(R)-1,1′-Binaphthalene-2,2′-diol–(Z)-N-ethyl­ideneethanamine N-oxide (1/1)

Bo Shao; Hai-Bin Wang

doi:10.1107/S1600536812007477

. 2012 Mar 3;68(Pt 4):o948. doi: 10.1107/S1600536812007477

(R)-1,1′-Binaphthalene-2,2′-diol–(Z)-N-ethylideneethanamine N-oxide (1/1)

Bo Shao ^a, Hai-Bin Wang ^b,^*

PMCID: PMC3343929 PMID: 22590010

Abstract

In the title compound, C₄H₉NO·C₂₀H₁₄O₂, the dihedral angle between the naphthalene ring systems of the binaphthalenediol molecule is 77.53 (14)°. In the crystal, the two components are linked by O—H⋯O hydrogen bonds, forming a zigzag chain along the c axis.

Related literature

For applications of 2,2′-dihydroxy-1,1′-dinaphthalene in asymmetric synthesis, see: Noyori et al. (1984 ▶); Reeder et al. (1994 ▶); Toda et al. (1989 ▶); Zhang & Schuster (1994 ▶). For related literature on oxidation of hydroxylamines to nitrones, see: Cicchi et al. (2001 ▶); Engel et al. (1997 ▶); Liu et al. (2004 ▶).

Experimental

Crystal data

C₄H₉NO·C₂₀H₁₄O₂
M _r = 373.43
Trigonal,
a = 8.9579 (6) Å
c = 21.187 (3) Å
V = 1472.4 (2) Å³
Z = 3
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 273 K
0.31 × 0.22 × 0.18 mm

Data collection

Bruker APEX area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ▶) T _min = 0.964, T _max = 0.977
7771 measured reflections
1732 independent reflections
1662 reflections with I > 2σ(I)
R _int = 0.033

Refinement

R[F ² > 2σ(F ²)] = 0.053
wR(F ²) = 0.115
S = 1.19
1732 reflections
257 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.19 e Å⁻³
Δρ_min = −0.26 e Å⁻³

Data collection: SMART (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812007477/is5033sup1.cif

e-68-0o948-sup1.cif^{(21.3KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812007477/is5033Isup2.hkl

e-68-0o948-Isup2.hkl^{(83.7KB, hkl)}

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

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯O3	0.82	1.90	2.706 (5)	167
O2—H2⋯O3ⁱ	0.82	1.96	2.763 (5)	168

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Symmetry code: (i) Inline graphic .

Acknowledgments

The authors thank Mr X.-J. Ma for preparing the sample, and Mr X.-J. Ma and Mr H.-Y. Li for collecting the diffraction data.

supplementary crystallographic information

Comment

2,2'-Dihydroxy-1,1'-dinaphthalene (binaphthol) is an important chemical as a precursor for catalysis in asymmetric synthesis, as a chiral host for molecular recognition and enantiomer separation and also as intermediates for the synthesis of chiral materials (Noyori et al., 1984; Toda et al., 1989; Reeder et al., 1994; Zhang & Schuster, 1994). N,N-diethylhydroxylamine is easily oxidized to form E and Z type of N-ethylideneethanamine N-oxide (ELDEA) (Engel et al., 1997; Liu et al., 2004; Cicchi et al., 2001). In this study, only the Z type of ELDEA is trapped by the (R)-binaphthol to form the title complex, (I) (Scheme 1 and Fig. 1).

The asymmetric unit comprises a ELDEA (Z type) molecule and a (R)-binaphthol molecule, which are linked by an intermolecular O—H···O hydrogen bond (Table 1). The two naphthyl groups are almost perpendicular to each other with a dihedral angle being 77.53 (14)°. The N1—O3 length [1.313 (5) Å] of ELDEA is characteristic of the N—O single bond, while the N1═C22 bond [1.265 (7) Å] is a double bond. Because of the existence of N1═C22 double bond, the O3/N1/C21/C22/C24 plane is almost planar. The ELDEA is connected to two H atoms from different binaphthol molecules through O—H···O hydrogen bonds (Fig. 2 and Table 1), forming infinite chains running along the c axis.

Experimental

The (R)-1,1'-bi-2-naphthol (2.9 g) and N,N-diethylhydroxylamine (0.9 g) were mixed and dissolved in sufficient ethanol 30 ml by heating to a temperature of 353 K where a clear solution was resulted, then refluxed for 5 h. The materials of experiment were exposed in air. Single crystals of (I) (2.7 g) were formed form an ethanol solution by gradual evaporation for two weeks at room temperature.