PMCCPMCCPMCC

Search tips
Search criteria 

Advanced

 
Logo of actaeInternational Union of Crystallographysearchopen accessarticle submissionjournal home pagethis article
 
Acta Crystallogr Sect E Struct Rep Online. 2008 October 1; 64(Pt 10): m1341–m1342.
Published online 2008 September 27. doi:  10.1107/S1600536808030535
PMCID: PMC2959230

Poly[bis­(μ3-acetato-κ4 O,O′:O:O′)bis­(μ2-acetato-κ3 O,O′:O)(μ2-2,5-dimethyl­benzene-1,4-diol-κ2 O:O′)dilead(II)]

Abstract

The title compound, [Pb2(C2H3O2)4(C8H10O2)]n, has a polymeric structure, with acetatolead(II) chains and 2,5-dimethyl­benzene-1,4-diol mol­ecules forming bridges between two PbII ions from neighbouring chains. Each PbII centre is surrounded by eight O atoms; four belong to bidentate acetate ions, three to neighbouring bridging acetate groups and one to the 2,5-dimethyl­benzene-1,4-diol mol­ecule. The PbII ions are chelated symmetrically and asymmetrically by acetate ligands. The coordination environment of the PbII ion can be described as a hemidirected PbIIO6 core with the empty space around the metal ion filled by the stereochemically active 6s 2 electron pair and two longer Pb—O contacts. The Pb—O distances are in the range of 2.355 (3)–2.994 (3) Å. Additionally, the crystal structure is stabilized by O—H(...)O hydrogen bonds.

Related literature

Other crystal structures containing polymeric lead(II) acetate were reported by: Rajaram & Rao (1982 [triangle]); Bryant et al. (1984 [triangle]); Harrowfield et al. (1996 [triangle]). Van der Waals radii of lead(II) and oxygen were presented by Bondi (1964 [triangle]). The synthesis of the title compound was carried out similarly to the method used for obtaining the bis­(2,4-penta­nedionato)lead(II) complex described by Lyczko et al. (2006 [triangle]). Hemi- and holodirected geometries of lead(II) complexes and the role of the 6s 2 lone electron pair of the lead(II) ion were discussed by Shimoni-Livny et al. (1998 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-64-m1341-scheme1.jpg

Experimental

Crystal data

  • [Pb2(C2H3O2)4(C8H10O2)]
  • M r = 788.72
  • Triclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-m1341-efi1.jpg
  • a = 7.4905 (11) Å
  • b = 7.5526 (10) Å
  • c = 10.2522 (15) Å
  • α = 93.043 (11)°
  • β = 100.787 (12)°
  • γ = 116.377 (14)°
  • V = 504.28 (12) Å3
  • Z = 1
  • Mo Kα radiation
  • μ = 16.72 mm−1
  • T = 100 (2) K
  • 0.35 × 0.26 × 0.14 mm

Data collection

  • Kuma KM-4 four-circle CCD diffractometer
  • Absorption correction: analytical (CrysAlis RED; Oxford Diffraction, 2005 [triangle]) T min = 0.040, T max = 0.227
  • 9065 measured reflections
  • 2432 independent reflections
  • 2317 reflections with I > 2σ(I)
  • R int = 0.041

Refinement

  • R[F 2 > 2σ(F 2)] = 0.017
  • wR(F 2) = 0.043
  • S = 1.07
  • 2432 reflections
  • 132 parameters
  • H-atom parameters constrained
  • Δρmax = 1.30 e Å−3
  • Δρmin = −1.67 e Å−3

Data collection: CrysAlis CCD (Oxford Diffraction, 2005 [triangle]); cell refinement: CrysAlis RED (Oxford Diffraction, 2005 [triangle]); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: Mercury (Macrae et al., 2006 [triangle]); software used to prepare material for publication: SHELXL97.

Table 1
Selected bond lengths (Å)
Table 2
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808030535/nc2114sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808030535/nc2114Isup2.hkl

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

Acknowledgments

The authors thank Warsaw University and the Institute of Nuclear Chemistry and Technology for financial support.

supplementary crystallographic information

Comment

The aim of this work was to synthesize the complex between PbII ions and 3-methyl-2,4-pentanedione. Unexpectedly, under the reaction conditions (see Experimental), instead of the bis(3-methyl-2,4-pentanedionato)lead(II) complex, the title compound was obtained.

The structure of this compound consists of polymeric chains of lead(II) acetate linked via 2,5-dimethylbenzene-1,4-diol molecules, each bridging two PbII ions from neighbouring chains. As shown in Fig. 1 the title compound contains eight-coordinated PbII ions. Each PbII centre binds strongly four O atoms from bidentate acetate ions in a nearly pyramidal configuration with Pb—O bond lengths in the range of 2.355 (3)–2.700 (3) Å, and additionally two O atoms from neighbouring bridging acetate groups of the same chain at 2.618 (2) and 2.766 (3) Å. The PbII ions are chelated symmetrically [Pb—O = 2.493 (3) and 2.499 (3) Å] and asymmetrically [2.355 (3) and 2.700 (3) Å] by acetato ligands. The coordination sphere of the metal ion is completed by two additional O atoms at distances of about 2.99 Å, the first from the acetate group of the neighbouring chain and the second from the 2,5-dimethylbenzene-1,4-diol molecule. These two contacts are much longer than the Pb—O bonds in the chelate but shorter than the sum of the van der Waals radii of lead(II) and oxygen (3.44 Å; Bondi, 1964) indicating some weak interactions. The crystal structure is also stabilized by O—H···O hydrogen bonds. The OH groups of the 2,5-dimethylbenzene-1,4-diol molecule form hydrogen bonds with a H···O distance of 1.87 Å to O atoms from neighbouring CH3COO- ions (Fig. 2). The resulting coordination sphere of the PbII ion in the title compound has a hemidirected geometry (Shimoni-Livny et al., 1998). It contains the PbIIO6 core with the empty space at one side of the metal ion filled by stereochemically active electron pair and two longer Pb—O contacts of 2.993 (3) and 2.994 (3) Å. The 6s2 electron pair is located opposite to the shortest Pb—O bond length [2.355 (3) Å] and between two longest Pb—O contacts of about 2.99 Å.

Identical polymeric acetato-lead(II) chains are present in the lead(II) acetate trihydrate structure, where the metal ions are nine-coordinated (PbIIO9) with two bidentate acetate groups, three coordinated water molecules and two bridging distances to O atoms from the neighbouring acetate groups (Rajaram & Rao, 1982; Bryant et al., 1984). In another polymeric structure of lead(II) acetate the PbII ions are eight-coordinated with the PbIIO6N2 core containing in addition two N atoms from two 2-pyridylamine molecules (Harrowfield et al., 1996).

Experimental

The title compound was obtained unintentionally in an attempt to synthesize single crystals of the bis(3-methyl-2,4-pentanedionato)lead(II) complex. Small pieces of lead foil (0.26 g) were heated (~50 °C) for a few weeks in a mixture of 3-methyl-2,4-pentanedione (2 ml) and toluene (2 ml) under reflux. The synthesis was carried out similarly to that used for the preparation of crystals of the bis(2,4-pentanedionato)lead(II) complex (Lyczko et al., 2006). After heating the reaction mixture was stored for a few months until it converted into an orange–brown solid. Colourless crystals of the title compound were separated from the reaction mixture. Analysis, calculated for C16H22O10Pb2: C 24.36, H 2.81%; found: C 24.14, H 2.88%.

Refinement

H atoms were placed in calculated positions (O—H H atoms allowed to rotate but not to tip) with C—H = 0.98 Å (CH3), C—H = 0.95 Å (aromatic H atoms), O—H = 0.84 Å and were refined isotropic with Uiso(H) = 1.5Ueq(C, O) and Uiso(H) = 1.2Ueq(C) for aromatic H atoms using a riding model.

Figures

Fig. 1.
A fragment of the polymeric structure of the title compound with labelling showing the environment of the lead atom. Displacement ellipsoids of non-hydrogen atoms are drawn at the 50% probability level. [Symmetry codes: (i) -x + 1, -y + 1, -z; (ii) -x, ...
Fig. 2.
A packing diagram of the title compound. Hydrogen bonding is shown as blue dashed lines.

Crystal data

[Pb2(C2H3O2)4(C8H10O2)]Z = 1
Mr = 788.72F(000) = 362
Triclinic, P1Dx = 2.597 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 7.4905 (11) ÅCell parameters from 9065 reflections
b = 7.5526 (10) Åθ = 3.0–28.7°
c = 10.2522 (15) ŵ = 16.72 mm1
α = 93.043 (11)°T = 100 K
β = 100.787 (12)°Prismatic, colourless
γ = 116.377 (14)°0.35 × 0.26 × 0.14 mm
V = 504.28 (12) Å3

Data collection

Kuma KM-4 four-circle CCD diffractometer2432 independent reflections
Radiation source: fine-focus sealed tube2317 reflections with I > 2σ(I)
graphiteRint = 0.041
Detector resolution: 8.6479 pixels mm-1θmax = 28.7°, θmin = 3.1°
ω scansh = −9→9
Absorption correction: analytical (CrysAlis RED; Oxford Diffraction, 2005)k = −10→10
Tmin = 0.040, Tmax = 0.227l = −13→13
9065 measured reflections

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.017H-atom parameters constrained
wR(F2) = 0.043w = 1/[σ2(Fo2) + (0.0223P)2 + 0.6288P] where P = (Fo2 + 2Fc2)/3
S = 1.07(Δ/σ)max = 0.001
2432 reflectionsΔρmax = 1.30 e Å3
132 parametersΔρmin = −1.67 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0077 (5)

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 (Å2)

xyzUiso*/Ueq
Pb10.205617 (17)0.362095 (17)0.046792 (11)0.00910 (6)
O10.4490 (4)0.6463 (4)−0.0457 (2)0.0121 (5)
O20.1324 (4)0.6005 (4)−0.0858 (3)0.0154 (5)
O30.1663 (4)0.2264 (4)−0.1751 (2)0.0148 (5)
O4−0.1191 (4)0.0447 (4)−0.1145 (3)0.0214 (6)
C10.3154 (5)0.6990 (5)−0.0954 (3)0.0111 (6)
C20.3723 (6)0.8784 (6)−0.1662 (4)0.0155 (7)
H2A0.51800.9365−0.16680.023*
H2B0.34660.9780−0.11920.023*
H2C0.28960.8380−0.25890.023*
C3−0.0132 (5)0.0788 (6)−0.1992 (4)0.0135 (7)
C4−0.0903 (6)−0.0587 (6)−0.3316 (4)0.0212 (8)
H4A−0.0509−0.1658−0.32160.032*
H4B−0.03010.0174−0.40020.032*
H4C−0.2400−0.1172−0.35880.032*
C50.5070 (5)0.5941 (5)0.3871 (3)0.0124 (7)
O50.5039 (4)0.6836 (4)0.2743 (3)0.0166 (5)
H50.62160.73560.25910.025*
C60.3672 (5)0.5861 (6)0.4637 (4)0.0129 (7)
C70.3647 (5)0.4909 (5)0.5766 (3)0.0133 (7)
H70.27200.48410.63030.016*
C80.2300 (6)0.6797 (7)0.4230 (4)0.0207 (8)
H8A0.15260.67320.49140.031*
H8B0.13440.60740.33660.031*
H8C0.31330.81990.41450.031*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Pb10.00762 (8)0.00740 (8)0.01117 (8)0.00219 (6)0.00281 (5)0.00244 (5)
O10.0087 (12)0.0098 (12)0.0179 (12)0.0040 (10)0.0032 (9)0.0049 (10)
O20.0082 (12)0.0150 (13)0.0246 (14)0.0054 (11)0.0062 (10)0.0077 (11)
O30.0130 (12)0.0112 (12)0.0157 (12)0.0012 (11)0.0048 (9)0.0017 (10)
O40.0123 (13)0.0247 (16)0.0203 (14)0.0021 (12)0.0053 (10)0.0018 (12)
C10.0119 (16)0.0087 (16)0.0123 (16)0.0048 (14)0.0025 (12)0.0006 (13)
C20.0098 (17)0.0120 (18)0.0240 (19)0.0034 (15)0.0051 (14)0.0091 (15)
C30.0107 (17)0.0115 (17)0.0151 (16)0.0037 (15)−0.0002 (13)0.0028 (14)
C40.023 (2)0.0139 (19)0.0179 (18)0.0035 (17)0.0004 (15)−0.0014 (15)
C50.0120 (16)0.0105 (17)0.0090 (15)0.0010 (14)0.0011 (12)0.0005 (13)
O50.0146 (13)0.0202 (14)0.0150 (12)0.0062 (12)0.0061 (10)0.0089 (11)
C60.0110 (17)0.0105 (16)0.0145 (16)0.0036 (14)0.0013 (12)−0.0007 (13)
C70.0109 (16)0.0128 (17)0.0133 (16)0.0029 (14)0.0038 (12)0.0001 (14)
C80.0190 (19)0.025 (2)0.0224 (19)0.0138 (18)0.0055 (15)0.0065 (16)

Geometric parameters (Å, °)

Pb1—O32.355 (3)C2—H2C0.9800
Pb1—O12.493 (3)C3—C41.509 (5)
Pb1—O22.499 (3)C4—H4A0.9800
Pb1—O1i2.618 (2)C4—H4B0.9800
Pb1—O42.700 (3)C4—H4C0.9800
Pb1—O2ii2.767 (3)C5—O51.372 (4)
Pb1—O52.993 (3)C5—C7iv1.384 (5)
Pb1—O4iii2.994 (3)C5—C61.405 (5)
O1—C11.267 (4)O5—H50.8400
O1—Pb1i2.618 (2)C6—C71.393 (5)
O2—C11.263 (4)C6—C81.499 (5)
O3—C31.275 (4)C7—C5iv1.384 (5)
O4—C31.245 (4)C7—H70.9500
C1—C21.500 (5)C8—H8A0.9800
C2—H2A0.9800C8—H8B0.9800
C2—H2B0.9800C8—H8C0.9800
O3—Pb1—O175.58 (9)O4—C3—O3121.2 (3)
O3—Pb1—O277.94 (9)O4—C3—C4120.8 (3)
O1—Pb1—O252.08 (8)O3—C3—C4118.0 (3)
O3—Pb1—O1i75.04 (8)C3—C4—H4A109.5
O1—Pb1—O1i66.16 (9)C3—C4—H4B109.5
O2—Pb1—O1i116.77 (8)H4A—C4—H4B109.5
O3—Pb1—O450.93 (8)C3—C4—H4C109.5
O1—Pb1—O4121.84 (8)H4A—C4—H4C109.5
O2—Pb1—O491.50 (9)H4B—C4—H4C109.5
O1i—Pb1—O4111.98 (8)O5—C5—C7iv122.7 (3)
C1—O1—Pb194.0 (2)O5—C5—C6116.7 (3)
C1—O1—Pb1i149.3 (2)C7iv—C5—C6120.6 (3)
Pb1—O1—Pb1i113.84 (9)C5—O5—H5109.5
C1—O2—Pb193.8 (2)C7—C6—C5117.4 (3)
C3—O3—Pb1101.7 (2)C7—C6—C8122.9 (3)
C3—O4—Pb186.2 (2)C5—C6—C8119.8 (3)
O2—C1—O1120.1 (3)C5iv—C7—C6122.0 (3)
O2—C1—C2119.4 (3)C5iv—C7—H7119.0
O1—C1—C2120.6 (3)C6—C7—H7119.0
C1—C2—H2A109.5C6—C8—H8A109.5
C1—C2—H2B109.5C6—C8—H8B109.5
H2A—C2—H2B109.5H8A—C8—H8B109.5
C1—C2—H2C109.5C6—C8—H8C109.5
H2A—C2—H2C109.5H8A—C8—H8C109.5
H2B—C2—H2C109.5H8B—C8—H8C109.5
O3—Pb1—O1—C186.8 (2)O2—Pb1—O4—C374.2 (2)
O2—Pb1—O1—C11.04 (19)O1i—Pb1—O4—C3−45.6 (2)
O1i—Pb1—O1—C1166.6 (3)Pb1—O2—C1—O11.9 (3)
O4—Pb1—O1—C164.6 (2)Pb1—O2—C1—C2−178.1 (3)
O3—Pb1—O1—Pb1i−79.76 (11)Pb1—O1—C1—O2−1.9 (3)
O2—Pb1—O1—Pb1i−165.57 (16)Pb1i—O1—C1—O2153.6 (3)
O1i—Pb1—O1—Pb1i0.0Pb1—O1—C1—C2178.1 (3)
O4—Pb1—O1—Pb1i−101.97 (11)Pb1i—O1—C1—C2−26.4 (6)
O3—Pb1—O2—C1−82.0 (2)Pb1—O4—C3—O3−1.8 (3)
O1—Pb1—O2—C1−1.05 (19)Pb1—O4—C3—C4175.7 (3)
O1i—Pb1—O2—C1−15.8 (2)Pb1—O3—C3—O42.1 (4)
O4—Pb1—O2—C1−131.5 (2)Pb1—O3—C3—C4−175.4 (3)
O1—Pb1—O3—C3−156.6 (2)O5—C5—C6—C7178.3 (3)
O2—Pb1—O3—C3−103.1 (2)C7iv—C5—C6—C70.3 (6)
O1i—Pb1—O3—C3134.7 (2)O5—C5—C6—C8−2.3 (5)
O4—Pb1—O3—C3−1.1 (2)C7iv—C5—C6—C8179.8 (4)
O3—Pb1—O4—C31.1 (2)C5—C6—C7—C5iv−0.3 (6)
O1—Pb1—O4—C329.2 (2)C8—C6—C7—C5iv−179.8 (4)

Symmetry codes: (i) −x+1, −y+1, −z; (ii) −x, −y+1, −z; (iii) −x, −y, −z; (iv) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O5—H5···O3i0.841.872.668 (4)159.

Symmetry codes: (i) −x+1, −y+1, −z.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: NC2114).

References

  • Bondi, A. (1964). J. Phys. Chem.68, 441–451.
  • Bryant, R. G., Chacko, V. P. & Etter, M. C. (1984). Inorg. Chem.23, 3580–3584.
  • Harrowfield, J. M., Miyamae, H., Skelton, B. W., Soudi, A. A. & White, A. H. (1996). Aust. J. Chem.49, 1121–1125.
  • Lyczko, K., Narbutt, J., Paluchowska, B., Maurin, J. K. & Persson, I. (2006). Dalton Trans. pp. 3972–3976. [PubMed]
  • Macrae, C. F., Edgington, P. R., McCabe, P., Pidcock, E., Shields, G. P., Taylor, R., Towler, M. & van de Streek, J. (2006). J. Appl. Cryst.39, 453–457.
  • Oxford Diffraction (2005). CrysAlis RED and CrysAlis CCD Oxford Diffraction Poland, Wrocław, Poland.
  • Rajaram, R. K. & Rao, J. K. M. (1982). Z. Kristallogr.160, 225–233.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Shimoni-Livny, L., Glusker, J. P. & Bock, Ch. W. (1998). Inorg. Chem.37, 1853–1867.

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography