Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807036884/rk2028sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807036884/rk2028Isup2.hkl |
CCDC reference: 660336
Single crystals of (I) were obtained by slow evaporation method. A solution of 100 mg 3-aminophenol dissolved in 2 ml of 1-butanol was heated at 343 K. The clear solution was obtained, added to the 1 ml of hydrobromic acid (2 M) and then left at room temperature. The crystals of (I) were collected by vacuum filtration, washed out with cold acetone and dried in air.
All N– and O-bound H atoms were located in difference Fourier map. The positions and isotropic parameters of N-bound H atoms were refined, but O-bound H atom was treated as riding atom. Aromatic H atoms were placed in calculated positions and treated as riding on their parent C atoms, with C–H = 0.93 Å and Uiso(H) = 1.2Ueq(C) for Csp2.
This work is part of our research on intermolecular interactions in hydrogen-bonded ionic crystals, acid salts. The title compound (I), C6H8NO+ Br-, was originally prepared as part of salt screening of the hydroxy- and carboxyanilines.
The molecular structure of (I) is shown in Fig. 1. The asymmetric unit consists of 3-hydroxyanilinium cation with protonated amino-group and bromine anion. All bond lengths and bond angles correspond to the geometry parameters expected for atom types and the type of hybridization (Allen et al., 1987). The ions are connected in three-dimensional hydrogen-bonded network via O–H···Br, N–H···Br, and N–H···O hydrogen bonds. All ammonium group H atoms are involved in the hydrogen bonding with two Br atoms and O-atom of hydroxyl group of neighbouring cation, with three-centred geometry motif observed. Four characteristic graph-set motifs can be recognized: C21(8), C32(6), R42(8) and R64(12) in the notation of Bernstein et al., (1995). Two infinite one-dimensional chains are detected with the donor participations of H31A in C21(8) motif and H31B and H31C in C32(6) graph-set motif. An eight-membered ring moiety [R42(8)] is formed of two hydroxyanilinium cations and two bridging bromine anions through the N31–H31A···Br1···H31B–N31 hydrogen bonds. The centre of 8-membered ring is situated on a crystallographic centre of symmetry. A twelve-membered ring moiety [R64(12)] is formed of four hydroxyanilinium cations and two bridging bromine anions by means of O1–H1···Br1···H31A–N31–H31C···O1 hydrogen bonding. The aggregation of two ring moieties results in infinite one-dimensional chains spreading along the c axis, with intercalated array of bromine ions, Fig. 2. The bromine anions act as acceptor atoms for two different H atoms, one of the ammonium group, and one of the hydroxyl group. Fig. 3 neatly shows two-dimensional packing of ions in ac plane where layers of 3-hydroxyanilinium cations are embedded between ionic layers of bromide anions, forming of alternating hydrocarbon-ionic structure.
For related literature, see: Lemmerer & Billing (2006); Bernstein et al. (1995). For bond length data, see: Allen et al. (1987).
Data collection: CrysAlis CCD (Oxford Diffraction, 2003); cell refinement: CrysAlis RED (Oxford Diffraction, 2003); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999), PARST97 (Nardelli, 1995) and Mercury (Version 1.4; Macrae et al., 2006).
C6H8NO+·Br− | Z = 4 |
Mr = 190.03 | F(000) = 376 |
Monoclinic, P21/n | Dx = 1.707 Mg m−3 |
Hall symbol: -P 2yn | Mo Kα radiation, λ = 0.71073 Å |
a = 7.6661 (14) Å | µ = 5.48 mm−1 |
b = 6.1482 (9) Å | T = 295 K |
c = 15.792 (2) Å | Prism, colourles |
β = 96.437 (13)° | 0.45 × 0.11 × 0.11 mm |
V = 739.6 (2) Å3 |
Oxford Diffraction Xcalibur CCD diffractometer | 1786 independent reflections |
Radiation source: fine-focus sealed tube | 1554 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.037 |
ω scans | θmax = 28.1°, θmin = 4.2° |
Absorption correction: analytical (Alcock, 1970) | h = −10→10 |
Tmin = 0.182, Tmax = 0.605 | k = −8→8 |
7503 measured reflections | l = −20→20 |
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)] = 0.030 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.082 | w = 1/[σ2(Fo2) + (0.0427P)2 + 0.1564P] where P = (Fo2 + 2Fc2)/3 |
S = 0.95 | (Δ/σ)max = 0.004 |
1786 reflections | Δρmax = 0.53 e Å−3 |
95 parameters | Δρmin = −0.56 e Å−3 |
0 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.017 (2) |
C6H8NO+·Br− | V = 739.6 (2) Å3 |
Mr = 190.03 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 7.6661 (14) Å | µ = 5.48 mm−1 |
b = 6.1482 (9) Å | T = 295 K |
c = 15.792 (2) Å | 0.45 × 0.11 × 0.11 mm |
β = 96.437 (13)° |
Oxford Diffraction Xcalibur CCD diffractometer | 1786 independent reflections |
Absorption correction: analytical (Alcock, 1970) | 1554 reflections with I > 2σ(I) |
Tmin = 0.182, Tmax = 0.605 | Rint = 0.037 |
7503 measured reflections |
R[F2 > 2σ(F2)] = 0.030 | 0 restraints |
wR(F2) = 0.082 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.95 | Δρmax = 0.53 e Å−3 |
1786 reflections | Δρmin = −0.56 e Å−3 |
95 parameters |
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 > 2σ(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 | ||
Br1 | 0.80396 (3) | 0.27270 (4) | 1.015679 (15) | 0.04682 (14) | |
O1 | 0.4811 (2) | 0.3603 (3) | 0.87080 (11) | 0.0526 (5) | |
H1 | 0.5343 | 0.3778 | 0.9183 | 0.079* | |
N31 | 0.3571 (4) | 0.7140 (4) | 0.59956 (15) | 0.0446 (5) | |
C1 | 0.5036 (3) | 0.5387 (4) | 0.82171 (15) | 0.0398 (5) | |
C2 | 0.4210 (3) | 0.5363 (4) | 0.73883 (14) | 0.0383 (5) | |
H2 | 0.3531 | 0.4181 | 0.7184 | 0.046* | |
C3 | 0.4423 (3) | 0.7140 (4) | 0.68767 (15) | 0.0366 (5) | |
C4 | 0.5425 (3) | 0.8913 (4) | 0.71549 (16) | 0.0457 (6) | |
H4 | 0.5557 | 1.0086 | 0.6796 | 0.055* | |
C5 | 0.6225 (3) | 0.8901 (4) | 0.79794 (17) | 0.0505 (6) | |
H5 | 0.6907 | 1.0084 | 0.8179 | 0.061* | |
C6 | 0.6033 (4) | 0.7159 (4) | 0.85170 (19) | 0.0473 (6) | |
H6 | 0.6571 | 0.7180 | 0.9075 | 0.057* | |
H31A | 0.331 (4) | 0.581 (6) | 0.5828 (18) | 0.058 (8)* | |
H31B | 0.424 (5) | 0.766 (5) | 0.567 (3) | 0.071 (12)* | |
H31C | 0.260 (6) | 0.787 (6) | 0.599 (2) | 0.073 (12)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Br1 | 0.0570 (2) | 0.04004 (18) | 0.04346 (18) | 0.00182 (10) | 0.00558 (11) | 0.00423 (9) |
O1 | 0.0576 (11) | 0.0510 (11) | 0.0477 (10) | −0.0046 (9) | −0.0012 (8) | 0.0104 (8) |
N31 | 0.0545 (13) | 0.0391 (12) | 0.0397 (11) | 0.0020 (11) | 0.0031 (10) | −0.0012 (9) |
C1 | 0.0372 (11) | 0.0413 (13) | 0.0419 (12) | 0.0029 (9) | 0.0084 (9) | 0.0001 (10) |
C2 | 0.0359 (11) | 0.0339 (12) | 0.0451 (12) | −0.0015 (9) | 0.0050 (9) | −0.0044 (9) |
C3 | 0.0349 (10) | 0.0369 (12) | 0.0385 (12) | 0.0046 (9) | 0.0064 (9) | −0.0043 (9) |
C4 | 0.0486 (13) | 0.0364 (13) | 0.0530 (14) | −0.0040 (10) | 0.0100 (11) | −0.0029 (11) |
C5 | 0.0496 (14) | 0.0406 (14) | 0.0610 (16) | −0.0088 (11) | 0.0053 (12) | −0.0091 (12) |
C6 | 0.0446 (13) | 0.0519 (15) | 0.0443 (14) | −0.0017 (11) | −0.0003 (10) | −0.0084 (11) |
O1—C1 | 1.365 (3) | C2—C3 | 1.379 (3) |
O1—H1 | 0.8200 | C2—H2 | 0.9300 |
N31—C3 | 1.470 (3) | C3—C4 | 1.377 (3) |
N31—H31A | 0.88 (3) | C4—C5 | 1.376 (4) |
N31—H31B | 0.83 (4) | C4—H4 | 0.9300 |
N31—H31C | 0.87 (4) | C5—C6 | 1.385 (4) |
C1—C6 | 1.384 (3) | C5—H5 | 0.9300 |
C1—C2 | 1.389 (3) | C6—H6 | 0.9300 |
C1—O1—H1 | 109.5 | C4—C3—C2 | 122.6 (2) |
C3—N31—H31A | 110.4 (18) | C4—C3—N31 | 118.4 (2) |
C3—N31—H31B | 110 (3) | C2—C3—N31 | 119.0 (2) |
H31A—N31—H31B | 108 (3) | C5—C4—C3 | 118.1 (2) |
C3—N31—H31C | 107 (2) | C5—C4—H4 | 120.9 |
H31A—N31—H31C | 109 (3) | C3—C4—H4 | 120.9 |
H31B—N31—H31C | 113 (3) | C4—C5—C6 | 121.2 (2) |
O1—C1—C6 | 122.6 (2) | C4—C5—H5 | 119.4 |
O1—C1—C2 | 117.0 (2) | C6—C5—H5 | 119.4 |
C6—C1—C2 | 120.5 (2) | C1—C6—C5 | 119.5 (2) |
C3—C2—C1 | 118.2 (2) | C1—C6—H6 | 120.3 |
C3—C2—H2 | 120.9 | C5—C6—H6 | 120.3 |
C1—C2—H2 | 120.9 |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···Br1 | 0.82 | 2.52 | 3.222 (2) | 145 |
N31—H31A···Br1i | 0.88 (4) | 2.42 (4) | 3.279 (3) | 168 (3) |
N31—H31B···Br1ii | 0.84 (4) | 2.57 (5) | 3.355 (3) | 156 (4) |
N31—H31C···O1iii | 0.87 (4) | 2.01 (5) | 2.833 (4) | 158 (4) |
Symmetry codes: (i) x−1/2, −y+1/2, z−1/2; (ii) −x+3/2, y+1/2, −z+3/2; (iii) −x+1/2, y+1/2, −z+3/2. |
Experimental details
Crystal data | |
Chemical formula | C6H8NO+·Br− |
Mr | 190.03 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 295 |
a, b, c (Å) | 7.6661 (14), 6.1482 (9), 15.792 (2) |
β (°) | 96.437 (13) |
V (Å3) | 739.6 (2) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 5.48 |
Crystal size (mm) | 0.45 × 0.11 × 0.11 |
Data collection | |
Diffractometer | Oxford Diffraction Xcalibur CCD |
Absorption correction | Analytical (Alcock, 1970) |
Tmin, Tmax | 0.182, 0.605 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7503, 1786, 1554 |
Rint | 0.037 |
(sin θ/λ)max (Å−1) | 0.662 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.030, 0.082, 0.95 |
No. of reflections | 1786 |
No. of parameters | 95 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.53, −0.56 |
Computer programs: CrysAlis CCD (Oxford Diffraction, 2003), CrysAlis RED (Oxford Diffraction, 2003), CrysAlis RED, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 (Farrugia, 1997), WinGX (Farrugia, 1999), PARST97 (Nardelli, 1995) and Mercury (Version 1.4; Macrae et al., 2006).
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···Br1 | 0.820 | 2.518 | 3.222 (2) | 145 |
N31—H31A···Br1i | 0.88 (4) | 2.42 (4) | 3.279 (3) | 168 (3) |
N31—H31B···Br1ii | 0.84 (4) | 2.57 (5) | 3.355 (3) | 156 (4) |
N31—H31C···O1iii | 0.87 (4) | 2.01 (5) | 2.833 (4) | 158 (4) |
Symmetry codes: (i) x−1/2, −y+1/2, z−1/2; (ii) −x+3/2, y+1/2, −z+3/2; (iii) −x+1/2, y+1/2, −z+3/2. |
This work is part of our research on intermolecular interactions in hydrogen-bonded ionic crystals, acid salts. The title compound (I), C6H8NO+ Br-, was originally prepared as part of salt screening of the hydroxy- and carboxyanilines.
The molecular structure of (I) is shown in Fig. 1. The asymmetric unit consists of 3-hydroxyanilinium cation with protonated amino-group and bromine anion. All bond lengths and bond angles correspond to the geometry parameters expected for atom types and the type of hybridization (Allen et al., 1987). The ions are connected in three-dimensional hydrogen-bonded network via O–H···Br, N–H···Br, and N–H···O hydrogen bonds. All ammonium group H atoms are involved in the hydrogen bonding with two Br atoms and O-atom of hydroxyl group of neighbouring cation, with three-centred geometry motif observed. Four characteristic graph-set motifs can be recognized: C21(8), C32(6), R42(8) and R64(12) in the notation of Bernstein et al., (1995). Two infinite one-dimensional chains are detected with the donor participations of H31A in C21(8) motif and H31B and H31C in C32(6) graph-set motif. An eight-membered ring moiety [R42(8)] is formed of two hydroxyanilinium cations and two bridging bromine anions through the N31–H31A···Br1···H31B–N31 hydrogen bonds. The centre of 8-membered ring is situated on a crystallographic centre of symmetry. A twelve-membered ring moiety [R64(12)] is formed of four hydroxyanilinium cations and two bridging bromine anions by means of O1–H1···Br1···H31A–N31–H31C···O1 hydrogen bonding. The aggregation of two ring moieties results in infinite one-dimensional chains spreading along the c axis, with intercalated array of bromine ions, Fig. 2. The bromine anions act as acceptor atoms for two different H atoms, one of the ammonium group, and one of the hydroxyl group. Fig. 3 neatly shows two-dimensional packing of ions in ac plane where layers of 3-hydroxyanilinium cations are embedded between ionic layers of bromide anions, forming of alternating hydrocarbon-ionic structure.