Triethyl­ammonium (S)-(−)-O-[1-(2-naphth­yl)eth­yl] (4-meth­oxy­phen­yl)dithio­phospho­nate

Samet Solak; Mehmet Karakuş; Barış Tercan; Tuncer Hökelek

doi:10.1107/S1600536811015820

. 2011 Apr 29;67(Pt 5):o1260–o1261. doi: 10.1107/S1600536811015820

Triethylammonium (S)-(−)-O-[1-(2-naphthyl)ethyl] (4-methoxyphenyl)dithiophosphonate

Samet Solak ^a, Mehmet Karakuş ^a, Barış Tercan ^b, Tuncer Hökelek ^c,^*

PMCID: PMC3089098 PMID: 21754549

Abstract

The crystal structure of the title compound, C₆H₁₆N⁺·C₁₉H₁₈O₂PS₂ ⁻, consists of the dithiophosphonate anions and the triethylammonium cations, which are linked by N—H⋯S hydrogen bonds and weak C—H⋯O hydrogen bonds. In the anion, the benzene ring is oriented with respect to the naphthalene ring system at a dihedral angle of 24.92 (5)°. In the crystal, weak C—H⋯π interactions also occur.

Related literature

For dithiophosphorus compounds and their complexes, see: Heiduc et al. (2006 ▶); Karakuş et al. (2007 ▶); Gataulina et al. (2008 ▶). For the roles of dithiophosphorus compounds in agricultural, industrial and medicinal products such as additives to lubricant oils, solvent extraction reagents for metals, floatation agents for minerals, pesticides and insecticides, see: Thomas et al. (2001 ▶); Gray et al. (2003 ▶). For the synthetic routes reported for dithiophosphorus-type ligands, see: Alberti et al. (2007 ▶). For the preparation of ferrocenyl and aryldithiophosphonates and their complexes with a range of transition metals, see: Gray et al. (2004 ▶). For bond-length data, see: Allen et al. (1987 ▶).

Experimental

Crystal data

C₆H₁₆N⁺·C₁₉H₁₈O₂PS₂ ⁻
M _r = 475.62
Orthorhombic,
a = 9.3782 (3) Å
b = 12.3467 (5) Å
c = 21.9651 (8) Å
V = 2543.33 (16) Å³
Z = 4
Mo Kα radiation
μ = 0.29 mm⁻¹
T = 294 K
0.52 × 0.36 × 0.32 mm

Data collection

Bruker Kappa APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T _min = 0.862, T _max = 0.912
43596 measured reflections
6343 independent reflections
5946 reflections with I > 2σ(I)
R _int = 0.030

Refinement

R[F ² > 2σ(F ²)] = 0.036
wR(F ²) = 0.094
S = 1.06
6343 reflections
289 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.78 e Å⁻³
Δρ_min = −0.26 e Å⁻³
Absolute structure: Flack (1983 ▶), 2752 Friedel pairs
Flack parameter: −0.01 (6)

Data collection: APEX2 (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: ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶) and PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811015820/xu5201sup1.cif

e-67-o1260-sup1.cif^{(23.6KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811015820/xu5201Isup2.hkl

e-67-o1260-Isup2.hkl^{(304.2KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811015820/xu5201Isup3.cml

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

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

Cg1 and Cg2 are the centroids of the C1–C6 and C10–C13/C18/C19 rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯S2ⁱ	0.84 (3)	2.52 (3)	3.2911 (17)	154 (2)
C20—H20A⋯O1	0.97	2.56	3.505 (2)	166
C7—H7B⋯Cg2ⁱⁱ	0.96	2.90	3.658 (3)	137
C24—H24B⋯Cg1ⁱⁱⁱ	0.97	2.79	3.750 (2)	171

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

Acknowledgments

The authors are indebted to Anadolu University and the Medicinal Plants and Medicine Research Centre of Anadolu University, Eskişehir, Turkey, for the use of the diffractometer. This work was supported financially by the Scientific and Technological Research Council of Turkey (grant No. 107T817).

supplementary crystallographic information

Comment

Dithiophosphorus compounds and their complexes have been widely investigated in last decades (Heiduc et al., 2006; Karakuş et al., 2007; Gataulina et al., 2008). They have been utilized in agricultural, industrial and medicinal products such as additive to lubricant oils, solvent extraction reagents for metals, floatation agents for minerals, pectidites and insecticides (Thomas et al., 2001; Gray et al., 2003). For example, tin diphenyldithiophosphinato complexes show an antiproliferation activity towards certain leukaemia cells (Gray et al., 2003). In general, dithiophosphorus type ligands are not commercially available, but a few synthetic routes were reported in the literature (Alberti et al., 2007). When compared to the other dithiophosphorus derivatives, there is very limited research on dithiophosphonates in the last century, due to the difficulties in sythesizing these compounds. Recently, ferrocenyl and aryldithiophosphonates and their complexes with a range of transition metals were prepared by Woolins et al. (Gray et al., 2003; Gray et al., 2004). The present study was undertaken to ascertain the crystal structure of the title compound to contribute to this relatively less developed area.

The title compound consists of a dithiophosphonate bridged napthylethyl and methoxyphenyl groups and a triethylammonium moiety linked by a C-H···O hydrogen bond (Table 1 and Fig. 1), where the bond lengths are close to standard values (Allen et al., 1987).

An examination of the deviations from the least-squares planes through individual rings shows that rings A (C1—C6), B (C10—C13/C18/C19) and C (C13—C18) are planar. The naphthalene group, containing the rings B and C are also nearly planar [with a maximum deviation of -0.022 (2) Å for atom C13] with a dihedral angle of B/C = 1.67 (7)°. Ring A is oriented with respect to the planar naphthalene group at a dihedral angle of 24.92 (5)°.

In the crystal, C—H···O and N-H···S hydrogen bonds link the molecules into chains along [100] (Table 1 and Fig. 2). There also exist two weak C-H···π interactions (Table 1).

Experimental

For the preparation of the title compound, (I), 2,4-bis(4-methoxyphenyl)-1,3,2,4-dithiadiphosphetane-2,4-disulfide (0.51 g, 1.23 mmol) and (S)-(-)-1-(2-naphthyl)ethanol (0.43 g, 2.46 mmol) were suspended in toluene (20 ml). The mixture was refluxed until all solids had dissolved. The yellow solution was cooled to room temperature, filtered and treated with excess triethyl amine. The product was precipitated at 291 K from hexane/toluene (1:4) as colorless crystals. They were isolated by filtration, washed with n-pentane and dried in air (yield; 0.85 g, 72.64%, m.p. 359-360 K).