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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 π–π stacking between L ligands in adjacent chains [minimum centroid–centroid separation = 3.462 (3) Å] leads to a two-dimensional supra­molecular array.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807053743/hb2602sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807053743/hb2602Isup2.hkl
Contains datablock I

CCDC reference: 672583

Key indicators

  • Single-crystal X-ray study
  • T = 293 K
  • Mean [sigma](C-C) = 0.007 Å
  • R factor = 0.036
  • wR factor = 0.061
  • Data-to-parameter ratio = 16.6

checkCIF/PLATON results

No syntax errors found



Alert level C PLAT154_ALERT_1_C The su's on the Cell Angles are Equal (x 10000) 3000 Deg. PLAT241_ALERT_2_C Check High Ueq as Compared to Neighbors for O1 PLAT241_ALERT_2_C Check High Ueq as Compared to Neighbors for O2 PLAT241_ALERT_2_C Check High Ueq as Compared to Neighbors for O4
Alert level G PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature 293 K PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature . 293 K PLAT794_ALERT_5_G Check Predicted Bond Valency for Pb1 (2) 2.05
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 4 ALERT level C = Check and explain 3 ALERT level G = General alerts; check 3 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 3 ALERT type 2 Indicator that the structure model may be wrong or deficient 0 ALERT type 3 Indicator that the structure quality may be low 0 ALERT type 4 Improvement, methodology, query or suggestion 1 ALERT type 5 Informative message, check

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 = 653.63F(000) = 628
Triclinic, P1Dx = 1.880 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 8.3044 (17) ÅCell parameters from 10181 reflections
b = 11.021 (2) Åθ = 3.0–27.5°
c = 12.746 (3) ŵ = 7.35 mm1
α = 89.35 (3)°T = 293 K
β = 86.73 (3)°Block, colorless
γ = 82.49 (3)°0.18 × 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)
Graphite monochromatorRint = 0.041
Detector resolution: 10.0 pixels mm-1θmax = 27.5°, θmin = 3.0°
ω scanh = 1010
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)
k = 1414
Tmin = 0.254, Tmax = 0.333l = 1614
11422 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.037Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.061H-atom parameters constrained
S = 1.06 w = 1/[σ2(Fo2) + (0.0096P)2 + 1.8148P]
where P = (Fo2 + 2Fc2)/3
5231 reflections(Δ/σ)max = 0.002
316 parametersΔρmax = 0.77 e Å3
0 restraintsΔρmin = 0.70 e Å3
Crystal data top
[Pb(C4H2O4)(C24H16N2)]γ = 82.49 (3)°
Mr = 653.63V = 1154.7 (4) Å3
Triclinic, P1Z = 2
a = 8.3044 (17) ÅMo Kα radiation
b = 11.021 (2) ŵ = 7.35 mm1
c = 12.746 (3) ÅT = 293 K
α = 89.35 (3)°0.18 × 0.16 × 0.15 mm
β = 86.73 (3)°
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)] = 0.0370 restraints
wR(F2) = 0.061H-atom parameters constrained
S = 1.06Δρmax = 0.77 e Å3
5231 reflectionsΔρmin = 0.70 e Å3
316 parameters
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)
H20.47440.11580.47500.052*
C30.1800 (6)0.0473 (4)0.0722 (4)0.0401 (12)
C40.0161 (6)0.0255 (4)0.0441 (4)0.0419 (12)
H40.07060.04940.09200.050*
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)
H110.43570.18650.11970.059*
C120.3552 (7)0.3488 (4)0.1829 (4)0.0470 (13)
H120.37290.32240.25220.056*
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)
H150.19180.68680.06900.062*
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)
H180.46100.49220.34030.054*
C190.3443 (8)0.6296 (5)0.4222 (4)0.0549 (15)
H190.41890.62410.47980.066*
C200.2103 (7)0.7165 (5)0.4208 (4)0.0511 (14)
H200.19560.77150.47630.061*
C210.0971 (7)0.7223 (5)0.3369 (4)0.0497 (14)
H210.00470.78000.33670.060*
C220.1207 (6)0.6426 (4)0.2533 (4)0.0441 (12)
H220.04350.64700.19720.053*
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*
C260.0836 (8)0.9160 (5)0.3970 (5)0.0584 (16)
H260.13880.98880.42420.070*
C270.1433 (7)0.8071 (5)0.4188 (5)0.0572 (16)
H270.23720.80590.46210.069*
C280.0632 (6)0.6999 (4)0.3762 (4)0.0454 (13)
H280.10430.62640.39000.054*
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, º) 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.

Experimental details

Crystal data
Chemical formula[Pb(C4H2O4)(C24H16N2)]
Mr653.63
Crystal system, space groupTriclinic, P1
Temperature (K)293
a, b, c (Å)8.3044 (17), 11.021 (2), 12.746 (3)
α, β, γ (°)89.35 (3), 86.73 (3), 82.49 (3)
V3)1154.7 (4)
Z2
Radiation typeMo Kα
µ (mm1)7.35
Crystal size (mm)0.18 × 0.16 × 0.15
Data collection
DiffractometerRigaku R-AXIS RAPID
diffractometer
Absorption correctionMulti-scan
(ABSCOR; Higashi, 1995)
Tmin, Tmax0.254, 0.333
No. of measured, independent and
observed [I > 2σ(I)] reflections
11422, 5231, 4411
Rint0.041
(sin θ/λ)max1)0.649
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.037, 0.061, 1.06
No. of reflections5231
No. of parameters316
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.77, 0.70

Computer programs: PROCESS-AUTO (Rigaku, 1998), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL-Plus (Sheldrick, 1990).

Selected bond lengths (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)
 

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