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Acta Crystallogr Sect E Struct Rep Online. Oct 1, 2012; 68(Pt 10): m1310.
Published online Sep 29, 2012. doi:  10.1107/S1600536812040196
PMCID: PMC3470178
μ-Oxalato-κ4 O 1,O 2:O 1′,O 2′-bis­[aqua­(2,2′-bipyridine-κN)(nitrato-κ2 O,O′)lead(II)]
Gang-Hong Pan,a Jin-Niu Tang,a Zhong-Jing Huang,a* Long Li,a and Chun-Mei Zhanga
aCollege of Chemistry and Chemical Engineering, Guangxi University for Nationalities, Nanning 530006, People’s Republic of China
Correspondence e-mail: tangjinniu/at/126.com
Received July 25, 2012; Accepted September 22, 2012.
The title compound, [Pb2(C2O4)(NO3)2(C10H8N2)2(H2O)2], was synthesized hydro­thermally. The binuclear complex mol­ecule is centrosymmetric, the inversion centre being located at the mid-point of the oxalate C—C bond. The PbII ion is hepta­coordinated by the O atom of one water mol­ecule, two oxalate O atoms, two nitrate O atoms and two 2,2′-bipyridine N atoms, forming an irregular coordination environemnt. Inter­molecular O—H(...)O hydrogen bonds between water mol­ecules and oxalate and nitrate ions result in the formation of layers parallel to (010). π–π inter­actions between pyridine rings in adjacent layers, with centroid–centroid distances of 3.584 (2) Å, stabilize the structural set-up.
Related literature  
For general background to this class of compounds, see: Fan & Zhu (2006 [triangle]); Hamilton et al. (2004 [triangle]); Hagrman & Zubieta (2000 [triangle]); Li et al. (2002 [triangle]).
An external file that holds a picture, illustration, etc.
Object name is e-68-m1310-scheme1.jpg Object name is e-68-m1310-scheme1.jpg
Crystal data  
  • [Pb2(C2O4)(NO3)2(C10H8N2)2(H2O)2]
  • M r = 974.82
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-68-m1310-efi1.jpg
  • a = 9.5791 (19) Å
  • b = 20.6330 (14) Å
  • c = 6.7649 (15) Å
  • β = 91.687 (1)°
  • V = 1336.5 (4) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 12.66 mm−1
  • T = 296 K
  • 0.29 × 0.28 × 0.26 mm
Data collection  
  • Bruker SMART CCD diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2003 [triangle]) T min = 0.120, T max = 0.137
  • 7096 measured reflections
  • 2336 independent reflections
  • 2082 reflections with I > 2σ(I)
  • R int = 0.038
Refinement  
  • R[F 2 > 2σ(F 2)] = 0.031
  • wR(F 2) = 0.082
  • S = 1.07
  • 2336 reflections
  • 190 parameters
  • H-atom parameters constrained
  • Δρmax = 2.68 e Å−3
  • Δρmin = −1.19 e Å−3
Data collection: SMART (Bruker, 2003 [triangle]); cell refinement: SAINT (Bruker, 2003 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: DIAMOND (Brandenburg, 2009 [triangle]); software used to prepare material for publication: SHELXTL (Sheldrick, 2008 [triangle]).
Table 1
Table 1
Hydrogen-bond geometry (Å, °)
Supplementary Material
Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812040196/wm2667sup1.cif
Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812040196/wm2667Isup2.hkl
Additional supplementary materials: crystallographic information; 3D view; checkCIF report
Acknowledgments
This work was supported by the Innovation Project of Guangxi University for Nationalities.
supplementary crystallographic information
Comment
Complexes containing PbII (Fan & Zhu et al., 2006) are interesting because of the variety of their structures and their potential applications, especially in environmental protection, e.g heavy metal removal. It is known that the introduction of chelating ligands such as 2,2'-bipyridine causes the passivation of metal sites via the N donors of the organic groups and may induce new structural evolution (Hamilton et al., 2004; Hagrman & Zubieta, 2000; Li et al., 2002).
In the title binuclear lead(II) compound, [Pb2(C2O4)(NO3)2(H2O)2(C10H8N2)2], a centrosymmetric molcule is present, with the centre of symmetry at the mid-point of the C—C oxalate bond (Fig. 1). The PbII ion is hepta-coordinated in an irregular fashion by one water molecule, two nitrate oxygen atoms, two oxalate oxygen atoms, and two nitrogen atoms from 2,2'-bipyridine. The supramolecular assembly in the title compound is completed by O—H···O hydrogen bonds between the coordinating water molecules and oxalate and nitrate O atoms (Table 1), resulting in the formation of layers parallel to (010) (Fig. 2). The structure is further extended by π—π stacking interactions between 2,2'-bipyridine molecules of adjacent layers. They overlap with a centroid-to-centroid distance of 3.584 (2) Å.
Experimental
A mixture of oxalic acid (0.0634 g, 0.5 mmol), 2,2'-bipyridine (0.0781 g, 0.5mmol), Pb(NO3)2 (0.3312 g, 1mmol), NaOH (0.0400 g, 1mmol), water (10 ml) and ethanol (5 ml) was placed in a Parr Teflon-lined stainless steel vessel (25 cm3). The vessel was then sealed and heated at 403 K for 3 days. Afterwards the mixture was slowly cooled to room temperature, colorless block-shaped crystals of the complex were obtained. Elemental analysis calculated (%wt): C 27.11; H 2.07; N 8.62; found (%wt): C 27.06; H 2.03; N 8.51.
Refinement
H atoms were positioned geometrically and refined as riding atoms, with C—H = 0.93 Å and Uiso(H) = 1.2Ueq(C) for aromatic H atoms. H atoms of the water molecule were located in a difference Fourier map and refined as riding, with O—H = 0.85 Å and with Uiso(H) = 1.2Ueq(O). The maximum remaining electron density is found 0.97 Å from Pb1, and the minimum density 0.91 Å from the same atom.
Figures
Fig. 1.
Fig. 1.
The coordination environment around PbII in the title compound with the atom-labeling scheme. Displacement ellipsoids for non-hydrogen atoms are drawn at the 30% probability level. [Symmetry code: (i) -x+1, -y+1, -z+1.]
Fig. 2.
Fig. 2.
O—H···O hydrogen bonding (purple dashed lines) and π—π stacking interactions (blue dashed lines) in the structure of the title compound. All H atoms were omitted for clarity.
Crystal data
[Pb2(C2O4)(NO3)2(C10H8N2)2(H2O)2]F(000) = 908
Mr = 974.82Dx = 2.422 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 3490 reflections
a = 9.5791 (19) Åθ = 2.3–28.3°
b = 20.6330 (14) ŵ = 12.66 mm1
c = 6.7649 (15) ÅT = 296 K
β = 91.687 (1)°Block, colorless
V = 1336.5 (4) Å30.29 × 0.28 × 0.26 mm
Z = 2
Data collection
Bruker SMART CCD diffractometer2336 independent reflections
Radiation source: fine-focus sealed tube2082 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.038
phi and ω scansθmax = 25.0°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Bruker, 2003)h = −11→10
Tmin = 0.120, Tmax = 0.137k = −24→24
7096 measured reflectionsl = −7→8
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)] = 0.031Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.082H-atom parameters constrained
S = 1.07w = 1/[σ2(Fo2) + (0.035P)2 + 5.1328P] where P = (Fo2 + 2Fc2)/3
2336 reflections(Δ/σ)max = 0.001
190 parametersΔρmax = 2.68 e Å3
0 restraintsΔρmin = −1.19 e Å3
Special details
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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
Pb10.68880 (3)0.537173 (12)0.87652 (4)0.03036 (13)
N10.7954 (9)0.3925 (3)0.8164 (10)0.0504 (18)
N20.6271 (6)0.6548 (3)0.8129 (9)0.0345 (14)
N30.8863 (6)0.6061 (3)0.7555 (8)0.0317 (13)
O10.6656 (8)0.4032 (3)0.7926 (12)0.0678 (18)
O20.8406 (9)0.3377 (3)0.8302 (12)0.084 (2)
O30.8765 (6)0.4408 (3)0.8182 (10)0.0563 (16)
O50.6731 (5)0.5291 (2)0.5190 (8)0.0393 (13)
O60.5602 (5)0.4830 (3)0.2626 (7)0.0411 (12)
O70.8279 (6)0.5894 (3)1.2112 (8)0.0463 (13)
H7A0.82890.56001.29930.056*
H7B0.91230.59561.18050.056*
C10.4989 (8)0.6777 (4)0.8412 (12)0.0449 (19)
H10.42750.64800.86070.054*
C20.4664 (9)0.7424 (4)0.8432 (13)0.052 (2)
H20.37550.75620.86330.062*
C30.5712 (9)0.7861 (4)0.8148 (12)0.049 (2)
H30.55210.83030.81550.058*
C40.7051 (9)0.7647 (4)0.7851 (12)0.0408 (18)
H40.77720.79400.76610.049*
C50.7308 (8)0.6978 (3)0.7841 (10)0.0332 (16)
C60.8707 (7)0.6707 (3)0.7405 (10)0.0294 (15)
C70.9824 (8)0.7097 (4)0.6843 (12)0.0425 (18)
H70.97150.75440.67370.051*
C81.1074 (8)0.6813 (4)0.6453 (13)0.051 (2)
H81.18280.70670.60910.061*
C91.1214 (8)0.6160 (4)0.6595 (13)0.047 (2)
H91.20560.59610.63150.057*
C101.0100 (8)0.5801 (4)0.7156 (11)0.0384 (17)
H101.02060.53540.72670.046*
C110.5660 (7)0.5032 (3)0.4367 (11)0.0319 (15)
Atomic displacement parameters (Å2)
U11U22U33U12U13U23
Pb10.02946 (19)0.03118 (19)0.03045 (19)−0.00956 (10)0.00100 (11)0.00129 (10)
N10.066 (5)0.037 (4)0.048 (4)0.001 (4)0.006 (3)0.002 (3)
N20.032 (3)0.036 (3)0.035 (3)0.003 (3)0.002 (3)−0.002 (3)
N30.031 (3)0.029 (3)0.035 (3)−0.007 (2)0.002 (2)−0.001 (3)
O10.063 (5)0.044 (4)0.097 (5)−0.009 (3)−0.001 (4)0.006 (4)
O20.119 (7)0.032 (4)0.101 (6)0.018 (4)0.009 (5)0.004 (4)
O30.043 (3)0.042 (3)0.083 (5)−0.008 (3)−0.005 (3)0.006 (3)
O50.027 (3)0.051 (3)0.040 (3)−0.011 (2)0.003 (2)−0.001 (2)
O60.029 (3)0.065 (3)0.030 (3)−0.013 (2)0.004 (2)−0.012 (3)
O70.040 (3)0.055 (3)0.044 (3)−0.005 (3)0.003 (2)0.006 (3)
C10.032 (4)0.062 (6)0.041 (5)0.001 (4)0.005 (3)−0.001 (4)
C20.043 (5)0.066 (6)0.047 (5)0.023 (4)0.005 (4)−0.008 (4)
C30.065 (6)0.039 (5)0.041 (5)0.017 (4)−0.007 (4)−0.005 (4)
C40.049 (5)0.038 (4)0.035 (4)0.006 (4)−0.001 (3)−0.002 (3)
C50.041 (4)0.030 (4)0.028 (4)0.000 (3)0.001 (3)−0.005 (3)
C60.034 (4)0.028 (4)0.026 (4)−0.005 (3)0.000 (3)0.000 (3)
C70.042 (4)0.036 (4)0.050 (5)−0.016 (3)0.004 (3)0.004 (3)
C80.034 (4)0.061 (6)0.058 (6)−0.019 (4)0.011 (4)0.001 (4)
C90.035 (4)0.057 (5)0.051 (5)0.000 (4)0.015 (3)−0.003 (4)
C100.037 (4)0.036 (4)0.042 (5)0.000 (3)0.006 (3)−0.004 (3)
C110.026 (4)0.033 (4)0.037 (4)−0.001 (3)0.003 (3)−0.001 (3)
Geometric parameters (Å, º)
Pb1—O52.425 (5)C1—C21.371 (12)
Pb1—N32.522 (5)C1—H10.9300
Pb1—N22.532 (6)C2—C31.368 (12)
Pb1—O6i2.572 (5)C2—H20.9300
Pb1—O32.718 (6)C3—C41.377 (11)
Pb1—O72.809 (6)C3—H30.9300
N1—O21.214 (9)C4—C51.401 (10)
N1—O31.263 (9)C4—H40.9300
N1—O11.269 (10)C5—C61.490 (10)
N2—C11.334 (9)C6—C71.401 (9)
N2—C51.351 (9)C7—C81.366 (11)
N3—C101.336 (9)C7—H70.9300
N3—C61.344 (9)C8—C91.358 (12)
O5—C111.270 (9)C8—H80.9300
O6—C111.249 (9)C9—C101.362 (11)
O6—Pb1i2.572 (5)C9—H90.9300
O7—H7A0.8500C10—H100.9300
O7—H7B0.8499C11—C11i1.554 (13)
O5—Pb1—N374.93 (17)C2—C1—H1118.1
O5—Pb1—N283.62 (18)C3—C2—C1118.2 (8)
N3—Pb1—N265.04 (19)C3—C2—H2120.9
O5—Pb1—O6i66.07 (16)C1—C2—H2120.9
N3—Pb1—O6i131.97 (18)C2—C3—C4120.0 (8)
N2—Pb1—O6i83.30 (19)C2—C3—H3120.0
O5—Pb1—O380.03 (19)C4—C3—H3120.0
N3—Pb1—O381.95 (18)C3—C4—C5118.8 (8)
N2—Pb1—O3146.01 (19)C3—C4—H4120.6
O6i—Pb1—O3116.03 (18)C5—C4—H4120.6
O5—Pb1—O7147.62 (16)N2—C5—C4121.1 (7)
N3—Pb1—O772.69 (17)N2—C5—C6116.8 (6)
N2—Pb1—O782.64 (18)C4—C5—C6122.0 (7)
O6i—Pb1—O7140.35 (16)N3—C6—C7120.5 (7)
O3—Pb1—O795.61 (18)N3—C6—C5117.1 (6)
O2—N1—O3121.0 (8)C7—C6—C5122.4 (6)
O2—N1—O1121.2 (8)C8—C7—C6119.1 (7)
O3—N1—O1117.7 (7)C8—C7—H7120.4
C1—N2—C5118.2 (7)C6—C7—H7120.4
C1—N2—Pb1121.7 (5)C9—C8—C7119.8 (7)
C5—N2—Pb1119.0 (5)C9—C8—H8120.1
C10—N3—C6118.7 (6)C7—C8—H8120.1
C10—N3—Pb1121.2 (5)C8—C9—C10118.9 (8)
C6—N3—Pb1120.0 (4)C8—C9—H9120.5
N1—O3—Pb199.7 (5)C10—C9—H9120.5
C11—O5—Pb1119.4 (4)N3—C10—C9123.0 (7)
C11—O6—Pb1i114.5 (4)N3—C10—H10118.5
Pb1—O7—H7A106.6C9—C10—H10118.5
Pb1—O7—H7B107.0O6—C11—O5124.5 (6)
H7A—O7—H7B106.7O6—C11—C11i118.5 (8)
N2—C1—C2123.8 (8)O5—C11—C11i117.0 (8)
N2—C1—H1118.1
Symmetry code: (i) −x+1, −y+1, −z+1.
Hydrogen-bond geometry (Å, º)
D—H···AD—HH···AD···AD—H···A
O7—H7A···O5ii0.852.232.875 (7)133
O7—H7B···O3iii0.852.162.912 (8)148
Symmetry codes: (ii) x, y, z+1; (iii) −x+2, −y+1, −z+2.
Footnotes
Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: WM2667).
References
  • Brandenburg, K. (2009). DIAMOND Crystal Impact GbR, Bonn, Germany.
  • Bruker (2003). SMART, SAINT and SADABS Bruker AXS Inc., Madison, Wisconsin, USA.
  • Fan, S. R. & Zhu, L. G. (2006). Inorg. Chem. 45, 7935–7942. [PubMed]
  • Hagrman, P. J. & Zubieta, J. (2000). Inorg. Chem. 39, 3252–3260. [PubMed]
  • Hamilton, B. H., Kelley, K. A., Wagler, T. A., Espe, M. P. & Ziegler, C. J. (2004). Inorg. Chem. 43, 50–56. [PubMed]
  • Li, Y. G., Wang, E. B., Zhang, H., Luan, G. L. & Hu, C. W. (2002). J. Solid State Chem. 163, 10–16.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
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