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In the title compounds, C7H8NO2+·Br, (I), and C7H8NO2+·I, (II), the asymmetric unit contains a discrete 3-carboxy­anilinium cation, with a protonated amine group, and a halide anion. The compounds are not isostructural, and the crystal structures of (I) and (II) are characterized by different two-dimensional hydrogen-bonded networks. The ions in (I) are connected into ladder-like ribbons via N—H...Br hydrogen bonds, while classic cyclic O—H...O hydrogen bonds between adjacent carboxylic acid functions link adjacent ribbons to give three characteristic graph-set motifs, viz. C21(4), R42(8) and R22(8). The ions in (II) are connected via N—H...I, N—H...O and O—H...I hydrogen bonds, also with three characteristic graph-set motifs, viz. C(7), C21(4) and R42(18), but an O—H...O inter­action is not present.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270108001078/ln3083sup1.cif
Contains datablocks I, II, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270108001078/ln3083Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270108001078/ln3083IIsup3.hkl
Contains datablock II

CCDC references: 681569; 681570

Comment top

Predictable and reliable noncovalent interactions play a major role in the formation of supramolecular systems. In the area of supramolecular research and crystal engineering, most common supramolecular synthons are based on hydrogen bonds, ππ interactions, van der Waals forces and, most recently, halogen bonds (Desiraju, 1989; Metrangolo & Resnati, 2001; Cinčić et al., 2008). This paper reports a part of our research on intermolecular interactions in hydrogen-bonded ionic crystals of acid salts (Cinčić & Kaitner, 2007a,b). The title compounds were originally [appears to be a word missing here; studied? reported?] during salt screening of the hydroxy- and carboxyanilines. 3-Aminobenzoic acid is a less studied isomer than 2– and 4–aminobenzoic acids. 2-Aminobenzoic (anthranilic) acid is known as vitamin L and as trimorphic material it has been widely studied (Boone et al., 1977; Brown & Ehrenberg, 1985; Takazawa et al., 1986). 4-Aminobenzoic acid is widely known as bacterial vitamin H and as one of the components of vitamin B complex.

In the structures of the title bromide, (I), and iodide, (II), salts, the bond lengths and bond angles correspond to those expected for the atom types and the type of hybridization (Allen et al., 1987). The asymmetric unit in both (I) and (II) contains a discrete 3-carboxyanilinium cation with a protonated amine group and a halide anion (Figs. 1 and 2). Compound (I) is isostructural with the analogous chloride salt (Arora et al., 1973), although the earlier work assigned the unit-cell dimensions in a different sequence (c, b, a relative to the currently used unit cell). Because of the difference in anionic radii, the volume of the unit cell in (I) is about 15.6 Å3 larger than that of the chloride salt. Compound (II) is not isostructural with the chloride and bromide salts. This may be a consequence of the packing inefficiency caused by the large iodide ion and results in a different crystal packing and hydrogen-bonding arrangement, as described below.

In (I), the ions are connected into a two-dimensional hydrogen-bonded network parallel to the (100) plane via O—H···O and N—H···Br hydrogen bonds (Table 1). All ammonium group H atoms are involved in hydrogen bonds with three different Br- ions and each anion accepts hydrogen bonds from three different cations. Two of these interactions link the anions and cations in an alternating fashion into extended chains along the [010] direction, which can be described by a graph-set motif of C21(4) (Bernstein et al., 1995). The third interaction is a cross-link from an adjacent chain, which serves to complete a ladder-like ribbon composed of two chains as the ladder uprights, while each rung is formed by an ammonium group and a Br- ion, with the directionality of the rung alternating along the ladder (Fig. 3). The remainder of each cation extends out from the rung on each side of the ladder. The centrosymmetric hydrogen-bonded rings formed by adjacent rungs of the ladder can be described by the graph-set motif of R42(8). There are actually two different symmetry-independent eight-membered rings of this type in the ladder, because adjacent rings are not related by a single unit cell translation. At the same time, the carboxylic acid group at the opposite end of the carboxyanilinium cation forms a centrosymmetric hydrogen-bonded dimer with its counterpart in a cation from an adjacent ribbon (Fig. 3). These interactions lead to a graph-set motif of R22(8), which is a characteristic feature found in most salts of 3- and 4-aminobenzoic acid (Cambridge Structural Database; Allen, 2002). The very similar covalent bond distances found between the carboxylic acid O atoms and the C atom indicate that the acidic H atom is disordered across both O atoms, so that the hydrogen-bonded dimer is disordered. The disordered H atom occupies the sites on atoms O1A and O1B almost equally. The cross-linking of the ribbons by the carboxylic acid interactions results in a two-dimensional hydrogen-bonded sheet-like structure overall (Fig. 3). Adjacent sheets are stacked in the [100] direction to give a three-dimensional framework, where the inter-planar distance between the aromatic rings of each sheet is ca 3.36 Å and a weak inter-layer C—H···Br [C4···Br1(-x, -y + 2, -z + 2) = 3.664 (4) Å] interaction is present. The inter-planar distance between aromatic rings of each sheet in the isostructural chloride salt is, as expected, smaller at ca 3.04 Å.

The supramolecular structure of (II) differs markedly from that of (I). The ions are connected into a two-dimensional hydrogen-bonded network, this time parallel to the (010) plane, via O—H···I, N—H···I and N—H···O hydrogen bonds. Unexpectedly, there are no centrosymmetric hydrogen-bonded dimers between the carboxylic acid groups of adjacent 3-carboxyanilinium cations. The carbonyl O atom participates in hydrogen bonding with another neighbouring cation through an N—H···O hydrogen bond. This interaction links the glide-plane-related cations into zigzag chains, which run parallel to the [100] direction and which can be described by a graph-set motif of C(7) (Fig. 4). The carboxylic acid H atom participates in hydrogen bonding with a neighbouring anion through an O—H···I hydrogen bond. As in (I), all ammonium group H atoms are involved in hydrogen bonds, but this time with two different I- ions and with the carbonyl O atom of a neighbouring cation, while each anion accepts three hydrogen bonds. The two ammonium-anion interactions link the anions and cations in an alternating fashion into extended chains along the [001] direction, which, as in (I), can be described by a graph-set motif of C21(4). However, the cross-linking of adjacent chains into a ladder-like ribbon involving just the ammonium groups and anions is not present. Instead, the O—H···I interaction forms the link between adjacent chains to give a different type of ladder with much longer rungs than in (I) and the cations do not protrude outside the ladder uprights (Fig. 5); instead the cation itself forms the rung. The centrosymmetric hydrogen-bonded rings formed by adjacent rungs of the ladder can be described by the graph-set motif of R42(18) and, again, there are two symmetry-independent adjacent eighteen-membered rings of this type in the ladder. The aggregation of ring and chain motifs in (II) also leads to a two-dimensional hydrogen-bonded sheet-like structure. The distance between planes calculated through the I anions of each sheet is ca 2.75 Å.

Fig. 6 clearly compares the packing arrangement of both compounds in which layers of 3-carboxyanilinium cations 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 either crystal structure. The shortest centroid-to-centroid distances in (I) and (II) are ca 4.55 and 4.24 Å, respectively.

Related literature top

For related literature, see: Allen (2002); Allen et al. (1987); Arora et al. (1973); Bernstein et al. (1995); Boone et al. (1977); Brown & Ehrenberg (1985); Cinčić & Kaitner (2007a, 2007b); Cinčić et al. (2008); Desiraju (1989); Metrangolo & Resnati (2001); Takazawa et al. (1986).

Experimental top

For the preparation of (I), 3-aminobenzoic acid (100 mg, 0,73 mmol) was dissolved in hot ethanol (2 ml). The clear solution was added to hydrobromic acid (1 ml, 2 M) and then cooled to room temperature. Colourless crystals of (I) were grown by slow evaporation. For the preparation of (II), 3-aminobenzoic acid (100 mg, 0,73 mmol) was dissolved in hot acetone (2 ml). The clear solution was added to hydroiodic acid (2 ml, 2 M) and then cooled to room temperature. Colourless crystals of (II) were grown by slow evaporation. The crystals of (I) and (II) were collected by vacuum filtration, washed with cold acetone and dried in air. In a nitrogen atmosphere, (I) and (II) melt at 558 and 544 K, respectively.

Refinement top

For both compounds, all N– and O-bound H atoms were located in difference Fourier maps, and for (I) their positions were then held fixed. For (II), the positions of the N-bound H atoms were refined, but the O-bound H atom was fixed in its as-found position. The isotropic displacement parameters were refined for these atoms. 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 (II), the largest peak of residual electron density is 1.10 Å from atom H5.

Computing details top

For both 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 (Macrae et al., 2006) and POVRay (Persistence of Vision Pty, 2004).

Figures top
[Figure 1] Fig. 1. The asymmetric unit of (I), 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. The minor disordered H atom of the carboxylic acid group has been omitted.
[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.
[Figure 3] Fig. 3. A view of the two-dimensional hydrogen-bonded network parallel to the (100) plane of (I), showing the aggregation of three hydrogen-bonding motifs, C21(4), R22(8) and R42(8). Hydrogen bonds are drawn as dotted lines and C-bound H atoms have been omitted. Atoms marked with an ampersand (&), at sign (@), hash (#), dollar sign ($), asterisk (*) and percent sign (%) are at the symmetry positions (-x + 1, -y + 1, -z + 2), (x, y - 1, z), (-x + 1, -y, -z + 1), (x, y, z - 1), (-x + 1, -y + 1, -z + 1) and (x, y - 1, z - 1), respectively.
[Figure 4] Fig. 4. A view of part of the crystal structure of (II), showing the formation of two chain motifs spreading parallel to [100] and [001]. Hydrogen bonds are drawn as dotted lines and C-bound H atoms have been omitted. Atoms marked with the suffixes a, b and c are at the symmetry positions (x + 1/2, -y + 1, -z + 3/2), (x - 1/2, -y + 1, -z + 5/2) and (-x + 1/2, y, z + 1/2), respectively.
[Figure 5] Fig. 5. A view of the one-dimensional hydrogen-bonded ladder parallel to [001], showing the aggregation of R42(18) hydrogen-bonding motifs. Hydrogen bonds are drawn as dotted lines and C-bound H atoms have been omitted. Atoms marked with the suffix d are at the symmetry position (-x + 1, -y + 1, -z + 1).
[Figure 6] Fig. 6. Packing diagrams of (I) and (II) viewed along the b and a axes, respectively. The anions are shown as spheres.
(I) 3-carboxyanilinium bromide top
Crystal data top
C7H8NO2+·BrZ = 2
Mr = 218.05F(000) = 216
Triclinic, P1Dx = 1.810 Mg m3
Hall symbol: -P 1Melting point: 558 K
a = 4.5536 (4) ÅMo Kα radiation, λ = 0.71073 Å
b = 6.0010 (7) ÅCell parameters from 3140 reflections
c = 15.011 (2) Åθ = 4–35°
α = 99.025 (11)°µ = 5.08 mm1
β = 90.581 (11)°T = 295 K
γ = 98.832 (11)°Prism, colourless
V = 400.05 (8) Å30.46 × 0.17 × 0.05 mm
Data collection top
Oxford Diffraction Xcalibur CCD
diffractometer
1735 independent reflections
Radiation source: fine-focus sealed tube1503 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.014
ω scanθmax = 27.0°, θmin = 3.9°
Absorption correction: analytical
(Alcock, 1970)
h = 55
Tmin = 0.276, Tmax = 0.760k = 77
5296 measured reflectionsl = 1919
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.029Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.077H-atom parameters constrained
S = 1.20 w = 1/[σ2(Fo2) + (0.0165P)2 + 0.9328P]
where P = (Fo2 + 2Fc2)/3
1735 reflections(Δ/σ)max = 0.002
104 parametersΔρmax = 0.68 e Å3
0 restraintsΔρmin = 0.49 e Å3
Crystal data top
C7H8NO2+·Brγ = 98.832 (11)°
Mr = 218.05V = 400.05 (8) Å3
Triclinic, P1Z = 2
a = 4.5536 (4) ÅMo Kα radiation
b = 6.0010 (7) ŵ = 5.08 mm1
c = 15.011 (2) ÅT = 295 K
α = 99.025 (11)°0.46 × 0.17 × 0.05 mm
β = 90.581 (11)°
Data collection top
Oxford Diffraction Xcalibur CCD
diffractometer
1735 independent reflections
Absorption correction: analytical
(Alcock, 1970)
1503 reflections with I > 2σ(I)
Tmin = 0.276, Tmax = 0.760Rint = 0.014
5296 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0290 restraints
wR(F2) = 0.077H-atom parameters constrained
S = 1.20Δρmax = 0.68 e Å3
1735 reflectionsΔρmin = 0.49 e Å3
104 parameters
Special details top

Experimental. Thermal analyses (differential scanning calorimetry) of the purified salts were performed using the Mettler Toledo DSC823 Module and the STARe Software 9.01 package (Mettler Toledo AG, Schwerzenbach, Switzerland).

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)
Br10.12418 (9)0.77886 (6)1.07436 (3)0.04053 (13)
O1A0.2840 (8)0.2205 (6)0.51267 (19)0.0588 (9)
O1B0.6084 (7)0.1283 (5)0.60746 (19)0.0545 (8)
N310.5617 (8)0.6748 (5)0.90013 (19)0.0380 (7)
C10.3591 (8)0.4405 (6)0.6583 (2)0.0340 (7)
C20.4849 (8)0.4637 (6)0.7456 (2)0.0328 (7)
H20.60290.36060.76050.039*
C30.4284 (8)0.6432 (6)0.8085 (2)0.0306 (7)
C40.2583 (8)0.8012 (6)0.7883 (2)0.0371 (8)
H40.22730.92270.83200.044*
C50.1342 (9)0.7761 (7)0.7021 (3)0.0429 (9)
H50.01770.88060.68750.052*
C60.1834 (9)0.5955 (7)0.6375 (2)0.0406 (8)
H60.09810.57810.57970.049*
C70.4220 (9)0.2499 (6)0.5888 (2)0.0378 (8)
H1A0.32910.10790.47630.057*0.54 (7)
H1B0.65000.03550.56360.057*0.46 (7)
H31A0.67090.56150.90540.063 (14)*
H31B0.41740.65370.94210.052 (13)*
H31C0.68280.81340.91060.053 (13)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Br10.0493 (2)0.0331 (2)0.0391 (2)0.01758 (15)0.00294 (15)0.00504 (14)
O1A0.076 (2)0.0614 (19)0.0352 (15)0.0262 (17)0.0108 (14)0.0178 (14)
O1B0.072 (2)0.0511 (17)0.0390 (15)0.0270 (16)0.0034 (14)0.0127 (13)
N310.0539 (19)0.0350 (16)0.0255 (14)0.0162 (15)0.0017 (13)0.0029 (12)
C10.0398 (19)0.0319 (17)0.0277 (16)0.0042 (15)0.0039 (14)0.0027 (13)
C20.0406 (19)0.0275 (16)0.0300 (17)0.0092 (14)0.0005 (14)0.0007 (13)
C30.0337 (17)0.0322 (17)0.0244 (15)0.0056 (14)0.0040 (13)0.0006 (13)
C40.038 (2)0.0341 (18)0.0379 (19)0.0105 (15)0.0065 (15)0.0021 (15)
C50.046 (2)0.040 (2)0.046 (2)0.0166 (17)0.0026 (17)0.0053 (17)
C60.047 (2)0.043 (2)0.0313 (18)0.0079 (17)0.0048 (15)0.0023 (15)
C70.042 (2)0.0383 (19)0.0296 (17)0.0052 (16)0.0006 (15)0.0047 (15)
Geometric parameters (Å, º) top
O1A—C71.273 (4)C1—C71.487 (5)
O1A—H1A0.851C2—C31.374 (4)
O1B—C71.257 (5)C2—H20.9300
O1B—H1B0.836C3—C41.379 (5)
N31—C31.471 (4)C4—C51.384 (5)
N31—H31A0.914C4—H40.9300
N31—H31B0.923C5—C61.384 (5)
N31—H31C0.915C5—H50.9300
C1—C61.385 (5)C6—H60.9300
C1—C21.402 (5)
C7—O1A—H1A112.6C2—C3—N31119.3 (3)
C7—O1B—H1B114.2C4—C3—N31118.1 (3)
C3—N31—H31A110.4C3—C4—C5119.0 (3)
C3—N31—H31B111.1C3—C4—H4120.5
H31A—N31—H31B102.6C5—C4—H4120.5
C3—N31—H31C108.3C4—C5—C6120.0 (3)
H31A—N31—H31C109.5C4—C5—H5120.0
H31B—N31—H31C114.9C6—C5—H5120.0
C6—C1—C2120.2 (3)C5—C6—C1120.3 (3)
C6—C1—C7120.9 (3)C5—C6—H6119.8
C2—C1—C7118.9 (3)C1—C6—H6119.8
C3—C2—C1118.0 (3)O1B—C7—O1A123.5 (3)
C3—C2—H2121.0O1B—C7—C1119.0 (3)
C1—C2—H2121.0O1A—C7—C1117.5 (3)
C2—C3—C4122.5 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N31—H31B···Br10.922.493.342 (3)154
N31—H31A···Br1i0.912.433.334 (4)169
N31—H31C···Br1ii0.922.443.332 (3)163
O1A—H1A···O1Biii0.851.802.650 (4)174
O1B—H1B···O1Aiii0.841.832.650 (4)165
Symmetry codes: (i) x+1, y+1, z+2; (ii) x+1, y+2, z+2; (iii) x+1, y, z+1.
(II) 3-carboxyanilinium iodide top
Crystal data top
C7H8NO2+·IDx = 1.969 Mg m3
Mr = 265.04Melting point: 544 K
Orthorhombic, PccnMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ab 2acCell parameters from 6208 reflections
a = 11.1815 (6) Åθ = 4–35°
b = 23.1582 (8) ŵ = 3.53 mm1
c = 6.9066 (4) ÅT = 295 K
V = 1788.42 (15) Å3Prism, colourless
Z = 80.53 × 0.11 × 0.04 mm
F(000) = 1008
Data collection top
Oxford Diffraction Xcalibur CCD
diffractometer
1944 independent reflections
Radiation source: fine-focus sealed tube1544 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.028
ω scanθmax = 27.0°, θmin = 3.9°
Absorption correction: analytical
(Alcock, 1970)
h = 1414
Tmin = 0.387, Tmax = 0.923k = 2929
17853 measured reflectionsl = 88
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)] = 0.030H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.078 w = 1/[σ2(Fo2) + (0.0322P)2 + 2.7111P]
where P = (Fo2 + 2Fc2)/3
S = 1.25(Δ/σ)max = 0.005
1944 reflectionsΔρmax = 1.34 e Å3
114 parametersΔρmin = 0.73 e Å3
0 restraintsExtinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0044 (3)
Crystal data top
C7H8NO2+·IV = 1788.42 (15) Å3
Mr = 265.04Z = 8
Orthorhombic, PccnMo Kα radiation
a = 11.1815 (6) ŵ = 3.53 mm1
b = 23.1582 (8) ÅT = 295 K
c = 6.9066 (4) Å0.53 × 0.11 × 0.04 mm
Data collection top
Oxford Diffraction Xcalibur CCD
diffractometer
1944 independent reflections
Absorption correction: analytical
(Alcock, 1970)
1544 reflections with I > 2σ(I)
Tmin = 0.387, Tmax = 0.923Rint = 0.028
17853 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0300 restraints
wR(F2) = 0.078H atoms treated by a mixture of independent and constrained refinement
S = 1.25Δρmax = 1.34 e Å3
1944 reflectionsΔρmin = 0.73 e Å3
114 parameters
Special details top

Experimental. Thermal analyses (differential scanning calorimetry) of the purified salts were performed using the Mettler Toledo DSC823 Module and the STARe Software 9.01 package (Mettler Toledo AG, Schwerzenbach, Switzerland).

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
I10.40802 (2)0.690576 (10)0.81691 (4)0.04177 (13)
O1A0.4286 (3)0.54631 (14)0.7787 (7)0.0744 (12)
O1B0.2314 (3)0.54127 (13)0.7827 (6)0.0659 (10)
N310.5934 (3)0.35032 (16)0.6822 (6)0.0391 (7)
C10.3445 (3)0.45514 (16)0.7357 (6)0.0379 (8)
C20.4586 (3)0.43255 (16)0.7217 (5)0.0384 (8)
H20.52520.45650.73060.046*
C30.4722 (3)0.37411 (15)0.6943 (5)0.0347 (8)
C40.3756 (4)0.33741 (17)0.6809 (6)0.0457 (9)
H40.38680.29790.66390.055*
C50.2618 (4)0.36028 (18)0.6930 (6)0.0488 (10)
H50.19560.33620.68200.059*
C60.2459 (4)0.41898 (18)0.7216 (6)0.0471 (9)
H60.16910.43420.73150.056*
C70.3273 (4)0.51818 (17)0.7669 (7)0.0463 (9)
H1A0.42500.58510.78410.11 (2)*
H31A0.615 (6)0.331 (3)0.775 (11)0.09 (2)*
H31B0.637 (5)0.381 (2)0.684 (6)0.054 (14)*
H31C0.601 (5)0.327 (3)0.574 (10)0.081 (19)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
I10.04611 (19)0.03067 (16)0.04853 (19)0.00100 (9)0.00021 (11)0.00138 (10)
O1A0.0431 (18)0.0313 (16)0.149 (4)0.0016 (13)0.002 (2)0.014 (2)
O1B0.0375 (16)0.0435 (16)0.117 (3)0.0118 (13)0.0031 (18)0.0095 (18)
N310.0333 (16)0.0300 (16)0.054 (2)0.0058 (13)0.0003 (15)0.0030 (15)
C10.0310 (18)0.0375 (18)0.045 (2)0.0013 (15)0.0026 (16)0.0011 (15)
C20.0324 (17)0.0356 (18)0.047 (2)0.0009 (15)0.0000 (16)0.0002 (15)
C30.0326 (18)0.0298 (16)0.042 (2)0.0021 (14)0.0016 (15)0.0002 (14)
C40.047 (2)0.0324 (18)0.058 (3)0.0038 (16)0.0025 (18)0.0032 (17)
C50.0353 (19)0.042 (2)0.069 (3)0.0100 (17)0.0015 (19)0.0025 (19)
C60.0305 (18)0.055 (2)0.056 (2)0.0024 (17)0.0007 (17)0.0007 (19)
C70.039 (2)0.0376 (19)0.062 (3)0.0020 (16)0.0008 (19)0.0002 (17)
Geometric parameters (Å, º) top
O1A—C71.309 (5)C1—C71.488 (5)
O1A—H1A0.900C2—C31.375 (5)
O1B—C71.202 (5)C2—H20.9300
N31—C31.465 (5)C3—C41.378 (5)
N31—H31A0.82 (8)C4—C51.380 (6)
N31—H31B0.86 (6)C4—H40.9300
N31—H31C0.93 (7)C5—C61.385 (6)
C1—C21.383 (5)C5—H50.9300
C1—C61.388 (6)C6—H60.9300
C7—O1A—H1A117.4C2—C3—N31118.7 (3)
C3—N31—H31A116 (5)C4—C3—N31119.3 (3)
C3—N31—H31B103 (3)C3—C4—C5118.8 (4)
H31A—N31—H31B105 (6)C3—C4—H4120.6
C3—N31—H31C111 (3)C5—C4—H4120.6
H31A—N31—H31C107 (7)C4—C5—C6120.3 (4)
H31B—N31—H31C116 (5)C4—C5—H5119.9
C2—C1—C6120.0 (4)C6—C5—H5119.9
C2—C1—C7120.0 (3)C5—C6—C1120.0 (4)
C6—C1—C7119.9 (3)C5—C6—H6120.0
C3—C2—C1118.9 (4)C1—C6—H6120.0
C3—C2—H2120.5O1B—C7—O1A123.0 (4)
C1—C2—H2120.5O1B—C7—C1124.4 (4)
C2—C3—C4122.0 (4)O1A—C7—C1112.6 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1A—H1A···I10.902.463.359 (3)176
N31—H31A···I1i0.82 (7)2.87 (7)3.587 (4)147 (6)
N31—H31B···O1Bii0.86 (6)2.10 (6)2.957 (5)173 (5)
N31—H31C···I1iii0.93 (7)2.73 (7)3.575 (4)151 (6)
Symmetry codes: (i) x+1, y+1, z+2; (ii) x+1/2, y+1, z+3/2; (iii) x+1, y+1, z+1.

Experimental details

(I)(II)
Crystal data
Chemical formulaC7H8NO2+·BrC7H8NO2+·I
Mr218.05265.04
Crystal system, space groupTriclinic, P1Orthorhombic, Pccn
Temperature (K)295295
a, b, c (Å)4.5536 (4), 6.0010 (7), 15.011 (2)11.1815 (6), 23.1582 (8), 6.9066 (4)
α, β, γ (°)99.025 (11), 90.581 (11), 98.832 (11)90, 90, 90
V3)400.05 (8)1788.42 (15)
Z28
Radiation typeMo KαMo Kα
µ (mm1)5.083.53
Crystal size (mm)0.46 × 0.17 × 0.050.53 × 0.11 × 0.04
Data collection
DiffractometerOxford Diffraction Xcalibur CCD
diffractometer
Oxford Diffraction Xcalibur CCD
diffractometer
Absorption correctionAnalytical
(Alcock, 1970)
Analytical
(Alcock, 1970)
Tmin, Tmax0.276, 0.7600.387, 0.923
No. of measured, independent and
observed [I > 2σ(I)] reflections
5296, 1735, 1503 17853, 1944, 1544
Rint0.0140.028
(sin θ/λ)max1)0.6390.639
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.029, 0.077, 1.20 0.030, 0.078, 1.25
No. of reflections17351944
No. of parameters104114
H-atom treatmentH-atom parameters constrainedH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.68, 0.491.34, 0.73

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 (Macrae et al., 2006) and POVRay (Persistence of Vision Pty, 2004).

Hydrogen-bond geometry (Å, º) for (I) top
D—H···AD—HH···AD···AD—H···A
N31—H31B···Br10.922.493.342 (3)154
N31—H31A···Br1i0.912.433.334 (4)169
N31—H31C···Br1ii0.922.443.332 (3)163
O1A—H1A···O1Biii0.851.802.650 (4)174
O1B—H1B···O1Aiii0.841.832.650 (4)165
Symmetry codes: (i) x+1, y+1, z+2; (ii) x+1, y+2, z+2; (iii) x+1, y, z+1.
Hydrogen-bond geometry (Å, º) for (II) top
D—H···AD—HH···AD···AD—H···A
O1A—H1A···I10.902.463.359 (3)176
N31—H31A···I1i0.82 (7)2.87 (7)3.587 (4)147 (6)
N31—H31B···O1Bii0.86 (6)2.10 (6)2.957 (5)173 (5)
N31—H31C···I1iii0.93 (7)2.73 (7)3.575 (4)151 (6)
Symmetry codes: (i) x+1, y+1, z+2; (ii) x+1/2, y+1, z+3/2; (iii) x+1, y+1, z+1.
 

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