Literature DB >> 21754614

catena-Poly[[bis(pyridine)-lead(II)]bis(μ-penta-fluoro-benzene-thiol-ato)].

Sarah E Appleton, Glen G Briand, Andreas Decken, Anita S Smith.

Abstract

The title compound, [Pb(C(6)F(5)S)(2)(C(5)H(5)N)(2)](n), shows the Pb(II) atom in a ψ-trigonal bipyramidal S(2)N(2) bonding environment. Pyridine N atoms occupy axial sites, while thiol-ate S atoms and a stereochemically active lone pair occupy equatorial sites. Very long inter-molecular Pb⋯S inter-actions [3.618 (4) and 3.614 (4) Å] yield a weakly associated one-dimensional polymeric structure extending parallel to [010].

Entities: Chemical Disease Species

Year: 2011 PMID： 21754614 PMCID： PMC3120355 DOI： 10.1107/S160053681101659X

Source DB: PubMed Journal: Acta Crystallogr Sect E Struct Rep Online ISSN： 1600-5368

Related literature

Lead(II) thiolates tend to form polymeric structures in the solid state via intermolecular Pb⋯S interactions, see: Davidovich et al. (2010 ▶) and references therein; Eichhöfer (2005 ▶). However, the bonding environment at lead and the degree of intermolecular bonding may be altered via the introduction of Lewis base ligands that occupy metal coordination sites, see: Appleton et al. (2004 ▶); Briand et al. (2007 ▶). It has been shown that [(F5C6S)2Pb]n exhibits a three-dimensional framework structure containing hexacoordinated PbII atoms (Fleischer et al., 2006 ▶). For van der Waals radii, see: Bondi (1964 ▶); Brown (1978 ▶).

Experimental

Crystal data

[Pb(C6F5S)2C5H5N)2] M = 763.63 Monoclinic, a = 19.9288 (19) Å b = 5.0416 (5) Å c = 24.9155 (19) Å β = 111.339 (3)° V = 2331.7 (4) Å3 Z = 4 Mo Kα radiation μ = 7.51 mm−1 T = 198 K 0.57 × 0.15 × 0.10 mm

Data collection

Bruker SMART1000/P4 diffractometer Absorption correction: multi-scan (SADABS; Sheldrick, 2008a ▶) T min = 0.099, T max = 0.521 6756 measured reflections 2575 independent reflections 2421 reflections with I > 2σ(I) R int = 0.055

Refinement

R[F 2 > 2σ(F 2)] = 0.040 wR(F 2) = 0.097 S = 1.06 2575 reflections 168 parameters H-atom parameters constrained Δρmax = 3.83 e Å−3 Δρmin = −2.71 e Å−3 Data collection: SMART (Bruker, 1999 ▶); cell refinement: SAINT (Bruker, 2006 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008b ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008b ▶); molecular graphics: SHELXTL (Sheldrick, 2008b ▶); software used to prepare material for publication: SHELXTL. Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053681101659X/hg5027sup1.cif Supplementary material file. DOI: 10.1107/S160053681101659X/hg5027Isup2.cdx Structure factors: contains datablocks I. DOI: 10.1107/S160053681101659X/hg5027Isup3.hkl Additional supplementary materials: crystallographic information; 3D view; checkCIF report

[Pb(C₆F₅S)₂C₅H₅N)₂]	F(000) = 1440
M_r = 763.63	D_x = 2.175 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 5261 reflections
a = 19.9288 (19) Å	θ = 2.2–27.9°
b = 5.0416 (5) Å	µ = 7.51 mm⁻¹
c = 24.9155 (19) Å	T = 198 K
β = 111.339 (3)°	Parallelepiped, colourless
V = 2331.7 (4) Å³	0.57 × 0.15 × 0.10 mm
Z = 4

Bruker SMART1000/P4 diffractometer	2575 independent reflections
Radiation source: fine-focus sealed tube, K760	2421 reflections with I > 2σ(I)
graphite	R_int = 0.055
φ and ω scans	θ_max = 27.5°, θ_min = 4.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 2008a)	h = −25→25
T_min = 0.099, T_max = 0.521	k = −6→6
6756 measured reflections	l = −30→32

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.097	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.0608P)²] where P = (F_o² + 2F_c²)/3
2575 reflections	(Δ/σ)_max = 0.001
168 parameters	Δρ_max = 3.83 e Å⁻³
0 restraints	Δρ_min = −2.70 e Å⁻³

Experimental. Crystal decay was monitored by repeating the initial 50 frames at the end of the data collection and analyzing duplicate reflections.FT—IR (cm^-1): 669 w, 702 m, 750 m, 825 vw, 856 s, 972 s, 1001 m, 1153 w, 1215 w, 1263 vw, 1444 s, 1477 versus, 1510 s, 1595 m, 1608 vw, 2341 m, 2360 s. FT-Raman (cm^-1): 74 s, 101 versus, 175 vw, 201 vw, 268 versus, 317 vw, 372 vw, 387 w, 444 vw, 513 m, 584 w, 859 m, 1003 s, 1032 m, 1277 vw, 1393 m, 1636 versus, 3069 m. NMR data (thf-d₈, p.p.m.): ¹H NMR, δ = 7.36 (m, 4H, NC₅H₅), 7.77 (tt, 2H, ³J (¹H-¹H) = 8 Hz, ⁴J (¹H-¹H) = 2 Hz, NC₅H₅), 8.67 (m, 4H, NC₅H₅); ¹³C{¹H} NMR, δ = 115.8 (tm, ²J (¹³C-¹⁹F) = 22 Hz, SC₆F₅), 124.2 (s, NC₅H₅), 136.7 (s, NC₅H₅), 137.1 (dm, ¹J (¹³C-¹⁹F) = 245 Hz, SC₆F₅), 137.7 (dm, ¹J (¹³C-¹⁹F) = 247 Hz, SC₆F₅), 148.4 (dm, ¹J (¹³C-¹⁹F) = 226 Hz, SC₆F₅), 149.4 (s, NC₅H₅); ¹⁹F NMR, δ = -166.2 (m, SC₆F₅), -164.5 (m, SC₆F₅), -133.9 (m, SC₆F₅).

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	U_iso*/U_eq
Pb	0.0000	0.57741 (4)	0.2500	0.02457 (12)
S1	−0.00240 (9)	0.9584 (2)	0.17593 (6)	0.0308 (3)
F2	−0.1488 (2)	0.9328 (7)	0.0811 (2)	0.0491 (11)
F3	−0.1937 (2)	0.5959 (8)	−0.0085 (2)	0.0643 (15)
F4	−0.1038 (2)	0.2260 (7)	−0.02233 (17)	0.0513 (10)
F5	0.03376 (19)	0.1979 (7)	0.05311 (15)	0.0416 (8)
F6	0.0806 (2)	0.5350 (7)	0.14221 (17)	0.0404 (8)
N1	0.1419 (3)	0.5895 (8)	0.2954 (3)	0.0333 (11)
C1	−0.0321 (3)	0.7450 (9)	0.1159 (2)	0.0261 (10)
C2	−0.1022 (3)	0.7539 (11)	0.0757 (2)	0.0324 (11)
C3	−0.1263 (4)	0.5816 (11)	0.0295 (3)	0.0369 (14)
C4	−0.0802 (4)	0.3944 (11)	0.0226 (3)	0.0341 (13)
C5	−0.0113 (3)	0.3793 (11)	0.0607 (3)	0.0304 (12)
C6	0.0123 (3)	0.5558 (9)	0.1063 (3)	0.0278 (11)
C7	0.1855 (3)	0.7571 (12)	0.2823 (3)	0.0408 (13)
H7	0.1652	0.8817	0.2534	0.049*
C8	0.2590 (4)	0.7531 (14)	0.3097 (3)	0.0512 (17)
H8	0.2880	0.8719	0.2994	0.061*
C9	0.2891 (4)	0.5700 (12)	0.3528 (4)	0.052 (2)
H9	0.3387	0.5646	0.3726	0.062*
C10	0.2453 (4)	0.3984 (13)	0.3659 (4)	0.053 (2)
H10	0.2645	0.2719	0.3946	0.063*
C11	0.1719 (4)	0.4119 (11)	0.3363 (3)	0.0426 (16)
H11	0.1423	0.2918	0.3455	0.051*

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Pb	0.02186 (16)	0.02276 (15)	0.02304 (18)	0.000	0.00096 (12)	0.000
S1	0.0382 (8)	0.0238 (6)	0.0243 (7)	−0.0012 (5)	0.0040 (6)	−0.0011 (5)
F2	0.036 (2)	0.054 (2)	0.045 (3)	0.0214 (16)	0.0000 (19)	−0.0131 (16)
F3	0.031 (2)	0.089 (3)	0.052 (3)	0.0185 (19)	−0.011 (2)	−0.030 (2)
F4	0.046 (2)	0.055 (2)	0.042 (2)	0.0075 (18)	0.0033 (18)	−0.0236 (18)
F5	0.0405 (19)	0.0421 (18)	0.042 (2)	0.0155 (16)	0.0150 (17)	−0.0039 (15)
F6	0.0235 (17)	0.050 (2)	0.038 (2)	0.0079 (15)	−0.0006 (16)	−0.0015 (16)
N1	0.022 (2)	0.034 (2)	0.037 (3)	0.0008 (17)	0.003 (2)	0.0018 (18)
C1	0.029 (2)	0.023 (2)	0.023 (3)	0.001 (2)	0.006 (2)	0.0051 (19)
C2	0.028 (2)	0.037 (3)	0.029 (3)	0.010 (2)	0.006 (2)	−0.004 (2)
C3	0.027 (3)	0.045 (3)	0.029 (3)	0.007 (2)	−0.002 (3)	−0.008 (2)
C4	0.034 (3)	0.038 (3)	0.027 (3)	0.003 (2)	0.008 (3)	−0.008 (2)
C5	0.031 (3)	0.032 (2)	0.029 (3)	0.010 (2)	0.012 (3)	0.001 (2)
C6	0.023 (3)	0.030 (3)	0.026 (3)	0.0005 (19)	0.004 (2)	0.0038 (19)
C7	0.033 (3)	0.040 (3)	0.041 (4)	−0.003 (3)	0.005 (3)	0.006 (3)
C8	0.033 (3)	0.054 (4)	0.061 (5)	−0.013 (3)	0.010 (3)	0.003 (3)
C9	0.027 (3)	0.056 (4)	0.061 (5)	−0.001 (3)	0.003 (3)	−0.001 (3)
C10	0.039 (4)	0.049 (4)	0.051 (5)	0.005 (3)	−0.005 (4)	0.009 (3)
C11	0.032 (3)	0.040 (3)	0.047 (4)	−0.002 (2)	0.005 (3)	0.010 (2)

Pb—N1	2.636 (5)	C2—C3	1.382 (8)
Pb—N1ⁱ	2.636 (5)	C3—C4	1.371 (8)
Pb—S1ⁱ	2.6519 (14)	C4—C5	1.359 (9)
Pb—S1	2.6519 (14)	C5—C6	1.384 (8)
S1—C1	1.761 (5)	C7—C8	1.373 (8)
F2—C2	1.336 (6)	C7—H7	0.9300
F3—C3	1.334 (8)	C8—C9	1.378 (11)
F4—C4	1.345 (7)	C8—H8	0.9300
F5—C5	1.342 (6)	C9—C10	1.350 (12)
F6—C6	1.334 (7)	C9—H9	0.9300
N1—C11	1.326 (8)	C10—C11	1.380 (10)
N1—C7	1.335 (8)	C10—H10	0.9300
C1—C6	1.379 (8)	C11—H11	0.9300
C1—C2	1.392 (7)

N1—Pb—N1ⁱ	177.34 (18)	F5—C5—C4	119.8 (5)
N1—Pb—S1ⁱ	86.55 (12)	F5—C5—C6	120.7 (5)
N1ⁱ—Pb—S1ⁱ	91.52 (12)	C4—C5—C6	119.5 (5)
N1—Pb—S1	91.52 (12)	F6—C6—C1	120.1 (5)
N1ⁱ—Pb—S1	86.55 (12)	F6—C6—C5	117.3 (5)
S1ⁱ—Pb—S1	87.18 (6)	C1—C6—C5	122.7 (5)
C1—S1—Pb	93.67 (16)	N1—C7—C8	122.8 (6)
C11—N1—C7	117.6 (6)	N1—C7—H7	118.6
C11—N1—Pb	115.3 (4)	C8—C7—H7	118.6
C7—N1—Pb	127.0 (4)	C7—C8—C9	118.7 (7)
C6—C1—C2	115.9 (5)	C7—C8—H8	120.6
C6—C1—S1	122.1 (4)	C9—C8—H8	120.6
C2—C1—S1	122.0 (4)	C10—C9—C8	118.7 (7)
F2—C2—C3	117.8 (5)	C10—C9—H9	120.6
F2—C2—C1	120.1 (5)	C8—C9—H9	120.6
C3—C2—C1	122.1 (5)	C9—C10—C11	119.6 (7)
F3—C3—C4	119.8 (5)	C9—C10—H10	120.2
F3—C3—C2	120.7 (5)	C11—C10—H10	120.2
C4—C3—C2	119.5 (6)	N1—C11—C10	122.5 (7)
F4—C4—C5	120.3 (5)	N1—C11—H11	118.7
F4—C4—C3	119.4 (6)	C10—C11—H11	118.7
C5—C4—C3	120.3 (5)

3 in total

1. A short history of SHELX.

Authors: George M Sheldrick
Journal: Acta Crystallogr A Date: 2007-12-21 Impact factor: 2.290

2. Monomeric, one- and two-dimensional networks incorporating (2,6-Me2C6H3S)2Pb building blocks.

Authors: Sarah E Appleton; Glen G Briand; Andreas Decken; Anita S Smith
Journal: Dalton Trans Date: 2004-09-29 Impact factor: 4.390

3. Probing lead(II) bonding environments in 4-substituted pyridine adducts of (2,6-Me2C6H3S)2Pb: an X-ray structural and solid-state 207Pb NMR study.

Authors: Glen G Briand; Andrew D Smith; Gabriele Schatte; Aaron J Rossini; Robert W Schurko
Journal: Inorg Chem Date: 2007-09-15 Impact factor: 5.165