Poly[1,4-bis-(ammonio-meth-yl)cyclo-hexane [di-μ-bromido-dibromido-plumbate(II)]].

The title compound, {(C(8)H(20)N(2))[PbBr(4)]}(n), crystallizes as an inorganic-organic hybrid with alternating layers of diammonium cations and two-dimensional corner-sharing PbBr(6) octa-hedra extending parallel to the bc plane, which are eclipsed relative to one another. Both PbBr(6) octa-hedra and the organic cation exhibit symmetry. The cations inter-act via N-H⋯Br hydrogen bonding in the right-angled halogen sub-type of the terminal halide hydrogen-bonding motif.

Related literature

For hydrogen-bonding nomenclature for inorganic–organic hybrids, see: Mitzi (1999 ▶). Hybrid structures containing diammonium cations have been synthesized by Dobrzycki & Woźniak (2008 ▶) and Zhu et al. (2003 ▶). The semiconducting properties of similar hybrids were demonstrated by Mitzi (2004 ▶). For the related chloridoplumbate(II), see: Rayner & Billing (2010a ▶) and for the isotypic iodidoplumbate(II), see: Rayner & Billing (2010b ▶).

Experimental

Crystal data

(C8H20N2)[PbBr4]

M = 671.09

Monoclinic,

a = 12.1042 (6) Å

b = 8.1955 (4) Å

c = 8.2160 (4) Å

β = 95.693 (1)°

V = 811.01 (7) Å3

Z = 2

Mo Kα radiation

μ = 20.23 mm−1

T = 173 K

0.20 × 0.14 × 0.02 mm

Data collection

Bruker APEXII CCD area-detector diffractometer

Absorption correction: integration (XPREP; Bruker, 2005 ▶) T min = 0.091, T max = 0.656

10495 measured reflections

1966 independent reflections

1742 reflections with I > 2σ(I)

R int = 0.063

Refinement

R[F 2 > 2σ(F 2)] = 0.021

wR(F 2) = 0.047

S = 0.81

1966 reflections

70 parameters

H-atom parameters constrained

Δρmax = 0.78 e Å−3

Δρmin = −2.31 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/S1600536810016806/wm2338sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810016806/wm2338Isup2.hkl

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

(C8H20N2)[PbBr4]	F(000) = 608
Mr = 671.09	Dx = 2.748 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 5293 reflections
a = 12.1042 (6) Å	θ = 3.0–28.2°
b = 8.1955 (4) Å	µ = 20.23 mm−1
c = 8.2160 (4) Å	T = 173 K
β = 95.693 (1)°	Plate, colourless
V = 811.01 (7) Å3	0.20 × 0.14 × 0.02 mm
Z = 2

Bruker APEXII CCD area-detector diffractometer	1966 independent reflections
Radiation source: fine-focus sealed tube	1742 reflections with I > 2σ(I)
graphite	Rint = 0.063
φ and ω scans	θmax = 28.0°, θmin = 1.7°
Absorption correction: integration (XPREP; Bruker, 2005)	h = −15→15
Tmin = 0.091, Tmax = 0.656	k = −10→10
10495 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)] = 0.021	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.047	H-atom parameters constrained
S = 0.81	w = 1/[σ2(Fo2) + (0.0349P)2 + 0.0549P] where P = (Fo2 + 2Fc2)/3
1966 reflections	(Δ/σ)max = 0.011
70 parameters	Δρmax = 0.78 e Å−3
0 restraints	Δρmin = −2.31 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	0.2360 (3)	−0.0472 (4)	0.4803 (5)	0.0262 (8)
H1A	0.2798	−0.0711	0.5858	0.031*
H1B	0.2282	−0.1498	0.4166	0.031*
C2	0.1224 (3)	0.0131 (4)	0.5124 (4)	0.0216 (8)
H2	0.1325	0.1095	0.5871	0.026*
C3	0.0636 (3)	−0.1206 (4)	0.6011 (4)	0.0257 (8)
H3A	0.0558	−0.2192	0.5312	0.031*
H3B	0.1093	−0.1499	0.7035	0.031*
C4	0.0501 (3)	0.0661 (5)	0.3589 (4)	0.0247 (7)
H4A	0.0869	0.1569	0.3058	0.030*
H4B	0.0419	−0.0261	0.2807	0.030*
N1	0.2966 (2)	0.0758 (4)	0.3879 (4)	0.0230 (6)
H1C	0.3644	0.0356	0.3700	0.035*
H1D	0.3054	0.1695	0.4473	0.035*
H1E	0.2569	0.0972	0.2904	0.035*
Br1	0.25157 (3)	0.02969 (4)	−0.01928 (4)	0.02426 (9)
Br2	0.50023 (3)	0.18890 (4)	−0.31018 (4)	0.02370 (9)
Pb1	0.5000	0.0000	0.0000	0.01590 (6)

	U11	U22	U33	U12	U13	U23
C1	0.024 (2)	0.0232 (17)	0.0322 (19)	0.0000 (15)	0.0076 (16)	0.0042 (14)
C2	0.024 (2)	0.0206 (17)	0.0210 (17)	−0.0015 (13)	0.0039 (15)	−0.0010 (12)
C3	0.0206 (19)	0.0285 (18)	0.0277 (18)	0.0035 (15)	0.0011 (15)	0.0101 (14)
C4	0.0213 (19)	0.0285 (18)	0.0246 (17)	−0.0011 (15)	0.0040 (14)	0.0042 (14)
N1	0.0203 (16)	0.0229 (15)	0.0267 (15)	−0.0014 (12)	0.0065 (12)	−0.0019 (12)
Br1	0.0241 (2)	0.02380 (17)	0.02478 (17)	−0.00282 (13)	0.00175 (14)	−0.00035 (12)
Br2	0.0311 (2)	0.02090 (17)	0.01975 (16)	0.00481 (13)	0.00579 (13)	0.00695 (12)
Pb1	0.02093 (10)	0.01395 (9)	0.01320 (9)	0.00121 (6)	0.00358 (6)	0.00007 (5)

C1—N1	1.497 (4)	C4—H4B	0.9900
C1—C2	1.509 (5)	N1—H1C	0.9100
C1—H1A	0.9900	N1—H1D	0.9100
C1—H1B	0.9900	N1—H1E	0.9100
C2—C3	1.531 (4)	Br1—Pb1	3.0054 (4)
C2—C4	1.526 (5)	Br2—Pb1	2.9821 (3)
C2—H2	1.0000	Br2—Pb1ii	2.9886 (3)
C3—C4i	1.514 (5)	Pb1—Br2iii	2.9821 (3)
C3—H3A	0.9900	Pb1—Br2iv	2.9886 (3)
C3—H3B	0.9900	Pb1—Br2v	2.9886 (3)
C4—C3i	1.514 (5)	Pb1—Br1iii	3.0054 (4)
C4—H4A	0.9900
N1—C1—C2	111.7 (3)	H4A—C4—H4B	108.0
N1—C1—H1A	109.3	C1—N1—H1C	109.5
C2—C1—H1A	109.3	C1—N1—H1D	109.5
N1—C1—H1B	109.3	H1C—N1—H1D	109.5
C2—C1—H1B	109.3	C1—N1—H1E	109.5
H1A—C1—H1B	108.0	H1C—N1—H1E	109.5
C1—C2—C3	108.9 (3)	H1D—N1—H1E	109.5
C1—C2—C4	114.0 (3)	Pb1—Br2—Pb1ii	152.724 (12)
C3—C2—C4	110.0 (3)	Br2iii—Pb1—Br2	180.000 (11)
C1—C2—H2	107.9	Br2iii—Pb1—Br2iv	89.827 (4)
C3—C2—H2	107.9	Br2—Pb1—Br2iv	90.173 (4)
C4—C2—H2	107.9	Br2iii—Pb1—Br2v	90.173 (4)
C4i—C3—C2	111.6 (3)	Br2—Pb1—Br2v	89.827 (4)
C4i—C3—H3A	109.3	Br2iv—Pb1—Br2v	180.000 (15)
C2—C3—H3A	109.3	Br2iii—Pb1—Br1	90.075 (10)
C4i—C3—H3B	109.3	Br2—Pb1—Br1	89.925 (10)
C2—C3—H3B	109.3	Br2iv—Pb1—Br1	84.697 (10)
H3A—C3—H3B	108.0	Br2v—Pb1—Br1	95.303 (10)
C3i—C4—C2	111.3 (3)	Br2iii—Pb1—Br1iii	89.925 (10)
C3i—C4—H4A	109.4	Br2—Pb1—Br1iii	90.075 (10)
C2—C4—H4A	109.4	Br2iv—Pb1—Br1iii	95.303 (10)
C3i—C4—H4B	109.4	Br2v—Pb1—Br1iii	84.697 (10)
C2—C4—H4B	109.4	Br1—Pb1—Br1iii	180.000 (13)
N1—C1—C2—C3	177.9 (3)	C3—C2—C4—C3i	55.8 (4)
N1—C1—C2—C4	54.7 (4)	Pb1ii—Br2—Pb1—Br2iv	−0.28 (4)
C1—C2—C3—C4i	178.5 (3)	Pb1ii—Br2—Pb1—Br2v	179.72 (4)
C4—C2—C3—C4i	−56.0 (4)	Pb1ii—Br2—Pb1—Br1	84.42 (3)
C1—C2—C4—C3i	178.4 (3)	Pb1ii—Br2—Pb1—Br1iii	−95.58 (3)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1C···Br2iii	0.91	2.54	3.387 (3)	154
N1—H1D···Br1iv	0.91	2.57	3.378 (3)	148
N1—H1D···Br2vi	0.91	2.94	3.446 (3)	117
N1—H1E···Br1	0.91	2.60	3.357 (3)	141

Table 1

Selected bond lengths (Å)

Pb1—Br2i	2.9821 (3)
Pb1—Br2ii	2.9886 (3)
Pb1—Br1i	3.0054 (4)

Symmetry codes: (i) ; (ii) .

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1C⋯Br2i	0.91	2.54	3.387 (3)	154
N1—H1D⋯Br1ii	0.91	2.57	3.378 (3)	148
N1—H1D⋯Br2iii	0.91	2.94	3.446 (3)	117
N1—H1E⋯Br1	0.91	2.60	3.357 (3)	141

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