metal-organic compounds
μ-Oxalato-κ4O1,O2:O1′,O2′-bis[aqua(2,2′-bipyridine-κN)(nitrato-κ2O,O′)lead(II)]
aCollege of Chemistry and Chemical Engineering, Guangxi University for Nationalities, Nanning 530006, People's Republic of China
*Correspondence e-mail: tangjinniu@126.com
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); Hamilton et al. (2004); Hagrman & Zubieta (2000); Li et al. (2002).
Experimental
Crystal data
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Refinement
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Data collection: SMART (Bruker, 2003); cell SAINT (Bruker, 2003); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2009); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
Supporting information
https://doi.org/10.1107/S1600536812040196/wm2667sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812040196/wm2667Isup2.hkl
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.
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.
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.
For general background to this class of compounds, see: Fan & Zhu (2006); Hamilton et al. (2004); Hagrman & Zubieta (2000); Li et al. (2002).
Data collection: SMART (Bruker, 2003); cell
SAINT (Bruker, 2003); data reduction: SAINT (Bruker, 2003); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2009); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).[Pb2(C2O4)(NO3)2(C10H8N2)2(H2O)2] | F(000) = 908 |
Mr = 974.82 | Dx = 2.422 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 3490 reflections |
a = 9.5791 (19) Å | θ = 2.3–28.3° |
b = 20.6330 (14) Å | µ = 12.66 mm−1 |
c = 6.7649 (15) Å | T = 296 K |
β = 91.687 (1)° | Block, colorless |
V = 1336.5 (4) Å3 | 0.29 × 0.28 × 0.26 mm |
Z = 2 |
Bruker SMART CCD diffractometer | 2336 independent reflections |
Radiation source: fine-focus sealed tube | 2082 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.038 |
phi and ω scans | θmax = 25.0°, θmin = 2.0° |
Absorption correction: multi-scan (SADABS; Bruker, 2003) | h = −11→10 |
Tmin = 0.120, Tmax = 0.137 | k = −24→24 |
7096 measured reflections | l = −7→8 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.031 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.082 | H-atom parameters constrained |
S = 1.07 | w = 1/[σ2(Fo2) + (0.035P)2 + 5.1328P] where P = (Fo2 + 2Fc2)/3 |
2336 reflections | (Δ/σ)max = 0.001 |
190 parameters | Δρmax = 2.68 e Å−3 |
0 restraints | Δρmin = −1.19 e Å−3 |
[Pb2(C2O4)(NO3)2(C10H8N2)2(H2O)2] | V = 1336.5 (4) Å3 |
Mr = 974.82 | Z = 2 |
Monoclinic, P21/c | Mo Kα radiation |
a = 9.5791 (19) Å | µ = 12.66 mm−1 |
b = 20.6330 (14) Å | T = 296 K |
c = 6.7649 (15) Å | 0.29 × 0.28 × 0.26 mm |
β = 91.687 (1)° |
Bruker SMART CCD diffractometer | 2336 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2003) | 2082 reflections with I > 2σ(I) |
Tmin = 0.120, Tmax = 0.137 | Rint = 0.038 |
7096 measured reflections |
R[F2 > 2σ(F2)] = 0.031 | 0 restraints |
wR(F2) = 0.082 | H-atom parameters constrained |
S = 1.07 | Δρmax = 2.68 e Å−3 |
2336 reflections | Δρmin = −1.19 e Å−3 |
190 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
Pb1 | 0.68880 (3) | 0.537173 (12) | 0.87652 (4) | 0.03036 (13) | |
N1 | 0.7954 (9) | 0.3925 (3) | 0.8164 (10) | 0.0504 (18) | |
N2 | 0.6271 (6) | 0.6548 (3) | 0.8129 (9) | 0.0345 (14) | |
N3 | 0.8863 (6) | 0.6061 (3) | 0.7555 (8) | 0.0317 (13) | |
O1 | 0.6656 (8) | 0.4032 (3) | 0.7926 (12) | 0.0678 (18) | |
O2 | 0.8406 (9) | 0.3377 (3) | 0.8302 (12) | 0.084 (2) | |
O3 | 0.8765 (6) | 0.4408 (3) | 0.8182 (10) | 0.0563 (16) | |
O5 | 0.6731 (5) | 0.5291 (2) | 0.5190 (8) | 0.0393 (13) | |
O6 | 0.5602 (5) | 0.4830 (3) | 0.2626 (7) | 0.0411 (12) | |
O7 | 0.8279 (6) | 0.5894 (3) | 1.2112 (8) | 0.0463 (13) | |
H7A | 0.8289 | 0.5600 | 1.2993 | 0.056* | |
H7B | 0.9123 | 0.5956 | 1.1805 | 0.056* | |
C1 | 0.4989 (8) | 0.6777 (4) | 0.8412 (12) | 0.0449 (19) | |
H1 | 0.4275 | 0.6480 | 0.8607 | 0.054* | |
C2 | 0.4664 (9) | 0.7424 (4) | 0.8432 (13) | 0.052 (2) | |
H2 | 0.3755 | 0.7562 | 0.8633 | 0.062* | |
C3 | 0.5712 (9) | 0.7861 (4) | 0.8148 (12) | 0.049 (2) | |
H3 | 0.5521 | 0.8303 | 0.8155 | 0.058* | |
C4 | 0.7051 (9) | 0.7647 (4) | 0.7851 (12) | 0.0408 (18) | |
H4 | 0.7772 | 0.7940 | 0.7661 | 0.049* | |
C5 | 0.7308 (8) | 0.6978 (3) | 0.7841 (10) | 0.0332 (16) | |
C6 | 0.8707 (7) | 0.6707 (3) | 0.7405 (10) | 0.0294 (15) | |
C7 | 0.9824 (8) | 0.7097 (4) | 0.6843 (12) | 0.0425 (18) | |
H7 | 0.9715 | 0.7544 | 0.6737 | 0.051* | |
C8 | 1.1074 (8) | 0.6813 (4) | 0.6453 (13) | 0.051 (2) | |
H8 | 1.1828 | 0.7067 | 0.6091 | 0.061* | |
C9 | 1.1214 (8) | 0.6160 (4) | 0.6595 (13) | 0.047 (2) | |
H9 | 1.2056 | 0.5961 | 0.6315 | 0.057* | |
C10 | 1.0100 (8) | 0.5801 (4) | 0.7156 (11) | 0.0384 (17) | |
H10 | 1.0206 | 0.5354 | 0.7267 | 0.046* | |
C11 | 0.5660 (7) | 0.5032 (3) | 0.4367 (11) | 0.0319 (15) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Pb1 | 0.02946 (19) | 0.03118 (19) | 0.03045 (19) | −0.00956 (10) | 0.00100 (11) | 0.00129 (10) |
N1 | 0.066 (5) | 0.037 (4) | 0.048 (4) | 0.001 (4) | 0.006 (3) | 0.002 (3) |
N2 | 0.032 (3) | 0.036 (3) | 0.035 (3) | 0.003 (3) | 0.002 (3) | −0.002 (3) |
N3 | 0.031 (3) | 0.029 (3) | 0.035 (3) | −0.007 (2) | 0.002 (2) | −0.001 (3) |
O1 | 0.063 (5) | 0.044 (4) | 0.097 (5) | −0.009 (3) | −0.001 (4) | 0.006 (4) |
O2 | 0.119 (7) | 0.032 (4) | 0.101 (6) | 0.018 (4) | 0.009 (5) | 0.004 (4) |
O3 | 0.043 (3) | 0.042 (3) | 0.083 (5) | −0.008 (3) | −0.005 (3) | 0.006 (3) |
O5 | 0.027 (3) | 0.051 (3) | 0.040 (3) | −0.011 (2) | 0.003 (2) | −0.001 (2) |
O6 | 0.029 (3) | 0.065 (3) | 0.030 (3) | −0.013 (2) | 0.004 (2) | −0.012 (3) |
O7 | 0.040 (3) | 0.055 (3) | 0.044 (3) | −0.005 (3) | 0.003 (2) | 0.006 (3) |
C1 | 0.032 (4) | 0.062 (6) | 0.041 (5) | 0.001 (4) | 0.005 (3) | −0.001 (4) |
C2 | 0.043 (5) | 0.066 (6) | 0.047 (5) | 0.023 (4) | 0.005 (4) | −0.008 (4) |
C3 | 0.065 (6) | 0.039 (5) | 0.041 (5) | 0.017 (4) | −0.007 (4) | −0.005 (4) |
C4 | 0.049 (5) | 0.038 (4) | 0.035 (4) | 0.006 (4) | −0.001 (3) | −0.002 (3) |
C5 | 0.041 (4) | 0.030 (4) | 0.028 (4) | 0.000 (3) | 0.001 (3) | −0.005 (3) |
C6 | 0.034 (4) | 0.028 (4) | 0.026 (4) | −0.005 (3) | 0.000 (3) | 0.000 (3) |
C7 | 0.042 (4) | 0.036 (4) | 0.050 (5) | −0.016 (3) | 0.004 (3) | 0.004 (3) |
C8 | 0.034 (4) | 0.061 (6) | 0.058 (6) | −0.019 (4) | 0.011 (4) | 0.001 (4) |
C9 | 0.035 (4) | 0.057 (5) | 0.051 (5) | 0.000 (4) | 0.015 (3) | −0.003 (4) |
C10 | 0.037 (4) | 0.036 (4) | 0.042 (5) | 0.000 (3) | 0.006 (3) | −0.004 (3) |
C11 | 0.026 (4) | 0.033 (4) | 0.037 (4) | −0.001 (3) | 0.003 (3) | −0.001 (3) |
Pb1—O5 | 2.425 (5) | C1—C2 | 1.371 (12) |
Pb1—N3 | 2.522 (5) | C1—H1 | 0.9300 |
Pb1—N2 | 2.532 (6) | C2—C3 | 1.368 (12) |
Pb1—O6i | 2.572 (5) | C2—H2 | 0.9300 |
Pb1—O3 | 2.718 (6) | C3—C4 | 1.377 (11) |
Pb1—O7 | 2.809 (6) | C3—H3 | 0.9300 |
N1—O2 | 1.214 (9) | C4—C5 | 1.401 (10) |
N1—O3 | 1.263 (9) | C4—H4 | 0.9300 |
N1—O1 | 1.269 (10) | C5—C6 | 1.490 (10) |
N2—C1 | 1.334 (9) | C6—C7 | 1.401 (9) |
N2—C5 | 1.351 (9) | C7—C8 | 1.366 (11) |
N3—C10 | 1.336 (9) | C7—H7 | 0.9300 |
N3—C6 | 1.344 (9) | C8—C9 | 1.358 (12) |
O5—C11 | 1.270 (9) | C8—H8 | 0.9300 |
O6—C11 | 1.249 (9) | C9—C10 | 1.362 (11) |
O6—Pb1i | 2.572 (5) | C9—H9 | 0.9300 |
O7—H7A | 0.8500 | C10—H10 | 0.9300 |
O7—H7B | 0.8499 | C11—C11i | 1.554 (13) |
O5—Pb1—N3 | 74.93 (17) | C2—C1—H1 | 118.1 |
O5—Pb1—N2 | 83.62 (18) | C3—C2—C1 | 118.2 (8) |
N3—Pb1—N2 | 65.04 (19) | C3—C2—H2 | 120.9 |
O5—Pb1—O6i | 66.07 (16) | C1—C2—H2 | 120.9 |
N3—Pb1—O6i | 131.97 (18) | C2—C3—C4 | 120.0 (8) |
N2—Pb1—O6i | 83.30 (19) | C2—C3—H3 | 120.0 |
O5—Pb1—O3 | 80.03 (19) | C4—C3—H3 | 120.0 |
N3—Pb1—O3 | 81.95 (18) | C3—C4—C5 | 118.8 (8) |
N2—Pb1—O3 | 146.01 (19) | C3—C4—H4 | 120.6 |
O6i—Pb1—O3 | 116.03 (18) | C5—C4—H4 | 120.6 |
O5—Pb1—O7 | 147.62 (16) | N2—C5—C4 | 121.1 (7) |
N3—Pb1—O7 | 72.69 (17) | N2—C5—C6 | 116.8 (6) |
N2—Pb1—O7 | 82.64 (18) | C4—C5—C6 | 122.0 (7) |
O6i—Pb1—O7 | 140.35 (16) | N3—C6—C7 | 120.5 (7) |
O3—Pb1—O7 | 95.61 (18) | N3—C6—C5 | 117.1 (6) |
O2—N1—O3 | 121.0 (8) | C7—C6—C5 | 122.4 (6) |
O2—N1—O1 | 121.2 (8) | C8—C7—C6 | 119.1 (7) |
O3—N1—O1 | 117.7 (7) | C8—C7—H7 | 120.4 |
C1—N2—C5 | 118.2 (7) | C6—C7—H7 | 120.4 |
C1—N2—Pb1 | 121.7 (5) | C9—C8—C7 | 119.8 (7) |
C5—N2—Pb1 | 119.0 (5) | C9—C8—H8 | 120.1 |
C10—N3—C6 | 118.7 (6) | C7—C8—H8 | 120.1 |
C10—N3—Pb1 | 121.2 (5) | C8—C9—C10 | 118.9 (8) |
C6—N3—Pb1 | 120.0 (4) | C8—C9—H9 | 120.5 |
N1—O3—Pb1 | 99.7 (5) | C10—C9—H9 | 120.5 |
C11—O5—Pb1 | 119.4 (4) | N3—C10—C9 | 123.0 (7) |
C11—O6—Pb1i | 114.5 (4) | N3—C10—H10 | 118.5 |
Pb1—O7—H7A | 106.6 | C9—C10—H10 | 118.5 |
Pb1—O7—H7B | 107.0 | O6—C11—O5 | 124.5 (6) |
H7A—O7—H7B | 106.7 | O6—C11—C11i | 118.5 (8) |
N2—C1—C2 | 123.8 (8) | O5—C11—C11i | 117.0 (8) |
N2—C1—H1 | 118.1 |
Symmetry code: (i) −x+1, −y+1, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
O7—H7A···O5ii | 0.85 | 2.23 | 2.875 (7) | 133 |
O7—H7B···O3iii | 0.85 | 2.16 | 2.912 (8) | 148 |
Symmetry codes: (ii) x, y, z+1; (iii) −x+2, −y+1, −z+2. |
Experimental details
Crystal data | |
Chemical formula | [Pb2(C2O4)(NO3)2(C10H8N2)2(H2O)2] |
Mr | 974.82 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 296 |
a, b, c (Å) | 9.5791 (19), 20.6330 (14), 6.7649 (15) |
β (°) | 91.687 (1) |
V (Å3) | 1336.5 (4) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 12.66 |
Crystal size (mm) | 0.29 × 0.28 × 0.26 |
Data collection | |
Diffractometer | Bruker SMART CCD |
Absorption correction | Multi-scan (SADABS; Bruker, 2003) |
Tmin, Tmax | 0.120, 0.137 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7096, 2336, 2082 |
Rint | 0.038 |
(sin θ/λ)max (Å−1) | 0.594 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.031, 0.082, 1.07 |
No. of reflections | 2336 |
No. of parameters | 190 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 2.68, −1.19 |
Computer programs: SMART (Bruker, 2003), SAINT (Bruker, 2003), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg, 2009), SHELXTL (Sheldrick, 2008).
D—H···A | D—H | H···A | D···A | D—H···A |
O7—H7A···O5i | 0.85 | 2.23 | 2.875 (7) | 132.6 |
O7—H7B···O3ii | 0.85 | 2.16 | 2.912 (8) | 147.7 |
Symmetry codes: (i) x, y, z+1; (ii) −x+2, −y+1, −z+2. |
Acknowledgements
This work was supported by the Innovation Project of Guangxi University for Nationalities.
References
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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.