catena-Poly[[[O,O′-bis­(2-methyl­phen­yl) dithio­phosphato-κ2 S,S]lead(II)]-μ-O,O′-bis­(2-methyl­phen­yl) dithio­phosphato-κ3 S,S′:S]

Ray J Butcher; Raju Ratnani; Sema Öztürk Yildirim; Oluwaseun Falola

doi:10.1107/S1600536812047964

. 2012 Dec 8;69(Pt 1):m29–m30. doi: 10.1107/S1600536812047964

catena-Poly[[[O,O′-bis(2-methylphenyl) dithiophosphato-κ² S,S]lead(II)]-μ-O,O′-bis(2-methylphenyl) dithiophosphato-κ³ S,S′:S]

Ray J Butcher ^a,^*, Raju Ratnani ^b,^‡, Sema Öztürk Yildirim ^a,^c, Oluwaseun Falola ^a

PMCID: PMC3588372 PMID: 23476328

Abstract

In the title compound, [Pb(C₁₄H₁₄O₂PS₂)₂]_n, the metal atom is surrounded by two O,O′-bis(2-methylphenyl) dithiophosphate ligands bonding through the S-donor atoms. Three of the Pb—S bond lengths are are close to each other at 2.7710 (18), 2.8104 (16) and 2.8205 (16) Å, while the fourth Pb—S bond is elongated at 3.0910 (18) Å and reflects the fact that this atom is involved in intermolecular bridging to an adjacent Pb^II atom [Pb—S = 3.145 (2) Å]. The bond angles demonstrate that the Pb^II atom contains a stereochemically active lone pair with a distorted octahedral geometry about the Pb^II atom. This distortion is shown by the S—Pb—S bite angles of 73.63 (4) and 69.50 (4)°, while the remaining S—Pb—S angles range from 81.03 (5) to 143.66 (5)°. One of the benzene rings shows positional disorder over two orientations with occupancy factors of 0.747 (11) and 0.253 (11).

Related literature

For applications of related O,O′-dialkyl derivatives of phosphorus(V) dithioacids, see: Lawton & Kokotailo (1969 ▶, 1972 ▶); Ito (1972 ▶); Harrison et al. (1988 ▶). For general and convenient methods for the preparation of dithiophosphato salt derivatives and their metal derivatives, see: Bajia et al. (2009 ▶); Maheshwari et al. (2009 ▶); Lawton & Kokotailo (1969 ▶, 1972 ▶); Ito (1972 ▶); Harrison et al. (1988 ▶); Van Zyl & Fackler, (2000 ▶); Van Zyl (2010 ▶). For VSEPR theory, see: Gillespie & Nyholm (1957 ▶). For stereochemically active lone pairs in Pb²⁺ complexes, see: Davidovich et al. (2010 ▶); Ito & Maeda (2004 ▶); Larsson et al. (2004 ▶); Lawton & Kokotailo (1972 ▶).

Experimental

Crystal data

[Pb(C₁₄H₁₄O₂PS₂)₂]
M _r = 825.87
Monoclinic,
a = 12.0263 (6) Å
b = 10.7420 (4) Å
c = 13.0499 (8) Å
β = 112.849 (6)°
V = 1553.58 (15) Å³
Z = 2
Cu Kα radiation
μ = 14.31 mm⁻¹
T = 123 K
0.46 × 0.05 × 0.03 mm

Data collection

Agilent Xcalibur (Ruby, Gemini) diffractometer
Absorption correction: analytical [CrysAlis PRO (Agilent, 2011 ▶), using a multi-faceted crystal model (Clark & Reid, 1995 ▶)] T _min = 0.094, T _max = 0.675
10226 measured reflections
4494 independent reflections
4269 reflections with I > 2σ(I)
R _int = 0.045

Refinement

R[F ² > 2σ(F ²)] = 0.030
wR(F ²) = 0.075
S = 1.03
4494 reflections
406 parameters
55 restraints
H-atom parameters constrained
Δρ_max = 1.12 e Å⁻³
Δρ_min = −1.15 e Å⁻³
Absolute structure: Flack (1983 ▶), 1093 Friedel pairs
Flack parameter: −0.03 (8)

Data collection: CrysAlis PRO (Agilent, 2011 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; 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: SHELXTL.

Supplementary Material

Click here for additional data file.^{(40.2KB, cif)}

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812047964/bt6859sup1.cif

e-69-00m29-sup1.cif^{(40.2KB, cif)}

Click here for additional data file.^{(220.2KB, hkl)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812047964/bt6859Isup2.hkl

e-69-00m29-Isup2.hkl^{(220.2KB, hkl)}

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

Acknowledgments

RJB acknowledges the NSF–MRI program (grant No. CHE-0619278) for funds to purchase the diffractometer.

supplementary crystallographic information

Comment

O,O'-Dialkyl derivatives of phosphorus(V) dithioacids are characterized by wide possibilities for practical applications in various areas, namely, as flotation reagents (in the concentration of sulfide ores of nonferrous metals), fungicides, insecticides, herbicides, antioxidants, additives to lubricating oils, and technological precursors of film sulfides of transition and nontransition metals. The structural variety of metal complexes with dialkyldithiophosphates has been explained in terms of coordination chemistry by the ability of these compounds to perform different structural functions and act as bidentate terminal, bidentate bridging or combined ligands. As a result, compounds with different types of structural organization can be formed: mono-, bi-, tetra-, or polynuclear complexes. A unique alternation of the conformationally different (`chair`-`saddle`) eight-membered rings [Cd₂S₄P₂] has been revealed in the chains of polynuclear cadmium(II) complexes [Cd{S(S)P(OR)₂}₂]_n (Lawton & Kokotailo, 1969; Lawton & Kokotailo, 1972; Ito, 1972; Harrison et al., 1988). General and convenient methods to prepare dithiophosphato salt derivatives have been reported (Van Zyl & Fackler, 2000; Van Zyl, 2010). In view of the importance of these compounds and in continuation of our earlier work (Bajia et al., 2009; Maheshwari et al., 2009) we have undertaken the crystal structure determination of the title compound, and the results are presented here. Pb²⁺ complexes of these types of ligands are of particular interest because of the possibility of exhibiting stereochemically active lone pairs (Davidovich et al., 2010; Ito & Maeda, 2004; Larsson et al., 2004; Lawton & Kokotailo, 1972).

The X-ray study confirmed the molecular structure and atomic connectivity for (I), as illustrated in Fig. 1. The structure consists of a linear zigzag chain of molecules in the b direction composed of one Pb atom and two chelating bis(2-methylphenyl) phosphato ligands and linked by Pb—S—Pb bonds. The two bis(2-methylphenyl) phosphato ligands are coordinated through both S atoms to the metal. Three of the Pb—S bond lengths are insignificantly different at 2.7710 (18), 2.8104 (16) and 2.8205 (16) Å, while the fourth Pb—S bond is elongated at 3.0910 (18) Å and reflects the fact that this atom is involved in intermolecular bridging (symmetry code, 2 - x,1/2 + y,1 - z) to an adjacent Pb (intermolecular Pb—S distance, 3.145 (2) Å).

The bond angles reflect the fact that Pb contains a stereochemically active lone pair so the geometry about the Pb is best described using VSEPR theory as AX₅E (Gillespie & Nyholm, 1957) and is thus distorted octahedral. The S—Pb—S bite angles are small at 73.63 (4) and 69.50 (4)° while the remaining S—Pb—S angles range from 81.03 (5) to 143.66 (5)°. Thus the relative bond distances and angles for the title compound agree with the presence of an electron lone pair in a distorted octahedral PbS₅E (with one S as a bridging ligand) environment. Evidence for the presence of a stereochemically active electron lone pair of the lead atom has also been reported for other Pb²⁺ complexes with similar ligands (Davidovich et al., 2010; Ito & Maeda, 2004; Larsson et al., 2004; Lawton & Kokotailo, 1972).

In the molecule one of the 1-methoxy-2-methyl-benzene rings (O4—C22—C28) shows positional disorder over two orientations with occupancy ratio of 0.747 (11):0.253 (11).

No evidence for C—H···O or C—H···S interactions were found in the crystal.

Experimental

Title compound was published methods (Bajia et al., 2009; Maheshwari et al., 2009; Lawton & Kokotailo, 1969; Lawton & Kokotailo, 1972; Ito, 1972; Harrison et al., 1988). Crystals were grown by slow evaporation of a mixture of absolute ethyl alcohol (90%) and chloroform (10%) solution.