1,1′-Binaphthalene-2,2′-diyl hydrogen phosphate

Susanta K Nayak; S Chandrasekhar; T N Guru Row

doi:10.1107/S1600536807064343

. 2007 Dec 12;64(Pt 1):o256. doi: 10.1107/S1600536807064343

1,1′-Binaphthalene-2,2′-diyl hydrogen phosphate

Susanta K Nayak ^a, S Chandrasekhar ^b, T N Guru Row ^a,^*

PMCID: PMC2915313 PMID: 21200821

Abstract

The title compound, racemic bnppa, C₂₀H₁₃O₄P, crystallizes with four molecules in the asymmetric unit. Two independent centrosymmetric O—H⋯O hydrogen-bonded tetramers, each involving two of the symmetry-independent molecules in the asymmetric unit generate the packing motif in the crystal structure. The hydrophobic parts of the tetramers connect to their neighbours via C—H⋯π and π–π interactions [3.899 (2), 3.895 (2) and 3.803 (2) Å within the symmetric unit, 3.851 (2), 4.000 (2), 3.988 (2) and 3.905 (2) Å across centres of symmetry].

Related literature

For details on bnppa as an optical resolution agent of amines, see: Fujii & Hirayamma (2002 ▶); Arnold et al. (1983 ▶); Wilen et al. (1991 ▶). For the conglomerate nature of racemates, see: Jacques et al. (1981 ▶). For related literature, see: An et al. (1996 ▶); Bernstein et al. (1995 ▶); Etter & Baures (1988 ▶).

Experimental

Crystal data

C₂₀H₁₃O₄P
M _r = 348.27
Triclinic,
a = 14.2152 (14) Å
b = 14.6480 (14) Å
c = 15.6397 (15) Å
α = 87.710 (2)°
β = 88.074 (2)°
γ = 83.952 (2)°
V = 3234.4 (5) Å³
Z = 8
Mo Kα radiation
μ = 0.19 mm⁻¹
T = 292 (2) K
0.31 × 0.07 × 0.06 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.939, T _max = 0.989
32848 measured reflections
12219 independent reflections
7419 reflections with I > 2σ(I)
R _int = 0.053

Refinement

R[F ² > 2σ(F ²)] = 0.068
wR(F ²) = 0.160
S = 1.06
12219 reflections
901 parameters
H-atom parameters constrained
Δρ_max = 0.31 e Å⁻³
Δρ_min = −0.34 e Å⁻³

Data collection: SMART (Bruker, 2004 ▶); cell refinement: SAINT (Bruker, 2004 ▶); data reduction: SAINT; program(s) used to solve structure: WinGX (Farrugia, 1999 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1999 ▶) and CAMERON (Watkin et al., 1993 ▶); software used to prepare material for publication: PLATON (Spek, 2003 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536807064343/ln2013sup1.cif

e-64-0o256-sup1.cif^{(47.4KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536807064343/ln2013Isup2.hkl

e-64-0o256-Isup2.hkl^{(585.3KB, hkl)}

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

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

Cg1 and Cg2 are the centroids of the C64–C69 and C12–C17 rings.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O4—H1O⋯O7	0.82	1.78	2.475 (4)	141
O8—H2O⋯O3ⁱ	0.82	1.77	2.450 (4)	139
O16—H4O⋯O12ⁱⁱ	0.82	1.99	2.441 (4)	114
O11—H30⋯O15	0.82	1.71	2.477 (4)	154
C22—H22⋯O11ⁱⁱⁱ	0.93	2.51	3.435 (4)	174
C59—H59⋯O7^iv	0.93	2.56	3.478 (4)	167
C27—H27⋯Cg1	0.93	2.75	3.567 (5)	147
C54—H54⋯Cg2^v	0.93	2.77	3.535 (5)	140

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) .

Acknowledgments

The authors thank DST-IRHPA for the CCD X-ray facility at IISc and CSIR (SRF), India, for financial support.

supplementary crystallographic information

Comment

We have been investigating the conglomerate nature of racemates in our laboratory, as very few structures show the features of conglomerates (Jacques et al., 1981). Optically active 1,1'-binaphthalene-2,2'-diyl hydrogen phosphate (bnppa) has been used as a good optical resolution agent for amines (Fujii et al., 2002; Arnold et al., 1983; Wilen et al., 1991). However, the procedure adopted in the preparation yields only racemic bnppa crystals (Scheme).

The compound crystallizes in a triclinic space group P-1, with Z = 8. Of the four molecules in the asymmetric unit (Fig. 1), pairs are connected through intermolecular O—H···O hydrogen bonds (Table 1) and two such motifs form independent centrosymmetric tetramers (Fig. 2) though additional O—H···O hydrogen bonds. The packing in the crystal structure is hence through tetrameric O—H···O hydrogen bonded systems [Etter's graph set symbol R₄⁴(16)] (Bernstein et al., 1995). Further, the hydrophobic parts of the symmetry-independent parts of the tetramers are linked via C—H···π interactions [C27—H27···π (C64/C65/C66/C67/C68/C69) = 2.75 Å, C54—H54···π (C12/C13/C14/C14/C15/C16/C17 = 2.77 Å)]. There are several π···π interactions within the symmetric unit [3.899 (2), 3.895 (2) and 3.803 (2) Å], as well as others across centres of symmetry [3.851 (2), 4.000 (2), 3.988 (2) and 3.905 (2) Å]. Table 1 lists all O—H···0 hydrogen bonds along with two C—H..O interactions which form as a consequence of tetramer formation.

Experimental

Racemic binaphthylphosphoylchloride (29.2 g, 80 mmol) prepared by a known procedure (An et al., 1996) was dissolved in 1.4 l. of 2% Na₂CO₃ solution and heated until a clear solution formed. The solution, on keeping at 273 K for 12 h, yields a grey precipitate. The precipitate was collected by filtration, washed with 100 ml of 2% Na₂CO₃ solution and suspended in 650 ml of water. 50 ml of conc. HCl was then added to this while stirring. The mixture was heated to 368 K for 5 minutes and was kept at 277 K for 14 h. The resulting white crystalline mass was separated by filtration followed by washing with cold water and dried to obtain bnppa in 59.2% yield (m.p. 621 K). Plate-like colourless crystals of bnppa were grown in acetonitrile and water (2:1 v/v) with triphenyphosphine oxide as an additive promotor in the ratio 50:50 (Etter et al., 1988) by slow evaporation at room temperature.