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In the title PbII coordination polymer, [Pb(C16H10O4)(C14H8N4)(C3H7NO)]n, each PbII atom is eight-coordinated by two chelating N atoms from one pyrazino[2,3-f][1,10]phenanthroline (L) ligand, one dimethyl­formamide (DMF) O atom and five carboxyl­ate O atoms from three different 4,4′-ethylene­dibenzoate (eedb) ligands. The eedb dianions bridge neigh­bouring PbII centres through four typical Pb—O bonds and one longer Pb—O interaction to form a two-dimensional structure. The C atoms from the L and eedb ligands form C—H...O hydrogen bonds with the O atoms of eedb and DMF ligands, which further stabilize the structure. The title compound is the first PbII coordination polymer incorporating the L ligand.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270109005253/gg3189sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270109005253/gg3189Isup2.hkl
Contains datablock I

CCDC reference: 730076

Comment top

The rational design and synthesis of metal–organic coordination polymers with novel topological structures have attracted great interest from chemists because of their potential applications as functional solid materials, as well as their fascinating framework structures (Eddaoudi et al., 2001; Hagrman et al., 1999; Noveron et al., 2002; Yang et al., 2008). Until recently, research on coordination polymers has mainly focused on incorporation of s-, d- and even f-block metal ions as the coordination centres, while less consideration has been given to the metals of the p block (Xu et al., 2005). p-Block metal–organic materials may be important in applications such as electroluminescent devices or organic light-emitting diodes (OLEDs), and so have stimulated much interest (Tsuboi & Sifsten, 1991; Singh & Richter, 2004). As far as the intrinsic appeal of PbII is concerned, the presence of a 6s2 outer electron configuration not only leads to interesting topological arrangements, but also plays an important role in the luminescence action of the resulting complex (Deo & Godwin, 2000; Li & Lu, 2000). Lead(II), as a toxic heavy metal, is commonly found in critical life cycles due to its widespread use in numerous industrial applications (Andersen et al., 2006). The possible molecular mechanisms of the toxicity of PbII may affect several different types of protein. Therefore, good knowledge of the coordination properties of PbII, including aspects such as the lone pair of electrons, the coordination number and the coordination geometry, is crucial for understanding the toxicological properties of lead(II).

1,10-Phenanthroline (phen) has been widely used to build supramolecular architectures because of its excellent coordinating ability and large conjugated system that can easily form ππ interactions (Wang et al., 2005; Tong et al., 2000; Zheng et al., 2001). However, far less attention has been given to its derivatives (Yang, Ma et al., 2007; Yang, Li et al., 2007). Pyrazino[2,3-f][1,10]phenanthroline (L) is an important phen derivative. It possesses aromatic systems and is a good candidate for the construction of metal–organic supramolecular architectures (Wang et al., 2007). To the best of our knowledge, coordination polymers constructed from a PbII dicarboxylate ligand and L have not been documented so far (Yang, Ma et al., 2007). Here, we have selected the ethylene-4,4'-dibenzoate dianion (eedb) as an organic linker and L as an N-donor chelating ligand, generating the title new PbII coordination polymer, [Pb(eedb)(L)(DMF)] (DMF is dimethylformamide), (I), the structure of which we now report.

Selected bond lengths and angles for (I) are given in Table 1. As shown in Fig. 1, each PbII atom is eight-coordinated by two N atoms from one L ligand, one DMF O atom, and five carboxylate O atoms from three different eedb ligands (comprising four typical Pb—O bonds and one longer Pb···O interaction). The average Pb—O distance in (I) (Table 1) is comparable with that found in another crystallographically characterized PbII complex, [Pb(bpno)(NO3)2(H2O)]n (bpno is 4,4'-bipyridine N,N'-dioxide; Xu et al., 2005).

As depicted in Fig. 2, the eedb dianions bridge two neighbouring PbII centres, resulting in a one-dimensional chain structure along the b axis. It is noted that the L ligands are extended on both sides of the chains. Clearly, the N-containing chelating L ligand plays an important role in the formation of the chain structure. Two N atoms from the L ligand occupy two coordination positions of the PbII atom, while the remaining coordination positions are available for eedb ligands, allowing the formation of the chain structure. The L ligands from neighbouring chains are well matched [Meaning not clear - please rephrase] with eedb ligands, and adjacent chains are linked through ππ stacking interactions between L and eedb, with a centroid-to-centroid distance of 3.52 (3) Å (face-to-face distance of 3.41 Å), extending the chains into a three-dimensional supramolecular framework in the bc plane (Fig. 3). It is believed that the very strong ππ stacking interactions play an important role in stabilizing the chain structure and the supramolecular architecture. To the best of our knowledge, no other PbII coordination polymer containing the chelating ligand L has been reported so far, although several PbII complexes including phen-like chelating ligands have been reported (Yang, Ma et al., 2007). Finally, C—H···O interactions further stabilize the structure of (I) (Table 2).

It is noteworthy that the structure of (I) is different from that of the related structure [Zn(eedb)(L)(H2O)].0.5DMF (Wang et al., 2008), in which the eedb dianions bridge neighbouring ZnII centres to give a one-dimensional chain structure in the ab plane. In that structure, a three-dimensional supramolecular architecture is formed through two types of ππ interactions between neighbouring chains. One is between the centrosymmetrically related L ligands, and the second is between L and eedb ligands. The structure of (I) is also entirely different from that of the related polymer [Cd2(L)2(1,4-ndc)2] (1,4-ndc is 1,4-naphthalenedicarboxylate; Qiao et al., 2008), in which the 1,4-ndc ligands link the CdII centres to give an interesting six-connected three-dimensional α-Po-related architecture.

The stereochemical activity of the PbII lone pair of electrons is an interesting topic and often discussed. The geometries of PbII complexes can be classified as holo- and hemidirected. Holodirected refers to PbII complexes in which the bonds to the ligand atoms are located throughout the surface of an encompassing sphere, while hemidirected refers to those cases in which the bonds to the ligand atoms are directed through only part of an encompassing sphere (Shimoni-Livny et al., 1998). In compound (I), the central PbII atom is eight-coordinated by two N atoms, one DMF molecule and five carboxylate O atoms. The coordination of the ligands at the opening [Opening of what?] does not leave room for a lone pair of electrons. Therefore, this coordination environment can be considered somewhat holodirected. To date, several PbII coordination polymers with different phen derivatives have been reported (Yang, Li et al., 2007). The PbII coordination geometry of the polymer [Pb(1,4-ndc)(tcpn)2] [tcpn is 2-(1H-1,3,7,8-tetraazacyclopenta[l]phenanthren-2-yl)naphthol] is very similar to that observed in (I). In that structure, the PbII atom is also eight-coordinated by four N atoms and four carboxylate O atoms, and the bonds to the ligand atoms are distributed throughout the surface of the encompassing PbII sphere. Therefore, the coordination environment of the PbII atom can also be considered holodirected.

Experimental top

Pb(NO3)2 (0.166 g, 0.5 mmol), H2eedb (0.133 g, 0.5 mmol) and L (0.121 g, 0.5 mmol) were dissolved in a mixture of DMF (6 ml) and distilled water (8 ml). The resulting mixture was stirred for about 1 h at room temperature, sealed in a 23 ml Teflon-lined stainless steel autoclave and heated at 398 K for 5 d under autogenous pressure. The reaction system was gradually cooled to room temperature at a rate of 10 K h-1. Pale-yellow crystals of (I) suitable for single-crystal X-ray diffraction analysis were collected from the final reaction system by filtration, washed several times with DMF, and dried in air at ambient temperature (yield 72%, based on PbII).

Refinement top

Carbon-bound H atoms were positioned geometrically, with C—H = 0.93 Å, and refined as riding, with Uiso(H) = 1.2Ueq(C). As the N-heterocycle displays a minor spread of C—C distances, the central six-carbon ring was refined as a rigid hexagon with sides of 1.39 Å. The DMF is disordered over two sites with site occupancies 0.5:0.5. The CO distances were restrained to 1.25 (1) Å, Ccarbonyl—N to 1.35 (1) Å and N—Cmethyl to 1.45 (1) Å. Each component was restrained to be nearly planar. The anisotropic displacement parameters were restrained to be nearly isotropic. The displacement parameters of the O5/O5' pair were restrained to be identical. The final difference Fourier map has a large peak at 1 Å from Pb1 but is otherwise featureless.

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SMART (Bruker, 1997); data reduction: SAINT (Bruker, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL-Plus (Sheldrick, 2008); software used to prepare material for publication: publCIF (Westrip, 2009).

Figures top
[Figure 1] Fig. 1. A view of the local coordination of the PbII cation in (I), showing the atom-numbering scheme. Only one conformation of the DMF molecule is shown. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii. [Symmetry codes: (i) 1 - x, 1 - y, 1 - z; (ii) 2 - x, 1/2 + y, 1/2 - z.]
[Figure 2] Fig. 2. A view of the one-dimensional chain of (I) along the b axis.
[Figure 3] Fig. 3. A view of the three-dimensional supramolecular structure of (I).
Poly[(N,N-dimethylformamide-κO)(pyrazino[2,3- f][1,10]phenanthroline-κ2N8,N9)(µ3-ethylene- 4,4'-dibenzoato-κ5O,O':O':O'',O''')lead(II)] top
Crystal data top
[Pb(C16H10O4)(C14H8N4)(C3H7NO)]F(000) = 1520
Mr = 778.77Dx = 1.818 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 5805 reflections
a = 9.0255 (7) Åθ = 2.4–25.4°
b = 25.5628 (19) ŵ = 5.98 mm1
c = 12.6422 (9) ÅT = 295 K
β = 102.751 (1)°Block, yellow
V = 2844.8 (4) Å30.23 × 0.20 × 0.18 mm
Z = 4
Data collection top
Bruker APEX
diffractometer
5224 independent reflections
Radiation source: fine-focus sealed tube4134 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.046
ϕ and ω scansθmax = 25.4°, θmin = 1.6°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
h = 1010
Tmin = 0.340, Tmax = 0.412k = 1230
14893 measured reflectionsl = 1515
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)] = 0.039Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.089H-atom parameters constrained
S = 1.03 w = 1/[σ2(Fo2) + (0.0399P)2 + 4.4812P]
where P = (Fo2 + 2Fc2)/3
5224 reflections(Δ/σ)max = 0.001
428 parametersΔρmax = 1.95 e Å3
72 restraintsΔρmin = 0.92 e Å3
Crystal data top
[Pb(C16H10O4)(C14H8N4)(C3H7NO)]V = 2844.8 (4) Å3
Mr = 778.77Z = 4
Monoclinic, P21/cMo Kα radiation
a = 9.0255 (7) ŵ = 5.98 mm1
b = 25.5628 (19) ÅT = 295 K
c = 12.6422 (9) Å0.23 × 0.20 × 0.18 mm
β = 102.751 (1)°
Data collection top
Bruker APEX
diffractometer
5224 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
4134 reflections with I > 2σ(I)
Tmin = 0.340, Tmax = 0.412Rint = 0.046
14893 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.03972 restraints
wR(F2) = 0.089H-atom parameters constrained
S = 1.03Δρmax = 1.95 e Å3
5224 reflectionsΔρmin = 0.92 e Å3
428 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*/UeqOcc. (<1)
Pb10.45452 (3)0.585997 (9)0.483565 (19)0.02326 (9)
O10.6637 (5)0.52420 (18)0.4907 (4)0.0301 (11)
O20.6154 (6)0.5642 (2)0.3318 (4)0.0390 (12)
O31.3624 (5)0.15296 (17)0.0077 (3)0.0275 (11)
O41.5564 (5)0.17430 (18)0.1258 (4)0.0311 (11)
N10.5570 (6)0.5704 (2)0.6895 (4)0.0242 (12)
N20.4967 (8)0.5918 (2)1.0566 (5)0.0439 (17)
N30.2946 (6)0.6750 (2)0.9881 (4)0.0322 (14)
N40.3587 (6)0.6508 (2)0.6228 (4)0.0241 (12)
C10.6833 (8)0.5301 (3)0.3943 (6)0.0288 (16)
C20.7903 (7)0.4924 (3)0.3572 (6)0.0288 (16)
C30.7983 (8)0.4897 (3)0.2501 (7)0.0409 (19)
H30.74110.51230.19940.049*
C40.8934 (9)0.4528 (3)0.2184 (7)0.047 (2)
H40.89700.44990.14570.057*
C50.9842 (8)0.4197 (3)0.2956 (7)0.0410 (19)
C60.9773 (8)0.4248 (3)0.4012 (7)0.0399 (19)
H61.03940.40400.45310.048*
C70.8802 (7)0.4601 (3)0.4332 (7)0.0345 (18)
H70.87510.46220.50580.041*
C81.0836 (9)0.3772 (3)0.2683 (7)0.044 (2)
H81.15860.36390.32440.053*
C91.0732 (9)0.3577 (3)0.1736 (7)0.045 (2)
H91.00360.37220.11560.054*
C101.1694 (8)0.3124 (3)0.1521 (7)0.0404 (19)
C111.1249 (8)0.2881 (3)0.0519 (7)0.045 (2)
H111.03960.30000.00240.054*
C121.2076 (8)0.2460 (3)0.0255 (6)0.0376 (18)
H121.17610.22980.04170.045*
C131.3364 (7)0.2275 (2)0.0974 (5)0.0229 (14)
C141.3782 (8)0.2521 (3)0.1975 (6)0.0319 (16)
H141.46380.24040.24710.038*
C151.2958 (8)0.2936 (3)0.2253 (6)0.0356 (18)
H151.32540.30900.29340.043*
C161.4257 (8)0.1825 (2)0.0710 (5)0.0255 (15)
C170.6550 (7)0.5318 (3)0.7235 (5)0.0279 (16)
H170.69860.51500.67260.033*
C180.6962 (7)0.5150 (3)0.8308 (5)0.0301 (16)
H180.76550.48790.85100.036*
C190.6316 (8)0.5395 (3)0.9054 (6)0.0323 (17)
H190.65650.52880.97740.039*
C200.5265 (4)0.58133 (14)0.8739 (3)0.0283 (15)
C210.4915 (4)0.59616 (14)0.7655 (3)0.0221 (14)
C270.3910 (5)0.63713 (15)0.7316 (2)0.0222 (14)
C260.3255 (4)0.66328 (13)0.8062 (3)0.0245 (15)
C250.3605 (5)0.64846 (16)0.9147 (3)0.0286 (16)
C220.4610 (5)0.60748 (17)0.9485 (2)0.0324 (17)
C230.4331 (9)0.6176 (3)1.1243 (6)0.045 (2)
H230.45560.60821.19720.055*
C240.3323 (9)0.6588 (3)1.0902 (6)0.043 (2)
H240.28960.67571.14150.052*
C280.2229 (7)0.7054 (2)0.7669 (5)0.0255 (15)
H280.17650.72380.81430.031*
C290.1937 (7)0.7183 (3)0.6584 (6)0.0304 (16)
H290.12700.74530.63150.037*
C300.2653 (7)0.6904 (2)0.5904 (6)0.0278 (16)
H300.24670.70010.51780.033*
O50.188 (2)0.5824 (8)0.2910 (14)0.067 (2)0.33
N50.034 (2)0.6263 (6)0.2463 (14)0.044 (8)0.33
C310.0558 (19)0.5846 (7)0.2381 (17)0.061 (8)0.33
H310.01710.55720.19170.073*0.33
C320.015 (4)0.6710 (10)0.316 (2)0.082 (10)0.33
H32A0.01770.66670.38290.123*0.33
H32B0.02860.70240.28060.123*0.33
H32C0.12370.67350.33110.123*0.33
C330.192 (2)0.6330 (11)0.188 (2)0.055 (8)0.33
H33A0.21760.60630.13370.083*0.33
H33B0.20370.66680.15370.083*0.33
H33C0.25740.63050.23800.083*0.33
O5'0.0340 (10)0.5715 (3)0.0756 (8)0.067 (2)0.67
N5'0.0390 (9)0.6231 (3)0.2045 (10)0.041 (3)0.67
C31'0.0554 (12)0.6017 (3)0.1066 (10)0.049 (3)0.67
H31'0.14340.61030.05590.058*0.67
C32'0.0962 (15)0.6112 (6)0.2885 (10)0.062 (4)0.67
H32D0.06640.59480.34890.093*0.67
H32E0.15000.64300.31220.093*0.67
H32F0.16100.58800.25960.093*0.67
C33'0.1524 (16)0.6576 (5)0.2306 (13)0.064 (4)0.67
H33D0.20990.67320.16520.096*0.67
H33E0.10350.68460.27870.096*0.67
H33F0.21920.63810.26510.096*0.67
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Pb10.02697 (14)0.01988 (14)0.02203 (14)0.00089 (12)0.00348 (9)0.00001 (12)
O10.034 (3)0.031 (3)0.026 (3)0.003 (2)0.005 (2)0.001 (2)
O20.050 (3)0.038 (3)0.029 (3)0.021 (3)0.009 (2)0.009 (2)
O30.033 (3)0.024 (3)0.024 (3)0.004 (2)0.003 (2)0.004 (2)
O40.027 (3)0.029 (3)0.034 (3)0.005 (2)0.001 (2)0.006 (2)
N10.022 (3)0.021 (3)0.027 (3)0.001 (2)0.001 (2)0.000 (2)
N20.062 (4)0.049 (4)0.021 (3)0.031 (4)0.009 (3)0.006 (3)
N30.038 (3)0.032 (3)0.025 (3)0.005 (3)0.001 (3)0.004 (3)
N40.028 (3)0.020 (3)0.023 (3)0.002 (2)0.004 (2)0.003 (2)
C10.031 (4)0.025 (4)0.030 (4)0.002 (3)0.005 (3)0.006 (3)
C20.025 (3)0.027 (4)0.035 (4)0.004 (3)0.007 (3)0.004 (3)
C30.045 (5)0.037 (5)0.047 (5)0.002 (4)0.024 (4)0.006 (4)
C40.055 (5)0.054 (5)0.041 (5)0.013 (4)0.028 (4)0.018 (4)
C50.032 (4)0.028 (4)0.065 (6)0.005 (3)0.014 (4)0.002 (4)
C60.034 (4)0.028 (4)0.060 (6)0.003 (3)0.014 (4)0.007 (4)
C70.026 (4)0.024 (4)0.053 (5)0.001 (3)0.006 (3)0.002 (4)
C80.039 (5)0.044 (5)0.048 (5)0.010 (4)0.007 (4)0.003 (4)
C90.039 (5)0.049 (5)0.046 (5)0.014 (4)0.005 (4)0.010 (4)
C100.026 (4)0.035 (4)0.063 (6)0.002 (3)0.016 (4)0.009 (4)
C110.031 (4)0.041 (5)0.058 (5)0.008 (4)0.000 (4)0.008 (4)
C120.034 (4)0.033 (4)0.043 (4)0.008 (3)0.003 (3)0.008 (4)
C130.023 (3)0.019 (3)0.028 (4)0.005 (3)0.009 (3)0.005 (3)
C140.027 (4)0.035 (4)0.035 (4)0.010 (3)0.009 (3)0.002 (3)
C150.039 (4)0.030 (4)0.040 (4)0.013 (3)0.016 (4)0.020 (3)
C160.033 (4)0.019 (3)0.024 (4)0.005 (3)0.005 (3)0.004 (3)
C170.030 (4)0.028 (4)0.023 (4)0.002 (3)0.000 (3)0.007 (3)
C180.037 (4)0.023 (4)0.028 (4)0.014 (3)0.002 (3)0.003 (3)
C190.045 (4)0.029 (4)0.020 (4)0.009 (3)0.000 (3)0.001 (3)
C200.037 (4)0.024 (4)0.021 (3)0.004 (3)0.001 (3)0.002 (3)
C210.026 (3)0.016 (3)0.023 (3)0.002 (3)0.003 (3)0.000 (3)
C270.022 (3)0.015 (3)0.027 (4)0.002 (3)0.003 (3)0.001 (3)
C260.024 (3)0.017 (3)0.033 (4)0.004 (3)0.007 (3)0.003 (3)
C250.031 (4)0.026 (4)0.027 (4)0.001 (3)0.002 (3)0.002 (3)
C220.033 (4)0.033 (4)0.027 (4)0.007 (3)0.001 (3)0.003 (3)
C230.064 (5)0.046 (5)0.025 (4)0.024 (4)0.006 (4)0.001 (4)
C240.058 (5)0.048 (5)0.024 (4)0.013 (4)0.010 (4)0.007 (4)
C280.021 (3)0.022 (4)0.032 (4)0.003 (3)0.001 (3)0.005 (3)
C290.025 (4)0.023 (4)0.042 (4)0.001 (3)0.003 (3)0.004 (3)
C300.033 (4)0.020 (4)0.027 (4)0.000 (3)0.002 (3)0.005 (3)
O50.065 (4)0.067 (5)0.064 (5)0.015 (4)0.005 (4)0.000 (4)
N50.041 (11)0.046 (11)0.040 (11)0.002 (8)0.001 (8)0.007 (8)
C310.067 (11)0.050 (11)0.070 (11)0.000 (9)0.023 (9)0.006 (9)
C320.080 (12)0.083 (13)0.080 (13)0.001 (9)0.011 (9)0.009 (9)
C330.056 (11)0.054 (11)0.054 (11)0.007 (9)0.011 (8)0.005 (8)
O5'0.065 (4)0.067 (5)0.064 (5)0.015 (4)0.005 (4)0.000 (4)
N5'0.030 (5)0.049 (6)0.043 (7)0.004 (5)0.006 (5)0.013 (5)
C31'0.042 (6)0.042 (6)0.061 (7)0.013 (5)0.012 (5)0.006 (5)
C32'0.069 (7)0.064 (7)0.049 (7)0.004 (7)0.003 (6)0.002 (6)
C33'0.064 (7)0.065 (8)0.070 (8)0.016 (7)0.029 (6)0.010 (7)
Geometric parameters (Å, º) top
Pb1—O12.448 (4)C14—H140.9300
Pb1—O22.707 (5)C15—H150.9300
Pb1—O3i2.352 (4)C16—Pb1iii2.839 (7)
Pb1—O4i2.638 (4)C17—C181.392 (9)
Pb1—O1ii3.055 (5)C17—H170.9300
Pb1—O53.023 (17)C18—C191.366 (9)
Pb1—N12.594 (5)C18—H180.9300
Pb1—N42.695 (5)C19—C201.427 (7)
O1—C11.278 (8)C19—H190.9300
O2—C11.243 (8)C20—C211.3900
O3—C161.279 (7)C20—C221.3900
O3—Pb1iii2.352 (4)C21—C271.3900
O4—C161.247 (7)C27—C261.3900
O4—Pb1iii2.638 (4)C26—C251.3900
N1—C171.331 (8)C26—C281.436 (7)
N1—C211.399 (6)C25—C221.3900
N2—C231.310 (9)C23—C241.396 (10)
N2—C221.392 (6)C23—H230.9300
N3—C241.326 (9)C24—H240.9300
N3—C251.386 (6)C28—C291.378 (9)
N4—C301.324 (8)C28—H280.9300
N4—C271.386 (6)C29—C301.382 (9)
C1—C21.511 (9)C29—H290.9300
C2—C31.374 (10)C30—H300.9300
C2—C71.385 (9)O5—C311.233 (10)
C3—C41.393 (10)N5—C311.360 (10)
C3—H30.9300N5—C321.452 (10)
C4—C51.409 (11)N5—C331.459 (10)
C4—H40.9300C31—H310.9300
C5—C61.356 (11)C32—H32A0.9600
C5—C81.498 (11)C32—H32B0.9600
C6—C71.379 (10)C32—H32C0.9600
C6—H60.9300C33—H33A0.9600
C7—H70.9300C33—H33B0.9600
C8—C91.281 (10)C33—H33C0.9600
C8—H80.9300O5'—C31'1.240 (8)
C9—C101.508 (11)N5'—C31'1.332 (16)
C9—H90.9300N5'—C33'1.443 (9)
C10—C151.386 (10)N5'—C32'1.462 (9)
C10—C111.388 (11)C31'—H31'0.9300
C11—C121.393 (10)C32'—H32D0.9600
C11—H110.9300C32'—H32E0.9600
C12—C131.390 (9)C32'—H32F0.9600
C12—H120.9300C33'—H33D0.9600
C13—C141.388 (9)C33'—H33E0.9600
C13—C161.485 (9)C33'—H33F0.9600
C14—C151.386 (9)
O3i—Pb1—O187.19 (16)C15—C14—C13121.7 (7)
O3i—Pb1—N184.09 (15)C15—C14—H14119.2
O1—Pb1—N176.25 (16)C13—C14—H14119.2
O3i—Pb1—O4i52.34 (14)C14—C15—C10120.3 (7)
O1—Pb1—O4i120.71 (15)C14—C15—H15119.9
N1—Pb1—O4i128.44 (15)C10—C15—H15119.9
O3i—Pb1—N477.60 (15)O4—C16—O3122.6 (6)
O1—Pb1—N4136.76 (15)O4—C16—C13119.9 (6)
N1—Pb1—N462.21 (16)O3—C16—C13117.5 (6)
O4i—Pb1—N480.59 (15)O4—C16—Pb1iii68.0 (3)
O3i—Pb1—O276.74 (16)O3—C16—Pb1iii55.0 (3)
O1—Pb1—O250.46 (14)C13—C16—Pb1iii169.4 (4)
N1—Pb1—O2123.45 (15)N1—C17—C18124.0 (6)
O4i—Pb1—O276.61 (15)N1—C17—H17118.0
N4—Pb1—O2152.76 (16)C18—C17—H17118.0
O3i—Pb1—O5122.6 (4)C19—C18—C17117.9 (6)
O1—Pb1—O5118.7 (4)C19—C18—H18121.1
N1—Pb1—O5148.0 (4)C17—C18—H18121.1
O4i—Pb1—O570.9 (4)C18—C19—C20120.7 (6)
N4—Pb1—O5103.4 (4)C18—C19—H19119.6
O2—Pb1—O583.0 (4)C20—C19—H19119.6
C16i—Pb1—O596.3 (4)C21—C20—C22120.0
O3i—Pb1—O1ii155.40 (13)C21—C20—C19118.1 (4)
O1—Pb1—O1ii71.68 (15)C22—C20—C19121.9 (4)
N1—Pb1—O1ii78.86 (14)C20—C21—C27120.0
O4i—Pb1—O1ii150.62 (13)C20—C21—N1120.7 (3)
N4—Pb1—O1ii109.10 (14)C27—C21—N1119.3 (3)
O2—Pb1—O1ii98.05 (14)N4—C27—C26121.6 (3)
O5—Pb1—O1ii79.8 (4)N4—C27—C21118.4 (3)
C1—O1—Pb199.0 (4)C26—C27—C21120.0
C1—O2—Pb187.7 (4)C27—C26—C25120.0
C16—O3—Pb1iii98.5 (4)C27—C26—C28117.7 (4)
C16—O4—Pb1iii86.0 (4)C25—C26—C28122.3 (4)
C17—N1—C21118.6 (5)N3—C25—C26119.3 (4)
C17—N1—Pb1120.2 (4)N3—C25—C22120.7 (4)
C21—N1—Pb1120.4 (3)C26—C25—C22120.0
C23—N2—C22117.1 (6)C25—C22—C20120.0
C24—N3—C25116.3 (6)C25—C22—N2120.9 (4)
C30—N4—C27118.6 (5)C20—C22—N2119.1 (4)
C30—N4—Pb1122.9 (4)N2—C23—C24121.9 (7)
C27—N4—Pb1117.8 (3)N2—C23—H23119.1
O2—C1—O1122.4 (6)C24—C23—H23119.1
O2—C1—C2120.6 (6)N3—C24—C23123.1 (7)
O1—C1—C2116.9 (6)N3—C24—H24118.4
C3—C2—C7120.3 (7)C23—C24—H24118.4
C3—C2—C1120.9 (6)C29—C28—C26119.4 (6)
C7—C2—C1118.8 (7)C29—C28—H28120.3
C2—C3—C4119.1 (8)C26—C28—H28120.3
C2—C3—H3120.4C28—C29—C30118.9 (6)
C4—C3—H3120.4C28—C29—H29120.6
C3—C4—C5120.6 (8)C30—C29—H29120.6
C3—C4—H4119.7N4—C30—C29123.8 (6)
C5—C4—H4119.7N4—C30—H30118.1
C6—C5—C4118.6 (7)C29—C30—H30118.1
C6—C5—C8117.2 (7)C31—O5—Pb1159.7 (13)
C4—C5—C8124.2 (8)C31—N5—C32124 (2)
C5—C6—C7121.5 (8)C31—N5—C33126 (2)
C5—C6—H6119.3C32—N5—C33110.4 (19)
C7—C6—H6119.3O5—C31—N5121 (2)
C6—C7—C2119.9 (8)O5—C31—H31119.4
C6—C7—H7120.0N5—C31—H31119.4
C2—C7—H7120.0C31'—N5'—C33'121.6 (11)
C9—C8—C5125.0 (8)C31'—N5'—C32'119.5 (10)
C9—C8—H8117.5C33'—N5'—C32'118.8 (13)
C5—C8—H8117.5O5'—C31'—N5'127.1 (12)
C8—C9—C10122.7 (8)O5'—C31'—H31'116.5
C8—C9—H9118.7N5'—C31'—H31'116.5
C10—C9—H9118.7N5'—C32'—H32D109.5
C15—C10—C11119.0 (7)N5'—C32'—H32E109.5
C15—C10—C9124.5 (7)H32D—C32'—H32E109.5
C11—C10—C9116.5 (7)N5'—C32'—H32F109.5
C10—C11—C12120.1 (7)H32D—C32'—H32F109.5
C10—C11—H11119.9H32E—C32'—H32F109.5
C12—C11—H11119.9N5'—C33'—H33D109.5
C13—C12—C11121.3 (7)N5'—C33'—H33E109.5
C13—C12—H12119.3H33D—C33'—H33E109.5
C11—C12—H12119.3N5'—C33'—H33F109.5
C14—C13—C12117.6 (6)H33D—C33'—H33F109.5
C14—C13—C16120.2 (6)H33E—C33'—H33F109.5
C12—C13—C16122.2 (6)
O3i—Pb1—O1—C178.5 (4)C13—C14—C15—C101.1 (10)
N1—Pb1—O1—C1163.1 (4)C11—C10—C15—C141.6 (11)
O4i—Pb1—O1—C136.3 (4)C9—C10—C15—C14179.1 (7)
N4—Pb1—O1—C1147.1 (4)Pb1iii—O4—C16—O36.8 (6)
O2—Pb1—O1—C13.4 (4)Pb1iii—O4—C16—C13172.1 (6)
C16i—Pb1—O1—C157.7 (4)Pb1iii—O3—C16—O47.7 (7)
O5—Pb1—O1—C147.4 (6)Pb1iii—O3—C16—C13171.3 (5)
O1ii—Pb1—O1—C1114.2 (4)C14—C13—C16—O417.0 (9)
O3i—Pb1—O2—C1100.9 (4)C12—C13—C16—O4164.4 (6)
O1—Pb1—O2—C13.5 (4)C14—C13—C16—O3162.0 (6)
N1—Pb1—O2—C127.3 (5)C12—C13—C16—O316.6 (9)
O4i—Pb1—O2—C1154.8 (4)C14—C13—C16—Pb1iii119 (2)
N4—Pb1—O2—C1120.9 (4)C12—C13—C16—Pb1iii59 (3)
C16i—Pb1—O2—C1128.1 (4)C21—N1—C17—C180.5 (9)
O5—Pb1—O2—C1133.2 (5)Pb1—N1—C17—C18168.8 (5)
O1ii—Pb1—O2—C154.6 (4)N1—C17—C18—C190.2 (10)
O3i—Pb1—N1—C17100.2 (5)C17—C18—C19—C200.6 (10)
O1—Pb1—N1—C1711.6 (5)C18—C19—C20—C210.3 (8)
O4i—Pb1—N1—C17130.1 (4)C18—C19—C20—C22179.0 (5)
N4—Pb1—N1—C17179.2 (5)C22—C20—C21—C270.0
O2—Pb1—N1—C1730.3 (5)C19—C20—C21—C27179.3 (5)
C16i—Pb1—N1—C17111.9 (5)C22—C20—C21—N1179.7 (4)
O5—Pb1—N1—C17111.1 (8)C19—C20—C21—N10.5 (5)
O1ii—Pb1—N1—C1762.0 (5)C17—N1—C21—C200.8 (7)
O3i—Pb1—N1—C2190.7 (4)Pb1—N1—C21—C20168.4 (2)
O1—Pb1—N1—C21179.3 (4)C17—N1—C21—C27178.9 (4)
O4i—Pb1—N1—C2160.8 (4)Pb1—N1—C21—C2711.8 (5)
N4—Pb1—N1—C2111.7 (3)C30—N4—C27—C261.3 (7)
O2—Pb1—N1—C21160.6 (3)Pb1—N4—C27—C26169.3 (2)
C16i—Pb1—N1—C2179.0 (4)C30—N4—C27—C21178.7 (4)
O5—Pb1—N1—C2158.0 (8)Pb1—N4—C27—C2110.6 (5)
O1ii—Pb1—N1—C21107.1 (4)C20—C21—C27—N4179.9 (4)
O3i—Pb1—N4—C3088.7 (5)N1—C21—C27—N40.3 (5)
O1—Pb1—N4—C30160.8 (4)C20—C21—C27—C260.0
N1—Pb1—N4—C30178.5 (5)N1—C21—C27—C26179.7 (4)
O4i—Pb1—N4—C3035.4 (5)N4—C27—C26—C25179.9 (5)
O2—Pb1—N4—C3068.7 (6)C21—C27—C26—C250.0
C16i—Pb1—N4—C3061.7 (5)N4—C27—C26—C280.3 (5)
O5—Pb1—N4—C3032.3 (6)C21—C27—C26—C28179.8 (4)
O1ii—Pb1—N4—C30116.0 (5)C24—N3—C25—C26179.8 (5)
O3i—Pb1—N4—C27101.1 (4)C24—N3—C25—C220.4 (8)
O1—Pb1—N4—C2729.0 (5)C27—C26—C25—N3179.8 (5)
N1—Pb1—N4—C2711.3 (3)C28—C26—C25—N30.0 (5)
O4i—Pb1—N4—C27154.4 (4)C27—C26—C25—C220.0
O2—Pb1—N4—C27121.1 (4)C28—C26—C25—C22179.8 (5)
C16i—Pb1—N4—C27128.1 (4)N3—C25—C22—C20179.8 (5)
O5—Pb1—N4—C27137.9 (5)C26—C25—C22—C200.0
O1ii—Pb1—N4—C2754.3 (4)N3—C25—C22—N20.7 (6)
Pb1—O2—C1—O16.1 (7)C26—C25—C22—N2179.5 (5)
Pb1—O2—C1—C2171.9 (6)C21—C20—C22—C250.0
Pb1—O1—C1—O26.9 (7)C19—C20—C22—C25179.2 (5)
Pb1—O1—C1—C2171.2 (5)C21—C20—C22—N2179.5 (5)
O2—C1—C2—C39.6 (10)C19—C20—C22—N21.3 (6)
O1—C1—C2—C3168.5 (6)C23—N2—C22—C250.8 (9)
O2—C1—C2—C7170.8 (6)C23—N2—C22—C20179.7 (6)
O1—C1—C2—C711.1 (9)C22—N2—C23—C240.7 (12)
C7—C2—C3—C42.5 (10)C25—N3—C24—C230.3 (11)
C1—C2—C3—C4177.1 (6)N2—C23—C24—N30.5 (13)
C2—C3—C4—C52.2 (11)C27—C26—C28—C290.1 (7)
C3—C4—C5—C60.2 (11)C25—C26—C28—C29179.6 (5)
C3—C4—C5—C8176.8 (7)C26—C28—C29—C300.5 (9)
C4—C5—C6—C72.3 (11)C27—N4—C30—C292.0 (9)
C8—C5—C6—C7175.0 (6)Pb1—N4—C30—C29168.1 (5)
C5—C6—C7—C21.9 (11)C28—C29—C30—N41.6 (10)
C3—C2—C7—C60.5 (10)O3i—Pb1—O5—C31110 (4)
C1—C2—C7—C6179.1 (6)O1—Pb1—O5—C31144 (4)
C6—C5—C8—C9160.2 (8)N1—Pb1—O5—C3132 (4)
C4—C5—C8—C916.9 (12)O4i—Pb1—O5—C31101 (4)
C5—C8—C9—C10175.7 (7)N4—Pb1—O5—C3126 (4)
C8—C9—C10—C1512.8 (12)O2—Pb1—O5—C31179 (5)
C8—C9—C10—C11166.6 (8)C16i—Pb1—O5—C31107 (4)
C15—C10—C11—C120.8 (12)O1ii—Pb1—O5—C3181 (4)
C9—C10—C11—C12179.8 (7)Pb1—O5—C31—N551 (4)
C10—C11—C12—C130.6 (12)C32—N5—C31—O50.1 (3)
C11—C12—C13—C141.0 (11)C33—N5—C31—O5179.9 (3)
C11—C12—C13—C16179.7 (7)C33'—N5'—C31'—O5'179.7 (4)
C12—C13—C14—C150.2 (10)C32'—N5'—C31'—O5'0.3 (4)
C16—C13—C14—C15178.9 (6)
Symmetry codes: (i) x+2, y+1/2, z+1/2; (ii) x+1, y+1, z+1; (iii) x+2, y1/2, z+1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C8—H8···O3iv0.932.523.435 (9)168
C15—H15···O3iv0.932.653.567 (8)170
C17—H17···O10.932.262.968 (8)132
C18—H18···O5ii0.932.643.22 (2)121
C18—H18···O5ii0.932.393.309 (11)170
C23—H23···O2v0.932.273.090 (9)147
Symmetry codes: (ii) x+1, y+1, z+1; (iv) x, y+1/2, z+1/2; (v) x, y, z+1.

Experimental details

Crystal data
Chemical formula[Pb(C16H10O4)(C14H8N4)(C3H7NO)]
Mr778.77
Crystal system, space groupMonoclinic, P21/c
Temperature (K)295
a, b, c (Å)9.0255 (7), 25.5628 (19), 12.6422 (9)
β (°) 102.751 (1)
V3)2844.8 (4)
Z4
Radiation typeMo Kα
µ (mm1)5.98
Crystal size (mm)0.23 × 0.20 × 0.18
Data collection
DiffractometerBruker APEX
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.340, 0.412
No. of measured, independent and
observed [I > 2σ(I)] reflections
14893, 5224, 4134
Rint0.046
(sin θ/λ)max1)0.603
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.039, 0.089, 1.03
No. of reflections5224
No. of parameters428
No. of restraints72
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)1.95, 0.92

Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1999), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL-Plus (Sheldrick, 2008), publCIF (Westrip, 2009).

Selected geometric parameters (Å, º) top
Pb1—O12.448 (4)Pb1—O1ii3.055 (5)
Pb1—O22.707 (5)Pb1—O53.023 (17)
Pb1—O3i2.352 (4)Pb1—N12.594 (5)
Pb1—O4i2.638 (4)Pb1—N42.695 (5)
O3i—Pb1—O187.19 (16)O3i—Pb1—O5122.6 (4)
O3i—Pb1—N184.09 (15)O1—Pb1—O5118.7 (4)
O1—Pb1—N176.25 (16)N1—Pb1—O5148.0 (4)
O3i—Pb1—O4i52.34 (14)O4i—Pb1—O570.9 (4)
O1—Pb1—O4i120.71 (15)N4—Pb1—O5103.4 (4)
N1—Pb1—O4i128.44 (15)O2—Pb1—O583.0 (4)
O3i—Pb1—N477.60 (15)C16i—Pb1—O596.3 (4)
O1—Pb1—N4136.76 (15)O3i—Pb1—O1ii155.40 (13)
N1—Pb1—N462.21 (16)O1—Pb1—O1ii71.68 (15)
O4i—Pb1—N480.59 (15)N1—Pb1—O1ii78.86 (14)
O3i—Pb1—O276.74 (16)O4i—Pb1—O1ii150.62 (13)
O1—Pb1—O250.46 (14)N4—Pb1—O1ii109.10 (14)
N1—Pb1—O2123.45 (15)O2—Pb1—O1ii98.05 (14)
O4i—Pb1—O276.61 (15)O5—Pb1—O1ii79.8 (4)
N4—Pb1—O2152.76 (16)
Symmetry codes: (i) x+2, y+1/2, z+1/2; (ii) x+1, y+1, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C8—H8···O3iii0.932.523.435 (9)167.9
C15—H15···O3iii0.932.653.567 (8)169.9
C17—H17···O10.932.262.968 (8)132.1
C18—H18···O5ii0.932.643.22 (2)121.3
C18—H18···O5'ii0.932.393.309 (11)170.4
C23—H23···O2iv0.932.273.090 (9)146.5
Symmetry codes: (ii) x+1, y+1, z+1; (iii) x, y+1/2, z+1/2; (iv) x, y, z+1.
 

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