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Acta Crystallogr Sect E Struct Rep Online. 2009 October 1; 65(Pt 10): m1220.
Published online 2009 September 16. doi:  10.1107/S1600536809036150
PMCID: PMC2970293

Poly[di-μ2-chlorido(μ2-1,3-di-4-pyridylpropane-κ2 N:N′)lead(II)]

Abstract

The title PbII coordination polymer, [PbCl2(C13H14N2)], was prepared by the hydro­thermal reaction of PbCl2 with 4,4,-trimethyl­enedipyridine in a 1:1 ratio. It exhibits a two-dimensional layered structural motif consisting of PbCl2 chains and the flexible bridged 4,4′-trimethyl­enedipyridine ligand. The connections result in a cavity of about 4 × 15 Å.

Related literature

For crystal engineering based upon transition metal coordination polymers, see: Abrahams et al. (1999 [triangle]). For applications of these metal-organic frameworks, see: Moulton & Zaworotko (2001 [triangle]); Natarajan & Mahata (2009 [triangle]). For networks with main group metals as connected nodes, see: Shi et al. (2002 [triangle]). For the related structure, [PbCl2(4,4′-bipy)] (bipy is bipyridine), see: Nordell et al. (2004 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-65-m1220-scheme1.jpg

Experimental

Crystal data

  • [PbCl2(C13H14N2)]
  • M r = 476.35
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-m1220-efi1.jpg
  • a = 4.385 (2) Å
  • b = 15.455 (3) Å
  • c = 10.935 (2) Å
  • β = 97.65 (2)°
  • V = 734.5 (3) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 11.84 mm−1
  • T = 298 K
  • 0.19 × 0.15 × 0.11 mm

Data collection

  • Bruker SMART CCD diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 1996 [triangle]) T min = 0.139, T max = 0.277
  • 2401 measured reflections
  • 1283 independent reflections
  • 1109 reflections with I > 2σ(I)
  • R int = 0.033

Refinement

  • R[F 2 > 2σ(F 2)] = 0.033
  • wR(F 2) = 0.077
  • S = 1.01
  • 1283 reflections
  • 88 parameters
  • H-atom parameters constrained
  • Δρmax = 0.88 e Å−3
  • Δρmin = −1.16 e Å−3

Data collection: SMART (Bruker, 1996 [triangle]); cell refinement: SMART and SAINT (Bruker, 1996 [triangle]); data reduction: SHELXTL (Sheldrick, 2008 [triangle]); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809036150/pb2006sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809036150/pb2006Isup2.hkl

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

Acknowledgments

The authors thank the NNSFC (grant No. 20701014) and the SRP program of the SCUT for financial support.

supplementary crystallographic information

Comment

Crystal engineering based upon transition metal coordination polymers has made rapid progress (Abrahams et al., 1999). These metal organic frameworks attracted much attention in the field of host guest chemistry (Natarajan et al., 2009), which may find applications in catalysis, nonlinear optics, magnetism, molecular recognition and separation (Moulton et al., 2001). By comparison, the networks with main group metals as connected nodes have not been well documented (Shi et al., 2002). Recently, many lead halides based coordination polymers with nitrogen-containing ligand as bridge exhibit interesting physical properties and structural motifs (Nordell et al., 2004). Different linkers, such as 4,4,-bipy, pyrazine and bipyridyl-based butadiene are introduced to the construction of lead halide organic-inorganic hybrid compounds. Here we report the hydrothermal synthesis and structural characterization of a new coordination complex based on PbCl2 inorganic unit and 4,4,-trimethylenedipyridine. Hydrothermal reaction of PbCl2 and 4,4,-trimethylenedipyridine with equimolar amounts afford block-like crystals. They were characterized by single-crystal X-ray structural analysis. Details of crystallographic data for the title compounds 1 is listed in Table 1. The structure of PbCl2(4,4,-trimethylenedipyridine) framework is a two-dimensional-layered motif constructed by the [PbCl2]n chains and the flexible bridge 4,4,-trimethylenedipyridine ligand (Fig. 1). The crystal is monoclinic, space group P21/m, with the Pb, Cl1 and Cl2 atoms lying on a crystallographic mirror plane. Each lead metal center is six-coordinate geometry with four chloride ion on the square plane and two nitrogen donors at the axial direction. The bond distances of Pb—Cl range from 2.862 (6) Å to 2.982 (6) Å. And the bond distance of Pb—N is 2.667 (7) Å. These parameters are close to previous report (Nordell et al., 2004). The bond angles of Cl—Pb—Cl at the square plane vary from 81.15 (17) to 97.21 (17)°. And the trans N1—Pb1—N1 bond angle is 166.1 (3)°. These value indicate that the lead center is situated in a distorted octahedral environment and the lone pair in Pb(II) is stereochemically active. As showed in figure 2, The [PbCl2]n chains are linked into flat sheets by the 4,4,-trimethylenedipyridine bridges. The dimensions of the distorted square cavity are approximately 4*15 Å. The flexible of the spacers make the layer into an undulating structural motif. And the sheets stack along a axis at a distance of 4.69 Å.

Experimental

An aqueous mixture (10 ml) containing 4,4,-trimethylenedipyridine (0.1 g, 0.5 mmol), PbCl2 (0.139 g, 0.5 mmol) was placed in a Parr Teflonlined stainless steel vessel (25 ml), and the vessel was sealed and heated to 403.15 K for 24 h. 0.08 g block-like crystals were obtained.

Refinement

H atoms were positioned geometrically and refined using a riding model, with C—H = 0.93–0.97 Å and with Uiso(H) = 1.2 (1.5 for methyl groups) times Ueq(C). The non-hydrogen atoms were refined anisotropically. 41 low-theta reflections were omitted from the data set.

Figures

Fig. 1.
The molecular structure of (I), with atom labels and 50% probability displacement ellipsoids for non-H atoms.
Fig. 2.
The packing of (I), viewed down the c axis.

Crystal data

[PbCl2(C13H14N2)]F(000) = 444
Mr = 476.35Dx = 2.155 Mg m3
Monoclinic, P21/mMelting point: 533.15K K
Hall symbol: -P2ybMo Kα radiation, λ = 0.71073 Å
a = 4.385 (2) ÅCell parameters from 1283 reflections
b = 15.455 (3) Åθ = 2.6–25.0°
c = 10.935 (2) ŵ = 11.84 mm1
β = 97.65 (2)°T = 298 K
V = 734.5 (3) Å3Block, yellow
Z = 20.19 × 0.15 × 0.11 mm

Data collection

Bruker SMART CCD diffractometer1283 independent reflections
Radiation source: fine-focus sealed tube1109 reflections with I > 2σ(I)
graphiteRint = 0.033
ω scansθmax = 25.0°, θmin = 2.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)h = −5→5
Tmin = 0.139, Tmax = 0.277k = −15→18
2401 measured reflectionsl = −7→12

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.033Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.077H-atom parameters constrained
S = 1.01w = 1/[σ2(Fo2) + (0.0359P)2] where P = (Fo2 + 2Fc2)/3
1283 reflections(Δ/σ)max < 0.001
88 parametersΔρmax = 0.88 e Å3
0 restraintsΔρmin = −1.16 e Å3

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
Pb10.32077 (9)0.75000.28349 (4)0.03780 (17)
Cl20.7798 (10)0.75000.1052 (3)0.0748 (10)
Cl1−0.1094 (10)0.75000.4619 (3)0.0719 (10)
C50.6217 (18)0.4150 (5)0.2292 (8)0.0431 (19)
N10.3822 (16)0.5787 (4)0.2702 (7)0.0482 (17)
C20.412 (2)0.4554 (5)0.1409 (8)0.049 (2)
H2A0.34810.42780.06620.059*
C30.574 (2)0.5401 (5)0.3555 (8)0.057 (2)
H3A0.62880.56840.43030.068*
C10.297 (2)0.5358 (5)0.1631 (8)0.049 (2)
H1A0.15730.56160.10260.059*
C60.770 (2)0.3312 (5)0.2033 (9)0.055 (2)
H6A0.97110.32830.25270.066*
H6B0.80240.33020.11710.066*
C310.698 (2)0.4595 (5)0.3397 (9)0.055 (2)
H3B0.83350.43490.40300.066*
C70.584 (2)0.25000.2302 (11)0.040 (3)
H7A0.38630.25000.17830.048*
H7C0.54740.25000.31590.048*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Pb10.0342 (2)0.0274 (2)0.0527 (3)0.0000.00873 (17)0.000
Cl20.095 (3)0.082 (2)0.047 (2)0.0000.0061 (17)0.000
Cl10.102 (3)0.065 (2)0.048 (2)0.0000.0045 (18)0.000
C50.043 (5)0.026 (4)0.066 (6)−0.005 (3)0.027 (4)0.002 (4)
N10.057 (4)0.027 (3)0.062 (5)0.006 (3)0.016 (4)0.006 (3)
C20.062 (5)0.032 (4)0.052 (5)−0.003 (4)0.008 (4)−0.003 (4)
C30.081 (7)0.032 (4)0.056 (6)0.002 (4)0.003 (5)−0.001 (4)
C10.053 (5)0.032 (4)0.059 (6)−0.002 (4)−0.002 (4)0.009 (4)
C60.056 (5)0.032 (4)0.083 (7)−0.002 (4)0.029 (5)0.004 (4)
C310.060 (6)0.040 (4)0.066 (6)−0.007 (4)0.005 (5)0.006 (4)
C70.035 (6)0.023 (5)0.064 (7)0.0000.012 (5)0.000

Geometric parameters (Å, °)

Pb1—N1i2.667 (7)C2—C11.374 (10)
Pb1—N12.667 (7)C2—H2A0.9300
Pb1—Cl2ii2.862 (6)C3—C311.379 (11)
Pb1—Cl12.887 (5)C3—H3A0.9300
Pb1—Cl1iii2.957 (6)C1—H1A0.9300
Pb1—Cl22.982 (6)C6—C71.548 (10)
Cl2—Pb1iii2.862 (6)C6—H6A0.9700
Cl1—Pb1ii2.957 (6)C6—H6B0.9700
C5—C311.392 (12)C31—H3B0.9300
C5—C21.390 (12)C7—C6iv1.548 (10)
C5—C61.494 (11)C7—H7A0.9700
N1—C31.313 (11)C7—H7C0.9700
N1—C11.354 (11)
N1i—Pb1—N1166.1 (3)C1—C2—H2A119.8
N1i—Pb1—Cl2ii92.49 (16)C5—C2—H2A119.8
N1—Pb1—Cl2ii92.49 (16)N1—C3—C31123.2 (8)
N1i—Pb1—Cl196.69 (14)N1—C3—H3A118.4
N1—Pb1—Cl196.69 (14)C31—C3—H3A118.4
Cl2ii—Pb1—Cl184.43 (17)N1—C1—C2122.1 (7)
N1i—Pb1—Cl1iii87.32 (16)N1—C1—H1A119.0
N1—Pb1—Cl1iii87.32 (16)C2—C1—H1A119.0
Cl2ii—Pb1—Cl1iii178.36 (9)C5—C6—C7114.3 (7)
Cl1—Pb1—Cl1iii97.21 (17)C5—C6—H6A108.7
N1i—Pb1—Cl283.26 (14)C7—C6—H6A108.7
N1—Pb1—Cl283.26 (14)C5—C6—H6B108.7
Cl2ii—Pb1—Cl297.21 (17)C7—C6—H6B108.7
Cl1—Pb1—Cl2178.36 (11)H6A—C6—H6B107.6
Cl1iii—Pb1—Cl281.15 (17)C3—C31—C5120.1 (8)
Pb1iii—Cl2—Pb197.21 (17)C3—C31—H3B120.0
Pb1—Cl1—Pb1ii97.21 (17)C5—C31—H3B120.0
C31—C5—C2116.2 (7)C6—C7—C6iv108.3 (9)
C31—C5—C6122.2 (8)C6—C7—H7A110.0
C2—C5—C6121.5 (8)C6iv—C7—H7A110.0
C3—N1—C1117.9 (7)C6—C7—H7C110.0
C3—N1—Pb1118.2 (6)C6iv—C7—H7C110.0
C1—N1—Pb1121.0 (5)H7A—C7—H7C108.4
C1—C2—C5120.5 (8)

Symmetry codes: (i) x, −y+3/2, z; (ii) x−1, y, z; (iii) x+1, y, z; (iv) x, −y+1/2, z.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: PB2006).

References

  • Abrahams, B. F., Egan, S. J. & Robson, R. (1999). J. Am. Chem. Soc.121, 3535–3536.
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  • Moulton, B. & Zaworotko, M. J. (2001). Chem. Rev.101, 1629–1658. [PubMed]
  • Natarajan, S. & Mahata, P. (2009). Chem. Soc. Rev.38, 2304–2318. [PubMed]
  • Nordell, K. J., Schultz, K. N., Higgins, K. A. & Smith, M. D. (2004). Polyhedron, 23, 2161–2167.
  • Sheldrick, G. M. (1996). SADABS University of Göttingen, Germany.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Shi, Y. J., Li, L. H., Li, Y. Z., Xu, Y., Chen, X. T., Xue, Z. & You, X. Z. (2002). Inorg. Chem. Commun.5, 1090–1094.

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