In the title compounds, C
6H
5NH
3+·H
2PO
3- and C
6H
5NH
3+·C
2HO
4-·0.5H
2O, the NH
3+ groups of the anilinium ion are ordered at room temperature. The rotation of these groups along the N-C
aryl bond, which is often observed at room temperature in other anilinium compounds, is prevented by hydrogen bonds between the NH
3+ group and the anions. In both compounds, the geometry of the cation is significantly distorted from
D6h to a symmetry close to
C2v. The angle
ipso to the substituent is significantly larger than 120°, as expected from the
![[sigma]](/logos/entities/sigma_rmgif.gif)
-electron-withdrawing character of the NH
3+ group.
Supporting information
CCDC references: 150848; 150849
For both compounds, data collection: CAD-4 Software (Enraf-Nonius, 1989); cell refinement: CAD-4 Software; data reduction: HELENA (Spek, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXL97.
(I) Anilinium hydrogenphosphite
top
Crystal data top
| C6H8N+·H2PO3− | F(000) = 368 |
| Mr = 175.12 | Dx = 1.409 Mg m−3 |
| Monoclinic, P21/a | Mo Kα radiation, λ = 0.71073 Å |
| a = 6.216 (2) Å | Cell parameters from 25 reflections |
| b = 14.219 (6) Å | θ = 9.7–15.2° |
| c = 9.342 (3) Å | µ = 0.29 mm−1 |
| β = 90.91 (3)° | T = 293 K |
| V = 825.6 (5) Å3 | Prism, colourless |
| Z = 4 | 0.34 × 0.34 × 0.34 mm |
Data collection top
Enraf-Nonius CAD-4
diffractometer | Rint = 0.023 |
| Radiation source: fine-focus sealed tube | θmax = 26.0°, θmin = 3.6° |
| Graphite monochromator | h = −7→7 |
| profile data from ω–2θ scans | k = 0→17 |
| 3607 measured reflections | l = −11→11 |
| 1612 independent reflections | 3 standard reflections every 180 min |
| 1221 reflections with I > 2σ(I) | intensity decay: 1% |
Refinement top
| 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)] = 0.028 | All H-atom parameters refined |
| wR(F2) = 0.084 | w = 1/[σ2(Fo2) + (0.038P)2 + 0.3216P]
where P = (Fo2 + 2Fc2)/3 |
| S = 1.05 | (Δ/σ)max < 0.001 |
| 1612 reflections | Δρmax = 0.25 e Å−3 |
| 140 parameters | Δρmin = −0.25 e Å−3 |
| 0 restraints | Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
| Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.015 (2) |
Special details top
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 (Å2) top| | x | y | z | Uiso*/Ueq | |
| P1 | 0.03258 (8) | 0.36864 (3) | 0.40048 (5) | 0.03614 (17) | |
| H1 | −0.022 (3) | 0.3043 (14) | 0.491 (2) | 0.048 (6)* | |
| O1 | 0.1077 (2) | 0.32294 (10) | 0.26648 (14) | 0.0448 (4) | |
| O2 | −0.1538 (2) | 0.43441 (10) | 0.38316 (16) | 0.0503 (4) | |
| O3 | 0.2302 (2) | 0.41784 (12) | 0.47158 (17) | 0.0564 (5) | |
| H8 | 0.196 (5) | 0.464 (2) | 0.519 (3) | 0.085* | |
| C1 | 0.0613 (3) | 0.12860 (12) | 0.04184 (18) | 0.0335 (4) | |
| C2 | 0.2505 (3) | 0.09411 (16) | −0.0102 (2) | 0.0466 (5) | |
| H2 | 0.360 (4) | 0.0804 (17) | 0.054 (3) | 0.061 (7)* | |
| C3 | 0.2716 (4) | 0.08397 (19) | −0.1567 (3) | 0.0584 (6) | |
| H3 | 0.401 (4) | 0.0613 (18) | −0.190 (3) | 0.072 (8)* | |
| C4 | 0.1064 (4) | 0.10847 (18) | −0.2485 (3) | 0.0601 (6) | |
| H4 | 0.121 (4) | 0.101 (2) | −0.349 (3) | 0.074 (8)* | |
| C5 | −0.0816 (4) | 0.14348 (19) | −0.1948 (2) | 0.0607 (6) | |
| H5 | −0.201 (5) | 0.162 (2) | −0.260 (3) | 0.083 (9)* | |
| C6 | −0.1051 (4) | 0.15338 (16) | −0.0487 (2) | 0.0482 (5) | |
| H6 | −0.234 (4) | 0.1749 (18) | −0.012 (3) | 0.060 (7)* | |
| N | 0.0369 (3) | 0.14186 (13) | 0.19561 (17) | 0.0369 (4) | |
| H7A | 0.133 (4) | 0.1060 (17) | 0.253 (3) | 0.055 (6)* | |
| H7B | −0.097 (4) | 0.1337 (17) | 0.218 (3) | 0.057 (7)* | |
| H7C | 0.071 (4) | 0.2033 (19) | 0.222 (3) | 0.060 (7)* | |
Atomic displacement parameters (Å2) top| | U11 | U22 | U33 | U12 | U13 | U23 |
| P1 | 0.0381 (3) | 0.0390 (3) | 0.0314 (2) | 0.0007 (2) | 0.00316 (17) | −0.0048 (2) |
| O1 | 0.0461 (8) | 0.0472 (8) | 0.0411 (8) | −0.0013 (6) | 0.0051 (6) | −0.0141 (6) |
| O2 | 0.0365 (7) | 0.0567 (9) | 0.0575 (9) | 0.0059 (6) | −0.0077 (6) | −0.0239 (7) |
| O3 | 0.0450 (9) | 0.0612 (10) | 0.0624 (10) | 0.0150 (7) | −0.0171 (7) | −0.0274 (8) |
| C1 | 0.0377 (9) | 0.0282 (8) | 0.0347 (9) | −0.0031 (8) | 0.0006 (7) | −0.0051 (7) |
| C2 | 0.0418 (11) | 0.0513 (12) | 0.0465 (11) | 0.0052 (10) | −0.0007 (9) | −0.0069 (9) |
| C3 | 0.0546 (14) | 0.0668 (16) | 0.0543 (13) | 0.0054 (12) | 0.0150 (11) | −0.0135 (11) |
| C4 | 0.0786 (17) | 0.0638 (15) | 0.0381 (11) | −0.0033 (13) | 0.0048 (11) | −0.0094 (10) |
| C5 | 0.0679 (15) | 0.0716 (16) | 0.0422 (12) | 0.0084 (13) | −0.0133 (11) | −0.0042 (11) |
| C6 | 0.0454 (12) | 0.0560 (13) | 0.0432 (11) | 0.0093 (10) | −0.0039 (9) | −0.0065 (9) |
| N | 0.0355 (9) | 0.0404 (9) | 0.0349 (8) | −0.0003 (7) | −0.0002 (7) | −0.0034 (7) |
Geometric parameters (Å, º) top
| P1—O1 | 1.4919 (14) | C3—C4 | 1.372 (4) |
| P1—O2 | 1.4954 (15) | C3—H3 | 0.92 (3) |
| P1—O3 | 1.5538 (16) | C4—C5 | 1.373 (4) |
| P1—H1 | 1.29 (2) | C4—H4 | 0.95 (3) |
| O3—H8 | 0.82 (3) | C5—C6 | 1.382 (3) |
| C1—C2 | 1.370 (3) | C5—H5 | 0.99 (3) |
| C1—C6 | 1.371 (3) | C6—H6 | 0.93 (3) |
| C1—N | 1.459 (2) | N—H7A | 0.94 (3) |
| C2—C3 | 1.385 (3) | N—H7B | 0.87 (3) |
| C2—H2 | 0.92 (2) | N—H7C | 0.93 (3) |
| | | |
| O1—P1—O2 | 115.70 (8) | C3—C4—C5 | 119.8 (2) |
| O1—P1—O3 | 107.40 (9) | C3—C4—H4 | 120.4 (16) |
| O2—P1—O3 | 111.75 (9) | C5—C4—H4 | 119.8 (16) |
| O1—P1—H1 | 109.0 (9) | C4—C5—C6 | 120.1 (2) |
| O2—P1—H1 | 107.7 (9) | C4—C5—H5 | 120.7 (17) |
| O3—P1—H1 | 104.6 (9) | C6—C5—H5 | 119.2 (17) |
| P1—O3—H8 | 112 (2) | C1—C6—C5 | 119.5 (2) |
| C2—C1—C6 | 121.09 (18) | C1—C6—H6 | 120.0 (15) |
| C2—C1—N | 119.90 (17) | C5—C6—H6 | 120.5 (15) |
| C6—C1—N | 118.99 (17) | C1—N—H7A | 114.5 (14) |
| C1—C2—C3 | 118.9 (2) | C1—N—H7B | 109.7 (16) |
| C1—C2—H2 | 118.2 (15) | H7A—N—H7B | 113 (2) |
| C3—C2—H2 | 122.9 (15) | C1—N—H7C | 110.7 (15) |
| C4—C3—C2 | 120.6 (2) | H7A—N—H7C | 103 (2) |
| C4—C3—H3 | 121.5 (17) | H7B—N—H7C | 106 (2) |
| C2—C3—H3 | 117.9 (17) | | |
| | | |
| C6—C1—C2—C3 | −0.4 (3) | C3—C4—C5—C6 | −0.5 (4) |
| N—C1—C2—C3 | −178.7 (2) | C2—C1—C6—C5 | 0.0 (3) |
| C1—C2—C3—C4 | 0.3 (4) | N—C1—C6—C5 | 178.3 (2) |
| C2—C3—C4—C5 | 0.1 (4) | C4—C5—C6—C1 | 0.5 (4) |
Hydrogen-bond geometry (Å, º) top
| D—H···A | D—H | H···A | D···A | D—H···A |
| O3—H8···O2i | 0.82 (3) | 1.74 (3) | 2.550 (2) | 173 (3) |
| N—H7A···O2ii | 0.94 (3) | 1.88 (3) | 2.799 (2) | 165 (2) |
| N—H7B···O1iii | 0.87 (3) | 2.00 (3) | 2.804 (2) | 154 (2) |
| N—H7C···O1 | 0.93 (3) | 1.77 (3) | 2.693 (2) | 174 (2) |
| Symmetry codes: (i) −x, −y+1, −z+1; (ii) x+1/2, −y+1/2, z; (iii) x−1/2, −y+1/2, z. |
(II) Anilinium hydrogenoxalate monohydrate
top
Crystal data top
| C6H8N+·HC2O4−·0.5H2O | F(000) = 808 |
| Mr = 192.17 | Dx = 1.418 Mg m−3 |
| Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
| a = 23.9825 (19) Å | Cell parameters from 25 reflections |
| b = 5.7253 (14) Å | θ = 11.4–16.3° |
| c = 13.891 (2) Å | µ = 0.12 mm−1 |
| β = 109.340 (11)° | T = 293 K |
| V = 1799.7 (5) Å3 | Prism, white |
| Z = 8 | 0.49 × 0.48 × 0.29 mm |
Data collection top
Enraf-Nonius CAD-4
diffractometer | Rint = 0.005 |
| Radiation source: fine-focus sealed tube | θmax = 27.5°, θmin = 3.0° |
| Graphite monochromator | h = 0→30 |
| profile data from ω–2θ scans | k = 0→7 |
| 2189 measured reflections | l = −18→17 |
| 2062 independent reflections | 3 standard reflections every 180 min |
| 1735 reflections with I > 2σ(I) | intensity decay: 1.7% |
Refinement top
| 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)] = 0.034 | All H-atom parameters refined |
| wR(F2) = 0.101 | w = 1/[σ2(Fo2) + (0.0529P)2 + 0.8427P]
where P = (Fo2 + 2Fc2)/3 |
| S = 1.05 | (Δ/σ)max < 0.001 |
| 2062 reflections | Δρmax = 0.31 e Å−3 |
| 164 parameters | Δρmin = −0.16 e Å−3 |
| 0 restraints | Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
| Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0211 (14) |
Special details top
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 (Å2) top| | x | y | z | Uiso*/Ueq | |
| N1 | 0.07951 (5) | 0.24192 (19) | 0.23798 (8) | 0.0370 (3) | |
| H1A | 0.0555 (8) | 0.109 (3) | 0.2298 (13) | 0.059 (5)* | |
| H1B | 0.0739 (7) | 0.300 (3) | 0.1764 (13) | 0.049 (4)* | |
| H1C | 0.0685 (8) | 0.346 (3) | 0.2793 (14) | 0.060 (5)* | |
| C1 | 0.14192 (5) | 0.1901 (2) | 0.28895 (8) | 0.0364 (3) | |
| C2 | 0.15779 (7) | −0.0203 (3) | 0.33765 (11) | 0.0508 (4) | |
| H2 | 0.1267 (9) | −0.138 (4) | 0.3347 (14) | 0.071 (5)* | |
| C3 | 0.21687 (8) | −0.0640 (4) | 0.38763 (13) | 0.0672 (5) | |
| H3 | 0.2272 (10) | −0.219 (4) | 0.4185 (17) | 0.084 (6)* | |
| C4 | 0.25867 (8) | 0.1007 (4) | 0.38970 (13) | 0.0691 (5) | |
| H4 | 0.2986 (9) | 0.073 (4) | 0.4193 (15) | 0.082 (6)* | |
| C5 | 0.24243 (8) | 0.3083 (4) | 0.33934 (15) | 0.0664 (5) | |
| H5 | 0.2717 (10) | 0.419 (4) | 0.3392 (16) | 0.082 (6)* | |
| C6 | 0.18346 (7) | 0.3548 (3) | 0.28811 (12) | 0.0513 (4) | |
| H6 | 0.1705 (8) | 0.497 (4) | 0.2534 (14) | 0.064 (5)* | |
| O1 | 0.06771 (5) | 0.68721 (14) | 0.53305 (7) | 0.0458 (3) | |
| O2 | 0.05456 (5) | 0.53471 (16) | 0.38059 (6) | 0.0467 (3) | |
| O3 | 0.08251 (5) | 0.25105 (17) | 0.61327 (6) | 0.0516 (3) | |
| O4 | 0.06044 (5) | 0.10789 (15) | 0.45603 (7) | 0.0491 (3) | |
| H4A | 0.0644 (9) | −0.024 (4) | 0.4854 (17) | 0.075 (6)* | |
| C7 | 0.06364 (5) | 0.52080 (18) | 0.47337 (8) | 0.0298 (2) | |
| C8 | 0.07027 (5) | 0.27599 (18) | 0.52312 (8) | 0.0298 (2) | |
| O5 | 0.0000 | 0.8901 (2) | 0.2500 | 0.0375 (3) | |
| H5A | 0.0159 (8) | 0.793 (3) | 0.3006 (13) | 0.062 (5)* | |
Atomic displacement parameters (Å2) top| | U11 | U22 | U33 | U12 | U13 | U23 |
| N1 | 0.0476 (6) | 0.0319 (5) | 0.0335 (5) | 0.0014 (4) | 0.0159 (4) | −0.0002 (4) |
| C1 | 0.0469 (6) | 0.0353 (6) | 0.0288 (5) | 0.0029 (5) | 0.0150 (5) | −0.0023 (4) |
| C2 | 0.0635 (9) | 0.0417 (8) | 0.0435 (7) | 0.0034 (7) | 0.0127 (6) | 0.0062 (6) |
| C3 | 0.0753 (11) | 0.0614 (10) | 0.0525 (9) | 0.0187 (9) | 0.0046 (8) | 0.0092 (8) |
| C4 | 0.0523 (9) | 0.0878 (14) | 0.0563 (9) | 0.0158 (9) | 0.0035 (7) | −0.0061 (9) |
| C5 | 0.0517 (9) | 0.0755 (12) | 0.0721 (11) | −0.0089 (9) | 0.0209 (8) | −0.0064 (9) |
| C6 | 0.0546 (8) | 0.0444 (8) | 0.0575 (8) | −0.0014 (6) | 0.0220 (7) | 0.0041 (7) |
| O1 | 0.0810 (7) | 0.0201 (4) | 0.0366 (5) | 0.0011 (4) | 0.0200 (4) | −0.0021 (3) |
| O2 | 0.0838 (7) | 0.0285 (4) | 0.0316 (4) | 0.0133 (4) | 0.0243 (4) | 0.0062 (3) |
| O3 | 0.0875 (7) | 0.0334 (5) | 0.0283 (5) | −0.0027 (5) | 0.0117 (4) | 0.0043 (3) |
| O4 | 0.0934 (8) | 0.0192 (4) | 0.0356 (5) | 0.0014 (4) | 0.0227 (5) | −0.0006 (3) |
| C7 | 0.0402 (6) | 0.0202 (5) | 0.0302 (5) | 0.0031 (4) | 0.0133 (4) | 0.0018 (4) |
| C8 | 0.0394 (6) | 0.0209 (5) | 0.0291 (5) | 0.0006 (4) | 0.0114 (4) | 0.0007 (4) |
| O5 | 0.0548 (7) | 0.0255 (6) | 0.0291 (6) | 0.000 | 0.0099 (5) | 0.000 |
Geometric parameters (Å, º) top
| N1—C1 | 1.4587 (16) | C4—H4 | 0.92 (2) |
| N1—H1A | 0.939 (19) | C5—C6 | 1.382 (2) |
| N1—H1B | 0.886 (17) | C5—H5 | 0.95 (2) |
| N1—H1C | 0.926 (19) | C6—H6 | 0.94 (2) |
| C1—C2 | 1.3725 (19) | O1—C7 | 1.2453 (14) |
| C1—C6 | 1.375 (2) | O2—C7 | 1.2365 (14) |
| C2—C3 | 1.379 (2) | O3—C8 | 1.1963 (14) |
| C2—H2 | 1.00 (2) | O4—C8 | 1.3057 (14) |
| C3—C4 | 1.369 (3) | O4—H4A | 0.85 (2) |
| C3—H3 | 0.98 (2) | C7—C8 | 1.5475 (15) |
| C4—C5 | 1.369 (3) | O5—H5A | 0.877 (18) |
| | | |
| C1—N1—H1A | 112.4 (11) | C5—C4—H4 | 117.0 (15) |
| C1—N1—H1B | 110.5 (10) | C3—C4—H4 | 122.5 (15) |
| H1A—N1—H1B | 107.4 (15) | C4—C5—C6 | 119.99 (17) |
| C1—N1—H1C | 106.7 (11) | C4—C5—H5 | 119.8 (14) |
| H1A—N1—H1C | 108.2 (15) | C6—C5—H5 | 120.2 (14) |
| H1B—N1—H1C | 111.7 (15) | C1—C6—C5 | 118.96 (16) |
| C2—C1—C6 | 121.53 (13) | C1—C6—H6 | 118.5 (11) |
| C2—C1—N1 | 119.35 (12) | C5—C6—H6 | 122.5 (11) |
| C6—C1—N1 | 119.11 (12) | C8—O4—H4A | 110.4 (15) |
| C1—C2—C3 | 118.58 (16) | O2—C7—O1 | 126.34 (10) |
| C1—C2—H2 | 119.5 (12) | O2—C7—C8 | 118.71 (9) |
| C3—C2—H2 | 121.9 (12) | O1—C7—C8 | 114.95 (9) |
| C4—C3—C2 | 120.58 (17) | O3—C8—O4 | 125.65 (11) |
| C4—C3—H3 | 122.5 (13) | O3—C8—C7 | 121.93 (10) |
| C2—C3—H3 | 116.9 (13) | O4—C8—C7 | 112.41 (9) |
| C5—C4—C3 | 120.32 (16) | | |
| | | |
| C6—C1—C2—C3 | 0.8 (2) | N1—C1—C6—C5 | 177.89 (13) |
| N1—C1—C2—C3 | −178.38 (13) | C4—C5—C6—C1 | 0.1 (3) |
| C1—C2—C3—C4 | 0.9 (3) | O2—C7—C8—O3 | 175.55 (12) |
| C2—C3—C4—C5 | −2.1 (3) | O1—C7—C8—O3 | −5.00 (17) |
| C3—C4—C5—C6 | 1.5 (3) | O2—C7—C8—O4 | −5.16 (15) |
| C2—C1—C6—C5 | −1.3 (2) | O1—C7—C8—O4 | 174.29 (11) |
Hydrogen-bond geometry (Å, º) top
| D—H···A | D—H | H···A | D···A | D—H···A |
| N1—H1A···O5i | 0.939 (19) | 1.915 (19) | 2.8163 (15) | 160.1 (16) |
| N1—H1B···O1ii | 0.886 (17) | 1.949 (17) | 2.7955 (15) | 159.3 (15) |
| N1—H1C···O2 | 0.926 (19) | 1.89 (2) | 2.8067 (14) | 171.2 (17) |
| O4—H4A···O1i | 0.85 (2) | 1.77 (2) | 2.6177 (14) | 173 (2) |
| O5—H5A···O2 | 0.877 (18) | 1.898 (19) | 2.7516 (13) | 163.8 (17) |
| Symmetry codes: (i) x, y−1, z; (ii) x, −y+1, z−1/2. |
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