Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807049951/om2168sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807049951/om2168Isup2.hkl |
CCDC reference: 667371
In a digestion bomb, a suspension of sodium metabisulfite (4.868 g; 25.6 mmol) in water (12.0 ml; 673 mmol) was added to 6-bromo-2-naphtol. Methylamine (40%; 6.0 ml; 69.7 mmol) and a magnetic bar were added to the reaction mixture upon which the bomb was sealed and put in a 140°C sand bath. The reaction was allowed to proceed with stirring for 4 days. The bomb was then cooled down to room temperature and 150 ml of dichloromethane was added. The resulting solution was washed with 5% sodium bicarbonate (3 x 100 ml). The combined organic layers were dried on sodium sulfate, filtered, and the solvent was removed under vacuum. The resulting crude solid was dissolved in a 50/50 dichloromethane/hexane solution and filtered upon which the filtrate was placed in a -78°C freezer overnight to afford yellow crystals of quality for X-ray determination (1.87 g; 59% yield). See (Gao et al., 2005) for complete characterization of 1.
All non-H atoms were refined anisotropically. The hydrogen atoms were placed at idealized positions with C—H = 0.93 Å and refined using a riding model. The N—H hygrogen was found in the Fourier map and freely refined.
The use of boronic acids as fluorescent anion or saccharide detectors generates a lot of interest in the scientific community. In the course of our study on the fluorescence of coordinated boronic acids (Sigouin et al., 2007), the synthesis of the previously reported precursor 6-(N-methyl)-2-bromonaphthalene, (1), has been carried out. (Gao et al., 2005) The C—Br distance observed for 1 (1.904 (2) Å) is similar to the average distance observed (1.897 Å) in the analogue 2,6-dibromonaphthalene, (2). (Chanh et al., 1976) The average C—C distance in 1 (1.397 Å) is within the range attributed for aromatic C—C bonds in bromine containing naphthalene products (Bienko et al., 2003; Brady et al., 1982; Chanh et al., 1973; Jameson & Penfold, 1965; and McCarthy & Huffman, 1984) and compares to the average C—C distance observed for 2 (1.403 Å). The nitrogen atom in the molecule is strongly sp2 hybridized with a small sp3 contribution. Indeed, the N—H bond distance of 0.80 (3) Å and the sum of the angles around the nitrogen atom was found to be 357°. Furthermore, C—N bond distances of 1.366 (3) Å and 1.410 (4) Å were observed for the aromatic and methyl carbons, respectively. This results in a high level of planarity in the molecule, all non-hydrogen atoms being in the same plane with an average deviation of 0.019 Å. The amine hydrogen was found to be slightly out of the plane, with a deviation of 0.20 (3) Å.
For related literature, see: Bienko et al. (2003); Brady et al. (1982); Chanh et al. (1973, 1976); Gao et al. (2005); Jameson & Penfold (1965); McCarthy & Huffman (1984); Sigouin et al. (2007).
Data collection: APEX2 (Bruker, 2005); cell refinement: APEX2 (Bruker, 2005); data reduction: SAINT (Bruker, 2003); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2001); software used to prepare material for publication: SHELXTL (Bruker, 2001).
C11H10BrN | F(000) = 472 |
Mr = 236.11 | Dx = 1.639 Mg m−3 |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P2ac2ab | Cell parameters from 6010 reflections |
a = 6.1511 (10) Å | θ = 2.3–27.9° |
b = 11.4414 (18) Å | µ = 4.25 mm−1 |
c = 13.593 (2) Å | T = 200 K |
V = 956.6 (3) Å3 | Block, yellow |
Z = 4 | 0.03 × 0.03 × 0.02 mm |
Bruker SMART APEXII CCD diffractometer | 2296 independent reflections |
Radiation source: fine-focus sealed tube | 2131 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.022 |
ω scans | θmax = 28.1°, θmin = 2.3° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2004) | h = −8→8 |
Tmin = 0.883, Tmax = 0.920 | k = −15→15 |
11718 measured reflections | l = −18→17 |
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)] = 0.023 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.059 | w = 1/[σ2(Fo2) + (0.0287P)2 + 0.1339P] where P = (Fo2 + 2Fc2)/3 |
S = 1.08 | (Δ/σ)max < 0.001 |
2296 reflections | Δρmax = 0.51 e Å−3 |
123 parameters | Δρmin = −0.28 e Å−3 |
0 restraints | Absolute structure: Flack (1983) |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.013 (11) |
C11H10BrN | V = 956.6 (3) Å3 |
Mr = 236.11 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 6.1511 (10) Å | µ = 4.25 mm−1 |
b = 11.4414 (18) Å | T = 200 K |
c = 13.593 (2) Å | 0.03 × 0.03 × 0.02 mm |
Bruker SMART APEXII CCD diffractometer | 2296 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2004) | 2131 reflections with I > 2σ(I) |
Tmin = 0.883, Tmax = 0.920 | Rint = 0.022 |
11718 measured reflections |
R[F2 > 2σ(F2)] = 0.023 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.059 | Δρmax = 0.51 e Å−3 |
S = 1.08 | Δρmin = −0.28 e Å−3 |
2296 reflections | Absolute structure: Flack (1983) |
123 parameters | Absolute structure parameter: 0.013 (11) |
0 restraints |
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. |
x | y | z | Uiso*/Ueq | ||
Br1 | 0.02701 (4) | 0.07982 (2) | 0.219138 (17) | 0.04903 (9) | |
N1 | 0.4568 (4) | 0.61887 (18) | 0.57589 (17) | 0.0505 (5) | |
H1 | 0.404 (6) | 0.627 (3) | 0.629 (2) | 0.065 (10)* | |
C1 | 0.1627 (4) | 0.20347 (18) | 0.29007 (15) | 0.0367 (4) | |
C2 | 0.0600 (3) | 0.25158 (17) | 0.36901 (14) | 0.0346 (4) | |
H2 | −0.0752 | 0.2235 | 0.3886 | 0.042* | |
C3 | 0.1590 (4) | 0.34425 (18) | 0.42120 (15) | 0.0333 (4) | |
C4 | 0.0647 (4) | 0.39478 (18) | 0.50625 (15) | 0.0378 (5) | |
H4 | −0.0688 | 0.3673 | 0.5285 | 0.045* | |
C5 | 0.1639 (4) | 0.4816 (2) | 0.55557 (17) | 0.0424 (5) | |
H5 | 0.0977 | 0.5122 | 0.6114 | 0.051* | |
C6 | 0.3677 (4) | 0.52793 (18) | 0.52452 (16) | 0.0385 (5) | |
C7 | 0.4655 (4) | 0.47950 (17) | 0.44267 (14) | 0.0363 (4) | |
H7 | 0.5990 | 0.5082 | 0.4215 | 0.044* | |
C8 | 0.3662 (4) | 0.38702 (16) | 0.39064 (14) | 0.0321 (4) | |
C9 | 0.4653 (4) | 0.33294 (19) | 0.30813 (14) | 0.0370 (4) | |
H9 | 0.5999 | 0.3597 | 0.2866 | 0.044* | |
C10 | 0.3683 (4) | 0.2428 (2) | 0.25961 (14) | 0.0394 (5) | |
H10 | 0.4379 | 0.2075 | 0.2066 | 0.047* | |
C11 | 0.6590 (5) | 0.6708 (2) | 0.5542 (2) | 0.0579 (7) | |
H11A | 0.7725 | 0.6140 | 0.5620 | 0.087* | |
H11B | 0.6839 | 0.7351 | 0.5982 | 0.087* | |
H11C | 0.6582 | 0.6987 | 0.4876 | 0.087* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Br1 | 0.05551 (14) | 0.04969 (14) | 0.04188 (12) | −0.01171 (11) | −0.00164 (10) | −0.00494 (10) |
N1 | 0.0664 (14) | 0.0419 (10) | 0.0433 (11) | −0.0044 (10) | 0.0010 (11) | −0.0046 (8) |
C1 | 0.0403 (11) | 0.0379 (10) | 0.0319 (9) | −0.0031 (8) | −0.0042 (9) | 0.0046 (9) |
C2 | 0.0303 (10) | 0.0379 (10) | 0.0357 (10) | −0.0005 (9) | −0.0016 (8) | 0.0074 (8) |
C3 | 0.0328 (12) | 0.0356 (10) | 0.0314 (10) | 0.0042 (9) | 0.0014 (8) | 0.0081 (8) |
C4 | 0.0338 (11) | 0.0392 (11) | 0.0404 (11) | 0.0047 (9) | 0.0071 (9) | 0.0078 (8) |
C5 | 0.0461 (14) | 0.0424 (12) | 0.0388 (11) | 0.0108 (11) | 0.0067 (10) | 0.0027 (9) |
C6 | 0.0489 (13) | 0.0302 (10) | 0.0364 (11) | 0.0069 (10) | −0.0021 (10) | 0.0061 (8) |
C7 | 0.0368 (11) | 0.0362 (10) | 0.0360 (10) | 0.0001 (10) | 0.0008 (9) | 0.0078 (8) |
C8 | 0.0311 (10) | 0.0326 (10) | 0.0325 (9) | 0.0032 (8) | 0.0003 (8) | 0.0076 (7) |
C9 | 0.0325 (10) | 0.0442 (11) | 0.0343 (9) | −0.0015 (9) | 0.0046 (8) | 0.0043 (8) |
C10 | 0.0402 (11) | 0.0452 (12) | 0.0328 (10) | 0.0001 (10) | 0.0035 (8) | 0.0016 (8) |
C11 | 0.0426 (16) | 0.0514 (15) | 0.0797 (19) | −0.0058 (12) | −0.0090 (14) | −0.0209 (14) |
Br1—C1 | 1.905 (2) | C9—C10 | 1.362 (3) |
C2—C1 | 1.361 (3) | C9—C8 | 1.419 (3) |
C2—C3 | 1.414 (3) | C9—H9 | 0.9300 |
C2—H2 | 0.9300 | C6—N1 | 1.368 (3) |
C1—C10 | 1.405 (3) | C6—C5 | 1.425 (3) |
C3—C4 | 1.417 (3) | C5—H5 | 0.9300 |
C3—C8 | 1.427 (3) | C10—H10 | 0.9300 |
C4—C5 | 1.344 (3) | C11—N1 | 1.410 (4) |
C4—H4 | 0.9300 | C11—H11A | 0.9600 |
C7—C6 | 1.381 (3) | C11—H11B | 0.9600 |
C7—C8 | 1.412 (3) | C11—H11C | 0.9600 |
C7—H7 | 0.9300 | N1—H1 | 0.80 (3) |
C1—C2—C3 | 119.93 (19) | C7—C6—C5 | 118.2 (2) |
C1—C2—H2 | 120.0 | C4—C5—C6 | 121.8 (2) |
C3—C2—H2 | 120.0 | C4—C5—H5 | 119.1 |
C2—C1—C10 | 121.4 (2) | C6—C5—H5 | 119.1 |
C2—C1—Br1 | 119.74 (16) | C7—C8—C9 | 122.5 (2) |
C10—C1—Br1 | 118.90 (17) | C7—C8—C3 | 119.9 (2) |
C2—C3—C4 | 122.64 (19) | C9—C8—C3 | 117.67 (19) |
C2—C3—C8 | 119.73 (19) | C9—C10—C1 | 119.6 (2) |
C4—C3—C8 | 117.6 (2) | C9—C10—H10 | 120.2 |
C5—C4—C3 | 121.5 (2) | C1—C10—H10 | 120.2 |
C5—C4—H4 | 119.2 | N1—C11—H11A | 109.5 |
C3—C4—H4 | 119.2 | N1—C11—H11B | 109.5 |
C6—C7—C8 | 121.0 (2) | H11A—C11—H11B | 109.5 |
C6—C7—H7 | 119.5 | N1—C11—H11C | 109.5 |
C8—C7—H7 | 119.5 | H11A—C11—H11C | 109.5 |
C10—C9—C8 | 121.7 (2) | H11B—C11—H11C | 109.5 |
C10—C9—H9 | 119.2 | C6—N1—C11 | 124.6 (2) |
C8—C9—H9 | 119.2 | C6—N1—H1 | 113 (2) |
N1—C6—C7 | 122.8 (2) | C11—N1—H1 | 120 (2) |
N1—C6—C5 | 119.0 (2) | ||
C3—C2—C1—C10 | 1.0 (3) | C6—C7—C8—C3 | 1.5 (3) |
C3—C2—C1—Br1 | −179.29 (15) | C10—C9—C8—C7 | 179.12 (19) |
C1—C2—C3—C4 | −177.36 (19) | C10—C9—C8—C3 | −0.4 (3) |
C1—C2—C3—C8 | 0.1 (3) | C2—C3—C8—C7 | −179.94 (18) |
C2—C3—C4—C5 | 178.9 (2) | C4—C3—C8—C7 | −2.3 (3) |
C8—C3—C4—C5 | 1.3 (3) | C2—C3—C8—C9 | −0.4 (3) |
C8—C7—C6—N1 | −178.84 (19) | C4—C3—C8—C9 | 177.21 (18) |
C8—C7—C6—C5 | 0.4 (3) | C8—C9—C10—C1 | 1.5 (3) |
C3—C4—C5—C6 | 0.5 (3) | C2—C1—C10—C9 | −1.8 (3) |
N1—C6—C5—C4 | 177.8 (2) | Br1—C1—C10—C9 | 178.48 (16) |
C7—C6—C5—C4 | −1.4 (3) | C7—C6—N1—C11 | −2.2 (4) |
C6—C7—C8—C9 | −178.03 (18) | C5—C6—N1—C11 | 178.6 (2) |
Experimental details
Crystal data | |
Chemical formula | C11H10BrN |
Mr | 236.11 |
Crystal system, space group | Orthorhombic, P212121 |
Temperature (K) | 200 |
a, b, c (Å) | 6.1511 (10), 11.4414 (18), 13.593 (2) |
V (Å3) | 956.6 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 4.25 |
Crystal size (mm) | 0.03 × 0.03 × 0.02 |
Data collection | |
Diffractometer | Bruker SMART APEXII CCD |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2004) |
Tmin, Tmax | 0.883, 0.920 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 11718, 2296, 2131 |
Rint | 0.022 |
(sin θ/λ)max (Å−1) | 0.662 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.023, 0.059, 1.08 |
No. of reflections | 2296 |
No. of parameters | 123 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.51, −0.28 |
Absolute structure | Flack (1983) |
Absolute structure parameter | 0.013 (11) |
Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2003), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 2001).
The use of boronic acids as fluorescent anion or saccharide detectors generates a lot of interest in the scientific community. In the course of our study on the fluorescence of coordinated boronic acids (Sigouin et al., 2007), the synthesis of the previously reported precursor 6-(N-methyl)-2-bromonaphthalene, (1), has been carried out. (Gao et al., 2005) The C—Br distance observed for 1 (1.904 (2) Å) is similar to the average distance observed (1.897 Å) in the analogue 2,6-dibromonaphthalene, (2). (Chanh et al., 1976) The average C—C distance in 1 (1.397 Å) is within the range attributed for aromatic C—C bonds in bromine containing naphthalene products (Bienko et al., 2003; Brady et al., 1982; Chanh et al., 1973; Jameson & Penfold, 1965; and McCarthy & Huffman, 1984) and compares to the average C—C distance observed for 2 (1.403 Å). The nitrogen atom in the molecule is strongly sp2 hybridized with a small sp3 contribution. Indeed, the N—H bond distance of 0.80 (3) Å and the sum of the angles around the nitrogen atom was found to be 357°. Furthermore, C—N bond distances of 1.366 (3) Å and 1.410 (4) Å were observed for the aromatic and methyl carbons, respectively. This results in a high level of planarity in the molecule, all non-hydrogen atoms being in the same plane with an average deviation of 0.019 Å. The amine hydrogen was found to be slightly out of the plane, with a deviation of 0.20 (3) Å.