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Acta Crystallogr Sect E Struct Rep Online. 2009 November 1; 65(Pt 11): o2964.
Published online 2009 October 31. doi:  10.1107/S1600536809045152
PMCID: PMC2971357

5-Amino-1-naphthol

Abstract

In the title compound, C10H9NO, the amino and the hydr­oxy groups act both as a single donor and a single acceptor in hydrogen bonding. In the crystal, mol­ecules are connected via chains of inter­molecular (...)N—H(...)O—H(...) inter­actions, forming a two-dimensional polymeric structure resembling the hydrogen-bonded mol­ecular assembly found in the crystal structure of naphthalene-1,5-diol. Within this layer, mol­ecules related by a translation along the a axis are arranged into slipped stacks via π–π stacking inter­actions [inter­planar distance = 3.450 (4) Å]. The amino N atom shows sp 3 hybridization and the two attached H atoms are located on the same side of the aromatic ring.

Related literature

For the crystal structure of 1,5-dihydroxy­naphthalene, see: Belskii et al. (1990 [triangle]). For amino-hydr­oxy group recognition and packing motifs of aminols, see: Ermer & Eling (1994 [triangle]); Hanessian et al. (1994 [triangle]); Allen et al. (1997 [triangle]); Dey et al. (2005 [triangle]).

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Object name is e-65-o2964-scheme1.jpg

Experimental

Crystal data

  • C10H9NO
  • M r = 159.18
  • Orthorhombic, An external file that holds a picture, illustration, etc.
Object name is e-65-o2964-efi1.jpg
  • a = 4.8607 (2) Å
  • b = 12.3175 (6) Å
  • c = 13.0565 (5) Å
  • V = 781.71 (6) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.09 mm−1
  • T = 130 K
  • 0.30 × 0.15 × 0.02 mm

Data collection

  • Kuma KM-4-CCD κ-geometry diffractometer
  • Absorption correction: none
  • 8484 measured reflections
  • 963 independent reflections
  • 726 reflections with I > 2σ(I)
  • R int = 0.037

Refinement

  • R[F 2 > 2σ(F 2)] = 0.036
  • wR(F 2) = 0.091
  • S = 1.06
  • 963 reflections
  • 121 parameters
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.17 e Å−3
  • Δρmin = −0.21 e Å−3

Data collection: CrysAlis CCD (Oxford Diffraction, 2007 [triangle]); cell refinement: CrysAlis RED (Oxford Diffraction, 2007 [triangle]); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 [triangle]) and Mercury (Macrae et al., 2006 [triangle]); software used to prepare material for publication: SHELXL97.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809045152/su2154sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809045152/su2154Isup2.hkl

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

supplementary crystallographic information

Comment

Amino-hydroxy group recognition has been at the focus of crystal engineering since Ermer & Eling (1994) and Hanessian et al. (1994) noticed the complementarity of hydroxy and amino groups as regards hydrogen-bond donors and acceptors. Shortly after it was demonstrated with simple 1,2- and 1,3-aminophenols that molecular features, such as functional groups, do not necessarily result in a single manner of the molecular arrangement, and that strong N—H···O and O—H···N hydrogen bonding is frequently unable to exclude other factors from controlling the crystal packing (Allen et al., 1997; Dey et al. 2005). Here we report on the crystal structure of a simple aminonaphthol which, as regards the substitution pattern, can be considered as an analogue of 1,4-aminophenol.

The molecular structure of the title compound is shown in Fig. 1, and the geometrical parameters are available in the archived CIF. Whereas 1,4-aminophenol forms a tetrahedral network, via N—H···O and O—H···N hydrogen bonds (Ermer & Eling, 1994), in the title compound the molecules are connected via chains of ···N—H···O—H··· interactions to form a two-dimensional polymeric structure (Fig. 2, Table 1). The two-dimensional assembly of the molecules joined by hydrogen bonding resembles that formed by 1,5-dihydroxynaphthalene (Belskii et al., 1990). One amino H-atom is not involved in hydrogen bonding and does not take part in any other specific interactions.

Experimental

Single crystals of the commercially available 5-amino-1-naphthol (Aldrich) were obtained from chloroform solution by slow evaporation.

Refinement

In the absence of significant anomalous scattering effects, Friedel pairs were averaged. All H-atoms were located in electron-density difference maps. The H-atoms of the OH and NH groups were freely refined: O-H = 0.94 (3) Å, N-H = 0.95 (3)- 0.96 (3) Å. The C-bound H-atoms were placed at calculated positions, with C—H = 0.93 Å, and refined as riding on their carrier C-atom, with Uiso(H) = 1.2Ueq(C). .

Figures

Fig. 1.
The molecular structure of the title compound, with displacement ellipsoids shown at the 30% probability level.
Fig. 2.
The crystal packing, viewed along the b-axis, of the title compound, showing the two-dimensional hydrogen-bonded assembly (hydrogen bonds are shown as dashed lines).

Crystal data

C10H9NODx = 1.353 Mg m3
Mr = 159.18Melting point: 461 K
Orthorhombic, P212121Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2abCell parameters from 2383 reflections
a = 4.8607 (2) Åθ = 4–27°
b = 12.3175 (6) ŵ = 0.09 mm1
c = 13.0565 (5) ÅT = 130 K
V = 781.71 (6) Å3Plate, pale pink
Z = 40.30 × 0.15 × 0.02 mm
F(000) = 336

Data collection

Kuma KM-4-CCD κ-geometry diffractometer726 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.037
graphiteθmax = 26.4°, θmin = 4.5°
ω scansh = −6→5
8484 measured reflectionsk = −15→15
963 independent reflectionsl = −16→16

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.036Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.091H atoms treated by a mixture of independent and constrained refinement
S = 1.06w = 1/[σ2(Fo2) + (0.0554P)2] where P = (Fo2 + 2Fc2)/3
963 reflections(Δ/σ)max = 0.001
121 parametersΔρmax = 0.17 e Å3
0 restraintsΔρmin = −0.21 e Å3

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.
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)

xyzUiso*/Ueq
C10.2605 (5)0.48405 (18)0.50574 (15)0.0232 (5)
C20.1125 (5)0.57846 (19)0.51109 (17)0.0269 (6)
H2−0.01350.58870.56380.032*
C30.1504 (5)0.65964 (19)0.43738 (17)0.0268 (6)
H30.04660.72300.44090.032*
C40.3386 (5)0.64703 (19)0.35998 (17)0.0248 (6)
H40.36300.70220.31220.030*
C50.6956 (5)0.53275 (18)0.27339 (16)0.0239 (6)
C60.8417 (5)0.43775 (19)0.26935 (17)0.0265 (6)
H60.97010.42690.21750.032*
C70.7983 (5)0.35673 (19)0.34304 (17)0.0283 (6)
H70.90090.29310.33990.034*
C80.6085 (5)0.36936 (19)0.41937 (17)0.0256 (6)
H80.57950.31410.46670.031*
C90.4571 (5)0.46670 (19)0.42580 (16)0.0215 (5)
C100.4964 (5)0.55036 (18)0.35220 (16)0.0215 (5)
O110.2370 (4)0.40173 (13)0.57550 (11)0.0289 (4)
H11O0.067 (7)0.404 (2)0.609 (2)0.058 (10)*
N120.7265 (5)0.61211 (18)0.19544 (14)0.0275 (5)
H12A0.699 (6)0.685 (2)0.2155 (18)0.044 (8)*
H12B0.899 (6)0.601 (2)0.1610 (19)0.038 (8)*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
C10.0231 (12)0.0279 (13)0.0186 (10)−0.0035 (12)−0.0020 (11)0.0014 (10)
C20.0250 (13)0.0332 (14)0.0226 (11)−0.0002 (12)0.0011 (11)−0.0024 (11)
C30.0261 (13)0.0255 (13)0.0288 (12)0.0028 (12)−0.0008 (11)−0.0047 (11)
C40.0250 (13)0.0272 (13)0.0223 (11)−0.0030 (11)−0.0017 (11)0.0001 (10)
C50.0244 (14)0.0283 (13)0.0192 (10)−0.0070 (11)−0.0053 (10)−0.0014 (10)
C60.0232 (13)0.0334 (13)0.0229 (11)0.0006 (12)0.0024 (10)−0.0056 (11)
C70.0294 (15)0.0244 (13)0.0311 (12)0.0055 (12)−0.0022 (11)−0.0044 (11)
C80.0273 (13)0.0278 (13)0.0216 (11)−0.0011 (11)−0.0013 (11)−0.0004 (10)
C90.0187 (12)0.0263 (13)0.0194 (10)−0.0006 (11)−0.0030 (10)−0.0036 (10)
C100.0204 (12)0.0249 (13)0.0191 (10)−0.0044 (11)−0.0044 (10)−0.0006 (10)
O110.0269 (9)0.0356 (10)0.0243 (8)−0.0003 (9)0.0036 (8)0.0061 (8)
N120.0271 (12)0.0316 (13)0.0237 (10)−0.0025 (12)0.0005 (10)0.0016 (9)

Geometric parameters (Å, °)

C1—O111.368 (2)C5—C101.430 (3)
C1—C21.369 (3)C6—C71.402 (3)
C1—C91.431 (3)C6—H60.9300
C2—C31.400 (3)C7—C81.367 (3)
C2—H20.9300C7—H70.9300
C3—C41.372 (3)C8—C91.409 (3)
C3—H30.9300C8—H80.9300
C4—C101.420 (3)C9—C101.422 (3)
C4—H40.9300O11—H11O0.94 (3)
C5—C61.370 (3)N12—H12A0.95 (3)
C5—N121.419 (3)N12—H12B0.96 (3)
O11—C1—C2123.5 (2)C7—C6—H6119.9
O11—C1—C9115.5 (2)C8—C7—C6121.4 (2)
C2—C1—C9120.99 (19)C8—C7—H7119.3
C1—C2—C3120.2 (2)C6—C7—H7119.3
C1—C2—H2119.9C7—C8—C9119.5 (2)
C3—C2—H2119.9C7—C8—H8120.2
C4—C3—C2120.9 (2)C9—C8—H8120.2
C4—C3—H3119.6C8—C9—C10120.4 (2)
C2—C3—H3119.6C8—C9—C1121.3 (2)
C3—C4—C10120.5 (2)C10—C9—C1118.3 (2)
C3—C4—H4119.7C4—C10—C9119.1 (2)
C10—C4—H4119.7C4—C10—C5123.0 (2)
C6—C5—N12120.4 (2)C9—C10—C5117.9 (2)
C6—C5—C10120.6 (2)C1—O11—H11O111.6 (18)
N12—C5—C10118.9 (2)C5—N12—H12A116.2 (15)
C5—C6—C7120.2 (2)C5—N12—H12B109.1 (15)
C5—C6—H6119.9H12A—N12—H12B113 (2)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O11—H11O···N12i0.94 (3)1.83 (3)2.749 (3)167 (3)
N12—H12B···O11ii0.96 (3)2.09 (3)3.046 (3)171 (2)

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: SU2154).

References

  • Allen, F. H., Hoy, V. J., Howard, J. A. K., Thalladi, V. R., Desiraju, G. R., Wilson, C. C. & McIntyre, G. J. (1997). J. Am. Chem. Soc.119, 3477–3480.
  • Belskii, V. K., Kharchenko, E. V., Sobolev, A. N., Zavodnik, V. E., Kolomiets, N. A., Prober, G. S. & Oleksenko, L. P. (1990). Zh. Strukt. Khim.31, 116–121.
  • Dey, A., Kirchner, M. T., Vangala, V. R., Desiraju, G. R., Mondal, R. & Howard, J. A. K. (2005). J. Am. Chem. Soc.127, 10545–10559. [PubMed]
  • Ermer, O. & Eling, A. J. (1994). J. Chem. Soc. Perkin Trans. 2, pp. 925–944.
  • Farrugia, L. J. (1997). J. Appl. Cryst.30, 565.
  • Hanessian, S., Gomtsyan, A., Simard, M. & Roelens, S. (1994). J. Am. Chem. Soc 116, 4495–4496.
  • Macrae, C. F., Edgington, P. R., McCabe, P., Pidcock, E., Shields, G. P., Taylor, R., Towler, M. & van de Streek, J. (2006). J. Appl. Cryst.39, 453–457.
  • Oxford Diffraction (2007). CrysAlis CCD and CrysAlis RED Oxford Diffraction, Abingdon, England.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]

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