164 (17) | −0.0048 (17) |
| N1 | 0.057 (2) | 0.059 (2) | 0.0480 (19) | 0.0099 (16) | −0.0074 (17) | −0.0047 (15) |
| C1 | 0.048 (2) | 0.053 (2) | 0.048 (2) | 0.011 (2) | −0.0035 (19) | −0.006 (2) |
| C2 | 0.067 (3) | 0.068 (3) | 0.060 (3) | −0.021 (2) | −0.008 (2) | −0.009 (2) |
| C3 | 0.063 (3) | 0.066 (3) | 0.050 (3) | −0.017 (2) | −0.001 (2) | −0.001 (2) |
| C4 | 0.042 (2) | 0.045 (2) | 0.041 (2) | 0.0082 (17) | −0.0029 (17) | −0.0057 (17) |
| C5 | 0.049 (2) | 0.054 (3) | 0.058 (3) | −0.005 (2) | −0.007 (2) | −0.006 (2) |
| C6 | 0.051 (3) | 0.061 (3) | 0.048 (2) | −0.004 (2) | 0.001 (2) | 0.0055 (19) |
| C7 | 0.107 (4) | 0.120 (5) | 0.047 (3) | 0.011 (4) | −0.007 (3) | 0.012 (3) |
| Br1 | 0.0493 (3) | 0.0461 (3) | 0.0531 (3) | 0.00163 (19) | −0.0010 (2) | −0.00423 (18) |
| O1—C1 | 1.354 (5) | C3—C4 | 1.361 (5) |
| O1—C7 | 1.424 (6) | C3—H3A | 0.9300 |
| N1—C4 | 1.465 (5) | C4—C5 | 1.369 (5) |
| N1—H1A | 0.8893 | C5—C6 | 1.387 (5) |
| N1—H1B | 0.8903 | C5—H5A | 0.9300 |
| N1—H1C | 0.8899 | C6—H6A | 0.9300 |
| C1—C6 | 1.360 (6) | C7—H7A | 0.9600 |
| C1—C2 | 1.377 (6) | C7—H7B | 0.9600 |
| C2—C3 | 1.370 (5) | C7—H7C | 0.9600 |
| C2—H2A | 0.9300 | ||
| C1—O1—C7 | 117.5 (4) | C3—C4—C5 | 120.4 (4) |
| C4—N1—H1A | 109.5 | C3—C4—N1 | 120.3 (4) |
| C4—N1—H1B | 109.2 | C5—C4—N1 | 119.4 (3) |
| H1A—N1—H1B | 109.5 | C4—C5—C6 | 119.4 (4) |
| C4—N1—H1C | 109.6 | C4—C5—H5A | 120.3 |
| H1A—N1—H1C | 109.6 | C6—C5—H5A | 120.3 |
| H1B—N1—H1C | 109.5 | C1—C6—C5 | 120.6 (4) |
| O1—C1—C6 | 125.9 (4) | C1—C6—H6A | 119.7 |
| O1—C1—C2 | 115.2 (4) | C5—C6—H6A | 119.7 |
| C6—C1—C2 | 118.9 (4) | O1—C7—H7A | 109.5 |
| C3—C2—C1 | 120.9 (4) | O1—C7—H7B | 109.5 |
| C3—C2—H2A | 119.5 | H7A—C7—H7B | 109.5 |
| C1—C2—H2A | 119.5 | O1—C7—H7C | 109.5 |
| C4—C3—C2 | 119.7 (4) | H7A—C7—H7C | 109.5 |
| C4—C3—H3A | 120.1 | H7B—C7—H7C | 109.5 |
| C2—C3—H3A | 120.1 |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N1—H1A···Br1 | 0.89 | 2.52 | 3.409 (3) | 177 |
| N1—H1B···Br1i | 0.89 | 2.55 | 3.314 (3) | 145 |
| N1—H1B···Br1ii | 0.89 | 3.00 | 3.430 (3) | 112 |
| N1—H1C···Br1iii | 0.89 | 2.57 | 3.300 (3) | 140 |
| Symmetry codes: (i) −x, −y+1, −z; (ii) x−1/2, −y+1/2, −z; (iii) −x+1/2, y−1/2, z. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N1—H1A···Br1 | 0.89 | 2.52 | 3.409 (3) | 177 |
| N1—H1B···Br1i | 0.89 | 2.55 | 3.314 (3) | 145 |
| N1—H1B···Br1ii | 0.89 | 3.00 | 3.430 (3) | 112 |
| N1—H1C···Br1iii | 0.89 | 2.57 | 3.300 (3) | 140 |
| Symmetry codes: (i) −x, −y+1, −z; (ii) x−1/2, −y+1/2, −z; (iii) −x+1/2, y−1/2, z. |
The author is grateful to the starter fund of Southeast University for financial support to buy the X-ray diffractometer.
Ben Amor, F., Soumhi, E. H., Ould Abdellahi, M. & Jouini, T. (1995). Acta Cryst. C51, 933–9352.
Ferguson, G. (1999). PRPKAPPA. University of Guelph, Canada.
Hang, T., Fu, D. W., Ye, Q. & Xiong, R. G. (2009). Cryst. Growth Des. 9, 2026–2029.
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.
Soumhi, E. H., Saadoune, I. & Driss, A. (2006). Acta Cryst. E62, o212–o214.
Tan, T.-F., Han, J., Pang, M.-L., Song, H.-B., Ma, Y.-X. & Mang, J.-B. (2006). Cryst. Growth Des. 6, 1186–1193.
This study is a part of systematic investigation of dielectric-ferroelectric materials, including organic ligands (Li et al., 2008), metal-organic coordination compounds (Hang et al., 2009) and organic-inorganic hybrids. The title compound, 4-methoxyanilinium bromide, (I), has no dielectric disuniform from 80 K to 450 K, (m.p. 458–459 K). In this article, the crystal structure of (I) has been presented.
The asymmetric unit of the title compound is built up from an almost planar 4-methoxybenzenamine cation wherein O1 lies 0.049 (3) Å out of the plane formed by its non-hydrogen atoms and a Br- anion (Fig. 1). The strong N—H···Br hydrogen bonding (N···Br distances 3.300 (3)–3.430 (3) Å) contribute to the stability of the crystal structure and lead the cations and anions to tridimensional network (Fig 2). The crystal structures containing 4-methoxybenzenamine cation have been reported (Tan et al., 2006; Soumhi et al., 2006; Ben Amor et al., 1995).