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Acta Crystallogr Sect E Struct Rep Online. 2009 January 1; 65(Pt 1): m54.
Published online 2008 December 13. doi:  10.1107/S1600536808041317
PMCID: PMC2967897

Bis(imidazo[4,5-f][1,10]phenanthroline)dinitratolead(II)

Abstract

In the title compound, [Pb(NO3)2(C13H8N4)2], the PbII atom (site symmetry 2) is hexa­coordinated by four N atoms from two N,N′-bidentate imidazo[4,5-f][1,10]phenanthroline (L) ligands and two O atoms from two weakly coordinated nitrate ions [Pb—O = 2.872 (5) Å] in an irregular arrangement, which may be ascribed to the stereochemically active lone pair of electrons on the metal ion. In the crystal, inter­molecular bifurcated N—H(...)(O,O) hydrogen bonds connect the mol­ecules into chains propagating along [100]. Adjacent chains inter­act by strong aromatic π–π stacking inter­actions, with a centroid–centroid distance of 3.483 (2) Å.

Related literature

For the ligand synthesis, see: Steck & Day (1943 [triangle]). For background, see: Che et al. (2006 [triangle], 2008 [triangle]); Thomas et al. (2008 [triangle]); Xu et al. (2008 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-65-00m54-scheme1.jpg

Experimental

Crystal data

  • [Pb(NO3)2(C13H8N4)2]
  • M r = 771.68
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-00m54-efi4.jpg
  • a = 19.203 (4) Å
  • b = 7.3948 (15) Å
  • c = 17.392 (4) Å
  • β = 100.48 (3)°
  • V = 2428.5 (8) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 7.02 mm−1
  • T = 292 (2) K
  • 0.56 × 0.22 × 0.11 mm

Data collection

  • Bruker SMART CCD diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2002 [triangle]) T min = 0.165, T max = 0.453
  • 10060 measured reflections
  • 2402 independent reflections
  • 2170 reflections with I > 2σ(I)
  • R int = 0.049

Refinement

  • R[F 2 > 2σ(F 2)] = 0.026
  • wR(F 2) = 0.064
  • S = 1.05
  • 2402 reflections
  • 195 parameters
  • H-atom parameters constrained
  • Δρmax = 0.89 e Å−3
  • Δρmin = −0.63 e Å−3

Data collection: SMART (Bruker, 2002 [triangle]); cell refinement: SAINT (Bruker, 2002 [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: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXTL.

Table 1
Selected bond lengths (Å)
Table 2
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808041317/hb2871sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808041317/hb2871Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

The authors thank the Natural Science Foundation of Jiangsu University and the Natural Science Foundation of Jilin Normal University for support.

supplementary crystallographic information

Comment

1,10-Phenanthroline and its derivatives are very important heteroaromatic N-donor chelating ligands for the construction of coordination compounds. (Che et al., 2008; Xu et al., 2008; Che et al., 2006). Whereas, only a handful of supramolecular architectures based on imidazo[4,5-f][1,10]phenanthroline ligand (L) have been described (Thomas et al., 2008). The present attempt at synthesizing a new lead complex with L ligand gave the title complex, [Pb(C13H8N4)2(NO3)2] (I), whose structure is reported here.

In the title compound I, each Pb atom is hexacoordinated by four N atoms (N1, N1i, N2, N2i) from two L ligand and two O (O1, O1i) atoms from two NO3- ions (Fig. 1). The Pb—N bond lengths are normal (Table 1), however, O1 and O1i could be described as being semicoordinated with long Pb—O lengths of 2.872 (5) Å. The PbN4O2 coordination polyhedron approximates a distorted octahedral configuration.

In the crystal structure, the mononuclear complex molecules are linked via intermolecular N—H···O and N—H··· N hydrogen bonds (Table 2) forming one-dimensional chains along [100] (Fig. 2). Withal, one-dimensional chains are stabilized by π-π interactions between the L rings planes of neighboring molecules with distances of 3.442 Å (Fig. 3), leading to a three-dimensional network.

Experimental

The L ligand was synthesized according to the literature method of Steck & Day (1943). A mixture of Pb(NO3)2 (0.5 mmol) and the ligand (1 mmol) was dissolved in 15 ml distilled water, then followed by addition of NaOH until the pH value of the system approximately 6.0. Finally the resulting solution was sealed into a 23 ml Teflon-lined stainless steel autoclave and heated at 413 K for 3 d under autogenous pressure. The reaction autoclave slowly cooled to room temperature, yielding yellow block-like crystals of (I) in 62% yield based on Pb.

Refinement

All H atoms on C atoms were positioned geometrically (C—H = 0.93 Å) and refined as riding, with Uiso(H)= 1.2Ueq(C). The hydrogen atoms of water molecules were located from difference Fourier maps and their positions and Uiso values were refined freely.

Figures

Fig. 1.
A view of (I). Displacement ellipsoids are drawn at the 30% probability level (arbitrary spheres for the H atoms). Dashed lines indicate semicoordinated bonds [Symmetry code: (i) -x + 1, y, -z + 1/2].
Fig. 2.
A packing diagram of the title compound, showing a one-dimensional chain-like structure generated by the intermolecular hydrogen bonding. H atoms have been omitted [Symmetry code: (A) -x + 1, -y - 1/2, z - 1/2].

Crystal data

[Pb(NO3)2(C13H8N4)2]F(000) = 1488
Mr = 771.68Dx = 2.111 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 3904 reflections
a = 19.203 (4) Åθ = 2.2–26.1°
b = 7.3948 (15) ŵ = 7.02 mm1
c = 17.392 (4) ÅT = 292 K
β = 100.48 (3)°Block, yellow
V = 2428.5 (8) Å30.56 × 0.22 × 0.11 mm
Z = 4

Data collection

Bruker SMART CCD diffractometer2402 independent reflections
Radiation source: fine-focus sealed tube2170 reflections with I > 2σ(I)
graphiteRint = 0.049
ω scansθmax = 26.1°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2002)h = −23→23
Tmin = 0.165, Tmax = 0.453k = −9→9
10060 measured reflectionsl = −20→21

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)] = 0.026Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.064H-atom parameters constrained
S = 1.05w = 1/[σ2(Fo2) + (0.0304P)2] where P = (Fo2 + 2Fc2)/3
2402 reflections(Δ/σ)max = 0.005
195 parametersΔρmax = 0.89 e Å3
0 restraintsΔρmin = −0.63 e Å3

Special details

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)

xyzUiso*/Ueq
C10.3676 (2)−0.2885 (6)0.1841 (2)0.0361 (10)
H10.3576−0.26440.23340.043*
C20.3181 (3)−0.3843 (7)0.1316 (3)0.0472 (12)
H20.2772−0.42830.14660.057*
C30.3303 (2)−0.4130 (6)0.0577 (3)0.0411 (11)
H30.2973−0.47490.02140.049*
C40.3927 (2)−0.3486 (5)0.0372 (2)0.0270 (9)
C50.4423 (2)−0.2606 (5)0.0951 (2)0.0242 (8)
C60.5099 (2)−0.1997 (5)0.0783 (2)0.0242 (8)
C70.6190 (2)−0.0678 (6)0.1228 (3)0.0329 (9)
H70.6505−0.01170.16270.040*
C80.6394 (2)−0.0921 (6)0.0507 (2)0.0354 (10)
H80.6845−0.05800.04390.043*
C90.4103 (2)−0.3613 (5)−0.0386 (2)0.0284 (9)
C100.5268 (2)−0.2217 (5)0.0028 (2)0.0251 (8)
C110.4729 (2)−0.2999 (5)−0.0565 (2)0.0272 (9)
C120.4129 (3)−0.3952 (6)−0.1631 (2)0.0386 (11)
H120.3985−0.4253−0.21550.046*
C130.5931 (2)−0.1660 (5)−0.0100 (2)0.0296 (9)
H130.6055−0.1790−0.05900.035*
N50.2959 (2)0.1066 (5)0.1716 (2)0.0387 (9)
O20.2564 (2)0.0783 (8)0.2184 (3)0.0874 (14)
N10.42843 (17)−0.2294 (4)0.16763 (18)0.0268 (7)
N20.55658 (17)−0.1214 (4)0.13726 (18)0.0262 (7)
N30.3723 (2)−0.4235 (5)−0.1083 (2)0.0359 (8)
H3A0.3307−0.4711−0.11560.043*
N40.4751 (2)−0.3210 (4)−0.13538 (18)0.0341 (8)
O10.35914 (17)0.1449 (5)0.19411 (19)0.0508 (9)
O30.2706 (2)0.0901 (7)0.1014 (2)0.0747 (12)
Pb0.50000.01345 (3)0.25000.02722 (9)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
C10.034 (3)0.047 (2)0.030 (2)−0.005 (2)0.013 (2)0.0003 (19)
C20.032 (3)0.068 (3)0.044 (3)−0.018 (2)0.013 (2)−0.006 (2)
C30.032 (3)0.055 (3)0.035 (3)−0.017 (2)0.003 (2)−0.008 (2)
C40.024 (2)0.0303 (19)0.026 (2)−0.0021 (16)0.0025 (17)0.0008 (16)
C50.022 (2)0.0264 (18)0.024 (2)0.0013 (16)0.0046 (17)0.0018 (15)
C60.024 (2)0.0247 (18)0.023 (2)0.0014 (15)0.0024 (17)0.0016 (15)
C70.025 (2)0.041 (2)0.031 (2)−0.0063 (19)0.0020 (19)−0.0061 (18)
C80.027 (3)0.046 (2)0.035 (3)−0.005 (2)0.010 (2)0.0001 (19)
C90.026 (2)0.032 (2)0.025 (2)−0.0007 (17)−0.0023 (18)−0.0004 (16)
C100.023 (2)0.0264 (19)0.025 (2)0.0021 (17)0.0033 (16)0.0028 (15)
C110.032 (2)0.0283 (19)0.021 (2)0.0018 (17)0.0034 (17)0.0013 (15)
C120.047 (3)0.043 (2)0.022 (2)0.000 (2)−0.003 (2)−0.0042 (18)
C130.030 (2)0.041 (2)0.020 (2)0.0006 (18)0.0111 (18)−0.0019 (16)
N50.035 (2)0.051 (2)0.030 (2)0.0030 (18)0.0059 (18)−0.0036 (16)
O20.048 (3)0.171 (4)0.049 (3)−0.009 (3)0.024 (2)0.008 (3)
N10.0184 (18)0.0355 (17)0.0273 (18)−0.0007 (14)0.0065 (14)0.0000 (13)
N20.0235 (19)0.0331 (17)0.0217 (17)−0.0045 (14)0.0031 (14)−0.0022 (13)
N30.031 (2)0.0431 (19)0.032 (2)−0.0073 (17)0.0007 (17)−0.0029 (16)
N40.041 (2)0.0406 (19)0.0202 (18)−0.0029 (17)0.0032 (16)−0.0022 (14)
O10.0265 (19)0.068 (2)0.053 (2)−0.0076 (16)−0.0049 (16)−0.0099 (17)
O30.054 (3)0.133 (4)0.034 (2)−0.016 (3)−0.0015 (19)−0.009 (2)
Pb0.02505 (15)0.03545 (14)0.02129 (13)0.0000.00458 (9)0.000

Geometric parameters (Å, °)

C1—N11.327 (5)C9—N31.376 (5)
C1—C21.387 (6)C10—C131.393 (6)
C1—H10.9300C10—C111.442 (5)
C2—C31.364 (6)C11—N41.390 (5)
C2—H20.9300C12—N41.323 (5)
C3—C41.396 (6)C12—N31.353 (6)
C3—H30.9300C12—H120.9300
C4—C51.413 (5)C13—H130.9300
C4—C91.423 (5)N5—O21.227 (5)
C5—N11.355 (5)N5—O31.235 (5)
C5—C61.453 (5)N5—O11.239 (5)
C6—N21.362 (5)Pb—N12.540 (3)
C6—C101.418 (5)Pb—N22.606 (3)
C7—N21.329 (5)Pb—O12.872 (5)
C7—C81.392 (6)N3—H3A0.8600
C7—H70.9300Pb—N1i2.540 (3)
C8—C131.365 (6)Pb—N2i2.606 (3)
C8—H80.9300O1—Pbi2.872 (5)
C9—C111.372 (6)
N1—C1—C2123.5 (4)C9—C11—N4111.8 (4)
N1—C1—H1118.3C9—C11—C10121.0 (3)
C2—C1—H1118.3N4—C11—C10127.1 (4)
C3—C2—C1119.0 (4)N4—C12—N3113.9 (4)
C3—C2—H2120.5N4—C12—H12123.0
C1—C2—H2120.5N3—C12—H12123.0
C2—C3—C4119.4 (4)C8—C13—C10118.7 (4)
C2—C3—H3120.3C8—C13—H13120.6
C4—C3—H3120.3C10—C13—H13120.6
C3—C4—C5118.3 (4)O2—N5—O3117.3 (4)
C3—C4—C9125.0 (4)O2—N5—O1121.2 (4)
C5—C4—C9116.6 (4)O3—N5—O1121.4 (4)
N1—C5—C4121.4 (3)C1—N1—C5118.4 (3)
N1—C5—C6118.0 (3)C1—N1—Pb121.2 (3)
C4—C5—C6120.7 (3)C5—N1—Pb117.9 (2)
N2—C6—C10121.1 (4)C7—N2—C6118.5 (3)
N2—C6—C5118.0 (3)C7—N2—Pb122.8 (3)
C10—C6—C5120.9 (3)C6—N2—Pb115.0 (2)
N2—C7—C8122.9 (4)C12—N3—C9106.7 (4)
N2—C7—H7118.6C12—N3—H3A126.7
C8—C7—H7118.6C9—N3—H3A126.7
C13—C8—C7119.9 (4)C12—N4—C11102.6 (4)
C13—C8—H8120.1N1—Pb—N1i90.01 (14)
C7—C8—H8120.1N1—Pb—N2i84.09 (10)
C11—C9—N3105.0 (3)N1i—Pb—N2i64.03 (10)
C11—C9—C4123.6 (4)N1—Pb—N264.03 (10)
N3—C9—C4131.4 (4)N1i—Pb—N284.09 (10)
C13—C10—C6118.9 (4)N2i—Pb—N2135.02 (14)
C13—C10—C11124.2 (3)O1—Pb—N170.65 (10)
C6—C10—C11116.9 (4)O1—Pb—N2111.75 (10)
N1—C1—C2—C3−3.2 (7)C11—C10—C13—C8179.3 (4)
C1—C2—C3—C41.2 (7)C2—C1—N1—C51.6 (6)
C2—C3—C4—C52.1 (7)C2—C1—N1—Pb163.1 (4)
C2—C3—C4—C9−176.7 (4)C4—C5—N1—C12.0 (5)
C3—C4—C5—N1−3.8 (6)C6—C5—N1—C1−178.4 (3)
C9—C4—C5—N1175.1 (3)C4—C5—N1—Pb−160.2 (3)
C3—C4—C5—C6176.6 (4)C6—C5—N1—Pb19.5 (4)
C9—C4—C5—C6−4.5 (5)C8—C7—N2—C6−1.5 (6)
N1—C5—C6—N22.6 (5)C8—C7—N2—Pb−158.6 (3)
C4—C5—C6—N2−177.7 (3)C10—C6—N2—C7−0.9 (5)
N1—C5—C6—C10−177.6 (3)C5—C6—N2—C7178.9 (3)
C4—C5—C6—C102.0 (5)C10—C6—N2—Pb157.9 (3)
N2—C7—C8—C133.2 (7)C5—C6—N2—Pb−22.3 (4)
C3—C4—C9—C11−178.6 (4)N4—C12—N3—C90.6 (5)
C5—C4—C9—C112.6 (6)C11—C9—N3—C12−0.5 (4)
C3—C4—C9—N34.8 (7)C4—C9—N3—C12176.5 (4)
C5—C4—C9—N3−173.9 (4)N3—C12—N4—C11−0.4 (5)
N2—C6—C10—C131.6 (5)C9—C11—N4—C120.1 (4)
C5—C6—C10—C13−178.1 (3)C10—C11—N4—C12−178.9 (4)
N2—C6—C10—C11−177.7 (3)C1—N1—Pb—N1i93.6 (3)
C5—C6—C10—C112.5 (5)C5—N1—Pb—N1i−104.8 (3)
N3—C9—C11—N40.2 (4)C1—N1—Pb—N2i29.7 (3)
C4—C9—C11—N4−177.1 (4)C5—N1—Pb—N2i−168.7 (3)
N3—C9—C11—C10179.3 (3)C1—N1—Pb—N2177.0 (3)
C4—C9—C11—C102.0 (6)C5—N1—Pb—N2−21.4 (2)
C13—C10—C11—C9176.2 (4)C7—N2—Pb—N1179.9 (3)
C6—C10—C11—C9−4.5 (5)C6—N2—Pb—N122.2 (2)
C13—C10—C11—N4−4.9 (6)C7—N2—Pb—N1i−87.2 (3)
C6—C10—C11—N4174.4 (4)C6—N2—Pb—N1i115.1 (3)
C7—C8—C13—C10−2.3 (6)C7—N2—Pb—N2i−130.6 (3)
C6—C10—C13—C80.0 (6)C6—N2—Pb—N2i71.7 (2)

Symmetry codes: (i) −x+1, y, −z+1/2.

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N3—H3A···O3ii0.862.193.030 (6)165
N3—H3A···O2ii0.862.353.059 (6)140

Symmetry codes: (ii) −x+1/2, −y−1/2, −z.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HB2871).

References

  • Bruker (2002). SMART, SAINT and SADABS Bruker AXS Inc., Madison, Wisconsin, USA.
  • Che, G.-B., Liu, C.-B., Liu, B., Wang, Q.-W. & Xu, Z.-L. (2008). CrystEngComm, 10, 184–191.
  • Che, G.-B., Xu, Z.-L. & Liu, C.-B. (2006). Acta Cryst. E62, m1695–m1696.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Steck, E. A. & Day, A. R. (1943). J. Am. Chem. Soc 65, 452–456.
  • Thomas, C., Jan, R., Peter, N., Kris, D., Kristof, V. H., Luc, V. M., Shengbin, L., Steven, D. F., Daniel, G., Bertrand, D. & Koen, B. (2008). Chem. Mater.20, 1278–1291.
  • Xu, Z.-L., Li, X.-Y., Che, G.-B., Liu, C.-B. & Wang, Q.-W. (2008). Chin. J. Struct. Chem.27, 593–597.

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