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In the structure of the title compound, C11H10BrN, all the atoms are coplanar, with the exception of two methyl H atoms, and the geometric parameters around the N atom are consistent with an sp2-hybridized atom.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807049951/om2168sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807049951/om2168Isup2.hkl
Contains datablock I

CCDC reference: 667371

Key indicators

  • Single-crystal X-ray study
  • T = 200 K
  • Mean [sigma](C-C) = 0.003 Å
  • R factor = 0.023
  • wR factor = 0.059
  • Data-to-parameter ratio = 18.7

checkCIF/PLATON results

No syntax errors found



Alert level C PLAT420_ALERT_2_C D-H Without Acceptor N1 - H1 ... ?
Alert level G REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is correct. If it is not, please give the correct count in the _publ_section_exptl_refinement section of the submitted CIF. From the CIF: _diffrn_reflns_theta_max 28.07 From the CIF: _reflns_number_total 2296 Count of symmetry unique reflns 1359 Completeness (_total/calc) 168.95% TEST3: Check Friedels for noncentro structure Estimate of Friedel pairs measured 937 Fraction of Friedel pairs measured 0.689 Are heavy atom types Z>Si present yes
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 1 ALERT level C = Check and explain 1 ALERT level G = General alerts; check 0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 1 ALERT type 2 Indicator that the structure model may be wrong or deficient 0 ALERT type 3 Indicator that the structure quality may be low 1 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check

Comment top

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.

Related literature top

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).

Experimental top

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.

Refinement top

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.

Structure description top

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).

Computing details top

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).

Figures top
[Figure 1] Fig. 1. ORTEP view of 1 showing the numbering scheme adopted. Anisotropic atomic displacement ellipsoids for the non-hydrogen atoms are shown at the 50% probability level. Amide hydrogen atom is represented by a sphere of arbitrary size.
6-Bromo-N-methylnaphthalen-2-amine top
Crystal data top
C11H10BrNF(000) = 472
Mr = 236.11Dx = 1.639 Mg m3
Orthorhombic, P212121Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P2ac2abCell parameters from 6010 reflections
a = 6.1511 (10) Åθ = 2.3–27.9°
b = 11.4414 (18) ŵ = 4.25 mm1
c = 13.593 (2) ÅT = 200 K
V = 956.6 (3) Å3Block, yellow
Z = 40.03 × 0.03 × 0.02 mm
Data collection top
Bruker SMART APEXII CCD
diffractometer
2296 independent reflections
Radiation source: fine-focus sealed tube2131 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.022
ω scansθmax = 28.1°, θmin = 2.3°
Absorption correction: multi-scan
(SADABS; Sheldrick, 2004)
h = 88
Tmin = 0.883, Tmax = 0.920k = 1515
11718 measured reflectionsl = 1817
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)] = 0.023H 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 reflectionsΔρmax = 0.51 e Å3
123 parametersΔρmin = 0.28 e Å3
0 restraintsAbsolute structure: Flack (1983)
Primary atom site location: structure-invariant direct methodsAbsolute structure parameter: 0.013 (11)
Crystal data top
C11H10BrNV = 956.6 (3) Å3
Mr = 236.11Z = 4
Orthorhombic, P212121Mo Kα radiation
a = 6.1511 (10) ŵ = 4.25 mm1
b = 11.4414 (18) ÅT = 200 K
c = 13.593 (2) Å0.03 × 0.03 × 0.02 mm
Data collection top
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 = 0.920Rint = 0.022
11718 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.023H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.059Δρmax = 0.51 e Å3
S = 1.08Δρmin = 0.28 e Å3
2296 reflectionsAbsolute structure: Flack (1983)
123 parametersAbsolute structure parameter: 0.013 (11)
0 restraints
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
Br10.02701 (4)0.07982 (2)0.219138 (17)0.04903 (9)
N10.4568 (4)0.61887 (18)0.57589 (17)0.0505 (5)
H10.404 (6)0.627 (3)0.629 (2)0.065 (10)*
C10.1627 (4)0.20347 (18)0.29007 (15)0.0367 (4)
C20.0600 (3)0.25158 (17)0.36901 (14)0.0346 (4)
H20.07520.22350.38860.042*
C30.1590 (4)0.34425 (18)0.42120 (15)0.0333 (4)
C40.0647 (4)0.39478 (18)0.50625 (15)0.0378 (5)
H40.06880.36730.52850.045*
C50.1639 (4)0.4816 (2)0.55557 (17)0.0424 (5)
H50.09770.51220.61140.051*
C60.3677 (4)0.52793 (18)0.52452 (16)0.0385 (5)
C70.4655 (4)0.47950 (17)0.44267 (14)0.0363 (4)
H70.59900.50820.42150.044*
C80.3662 (4)0.38702 (16)0.39064 (14)0.0321 (4)
C90.4653 (4)0.33294 (19)0.30813 (14)0.0370 (4)
H90.59990.35970.28660.044*
C100.3683 (4)0.2428 (2)0.25961 (14)0.0394 (5)
H100.43790.20750.20660.047*
C110.6590 (5)0.6708 (2)0.5542 (2)0.0579 (7)
H11A0.77250.61400.56200.087*
H11B0.68390.73510.59820.087*
H11C0.65820.69870.48760.087*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Br10.05551 (14)0.04969 (14)0.04188 (12)0.01171 (11)0.00164 (10)0.00494 (10)
N10.0664 (14)0.0419 (10)0.0433 (11)0.0044 (10)0.0010 (11)0.0046 (8)
C10.0403 (11)0.0379 (10)0.0319 (9)0.0031 (8)0.0042 (9)0.0046 (9)
C20.0303 (10)0.0379 (10)0.0357 (10)0.0005 (9)0.0016 (8)0.0074 (8)
C30.0328 (12)0.0356 (10)0.0314 (10)0.0042 (9)0.0014 (8)0.0081 (8)
C40.0338 (11)0.0392 (11)0.0404 (11)0.0047 (9)0.0071 (9)0.0078 (8)
C50.0461 (14)0.0424 (12)0.0388 (11)0.0108 (11)0.0067 (10)0.0027 (9)
C60.0489 (13)0.0302 (10)0.0364 (11)0.0069 (10)0.0021 (10)0.0061 (8)
C70.0368 (11)0.0362 (10)0.0360 (10)0.0001 (10)0.0008 (9)0.0078 (8)
C80.0311 (10)0.0326 (10)0.0325 (9)0.0032 (8)0.0003 (8)0.0076 (7)
C90.0325 (10)0.0442 (11)0.0343 (9)0.0015 (9)0.0046 (8)0.0043 (8)
C100.0402 (11)0.0452 (12)0.0328 (10)0.0001 (10)0.0035 (8)0.0016 (8)
C110.0426 (16)0.0514 (15)0.0797 (19)0.0058 (12)0.0090 (14)0.0209 (14)
Geometric parameters (Å, º) top
Br1—C11.905 (2)C9—C101.362 (3)
C2—C11.361 (3)C9—C81.419 (3)
C2—C31.414 (3)C9—H90.9300
C2—H20.9300C6—N11.368 (3)
C1—C101.405 (3)C6—C51.425 (3)
C3—C41.417 (3)C5—H50.9300
C3—C81.427 (3)C10—H100.9300
C4—C51.344 (3)C11—N11.410 (4)
C4—H40.9300C11—H11A0.9600
C7—C61.381 (3)C11—H11B0.9600
C7—C81.412 (3)C11—H11C0.9600
C7—H70.9300N1—H10.80 (3)
C1—C2—C3119.93 (19)C7—C6—C5118.2 (2)
C1—C2—H2120.0C4—C5—C6121.8 (2)
C3—C2—H2120.0C4—C5—H5119.1
C2—C1—C10121.4 (2)C6—C5—H5119.1
C2—C1—Br1119.74 (16)C7—C8—C9122.5 (2)
C10—C1—Br1118.90 (17)C7—C8—C3119.9 (2)
C2—C3—C4122.64 (19)C9—C8—C3117.67 (19)
C2—C3—C8119.73 (19)C9—C10—C1119.6 (2)
C4—C3—C8117.6 (2)C9—C10—H10120.2
C5—C4—C3121.5 (2)C1—C10—H10120.2
C5—C4—H4119.2N1—C11—H11A109.5
C3—C4—H4119.2N1—C11—H11B109.5
C6—C7—C8121.0 (2)H11A—C11—H11B109.5
C6—C7—H7119.5N1—C11—H11C109.5
C8—C7—H7119.5H11A—C11—H11C109.5
C10—C9—C8121.7 (2)H11B—C11—H11C109.5
C10—C9—H9119.2C6—N1—C11124.6 (2)
C8—C9—H9119.2C6—N1—H1113 (2)
N1—C6—C7122.8 (2)C11—N1—H1120 (2)
N1—C6—C5119.0 (2)
C3—C2—C1—C101.0 (3)C6—C7—C8—C31.5 (3)
C3—C2—C1—Br1179.29 (15)C10—C9—C8—C7179.12 (19)
C1—C2—C3—C4177.36 (19)C10—C9—C8—C30.4 (3)
C1—C2—C3—C80.1 (3)C2—C3—C8—C7179.94 (18)
C2—C3—C4—C5178.9 (2)C4—C3—C8—C72.3 (3)
C8—C3—C4—C51.3 (3)C2—C3—C8—C90.4 (3)
C8—C7—C6—N1178.84 (19)C4—C3—C8—C9177.21 (18)
C8—C7—C6—C50.4 (3)C8—C9—C10—C11.5 (3)
C3—C4—C5—C60.5 (3)C2—C1—C10—C91.8 (3)
N1—C6—C5—C4177.8 (2)Br1—C1—C10—C9178.48 (16)
C7—C6—C5—C41.4 (3)C7—C6—N1—C112.2 (4)
C6—C7—C8—C9178.03 (18)C5—C6—N1—C11178.6 (2)

Experimental details

Crystal data
Chemical formulaC11H10BrN
Mr236.11
Crystal system, space groupOrthorhombic, P212121
Temperature (K)200
a, b, c (Å)6.1511 (10), 11.4414 (18), 13.593 (2)
V3)956.6 (3)
Z4
Radiation typeMo Kα
µ (mm1)4.25
Crystal size (mm)0.03 × 0.03 × 0.02
Data collection
DiffractometerBruker SMART APEXII CCD
Absorption correctionMulti-scan
(SADABS; Sheldrick, 2004)
Tmin, Tmax0.883, 0.920
No. of measured, independent and
observed [I > 2σ(I)] reflections
11718, 2296, 2131
Rint0.022
(sin θ/λ)max1)0.662
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.023, 0.059, 1.08
No. of reflections2296
No. of parameters123
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.51, 0.28
Absolute structureFlack (1983)
Absolute structure parameter0.013 (11)

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2003), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 2001).

 

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