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Acta Crystallogr Sect E Struct Rep Online. 2008 June 1; 64(Pt 6): o977.
Published online 2008 May 3. doi:  10.1107/S1600536808012580
PMCID: PMC2961535

8-Bromo­naphthalen-1-amine

Abstract

The title compound, C10H8BrN, was obtained by slow addition of sodium azide to 8-bromo-1-naphthoic acid, followed by addition of aqueous ammonia. The crude product was crystallized from petroleum ether to give pink crystals. Compared to other 1,8-disubstituted naphthalene compounds, this compound exhibits less strain between the 1 and 8 substituents. Additionally, the NH protons form both intra- and inter­molecular hydrogen bonds. The naphthalene units are arranged in a herring-bone stacking motif.

Related literature

For examples of sterically crowded 1,8 dichalcogen naphthalenes, see: Aucott et al. (2004 [triangle]). For the synthesis, see: Herbert et al. (1987 [triangle]).

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Object name is e-64-0o977-scheme1.jpg

Experimental

Crystal data

  • C10H8BrN
  • M r = 222.08
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-0o977-efi1.jpg
  • a = 13.6692 (14) Å
  • b = 4.1579 (4) Å
  • c = 15.8256 (16) Å
  • β = 109.941 (3)°
  • V = 845.52 (15) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 4.81 mm−1
  • T = 125.1 K
  • 0.35 × 0.13 × 0.09 mm

Data collection

  • Rigaku SCXmini diffractometer
  • Absorption correction: multi-scan (ABSCOR; Higashi, 1995 [triangle]) T min = 0.381, T max = 0.649
  • 6823 measured reflections
  • 1527 independent reflections
  • 1281 reflections with F 2 > 2σ(F 2)
  • R int = 0.061

Refinement

  • R[F 2 > 2σ(F 2)] = 0.051
  • wR(F 2) = 0.116
  • S = 1.10
  • 1527 reflections
  • 110 parameters
  • H-atom parameters constrained
  • Δρmax = 1.76 e Å−3
  • Δρmin = −0.39 e Å−3

Data collection: SCXmini (Rigaku/MSC, 2006 [triangle]); cell refinement: PROCESS-AUTO (Rigaku, 1998 [triangle]); data reduction: PROCESS-AUTO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: CrystalStructure (Rigaku/MSC, 2006 [triangle]); software used to prepare material for publication: CrystalStructure.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808012580/si2087sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808012580/si2087Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

supplementary crystallographic information

Comment

Contrary to the formally bonded (and sterically strained) S—S or Te—Te atoms in positions 1 and 8 in previous naphthalene compounds (Aucott et al., 2004), the title compound C10H8BrN exhibits a somewhat unstrained, intramolecular non-bonded Br1···N1 distance of 3.070 (3) Å. The molecular structure of the title compound is shown in Figure 1. An intramolecular hydrogen bonding interaction between the N1—H1a···Br1 enables a close nonbonding Br1···N1 distance and at the same time leaves the molecule relatively unstrained.

The other NH proton is involved in the intermolecular hydrogen bond (Table 1) N1—H1b···N1 and forms an infinite zigzag chain. These chains have normal hydrophobic contact to each other (Figure 2). The naphthalene units are arranged in a herringbone stacking motif.

Experimental

The title compound was prepared by a method previously described (Herbert et al., 1987). Sodium azide (3.10 g, 0.048 mol) was added over a 10 minute period to a stirred suspension of 8-bromo-1-naphthoic acid (2.0 g, 0.008 mol) in concentrated sulfuric acid (7 ml) and chloroform (7 ml) at 45° C. Each successive portion of sodium azide being added after the effervescence resulting from the previous addition had subsided. The mixture was stirred for 90 minutes at 45°C and added to water (140 ml), and it was made alkaline with aqueous ammonia and extracted with chloroform (3 x 140 ml). The combined extracts were dried with magnesium sulfate and evaporated to give the desired product. Yield 1.30 g (73%). The black crude product was recrystallized from 60–80 petroleum ether to give pink crystals.

Refinement

C7 was refined subject to an ISOR constraint. All H atoms were included in calculated positions (C—H distances are 0.95 Å, N—H distances are 0.98 Å) and were refined as riding atoms with Uiso(H) = 1.2 Ueq(parent carbon atom) The N—H protons were refined subject to a distance constraint but with a riding thermal parameter.

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 > 2sigma(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.

Figures

Fig. 1.
The structure of the title compound with labelled atoms and with displacement ellipsoids for non-H atoms drawn at the 50% probability level. The intramolecular hydrogen bond is indicated by a dashed line.
Fig. 2.
Packing diagram illustrating the intermolecular hydrogen bonding.

Crystal data

C10H8BrNF000 = 440.00
Mr = 222.08Dx = 1.744 Mg m3
Monoclinic, P21/nMelting point: 359 K
Hall symbol: -P 2ynMo Kα radiation λ = 0.71075 Å
a = 13.6692 (14) ÅCell parameters from 7235 reflections
b = 4.1579 (4) Åθ = 3.0–27.6º
c = 15.8256 (16) ŵ = 4.81 mm1
β = 109.941 (3)ºT = 125.1 K
V = 845.52 (15) Å3Prism, pink
Z = 40.35 × 0.13 × 0.09 mm

Data collection

Rigaku SCXmini diffractometer1281 reflections with F2 > 2σ(F2)
Detector resolution: 6.85 pixels mm-1Rint = 0.061
ω scansθmax = 25.4º
Absorption correction: multi-scan(ABSCOR; Higashi, 1995)h = −16→16
Tmin = 0.381, Tmax = 0.649k = −5→5
6823 measured reflectionsl = −19→19
1527 independent reflections

Refinement

Refinement on F2H-atom parameters constrained
Least-squares matrix: full  w = 1/[σ2(Fo2) + (0.0516P)2 + 2.4354P] where P = (Fo2 + 2Fc2)/3
R[F2 > 2σ(F2)] = 0.051(Δ/σ)max = 0.002
wR(F2) = 0.116Δρmax = 1.76 e Å3
S = 1.10Δρmin = −0.39 e Å3
1527 reflectionsExtinction correction: none
110 parameters

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

xyzUiso*/Ueq
Br(1)0.31174 (4)0.55948 (14)0.53932 (4)0.0293 (2)
N(1)0.3079 (3)0.8778 (7)0.71320 (17)0.0237 (10)
C(1)0.4427 (3)0.4617 (12)0.6330 (3)0.0198 (11)
C(2)0.5076 (4)0.2842 (13)0.6015 (3)0.0257 (12)
C(3)0.6037 (4)0.1842 (14)0.6610 (4)0.0304 (13)
C(4)0.6321 (4)0.2554 (12)0.7494 (4)0.0274 (13)
C(5)0.5666 (4)0.4409 (12)0.7842 (3)0.0224 (11)
C(6)0.5988 (4)0.5102 (13)0.8776 (4)0.0349 (15)
C(7)0.5414 (4)0.6701 (14)0.9140 (3)0.0263 (12)
C(8)0.4419 (4)0.8017 (14)0.8560 (3)0.0314 (13)
C(9)0.4054 (3)0.7493 (12)0.7623 (3)0.0206 (11)
C(10)0.4667 (3)0.5569 (11)0.7240 (3)0.0157 (10)
H(1a)0.29550.88860.64860.020*
H(2a)0.48720.22980.53960.031*
H(3a)0.64950.06510.63930.037*
H(4a)0.69710.18040.78920.033*
H(1b)0.29911.06810.74640.057*
H(6a)0.66520.43670.91520.042*
H(7a)0.56380.70060.97720.032*
H(8a)0.40100.92530.88200.038*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Br(1)0.0265 (3)0.0337 (3)0.0210 (3)0.0021 (2)−0.0007 (2)−0.0014 (2)
N(1)0.023 (2)0.020 (2)0.029 (2)0.0018 (19)0.011 (2)−0.0008 (18)
C(1)0.018 (2)0.025 (2)0.014 (2)−0.003 (2)0.003 (2)0.003 (2)
C(2)0.034 (3)0.021 (2)0.025 (3)−0.001 (2)0.014 (2)−0.001 (2)
C(3)0.027 (3)0.025 (3)0.046 (3)0.000 (2)0.021 (2)−0.001 (2)
C(4)0.016 (2)0.016 (3)0.045 (3)0.000 (2)0.004 (2)0.010 (2)
C(5)0.020 (2)0.016 (2)0.026 (2)−0.005 (2)0.001 (2)0.005 (2)
C(6)0.021 (2)0.022 (3)0.043 (3)−0.009 (2)−0.013 (2)0.016 (2)
C(7)0.0278 (14)0.0273 (15)0.0247 (14)−0.0040 (9)0.0100 (9)−0.0020 (9)
C(8)0.035 (3)0.026 (3)0.038 (3)−0.012 (2)0.019 (2)−0.010 (2)
C(9)0.024 (2)0.014 (3)0.026 (2)−0.009 (2)0.011 (2)−0.003 (2)
C(10)0.015 (2)0.014 (2)0.019 (2)−0.005 (2)0.007 (2)−0.0002 (19)

Geometric parameters (Å, °)

Br(1)—C(1)1.939 (4)C(8)—C(9)1.410 (7)
N(1)—C(9)1.400 (5)C(9)—C(10)1.435 (8)
C(1)—C(2)1.372 (8)N(1)—H(1a)0.98
C(1)—C(10)1.420 (7)N(1)—H(1b)0.98
C(2)—C(3)1.393 (7)C(2)—H(2a)0.95
C(3)—C(4)1.350 (8)C(3)—H(3a)0.95
C(4)—C(5)1.428 (8)C(4)—H(4a)0.95
C(5)—C(6)1.420 (8)C(6)—H(6a)0.95
C(5)—C(10)1.455 (6)C(7)—H(7a)0.95
C(6)—C(7)1.304 (9)C(8)—H(8a)0.95
C(7)—C(8)1.462 (7)
Br(1)—C(1)—C(2)112.2 (3)C(5)—C(10)—C(9)117.4 (4)
Br(1)—C(1)—C(10)123.4 (4)C(9)—N(1)—H(1a)113.0
C(2)—C(1)—C(10)124.4 (4)C(9)—N(1)—H(1b)106.2
C(1)—C(2)—C(3)119.4 (5)H(1a)—N(1)—H(1b)120.9
C(2)—C(3)—C(4)120.5 (6)C(1)—C(2)—H(2a)120.3
C(3)—C(4)—C(5)121.4 (4)C(3)—C(2)—H(2a)120.3
C(4)—C(5)—C(6)119.9 (4)C(2)—C(3)—H(3a)119.8
C(4)—C(5)—C(10)119.9 (4)C(4)—C(3)—H(3a)119.8
C(6)—C(5)—C(10)120.2 (5)C(3)—C(4)—H(4a)119.3
C(5)—C(6)—C(7)123.0 (4)C(5)—C(4)—H(4a)119.3
C(6)—C(7)—C(8)118.9 (5)C(5)—C(6)—H(6a)118.5
C(7)—C(8)—C(9)121.5 (5)C(7)—C(6)—H(6a)118.5
N(1)—C(9)—C(8)117.0 (5)C(6)—C(7)—H(7a)120.5
N(1)—C(9)—C(10)124.1 (4)C(8)—C(7)—H(7a)120.5
C(8)—C(9)—C(10)118.8 (4)C(7)—C(8)—H(8a)119.3
C(1)—C(10)—C(5)114.4 (4)C(9)—C(8)—H(8a)119.3
C(1)—C(10)—C(9)128.2 (4)
Br(1)—C(1)—C(2)—C(3)−177.8 (4)C(4)—C(5)—C(10)—C(9)−178.4 (5)
Br(1)—C(1)—C(10)—C(5)176.3 (3)C(6)—C(5)—C(10)—C(1)−178.0 (5)
Br(1)—C(1)—C(10)—C(9)−3.7 (8)C(6)—C(5)—C(10)—C(9)2.0 (7)
C(2)—C(1)—C(10)—C(5)−2.0 (8)C(10)—C(5)—C(6)—C(7)1.7 (9)
C(2)—C(1)—C(10)—C(9)178.0 (5)C(5)—C(6)—C(7)—C(8)−3.8 (9)
C(10)—C(1)—C(2)—C(3)0.6 (9)C(6)—C(7)—C(8)—C(9)2.4 (9)
C(1)—C(2)—C(3)—C(4)1.3 (9)C(7)—C(8)—C(9)—N(1)178.2 (5)
C(2)—C(3)—C(4)—C(5)−1.6 (9)C(7)—C(8)—C(9)—C(10)1.2 (8)
C(3)—C(4)—C(5)—C(6)179.7 (5)N(1)—C(9)—C(10)—C(1)0.0 (8)
C(3)—C(4)—C(5)—C(10)0.1 (6)N(1)—C(9)—C(10)—C(5)−180.0 (4)
C(4)—C(5)—C(6)—C(7)−177.9 (5)C(8)—C(9)—C(10)—C(1)176.8 (5)
C(4)—C(5)—C(10)—C(1)1.6 (7)C(8)—C(9)—C(10)—C(5)−3.2 (7)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N1—H1a···Br10.982.273.070 (3)138
N1—H1b···N1i0.982.203.073 (5)148

Symmetry codes: (i) −x+1/2, y+1/2, −z+3/2.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: SI2087).

References

  • Aucott, S. M., Milton, H. M., Robertson, S. D., Slawin, A. M. Z. & Woollins, J. D. (2004). Heteroatom. Chem.15, 531–542.
  • Herbert, J. M., Woodgate, P. D. & Denny, W. A. (1987). Heterocycles, 26, 1037–1041.
  • Higashi, T. (1995). ABSCOR Rigaku, Tokyo, Japan.
  • Rigaku (1998). PROCESS-AUTO Rigaku Corporation, Tokyo, Japan.
  • Rigaku/MSC (2006). CrystalStructure and SCXmini Benchtop Crystallography System Software Rigaku/MSC, The Woodlands, Texas, USA.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography