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Acta Crystallogr Sect E Struct Rep Online. 2010 October 1; 66(Pt 10): m1259.
Published online 2010 September 15. doi:  10.1107/S1600536810036263
PMCID: PMC2983224

1-Amino­pyridinium triiodidoplumbate(II)

Abstract

The title complex, (C5H7N2)[PbI3], consists of a 1-amino­pyridinium cation, disordered about a mirror plane, and a [PbI3] anion. The Pb2+ ion (site symmetry An external file that holds a picture, illustration, etc.
Object name is e-66-m1259-efi1.jpg) is surrounded by six I atoms in a slightly distorted octa­hedral coordination. The PbI6 octa­hedra share faces, building up 1[PbI6/2] chains running along [010]. The cations are situated between the chains. Coulombic attractions and van der Waals inter­actions between the inorganic and organic components are mainly responsible for the cohesion of the structure.

Related literature

For background to hybrid materials, see: Rogow et al. (2010 [triangle]); Thirumurugan & Rao (2008 [triangle]). For structures with lead halide building blocks, see: Li et al. (2008 [triangle]); Zhang et al. (2008 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-66-m1259-scheme1.jpg

Experimental

Crystal data

  • (C5H7N2)[PbI3]
  • M r = 683.03
  • Orthorhombic, An external file that holds a picture, illustration, etc.
Object name is e-66-m1259-efi2.jpg
  • a = 15.0417 (19) Å
  • b = 8.1316 (10) Å
  • c = 10.5625 (14) Å
  • V = 1291.9 (3) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 20.18 mm−1
  • T = 296 K
  • 0.6 × 0.2 × 0.1 mm

Data collection

  • Bruker SMART CCD area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2000 [triangle]) T min = 0.011, T max = 0.133
  • 10792 measured reflections
  • 1607 independent reflections
  • 1263 reflections with I > 2σ(I)
  • R int = 0.036

Refinement

  • R[F 2 > 2σ(F 2)] = 0.025
  • wR(F 2) = 0.056
  • S = 1.11
  • 1607 reflections
  • 61 parameters
  • 1 restraint
  • H-atom parameters constrained
  • Δρmax = 0.86 e Å−3
  • Δρmin = −1.05 e Å−3

Data collection: SMART (Bruker, 2000 [triangle]); cell refinement: SAINT (Bruker, 2000 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Table 1
Selected bond lengths (Å)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810036263/wm2395sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810036263/wm2395Isup2.hkl

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

Acknowledgments

The authors thank the Science and Technology Department of Jiangsu Province for financial support (grant No 10774076).

supplementary crystallographic information

Comment

Inorganic metal-halide building-blocks have received special attention with respect to the construction of inorganic-organic hybrid materials (Rogow et al., 2010; Thirumurugan et al., 2008). Among these materials octahedral building blocks of lead halides are frequently found and numerous crystal structures, from one-dimensional chains to three-dimensional frameworks (Li et al., 2008; Zhang et al., 2008), were observed. Herein we report the crystal structure of the title compound, (C5H7N2)[PbI3] (I).

Compound (I) crystallizes with one [PbI3]- anion and one 1-aminopyridinium cation in the asymmetric unit (Fig. 1). The cation is disordered about a mirror plane. The Pb2+ cation is coordinated by six iodide anions in a slightly distorted octahedral coordination geometry. The PbI6 octahedra share faces, resulting in anionic chains running along [010]. As show in Fig. 2., the straight inorganic chains are embedded in cationic stacks. Besides Coulomb attractions, only weak van der Waals interactions between the inorganic and organic components exist.

Experimental

A mixture of PbI2 (922 mg, 2.0 mmol) and 1-aminopyridinium iodide (190 mg, 2.0 mmol) in a molar ratio of 1:1 in DMF was slowly evaporated to produce orange needle-shaped crystals.

Refinement

The H atoms were placed in geometrically idealized positions and refined as riding atoms, with Uiso(H) = 1.2Ueq(C). The cation is disordered about a mirror plane. Atoms C3 and N1 occupy the same site with an occupation factor of 50%. The respective —NH2 group and the H atom show likewise half-occupation.

Figures

Fig. 1.
Part of the structure of (I), showing the atom-numbering scheme and displacement ellipsoids at the 30% probability level. Atom C3 and N1 are positionally disordered. H atoms have been omitted for clyrity. [Symmetry code: A x, 0.5 - y, z.]
Fig. 2.
The alignment of inorganic and organic components in the crystals of l along [010].

Crystal data

(C5H7N2)[PbI3]Z = 4
Mr = 683.03F(000) = 1168
Orthorhombic, PnmaDx = 3.512 Mg m3
Hall symbol: -P 2ac 2nMo Kα radiation, λ = 0.71073 Å
a = 15.0417 (19) ŵ = 20.18 mm1
b = 8.1316 (10) ÅT = 296 K
c = 10.5625 (14) ÅNeedle, orange
V = 1291.9 (3) Å30.6 × 0.2 × 0.1 mm

Data collection

Bruker SMART CCD area-detector diffractometer1607 independent reflections
Radiation source: fine-focus sealed tube1263 reflections with I > 2σ(I)
graphiteRint = 0.036
phi and ω scansθmax = 27.6°, θmin = 2.4°
Absorption correction: multi-scan (SADABS; Bruker, 2000)h = −19→19
Tmin = 0.011, Tmax = 0.133k = −10→10
10792 measured reflectionsl = −13→13

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)] = 0.025Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.056H-atom parameters constrained
S = 1.11w = 1/[σ2(Fo2) + (0.016P)2 + 2.8133P] where P = (Fo2 + 2Fc2)/3
1607 reflections(Δ/σ)max = 0.001
61 parametersΔρmax = 0.86 e Å3
1 restraintΔρmin = −1.05 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*/UeqOcc. (<1)
Pb10.50000.50000.50000.05028 (11)
I10.66188 (4)0.25000.44218 (7)0.06995 (19)
I20.45861 (4)0.25000.73162 (5)0.05961 (16)
I30.38187 (5)0.25000.33215 (6)0.06837 (19)
C10.0996 (6)0.1682 (10)0.4247 (8)0.100 (3)
H10.07080.11000.36090.120*
C20.1419 (7)0.0883 (12)0.5186 (9)0.103 (3)
H20.1424−0.02610.51970.123*
C30.1824 (5)0.1708 (11)0.6087 (7)0.100 (3)0.50
H30.21140.11420.67310.120*0.50
N10.1824 (5)0.1708 (11)0.6087 (7)0.100 (3)0.50
N20.2230 (10)0.132 (2)0.7177 (16)0.121 (5)0.50
H2A0.24150.20910.76720.146*0.50
H2B0.23070.03100.73820.146*0.50

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Pb10.0585 (2)0.03787 (16)0.05448 (19)0.00017 (13)0.00130 (15)−0.00097 (14)
I10.0549 (3)0.0611 (4)0.0938 (5)0.0000.0189 (3)0.000
I20.0727 (4)0.0575 (3)0.0486 (3)0.0000.0023 (3)0.000
I30.0753 (4)0.0603 (4)0.0696 (4)0.000−0.0268 (3)0.000
C10.120 (7)0.100 (6)0.081 (5)−0.001 (5)−0.015 (5)−0.010 (5)
C20.104 (7)0.089 (6)0.114 (8)−0.005 (5)0.008 (6)0.004 (6)
C30.064 (4)0.162 (9)0.074 (5)0.010 (4)0.010 (3)0.026 (5)
N10.064 (4)0.162 (9)0.074 (5)0.010 (4)0.010 (3)0.026 (5)
N20.111 (11)0.121 (12)0.133 (13)0.004 (10)−0.004 (11)0.029 (11)

Geometric parameters (Å, °)

Pb1—I3i3.2301 (5)C1—C1iii1.331 (16)
Pb1—I33.2301 (5)C1—C21.345 (12)
Pb1—I13.2303 (5)C1—H10.9300
Pb1—I1i3.2303 (5)C2—C31.315 (11)
Pb1—I23.2412 (5)C2—H20.9300
Pb1—I2i3.2412 (5)C3—C3iii1.288 (18)
I1—Pb1ii3.2303 (5)C3—H30.9300
I2—Pb1ii3.2412 (5)N2—H2A0.8600
I3—Pb1ii3.2301 (5)N2—H2B0.8600
I3i—Pb1—I3180.0I2—Pb1—I2i180.0
I3i—Pb1—I194.886 (17)Pb1ii—I1—Pb178.000 (17)
I3—Pb1—I185.114 (17)Pb1ii—I2—Pb177.688 (16)
I3i—Pb1—I1i85.114 (17)Pb1—I3—Pb1ii78.007 (16)
I3—Pb1—I1i94.886 (17)C1iii—C1—C2118.9 (6)
I1—Pb1—I1i180.0C1iii—C1—H1120.6
I3i—Pb1—I294.940 (16)C2—C1—H1120.6
I3—Pb1—I285.060 (16)C3—C2—C1120.4 (9)
I1—Pb1—I283.844 (15)C3—C2—H2119.8
I1i—Pb1—I296.156 (15)C1—C2—H2119.8
I3i—Pb1—I2i85.060 (16)C3iii—C3—C2120.7 (6)
I3—Pb1—I2i94.940 (16)C3iii—C3—H3119.7
I1—Pb1—I2i96.156 (15)C2—C3—H3119.7
I1i—Pb1—I2i83.844 (15)H2A—N2—H2B120.0

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: WM2395).

References

  • Bruker (2000). SMART, SAINT and SADABS Bruker AXS Inc., Madison, Wisconsin, USA.
  • Li, Y., Zheng, G., Lin, C. & Lin, J. (2008). Cryst. Growth Des.8, 1990–1996.
  • Rogow, D. L., Russell, M. P., Wayman, L. M., Swanson, C. H., Oliver, A. G. & Oliver, S. R. J. (2010). Cryst. Growth Des.10, 823–829.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Thirumurugan, A. & Rao, C. N. R. (2008). Cryst. Growth Des.8, 1640–1644.
  • Zhang, Z. J., Xiang, S. C. & Guo, G. C. (2008). Angew. Chem. Int. Ed.47, 4149–4152. [PubMed]

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography