Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270102004882/bm1494sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270102004882/bm1494Isup2.hkl |
CCDC reference: 187933
4-Bromo-N,N-dimethylaniline (2.14 g, 7.62 mmol) was dissolved in ethanol (10 ml) and 48% hydrobromic acid (1.22 ml) was added slowly with stirring. Further ethanol (10 ml) was added and the solution stirred for 2 h. The solution was then evaporated to dryness and the residue taken up in the minimum of ethanol. Addition of diethyl ether (30 ml) precipitated the product as a white solid, which was filtered off, washed with diethyl ether and dried in vacuo. Analysis, found: C 34.22, H 3.96, N 4.75%; calculated: C 34.20, H 3.95, N 4.98%. Single crystals of (I) were obtained from ethanol-diethyl ether.
The following faces (with distances from a common point in mm) were indexed and used for a numerical absorption correction: 110 0.087, 110 0.070, 001 0.212, 001 0.178, 110 0.063 and 110 0.080. H atoms were visible in difference syntheses. The H atom bonded to N was refined freely. Methyl groups were idealized and refined as rigid groups allowed to rotate but not tip. Other H atoms were included using a riding model starting from calculated positions. Aromatic C—H distances were fixed to 0.95 Å and methyl C—H to 0.98 Å, and Uiso(H) was set to 1.2Ueq of the parent atom.
Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP (Siemens, 1994); software used to prepare material for publication: SHELXL97.
C8H11BrN+·Br− | F(000) = 544 |
Mr = 281.00 | Dx = 1.922 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 9.9511 (12) Å | Cell parameters from 11315 reflections |
b = 7.6156 (10) Å | θ = 2–28° |
c = 13.5616 (16) Å | µ = 8.29 mm−1 |
β = 109.104 (3)° | T = 143 K |
V = 971.1 (2) Å3 | Square prism, colourless |
Z = 4 | 0.40 × 0.16 × 0.13 mm |
Bruker SMART1000 CCD area-detector diffractometer | 2837 independent reflections |
Radiation source: fine-focus sealed tube | 2457 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.059 |
Detector resolution: 8.192 pixels mm-1 | θmax = 30.0°, θmin = 2.2° |
ω and ϕ scans | h = −14→14 |
Absorption correction: numerical (XPREP; Siemens, 1994) | k = −10→10 |
Tmin = 0.113, Tmax = 0.379 | l = −19→19 |
20417 measured reflections |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.018 | Hydrogen site location: difference Fourier map |
wR(F2) = 0.043 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.04 | w = 1/[σ2(Fo2) + (0.0195P)2 + 0.1484P] where P = (Fo2 + 2Fc2)/3 |
2837 reflections | (Δ/σ)max = 0.002 |
106 parameters | Δρmax = 0.42 e Å−3 |
0 restraints | Δρmin = −0.57 e Å−3 |
C8H11BrN+·Br− | V = 971.1 (2) Å3 |
Mr = 281.00 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 9.9511 (12) Å | µ = 8.29 mm−1 |
b = 7.6156 (10) Å | T = 143 K |
c = 13.5616 (16) Å | 0.40 × 0.16 × 0.13 mm |
β = 109.104 (3)° |
Bruker SMART1000 CCD area-detector diffractometer | 2837 independent reflections |
Absorption correction: numerical (XPREP; Siemens, 1994) | 2457 reflections with I > 2σ(I) |
Tmin = 0.113, Tmax = 0.379 | Rint = 0.059 |
20417 measured reflections |
R[F2 > 2σ(F2)] = 0.018 | 0 restraints |
wR(F2) = 0.043 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.04 | Δρmax = 0.42 e Å−3 |
2837 reflections | Δρmin = −0.57 e Å−3 |
106 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. Non-bonded distances: 3.6331 (0.0004) Br1 - Br2_$5 169.54 (0.04) C4 - Br1 - Br2_$5 $5 - x + 1, -y + 1/2, -z + 1/2 Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane) 0.4334 (0.0032) x - 7.0081 (0.0020) y + 4.7909 (0.0058) z = 0.6644 (0.0031) * 0.0089 (0.0013) C1 * 0.0318 (0.0011) C2 * 0.0426 (0.0011) C3 * 0.0299 (0.0012) C4 * 0.0424 (0.0011) C5 * 0.0275 (0.0011) C6 * -0.0902 (0.0009) N * -0.0930 (0.0007) Br1 Rms deviation of fitted atoms = 0.0538 |
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. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.26871 (15) | 0.17598 (19) | 0.37364 (11) | 0.0178 (3) | |
C2 | 0.40844 (15) | 0.2205 (2) | 0.43089 (12) | 0.0208 (3) | |
H2 | 0.4304 | 0.2674 | 0.4993 | 0.025* | |
C3 | 0.51513 (16) | 0.1956 (2) | 0.38713 (12) | 0.0216 (3) | |
H3 | 0.6108 | 0.2253 | 0.4252 | 0.026* | |
C4 | 0.48057 (16) | 0.12709 (18) | 0.28734 (12) | 0.0195 (3) | |
C5 | 0.34207 (15) | 0.07834 (19) | 0.23118 (12) | 0.0199 (3) | |
H5 | 0.3206 | 0.0282 | 0.1636 | 0.024* | |
C6 | 0.23509 (15) | 0.10383 (18) | 0.27502 (12) | 0.0194 (3) | |
H6 | 0.1398 | 0.0719 | 0.2374 | 0.023* | |
N | 0.15816 (13) | 0.21601 (16) | 0.42150 (10) | 0.0180 (2) | |
H0 | 0.1603 (19) | 0.333 (3) | 0.4362 (14) | 0.021 (4)* | |
C7 | 0.18369 (18) | 0.1234 (2) | 0.52361 (12) | 0.0238 (3) | |
H7A | 0.1722 | −0.0034 | 0.5115 | 0.029* | |
H7B | 0.1151 | 0.1648 | 0.5563 | 0.029* | |
H7C | 0.2805 | 0.1482 | 0.5698 | 0.029* | |
C8 | 0.00855 (16) | 0.1847 (2) | 0.35287 (13) | 0.0245 (3) | |
H8A | −0.0085 | 0.2464 | 0.2865 | 0.029* | |
H8B | −0.0573 | 0.2285 | 0.3874 | 0.029* | |
H8C | −0.0067 | 0.0585 | 0.3397 | 0.029* | |
Br1 | 0.623884 (15) | 0.10988 (2) | 0.223544 (12) | 0.02322 (5) | |
Br2 | 0.143085 (15) | 0.631082 (19) | 0.433847 (11) | 0.02023 (4) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0188 (6) | 0.0155 (6) | 0.0182 (7) | 0.0006 (5) | 0.0049 (5) | 0.0013 (5) |
C2 | 0.0211 (7) | 0.0216 (7) | 0.0167 (7) | −0.0009 (5) | 0.0022 (5) | −0.0013 (5) |
C3 | 0.0176 (7) | 0.0208 (7) | 0.0232 (7) | −0.0011 (5) | 0.0021 (6) | −0.0001 (5) |
C4 | 0.0195 (6) | 0.0161 (6) | 0.0227 (7) | 0.0024 (5) | 0.0065 (5) | 0.0016 (5) |
C5 | 0.0213 (7) | 0.0182 (6) | 0.0187 (7) | −0.0001 (5) | 0.0047 (5) | −0.0019 (5) |
C6 | 0.0178 (6) | 0.0186 (7) | 0.0199 (7) | −0.0013 (5) | 0.0036 (5) | −0.0008 (5) |
N | 0.0192 (6) | 0.0165 (6) | 0.0173 (6) | 0.0008 (4) | 0.0047 (5) | −0.0002 (4) |
C7 | 0.0298 (8) | 0.0230 (7) | 0.0195 (7) | 0.0027 (6) | 0.0095 (6) | 0.0033 (6) |
C8 | 0.0179 (7) | 0.0314 (8) | 0.0234 (8) | −0.0020 (6) | 0.0056 (6) | −0.0033 (6) |
Br1 | 0.02030 (8) | 0.02267 (8) | 0.02798 (9) | −0.00024 (5) | 0.00965 (6) | −0.00246 (6) |
Br2 | 0.01954 (7) | 0.01842 (7) | 0.02114 (8) | −0.00044 (5) | 0.00447 (5) | −0.00222 (5) |
C1—C6 | 1.382 (2) | C3—H3 | 0.9500 |
C1—C2 | 1.394 (2) | C5—H5 | 0.9500 |
C1—N | 1.4805 (18) | C6—H6 | 0.9500 |
C2—C3 | 1.388 (2) | N—H0 | 0.91 (2) |
C3—C4 | 1.385 (2) | C7—H7A | 0.9800 |
C4—C5 | 1.389 (2) | C7—H7B | 0.9800 |
C4—Br1 | 1.8992 (15) | C7—H7C | 0.9800 |
C5—C6 | 1.392 (2) | C8—H8A | 0.9800 |
N—C8 | 1.4942 (19) | C8—H8B | 0.9800 |
N—C7 | 1.4998 (19) | C8—H8C | 0.9800 |
C2—H2 | 0.9500 | ||
C6—C1—C2 | 121.13 (13) | C6—C5—H5 | 120.4 |
C6—C1—N | 121.80 (12) | C1—C6—H6 | 120.3 |
C2—C1—N | 117.03 (13) | C5—C6—H6 | 120.3 |
C3—C2—C1 | 119.44 (14) | C1—N—H0 | 109.2 (11) |
C4—C3—C2 | 119.28 (14) | C8—N—H0 | 103.9 (11) |
C3—C4—C5 | 121.39 (14) | C7—N—H0 | 105.9 (11) |
C3—C4—Br1 | 119.20 (11) | N—C7—H7A | 109.5 |
C5—C4—Br1 | 119.34 (11) | N—C7—H7B | 109.5 |
C4—C5—C6 | 119.25 (14) | H7A—C7—H7B | 109.5 |
C1—C6—C5 | 119.46 (13) | N—C7—H7C | 109.5 |
C1—N—C8 | 115.20 (12) | H7A—C7—H7C | 109.5 |
C1—N—C7 | 112.48 (11) | H7B—C7—H7C | 109.5 |
C8—N—C7 | 109.46 (12) | N—C8—H8A | 109.5 |
C3—C2—H2 | 120.3 | N—C8—H8B | 109.5 |
C1—C2—H2 | 120.3 | H8A—C8—H8B | 109.5 |
C4—C3—H3 | 120.4 | N—C8—H8C | 109.5 |
C2—C3—H3 | 120.4 | H8A—C8—H8C | 109.5 |
C4—C5—H5 | 120.4 | H8B—C8—H8C | 109.5 |
C6—C1—C2—C3 | 1.5 (2) | N—C1—C6—C5 | 176.23 (13) |
N—C1—C2—C3 | −176.15 (13) | C4—C5—C6—C1 | −0.4 (2) |
C1—C2—C3—C4 | 0.0 (2) | C6—C1—N—C8 | −4.11 (19) |
C2—C3—C4—C5 | −1.7 (2) | C2—C1—N—C8 | 173.51 (13) |
C2—C3—C4—Br1 | 175.24 (11) | C6—C1—N—C7 | 122.27 (15) |
C3—C4—C5—C6 | 1.9 (2) | C2—C1—N—C7 | −60.11 (16) |
Br1—C4—C5—C6 | −175.04 (11) | C2—C1—N—H0 | 57.1 (12) |
C2—C1—C6—C5 | −1.3 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
N—H0···Br2 | 0.91 (2) | 2.28 (2) | 3.1716 (13) | 167.3 (16) |
C3—H3···Br2i | 0.95 | 2.79 | 3.7147 (15) | 165 |
C6—H6···Br2ii | 0.95 | 3.04 | 3.9052 (15) | 152 |
C7—H7A···Br2iii | 0.98 | 2.96 | 3.9216 (16) | 168 |
C7—H7B···Br2iv | 0.98 | 3.04 | 3.9537 (16) | 155 |
C8—H8A···Br2ii | 0.98 | 2.98 | 3.7043 (17) | 132 |
C8—H8B···Br2iv | 0.98 | 3.02 | 3.9331 (16) | 156 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x, y−1/2, −z+1/2; (iii) x, y−1, z; (iv) −x, −y+1, −z+1. |
Experimental details
Crystal data | |
Chemical formula | C8H11BrN+·Br− |
Mr | 281.00 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 143 |
a, b, c (Å) | 9.9511 (12), 7.6156 (10), 13.5616 (16) |
β (°) | 109.104 (3) |
V (Å3) | 971.1 (2) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 8.29 |
Crystal size (mm) | 0.40 × 0.16 × 0.13 |
Data collection | |
Diffractometer | Bruker SMART1000 CCD area-detector diffractometer |
Absorption correction | Numerical (XPREP; Siemens, 1994) |
Tmin, Tmax | 0.113, 0.379 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 20417, 2837, 2457 |
Rint | 0.059 |
(sin θ/λ)max (Å−1) | 0.704 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.018, 0.043, 1.04 |
No. of reflections | 2837 |
No. of parameters | 106 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.42, −0.57 |
Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1998), SAINT, SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), XP (Siemens, 1994), SHELXL97.
C1—N | 1.4805 (18) | N—C8 | 1.4942 (19) |
C4—Br1 | 1.8992 (15) | N—C7 | 1.4998 (19) |
C6—C1—C2 | 121.13 (13) | C1—N—C7 | 112.48 (11) |
C3—C4—C5 | 121.39 (14) | C8—N—C7 | 109.46 (12) |
C1—N—C8 | 115.20 (12) | ||
C2—C1—N—C8 | 173.51 (13) | C2—C1—N—H0 | 57.1 (12) |
D—H···A | D—H | H···A | D···A | D—H···A |
N—H0···Br2 | 0.91 (2) | 2.28 (2) | 3.1716 (13) | 167.3 (16) |
C3—H3···Br2i | 0.95 | 2.79 | 3.7147 (15) | 165 |
C6—H6···Br2ii | 0.95 | 3.04 | 3.9052 (15) | 152 |
C7—H7A···Br2iii | 0.98 | 2.96 | 3.9216 (16) | 168 |
C7—H7B···Br2iv | 0.98 | 3.04 | 3.9537 (16) | 155 |
C8—H8A···Br2ii | 0.98 | 2.98 | 3.7043 (17) | 132 |
C8—H8B···Br2iv | 0.98 | 3.02 | 3.9331 (16) | 156 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x, y−1/2, −z+1/2; (iii) x, y−1, z; (iv) −x, −y+1, −z+1. |
We are interested in the variety of secondary interactions in halopyridinium and haloanilinium halides, and have published the structures of 4-halopyridinium halides (Jones et al., 1999), 2-, 3- and various di-halopyridinium halides (Jones & Freytag, 2001), haloanilinium halides (Gray & Jones, 2002a) and dichloroanilinium chlorides (Gray & Jones, 2002b). These series of structures involve halogen-halogen contacts, classical N—H···halide hydrogen bonds and, in some cases, weak C—H···halide hydrogen bonds. The anilinium derivatives generally form structures with hydrophilic layers, and these consist of hydrogen-bonded rings of graph set R2nn(4n), in which two of the three H atoms from each of n NH3+ groups are the donors and n halide ions are the acceptors (n = 2–4). We then wished to investigate the effect of blocking some of the hydrogen-bond donors, and so present here the structure of 4-bromo-N,N-dimethylanilinium bromide, (I). \sch
The bond lengths and angles of (I) (Fig. 1) may be considered normal. The conformation of the dimethylamino group is such that the C2—C1—N—C8 grouping is approximately antiperiplanar [torsion angle 173.51 (13)°]. The ring is planar (the r.m.s. deviation of the six C atoms is 0.008 Å) and the Br and N substituents are slightly displaced to one side of the plane by 0.098 (2) and 0.150 (2) Å, respectively.
There are three predominant secondary interactions that determine the packing of (I). Firstly, a classical, approximately linear, N—H···Br- hydrogen bond is observed (Table 2). Secondly, the `weak' C3—H3···Br- hydrogen bond is by far the shortest of several such interactions (Table 2); if the C—H bond length is set to 1.08 Å, then the normalized H···Br distance (Steiner, 1998) is only 2.66 Å. Finally, a Br1···Br2(1 - x, y - 1/2, 1/2 - z) contact of 3.6331 (4) Å (cf. sum of van der Waals radii 3.70 Å; Reference?) connects cation and anion; as usual (see e.g. Jones et al., 1999), the C—Br···Br- angle is approximately linear, at 169.54 (4)°.
The combined effect of the two hydrogen bonds is to link two cations and two anions to form inversion-symmetric rings of graph set R42(14) (Fig. 2). These are linked by the Br···Br interactions to form layers parallel to the bc plane.
The blocking of two hydrogen-bond donors by methyl groups in (I) has thus reduced the dimensionality of the hydrogen-bonding pattern, from a two-dimensional array of classical hydrogen bonds to a zero-dimensional pattern of one classical and one `weak' hydrogen bond. An intermediate type of system might be expected for an aniline derivative bearing the –N+(CH3)H2 group. Corresponding studies are in progress.