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Linear chain bis­(μ O,O′ di­methyl di­thio­phosphato)­lead(II)

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Acta Cryst.(2004). E60, m1349±m1350 DOI: 10.1107/S1600536804020914 Ito and Maeda [Pb(C2H6O2PS2)2]

m1349

Acta Crystallographica Section E Structure Reports Online

ISSN 1600-5368

Linear-chain bis(

l

-

O,O

000

-dimethyl

dithio-phosphato)lead(II)

Tetsuzo Ito* and Yoshinori Maeda

Department of Applied Chemistry, Faculty of Engineering, Kanagawa Institute of Technology, Atsugi, Kanagawa 243-0292, Japan

Correspondence e-mail: ito@chem.kanagawa-it.ac.jp

Key indicators

Single-crystal X-ray study

T= 296 K

Mean(O±C) = 0.012 AÊ

Rfactor = 0.029

wRfactor = 0.028

Data-to-parameter ratio = 13.4

For details of how these key indicators were automatically derived from the article, see http://journals.iucr.org/e.

#2004 International Union of Crystallography Printed in Great Britain ± all rights reserved

The title compound, [Pb(C2H6O2PS2)2], has a twofold rotation

axis passing through the Pb atom along thebaxis. One of the two unique S atoms in a formula unit and its symmetry-equivalent S atom bridge two adjacent Pb atoms, forming a polymeric linear chain along the c axis. The Pb atom is coordinated by six S atoms in a distorted octahedral arrangement. The six PbÐS distances are in the range 2.860 (2)±3.145 (2) AÊ, with an average of 3.01 (8) AÊ.

Comment

As part of a study of metal xanthates and dialkyldithio-phosphates (Ito, 2003, 2004), the crystal structure of the title compound, (I), has been determined. A displacement ellipsoid plot of (I) is shown in Fig. 1. Atom S2 and its symmetry-equivalent S2iiatom (symmetry code as in Table 1) bridge two

adjacent Pb atoms, forming a linear chain. Of the six S atoms coordinated to the Pb atom, four S atoms are approximately coplanar with the Pb atom. Mean-plane calculations (Ito, 1982) show that the maximum deviations from the plane de®ned by seven atoms, viz. Pb(S2P)2, are 0.164 (2) and

ÿ0.164 (2) AÊ for atoms S1 and S1ii, respectively. The plane

normal is perpendicular to the baxis because of the twofold symmetry along thebaxis.

The distorted octahedral coordination around the Pb atom and the structure of the linear chain in (I) are very similar to those in a diisopropyl analogue, bis(O,O0 -diisopropyldithio-phosphato)lead(II), (II) (Lawton & Kokotailo, 1972), with PbÐS distances ranging from 2.761 (7) to 3.232 (10) AÊ. Those authors explained the abnormally large S2ÐPbÐS4 angle of 152.3 (1)in (II), which corresponds to the S2ÐPbÐS2iiangle

of 144.33 (7) in (I), by the existence of a stereochemically active lone pair of electrons oriented in a direction which approximately bisects the large S2ÐPbÐS4 angle. According to this interpretation, the coordination around the Pb atom is a distorted pentagonal bipyramid in which the lone pair

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occupies an equatorial position. On the other hand, in a diethyl analogue, bis(O,O0-diethyldithiophosphato)lead(II), (III) (Ito, 1972), the sulfur coordination around the Pb atom is distorted tetragonal pyramidal, with PbÐS distances ranging from 2.754 (6) to 3.022 (6) AÊ. Above the apex Pb atom, two S atoms of the adjacent unit approach with contact Pb S distances of 3.469 (6) and 3.478 (6) AÊ. Comparison of the structures (I), (II) and (III) suggests that the differences in the sulfur coordination around the Pb atoms in these compounds probably arise from the packing characteristics of dialkyl groups in the crystalline state.

Experimental

Potassium dimethyldithiophosphate (6.0 g) and lead nitrate (5.3 g) were each dissolved in pure water (20 ml). A powder of (I) was precipitated by combining the two solutions. Recrystallization from an acetone solution at 273 K gave colourless prismatic crystals of (I).

Crystal data

[Pb(C2H6O2PS2)2]

Mr= 521.56 Orthorhombic,Pbcn a= 17.738 (3) AÊ b= 9.218 (2) AÊ c= 9.216 (1) AÊ V= 1506.9 (4) AÊ3

Z= 4

Dx= 2.299 Mg mÿ3 Dm= 2.292 Mg mÿ3

Dmmeasured by ¯otation in zinc iodide (aq)

Mo Kradiation Cell parameters from 25

re¯ections = 15.9±16.5 = 11.97 mmÿ1

T= 296 K Prism, colourless 0.160.120.12 mm

Data collection

Rigaku AFC-5Sdiffractometer !±2scans

Absorption correction: scan (Northet al., 1968) Tmin= 0.146,Tmax= 0.238

1834 measured re¯ections 1727 independent re¯ections 1005 re¯ections withI> 3(I)

Rint= 0.007

max= 27.5

h= 0!23 k= 0!11 l=ÿ11!0 3 standard re¯ections

every 150 re¯ections intensity decay: 0.2%

Re®nement

Re®nement onF R= 0.029 wR= 0.028 S= 1.26 1005 re¯ections 75 parameters

H-atom parameters constrained w= 1/2(Fo)

(/)max< 0.001

max= 1.40 e AÊÿ3

min=ÿ0.92 e AÊÿ3

Table 1

Selected geometric parameters (AÊ,).

PbÐS1 2.860 (2)

PbÐS2 3.145 (2)

PbÐS2i 3.033 (2)

S1ÐP1 1.976 (3)

S2ÐP1 1.987 (3)

P1ÐO1 1.585 (6)

P1ÐO2 1.579 (7)

O1ÐC1 1.463 (9)

O2ÐC2 1.452 (11)

S1ÐPbÐS1ii 76.0 (1)

S1ÐPbÐS2 68.04 (6)

S1ÐPbÐS2i 91.28 (6)

S1ÐPbÐS2iii 94.75 (7)

S1ÐPbÐS2ii 143.50 (6)

S2ÐPbÐS2i 80.14 (7)

S2ÐPbÐS2ii 148.33 (7)

S2ÐPbÐS2iii 97.75 (6)

S2iÐPbÐS2iii 172.34 (7)

Symmetry codes: (i) 1ÿx;ÿy;1ÿz; (ii) 1ÿx;y;1

2ÿz; (iii)x;ÿy;zÿ12.

Table 2

Contact distances (AÊ).

Pb O1i 3.012 (6)

S1 C1iv 3.448 (9) S2 O1

iii 3.336 (6)

Symmetry codes: (i) 1ÿx;ÿy;1ÿz; (iii)x;ÿy;zÿ1

2; (iv)x;1ÿy;zÿ12.

H atoms were placed in geometrically calculated positions (CÐH = 0.95 AÊ) and allowed to ride on their parent atoms, withUiso = 1.2Ueq(parent atom).

Data collection: MSC/AFC Diffractometer Control Software

(Molecular Structure Corporation, 1988); cell re®nement:MSC/AFC Diffractometer Control Software; data reduction: CrystalStructure

(Rigaku/MSC, 2002); program(s) used to solve structure: SIR92 (Altomareet al., 1994); program(s) used to re®ne structure: Crystal-Structure; molecular graphics:ORTEPIII (Burnett & Johnson, 1996); software used to prepare material for publication:CrystalStructure.

References

Altomare, A., Cascarano, G., Giacovazzo, C., Guagliardi, A., Burla, M. C., Polidori, G. & Camalli, M. (1994).J. Appl. Cryst.27, 435.

Burnett, M. N. & Johnson, C. K. (1996).ORTEPIII. Report ORNL-6895. Oak Ridge National Laboratory, Tennessee, USA.

Ito, T. (1972).Acta Cryst.B28, 1034±1040. Ito, T. (1982).Acta Cryst.A38, 869±870. Ito, T. (2003).Acta Cryst.E59, m892±m893. Ito, T. (2004).Acta Cryst.E60, m783±m784.

Lawton, S. L. & Kokotailo, G. (1972).Inorg. Chem.11, 363±368.

Molecular Structure Corporation (1988).MSC/AFC Diffractometer Control Software. MSC, 3200 Research Forest Drive, The Woodlands, TX 77381, USA.

North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968).Acta Cryst.A24, 351± 359.

Rigaku/MSC (2002).CrystalStructure.Version. 3.00. Rigaku/MSC, 9009 New Trails Drive The Woodlands, TX 77381±5209, USA.

Figure 1

A view of part of the crystal structure of (I), showing 50% probability

displacement ellipsoids. Atoms Pbi and Pbiii are related by a unit

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supporting information

sup-1

Acta Cryst. (2004). E60, m1349–m1350

supporting information

Acta Cryst. (2004). E60, m1349–m1350 [https://doi.org/10.1107/S1600536804020914]

Linear-chain bis(

µ

-

O,O

-dimethyl dithiophosphato)lead(II)

Tetsuzo Ito and Yoshinori Maeda

(I)

Crystal data

[Pb(C2H6O2PS2)2]

Mr = 521.56

Orthorhombic, Pbcn

Hall symbol: -P 2n 2ab

a = 17.738 (3) Å

b = 9.218 (2) Å

c = 9.216 (1) Å

V = 1506.9 (4) Å3

Z = 4

F(000) = 976.00

Dx = 2.299 Mg m−3

Dm = 2.292 Mg m−3

Dm measured by flotation in zinc iodide (aq) Mo radiation, λ = 0.7107 Å

Cell parameters from 25 reflections

θ = 15.9–16.5°

µ = 11.97 mm−1

T = 296 K Prism, colorless 0.16 × 0.12 × 0.12 mm

Data collection

Rigaku AFC-5S diffractometer

ω–2θ scans

Absorption correction: ψ scan (North et al., 1968)

Tmin = 0.146, Tmax = 0.238 1834 measured reflections 1727 independent reflections

1005 reflections with I > 3σ(I)

Rint = 0.007

θmax = 27.5°

h = 0→23

k = 0→11

l = −11→0

3 standard reflections every 150 reflections intensity decay: 0.2%

Refinement

Refinement on F R[F2 > 2σ(F2)] = 0.029

wR(F2) = 0.028

S = 1.26 1005 reflections 75 parameters

H-atom parameters constrained

Weighting scheme based on measured s.u.'s w = 1/σ2(F

o) (Δ/σ)max < 0.001 Δρmax = 1.40 e Å−3 Δρmin = −0.92 e Å−3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

x y z Uiso*/Ueq

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C2 0.7615 (6) 0.149 (1) 0.620 (1) 0.107 (5) H1 0.6516 0.3752 0.758 0.113* H2 0.5745 0.4215 0.694 0.113* H3 0.5781 0.3497 0.846 0.113* H4 0.7449 0.157 0.718 0.128* H5 0.7627 0.050 0.593 0.128* H6 0.8106 0.189 0.612 0.128*

Atomic displacement parameters (Å2)

U11 U22 U33 U12 U13 U23 Pb 0.0403 (2) 0.0318 (2) 0.0292 (2) 0.0000 0.0020 (4) 0.0000 S1 0.068 (2) 0.034 (1) 0.049 (1) −0.012 (1) −0.015 (1) 0.010 (1) S2 0.047 (1) 0.035 (1) 0.044 (1) 0.0048 (9) −0.001 (1) −0.001 (1) P1 0.045 (1) 0.039 (1) 0.034 (1) −0.012 (1) −0.005 (1) 0.004 (1) O1 0.103 (6) 0.041 (3) 0.032 (3) −0.023 (4) 0.009 (4) −0.008 (3) O2 0.047 (4) 0.069 (4) 0.077 (5) −0.023 (4) −0.010 (4) 0.023 (4) C1 0.17 (1) 0.052 (6) 0.064 (6) −0.033 (7) 0.00 (1) −0.026 (7) C2 0.055 (8) 0.13 (1) 0.14 (1) −0.024 (8) −0.045 (9) 0.05 (1)

Geometric parameters (Å, º)

Pb—S1 2.860 (2) P1—O2 1.579 (7) Pb—S1i 2.860 (2) O1—C1 1.463 (9) Pb—S2 3.145 (2) O2—C2 1.452 (11) Pb—S2i 3.145 (2) C1—H1 0.95 Pb—S2ii 3.033 (2) C1—H2 0.95 Pb—S2iii 3.033 (2) C1—H3 0.95 S1—P1 1.976 (3) C2—H4 0.95 S2—P1 1.987 (3) C2—H5 0.95 P1—O1 1.585 (6) C2—H6 0.95

Pb···O1ii 3.012 (6) S1···C1iv 3.448 (9) Pb···O1iii 3.012 (6) S2···O1iii 3.336 (6)

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supporting information

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Acta Cryst. (2004). E60, m1349–m1350

S2ii—Pb—S2i 97.75 (6) O2—C2—H5 108.5 S2iii—Pb—S2i 80.14 (7) H4—C2—H5 109.5 Pb—S1—P1 91.7 (1) O2—C2—H6 110.7 Pb—S2—P1 83.47 (9) H4—C2—H6 109.5 S1—P1—S2 116.42 (14) H5—C2—H6 109.5 S1—P1—O1 111.0 (3)

Pb—S1—P1—S2 6.0 (2) S1—P1—O2—C2 −178.6 (9) Pb—S1—P1—O1 −113.2 (4) S2—P1—O2—C2 −50.0 (7) Pb—S1—P1—O2 132.1 (4) O1—P1—O2—C2 63.2 (7) Pb—S1—P1—S2 6.0 (2) S1—P1—O1—C1 −60.7 (8) Pb—S1—P1—O1 −113.2 (4) S2—P1—O1—C1 173.1 (9) Pb—S1—P1—O2 132.1 (4) O2—P1—O1—C1 54.4 (8) S1—P1—O1—C1 −60.7 (8) S1—P1—O2—C2 −178.6 (9) S2—P1—O1—C1 173.1 (9) S2—P1—O2—C2 −50.0 (7) O2—P1—O1—C1 54.4 (8) O1—P1—O2—C2 63.2 (7)

References

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