catena-Poly[[[O,O′-bis­(2-methyl­phen­yl) dithio­phosphato-κ²S,S]lead(II)]-μ-O,O′-bis­(2-methyl­phen­yl) dithio­phosphato-κ³S,S′:S]

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).

Key indicators

• Single-crystal X-ray study
• T = 123 K
• Mean [sigma](C-C) = 0.012 Å
• Disorder in main residue
• R factor = 0.030
• wR factor = 0.075
• Data-to-parameter ratio = 11.1

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT915_ALERT_3_B Low Friedel Pair Coverage ......................         38 Perc.

Alert level C
PLAT342_ALERT_3_C Low Bond Precision on  C-C Bonds ...............     0.0123 Ang

Alert level G
REFLT03_ALERT_4_G  WARNING: Large fraction of Friedel related reflns may
                     be needed to determine absolute structure
           From the CIF: _diffrn_reflns_theta_max           75.59
           From the CIF: _reflns_number_total               4494
           Count of symmetry unique reflns         3401
           Completeness (_total/calc)            132.14%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured      1093
           Fraction of Friedel pairs measured     0.321
           Are heavy atom types Z>Si present        yes
PLAT002_ALERT_2_G Number of Distance or Angle Restraints on AtSite         16
PLAT003_ALERT_2_G Number of Uiso or Uij Restrained Atom Sites ....          9
PLAT004_ALERT_5_G Info: Polymeric Structure Found with Dimension .          1
PLAT005_ALERT_5_G No _iucr_refine_instructions_details  in the CIF          ?
PLAT301_ALERT_3_G Note: Main Residue  Disorder ...................         21 Perc.
PLAT779_ALERT_4_G Suspect or Irrelevant (Bond) Angle in CIF .... #          9
              O4   -P2   -O4A     1.555   1.555   1.555             21.90 Deg.
PLAT811_ALERT_5_G No ADDSYM Analysis: Too Many Excluded Atoms ....          !
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......         55
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600         52

   0 ALERT level A = Most likely a serious problem - resolve or explain
   1 ALERT level B = A potentially serious problem, consider carefully
   1 ALERT level C = Check. Ensure it is not caused by an omission or oversight
  10 ALERT level G = General information/check it is not something unexpected

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   2 ALERT type 2 Indicator that the structure model may be wrong or deficient
   4 ALERT type 3 Indicator that the structure quality may be low
   3 ALERT type 4 Improvement, methodology, query or suggestion
   3 ALERT type 5 Informative message, check

---

S1. 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.

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).

S2. 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.

S3. Refinement

All H atoms were positioned geometrically and refined as riding atoms, with C—H = 0.93 (CH) and 0.96(CH₃) Å and with U_iso(H) = 1.2U_eq(C). The highest residual electron density was found 0.69 Å from Pb the deepest hole 0.82 Å from Pb.

In the molecule one 1-methoxy-2-methyl-benzene ring (O4—C22—C28) shows positional disorder in a 0.747 (1):0.253 (1) ratio. The highest maximum (0.69 e/Å₃) in the final difference map is at 1.12 Å from Pb and the deepest hole (0.82 e/Å₃) is at -1.15 Å from Pb. Nine outliers, (-12 - 5 12), (-13 - 4 11), (-14 - 3 10), (-12 - 6 10), (-7 - 11 7), (-13 - 5 10), (0 - 8 12), (0 1 15) and (-5 - 12 6), were omitted in the final refinement.

The SIMU and DELU constraint instructions in SHELXL97 were used for atoms O4/O4a, C22/C22a, C23/C23a, C24/C24a, C25/C25a, C26/C26a, C27/C27a,C28/C28a and ISOR (0.01) was used for atoms C24a and C26a in order to model the disorder properly during the refinement.

Computing details

Data collection: CrysAlis PRO (Agilent, 2011); cell refinement: CrysAlis PRO (Agilent, 2011); data reduction: CrysAlis PRO (Agilent, 2011); 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 (Sheldrick, 2008).

Figures

	Fig. 1. A perspective view of the title compound, showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. Only major disordered component for the 1-methoxy-2-methyl-benzene ring is shown. Atoms labelled with suffix A were generated by the symmetry operator 2 - x, 0.5 + y, 1 - z.
	Fig. 2. Crystal packing diagram for the title compound.

catena-Poly[[[O,O'-bis(2-methylphenyl) dithiophosphato- κ²S,S]lead(II)]-µ-O,O'-bis(2-methylphenyl) dithiophosphato-κ³S,S':S]

Crystal data

[Pb(C14H14O2PS2)2]	F(000) = 808
Mr = 825.87	Dx = 1.765 Mg m^−3
Monoclinic, P21	Cu Kα radiation, λ = 1.54184 Å
Hall symbol: P 2yb	Cell parameters from 4674 reflections
a = 12.0263 (6) Å	θ = 3.7–75.4°
b = 10.7420 (4) Å	µ = 14.31 mm^−1
c = 13.0499 (8) Å	T = 123 K
β = 112.849 (6)°	Needle, colorless
V = 1553.58 (15) Å^3	0.46 × 0.05 × 0.03 mm
Z = 2

Data collection

Agilent Xcalibur (Ruby, Gemini) diffractometer	4494 independent reflections
Radiation source: Enhance (Cu) X-ray Source	4269 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.045
Detector resolution: 10.5081 pixels mm^-1	θmax = 75.6°, θmin = 3.7°
ω scans	h = −15→14
Absorption correction: analytical [CrysAlis PRO (Agilent, 2011), using a multi-faceted crystal model (Clark & Reid, 1995)]	k = −13→8
Tmin = 0.094, Tmax = 0.675	l = −14→16
10226 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.030	H-atom parameters constrained
wR(F^2) = 0.075	w = 1/[σ^2(Fo^2) + (0.0329P)^2 + 1.1401P] where P = (Fo^2 + 2Fc^2)/3
S = 1.03	(Δ/σ)max = 0.007
4494 reflections	Δρmax = 1.12 e Å^−3
406 parameters	Δρmin = −1.15 e Å^−3
55 restraints	Absolute structure: Flack (1983), 1093 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.03 (8)

Special details

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.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
P1	0.58111 (14)	0.59159 (15)	0.27999 (13)	0.0313 (3)
P2	0.94672 (15)	0.36924 (17)	0.63559 (15)	0.0397 (4)
S1	0.65999 (14)	0.43767 (15)	0.25837 (14)	0.0372 (3)
S2	0.68892 (13)	0.72496 (15)	0.37035 (14)	0.0360 (3)
S3	0.97595 (15)	0.29732 (17)	0.50949 (16)	0.0426 (4)
S4	0.84998 (14)	0.52418 (15)	0.60457 (14)	0.0428 (4)
Pb	0.874757 (17)	0.55165 (2)	0.403361 (19)	0.03788 (6)
O1	0.4862 (3)	0.5601 (6)	0.3355 (3)	0.0329 (9)
O2	0.5005 (4)	0.6443 (4)	0.1582 (4)	0.0354 (9)
O3	0.8792 (4)	0.2724 (5)	0.6864 (4)	0.0452 (12)
C1	0.4143 (5)	0.4517 (6)	0.3029 (5)	0.0334 (13)
C2	0.3246 (6)	0.4438 (7)	0.1981 (6)	0.0379 (14)
H2A	0.3119	0.5086	0.1476	0.045*
C3	0.2528 (7)	0.3365 (8)	0.1688 (7)	0.0470 (17)
H3A	0.1930	0.3288	0.0978	0.056*
C4	0.2710 (7)	0.2427 (7)	0.2451 (7)	0.0483 (17)
H4A	0.2230	0.1717	0.2261	0.058*
C5	0.3608 (7)	0.2538 (7)	0.3502 (7)	0.0453 (16)
H5A	0.3726	0.1893	0.4008	0.054*
C6	0.4350 (5)	0.3602 (6)	0.3828 (5)	0.0350 (13)
C7	0.5306 (6)	0.3735 (8)	0.4978 (7)	0.0502 (19)
H7A	0.5198	0.4510	0.5295	0.075*
H7B	0.6088	0.3722	0.4941	0.075*
H7C	0.5244	0.3059	0.5434	0.075*
C8	0.4551 (6)	0.7671 (6)	0.1443 (5)	0.0359 (13)
C9	0.3744 (6)	0.8024 (8)	0.1895 (6)	0.0424 (15)
H9A	0.3508	0.7464	0.2316	0.051*
C10	0.3283 (7)	0.9222 (8)	0.1720 (7)	0.0490 (17)
H10A	0.2754	0.9479	0.2042	0.059*
C11	0.3614 (8)	1.0035 (8)	0.1062 (7)	0.0534 (19)
H11A	0.3286	1.0832	0.0918	0.064*
C12	0.4437 (9)	0.9654 (8)	0.0621 (6)	0.054 (2)
H12A	0.4653	1.0207	0.0181	0.064*
C13	0.4950 (7)	0.8473 (7)	0.0814 (6)	0.0407 (15)
C14	0.5853 (8)	0.8076 (8)	0.0345 (7)	0.0540 (19)
H14A	0.6487	0.7610	0.0895	0.081*
H14B	0.6188	0.8798	0.0139	0.081*
H14C	0.5461	0.7565	−0.0299	0.081*
C15	0.9162 (7)	0.1475 (8)	0.7050 (7)	0.0428 (17)
C16	1.0210 (8)	0.1178 (10)	0.7962 (7)	0.051 (2)
H16A	1.0669	0.1801	0.8430	0.061*
C17	1.0567 (9)	−0.0087 (11)	0.8169 (9)	0.065 (3)
H17A	1.1253	−0.0315	0.8779	0.078*
C18	0.9857 (8)	−0.0971 (9)	0.7428 (9)	0.061 (2)
H18A	1.0086	−0.1803	0.7544	0.073*
C19	0.8856 (8)	−0.0673 (8)	0.6553 (8)	0.055 (2)
H19A	0.8409	−0.1305	0.6088	0.065*
C20	0.8456 (5)	0.0560 (12)	0.6314 (6)	0.0472 (15)
C21	0.7325 (7)	0.0918 (8)	0.5346 (7)	0.0509 (19)
H21A	0.7496	0.1594	0.4949	0.076*
H21B	0.6720	0.1171	0.5613	0.076*
H21C	0.7036	0.0217	0.4858	0.076*
O4	1.0800 (7)	0.3917 (8)	0.7289 (7)	0.043 (2)	0.747 (11)
C22	1.0991 (7)	0.4823 (6)	0.8088 (6)	0.040 (3)	0.747 (11)
C23	1.0368 (7)	0.4817 (8)	0.8790 (7)	0.058 (3)	0.747 (11)
H23	0.9802	0.4199	0.8721	0.069*	0.747 (11)
C24	1.0591 (9)	0.5736 (10)	0.9595 (6)	0.077 (6)	0.747 (11)
H24	1.0175	0.5733	1.0065	0.093*	0.747 (11)
C25	1.1437 (10)	0.6661 (8)	0.9699 (6)	0.080 (5)	0.747 (11)
H25	1.1586	0.7276	1.0238	0.096*	0.747 (11)
C26	1.2060 (8)	0.6666 (7)	0.8997 (8)	0.071 (5)	0.747 (11)
H26	1.2625	0.7285	0.9066	0.086*	0.747 (11)
C27	1.1836 (7)	0.5747 (7)	0.8192 (7)	0.058 (3)	0.747 (11)
C28	1.2475 (11)	0.5753 (14)	0.7405 (11)	0.064 (4)	0.747 (11)
H28A	1.3050	0.6422	0.7596	0.096*	0.747 (11)
H28B	1.1897	0.5867	0.6658	0.096*	0.747 (11)
H28C	1.2887	0.4976	0.7458	0.096*	0.747 (11)
O4A	1.0570 (17)	0.374 (2)	0.762 (2)	0.044 (6)	0.253 (11)
C22A	1.1269 (15)	0.4788 (17)	0.7926 (16)	0.054 (11)	0.253 (11)
C23A	1.2071 (17)	0.5125 (19)	0.7443 (16)	0.048 (8)	0.253 (11)
H23A	1.2118	0.4653	0.6863	0.057*	0.253 (11)
C24A	1.2802 (16)	0.617 (2)	0.7825 (18)	0.045 (8)	0.253 (11)
H24A	1.3339	0.6391	0.7502	0.055*	0.253 (11)
C25A	1.2731 (19)	0.6870 (18)	0.8691 (18)	0.060 (10)	0.253 (11)
H25A	1.3221	0.7567	0.8947	0.072*	0.253 (11)
C26A	1.193 (2)	0.653 (2)	0.9175 (16)	0.045 (8)	0.253 (11)
H26A	1.1882	0.7005	0.9755	0.054*	0.253 (11)
C27A	1.1198 (16)	0.549 (2)	0.8793 (16)	0.053 (7)	0.253 (11)
C28A	1.030 (3)	0.511 (6)	0.927 (3)	0.09 (2)	0.253 (11)
H28D	1.0442	0.4262	0.9514	0.134*	0.253 (11)
H28E	0.9498	0.5189	0.8710	0.134*	0.253 (11)
H28F	1.0381	0.5638	0.9889	0.134*	0.253 (11)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
P1	0.0341 (6)	0.0230 (7)	0.0404 (7)	0.0005 (5)	0.0186 (6)	0.0006 (5)
P2	0.0325 (7)	0.0354 (9)	0.0492 (9)	0.0053 (7)	0.0139 (6)	−0.0042 (7)
S1	0.0395 (7)	0.0256 (8)	0.0518 (8)	0.0014 (6)	0.0234 (6)	−0.0039 (6)
S2	0.0345 (7)	0.0259 (7)	0.0480 (8)	−0.0006 (6)	0.0163 (6)	−0.0032 (6)
S3	0.0477 (10)	0.0303 (8)	0.0595 (10)	0.0064 (8)	0.0314 (8)	0.0042 (7)
S4	0.0401 (7)	0.0366 (12)	0.0516 (8)	0.0103 (6)	0.0178 (6)	−0.0056 (6)
Pb	0.03314 (9)	0.02947 (11)	0.05628 (12)	−0.00011 (13)	0.02308 (8)	−0.00157 (14)
O1	0.0358 (16)	0.028 (2)	0.0381 (17)	−0.001 (2)	0.0180 (14)	0.001 (2)
O2	0.045 (2)	0.024 (2)	0.041 (2)	−0.0006 (18)	0.0196 (19)	0.0013 (17)
O3	0.042 (2)	0.047 (3)	0.051 (3)	0.010 (2)	0.024 (2)	0.002 (2)
C1	0.036 (3)	0.029 (3)	0.043 (3)	0.002 (2)	0.022 (2)	−0.003 (2)
C2	0.041 (3)	0.036 (4)	0.042 (3)	−0.004 (3)	0.021 (3)	0.000 (3)
C3	0.047 (4)	0.044 (4)	0.055 (4)	−0.008 (3)	0.025 (3)	−0.009 (3)
C4	0.058 (4)	0.031 (4)	0.067 (4)	−0.012 (3)	0.037 (4)	−0.010 (3)
C5	0.049 (3)	0.031 (4)	0.069 (4)	0.003 (3)	0.038 (3)	0.008 (3)
C6	0.035 (3)	0.033 (3)	0.045 (3)	0.007 (3)	0.024 (2)	0.010 (3)
C7	0.036 (3)	0.054 (5)	0.061 (4)	0.006 (3)	0.020 (3)	0.022 (4)
C8	0.040 (3)	0.028 (3)	0.038 (3)	−0.003 (3)	0.013 (2)	0.001 (2)
C9	0.042 (3)	0.041 (4)	0.046 (3)	0.004 (3)	0.019 (3)	0.002 (3)
C10	0.055 (4)	0.041 (4)	0.051 (4)	0.015 (3)	0.020 (3)	0.006 (3)
C11	0.075 (5)	0.040 (4)	0.052 (4)	0.015 (4)	0.032 (4)	0.006 (3)
C12	0.083 (5)	0.039 (4)	0.044 (4)	0.006 (4)	0.030 (4)	0.012 (3)
C13	0.054 (4)	0.028 (3)	0.042 (3)	0.003 (3)	0.021 (3)	−0.001 (3)
C14	0.079 (5)	0.038 (4)	0.058 (4)	−0.004 (4)	0.040 (4)	−0.001 (3)
C15	0.047 (4)	0.044 (4)	0.050 (4)	0.009 (3)	0.032 (3)	0.008 (3)
C16	0.050 (4)	0.062 (6)	0.045 (4)	0.012 (4)	0.024 (3)	0.006 (4)
C17	0.057 (5)	0.079 (7)	0.062 (5)	0.029 (5)	0.027 (4)	0.027 (5)
C18	0.059 (5)	0.044 (5)	0.095 (7)	0.012 (4)	0.046 (5)	0.019 (4)
C19	0.069 (5)	0.035 (4)	0.084 (6)	0.002 (4)	0.055 (5)	0.007 (4)
C20	0.044 (3)	0.047 (4)	0.063 (3)	0.001 (5)	0.034 (3)	0.010 (5)
C21	0.043 (3)	0.047 (4)	0.067 (5)	−0.003 (3)	0.027 (3)	0.001 (3)
O4	0.033 (4)	0.047 (4)	0.049 (4)	0.004 (3)	0.018 (3)	−0.007 (3)
C22	0.046 (5)	0.036 (6)	0.034 (5)	0.000 (4)	0.010 (4)	−0.007 (4)
C23	0.067 (7)	0.068 (8)	0.040 (6)	0.013 (6)	0.022 (5)	0.001 (5)
C24	0.087 (10)	0.098 (16)	0.037 (6)	0.031 (9)	0.012 (6)	−0.004 (7)
C25	0.087 (10)	0.064 (9)	0.052 (7)	0.012 (8)	−0.013 (7)	−0.013 (6)
C26	0.073 (9)	0.046 (7)	0.058 (8)	0.003 (7)	−0.015 (7)	−0.004 (6)
C27	0.050 (5)	0.054 (9)	0.055 (6)	0.001 (5)	0.003 (4)	0.017 (5)
C28	0.042 (6)	0.060 (10)	0.082 (8)	−0.012 (6)	0.014 (6)	0.020 (7)
O4A	0.014 (8)	0.058 (14)	0.056 (14)	0.003 (8)	0.010 (8)	−0.007 (11)
C22A	0.044 (17)	0.05 (2)	0.047 (18)	0.011 (15)	−0.003 (15)	0.016 (15)
C23A	0.028 (13)	0.044 (19)	0.067 (19)	−0.008 (12)	0.014 (13)	−0.015 (14)
C24A	0.039 (10)	0.044 (11)	0.051 (10)	−0.010 (8)	0.015 (8)	0.005 (8)
C25A	0.047 (17)	0.042 (18)	0.06 (2)	−0.017 (15)	−0.008 (15)	0.011 (15)
C26A	0.050 (11)	0.040 (11)	0.033 (10)	−0.003 (8)	0.005 (8)	−0.001 (8)
C27A	0.033 (10)	0.060 (16)	0.072 (15)	0.016 (18)	0.025 (10)	0.03 (2)
C28A	0.039 (15)	0.19 (8)	0.04 (2)	−0.01 (3)	0.015 (16)	−0.02 (3)

Geometric parameters (Å, º)

P1—O1	1.608 (4)	C15—C16	1.394 (11)
P1—O2	1.609 (5)	C15—C20	1.406 (14)
P1—S1	1.980 (2)	C16—C17	1.419 (13)
P1—S2	1.984 (2)	C16—H16A	0.9300
P2—O3	1.612 (6)	C17—C18	1.388 (15)
P2—O4	1.611 (8)	C17—H17A	0.9300
P2—O4A	1.67 (2)	C18—C19	1.337 (14)
P2—S3	1.969 (3)	C18—H18A	0.9300
P2—S4	1.980 (2)	C19—C20	1.403 (15)
S1—Pb	2.8205 (16)	C19—H19A	0.9300
S2—Pb	2.8104 (16)	C20—C21	1.503 (10)
S3—Pb	3.0910 (18)	C21—H21A	0.9600
S4—Pb	2.7710 (18)	C21—H21B	0.9600
O1—C1	1.414 (8)	C21—H21C	0.9600
O2—C8	1.413 (8)	O4—C22	1.379 (9)
O3—C15	1.404 (10)	C22—C23	1.3900
C1—C2	1.376 (9)	C22—C27	1.3900
C1—C6	1.384 (9)	C23—C24	1.3900
C2—C3	1.402 (10)	C23—H23	0.9300
C2—H2A	0.9300	C24—C25	1.3900
C3—C4	1.373 (12)	C24—H24	0.9300
C3—H3A	0.9300	C25—C26	1.3900
C4—C5	1.382 (12)	C25—H25	0.9300
C4—H4A	0.9300	C26—C27	1.3900
C5—C6	1.410 (10)	C26—H26	0.9300
C5—H5A	0.9300	C27—C28	1.502 (14)
C6—C7	1.501 (10)	C28—H28A	0.9600
C7—H7A	0.9600	C28—H28B	0.9600
C7—H7B	0.9600	C28—H28C	0.9600
C7—H7C	0.9600	O4A—C22A	1.371 (16)
C8—C9	1.370 (10)	C22A—C23A	1.3900
C8—C13	1.397 (10)	C22A—C27A	1.3900
C9—C10	1.384 (11)	C23A—C24A	1.3900
C9—H9A	0.9300	C23A—H23A	0.9300
C10—C11	1.387 (12)	C24A—C25A	1.3900
C10—H10A	0.9300	C24A—H24A	0.9300
C11—C12	1.387 (12)	C25A—C26A	1.3900
C11—H11A	0.9300	C25A—H25A	0.9300
C12—C13	1.391 (11)	C26A—C27A	1.3900
C12—H12A	0.9300	C26A—H26A	0.9300
C13—C14	1.500 (11)	C27A—C28A	1.50 (2)
C14—H14A	0.9600	C28A—H28D	0.9600
C14—H14B	0.9600	C28A—H28E	0.9600
C14—H14C	0.9600	C28A—H28F	0.9600
O1—P1—O2	104.9 (2)	H14A—C14—H14B	109.5
O1—P1—S1	110.6 (2)	C13—C14—H14C	109.5
O2—P1—S1	106.93 (19)	H14A—C14—H14C	109.5
O1—P1—S2	107.4 (2)	H14B—C14—H14C	109.5
O2—P1—S2	109.71 (19)	C16—C15—O3	119.2 (8)
S1—P1—S2	116.68 (10)	C16—C15—C20	122.0 (9)
O3—P2—O4	107.3 (4)	O3—C15—C20	118.9 (7)
O3—P2—O4A	87.0 (8)	C15—C16—C17	119.2 (9)
O4—P2—O4A	21.9 (7)	C15—C16—H16A	120.4
O3—P2—S3	111.9 (2)	C17—C16—H16A	120.4
O4—P2—S3	104.0 (3)	C18—C17—C16	117.7 (9)
O4A—P2—S3	120.3 (8)	C18—C17—H17A	121.2
O3—P2—S4	106.1 (2)	C16—C17—H17A	121.2
O4—P2—S4	111.2 (3)	C19—C18—C17	122.5 (9)
O4A—P2—S4	110.9 (8)	C19—C18—H18A	118.8
S3—P2—S4	116.12 (12)	C17—C18—H18A	118.8
P1—S1—Pb	84.63 (7)	C18—C19—C20	122.3 (9)
P1—S2—Pb	84.84 (7)	C18—C19—H19A	118.9
P2—S3—Pb	81.99 (8)	C20—C19—H19A	118.9
P2—S4—Pb	90.71 (8)	C19—C20—C15	116.4 (8)
S4—Pb—S2	81.03 (5)	C19—C20—C21	123.3 (9)
S4—Pb—S1	100.49 (5)	C15—C20—C21	120.3 (10)
S2—Pb—S1	73.63 (4)	C20—C21—H21A	109.5
S4—Pb—S3	69.50 (4)	C20—C21—H21B	109.5
S2—Pb—S3	143.66 (5)	H21A—C21—H21B	109.5
S1—Pb—S3	90.89 (5)	C20—C21—H21C	109.5
C1—O1—P1	119.7 (4)	H21A—C21—H21C	109.5
C8—O2—P1	120.7 (4)	H21B—C21—H21C	109.5
C15—O3—P2	120.7 (5)	C22—O4—P2	120.1 (6)
C2—C1—C6	123.2 (6)	O4—C22—C23	121.4 (6)
C2—C1—O1	120.1 (6)	O4—C22—C27	118.6 (6)
C6—C1—O1	116.6 (6)	C23—C22—C27	120.0
C1—C2—C3	118.9 (7)	C22—C23—C24	120.0
C1—C2—H2A	120.5	C22—C23—H23	120.0
C3—C2—H2A	120.5	C24—C23—H23	120.0
C4—C3—C2	119.9 (7)	C25—C24—C23	120.0
C4—C3—H3A	120.1	C25—C24—H24	120.0
C2—C3—H3A	120.1	C23—C24—H24	120.0
C3—C4—C5	119.9 (7)	C26—C25—C24	120.0
C3—C4—H4A	120.0	C26—C25—H25	120.0
C5—C4—H4A	120.0	C24—C25—H25	120.0
C4—C5—C6	121.9 (7)	C27—C26—C25	120.0
C4—C5—H5A	119.0	C27—C26—H26	120.0
C6—C5—H5A	119.0	C25—C26—H26	120.0
C1—C6—C5	116.1 (6)	C26—C27—C22	120.0
C1—C6—C7	122.0 (6)	C26—C27—C28	120.9 (8)
C5—C6—C7	121.9 (6)	C22—C27—C28	119.1 (8)
C6—C7—H7A	109.5	C22A—O4A—P2	118.4 (18)
C6—C7—H7B	109.5	O4A—C22A—C23A	122.3 (15)
H7A—C7—H7B	109.5	O4A—C22A—C27A	117.6 (15)
C6—C7—H7C	109.5	C23A—C22A—C27A	120.0
H7A—C7—H7C	109.5	C24A—C23A—C22A	120.0
H7B—C7—H7C	109.5	C24A—C23A—H23A	120.0
C9—C8—C13	123.0 (7)	C22A—C23A—H23A	120.0
C9—C8—O2	120.4 (6)	C25A—C24A—C23A	120.0
C13—C8—O2	116.6 (6)	C25A—C24A—H24A	120.0
C8—C9—C10	119.4 (7)	C23A—C24A—H24A	120.0
C8—C9—H9A	120.3	C24A—C25A—C26A	120.0
C10—C9—H9A	120.3	C24A—C25A—H25A	120.0
C9—C10—C11	119.7 (8)	C26A—C25A—H25A	120.0
C9—C10—H10A	120.2	C27A—C26A—C25A	120.0
C11—C10—H10A	120.2	C27A—C26A—H26A	120.0
C12—C11—C10	119.6 (8)	C25A—C26A—H26A	120.0
C12—C11—H11A	120.2	C26A—C27A—C22A	120.0
C10—C11—H11A	120.2	C26A—C27A—C28A	122 (2)
C11—C12—C13	122.1 (8)	C22A—C27A—C28A	118 (2)
C11—C12—H12A	118.9	C27A—C28A—H28D	109.5
C13—C12—H12A	118.9	C27A—C28A—H28E	109.5
C12—C13—C8	116.1 (7)	H28D—C28A—H28E	109.5
C12—C13—C14	121.7 (7)	C27A—C28A—H28F	109.5
C8—C13—C14	122.2 (7)	H28D—C28A—H28F	109.5
C13—C14—H14A	109.5	H28E—C28A—H28F	109.5
C13—C14—H14B	109.5
O1—P1—S1—Pb	−118.69 (17)	C10—C11—C12—C13	0.0 (14)
O2—P1—S1—Pb	127.58 (19)	C11—C12—C13—C8	2.5 (12)
S2—P1—S1—Pb	4.39 (10)	C11—C12—C13—C14	−179.2 (8)
O1—P1—S2—Pb	120.3 (2)	C9—C8—C13—C12	−2.9 (11)
O2—P1—S2—Pb	−126.2 (2)	O2—C8—C13—C12	175.9 (6)
S1—P1—S2—Pb	−4.41 (11)	C9—C8—C13—C14	178.8 (7)
O3—P2—S3—Pb	133.5 (2)	O2—C8—C13—C14	−2.4 (10)
O4—P2—S3—Pb	−110.9 (4)	P2—O3—C15—C16	75.9 (8)
O4A—P2—S3—Pb	−126.8 (9)	P2—O3—C15—C20	−104.6 (7)
S4—P2—S3—Pb	11.61 (11)	O3—C15—C16—C17	178.3 (9)
O3—P2—S4—Pb	−137.8 (2)	C20—C15—C16—C17	−1.1 (13)
O4—P2—S4—Pb	105.8 (3)	C15—C16—C17—C18	1.3 (15)
O4A—P2—S4—Pb	129.3 (8)	C16—C17—C18—C19	−1.1 (16)
S3—P2—S4—Pb	−12.84 (12)	C17—C18—C19—C20	0.7 (14)
P2—S4—Pb—S2	166.17 (8)	C18—C19—C20—C15	−0.4 (11)
P2—S4—Pb—S1	94.80 (8)	C18—C19—C20—C21	−179.1 (8)
P2—S4—Pb—S3	7.80 (7)	C16—C15—C20—C19	0.7 (10)
P1—S2—Pb—S4	−100.91 (7)	O3—C15—C20—C19	−178.7 (7)
P1—S2—Pb—S1	2.88 (7)	C16—C15—C20—C21	179.4 (7)
P1—S2—Pb—S3	−65.29 (11)	O3—C15—C20—C21	−0.1 (10)
P1—S1—Pb—S4	74.43 (7)	O3—P2—O4—C22	−87.1 (8)
P1—S1—Pb—S2	−2.89 (7)	O4A—P2—O4—C22	−65 (2)
P1—S1—Pb—S3	143.73 (7)	S3—P2—O4—C22	154.3 (7)
P2—S3—Pb—S4	−7.92 (7)	S4—P2—O4—C22	28.5 (8)
P2—S3—Pb—S2	−45.83 (12)	P2—O4—C22—C23	57.5 (9)
P2—S3—Pb—S1	−108.79 (8)	P2—O4—C22—C27	−123.2 (6)
O2—P1—O1—C1	76.3 (5)	O4—C22—C23—C24	179.3 (8)
S1—P1—O1—C1	−38.7 (5)	C27—C22—C23—C24	0.0
S2—P1—O1—C1	−167.0 (4)	C22—C23—C24—C25	0.0
O1—P1—O2—C8	77.3 (5)	C23—C24—C25—C26	0.0
S1—P1—O2—C8	−165.2 (4)	C24—C25—C26—C27	0.0
S2—P1—O2—C8	−37.8 (5)	C25—C26—C27—C22	0.0
O4—P2—O3—C15	−68.9 (6)	C25—C26—C27—C28	178.4 (8)
O4A—P2—O3—C15	−77.0 (10)	O4—C22—C27—C26	−179.3 (7)
S3—P2—O3—C15	44.6 (6)	C23—C22—C27—C26	0.0
S4—P2—O3—C15	172.1 (5)	O4—C22—C27—C28	2.3 (9)
P1—O1—C1—C2	−69.4 (7)	C23—C22—C27—C28	−178.4 (8)
P1—O1—C1—C6	114.0 (5)	O3—P2—O4A—C22A	−153.3 (16)
C6—C1—C2—C3	−2.2 (10)	O4—P2—O4A—C22A	47.8 (19)
O1—C1—C2—C3	−178.5 (6)	S3—P2—O4A—C22A	93.1 (16)
C1—C2—C3—C4	1.4 (11)	S4—P2—O4A—C22A	−47.2 (18)
C2—C3—C4—C5	−0.6 (12)	P2—O4A—C22A—C23A	−69 (2)
C3—C4—C5—C6	0.6 (12)	P2—O4A—C22A—C27A	114.4 (17)
C2—C1—C6—C5	2.0 (9)	O4A—C22A—C23A—C24A	−177 (2)
O1—C1—C6—C5	178.5 (5)	C27A—C22A—C23A—C24A	0.0
C2—C1—C6—C7	−177.7 (6)	C22A—C23A—C24A—C25A	0.0
O1—C1—C6—C7	−1.2 (9)	C23A—C24A—C25A—C26A	0.0
C4—C5—C6—C1	−1.2 (10)	C24A—C25A—C26A—C27A	0.0
C4—C5—C6—C7	178.6 (7)	C25A—C26A—C27A—C22A	0.0
P1—O2—C8—C9	−63.7 (8)	C25A—C26A—C27A—C28A	−179 (3)
P1—O2—C8—C13	117.6 (6)	O4A—C22A—C27A—C26A	177 (2)
C13—C8—C9—C10	0.7 (11)	C23A—C22A—C27A—C26A	0.0
O2—C8—C9—C10	−178.0 (6)	O4A—C22A—C27A—C28A	−5 (3)
C8—C9—C10—C11	2.0 (12)	C23A—C22A—C27A—C28A	179 (3)
C9—C10—C11—C12	−2.3 (13)