Poly[1,4-bis­(ammonio­meth­yl)cyclo­hexane [di-μ-iodido-diiodido­plumbate(II)]]

Abstract

The title compound, {(C₈H₂₀N₂)[PbI₄]}_n, is an inorganic–organic hybrid. The structure is composed of alternate layers of two-dimensional corner-sharing PbI₆ octa­hedra ( symmetry) and 1,4-bis­(ammonio­meth­yl)cyclo­hexane cations ( symmetry) extending parallel to the bc plane. The cations inter­act with the inorganic layer via N—H⋯I hydrogen bonding in the right-angled halogen sub-type of the terminal halide hydrogen-bonding motif.

Related literature

For other examples of inorganic–organic hybrid structures encorporating cyclic ammonium cations, see: Billing & Lemmerer (2006 ▶). For hydrogen-bonding nomenclature for inorganic–organic hybrids, see: Mitzi (1999 ▶). For the related chloridoplumbate(II), see: Rayner & Billing (2010a ▶) and for the isotypic bromidoplumbate(II), see: Rayner & Billing (2010b ▶).

Experimental

Crystal data

• (C₈H₂₀N₂)[PbI₄]

• M _r = 859.05

• Monoclinic,

• a = 12.2793 (17) Å

• b = 8.7413 (12) Å

• c = 8.7829 (13) Å

• β = 95.922 (3)°

• V = 937.7 (2) ų

• Z = 2

• Mo Kα radiation

• μ = 15.56 mm⁻¹

• T = 173 K

• 0.36 × 0.26 × 0.08 mm

Data collection

• Bruker APEXII CCD area-detector diffractometer

• Absorption correction: integration (XPREP; Bruker, 2005 ▶) T _min = 0.043, T _max = 0.288

• 5435 measured reflections

• 2264 independent reflections

• 2085 reflections with I > 2σ(I)

• R _int = 0.080

Refinement

• R[F ² > 2σ(F ²)] = 0.033

• wR(F ²) = 0.093

• S = 1.08

• 2264 reflections

• 70 parameters

• H-atom parameters constrained

• Δρ_max = 1.76 e Å⁻³

• Δρ_min = −2.79 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—I2i	3.1824 (5)
Pb1—I2ii	3.1875 (5)
Pb1—I1i	3.2243 (6)

Symmetry codes: (i) ; (ii) .

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1D⋯I1i	0.91	2.88	3.598 (5)	137
N1—H1E⋯I1iii	0.91	2.84	3.619 (6)	144
N1—H1E⋯I2iv	0.91	3.12	3.672 (6)	121
N1—H1C⋯I2	0.91	2.78	3.611 (6)	152

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

supplementary crystallographic information

Comment

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 iodide (presented here), the bromide (Rayner & Billing, 2010b) and chloride (Rayner & Billing, 2010a). The bromide and iodide hybrids are isotypic and crystallize in the monoclinic system with space group P2₁/c while the chloride hybrid crystallizes in the orthorhombic, Pnma system.

In the structure of the title compound the lead atoms in the PbI₆ octahedra occupy inversion centers, giving the octahedra 1 symmetry. The PbI₆ octahedra share corners to form layers extending parallel to the bc plane. Octahedra from alternate layers are eclipsed 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). Billing & Lemmerer (2006) reported a series of inorganic-organic hybrids encorpoating cyclic ammonium cations, however no diammonium cations were synthesized.

Experimental

A mixture of 0.050 g (0.11 mmol) PbI₂ and 0.017 g (0.17 mmol) 1,4-bis-(aminomethyl)-cyclohexane (mixture of isomers) was dissolved in 5 ml HI at 383 K and slow cooled at a rate of 0.069 K/min to yield yellow, 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 (1.76 e Å-3) was 0.955Å from Pb1.

Figures

Fig. 1.

The extended asymmetric unit of the title compound with atom labels. Displacement ellipsoids were drawn at the 50% probability level. Symmetry codes: (a) -x, -1/2+y, 3/2-z (b) -x, 1-y, 1-z (c) x, 3/2-y, -1/2+z (d) 1-x, 1-y, -z.

Fig. 2.

Packing diagram viewed along the a axis. Hydrogen bonds are drawn as dashed red lines.

Fig. 3.

Packing diagram viewed along the b axis. Hydrogen bonds are drawn as dashed red lines.

Crystal data

(C8H20N2)[PbI4]	F(000) = 752
Mr = 859.05	Dx = 3.043 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 6011 reflections
a = 12.2793 (17) Å	θ = 3.0–28.2°
b = 8.7413 (12) Å	µ = 15.56 mm−1
c = 8.7829 (13) Å	T = 173 K
β = 95.922 (3)°	Plate, orange
V = 937.7 (2) Å3	0.36 × 0.26 × 0.08 mm
Z = 2

Data collection

Bruker APEXII CCD area-detector diffractometer	2264 independent reflections
Radiation source: fine-focus sealed tube	2085 reflections with I > 2σ(I)
graphite	Rint = 0.080
φ and ω scans	θmax = 28.0°, θmin = 1.7°
Absorption correction: integration (XPREP; Bruker, 2005)	h = −16→16
Tmin = 0.043, Tmax = 0.288	k = −11→10
5435 measured reflections	l = −9→11

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)] = 0.033	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.093	H-atom parameters constrained
S = 1.08	w = 1/[σ2(Fo2) + (0.0511P)2 + 1.0393P] where P = (Fo2 + 2Fc2)/3
2264 reflections	(Δ/σ)max = 0.009
70 parameters	Δρmax = 1.76 e Å−3
0 restraints	Δρmin = −2.79 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	0.2676 (6)	0.0434 (9)	−0.4667 (9)	0.0333 (15)
H1A	0.2773	0.1355	−0.4011	0.040*
H1B	0.2216	0.0719	−0.5617	0.040*
C2	0.3794 (6)	−0.0123 (8)	−0.5065 (8)	0.0273 (15)
H2	0.3672	−0.0991	−0.5804	0.033*
C3	0.4366 (6)	0.1194 (9)	−0.5867 (8)	0.0306 (14)
H3A	0.3890	0.1529	−0.6785	0.037*
H3B	0.4475	0.2077	−0.5162	0.037*
C4	0.4542 (6)	−0.0685 (9)	−0.3667 (8)	0.0299 (14)
H4A	0.4654	0.0151	−0.2906	0.036*
H4B	0.4187	−0.1550	−0.3183	0.036*
N1	0.2111 (5)	−0.0797 (7)	−0.3841 (6)	0.0274 (12)
H1C	0.1450	−0.0448	−0.3610	0.041*
H1D	0.2531	−0.1050	−0.2962	0.041*
H1E	0.2012	−0.1637	−0.4451	0.041*
I1	−0.26315 (4)	0.02539 (5)	−0.02301 (5)	0.02714 (13)
I2	0.00031 (4)	0.18981 (5)	−0.30914 (4)	0.02605 (14)
Pb1	0.0000	0.0000	0.0000	0.01915 (11)

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
C1	0.036 (4)	0.026 (3)	0.039 (4)	0.002 (3)	0.005 (3)	0.004 (3)
C2	0.027 (4)	0.027 (4)	0.028 (3)	−0.003 (3)	0.003 (3)	−0.001 (2)
C3	0.028 (3)	0.030 (3)	0.034 (3)	0.000 (3)	0.001 (3)	0.010 (3)
C4	0.023 (3)	0.035 (4)	0.031 (3)	−0.003 (3)	0.002 (3)	0.008 (3)
N1	0.025 (3)	0.031 (3)	0.026 (3)	−0.004 (2)	0.003 (2)	−0.001 (2)
I1	0.0262 (2)	0.0257 (2)	0.0288 (2)	−0.00327 (17)	−0.00048 (18)	−0.00028 (16)
I2	0.0356 (2)	0.0218 (2)	0.0212 (2)	0.00569 (16)	0.00513 (16)	0.00779 (14)
Pb1	0.02537 (19)	0.01599 (17)	0.01602 (16)	0.00087 (11)	0.00182 (12)	0.00032 (10)

Geometric parameters (Å, °)

C1—N1	1.507 (9)	C4—H4B	0.9900
C1—C2	1.530 (10)	N1—H1C	0.9100
C1—H1A	0.9900	N1—H1D	0.9100
C1—H1B	0.9900	N1—H1E	0.9100
C2—C4	1.536 (10)	I1—Pb1	3.2243 (6)
C2—C3	1.554 (9)	I2—Pb1	3.1824 (5)
C2—H2	1.0000	I2—Pb1ii	3.1875 (5)
C3—C4i	1.510 (10)	Pb1—I2iii	3.1824 (5)
C3—H3A	0.9900	Pb1—I2iv	3.1875 (5)
C3—H3B	0.9900	Pb1—I2v	3.1875 (5)
C4—C3i	1.510 (10)	Pb1—I1iii	3.2243 (6)
C4—H4A	0.9900
N1—C1—C2	110.5 (6)	H4A—C4—H4B	108.1
N1—C1—H1A	109.5	C1—N1—H1C	109.5
C2—C1—H1A	109.5	C1—N1—H1D	109.5
N1—C1—H1B	109.5	H1C—N1—H1D	109.5
C2—C1—H1B	109.5	C1—N1—H1E	109.5
H1A—C1—H1B	108.1	H1C—N1—H1E	109.5
C4—C2—C1	113.3 (6)	H1D—N1—H1E	109.5
C4—C2—C3	109.8 (6)	Pb1—I2—Pb1ii	153.144 (15)
C1—C2—C3	109.0 (6)	I2—Pb1—I2iii	180.00 (2)
C4—C2—H2	108.2	I2—Pb1—I2iv	90.294 (11)
C1—C2—H2	108.2	I2iii—Pb1—I2iv	89.706 (11)
C3—C2—H2	108.2	I2—Pb1—I2v	89.706 (11)
C4i—C3—C2	111.1 (6)	I2iii—Pb1—I2v	90.294 (11)
C4i—C3—H3A	109.4	I2iv—Pb1—I2v	180.0
C2—C3—H3A	109.4	I2—Pb1—I1iii	89.999 (12)
C4i—C3—H3B	109.4	I2iii—Pb1—I1iii	90.001 (12)
C2—C3—H3B	109.4	I2iv—Pb1—I1iii	94.518 (12)
H3A—C3—H3B	108.0	I2v—Pb1—I1iii	85.482 (12)
C3i—C4—C2	110.6 (6)	I2—Pb1—I1	90.001 (12)
C3i—C4—H4A	109.5	I2iii—Pb1—I1	89.999 (12)
C2—C4—H4A	109.5	I2iv—Pb1—I1	85.482 (12)
C3i—C4—H4B	109.5	I2v—Pb1—I1	94.518 (12)
C2—C4—H4B	109.5	I1iii—Pb1—I1	180.0
N1—C1—C2—C4	−55.7 (8)	C3—C2—C4—C3i	−57.0 (9)
N1—C1—C2—C3	−178.2 (6)	Pb1ii—I2—Pb1—I2iv	−0.35 (4)
C4—C2—C3—C4i	57.3 (8)	Pb1ii—I2—Pb1—I2v	179.65 (4)
C1—C2—C3—C4i	−178.1 (6)	Pb1ii—I2—Pb1—I1iii	−94.87 (4)
C1—C2—C4—C3i	−179.1 (6)	Pb1ii—I2—Pb1—I1	85.13 (4)

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

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1D···I1iii	0.91	2.88	3.598 (5)	137
N1—H1E···I1v	0.91	2.84	3.619 (6)	144
N1—H1E···I2vi	0.91	3.12	3.672 (6)	121
N1—H1C···I2	0.91	2.78	3.611 (6)	152

Symmetry codes: (iii) −x, −y, −z; (v) −x, y−1/2, −z−1/2; (vi) −x, −y, −z−1.