Poly[1,4-bis-(ammonio-meth-yl)cyclo-hexane [di-μ-chlorido-dichloridoplumbate(II)]].

The title compound, {(C(8)H(20)N(2))[PbCl(4)]}(n), crystallizes as an layered inorganic-organic hybrid perovskite-type structure. Corner-sharing PbCl(6) octa-hedra 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 inter-act 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 = 493.25

Orthorhombic,

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 ▶) 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 ▶); 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 ▶).

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

(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

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 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

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.

	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)

	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

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

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

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) .