metal-organic compounds
Bis[O-isopropyl (4-ethoxyphenyl)dithiophosphonato-κ2S,S′]lead(II)
aSchool of Chemistry and Physics, University of KwaZulu-Natal, Westville Campus, Private Bag X54001, Durban 4000, South Africa
*Correspondence e-mail: vanzylw@ukzn.ac.za
The title compound, [Pb(C11H16O2PS2)2], is a neutral four-coordinate mononuclear complex with a distorted square-pyramidal geometry of the PbS4 core. The apical PbII atom of each pyramid is 1.33059 (3) Å above the basal S4 plane. The metal atom is surrounded by two chelating dithiophosphonate ligands binding through the S-donor atoms. The ligands are anisobidentate as the pyramid is comprised of Pb—S bond lengths that vary substantially [2.6999 (7), 2.7128 (6), 2.8877 (7) and 2.9472 (7) Å], clearly indicating two short and two longer bond lengths. The P—S bond lengths are also paired as shorter [1.9959 (9) and 1.9877 (8) Å] and slightly longer [2.0115 (9) and 2.0245 (9) Å], indicating an anisobidentate nature of the ligand whereby the shorter P—S bond has more double-bond character than the other. The S—Pb—S (chelating) bond angles range from 71.841 (18) to 72.692 (19)°, whilst the Pb—S—P bond angles range from 84.70 (3) to 90.51 (3)°.
Related literature
For information on dithiophosphonate compounds, see: Van Zyl & Fackler (2000); Van Zyl (2010). For similar lead(II) dithiophosphonate complexes, see: Gray et al. (2003, 2004).
Experimental
Crystal data
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Data collection: APEX2 (Bruker, 2006); cell SAINT (Bruker, 2006); 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.
Supporting information
10.1107/S1600536812046818/gk2529sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536812046818/gk2529Isup2.hkl
A colorless methanol (40 ml) solution of NH4[S2P(OiPr)(4-C6H4OEt)] (1.010 g, 3.443 mmol) was prepared. Another solution of Pb(NO3)2 (0.570 g, 1.721 mmol) in deionized water (20 ml) was prepared, and added to the colorless solution with stirring over a period of 5 min. This resulted in a white precipitate, which proved to be the formation of the title complex. The precipitate was collected by vacuum filtration, washed with water (3 x 10 ml) and allowed to dry under vacuum for a period of 3 hrs, yielding a dry, free-flowing white powder. Colorless crystals suitable for X-ray analysis were grown by the slow diffusion of hexane into a dichloromethane solution of the title complex. Yield: 0.926 g, 71%. M.p. 397–398 K.
31P NMR (CDCl3): δ (p.p.m.): 94.20. 1H NMR (CDCl3): δ (p.p.m.): 7.89(2H, dd, o-ArH), 6.89(2H, dd, m-ArH), 5.01(1H, d quart, CH), 4.03(2H, quart, ArOCH2), 1.39(3H, t, ArOCH2CH3), 1.32(6H, d, CH3). 13C NMR (CDCl3): δ (p.p.m.): 161.97 (p-ArC), 133.32 (ipso-Ar—C), 131.57 (m-ArC), 114.32 (o-ArC), 71.34 (CH), 64.03(ArOCH2), 24.85 (CH3), 14.91 (ArOCH2CH3).
All non-hydrogen atoms were refined anisotropically. All hydrogen atoms were placed in idealized positions and refined with geometrical constraints and constrained to ride on their parent atoms, with C–H = 0.95–1 00 Å,and Uiso(Haryl) = 1.2×UeqCaryl and Uiso(Hmethyl) = 1.5×UeqCmethyl.
Data collection: APEX2 (Bruker, 2006); cell
SAINT (Bruker, 2006); data reduction: SAINT (Bruker, 2006); 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 (Sheldrick, 2008).[Pb(C11H16O2PS2)2] | Z = 2 |
Mr = 757.85 | F(000) = 744 |
Triclinic, P1 | ?e |
Hall symbol: -P 1 | Dx = 1.744 Mg m−3 |
a = 10.2092 (8) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 11.7016 (10) Å | Cell parameters from 36710 reflections |
c = 12.9915 (10) Å | θ = 1.6–28.4° |
α = 89.297 (2)° | µ = 6.27 mm−1 |
β = 85.016 (2)° | T = 173 K |
γ = 69.034 (1)° | Block, colourless |
V = 1443.5 (2) Å3 | 0.16 × 0.14 × 0.11 mm |
Bruker Kappa DUO APEXII diffractometer | 7212 independent reflections |
Radiation source: fine-focus sealed tube | 6564 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.037 |
0.5° ϕ scans and ω scans | θmax = 28.4°, θmin = 1.6° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −13→13 |
Tmin = 0.434, Tmax = 0.546 | k = −15→15 |
36710 measured reflections | l = −17→17 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.020 | H-atom parameters constrained |
wR(F2) = 0.045 | w = 1/[σ2(Fo2) + (0.0234P)2 + 0.042P] where P = (Fo2 + 2Fc2)/3 |
S = 1.03 | (Δ/σ)max = 0.002 |
7212 reflections | Δρmax = 0.61 e Å−3 |
304 parameters | Δρmin = −0.63 e Å−3 |
Primary atom site location: structure-invariant direct methods |
[Pb(C11H16O2PS2)2] | γ = 69.034 (1)° |
Mr = 757.85 | V = 1443.5 (2) Å3 |
Triclinic, P1 | Z = 2 |
a = 10.2092 (8) Å | Mo Kα radiation |
b = 11.7016 (10) Å | µ = 6.27 mm−1 |
c = 12.9915 (10) Å | T = 173 K |
α = 89.297 (2)° | 0.16 × 0.14 × 0.11 mm |
β = 85.016 (2)° |
Bruker Kappa DUO APEXII diffractometer | 7212 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 6564 reflections with I > 2σ(I) |
Tmin = 0.434, Tmax = 0.546 | Rint = 0.037 |
36710 measured reflections |
R[F2 > 2σ(F2)] = 0.020 | 304 parameters |
wR(F2) = 0.045 | H-atom parameters constrained |
S = 1.03 | Δρmax = 0.61 e Å−3 |
7212 reflections | Δρmin = −0.63 e Å−3 |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
Pb1 | 0.563161 (9) | 0.892734 (7) | 0.676272 (7) | 0.02692 (3) | |
S1 | 0.48642 (6) | 0.83844 (6) | 0.47888 (5) | 0.03000 (13) | |
S2 | 0.80447 (7) | 0.77787 (6) | 0.55716 (5) | 0.03150 (13) | |
S3 | 0.55200 (7) | 0.68031 (6) | 0.75505 (5) | 0.03173 (14) | |
S4 | 0.75140 (7) | 0.82120 (5) | 0.84420 (5) | 0.03020 (13) | |
P1 | 0.69313 (6) | 0.77422 (5) | 0.43769 (5) | 0.02499 (13) | |
P2 | 0.67269 (7) | 0.68943 (5) | 0.86809 (5) | 0.02494 (13) | |
O1 | 0.8185 (2) | 1.06377 (17) | 0.08990 (14) | 0.0368 (4) | |
O2 | 0.74190 (18) | 0.64074 (14) | 0.38776 (13) | 0.0314 (4) | |
O3 | 0.31553 (18) | 0.75446 (15) | 1.26420 (13) | 0.0315 (4) | |
O4 | 0.79180 (18) | 0.55982 (14) | 0.88024 (13) | 0.0299 (4) | |
C1 | 0.7390 (2) | 0.8566 (2) | 0.33187 (18) | 0.0244 (5) | |
C2 | 0.7854 (2) | 0.9519 (2) | 0.35221 (19) | 0.0280 (5) | |
H2 | 0.7992 | 0.9676 | 0.4213 | 0.034* | |
C3 | 0.8118 (3) | 1.0243 (2) | 0.27399 (19) | 0.0295 (5) | |
H3 | 0.8416 | 1.0898 | 0.2894 | 0.035* | |
C4 | 0.7941 (3) | 1.0000 (2) | 0.17254 (19) | 0.0293 (5) | |
C5 | 0.7474 (3) | 0.9048 (2) | 0.15114 (19) | 0.0294 (5) | |
H5 | 0.7350 | 0.8885 | 0.0819 | 0.035* | |
C6 | 0.7191 (3) | 0.8344 (2) | 0.22993 (18) | 0.0276 (5) | |
H6 | 0.6861 | 0.7707 | 0.2148 | 0.033* | |
C7 | 0.8657 (3) | 1.1634 (3) | 0.1081 (2) | 0.0438 (7) | |
H7A | 0.9567 | 1.1329 | 0.1394 | 0.053* | |
H7B | 0.7958 | 1.2251 | 0.1558 | 0.053* | |
C8 | 0.8824 (4) | 1.2188 (3) | 0.0058 (2) | 0.0507 (8) | |
H8A | 0.9426 | 1.1547 | −0.0432 | 0.076* | |
H8B | 0.9257 | 1.2803 | 0.0139 | 0.076* | |
H8C | 0.7898 | 1.2578 | −0.0203 | 0.076* | |
C9 | 0.7074 (3) | 0.5436 (2) | 0.4444 (2) | 0.0361 (6) | |
H9 | 0.6554 | 0.5776 | 0.5125 | 0.043* | |
C10 | 0.6158 (4) | 0.5027 (3) | 0.3833 (3) | 0.0567 (9) | |
H10A | 0.5333 | 0.5735 | 0.3681 | 0.085* | |
H10B | 0.5850 | 0.4437 | 0.4230 | 0.085* | |
H10C | 0.6684 | 0.4639 | 0.3185 | 0.085* | |
C11 | 0.8454 (4) | 0.4454 (3) | 0.4627 (3) | 0.0702 (11) | |
H11A | 0.8952 | 0.4093 | 0.3962 | 0.105* | |
H11B | 0.8281 | 0.3817 | 0.5054 | 0.105* | |
H11C | 0.9029 | 0.4810 | 0.4983 | 0.105* | |
C12 | 0.5720 (3) | 0.7089 (2) | 0.99137 (18) | 0.0251 (5) | |
C13 | 0.4855 (3) | 0.8252 (2) | 1.02436 (19) | 0.0294 (5) | |
H13 | 0.4853 | 0.8933 | 0.9837 | 0.035* | |
C14 | 0.3992 (3) | 0.8444 (2) | 1.11533 (19) | 0.0297 (5) | |
H14 | 0.3414 | 0.9251 | 1.1376 | 0.036* | |
C15 | 0.3976 (3) | 0.7450 (2) | 1.17388 (18) | 0.0269 (5) | |
C16 | 0.4827 (3) | 0.6269 (2) | 1.14110 (19) | 0.0307 (5) | |
H16 | 0.4811 | 0.5588 | 1.1811 | 0.037* | |
C17 | 0.5694 (3) | 0.6088 (2) | 1.05057 (19) | 0.0297 (5) | |
H17 | 0.6275 | 0.5281 | 1.0283 | 0.036* | |
C18 | 0.2206 (3) | 0.8742 (2) | 1.2982 (2) | 0.0331 (6) | |
H18A | 0.1523 | 0.9098 | 1.2464 | 0.040* | |
H18B | 0.2738 | 0.9290 | 1.3069 | 0.040* | |
C19 | 0.1447 (3) | 0.8615 (2) | 1.3993 (2) | 0.0375 (6) | |
H19A | 0.0849 | 0.8141 | 1.3885 | 0.056* | |
H19B | 0.0861 | 0.9429 | 1.4273 | 0.056* | |
H19C | 0.2134 | 0.8193 | 1.4481 | 0.056* | |
C20 | 0.9080 (3) | 0.5123 (2) | 0.79867 (19) | 0.0305 (5) | |
H20 | 0.8964 | 0.5734 | 0.7425 | 0.037* | |
C21 | 0.9019 (3) | 0.3954 (2) | 0.7559 (2) | 0.0418 (7) | |
H21A | 0.9166 | 0.3347 | 0.8105 | 0.063* | |
H21B | 0.9756 | 0.3638 | 0.6990 | 0.063* | |
H21C | 0.8095 | 0.4117 | 0.7304 | 0.063* | |
C22 | 1.0424 (3) | 0.4935 (3) | 0.8471 (3) | 0.0529 (8) | |
H22A | 1.0400 | 0.5717 | 0.8750 | 0.079* | |
H22B | 1.1225 | 0.4615 | 0.7948 | 0.079* | |
H22C | 1.0525 | 0.4349 | 0.9032 | 0.079* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Pb1 | 0.02779 (5) | 0.02345 (5) | 0.02595 (5) | −0.00485 (3) | −0.00277 (4) | 0.00404 (3) |
S1 | 0.0212 (3) | 0.0358 (3) | 0.0304 (3) | −0.0072 (2) | −0.0021 (2) | 0.0031 (2) |
S2 | 0.0231 (3) | 0.0399 (3) | 0.0279 (3) | −0.0064 (2) | −0.0058 (2) | 0.0074 (3) |
S3 | 0.0417 (4) | 0.0317 (3) | 0.0279 (3) | −0.0191 (3) | −0.0099 (3) | 0.0051 (2) |
S4 | 0.0366 (4) | 0.0277 (3) | 0.0305 (3) | −0.0156 (3) | −0.0072 (3) | 0.0037 (2) |
P1 | 0.0224 (3) | 0.0250 (3) | 0.0244 (3) | −0.0050 (2) | −0.0013 (2) | 0.0044 (2) |
P2 | 0.0297 (3) | 0.0213 (3) | 0.0233 (3) | −0.0084 (2) | −0.0036 (2) | 0.0030 (2) |
O1 | 0.0457 (11) | 0.0417 (10) | 0.0306 (10) | −0.0245 (9) | −0.0069 (8) | 0.0114 (8) |
O2 | 0.0349 (10) | 0.0250 (8) | 0.0300 (9) | −0.0067 (7) | 0.0021 (8) | 0.0039 (7) |
O3 | 0.0326 (10) | 0.0268 (8) | 0.0324 (10) | −0.0093 (7) | 0.0048 (8) | −0.0016 (7) |
O4 | 0.0327 (10) | 0.0239 (8) | 0.0265 (9) | −0.0035 (7) | 0.0023 (7) | 0.0038 (7) |
C1 | 0.0196 (11) | 0.0246 (11) | 0.0244 (12) | −0.0028 (8) | −0.0013 (9) | 0.0046 (9) |
C2 | 0.0258 (13) | 0.0320 (12) | 0.0251 (12) | −0.0086 (10) | −0.0040 (10) | 0.0018 (9) |
C3 | 0.0290 (13) | 0.0303 (12) | 0.0322 (13) | −0.0139 (10) | −0.0052 (11) | 0.0027 (10) |
C4 | 0.0263 (13) | 0.0306 (12) | 0.0297 (13) | −0.0090 (10) | −0.0020 (10) | 0.0088 (10) |
C5 | 0.0316 (14) | 0.0305 (12) | 0.0249 (12) | −0.0093 (10) | −0.0043 (10) | 0.0027 (10) |
C6 | 0.0264 (13) | 0.0244 (11) | 0.0306 (13) | −0.0075 (9) | −0.0024 (10) | 0.0011 (9) |
C7 | 0.0547 (19) | 0.0535 (17) | 0.0378 (16) | −0.0360 (15) | −0.0109 (14) | 0.0127 (13) |
C8 | 0.070 (2) | 0.0589 (19) | 0.0415 (17) | −0.0446 (17) | −0.0103 (16) | 0.0164 (14) |
C9 | 0.0384 (15) | 0.0304 (13) | 0.0401 (15) | −0.0135 (11) | −0.0029 (12) | 0.0108 (11) |
C10 | 0.062 (2) | 0.057 (2) | 0.060 (2) | −0.0307 (17) | −0.0116 (18) | 0.0045 (16) |
C11 | 0.062 (2) | 0.0476 (19) | 0.106 (3) | −0.0207 (17) | −0.034 (2) | 0.035 (2) |
C12 | 0.0282 (13) | 0.0230 (10) | 0.0224 (11) | −0.0070 (9) | −0.0020 (10) | 0.0008 (9) |
C13 | 0.0328 (14) | 0.0227 (11) | 0.0307 (13) | −0.0074 (10) | −0.0035 (11) | 0.0042 (9) |
C14 | 0.0311 (13) | 0.0215 (11) | 0.0333 (13) | −0.0061 (9) | −0.0006 (11) | −0.0008 (9) |
C15 | 0.0281 (13) | 0.0278 (11) | 0.0254 (12) | −0.0104 (9) | −0.0037 (10) | −0.0013 (9) |
C16 | 0.0361 (14) | 0.0250 (11) | 0.0309 (13) | −0.0116 (10) | −0.0007 (11) | 0.0043 (10) |
C17 | 0.0336 (14) | 0.0220 (11) | 0.0298 (13) | −0.0058 (9) | −0.0009 (11) | 0.0017 (9) |
C18 | 0.0295 (14) | 0.0289 (12) | 0.0380 (15) | −0.0071 (10) | −0.0007 (11) | −0.0054 (10) |
C19 | 0.0309 (14) | 0.0423 (14) | 0.0382 (15) | −0.0132 (11) | 0.0042 (12) | −0.0093 (12) |
C20 | 0.0346 (14) | 0.0275 (12) | 0.0257 (12) | −0.0080 (10) | 0.0037 (11) | −0.0012 (9) |
C21 | 0.0446 (17) | 0.0352 (14) | 0.0438 (16) | −0.0140 (12) | 0.0062 (13) | −0.0100 (12) |
C22 | 0.0365 (17) | 0.065 (2) | 0.0524 (19) | −0.0132 (15) | 0.0009 (15) | −0.0208 (16) |
Pb1—S2 | 2.6999 (7) | C9—C10 | 1.480 (4) |
Pb1—S3 | 2.7128 (6) | C9—C11 | 1.502 (4) |
Pb1—S1 | 2.8877 (7) | C9—H9 | 1.0000 |
Pb1—S4 | 2.9472 (7) | C10—H10A | 0.9800 |
S1—P1 | 1.9959 (9) | C10—H10B | 0.9800 |
S2—P1 | 2.0115 (9) | C10—H10C | 0.9800 |
S3—P2 | 2.0245 (9) | C11—H11A | 0.9800 |
S4—P2 | 1.9877 (8) | C11—H11B | 0.9800 |
P1—O2 | 1.5877 (17) | C11—H11C | 0.9800 |
P1—C1 | 1.794 (2) | C12—C13 | 1.380 (3) |
P2—O4 | 1.5848 (16) | C12—C17 | 1.400 (3) |
P2—C12 | 1.797 (2) | C13—C14 | 1.381 (3) |
O1—C4 | 1.356 (3) | C13—H13 | 0.9500 |
O1—C7 | 1.441 (3) | C14—C15 | 1.386 (3) |
O2—C9 | 1.476 (3) | C14—H14 | 0.9500 |
O3—C15 | 1.363 (3) | C15—C16 | 1.392 (3) |
O3—C18 | 1.437 (3) | C16—C17 | 1.379 (3) |
O4—C20 | 1.471 (3) | C16—H16 | 0.9500 |
C1—C2 | 1.394 (3) | C17—H17 | 0.9500 |
C1—C6 | 1.399 (3) | C18—C19 | 1.500 (4) |
C2—C3 | 1.384 (3) | C18—H18A | 0.9900 |
C2—H2 | 0.9500 | C18—H18B | 0.9900 |
C3—C4 | 1.392 (3) | C19—H19A | 0.9800 |
C3—H3 | 0.9500 | C19—H19B | 0.9800 |
C4—C5 | 1.398 (3) | C19—H19C | 0.9800 |
C5—C6 | 1.382 (3) | C20—C22 | 1.503 (4) |
C5—H5 | 0.9500 | C20—C21 | 1.507 (3) |
C6—H6 | 0.9500 | C20—H20 | 1.0000 |
C7—C8 | 1.495 (4) | C21—H21A | 0.9800 |
C7—H7A | 0.9900 | C21—H21B | 0.9800 |
C7—H7B | 0.9900 | C21—H21C | 0.9800 |
C8—H8A | 0.9800 | C22—H22A | 0.9800 |
C8—H8B | 0.9800 | C22—H22B | 0.9800 |
C8—H8C | 0.9800 | C22—H22C | 0.9800 |
S2—Pb1—S3 | 93.09 (2) | C11—C9—H9 | 109.0 |
S2—Pb1—S1 | 72.692 (19) | C9—C10—H10A | 109.5 |
S3—Pb1—S1 | 91.516 (19) | C9—C10—H10B | 109.5 |
S2—Pb1—S4 | 82.708 (19) | H10A—C10—H10B | 109.5 |
S3—Pb1—S4 | 71.841 (18) | C9—C10—H10C | 109.5 |
S1—Pb1—S4 | 149.566 (17) | H10A—C10—H10C | 109.5 |
P1—S1—Pb1 | 85.24 (3) | H10B—C10—H10C | 109.5 |
P1—S2—Pb1 | 90.16 (3) | C9—C11—H11A | 109.5 |
P2—S3—Pb1 | 90.51 (3) | C9—C11—H11B | 109.5 |
P2—S4—Pb1 | 84.70 (3) | H11A—C11—H11B | 109.5 |
O2—P1—C1 | 100.90 (10) | C9—C11—H11C | 109.5 |
O2—P1—S1 | 110.94 (7) | H11A—C11—H11C | 109.5 |
C1—P1—S1 | 111.88 (8) | H11B—C11—H11C | 109.5 |
O2—P1—S2 | 111.34 (7) | C13—C12—C17 | 119.0 (2) |
C1—P1—S2 | 109.69 (8) | C13—C12—P2 | 118.89 (18) |
S1—P1—S2 | 111.63 (4) | C17—C12—P2 | 121.87 (17) |
O4—P2—C12 | 101.33 (10) | C12—C13—C14 | 121.2 (2) |
O4—P2—S4 | 112.17 (8) | C12—C13—H13 | 119.4 |
C12—P2—S4 | 111.43 (8) | C14—C13—H13 | 119.4 |
O4—P2—S3 | 109.88 (7) | C13—C14—C15 | 119.5 (2) |
C12—P2—S3 | 109.56 (9) | C13—C14—H14 | 120.2 |
S4—P2—S3 | 111.98 (4) | C15—C14—H14 | 120.2 |
C4—O1—C7 | 118.0 (2) | O3—C15—C14 | 123.9 (2) |
C9—O2—P1 | 119.79 (15) | O3—C15—C16 | 116.0 (2) |
C15—O3—C18 | 117.87 (18) | C14—C15—C16 | 120.1 (2) |
C20—O4—P2 | 119.72 (14) | C17—C16—C15 | 119.9 (2) |
C2—C1—C6 | 118.8 (2) | C17—C16—H16 | 120.0 |
C2—C1—P1 | 119.26 (18) | C15—C16—H16 | 120.0 |
C6—C1—P1 | 121.73 (18) | C16—C17—C12 | 120.2 (2) |
C3—C2—C1 | 121.4 (2) | C16—C17—H17 | 119.9 |
C3—C2—H2 | 119.3 | C12—C17—H17 | 119.9 |
C1—C2—H2 | 119.3 | O3—C18—C19 | 108.0 (2) |
C2—C3—C4 | 119.3 (2) | O3—C18—H18A | 110.1 |
C2—C3—H3 | 120.4 | C19—C18—H18A | 110.1 |
C4—C3—H3 | 120.4 | O3—C18—H18B | 110.1 |
O1—C4—C3 | 124.3 (2) | C19—C18—H18B | 110.1 |
O1—C4—C5 | 115.9 (2) | H18A—C18—H18B | 108.4 |
C3—C4—C5 | 119.8 (2) | C18—C19—H19A | 109.5 |
C6—C5—C4 | 120.5 (2) | C18—C19—H19B | 109.5 |
C6—C5—H5 | 119.8 | H19A—C19—H19B | 109.5 |
C4—C5—H5 | 119.8 | C18—C19—H19C | 109.5 |
C5—C6—C1 | 120.1 (2) | H19A—C19—H19C | 109.5 |
C5—C6—H6 | 119.9 | H19B—C19—H19C | 109.5 |
C1—C6—H6 | 119.9 | O4—C20—C22 | 107.2 (2) |
O1—C7—C8 | 107.2 (2) | O4—C20—C21 | 107.8 (2) |
O1—C7—H7A | 110.3 | C22—C20—C21 | 112.9 (2) |
C8—C7—H7A | 110.3 | O4—C20—H20 | 109.6 |
O1—C7—H7B | 110.3 | C22—C20—H20 | 109.6 |
C8—C7—H7B | 110.3 | C21—C20—H20 | 109.6 |
H7A—C7—H7B | 108.5 | C20—C21—H21A | 109.5 |
C7—C8—H8A | 109.5 | C20—C21—H21B | 109.5 |
C7—C8—H8B | 109.5 | H21A—C21—H21B | 109.5 |
H8A—C8—H8B | 109.5 | C20—C21—H21C | 109.5 |
C7—C8—H8C | 109.5 | H21A—C21—H21C | 109.5 |
H8A—C8—H8C | 109.5 | H21B—C21—H21C | 109.5 |
H8B—C8—H8C | 109.5 | C20—C22—H22A | 109.5 |
O2—C9—C10 | 108.7 (2) | C20—C22—H22B | 109.5 |
O2—C9—C11 | 106.4 (2) | H22A—C22—H22B | 109.5 |
C10—C9—C11 | 114.4 (3) | C20—C22—H22C | 109.5 |
O2—C9—H9 | 109.0 | H22A—C22—H22C | 109.5 |
C10—C9—H9 | 109.0 | H22B—C22—H22C | 109.5 |
S2—Pb1—S1—P1 | −3.39 (3) | C6—C1—C2—C3 | 0.0 (3) |
S3—Pb1—S1—P1 | −96.16 (3) | P1—C1—C2—C3 | −175.01 (18) |
S4—Pb1—S1—P1 | −40.94 (5) | C1—C2—C3—C4 | −1.2 (4) |
S3—Pb1—S2—P1 | 93.98 (3) | C7—O1—C4—C3 | −0.1 (4) |
S1—Pb1—S2—P1 | 3.36 (3) | C7—O1—C4—C5 | 179.5 (2) |
S4—Pb1—S2—P1 | 165.23 (3) | C2—C3—C4—O1 | −179.1 (2) |
S2—Pb1—S3—P2 | 87.41 (3) | C2—C3—C4—C5 | 1.3 (4) |
S1—Pb1—S3—P2 | 160.16 (3) | O1—C4—C5—C6 | −179.9 (2) |
S4—Pb1—S3—P2 | 6.13 (3) | C3—C4—C5—C6 | −0.2 (4) |
S2—Pb1—S4—P2 | −101.96 (3) | C4—C5—C6—C1 | −0.9 (4) |
S3—Pb1—S4—P2 | −6.27 (3) | C2—C1—C6—C5 | 1.0 (3) |
S1—Pb1—S4—P2 | −66.05 (4) | P1—C1—C6—C5 | 175.93 (18) |
Pb1—S1—P1—O2 | 129.49 (7) | C4—O1—C7—C8 | −179.2 (2) |
Pb1—S1—P1—C1 | −118.68 (9) | P1—O2—C9—C10 | 117.6 (2) |
Pb1—S1—P1—S2 | 4.68 (3) | P1—O2—C9—C11 | −118.6 (2) |
Pb1—S2—P1—O2 | −129.58 (7) | O4—P2—C12—C13 | 160.0 (2) |
Pb1—S2—P1—C1 | 119.60 (8) | S4—P2—C12—C13 | 40.5 (2) |
Pb1—S2—P1—S1 | −4.99 (4) | S3—P2—C12—C13 | −84.0 (2) |
Pb1—S4—P2—O4 | 132.71 (7) | O4—P2—C12—C17 | −25.8 (2) |
Pb1—S4—P2—C12 | −114.48 (9) | S4—P2—C12—C17 | −145.23 (19) |
Pb1—S4—P2—S3 | 8.62 (4) | S3—P2—C12—C17 | 90.3 (2) |
Pb1—S3—P2—O4 | −134.69 (7) | C17—C12—C13—C14 | 1.4 (4) |
Pb1—S3—P2—C12 | 114.82 (8) | P2—C12—C13—C14 | 175.8 (2) |
Pb1—S3—P2—S4 | −9.33 (4) | C12—C13—C14—C15 | −1.1 (4) |
C1—P1—O2—C9 | −172.27 (18) | C18—O3—C15—C14 | 2.8 (3) |
S1—P1—O2—C9 | −53.57 (19) | C18—O3—C15—C16 | −176.9 (2) |
S2—P1—O2—C9 | 71.40 (18) | C13—C14—C15—O3 | −179.5 (2) |
C12—P2—O4—C20 | −174.11 (17) | C13—C14—C15—C16 | 0.2 (4) |
S4—P2—O4—C20 | −55.17 (18) | O3—C15—C16—C17 | −179.9 (2) |
S3—P2—O4—C20 | 70.07 (17) | C14—C15—C16—C17 | 0.4 (4) |
O2—P1—C1—C2 | −145.78 (18) | C15—C16—C17—C12 | 0.0 (4) |
S1—P1—C1—C2 | 96.21 (19) | C13—C12—C17—C16 | −0.8 (4) |
S2—P1—C1—C2 | −28.2 (2) | P2—C12—C17—C16 | −175.1 (2) |
O2—P1—C1—C6 | 39.3 (2) | C15—O3—C18—C19 | −178.9 (2) |
S1—P1—C1—C6 | −78.67 (19) | P2—O4—C20—C22 | 119.9 (2) |
S2—P1—C1—C6 | 156.88 (17) | P2—O4—C20—C21 | −118.3 (2) |
Experimental details
Crystal data | |
Chemical formula | [Pb(C11H16O2PS2)2] |
Mr | 757.85 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 173 |
a, b, c (Å) | 10.2092 (8), 11.7016 (10), 12.9915 (10) |
α, β, γ (°) | 89.297 (2), 85.016 (2), 69.034 (1) |
V (Å3) | 1443.5 (2) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 6.27 |
Crystal size (mm) | 0.16 × 0.14 × 0.11 |
Data collection | |
Diffractometer | Bruker Kappa DUO APEXII diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.434, 0.546 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 36710, 7212, 6564 |
Rint | 0.037 |
(sin θ/λ)max (Å−1) | 0.669 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.020, 0.045, 1.03 |
No. of reflections | 7212 |
No. of parameters | 304 |
No. of restraints | ? |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.61, −0.63 |
Computer programs: APEX2 (Bruker, 2006), SAINT (Bruker, 2006), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).
Acknowledgements
The authors thank the National Research Foundation (NRF) and UKZN for financial support.
References
Bruker (2006). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Gray, I. P., Milton, H. L., Slawin, A. M. Z. & Woollins, J. D. (2003). Dalton Trans. pp. 3450–3457. Web of Science CSD CrossRef Google Scholar
Gray, I. P., Slawin, A. M. Z. & Woollins, J. D. (2004). Dalton Trans. pp. 2477–2486. Web of Science CSD CrossRef Google Scholar
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Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Van Zyl, W. E. (2010). Comments Inorg. Chem. 31, 13–45. Web of Science CrossRef CAS Google Scholar
Van Zyl, W. E. & Fackler, J. P. (2000). Phosphorus Sulfur Silicon Relat. Elem. 167, 117–132. Web of Science CrossRef CAS Google Scholar
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The phosphor-1,1,-dithiolate class of compounds is the heavier and softer congener of the more popular phosphonate derivatives. Several sub-categories are known which include the dithiophosphato [S2P(OR)2]¯, (R = typically alkyl), dithiophosphinato [S2PR2]¯ (R = alkyl or aryl), and dithiophosphonato [S2PR(OR')]¯, (R = typically aryl or ferrocenyl, R' = alkyl) monoanionic ligands. The latter may be described as a hybrid of the former two, and are also much less developed. Lead dithiophosphonate complexes have only been developed during the past 10 years (Gray et al., 2003; 2004) and the solid-state structure of the lead complexes deviate substantially from typical 4-coordinate transition-metals such as Ni(II), Cd(II), Hg(II) of the same ligand.
The title complex exhibits a structure that is built up of distorted square pyramids in dimeric pairs. The dimeric pair is characterised by intermolecular interactions between the Pb atom of one monomer with a S atom of adjacent unit, containing a Pb···S distance of 3.619 Å. Similar intermolecular interactions occur between the Pb atom of one monomeric unit and four carbon atoms in an adjacent aromatic ring in the Pb-Ar (Ar = aromatic ring) bond distance range of 3.421-3.597 Å. A related structure with a different alkoxy group was previously reported (Gray et al., 2004), showing similar inter Pb···S and Pb···Ar interactions, and intermolecular Pb-S bond lenghts. It was postulated that the aforementioned Pb···Ar interactions stabilized the dimeric structure. The structure reported by Gray et al. (2004) adopts a similar molecular unit, the lead also resides in the centre of a distorted pyramid, 1.30 Å above the basal S4 plane. General and convenient methods to prepare dithiophosphonate salt derivatives have been reported (Van Zyl & Fackler, 2000).