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In the title compounds, C6H5NH3+·H2PO3- and C6H5NH3+·C2HO4-·0.5H2O, the NH3+ groups of the anilinium ion are ordered at room temperature. The rotation of these groups along the N-Caryl bond, which is often observed at room temperature in other anilinium compounds, is prevented by hydrogen bonds between the NH3+ 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]-electron-withdrawing character of the NH3+ group.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270100008015/sk1377sup1.cif
Contains datablocks I, II, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270100008015/sk1377Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270100008015/sk1377IIsup3.hkl
Contains datablock II

CCDC references: 150848; 150849

Computing details top

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+·H2PO3F(000) = 368
Mr = 175.12Dx = 1.409 Mg m3
Monoclinic, P21/aMo Kα radiation, λ = 0.71073 Å
a = 6.216 (2) ÅCell parameters from 25 reflections
b = 14.219 (6) Åθ = 9.7–15.2°
c = 9.342 (3) ŵ = 0.29 mm1
β = 90.91 (3)°T = 293 K
V = 825.6 (5) Å3Prism, colourless
Z = 40.34 × 0.34 × 0.34 mm
Data collection top
Enraf-Nonius CAD-4
diffractometer
Rint = 0.023
Radiation source: fine-focus sealed tubeθmax = 26.0°, θmin = 3.6°
Graphite monochromatorh = 77
profile data from ω–2θ scansk = 017
3607 measured reflectionsl = 1111
1612 independent reflections3 standard reflections every 180 min
1221 reflections with I > 2σ(I) intensity decay: 1%
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.028All 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 reflectionsΔρmax = 0.25 e Å3
140 parametersΔρmin = 0.25 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction 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
xyzUiso*/Ueq
P10.03258 (8)0.36864 (3)0.40048 (5)0.03614 (17)
H10.022 (3)0.3043 (14)0.491 (2)0.048 (6)*
O10.1077 (2)0.32294 (10)0.26648 (14)0.0448 (4)
O20.1538 (2)0.43441 (10)0.38316 (16)0.0503 (4)
O30.2302 (2)0.41784 (12)0.47158 (17)0.0564 (5)
H80.196 (5)0.464 (2)0.519 (3)0.085*
C10.0613 (3)0.12860 (12)0.04184 (18)0.0335 (4)
C20.2505 (3)0.09411 (16)0.0102 (2)0.0466 (5)
H20.360 (4)0.0804 (17)0.054 (3)0.061 (7)*
C30.2716 (4)0.08397 (19)0.1567 (3)0.0584 (6)
H30.401 (4)0.0613 (18)0.190 (3)0.072 (8)*
C40.1064 (4)0.10847 (18)0.2485 (3)0.0601 (6)
H40.121 (4)0.101 (2)0.349 (3)0.074 (8)*
C50.0816 (4)0.14348 (19)0.1948 (2)0.0607 (6)
H50.201 (5)0.162 (2)0.260 (3)0.083 (9)*
C60.1051 (4)0.15338 (16)0.0487 (2)0.0482 (5)
H60.234 (4)0.1749 (18)0.012 (3)0.060 (7)*
N0.0369 (3)0.14186 (13)0.19561 (17)0.0369 (4)
H7A0.133 (4)0.1060 (17)0.253 (3)0.055 (6)*
H7B0.097 (4)0.1337 (17)0.218 (3)0.057 (7)*
H7C0.071 (4)0.2033 (19)0.222 (3)0.060 (7)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
P10.0381 (3)0.0390 (3)0.0314 (2)0.0007 (2)0.00316 (17)0.0048 (2)
O10.0461 (8)0.0472 (8)0.0411 (8)0.0013 (6)0.0051 (6)0.0141 (6)
O20.0365 (7)0.0567 (9)0.0575 (9)0.0059 (6)0.0077 (6)0.0239 (7)
O30.0450 (9)0.0612 (10)0.0624 (10)0.0150 (7)0.0171 (7)0.0274 (8)
C10.0377 (9)0.0282 (8)0.0347 (9)0.0031 (8)0.0006 (7)0.0051 (7)
C20.0418 (11)0.0513 (12)0.0465 (11)0.0052 (10)0.0007 (9)0.0069 (9)
C30.0546 (14)0.0668 (16)0.0543 (13)0.0054 (12)0.0150 (11)0.0135 (11)
C40.0786 (17)0.0638 (15)0.0381 (11)0.0033 (13)0.0048 (11)0.0094 (10)
C50.0679 (15)0.0716 (16)0.0422 (12)0.0084 (13)0.0133 (11)0.0042 (11)
C60.0454 (12)0.0560 (13)0.0432 (11)0.0093 (10)0.0039 (9)0.0065 (9)
N0.0355 (9)0.0404 (9)0.0349 (8)0.0003 (7)0.0002 (7)0.0034 (7)
Geometric parameters (Å, º) top
P1—O11.4919 (14)C3—C41.372 (4)
P1—O21.4954 (15)C3—H30.92 (3)
P1—O31.5538 (16)C4—C51.373 (4)
P1—H11.29 (2)C4—H40.95 (3)
O3—H80.82 (3)C5—C61.382 (3)
C1—C21.370 (3)C5—H50.99 (3)
C1—C61.371 (3)C6—H60.93 (3)
C1—N1.459 (2)N—H7A0.94 (3)
C2—C31.385 (3)N—H7B0.87 (3)
C2—H20.92 (2)N—H7C0.93 (3)
O1—P1—O2115.70 (8)C3—C4—C5119.8 (2)
O1—P1—O3107.40 (9)C3—C4—H4120.4 (16)
O2—P1—O3111.75 (9)C5—C4—H4119.8 (16)
O1—P1—H1109.0 (9)C4—C5—C6120.1 (2)
O2—P1—H1107.7 (9)C4—C5—H5120.7 (17)
O3—P1—H1104.6 (9)C6—C5—H5119.2 (17)
P1—O3—H8112 (2)C1—C6—C5119.5 (2)
C2—C1—C6121.09 (18)C1—C6—H6120.0 (15)
C2—C1—N119.90 (17)C5—C6—H6120.5 (15)
C6—C1—N118.99 (17)C1—N—H7A114.5 (14)
C1—C2—C3118.9 (2)C1—N—H7B109.7 (16)
C1—C2—H2118.2 (15)H7A—N—H7B113 (2)
C3—C2—H2122.9 (15)C1—N—H7C110.7 (15)
C4—C3—C2120.6 (2)H7A—N—H7C103 (2)
C4—C3—H3121.5 (17)H7B—N—H7C106 (2)
C2—C3—H3117.9 (17)
C6—C1—C2—C30.4 (3)C3—C4—C5—C60.5 (4)
N—C1—C2—C3178.7 (2)C2—C1—C6—C50.0 (3)
C1—C2—C3—C40.3 (4)N—C1—C6—C5178.3 (2)
C2—C3—C4—C50.1 (4)C4—C5—C6—C10.5 (4)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O3—H8···O2i0.82 (3)1.74 (3)2.550 (2)173 (3)
N—H7A···O2ii0.94 (3)1.88 (3)2.799 (2)165 (2)
N—H7B···O1iii0.87 (3)2.00 (3)2.804 (2)154 (2)
N—H7C···O10.93 (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) x1/2, y+1/2, z.
(II) Anilinium hydrogenoxalate monohydrate top
Crystal data top
C6H8N+·HC2O4·0.5H2OF(000) = 808
Mr = 192.17Dx = 1.418 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
a = 23.9825 (19) ÅCell parameters from 25 reflections
b = 5.7253 (14) Åθ = 11.4–16.3°
c = 13.891 (2) ŵ = 0.12 mm1
β = 109.340 (11)°T = 293 K
V = 1799.7 (5) Å3Prism, white
Z = 80.49 × 0.48 × 0.29 mm
Data collection top
Enraf-Nonius CAD-4
diffractometer
Rint = 0.005
Radiation source: fine-focus sealed tubeθmax = 27.5°, θmin = 3.0°
Graphite monochromatorh = 030
profile data from ω–2θ scansk = 07
2189 measured reflectionsl = 1817
2062 independent reflections3 standard reflections every 180 min
1735 reflections with I > 2σ(I) intensity decay: 1.7%
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.034All 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 reflectionsΔρmax = 0.31 e Å3
164 parametersΔρmin = 0.16 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction 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
xyzUiso*/Ueq
N10.07951 (5)0.24192 (19)0.23798 (8)0.0370 (3)
H1A0.0555 (8)0.109 (3)0.2298 (13)0.059 (5)*
H1B0.0739 (7)0.300 (3)0.1764 (13)0.049 (4)*
H1C0.0685 (8)0.346 (3)0.2793 (14)0.060 (5)*
C10.14192 (5)0.1901 (2)0.28895 (8)0.0364 (3)
C20.15779 (7)0.0203 (3)0.33765 (11)0.0508 (4)
H20.1267 (9)0.138 (4)0.3347 (14)0.071 (5)*
C30.21687 (8)0.0640 (4)0.38763 (13)0.0672 (5)
H30.2272 (10)0.219 (4)0.4185 (17)0.084 (6)*
C40.25867 (8)0.1007 (4)0.38970 (13)0.0691 (5)
H40.2986 (9)0.073 (4)0.4193 (15)0.082 (6)*
C50.24243 (8)0.3083 (4)0.33934 (15)0.0664 (5)
H50.2717 (10)0.419 (4)0.3392 (16)0.082 (6)*
C60.18346 (7)0.3548 (3)0.28811 (12)0.0513 (4)
H60.1705 (8)0.497 (4)0.2534 (14)0.064 (5)*
O10.06771 (5)0.68721 (14)0.53305 (7)0.0458 (3)
O20.05456 (5)0.53471 (16)0.38059 (6)0.0467 (3)
O30.08251 (5)0.25105 (17)0.61327 (6)0.0516 (3)
O40.06044 (5)0.10789 (15)0.45603 (7)0.0491 (3)
H4A0.0644 (9)0.024 (4)0.4854 (17)0.075 (6)*
C70.06364 (5)0.52080 (18)0.47337 (8)0.0298 (2)
C80.07027 (5)0.27599 (18)0.52312 (8)0.0298 (2)
O50.00000.8901 (2)0.25000.0375 (3)
H5A0.0159 (8)0.793 (3)0.3006 (13)0.062 (5)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.0476 (6)0.0319 (5)0.0335 (5)0.0014 (4)0.0159 (4)0.0002 (4)
C10.0469 (6)0.0353 (6)0.0288 (5)0.0029 (5)0.0150 (5)0.0023 (4)
C20.0635 (9)0.0417 (8)0.0435 (7)0.0034 (7)0.0127 (6)0.0062 (6)
C30.0753 (11)0.0614 (10)0.0525 (9)0.0187 (9)0.0046 (8)0.0092 (8)
C40.0523 (9)0.0878 (14)0.0563 (9)0.0158 (9)0.0035 (7)0.0061 (9)
C50.0517 (9)0.0755 (12)0.0721 (11)0.0089 (9)0.0209 (8)0.0064 (9)
C60.0546 (8)0.0444 (8)0.0575 (8)0.0014 (6)0.0220 (7)0.0041 (7)
O10.0810 (7)0.0201 (4)0.0366 (5)0.0011 (4)0.0200 (4)0.0021 (3)
O20.0838 (7)0.0285 (4)0.0316 (4)0.0133 (4)0.0243 (4)0.0062 (3)
O30.0875 (7)0.0334 (5)0.0283 (5)0.0027 (5)0.0117 (4)0.0043 (3)
O40.0934 (8)0.0192 (4)0.0356 (5)0.0014 (4)0.0227 (5)0.0006 (3)
C70.0402 (6)0.0202 (5)0.0302 (5)0.0031 (4)0.0133 (4)0.0018 (4)
C80.0394 (6)0.0209 (5)0.0291 (5)0.0006 (4)0.0114 (4)0.0007 (4)
O50.0548 (7)0.0255 (6)0.0291 (6)0.0000.0099 (5)0.000
Geometric parameters (Å, º) top
N1—C11.4587 (16)C4—H40.92 (2)
N1—H1A0.939 (19)C5—C61.382 (2)
N1—H1B0.886 (17)C5—H50.95 (2)
N1—H1C0.926 (19)C6—H60.94 (2)
C1—C21.3725 (19)O1—C71.2453 (14)
C1—C61.375 (2)O2—C71.2365 (14)
C2—C31.379 (2)O3—C81.1963 (14)
C2—H21.00 (2)O4—C81.3057 (14)
C3—C41.369 (3)O4—H4A0.85 (2)
C3—H30.98 (2)C7—C81.5475 (15)
C4—C51.369 (3)O5—H5A0.877 (18)
C1—N1—H1A112.4 (11)C5—C4—H4117.0 (15)
C1—N1—H1B110.5 (10)C3—C4—H4122.5 (15)
H1A—N1—H1B107.4 (15)C4—C5—C6119.99 (17)
C1—N1—H1C106.7 (11)C4—C5—H5119.8 (14)
H1A—N1—H1C108.2 (15)C6—C5—H5120.2 (14)
H1B—N1—H1C111.7 (15)C1—C6—C5118.96 (16)
C2—C1—C6121.53 (13)C1—C6—H6118.5 (11)
C2—C1—N1119.35 (12)C5—C6—H6122.5 (11)
C6—C1—N1119.11 (12)C8—O4—H4A110.4 (15)
C1—C2—C3118.58 (16)O2—C7—O1126.34 (10)
C1—C2—H2119.5 (12)O2—C7—C8118.71 (9)
C3—C2—H2121.9 (12)O1—C7—C8114.95 (9)
C4—C3—C2120.58 (17)O3—C8—O4125.65 (11)
C4—C3—H3122.5 (13)O3—C8—C7121.93 (10)
C2—C3—H3116.9 (13)O4—C8—C7112.41 (9)
C5—C4—C3120.32 (16)
C6—C1—C2—C30.8 (2)N1—C1—C6—C5177.89 (13)
N1—C1—C2—C3178.38 (13)C4—C5—C6—C10.1 (3)
C1—C2—C3—C40.9 (3)O2—C7—C8—O3175.55 (12)
C2—C3—C4—C52.1 (3)O1—C7—C8—O35.00 (17)
C3—C4—C5—C61.5 (3)O2—C7—C8—O45.16 (15)
C2—C1—C6—C51.3 (2)O1—C7—C8—O4174.29 (11)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···O5i0.939 (19)1.915 (19)2.8163 (15)160.1 (16)
N1—H1B···O1ii0.886 (17)1.949 (17)2.7955 (15)159.3 (15)
N1—H1C···O20.926 (19)1.89 (2)2.8067 (14)171.2 (17)
O4—H4A···O1i0.85 (2)1.77 (2)2.6177 (14)173 (2)
O5—H5A···O20.877 (18)1.898 (19)2.7516 (13)163.8 (17)
Symmetry codes: (i) x, y1, z; (ii) x, y+1, z1/2.
 

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