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

Experimental

Crystal data

• (C₈H₂₀N₂)[PbCl₄]

• M _r = 493.25

• Orthorhombic,

• a = 7.7990 (2) Å

• b = 24.0666 (6) Å

• c = 7.9348 (2) Å

• V = 1489.33 (7) ų

• 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 ▶) 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

• Δρ_max = 1.47 e Å⁻³

• Δρ_min = −3.53 e Å⁻³

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: SAINT (Bruker, 2005 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶) and DIAMOND (Brandenburg, 1999 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶) and PLATON (Spek, 2009 ▶).

Supplementary Material

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

Table 1. Selected bond lengths (Å).

Pb1—Cl3i	2.834 (2)
Pb1—Cl1ii	2.8723 (15)
Pb1—Cl2iii	2.900 (2)

Symmetry codes: (i) ; (ii) ; (iii) .

Table 2. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1C⋯Cl3iv	0.91	2.40	3.249 (5)	156
N1—H1D⋯Cl1v	0.91	2.44	3.196 (6)	141
N1—H1E⋯Cl1iii	0.91	2.39	3.212 (5)	150
N1—H1E⋯Cl2iii	0.91	2.84	3.337 (5)	115

Symmetry codes: (iii) ; (iv) ; (v) .

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 U_iso(H)=1.2U_eq(C) or 1.5U_eq(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 = 493.25	Dx = 2.200 Mg m−3
Orthorhombic, Pnma	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2n	Cell parameters from 6650 reflections
a = 7.7990 (2) Å	θ = 2.7–28.3°
b = 24.0666 (6) Å	µ = 12.02 mm−1
c = 7.9348 (2) Å	T = 173 K
V = 1489.33 (7) Å3	Plate, colourless
Z = 4	0.54 × 0.41 × 0.04 mm

Data collection

Bruker APEXII CCD area-detector diffractometer	1850 independent reflections
Radiation source: fine-focus sealed tube	1654 reflections with I > 2σ(I)
graphite	Rint = 0.049
φ and ω scans	θmax = 28.0°, θmin = 1.7°
Absorption correction: integration (XPREP; Bruker, 2005)	h = −10→10
Tmin = 0.032, Tmax = 0.685	k = −31→31
13290 measured reflections	l = −10→10

Refinement

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

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 (Ų)

	x	y	z	Uiso*/Ueq
C1	0.5490 (8)	0.6188 (2)	0.9551 (8)	0.0201 (12)
H1A	0.6135	0.6159	0.8480	0.024*
H1B	0.4429	0.6401	0.9326	0.024*
C2	0.5016 (8)	0.5612 (2)	1.0147 (8)	0.0201 (12)
H2	0.4256	0.5654	1.1154	0.024*
C3	0.3984 (9)	0.5318 (3)	0.8783 (8)	0.0256 (13)
H3A	0.4683	0.5293	0.7744	0.031*
H3B	0.2948	0.5540	0.8521	0.031*
C4	0.6555 (8)	0.5265 (3)	1.0676 (8)	0.0239 (13)
H4A	0.7150	0.5451	1.1623	0.029*
H4B	0.7369	0.5238	0.9723	0.029*
N1	0.6553 (7)	0.6496 (2)	1.0812 (7)	0.0213 (11)
H1C	0.6816	0.6838	1.0400	0.032*
H1D	0.7537	0.6303	1.1013	0.032*
H1E	0.5954	0.6532	1.1789	0.032*
Cl1	0.05791 (19)	0.63163 (6)	1.02923 (19)	0.0229 (3)
Cl2	−0.1125 (3)	0.7500	1.2974 (2)	0.0194 (4)
Cl3	0.2609 (3)	0.7500	0.6719 (3)	0.0238 (4)
Pb1	0.08434 (4)	0.7500	0.99093 (4)	0.01374 (9)

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
C1	0.019 (3)	0.018 (3)	0.023 (3)	0.002 (2)	−0.002 (2)	0.001 (2)
C2	0.020 (3)	0.021 (3)	0.019 (3)	0.000 (2)	−0.003 (2)	−0.001 (3)
C3	0.031 (4)	0.020 (3)	0.026 (3)	−0.004 (3)	−0.009 (3)	0.000 (2)
C4	0.023 (3)	0.021 (3)	0.028 (3)	−0.004 (3)	−0.005 (3)	−0.001 (3)
N1	0.023 (3)	0.018 (2)	0.023 (2)	−0.003 (2)	0.002 (2)	−0.003 (2)
Cl1	0.0202 (7)	0.0229 (7)	0.0257 (7)	0.0021 (5)	0.0001 (6)	−0.0037 (6)
Cl2	0.0170 (10)	0.0221 (9)	0.0192 (9)	0.000	0.0049 (7)	0.000
Cl3	0.0222 (10)	0.0297 (11)	0.0197 (9)	0.000	0.0056 (8)	0.000
Pb1	0.01269 (14)	0.01657 (14)	0.01196 (13)	0.000	0.00002 (12)	0.000

Geometric parameters (Å, °)

C1—N1	1.495 (8)	C4—H4B	0.9900
C1—C2	1.512 (8)	N1—H1C	0.9100
C1—H1A	0.9900	N1—H1D	0.9100
C1—H1B	0.9900	N1—H1E	0.9100
C2—C3	1.523 (8)	Cl1—Pb1	2.8723 (15)
C2—C4	1.521 (9)	Cl2—Pb1	2.8759 (19)
C2—H2	1.0000	Cl2—Pb1ii	2.9002 (19)
C3—C4i	1.525 (9)	Cl3—Pb1iii	2.834 (2)
C3—H3A	0.9900	Cl3—Pb1	2.882 (2)
C3—H3B	0.9900	Pb1—Cl3iv	2.834 (2)
C4—C3i	1.525 (9)	Pb1—Cl1v	2.8723 (15)
C4—H4A	0.9900	Pb1—Cl2vi	2.900 (2)
N1—C1—C2	112.4 (5)	C1—N1—H1C	109.5
N1—C1—H1A	109.1	C1—N1—H1D	109.5
C2—C1—H1A	109.1	H1C—N1—H1D	109.5
N1—C1—H1B	109.1	C1—N1—H1E	109.5
C2—C1—H1B	109.1	H1C—N1—H1E	109.5
H1A—C1—H1B	107.9	H1D—N1—H1E	109.5
C1—C2—C3	109.5 (5)	Pb1—Cl2—Pb1ii	157.64 (8)
C1—C2—C4	113.4 (5)	Pb1iii—Cl3—Pb1	145.68 (9)
C3—C2—C4	111.0 (5)	Cl3iv—Pb1—Cl1v	89.10 (3)
C1—C2—H2	107.6	Cl3iv—Pb1—Cl1	89.10 (3)
C3—C2—H2	107.6	Cl1v—Pb1—Cl1	165.31 (6)
C4—C2—H2	107.6	Cl3iv—Pb1—Cl2	84.87 (6)
C2—C3—C4i	111.8 (5)	Cl1v—Pb1—Cl2	82.66 (3)
C2—C3—H3A	109.2	Cl1—Pb1—Cl2	82.66 (3)
C4i—C3—H3A	109.2	Cl3iv—Pb1—Cl3	91.42 (3)
C2—C3—H3B	109.2	Cl1v—Pb1—Cl3	97.31 (3)
C4i—C3—H3B	109.2	Cl1—Pb1—Cl3	97.31 (3)
H3A—C3—H3B	107.9	Cl2—Pb1—Cl3	176.29 (6)
C2—C4—C3i	111.4 (5)	Cl3iv—Pb1—Cl2vi	171.75 (6)
C2—C4—H4A	109.3	Cl1v—Pb1—Cl2vi	89.84 (3)
C3i—C4—H4A	109.3	Cl1—Pb1—Cl2vi	89.84 (3)
C2—C4—H4B	109.3	Cl2—Pb1—Cl2vi	86.875 (17)
C3i—C4—H4B	109.3	Cl3—Pb1—Cl2vi	96.83 (6)
H4A—C4—H4B	108.0
N1—C1—C2—C3	−178.3 (5)	Pb1ii—Cl2—Pb1—Cl1v	89.76 (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—Cl2vi	180.0
C4—C2—C3—C4i	54.9 (8)	Pb1iii—Cl3—Pb1—Cl3iv	180.0
C1—C2—C4—C3i	−178.3 (5)	Pb1iii—Cl3—Pb1—Cl1v	90.72 (3)
C3—C2—C4—C3i	−54.6 (8)	Pb1iii—Cl3—Pb1—Cl1	−90.72 (3)
Pb1ii—Cl2—Pb1—Cl3iv	0.0	Pb1iii—Cl3—Pb1—Cl2vi	0.0

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···A	D—H	H···A	D···A	D—H···A
N1—H1C···Cl3iii	0.91	2.40	3.249 (5)	156
N1—H1D···Cl1vii	0.91	2.44	3.196 (6)	141
N1—H1E···Cl1vi	0.91	2.39	3.212 (5)	150
N1—H1E···Cl2vi	0.91	2.84	3.337 (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.