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Acta Crystallogr Sect E Struct Rep Online. 2010 June 1; 66(Pt 6): m659.
Published online 2010 May 15. doi:  10.1107/S1600536810016818
PMCID: PMC2979563

Poly[1,4-bis­(ammonio­meth­yl)cyclo­hexane [di-μ-chlorido-dichloridoplumbate(II)]]

Abstract

The title compound, {(C8H20N2)[PbCl4]}n, crystallizes as an layered inorganic–organic hybrid perovskite-type structure. Corner-sharing PbCl6 octa­hedra extend parallel to the ac plane. Adjacent layers are staggered relative to one another, with diammonium cations separating these layers. The cations exhibit An external file that holds a picture, illustration, etc.
Object name is e-66-0m659-efi1.jpg symmetry and inter­act with the inorganic sheets via N—H(...)Cl hydrogen bonding in the right-angled halogen sub-type of the terminal halide hydrogen-bonding motif.

Related literature

Similar structures have been reported by Billing & Lemmerer (2006 [triangle]) and Dobrzycki & Woźniak (2009 [triangle]). Structure–properties relation experiments have been performed by Mitzi et al. (2001 [triangle]). For hydrogen-bonding nomenclature for inorganic–organic hybrids, see: Mitzi (1999 [triangle]). For the bromido- and iodidoplumbate(II) analogues of the title compound, see: Rayner & Billing (2010a [triangle],b [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-66-0m659-scheme1.jpg

Experimental

Crystal data

  • (C8H20N2)[PbCl4]
  • M r = 493.25
  • Orthorhombic, An external file that holds a picture, illustration, etc.
Object name is e-66-0m659-efi2.jpg
  • a = 7.7990 (2) Å
  • b = 24.0666 (6) Å
  • c = 7.9348 (2) Å
  • V = 1489.33 (7) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 12.02 mm−1
  • T = 173 K
  • 0.54 × 0.41 × 0.04 mm

Data collection

  • Bruker APEXII CCD area-detector diffractometer
  • Absorption correction: integration (XPREP; Bruker, 2005 [triangle]) T min = 0.032, T max = 0.685
  • 13290 measured reflections
  • 1850 independent reflections
  • 1654 reflections with I > 2σ(I)
  • R int = 0.049

Refinement

  • R[F 2 > 2σ(F 2)] = 0.031
  • wR(F 2) = 0.067
  • S = 1.16
  • 1850 reflections
  • 73 parameters
  • H-atom parameters constrained
  • Δρmax = 1.47 e Å−3
  • Δρmin = −3.53 e Å−3

Data collection: APEX2 (Bruker, 2005 [triangle]); cell refinement: SAINT (Bruker, 2005 [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: ORTEP-3 for Windows (Farrugia, 1997 [triangle]) and DIAMOND (Brandenburg, 1999 [triangle]); software used to prepare material for publication: WinGX (Farrugia, 1999 [triangle]) and PLATON (Spek, 2009 [triangle]).

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

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810016818/wm2339sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810016818/wm2339Isup2.hkl

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

Acknowledgments

The University of the Witwatersrand and the National Research Fund (GUN: 2069064) are acknowledged for the funding and infrastructure required to perform the experiment.

supplementary crystallographic information

Comment

Inorganic-organic hybrid compounds have been investigated for their semiconduting and electronic properties (Mitzi et al., 2001). For literature regarding hydrogen bonding nomenclature for inorganic-organic hybrids, see: Mitzi (1999). The title structure (Fig. 1) is one of three 2-dimensional hybrid structures that we have synthesized encorporating this diammonium cation. The structures differ in terms of their halogen ligands, which include chloride (presented here), bromide (Rayner & Billing, 2010a) and iodide (Rayner & Billing, 2010b). The bromide and iodide hybrids crystallize in the monoclinic system with space group P21/c while the chloride hybrid crystallizes in the orthorhombic, Pnma system.

In the title structure the lead-chloride octahedra from alternate layers that are staggered relative to one another (Fig. 2). In all three structures only the trans form of the cation has been observed, giving the cation 1 symmetry (Fig. 3). The ammonium cations interact with the inorganic layer via N—H···X (X = Br, I and Cl) hydrogen bonding in the right-angled halogen subtype of the terminal halide hydrogen bonding motif (Mitzi, 1999). Similar inorganic-organic hybrid structures have been reported (Billing & Lemmerer, 2006; Dobrzycki & Woźniak, 2009), however very few hybrids encorporating diammonium cations have been synthesized.

Experimental

A mixture of 0.052 g (0.19 mmol) PbCl2 and 0.030 g (0.21 mmol) 1,4-bis-(aminomethyl)-cyclohexane (mixture of isomers) was dissolved in 5 ml HCl at 383 K and slow cooled at a rate of 0.069 K/min to yield colourless, plate-shaped single crystals suitable for X-ray analysis.

Refinement

The H atoms on the diammonium cation were refined using a riding-model, with C—H = 0.99 Å, N—H = 0.91 Å and with Uiso(H)=1.2Ueq(C) or 1.5Ueq(N). The highest residual electron density peak (1.47 e Å-3) was 0.822Å from Pb1.

Figures

Fig. 1.
The asymmetric unit of the title compound with atom labels. Displacement ellipsoids were drawn at the 50% probability level. Symmetry codes: (a) -1/2+x, 1/2-y, 3/2-z (b) 1/2+x, 1/2-y, 1/2-z (c) x, 1/2-y, z (d) 1-x, -y, -z.
Fig. 2.
Packing diagram viewed along the b axis. Hydrogen bonds are drawn as dashed red lines.
Fig. 3.
Packing diagram viewed along the c axis. Hydrogen bonds are drawn as dashed red lines.

Crystal data

(C8H20N2)[PbCl4]F(000) = 928
Mr = 493.25Dx = 2.200 Mg m3
Orthorhombic, PnmaMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2nCell parameters from 6650 reflections
a = 7.7990 (2) Åθ = 2.7–28.3°
b = 24.0666 (6) ŵ = 12.02 mm1
c = 7.9348 (2) ÅT = 173 K
V = 1489.33 (7) Å3Plate, colourless
Z = 40.54 × 0.41 × 0.04 mm

Data collection

Bruker APEXII CCD area-detector diffractometer1850 independent reflections
Radiation source: fine-focus sealed tube1654 reflections with I > 2σ(I)
graphiteRint = 0.049
[var phi] and ω scansθmax = 28.0°, θmin = 1.7°
Absorption correction: integration (XPREP; Bruker, 2005)h = −10→10
Tmin = 0.032, Tmax = 0.685k = −31→31
13290 measured reflectionsl = −10→10

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) = 0.067H-atom parameters constrained
S = 1.16w = 1/[σ2(Fo2) + (0.003P)2 + 19.9694P] where P = (Fo2 + 2Fc2)/3
1850 reflections(Δ/σ)max = 0.007
73 parametersΔρmax = 1.47 e Å3
0 restraintsΔρmin = −3.53 e Å3

Special details

Experimental. Numerical intergration absorption corrections based on indexed crystal faces were applied using the XPREP routine (Bruker, 2005)
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 > 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
C10.5490 (8)0.6188 (2)0.9551 (8)0.0201 (12)
H1A0.61350.61590.84800.024*
H1B0.44290.64010.93260.024*
C20.5016 (8)0.5612 (2)1.0147 (8)0.0201 (12)
H20.42560.56541.11540.024*
C30.3984 (9)0.5318 (3)0.8783 (8)0.0256 (13)
H3A0.46830.52930.77440.031*
H3B0.29480.55400.85210.031*
C40.6555 (8)0.5265 (3)1.0676 (8)0.0239 (13)
H4A0.71500.54511.16230.029*
H4B0.73690.52380.97230.029*
N10.6553 (7)0.6496 (2)1.0812 (7)0.0213 (11)
H1C0.68160.68381.04000.032*
H1D0.75370.63031.10130.032*
H1E0.59540.65321.17890.032*
Cl10.05791 (19)0.63163 (6)1.02923 (19)0.0229 (3)
Cl2−0.1125 (3)0.75001.2974 (2)0.0194 (4)
Cl30.2609 (3)0.75000.6719 (3)0.0238 (4)
Pb10.08434 (4)0.75000.99093 (4)0.01374 (9)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
C10.019 (3)0.018 (3)0.023 (3)0.002 (2)−0.002 (2)0.001 (2)
C20.020 (3)0.021 (3)0.019 (3)0.000 (2)−0.003 (2)−0.001 (3)
C30.031 (4)0.020 (3)0.026 (3)−0.004 (3)−0.009 (3)0.000 (2)
C40.023 (3)0.021 (3)0.028 (3)−0.004 (3)−0.005 (3)−0.001 (3)
N10.023 (3)0.018 (2)0.023 (2)−0.003 (2)0.002 (2)−0.003 (2)
Cl10.0202 (7)0.0229 (7)0.0257 (7)0.0021 (5)0.0001 (6)−0.0037 (6)
Cl20.0170 (10)0.0221 (9)0.0192 (9)0.0000.0049 (7)0.000
Cl30.0222 (10)0.0297 (11)0.0197 (9)0.0000.0056 (8)0.000
Pb10.01269 (14)0.01657 (14)0.01196 (13)0.0000.00002 (12)0.000

Geometric parameters (Å, °)

C1—N11.495 (8)C4—H4B0.9900
C1—C21.512 (8)N1—H1C0.9100
C1—H1A0.9900N1—H1D0.9100
C1—H1B0.9900N1—H1E0.9100
C2—C31.523 (8)Cl1—Pb12.8723 (15)
C2—C41.521 (9)Cl2—Pb12.8759 (19)
C2—H21.0000Cl2—Pb1ii2.9002 (19)
C3—C4i1.525 (9)Cl3—Pb1iii2.834 (2)
C3—H3A0.9900Cl3—Pb12.882 (2)
C3—H3B0.9900Pb1—Cl3iv2.834 (2)
C4—C3i1.525 (9)Pb1—Cl1v2.8723 (15)
C4—H4A0.9900Pb1—Cl2vi2.900 (2)
N1—C1—C2112.4 (5)C1—N1—H1C109.5
N1—C1—H1A109.1C1—N1—H1D109.5
C2—C1—H1A109.1H1C—N1—H1D109.5
N1—C1—H1B109.1C1—N1—H1E109.5
C2—C1—H1B109.1H1C—N1—H1E109.5
H1A—C1—H1B107.9H1D—N1—H1E109.5
C1—C2—C3109.5 (5)Pb1—Cl2—Pb1ii157.64 (8)
C1—C2—C4113.4 (5)Pb1iii—Cl3—Pb1145.68 (9)
C3—C2—C4111.0 (5)Cl3iv—Pb1—Cl1v89.10 (3)
C1—C2—H2107.6Cl3iv—Pb1—Cl189.10 (3)
C3—C2—H2107.6Cl1v—Pb1—Cl1165.31 (6)
C4—C2—H2107.6Cl3iv—Pb1—Cl284.87 (6)
C2—C3—C4i111.8 (5)Cl1v—Pb1—Cl282.66 (3)
C2—C3—H3A109.2Cl1—Pb1—Cl282.66 (3)
C4i—C3—H3A109.2Cl3iv—Pb1—Cl391.42 (3)
C2—C3—H3B109.2Cl1v—Pb1—Cl397.31 (3)
C4i—C3—H3B109.2Cl1—Pb1—Cl397.31 (3)
H3A—C3—H3B107.9Cl2—Pb1—Cl3176.29 (6)
C2—C4—C3i111.4 (5)Cl3iv—Pb1—Cl2vi171.75 (6)
C2—C4—H4A109.3Cl1v—Pb1—Cl2vi89.84 (3)
C3i—C4—H4A109.3Cl1—Pb1—Cl2vi89.84 (3)
C2—C4—H4B109.3Cl2—Pb1—Cl2vi86.875 (17)
C3i—C4—H4B109.3Cl3—Pb1—Cl2vi96.83 (6)
H4A—C4—H4B108.0
N1—C1—C2—C3−178.3 (5)Pb1ii—Cl2—Pb1—Cl1v89.76 (3)
N1—C1—C2—C4−53.7 (7)Pb1ii—Cl2—Pb1—Cl1−89.76 (3)
C1—C2—C3—C4i−179.2 (5)Pb1ii—Cl2—Pb1—Cl2vi180.0
C4—C2—C3—C4i54.9 (8)Pb1iii—Cl3—Pb1—Cl3iv180.0
C1—C2—C4—C3i−178.3 (5)Pb1iii—Cl3—Pb1—Cl1v90.72 (3)
C3—C2—C4—C3i−54.6 (8)Pb1iii—Cl3—Pb1—Cl1−90.72 (3)
Pb1ii—Cl2—Pb1—Cl3iv0.0Pb1iii—Cl3—Pb1—Cl2vi0.0

Symmetry codes: (i) −x+1, −y+1, −z+2; (ii) x−1/2, y, −z+5/2; (iii) x+1/2, y, −z+3/2; (iv) x−1/2, y, −z+3/2; (v) x, −y+3/2, z; (vi) x+1/2, y, −z+5/2.

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N1—H1C···Cl3iii0.912.403.249 (5)156
N1—H1D···Cl1vii0.912.443.196 (6)141
N1—H1E···Cl1vi0.912.393.212 (5)150
N1—H1E···Cl2vi0.912.843.337 (5)115

Symmetry codes: (iii) x+1/2, y, −z+3/2; (vii) x+1, y, z; (vi) x+1/2, y, −z+5/2.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: WM2339).

References

  • Billing, D. G. & Lemmerer, A. (2006). CrystEngComm, 8, 686–695.
  • Brandenburg, K. (1999). DIAMOND Crystal Impact GbR, Bonn, Germany.
  • Bruker (2005). APEX2, SAINT and XPREP Bruker AXS Inc., Madison, Wisconsin, USA.
  • Dobrzycki, L. & Woźniak, K. (2009). J. Mol. Struct.921, 18–33.
  • Farrugia, L. J. (1997). J. Appl. Cryst.30, 565.
  • Farrugia, L. J. (1999). J. Appl. Cryst.32, 837–838.
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  • Mitzi, D. B., Chondroudis, K. & Kagan, C. R. (2001). IBM J. Res. Dev.45, 29–33.
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  • Rayner, M. K. & Billing, D. G. (2010b). Acta Cryst. E66, m660. [PMC free article] [PubMed]
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Spek, A. L. (2009). Acta Cryst. D65, 148–155. [PMC free article] [PubMed]

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