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In the title compounds, namely 3-acetyl­anilinium bromide, C8H10NO+·Br, (I), 3-acetyl­anilinium nitrate, C8H10NO+·NO3, (II), and 3-acetyl­anilinium dihydrogen phosphate, C8H10NO+·H2PO4, (III), each asymmetric unit contains a discrete cation, with a protonated amino group, and an anion. In the crystal structure of (I), the ions are connected via N—H...Br and N—H...O hydrogen bonds into a chain of spiro-fused R22(14) and R24(8) rings. In compound (II), the non-H atoms of the cation all lie on a mirror plane in the space group Pnma, while the nitrate ion lies across a mirror plane. The crystal structures of compounds (II) and (III) are characterized by hydrogen-bonded networks in two and three dimensions, respectively. The ions in (II) are connected via N—H...O hydrogen bonds, with three characteristic graph-set motifs, viz. C22(6), R21(4) and R46(14). The ions in (III) are connected via N—H...O and O—H...O hydrogen bonds, with five characteristic graph-set motifs, viz. D, C(4), C12(4), R33(10) and R44(12). The significance of this study lies in its illustration of the differences between the supra­molecular aggregations in the bromide, nitrate and dihydrogen phosphate salts of a small organic mol­ecule. The different geometry of the counter-ions and their different potential for hydrogen-bond formation result in markedly different hydrogen-bonding arrangements.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270108028771/gd3241sup1.cif
Contains datablocks I, II, III, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270108028771/gd3241Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270108028771/gd3241IIsup3.hkl
Contains datablock II

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270108028771/gd3241IIIsup4.hkl
Contains datablock III

CCDC references: 707215; 707216; 707217

Comment top

The formation of multi-component ionic crystals, or salts, is of fundamental importance to the development of most active pharmaceutical ingredients (APIs), where the approach is used for both purification and physical property optimization. There is a wide range of acids and bases, with a range of pKa values, solubilities, molecular weights, geometry and other properties, used for salt formation to increase or decrease solubility, to improve stability or toxicity and to reduce hygroscopicity of APIs (Gould 1986; Stahl & Wermuth 2002). The ten most frequently occurring counterions of salts of small organic molecules in the Cambridge Structural Database (CSD, Version 5.25; Allen 2002), in order of decreasing occurrence, are chloride, bromide, nitrate, ammonium, sulfate, tosylate, dihydrogen phosphate, tartrate, ethylenediamine (di-ion) and maleate (mono-ion) (Haynes et al., 2005). Most of these counterions are in the pharmaceutical `Top Ten' list. The aim of this study lies in its illustration of the differences between the supramolecular aggregations in the bromide, nitrate and dihydrogen phosphate salts of a small organic molecule. The different geometry of the counterions and their different potential for hydrogen-bond formation result in markedly different hydrogen-bonding arrangements of the ions in the crystal structures.

The title compounds, 3-acetylanilinium bromide, (I), 3-acetylanilinium nitrate, (II) and 3-acetylanilinium dihydrogen phosphate, (III), were originally investigated during salt screening of aromatic monoamines and represent part of our research into hydrogen-bonded ionic crystals of acid salts (Cinčić & Kaitner 2008a,b). 3-Aminoacetophenone has been much less studied than similar organic molecules, such as 3- and 4-aminobenzoic acid or 4-aminoacetophenone. There are no entries in the CSD for any 3-acetylanilinium salt.

In compounds (I)–(III), the bond lengths and angles are all normal for their types (Allen et al., 1987). The asymmetric unit of each compound contains an anion and a discrete cation with a protonated amino group (Figs. 1–3).

In (I), the ions are connected via N—H···Br and N—H···O hydrogen bonds (Table 1) into one-dimensional hydrogen-bonded chains which run parallel to the [111] direction. All ammonium H atoms are involved in hydrogen bonds with two different Br- ions and with the carbonyl O atom of a neighbouring cation, while each anion accepts two hydrogen bonds. The centrosymmetric hydrogen-bonded rings formed by adjacent 3-acetylanilinium cations and two Br- anions can be described by the graph-set motif R24(8) (Bernstein et al., 1995). The carbonyl O atom participates in hydrogen-bonding with a neighbouring cation through an N—H···O hydrogen bond. This interaction links cations into another centrosymmetric hydrogen-bonded ring which can be described by the graph-set motif R22(14). The aggregation of two ring motifs results in an overall one-dimensional hydrogen-bonded chain structure along the [111] direction (Fig. 4).

The supramolecular structure of (II) differs markedly from that of (I). Atoms C7, C8 and O3 are coplanar with the phenyl ring and, together with atoms N1 and O1, lie on a mirror plane of symmetry where the two O atoms of the anion are crystallographically equivalent. The H atoms of the methyl and ammonium groups display symmetry-induced disorder over two sets of positions. The ions are connected via N—H···O hydrogen bonds (Table 2) into a two-dimensional hydrogen-bonded network parallel to the (100) plane. As in (I), all ammonium H atoms are involved in hydrogen bonds, but this time with three different NO3- ions, while each anion accepts four hydrogen bonds. Only two O atoms of the anion are involved in strong hydrogen bonds, while the third does not participate in any strong interaction. The anions and cations are connected via a three-centred hydrogen bond into a ring which can be described by the graph-set motif R21(4) (Fig. 5). Another ammonium–anion interaction links the anions and cations in an alternating fashion into extended chains along the [010] direction which can be described by the graph-set motif C22(6) (Fig. 5). There are no centrosymmetric hydrogen-bonded dimers of adjacent 3-acetylanilinium cations, as in (I). Also, the carbonyl O atom does not participate in any strong intermolecular interaction. The noncentrosymmetric hydrogen-bonded ring formed by three adjacent 3-acetylanilinium cations and three nitrate anions can be described by the graph-set motif R46(14) (Fig. 5). The aggregation of ring and chain motifs results in an overall two-dimensional hydrogen-bonded sheet-like structure (Fig. 6). Adjacent sheets are stacked in the [100] direction to give a three-dimensional framework, where the interplanar distance between the aromatic rings of each sheet is ca 3.30 Å.

In (III), the ions are connected into a three-dimensional hydrogen-bonded network via N—H···O and O—H···O hydrogen bonds (Table 3). All ammonium H atoms are involved in hydrogen bonds with three H2PO4- ions, while each anion accepts six hydrogen bonds. Similar to (II), the two ammonium–anion interactions link the anions and cations in an alternating fashion into extended chains along the [100] direction which can be described by the graph-set motif C12(4) (Fig. 7). The anions themselves are linked via an O—H···O interaction into chains, also along the [100] direction, which can be described by the graph-set motif C(4). The combination of these two chain motifs generates noncentrosymmetric fused rings which can be described by the graph-set motif R33(10) (Fig. 7). The centrosymmetric hydrogen-bonded ring formed by two adjacent 3-acetylanilinium cations and two H2PO4- anions can be described by the graph-set motif R44(12) (Fig. 8). The carbonyl O atom of the cation participates in a finite hydrogen-bonding motif, D, with a neighbouring anion through an O—H···O hydrogen bond. The combination of this finite motif and the R44(12) motif generates a sheet parallel to (100) (Fig. 8). The aggregation of all these ring and chain motifs results in an overall three-dimensional hydrogen-bonded framework.

Fig. 9 clearly compares the packing arrangements of (I)–(III). The crystal packings of all three compounds are characterized by layers of 3-acetylanilinium cations which are embedded between ionic layers of anions, forming an alternating hydrocarbon–ionic layer structure. No intermolecular ππ interactions are evident in the hydrocarbon layer in any crystal structure. The shortest centroid-to-centroid distances between adjacent cations in (I), (II) and (III) are ca 4.65, 4.00 and 4.67 Å, respectively.

Related literature top

For related literature, see: Allen (2002); Allen et al. (1987); Bernstein et al. (1995); Cinčić & Kaitner (2008a, 2008b); Gould (1986); Haynes et al. (2005); Stahl & Wermuth (2002).

Experimental top

For the preparation of (I), 3-aminoacetophenone (100 mg, 0.74 mmol) was dissolved in a hot mixture of ethanol and propan-2-ol (3 ml; 2:1 v/v). The resulting clear solution was added to aqueous hydrobromic acid (2 ml, 2 M) and cooled to room temperature, and colourless crystals were grown by slow evaporation. For the preparation of (II), 3-aminoacetophenone (100 mg, 0.74 mmol) was dissolved in hot ethanol (2 ml). The clear solution was added to aqueous nitric acid (1 ml, 2 M) and cooled to room temperature, and colourless crystals of (II) were grown by slow evaporation. For the preparation of (III), 3-aminoacetophenone (100 mg, 0,74 mmol) was dissolved in a hot mixture of ethanol and propan-2-ol (3 ml; 2:1 v/v). The clear solution was added to aqueous phosphoric acid (2 ml, 2 M) and cooled to room temperature, and colourless crystals of (III) were grown by slow evaporation. Crystals of (I), (II) and (III) were collected by vacuum filtration, washed with cold acetone and dried in air. In a nitrogen atmosphere, (I), (II) and (III) melt at 459, 425 and 447 K, respectively.

Refinement top

For (I) and (III), N-bound H atoms were located in difference Fourier maps. For (I), the positions and isotropic displacement parameters of N-bound H atoms were refined [N—H = 0.86 (3)–0.94 (3) Å]. The N-bound H atoms in (III) were fixed in their as-found positions (N—H = 0.91–0.96 Å). The H atoms of the methyl and ammonium groups in (II) display symmetry-induced disorder and were each modelled using two sets of half-occupancy H atoms. The N—H distance and C—N—H angles for N-bound H atoms were fixed, but the group was allowed to rotate around the C—N bound, with N—H = 0.89 Å and Uiso(H) = 1.5Ueq(N). For (III), hydroxyl H atoms were placed in calculated positions and treated as riding on their parent O atoms, with O—H = 0.82 Å and Uiso(H) = 1.5Ueq(O). Aromatic H atoms were placed in calculated positions and treated as riding on their parent C atoms [C—H = 0.93 Å and Uiso(H) = 1.2Ueq(C)]. For all compounds, the C—H distances and C—C—H angles for the methyl H atoms were fixed, but the group was allowed to rotate around the C—C bound, with C—H = 0.96 Å and Uiso(H) = 1.5Ueq(C).

Computing details top

For all compounds, data collection: CrysAlis CCD (Oxford Diffraction, 2003); cell refinement: CrysAlis RED (Oxford Diffraction, 2003); data reduction: CrysAlis RED (Oxford Diffraction, 2003); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999), PARST97 (Nardelli, 1995), Mercury (Version 1.4; Macrae et al., 2006) and POVRay (Persistence of Vision Team, 2004).

Figures top
[Figure 1] Fig. 1. The asymmetric unit of (I), showing the crystallographic numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.
[Figure 2] Fig. 2. The asymmetric unit of (II), showing the crystallographic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii. Only one set of disordered methyl and ammonium H atoms is shown.
[Figure 3] Fig. 3. The asymmetric unit of (III), showing the crystallographic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii.
[Figure 4] Fig. 4. A view of the one-dimensional hydrogen-bonded chain of (I), showing the aggregation of two hydrogen-bonding motifs, R22(14) and R24(8). Hydrogen bonds are drawn as dotted lines and C-bound H atoms have been omitted. Atoms marked with the suffixes a or b are at the symmetry positions (x - 1, y + 1, z - 1) and (-x - 1, 3 - y, -z), respectively.
[Figure 5] Fig. 5. A view of part of the crystal structure of (II), showing the aggregation of three hydrogen-bonding motifs, C22(6), R21(4) and R46(14). Hydrogen bonds are drawn as dotted lines. Atoms marked with an ampersand (&) or a dollar sign ($) are at the symmetry positions (x, y + 1, z) and (1/2 - x, y + 3/2, z + 1/2), respectively. One set of disordered ammonium H atoms and C-bound H atoms have been omitted.
[Figure 6] Fig. 6. A view of the two-dimensional hydrogen-bonded network of (II), parallel to the (100) plane. Hydrogen bonds are drawn as dotted lines. One set of disordered ammonium H atoms and C-bound H atoms have been omitted.
[Figure 7] Fig. 7. A view of part of the crystal structure of (III), showing the aggregation of three hydrogen-bonding motifs, C(4), C12(4) and R33(10). Hydrogen bonds are drawn as dotted lines and C-bound H atoms have been omitted. Atoms marked with a hash (#) or an `at' symbol (@) are at the symmetry positions (x - 1, y, z) and (x - 2, y, z), respectively.
[Figure 8] Fig. 8. A view of part of the crystal structure of (III), showing a sheet parallel to (100). Hydrogen bonds are drawn as dotted lines and C-bound H atoms have been omitted. Atoms marked with the suffixes c or d are at the symmetry positions (1 - x, y - 1/2, 1/2 - z) and (-x, 1 - y, 1 - z), respectively.
[Figure 9] Fig. 9. Packing diagrams for compounds (I), (II) and (III), viewed along the c axes for (I) and (II) and the a axis for (III). The anions are shown as ball-and-stick models and C-bound H atoms have been omitted.
(I) 3-acetylanilinium bromide top
Crystal data top
C8H10NO+·BrZ = 2
Mr = 216.08F(000) = 216
Triclinic, P1Dx = 1.694 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 5.0530 (4) ÅCell parameters from 5234 reflections
b = 9.4145 (9) Åθ = 5–32°
c = 9.5169 (9) ŵ = 4.79 mm1
α = 75.239 (8)°T = 295 K
β = 89.253 (9)°Prism, colourless
γ = 75.757 (10)°0.47 × 0.36 × 0.10 mm
V = 423.74 (7) Å3
Data collection top
Oxford Diffraction Xcalibur CCD
diffractometer
1809 independent reflections
Radiation source: fine-focus sealed tube1668 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.011
ω scansθmax = 27.0°, θmin = 4.2°
Absorption correction: analytical
(Alcock, 1970)
h = 66
Tmin = 0.155, Tmax = 0.631k = 1212
5468 measured reflectionsl = 1212
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)] = 0.018H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.049 w = 1/[σ2(Fo2) + (0.0269P)2 + 0.1584P]
where P = (Fo2 + 2Fc2)/3
S = 1.12(Δ/σ)max = 0.001
1809 reflectionsΔρmax = 0.33 e Å3
114 parametersΔρmin = 0.40 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.094 (4)
Crystal data top
C8H10NO+·Brγ = 75.757 (10)°
Mr = 216.08V = 423.74 (7) Å3
Triclinic, P1Z = 2
a = 5.0530 (4) ÅMo Kα radiation
b = 9.4145 (9) ŵ = 4.79 mm1
c = 9.5169 (9) ÅT = 295 K
α = 75.239 (8)°0.47 × 0.36 × 0.10 mm
β = 89.253 (9)°
Data collection top
Oxford Diffraction Xcalibur CCD
diffractometer
1809 independent reflections
Absorption correction: analytical
(Alcock, 1970)
1668 reflections with I > 2σ(I)
Tmin = 0.155, Tmax = 0.631Rint = 0.011
5468 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0180 restraints
wR(F2) = 0.049H atoms treated by a mixture of independent and constrained refinement
S = 1.12Δρmax = 0.33 e Å3
1809 reflectionsΔρmin = 0.40 e Å3
114 parameters
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
H1A0.084 (5)0.909 (3)0.698 (3)0.049 (6)*
H1C0.349 (5)0.812 (3)0.764 (3)0.046 (6)*
H1B0.308 (5)0.852 (3)0.610 (3)0.050 (6)*
Br10.34300 (3)0.906927 (19)0.346035 (17)0.03578 (9)
O10.4280 (3)0.28602 (16)1.02641 (15)0.0454 (3)
N10.2260 (3)0.82336 (17)0.69825 (17)0.0311 (3)
C10.1253 (3)0.43018 (18)0.82662 (17)0.0270 (3)
C20.2270 (3)0.55732 (18)0.81775 (17)0.0276 (3)
H20.36460.55350.88360.033*
C30.1212 (3)0.68851 (18)0.71044 (17)0.0268 (3)
C40.0842 (3)0.6972 (2)0.61118 (18)0.0315 (3)
H40.15280.78630.53900.038*
C50.1852 (4)0.5718 (2)0.62093 (19)0.0345 (4)
H50.32390.57690.55510.041*
C60.0824 (4)0.4378 (2)0.72788 (19)0.0323 (3)
H60.15180.35380.73350.039*
C70.2458 (3)0.28805 (19)0.94281 (17)0.0291 (3)
C80.1405 (4)0.1514 (2)0.9535 (2)0.0399 (4)
H8A0.22650.07271.03710.060*
H8B0.18090.11640.86730.060*
H8C0.05380.17690.96270.060*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Br10.03690 (12)0.03572 (12)0.02944 (12)0.00475 (7)0.00523 (7)0.00294 (7)
O10.0527 (8)0.0350 (7)0.0431 (7)0.0169 (6)0.0230 (6)0.0061 (6)
N10.0324 (7)0.0259 (7)0.0309 (7)0.0080 (6)0.0048 (6)0.0007 (6)
C10.0277 (7)0.0266 (8)0.0245 (7)0.0068 (6)0.0001 (6)0.0029 (6)
C20.0273 (7)0.0288 (8)0.0247 (7)0.0077 (6)0.0045 (6)0.0024 (6)
C30.0269 (7)0.0261 (8)0.0253 (7)0.0069 (6)0.0014 (6)0.0026 (6)
C40.0299 (8)0.0318 (8)0.0259 (8)0.0029 (7)0.0054 (6)0.0002 (6)
C50.0313 (8)0.0385 (9)0.0311 (8)0.0075 (7)0.0100 (7)0.0054 (7)
C60.0328 (8)0.0325 (9)0.0325 (8)0.0118 (7)0.0034 (7)0.0064 (7)
C70.0307 (8)0.0270 (8)0.0273 (7)0.0079 (6)0.0010 (6)0.0021 (6)
C80.0480 (10)0.0312 (9)0.0392 (9)0.0169 (8)0.0068 (8)0.0006 (7)
Geometric parameters (Å, º) top
O1—C71.218 (2)C3—C41.386 (2)
N1—C31.470 (2)C4—C51.380 (3)
N1—H1A0.94 (3)C4—H40.9300
N1—H1C0.86 (3)C5—C61.391 (2)
N1—H1B0.94 (3)C5—H50.9300
C1—C61.394 (2)C6—H60.9300
C1—C21.398 (2)C7—C81.489 (2)
C1—C71.499 (2)C8—H8A0.9600
C2—C31.379 (2)C8—H8B0.9600
C2—H20.9300C8—H8C0.9600
C3—N1—H1A111.1 (15)C3—C4—H4120.5
C3—N1—H1C113.8 (17)C4—C5—C6120.84 (15)
H1A—N1—H1C110 (2)C4—C5—H5119.6
C3—N1—H1B112.9 (15)C6—C5—H5119.6
H1A—N1—H1B104 (2)C5—C6—C1119.59 (16)
H1C—N1—H1B105 (2)C5—C6—H6120.2
C6—C1—C2119.75 (15)C1—C6—H6120.2
C6—C1—C7121.74 (15)O1—C7—C8121.19 (15)
C2—C1—C7118.51 (14)O1—C7—C1119.62 (15)
C3—C2—C1119.35 (14)C8—C7—C1119.19 (15)
C3—C2—H2120.3C7—C8—H8A109.5
C1—C2—H2120.3C7—C8—H8B109.5
C2—C3—C4121.43 (15)H8A—C8—H8B109.5
C2—C3—N1120.36 (14)C7—C8—H8C109.5
C4—C3—N1118.21 (14)H8A—C8—H8C109.5
C5—C4—C3119.05 (15)H8B—C8—H8C109.5
C5—C4—H4120.5
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1B···Br10.94 (3)2.45 (3)3.322 (2)156 (2)
N1—H1C···O1i0.86 (3)2.17 (3)2.974 (2)157 (2)
N1—H1A···Br1ii0.94 (3)2.38 (2)3.284 (1)163 (2)
Symmetry codes: (i) x+1, y+1, z+2; (ii) x, y+2, z+1.
(II) 3-acetylanilinium nitrate top
Crystal data top
C8H10NO+·NO3F(000) = 416
Mr = 198.18Dx = 1.437 Mg m3
Orthorhombic, PnmaMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2nCell parameters from 3490 reflections
a = 16.7754 (4) Åθ = 4–25°
b = 6.6044 (2) ŵ = 0.12 mm1
c = 8.2683 (2) ÅT = 295 K
V = 916.06 (4) Å3Prism, colourless
Z = 40.31 × 0.26 × 0.13 mm
Data collection top
Oxford Diffraction Xcalibur CCD
diffractometer
1086 independent reflections
Radiation source: fine-focus sealed tube824 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.020
ω scansθmax = 27.0°, θmin = 3.9°
Absorption correction: analytical
(Alcock, 1970)
h = 2121
Tmin = 0.968, Tmax = 0.987k = 88
9987 measured reflectionsl = 1010
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)] = 0.042H-atom parameters constrained
wR(F2) = 0.129 w = 1/[σ2(Fo2) + (0.0669P)2 + 0.2331P]
where P = (Fo2 + 2Fc2)/3
S = 1.12(Δ/σ)max < 0.001
1086 reflectionsΔρmax = 0.22 e Å3
85 parametersΔρmin = 0.16 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.029 (7)
Crystal data top
C8H10NO+·NO3V = 916.06 (4) Å3
Mr = 198.18Z = 4
Orthorhombic, PnmaMo Kα radiation
a = 16.7754 (4) ŵ = 0.12 mm1
b = 6.6044 (2) ÅT = 295 K
c = 8.2683 (2) Å0.31 × 0.26 × 0.13 mm
Data collection top
Oxford Diffraction Xcalibur CCD
diffractometer
1086 independent reflections
Absorption correction: analytical
(Alcock, 1970)
824 reflections with I > 2σ(I)
Tmin = 0.968, Tmax = 0.987Rint = 0.020
9987 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0420 restraints
wR(F2) = 0.129H-atom parameters constrained
S = 1.12Δρmax = 0.22 e Å3
1086 reflectionsΔρmin = 0.16 e Å3
85 parameters
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*/UeqOcc. (<1)
N10.24693 (11)0.25000.1370 (2)0.0517 (5)
O10.26880 (14)0.25000.0034 (2)0.0873 (7)
O20.23509 (8)0.08846 (19)0.21195 (15)0.0700 (4)
O30.04075 (11)0.25001.05502 (18)0.0662 (5)
N20.20049 (11)0.25000.5409 (2)0.0522 (5)
H2A0.20750.27250.43570.078*0.50
H2B0.22130.13050.56700.078*0.50
H2C0.22450.34710.59740.078*0.50
C10.01183 (12)0.25000.7771 (2)0.0434 (5)
C20.09282 (12)0.25000.7382 (2)0.0438 (5)
H20.13120.25000.81940.053*
C30.11501 (12)0.25000.5780 (2)0.0447 (5)
C40.06002 (15)0.25000.4548 (2)0.0509 (5)
H40.07640.25000.34730.061*
C50.01974 (14)0.25000.4938 (3)0.0555 (6)
H50.05770.25000.41180.067*
C60.04419 (13)0.25000.6538 (3)0.0498 (5)
H60.09830.25000.67860.060*
C70.01066 (13)0.25000.9518 (3)0.0496 (5)
C80.09734 (15)0.25000.9969 (3)0.0676 (7)
H8A0.12520.15220.93220.101*0.50
H8B0.11940.38200.97810.101*0.50
H8C0.10280.21581.10920.101*0.50
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.0516 (10)0.0543 (11)0.0492 (10)0.0000.0000 (8)0.000
O10.0968 (15)0.1110 (18)0.0543 (11)0.0000.0234 (10)0.000
O20.0943 (10)0.0477 (7)0.0679 (8)0.0028 (6)0.0075 (6)0.0030 (6)
O30.0651 (10)0.0921 (13)0.0415 (8)0.0000.0032 (7)0.000
N20.0568 (10)0.0526 (10)0.0471 (9)0.0000.0057 (8)0.000
C10.0486 (11)0.0388 (9)0.0429 (10)0.0000.0031 (8)0.000
C20.0467 (10)0.0464 (10)0.0384 (9)0.0000.0067 (8)0.000
C30.0525 (11)0.0384 (9)0.0430 (10)0.0000.0008 (8)0.000
C40.0701 (14)0.0443 (10)0.0383 (10)0.0000.0052 (9)0.000
C50.0644 (14)0.0525 (12)0.0496 (11)0.0000.0194 (10)0.000
C60.0482 (11)0.0475 (11)0.0538 (12)0.0000.0100 (9)0.000
C70.0530 (12)0.0476 (11)0.0480 (11)0.0000.0001 (9)0.000
C80.0571 (13)0.0794 (17)0.0663 (15)0.0000.0131 (12)0.000
Geometric parameters (Å, º) top
N1—O11.217 (2)C2—H20.9300
N1—O21.2498 (15)C3—C41.374 (3)
N1—O2i1.2498 (15)C4—C51.376 (4)
O3—C71.214 (3)C4—H40.9300
N2—C31.466 (3)C5—C61.385 (3)
N2—H2A0.8900C5—H50.9300
N2—H2B0.8900C6—H60.9300
N2—H2C0.8900C7—C81.501 (3)
C1—C61.386 (3)C8—H8A0.9600
C1—C21.396 (3)C8—H8B0.9600
C1—C71.493 (3)C8—H8C0.9600
C2—C31.376 (3)
O1—N1—O2121.39 (9)C3—C4—C5118.6 (2)
O1—N1—O2i121.39 (9)C3—C4—H4120.7
O2—N1—O2i117.21 (18)C5—C4—H4120.7
C3—N2—H2A109.5C4—C5—C6120.8 (2)
C3—N2—H2B109.5C4—C5—H5119.6
H2A—N2—H2B109.5C6—C5—H5119.6
C3—N2—H2C109.5C5—C6—C1120.1 (2)
H2A—N2—H2C109.5C5—C6—H6120.0
H2B—N2—H2C109.5C1—C6—H6120.0
C6—C1—C2119.38 (19)O3—C7—C1120.1 (2)
C6—C1—C7122.68 (19)O3—C7—C8120.9 (2)
C2—C1—C7117.95 (18)C1—C7—C8119.0 (2)
C3—C2—C1119.00 (18)C7—C8—H8A109.5
C3—C2—H2120.5C7—C8—H8B109.5
C1—C2—H2120.5H8A—C8—H8B109.5
C4—C3—C2122.1 (2)C7—C8—H8C109.5
C4—C3—N2120.11 (18)H8A—C8—H8C109.5
C2—C3—N2117.76 (18)H8B—C8—H8C109.5
Symmetry code: (i) x, y+1/2, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H2A···O20.892.262.979 (2)137
N2—H2A···O2i0.892.122.979 (2)163
N2—H2B···O2ii0.892.022.857 (2)157
N2—H2C···O2iii0.891.972.857 (2)172
Symmetry codes: (i) x, y+1/2, z; (ii) x+1/2, y, z+1/2; (iii) x+1/2, y+1/2, z+1/2.
(III) 3-acetylanilinium dihydrogen phosphate top
Crystal data top
C8H10NO+·H2O4PF(000) = 488
Mr = 233.16Dx = 1.480 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 2888 reflections
a = 4.6733 (2) Åθ = 4–25°
b = 10.5962 (4) ŵ = 0.26 mm1
c = 21.1801 (9) ÅT = 295 K
β = 93.631 (3)°Prism, colourless
V = 1046.72 (7) Å30.52 × 0.08 × 0.07 mm
Z = 4
Data collection top
Oxford Diffraction Xcalibur CCD
diffractometer
2270 independent reflections
Radiation source: fine-focus sealed tube1593 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.028
ω scansθmax = 27.0°, θmin = 3.9°
Absorption correction: analytical
(Alcock, 1970)
h = 55
Tmin = 0.879, Tmax = 0.986k = 1312
10065 measured reflectionsl = 2627
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)] = 0.047H-atom parameters constrained
wR(F2) = 0.150 w = 1/[σ2(Fo2) + (0.0746P)2 + 0.5152P]
where P = (Fo2 + 2Fc2)/3
S = 1.16(Δ/σ)max < 0.001
2270 reflectionsΔρmax = 0.48 e Å3
141 parametersΔρmin = 0.38 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.052 (7)
Crystal data top
C8H10NO+·H2O4PV = 1046.72 (7) Å3
Mr = 233.16Z = 4
Monoclinic, P21/cMo Kα radiation
a = 4.6733 (2) ŵ = 0.26 mm1
b = 10.5962 (4) ÅT = 295 K
c = 21.1801 (9) Å0.52 × 0.08 × 0.07 mm
β = 93.631 (3)°
Data collection top
Oxford Diffraction Xcalibur CCD
diffractometer
2270 independent reflections
Absorption correction: analytical
(Alcock, 1970)
1593 reflections with I > 2σ(I)
Tmin = 0.879, Tmax = 0.986Rint = 0.028
10065 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0470 restraints
wR(F2) = 0.150H-atom parameters constrained
S = 1.16Δρmax = 0.48 e Å3
2270 reflectionsΔρmin = 0.38 e Å3
141 parameters
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
P10.31660 (12)0.38250 (6)0.39549 (3)0.0375 (2)
O10.0660 (4)0.35625 (18)0.43449 (8)0.0472 (5)
O20.4202 (4)0.51558 (16)0.39925 (9)0.0446 (5)
O30.2065 (5)0.3485 (2)0.32609 (10)0.0704 (7)
H3A0.33760.35690.30250.106*
O40.5555 (4)0.2874 (2)0.41515 (16)0.0859 (9)
H4A0.68700.29450.39160.129*
O50.4268 (5)0.8522 (2)0.26528 (10)0.0615 (6)
N10.0857 (4)0.64195 (18)0.43749 (10)0.0376 (5)
C10.1007 (5)0.9169 (2)0.33820 (12)0.0409 (6)
C20.0868 (5)0.7941 (2)0.36229 (11)0.0367 (5)
H20.18650.72900.34400.044*
C30.0746 (5)0.7700 (2)0.41299 (11)0.0349 (5)
C40.2223 (6)0.8655 (2)0.44158 (13)0.0469 (6)
H40.33010.84840.47600.056*
C50.2061 (7)0.9869 (3)0.41791 (15)0.0554 (7)
H50.30411.05180.43680.067*
C60.0469 (6)1.0132 (2)0.36680 (13)0.0486 (6)
H60.03821.09520.35150.058*
C70.2794 (6)0.9376 (3)0.28374 (12)0.0478 (6)
C80.2801 (10)1.0632 (3)0.25226 (18)0.0808 (12)
H8A0.38061.05730.21420.121*
H8B0.37391.12360.28030.121*
H8C0.08621.08950.24200.121*
H1A0.10470.63890.48250.062 (9)*
H1B0.24260.60120.41960.055 (8)*
H1C0.08190.59360.42910.071 (10)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
P10.0311 (4)0.0328 (4)0.0497 (4)0.0005 (2)0.0113 (3)0.0020 (2)
O10.0353 (9)0.0613 (12)0.0461 (10)0.0039 (8)0.0107 (7)0.0022 (8)
O20.0416 (9)0.0326 (9)0.0604 (11)0.0003 (7)0.0094 (8)0.0029 (8)
O30.0700 (14)0.0896 (17)0.0540 (12)0.0261 (12)0.0246 (10)0.0291 (11)
O40.0363 (11)0.0384 (11)0.184 (3)0.0059 (8)0.0116 (13)0.0212 (14)
O50.0748 (14)0.0554 (12)0.0579 (12)0.0120 (10)0.0317 (11)0.0095 (9)
N10.0391 (11)0.0314 (10)0.0433 (11)0.0023 (8)0.0101 (8)0.0001 (8)
C10.0446 (13)0.0353 (12)0.0431 (13)0.0010 (10)0.0051 (10)0.0007 (10)
C20.0383 (12)0.0323 (12)0.0398 (12)0.0019 (9)0.0055 (9)0.0012 (9)
C30.0353 (11)0.0296 (11)0.0398 (12)0.0002 (9)0.0023 (9)0.0015 (9)
C40.0519 (14)0.0392 (14)0.0515 (15)0.0034 (11)0.0185 (12)0.0043 (11)
C50.0697 (18)0.0346 (14)0.0642 (18)0.0098 (12)0.0213 (14)0.0044 (12)
C60.0638 (16)0.0311 (13)0.0512 (15)0.0051 (11)0.0073 (12)0.0018 (11)
C70.0596 (16)0.0421 (14)0.0422 (13)0.0018 (12)0.0087 (12)0.0033 (11)
C80.126 (3)0.0463 (19)0.074 (2)0.0061 (19)0.044 (2)0.0170 (16)
Geometric parameters (Å, º) top
P1—O21.4915 (18)C1—C71.483 (4)
P1—O11.5011 (17)C2—C31.375 (3)
P1—O41.542 (2)C2—H20.9300
P1—O31.568 (2)C3—C41.386 (3)
O3—H3A0.8200C4—C51.384 (4)
O4—H4A0.8200C4—H40.9300
O5—C71.217 (3)C5—C61.380 (4)
N1—C31.455 (3)C5—H50.9300
N1—H1A0.964C6—H60.9300
N1—H1B0.912C7—C81.488 (4)
N1—H1C0.962C8—H8A0.9600
C1—C61.392 (3)C8—H8B0.9600
C1—C21.400 (3)C8—H8C0.9600
O2—P1—O1114.06 (11)C2—C3—N1119.07 (19)
O2—P1—O4112.13 (12)C4—C3—N1119.7 (2)
O1—P1—O4107.88 (13)C5—C4—C3118.7 (2)
O2—P1—O3110.70 (12)C5—C4—H4120.6
O1—P1—O3104.60 (11)C3—C4—H4120.6
O4—P1—O3106.98 (16)C6—C5—C4121.0 (2)
P1—O3—H3A109.5C6—C5—H5119.5
P1—O4—H4A109.5C4—C5—H5119.5
C3—N1—H1A113.07C5—C6—C1120.0 (2)
C3—N1—H1B109.84C5—C6—H6120.0
H1A—N1—H1B105.86C1—C6—H6120.0
C3—N1—H1C112.50O5—C7—C1119.8 (2)
H1A—N1—H1C107.0O5—C7—C8120.3 (3)
H1B—N1—H1C108.28C1—C7—C8119.9 (3)
C6—C1—C2119.1 (2)C7—C8—H8A109.5
C6—C1—C7123.3 (2)C7—C8—H8B109.5
C2—C1—C7117.6 (2)H8A—C8—H8B109.5
C3—C2—C1119.8 (2)C7—C8—H8C109.5
C3—C2—H2120.1H8A—C8—H8C109.5
C1—C2—H2120.1H8B—C8—H8C109.5
C2—C3—C4121.2 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1C···O20.961.932.878 (3)170
N1—H1A···O1i0.961.762.707 (3)168
N1—H1B···O2ii0.911.852.746 (3)169
O3—H3A···O5iii0.821.862.665 (3)165
O4—H4A···O1iv0.822.052.504 (3)115
Symmetry codes: (i) x, y+1, z+1; (ii) x1, y, z; (iii) x+1, y1/2, z+1/2; (iv) x+1, y, z.

Experimental details

(I)(II)(III)
Crystal data
Chemical formulaC8H10NO+·BrC8H10NO+·NO3C8H10NO+·H2O4P
Mr216.08198.18233.16
Crystal system, space groupTriclinic, P1Orthorhombic, PnmaMonoclinic, P21/c
Temperature (K)295295295
a, b, c (Å)5.0530 (4), 9.4145 (9), 9.5169 (9)16.7754 (4), 6.6044 (2), 8.2683 (2)4.6733 (2), 10.5962 (4), 21.1801 (9)
α, β, γ (°)75.239 (8), 89.253 (9), 75.757 (10)90, 90, 9090, 93.631 (3), 90
V3)423.74 (7)916.06 (4)1046.72 (7)
Z244
Radiation typeMo KαMo KαMo Kα
µ (mm1)4.790.120.26
Crystal size (mm)0.47 × 0.36 × 0.100.31 × 0.26 × 0.130.52 × 0.08 × 0.07
Data collection
DiffractometerOxford Diffraction Xcalibur CCD
diffractometer
Oxford Diffraction Xcalibur CCD
diffractometer
Oxford Diffraction Xcalibur CCD
diffractometer
Absorption correctionAnalytical
(Alcock, 1970)
Analytical
(Alcock, 1970)
Analytical
(Alcock, 1970)
Tmin, Tmax0.155, 0.6310.968, 0.9870.879, 0.986
No. of measured, independent and
observed [I > 2σ(I)] reflections
5468, 1809, 1668 9987, 1086, 824 10065, 2270, 1593
Rint0.0110.0200.028
(sin θ/λ)max1)0.6390.6390.639
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.018, 0.049, 1.12 0.042, 0.129, 1.12 0.047, 0.150, 1.16
No. of reflections180910862270
No. of parameters11485141
H-atom treatmentH atoms treated by a mixture of independent and constrained refinementH-atom parameters constrainedH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.33, 0.400.22, 0.160.48, 0.38

Computer programs: CrysAlis CCD (Oxford Diffraction, 2003), CrysAlis RED (Oxford Diffraction, 2003), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997), WinGX (Farrugia, 1999), PARST97 (Nardelli, 1995), Mercury (Version 1.4; Macrae et al., 2006) and POVRay (Persistence of Vision Team, 2004).

Hydrogen-bond geometry (Å, º) for (I) top
D—H···AD—HH···AD···AD—H···A
N1—H1B···Br10.94 (3)2.45 (3)3.322 (2)156 (2)
N1—H1C···O1i0.86 (3)2.17 (3)2.974 (2)157 (2)
N1—H1A···Br1ii0.94 (3)2.38 (2)3.284 (1)163 (2)
Symmetry codes: (i) x+1, y+1, z+2; (ii) x, y+2, z+1.
Hydrogen-bond geometry (Å, º) for (II) top
D—H···AD—HH···AD···AD—H···A
N2—H2A···O20.892.262.979 (2)137
N2—H2A···O2i0.892.122.979 (2)163
N2—H2B···O2ii0.892.022.857 (2)157
N2—H2C···O2iii0.891.972.857 (2)172
Symmetry codes: (i) x, y+1/2, z; (ii) x+1/2, y, z+1/2; (iii) x+1/2, y+1/2, z+1/2.
Hydrogen-bond geometry (Å, º) for (III) top
D—H···AD—HH···AD···AD—H···A
N1—H1C···O20.961.932.878 (3)170
N1—H1A···O1i0.961.762.707 (3)168
N1—H1B···O2ii0.911.852.746 (3)169
O3—H3A···O5iii0.821.862.665 (3)165
O4—H4A···O1iv0.822.052.504 (3)115
Symmetry codes: (i) x, y+1, z+1; (ii) x1, y, z; (iii) x+1, y1/2, z+1/2; (iv) x+1, y, z.
 

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