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Acta Cryst. (2007). E63, m2890    [ doi:10.1107/S1600536807053743 ]

catena-Poly[[(4,7-diphenyl-1,10-phenanthroline)lead(II)]-[mu]-fumarato]

Y.-B. Yin and H.-X. Yu

Abstract top

In the title compound, [Pb(C4H2O4)(C24H16N2)]n, the PbII atom is chelated by 4,7-diphenyl-1,10-phenanthroline (L) and also bonded to four O atoms from two fumarate dianions to yield an irregular PbN2O4 coordination polyhedron. The centrosymmetric fumarate ligands bridge neighboring PbII atoms to generate a chain structure. Aromatic [pi]-[pi] stacking between L ligands in adjacent chains [minimum centroid-centroid separation = 3.462 (3) Å] leads to a two-dimensional supramolecular array.

Comment top

Metal cations with an s2 electron configuration have important applications in electroluminescent devices or organic light-emitting diode technology (Fan & Zhu, 2006). Among them, the PbII coordination polymers have received much attention due to their interesting network topologies and properties (Yang et al., 2007). Herein, we present a new Pb(II) coordination polymer, namely the title compound, (I), [Pb(fum)(L)], where fum = the fumarate dianion and L = 4,7-diphenyl-1,10-phenanthroline.

In compound (I) the PbII atom is six-coordinated by four carboxylate O atoms from two different fum ligands and two N atoms from one L ligand (Table 1, Fig. 1). The resulting PbN2O6 polyhedron is irregular, perhaps caused, in part, by the stereochemical activity of the Pb lone pair of electrons. There are two fum half-molecules in the asymmetric unit, both being completed by inversion symmetry. The neighboring PbII atoms are linked by the fum dianions to form a chain structure and the L ligands are decorded on both sides of the chains (Fig. 2). Furthermore, π-π interactions [minimum centroid-centroid separation = 3.462 (3) Å]. between L ligands in neighboring chains yields a two-dimensional supramolecular layer structure (Fig. 3).

Related literature top

For studies on related lead(II) carboxylates, see: Fan & Zhu (2006); Yang et al. (2007).

Experimental top

A mixture of Pb(NO3)2 (1 mmol), H2fum (1 mmol) and L (1 mmol) were dissolved in 12 ml distilled water, followed by addition of triethylamine until the pH value of the system was adjusted to about 5.8. The resulting solution was sealed in a 23-ml Teflon-lined stainless steel autoclave and heated at 450 K for 10 days under autogenous pressure. Afterwards, the reaction system was slowly cooled to room temperature. Colourless blocks of (I) were collected.

Refinement top

All the H atoms were generated geometrically (C—H = 0.93 Å) and refined as riding with Uiso(H)= 1.2Ueq(C).

Computing details top

Data collection: PROCESS-AUTO (Rigaku, 1998); cell refinement: PROCESS-AUTO (Rigaku, 1998); data reduction: PROCESS-AUTO (Rigaku, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL-Plus (Sheldrick, 1990); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).

Figures top
[Figure 1] Fig. 1. The asymmetric unit of (I) expanded to show the complete fum dianions, with displacement ellipsoids for the non-hydrogen atoms drawn at the 30% probability level. H atoms omitted for clarity. Symmetry codes: (i) 1 − x, −y, 1 − z; (ii) −x, −y, −z.
[Figure 2] Fig. 2. View of the chain structure of (I). The hydrogen atoms are omitted for clarity.
[Figure 3] Fig. 3. The supramolecular layer structure of (I). The hydrogen atoms are omitted for clarity.
catena-Poly[[(4,7-diphenyl-1,10-phenanthroline)lead(II)]-µ-fumarato] top
Crystal data top
[Pb(C4H2O4)(C24H16N2)]Z = 2
Mr = 653.63F000 = 628
Triclinic, P1Dx = 1.880 Mg m−3
Hall symbol: -P 1Mo Kα radiation
λ = 0.71073 Å
a = 8.3044 (17) ÅCell parameters from 10181 reflections
b = 11.021 (2) Åθ = 3.0–27.5º
c = 12.746 (3) ŵ = 7.35 mm−1
α = 89.35 (3)ºT = 293 (2) K
β = 86.73 (3)ºBlock, colorless
γ = 82.49 (3)º0.18 × 0.16 × 0.15 mm
V = 1154.7 (4) Å3
Data collection top
Rigaku R-AXIS RAPID
diffractometer		5231 independent reflections
Radiation source: rotating anode4411 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.041
Detector resolution: 10.0 pixels mm-1θmax = 27.5º
T = 293(2) Kθmin = 3.0º
ω scanh = −10→10
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)		k = −14→14
Tmin = 0.254, Tmax = 0.333l = −16→14
11422 measured reflections
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.037H-atom parameters constrained
wR(F2) = 0.061  w = 1/[σ2(Fo2) + (0.0096P)2 + 1.8148P]
where P = (Fo2 + 2Fc2)/3
S = 1.06(Δ/σ)max = 0.002
5231 reflectionsΔρmax = 0.77 e Å−3
316 parametersΔρmin = −0.70 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
[Pb(C4H2O4)(C24H16N2)]γ = 82.49 (3)º
Mr = 653.63V = 1154.7 (4) Å3
Triclinic, P1Z = 2
a = 8.3044 (17) ÅMo Kα
b = 11.021 (2) ŵ = 7.35 mm−1
c = 12.746 (3) ÅT = 293 (2) K
α = 89.35 (3)º0.18 × 0.16 × 0.15 mm
β = 86.73 (3)º
Data collection top
Rigaku R-AXIS RAPID
diffractometer		5231 independent reflections
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)		4411 reflections with I > 2σ(I)
Tmin = 0.254, Tmax = 0.333Rint = 0.041
11422 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.037316 parameters
wR(F2) = 0.061H-atom parameters constrained
S = 1.06Δρmax = 0.77 e Å−3
5231 reflectionsΔρmin = −0.70 e Å−3
Special details top

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) top
xyzUiso*/Ueq
C10.4593 (6)0.0099 (5)0.3502 (4)0.0427 (12)
C20.4835 (6)−0.0340 (4)0.4607 (4)0.0432 (12)
H20.4744−0.11580.47500.052*
C30.1800 (6)0.0473 (4)0.0722 (4)0.0401 (12)
C40.0161 (6)0.0255 (4)0.0441 (4)0.0419 (12)
H4−0.07060.04940.09200.050*
C50.2750 (6)0.3741 (4)0.3041 (4)0.0400 (12)
H50.29810.31150.35260.048*
C60.1994 (7)0.4868 (4)0.3407 (4)0.0429 (12)
H60.17370.49790.41220.051*
C70.1623 (6)0.5819 (4)0.2720 (4)0.0384 (11)
C80.2041 (6)0.5598 (4)0.1626 (4)0.0377 (11)
C90.2769 (6)0.4420 (4)0.1324 (4)0.0342 (11)
C100.3062 (6)0.4128 (4)0.0226 (4)0.0356 (11)
C110.3919 (7)0.2663 (4)−0.1023 (4)0.0492 (14)
H110.43570.1865−0.11970.059*
C120.3552 (7)0.3488 (4)−0.1829 (4)0.0470 (13)
H120.37290.3224−0.25220.056*
C130.2933 (6)0.4686 (4)−0.1631 (4)0.0382 (11)
C140.2685 (6)0.5034 (4)−0.0553 (4)0.0362 (11)
C150.2079 (7)0.6242 (4)−0.0196 (4)0.0513 (15)
H150.19180.6868−0.06900.062*
C160.1732 (7)0.6510 (4)0.0830 (4)0.0517 (15)
H160.12850.73000.10220.062*
C170.2590 (6)0.5552 (4)−0.2513 (4)0.0372 (11)
C180.3689 (6)0.5503 (5)−0.3385 (4)0.0447 (13)
H180.46100.4922−0.34030.054*
C190.3443 (8)0.6296 (5)−0.4222 (4)0.0549 (15)
H190.41890.6241−0.47980.066*
C200.2103 (7)0.7165 (5)−0.4208 (4)0.0511 (14)
H200.19560.7715−0.47630.061*
C210.0971 (7)0.7223 (5)−0.3369 (4)0.0497 (14)
H210.00470.7800−0.33670.060*
C220.1207 (6)0.6426 (4)−0.2533 (4)0.0441 (12)
H220.04350.6470−0.19720.053*
C230.0785 (6)0.7009 (4)0.3128 (4)0.0387 (11)
C240.1379 (7)0.8109 (4)0.2931 (4)0.0446 (13)
H240.23310.81260.25130.054*
C250.0570 (8)0.9177 (5)0.3352 (5)0.0553 (16)
H250.09780.99130.32170.066*
C26−0.0836 (8)0.9160 (5)0.3970 (5)0.0584 (16)
H26−0.13880.98880.42420.070*
C27−0.1433 (7)0.8071 (5)0.4188 (5)0.0572 (16)
H27−0.23720.80590.46210.069*
C28−0.0632 (6)0.6999 (4)0.3762 (4)0.0454 (13)
H28−0.10430.62640.39000.054*
N10.3158 (5)0.3512 (3)0.2036 (3)0.0363 (9)
N20.3676 (5)0.2954 (3)−0.0021 (3)0.0416 (10)
O10.4253 (6)0.1240 (3)0.3391 (3)0.0647 (12)
O20.4774 (5)−0.0635 (3)0.2768 (3)0.0553 (10)
O30.1859 (4)0.1193 (3)0.1493 (3)0.0448 (9)
O40.3050 (5)−0.0021 (3)0.0238 (3)0.0571 (10)
Pb10.46035 (2)0.137456 (17)0.147460 (15)0.03580 (6)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.046 (3)0.047 (3)0.032 (3)0.007 (2)−0.004 (2)0.000 (2)
C20.049 (3)0.034 (3)0.043 (3)0.006 (2)0.000 (3)0.002 (2)
C30.045 (3)0.037 (3)0.039 (3)−0.007 (2)−0.002 (2)0.001 (2)
C40.038 (3)0.046 (3)0.041 (3)−0.006 (2)−0.002 (2)−0.009 (2)
C50.058 (3)0.033 (2)0.029 (3)−0.005 (2)−0.005 (2)−0.001 (2)
C60.059 (3)0.039 (3)0.028 (3)−0.001 (2)−0.001 (2)−0.008 (2)
C70.048 (3)0.031 (2)0.037 (3)−0.007 (2)−0.001 (2)−0.006 (2)
C80.049 (3)0.033 (2)0.030 (3)−0.004 (2)−0.001 (2)−0.004 (2)
C90.040 (3)0.032 (2)0.031 (3)−0.004 (2)−0.004 (2)−0.0037 (19)
C100.043 (3)0.033 (2)0.031 (3)−0.005 (2)−0.003 (2)−0.0052 (19)
C110.075 (4)0.034 (3)0.035 (3)0.005 (3)0.002 (3)−0.006 (2)
C120.069 (4)0.043 (3)0.027 (3)−0.002 (3)0.002 (3)−0.008 (2)
C130.045 (3)0.036 (2)0.034 (3)−0.006 (2)−0.001 (2)−0.001 (2)
C140.046 (3)0.033 (2)0.029 (3)−0.003 (2)0.000 (2)−0.0039 (19)
C150.084 (4)0.033 (3)0.034 (3)0.001 (3)0.003 (3)0.001 (2)
C160.082 (4)0.029 (2)0.041 (3)0.003 (3)−0.007 (3)−0.002 (2)
C170.045 (3)0.039 (3)0.030 (3)−0.012 (2)−0.003 (2)−0.003 (2)
C180.046 (3)0.052 (3)0.034 (3)−0.003 (2)0.004 (2)−0.003 (2)
C190.069 (4)0.064 (4)0.033 (3)−0.015 (3)0.005 (3)−0.002 (3)
C200.073 (4)0.049 (3)0.034 (3)−0.015 (3)−0.009 (3)0.005 (2)
C210.054 (4)0.046 (3)0.048 (4)−0.001 (3)−0.010 (3)0.005 (2)
C220.046 (3)0.046 (3)0.039 (3)0.000 (2)−0.002 (2)−0.005 (2)
C230.050 (3)0.039 (3)0.026 (3)−0.001 (2)−0.004 (2)−0.008 (2)
C240.064 (4)0.036 (3)0.034 (3)−0.009 (3)0.006 (3)−0.005 (2)
C250.080 (4)0.031 (3)0.053 (4)−0.003 (3)0.004 (3)−0.008 (2)
C260.071 (4)0.041 (3)0.059 (4)0.012 (3)−0.001 (3)−0.015 (3)
C270.054 (4)0.055 (3)0.058 (4)0.006 (3)0.011 (3)−0.004 (3)
C280.052 (3)0.036 (3)0.049 (3)−0.007 (2)−0.002 (3)−0.003 (2)
N10.048 (2)0.0306 (19)0.030 (2)−0.0017 (18)−0.0039 (18)−0.0042 (16)
N20.058 (3)0.034 (2)0.031 (2)0.0030 (19)−0.004 (2)−0.0079 (17)
O10.104 (3)0.046 (2)0.036 (2)0.020 (2)−0.007 (2)−0.0002 (17)
O20.077 (3)0.045 (2)0.043 (2)−0.0011 (19)−0.007 (2)−0.0109 (17)
O30.050 (2)0.048 (2)0.037 (2)−0.0123 (17)−0.0021 (17)−0.0103 (16)
O40.043 (2)0.065 (2)0.063 (3)−0.0025 (19)−0.003 (2)−0.022 (2)
Pb10.03826 (11)0.03501 (10)0.03301 (10)0.00104 (7)−0.00548 (7)−0.00209 (7)
Geometric parameters (Å, °) top
C1—O21.234 (6)C15—C161.351 (7)
C1—O11.260 (6)C15—H150.9300
C1—C21.499 (7)C16—H160.9300
C2—C2i1.321 (10)C17—C181.394 (6)
C2—H20.9300C17—C221.400 (7)
C3—O41.242 (6)C18—C191.379 (7)
C3—O31.277 (6)C18—H180.9300
C3—C41.477 (7)C19—C201.370 (8)
C4—C4ii1.319 (10)C19—H190.9300
C4—H40.9300C20—C211.378 (7)
C5—N11.324 (6)C20—H200.9300
C5—C61.390 (6)C21—C221.380 (7)
C5—H50.9300C21—H210.9300
C6—C71.373 (7)C22—H220.9300
C6—H60.9300C23—C241.382 (7)
C7—C81.433 (6)C23—C281.391 (7)
C7—C231.487 (6)C24—C251.375 (7)
C8—C91.407 (6)C24—H240.9300
C8—C161.430 (7)C25—C261.373 (8)
C9—N11.363 (6)C25—H250.9300
C9—C101.439 (6)C26—C271.377 (8)
C10—N21.361 (6)C26—H260.9300
C10—C141.419 (6)C27—C281.379 (7)
C11—N21.318 (6)C27—H270.9300
C11—C121.385 (7)C28—H280.9300
C11—H110.9300Pb1—N12.590 (4)
C12—C131.374 (6)Pb1—N22.645 (4)
C12—H120.9300Pb1—O12.449 (4)
C13—C141.426 (6)Pb1—O22.740 (4)
C13—C171.483 (6)Pb1—O32.313 (3)
C14—C151.431 (6)Pb1—O42.705 (4)
O2—C1—O1124.1 (5)C20—C19—H19119.9
O2—C1—C2120.2 (4)C18—C19—H19119.9
O1—C1—C2115.6 (4)C19—C20—C21120.0 (5)
C2i—C2—C1125.3 (6)C19—C20—H20120.0
C2i—C2—H2117.3C21—C20—H20120.0
C1—C2—H2117.3C20—C21—C22120.1 (5)
O4—C3—O3121.9 (5)C20—C21—H21120.0
O4—C3—C4121.8 (5)C22—C21—H21120.0
O3—C3—C4116.3 (4)C21—C22—C17121.1 (5)
C4ii—C4—C3124.6 (6)C21—C22—H22119.4
C4ii—C4—H4117.7C17—C22—H22119.4
C3—C4—H4117.7C24—C23—C28119.1 (4)
N1—C5—C6123.4 (4)C24—C23—C7123.0 (5)
N1—C5—H5118.3C28—C23—C7117.9 (4)
C6—C5—H5118.3C25—C24—C23120.3 (5)
C7—C6—C5120.4 (5)C25—C24—H24119.8
C7—C6—H6119.8C23—C24—H24119.8
C5—C6—H6119.8C26—C25—C24120.3 (5)
C6—C7—C8117.5 (4)C26—C25—H25119.9
C6—C7—C23119.5 (4)C24—C25—H25119.9
C8—C7—C23123.0 (4)C25—C26—C27120.2 (5)
C9—C8—C16118.7 (4)C25—C26—H26119.9
C9—C8—C7118.1 (4)C27—C26—H26119.9
C16—C8—C7123.1 (4)C26—C27—C28119.7 (5)
N1—C9—C8122.4 (4)C26—C27—H27120.2
N1—C9—C10117.8 (4)C28—C27—H27120.2
C8—C9—C10119.7 (4)C27—C28—C23120.4 (5)
N2—C10—C14122.3 (4)C27—C28—H28119.8
N2—C10—C9117.2 (4)C23—C28—H28119.8
C14—C10—C9120.5 (4)C5—N1—C9118.1 (4)
N2—C11—C12123.1 (5)C5—N1—Pb1119.9 (3)
N2—C11—H11118.5C9—N1—Pb1122.0 (3)
C12—C11—H11118.5C11—N2—C10118.1 (4)
C13—C12—C11121.6 (5)C11—N2—Pb1121.4 (3)
C13—C12—H12119.2C10—N2—Pb1120.3 (3)
C11—C12—H12119.2C1—O1—Pb199.2 (3)
C12—C13—C14116.6 (4)C1—O2—Pb186.1 (3)
C12—C13—C17120.1 (4)C3—O3—Pb1102.0 (3)
C14—C13—C17123.3 (4)C3—O4—Pb184.5 (3)
C10—C14—C13118.4 (4)O3—Pb1—O185.17 (14)
C10—C14—C15117.1 (4)O3—Pb1—N175.35 (12)
C13—C14—C15124.5 (4)O1—Pb1—N175.70 (12)
C16—C15—C14122.6 (5)O3—Pb1—N279.49 (13)
C16—C15—H15118.7O1—Pb1—N2137.38 (12)
C14—C15—H15118.7N1—Pb1—N262.03 (12)
C15—C16—C8121.0 (5)O3—Pb1—O451.31 (11)
C15—C16—H16119.5O1—Pb1—O4120.44 (14)
C8—C16—H16119.5N1—Pb1—O4118.64 (12)
C18—C17—C22117.1 (5)N2—Pb1—O478.77 (12)
C18—C17—C13119.0 (5)O3—Pb1—O284.60 (12)
C22—C17—C13123.8 (4)O1—Pb1—O249.85 (11)
C19—C18—C17121.5 (5)N1—Pb1—O2123.32 (11)
C19—C18—H18119.2N2—Pb1—O2161.17 (12)
C17—C18—H18119.2O4—Pb1—O283.44 (12)
C20—C19—C18120.1 (5)
Symmetry codes: (i) −x+1, −y, −z+1; (ii) −x, −y, −z.
Table 1
Selected geometric parameters (Å) top
Pb1—N12.590 (4)Pb1—O22.740 (4)
Pb1—N22.645 (4)Pb1—O32.313 (3)
Pb1—O12.449 (4)Pb1—O42.705 (4)
Acknowledgements top

The authors thank Qiqihar University for supporting this work.

references
References top

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Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.

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