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

Rayner, M.K.; Billing, D.G.

doi:10.1107/S160053681001682X

metal-organic compounds

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Volume 66| Part 6| June 2010| Page m660

https://doi.org/10.1107/S160053681001682X

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

Matthew Kyle Rayner ^a and David Gordon Billing ^a ^*

^aMolecular Sciences Institute, School of Chemistry, University of the Witwatersrand, Private Bag 3, PO Wits 2050, South Africa
^*Correspondence e-mail: david.billing@wits.ac.za

(Received 27 April 2010; accepted 7 May 2010; online 15 May 2010)

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 ( $[\overline{1}]$ symmetry) and 1,4-bis(ammoniomethyl)cyclohexane cations ( $[\overline{1}]$ 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, P 2₁ /c
a = 12.2793 (17) Å
b = 8.7413 (12) Å
c = 8.7829 (13) Å
β = 95.922 (3)°
V = 937.7 (2) Å³
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[F² > 2σ(F²)] = 0.033
wR(F²) = 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

Table 1
Selected bond lengths (Å)

Pb1—I2ⁱ	3.1824 (5)
Pb1—I2ⁱⁱ	3.1875 (5)
Pb1—I1ⁱ	3.2243 (6)
Symmetry codes: (i) -x, -y, -z; (ii) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

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⋯I2^iv	0.91	3.12	3.672 (6)	121
N1—H1C⋯I2	0.91	2.78	3.611 (6)	152
Symmetry codes: (i) -x, -y, -z; (iii) $[-x, y-{\script{1\over 2}}, -z-{\script{1\over 2}}]$ ; (iv) -x, -y, -z-1.

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 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S160053681001682X/wm2340sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S160053681001682X/wm2340Isup2.hkl

checkCIF report

Comment top

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.

Related literature top

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 top

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.

Structure description top

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).

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); 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).

Figures top

	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.

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

Crystal data top

(C₈H₂₀N₂)[PbI₄]	F(000) = 752
M_r = 859.05	D_x = 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 top

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

Refinement top

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(F_o²) + (0.0511P)² + 1.0393P] where P = (F_o² + 2F_c²)/3
2264 reflections	(Δ/σ)_max = 0.009
70 parameters	Δρ_max = 1.76 e Å⁻³
0 restraints	Δρ_min = −2.79 e Å⁻³

Crystal data top

(C₈H₂₀N₂)[PbI₄]	V = 937.7 (2) Å³
M_r = 859.05	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 12.2793 (17) Å	µ = 15.56 mm⁻¹
b = 8.7413 (12) Å	T = 173 K
c = 8.7829 (13) Å	0.36 × 0.26 × 0.08 mm
β = 95.922 (3)°

Data collection top

Bruker APEXII CCD area-detector diffractometer	2264 independent reflections
Absorption correction: integration (XPREP; Bruker, 2005)	2085 reflections with I > 2σ(I)
T_min = 0.043, T_max = 0.288	R_int = 0.080
5435 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.033	0 restraints
wR(F²) = 0.093	H-atom parameters constrained
S = 1.08	Δρ_max = 1.76 e Å⁻³
2264 reflections	Δρ_min = −2.79 e Å⁻³
70 parameters

Special details top

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) top

	x	y	z	U_iso*/U_eq
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 (Å²) top

	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, º) top

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—I2^iv	3.1875 (5)
C3—H3B	0.9900	Pb1—I2^v	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—I2^iv	90.294 (11)
C1—C2—H2	108.2	I2ⁱⁱⁱ—Pb1—I2^iv	89.706 (11)
C3—C2—H2	108.2	I2—Pb1—I2^v	89.706 (11)
C4ⁱ—C3—C2	111.1 (6)	I2ⁱⁱⁱ—Pb1—I2^v	90.294 (11)
C4ⁱ—C3—H3A	109.4	I2^iv—Pb1—I2^v	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	I2^iv—Pb1—I1ⁱⁱⁱ	94.518 (12)
H3A—C3—H3B	108.0	I2^v—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	I2^iv—Pb1—I1	85.482 (12)
C3ⁱ—C4—H4B	109.5	I2^v—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—I2^iv	−0.35 (4)
C4—C2—C3—C4ⁱ	57.3 (8)	Pb1ⁱⁱ—I2—Pb1—I2^v	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, º) top

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···I1^v	0.91	2.84	3.619 (6)	144
N1—H1E···I2^vi	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.

Experimental details

Crystal data
Chemical formula	(C₈H₂₀N₂)[PbI₄]
M_r	859.05
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	173
a, b, c (Å)	12.2793 (17), 8.7413 (12), 8.7829 (13)
β (°)	95.922 (3)
V (Å³)	937.7 (2)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	15.56
Crystal size (mm)	0.36 × 0.26 × 0.08

Data collection
Diffractometer	Bruker APEXII CCD area-detector
Absorption correction	Integration (XPREP; Bruker, 2005)
T_min, T_max	0.043, 0.288
No. of measured, independent and observed [I > 2σ(I)] reflections	5435, 2264, 2085
R_int	0.080
(sin θ/λ)_max (Å⁻¹)	0.660

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.033, 0.093, 1.08
No. of reflections	2264
No. of parameters	70
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.76, −2.79

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997) and DIAMOND (Brandenburg, 1999), WinGX (Farrugia, 1999) and PLATON (Spek, 2009).

Selected bond lengths (Å) top

Pb1—I2ⁱ	3.1824 (5)	Pb1—I1ⁱ	3.2243 (6)
Pb1—I2ⁱⁱ	3.1875 (5)

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

Hydrogen-bond geometry (Å, º) top

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···I2^iv	0.91	3.12	3.672 (6)	121
N1—H1C···I2	0.91	2.78	3.611 (6)	152

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

Acknowledgements

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

References

Billing, D. G. & Lemmerer, A. (2006). CrystEngComm, 9, 236–244. Web of Science CSD CrossRef Google Scholar
Brandenburg, K. (1999). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Bruker (2005). APEX2, SAINT and XPREP. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838. CrossRef CAS IUCr Journals Google Scholar
Mitzi, D. B. (1999). Prog. Inorg. Chem. 48, 1–121. Web of Science CrossRef CAS Google Scholar
Rayner, M. K. & Billing, D. G. (2010a). Acta Cryst. E66, m659. Web of Science CSD CrossRef IUCr Journals Google Scholar
Rayner, M. K. & Billing, D. G. (2010b). Acta Cryst. E66, m658. Web of Science CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar

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metal-organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

metal-organic compounds

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