The one-dimensional organic inorganic hybrid compound poly[(diethyl­ene­triamine)tetra-μ-iodido-dilead(II)]

Samet Kallel, E.; Boughzala, H.; Driss, A.; Abid, Y.

doi:10.1107/S1600536808013913

metal-organic compounds

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Volume 64| Part 7| July 2008| Page m921

doi:10.1107/S1600536808013913

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The one-dimensional organic inorganic hybrid compound poly[(diethylenetriamine)tetra-μ-iodido-dilead(II)]

E. Samet Kallel,^a H. Boughzala,^b ^* A. Driss ^c and Y. Abid ^a

^aLaboratoire de Physique appliquée (LPA), Faculté des Sciences de Sfax, 3018, BP 802, Tunisia, ^bLaboratoire de Matériaux et Cristallochimie, Institut préparatoire aux études ingénieur de Nabeul, 8000 Mrezga, Nabeul, Tunisia, and ^cLaboratoire de Cristallochimie et des Matériaux, Faculté des Sciences de Tunis, Tunisia
^*Correspondence e-mail: habib.boughzala@ipein.rnu.tn

(Received 24 April 2008; accepted 9 May 2008; online 13 June 2008)

A new organic–inorganic hybrid, [Pb₂I₄(C₄H₁₃N₃)]_n, was obtained by the reaction of C₄N₃H₁₀ and PbI₂ at room temperature. The structure is a three-dimensional polymer resulting from the association of PbI₆ octahedra and a mixed lead organic–inorganic PbI₄(C₄N₃H₁₃) coordination polyhedron. Both Pb atoms, two I atoms and one N atom lie on a mirror plane. N—H⋯I hydrogen bonds further connect the organic unit and some I atoms.

Related literature

For related literature, see: Lode & Krautscheild (2001 ); Krautscheild et al. (2001 ); Papavassiliou et al. (1999 ); Wang et al. (1995 ); Zhu et al. (2004 ).

Experimental

Crystal data

[Pb₂I₄(C₄H₁₃N₃)]
M_r = 1025.15
Orthorhombic, P n m a
a = 17.034 (6) Å
b = 9.218 (3) Å
c = 11.092 (4) Å
V = 1741.6 (10) Å³
Z = 4
Mo Kα radiation
μ = 26.38 mm⁻¹
T = 293 (2) K
0.2 × 0.05 × 0.05 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ) T_min = 0.095, T_max = 0.268
2906 measured reflections
1998 independent reflections
1202 reflections with I > 2σ(I)
R_int = 0.045
2 standard reflections frequency: 120 min intensity decay: 5%

Refinement

R[F² > 2σ(F²)] = 0.040
wR(F²) = 0.099
S = 1.00
1998 reflections
67 parameters
H-atom parameters constrained
Δρ_max = 1.57 e Å⁻³
Δρ_min = −1.58 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯I1ⁱ	0.90	2.93	3.791 (12)	160
N1—H1B⋯I2ⁱⁱ	0.90	2.88	3.746 (12)	163
N2—H2⋯I2ⁱⁱⁱ	0.91	3.19	3.731 (17)	121
Symmetry codes: (i) $[-x+{\script{1\over 2}}, -y, z+{\script{1\over 2}}]$ ; (ii) -x+1, -y, -z+1; (iii) $[x-{\script{1\over 2}}, y, -z+{\script{3\over 2}}]$ .

Data collection: CAD-4 EXPRESS (Duisenberg, 1992 ; Macíček & Yordanov, 1992 ); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1995 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2003 ) and DIAMOND (Brandenburg, 2006 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808013913/dn2346sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808013913/dn2346Isup2.hkl

checkCIF report

Comment top

The basic structure building block of this compound is made up of lead iodide octahedral [PbI₆] and a mixed lead organic-inorganic PbI₄(C₄N₃H₁₃) coordination polyhedron (Fig 1). Both Pb atoms , two I atoms and one N atom lie on a mirror plane. Atom Pb1 is located in the octahedral cavity of the inorganic chains while Pb2 is responsible of the connectivity between organic moiety and inorganic chains. To our knowledge, this is the first report of an organic-inorganic hybrid exhibiting this kind of lead connectivity.

A part of the inorganic back bone is staked as single chains of edge sharing Pb1I₆ octahedra, as shown in Fig 2. The halide atoms I3 are responsible for the edge sharing between Pb1I₆ neighboring octahedron to join infinite one dimensional chain (parallel to b axis). Within the octahedra the bond lengths around Pb1 range from 3.182 (2) to 3.319 (2) Å which indicate the dominant ionic character of the Pb—I bonds in the inorganic chains. The bond angles I—Pb1—I deviate slightly from ideal octahedral value of 90° and 180°, ranging from 88.39 (4)° to 92.98 (5)° for the adjacent iodides and from 176.76 (3)° to 179.59 (4)° for the opposite ones. This ideal octahedron indicates the unstereochemical activity of lead (II) lone pair electrons (Wang et al. 1995). Note that the regular octahedrons are a characteristic feature often encountered in the low dimensional lead iodide structures (Zhu et al., 2004).

As mentioned above, C₄N₃H₁₃ is in combination with inorganic moiety by three Pb2—N non covalent interaction and hydrogen bonds. The non centrosymmetric organic molecule is slightly twisted around the C—C bond as reflected by a torsion angle of 25.1 (14)°. Bond distances and angles appear to be within normal range.

It is note worthy that the yellow color observed for the title compound is in good accordance with a low dimensional network of lead octahedral (Lode et al., 2001; Krautscheild et al., 2001; Papavassiliou et al., 1999).

Related literature top

For related literature, see: Lode & Krautscheild (2001); Krautscheild et al. (2001); Papavassiliou et al. (1999); Wang et al. (1995); Zhu et al. (2004).

Experimental top

An aqueous solution of HI was added to the diethylentriamin to synthesis C₄H₁₃N₃I₃ salts. Under ambient conditions, stoechiometric amounts of C₄H₁₃N₃I₃ and PbI₂ with excess HI (to improve PbI₂ solubility), were sailed in DMF. The resulting solution was kept at room temperature. Yellow needle-like crystals are obtained five weeks later.

Computing details top

Data collection: CAD-4 EXPRESS (Duisenberg, 1992; Macíček & Yordanov, 1992); cell refinement: CAD-4 EXPRESS (Duisenberg, 1992; Macíček & Yordanov, 1992); data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2003) and DIAMOND (Brandenburg, 2006); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. : View of the C₄N₃H₁₃Pb₂I₄ with the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level. H atoms have been omitted for clarity. [Symmetry codes: (i)x, 1/2 - y, z; (ii) 1 - x, 1/2 + y,1 - z; (iii) 1 - x, –Y, 1 - z; (iv) 1/2 - x, -y, 1/2 + z; (v) x - 1/2,1/2 - y, 3/2 - z; (vi) 1/2 - x, 1/2 + y, 1/2 + z
	Fig. 2. : Packing view of C₄N₃H₁₃Pb₂I₄ viewed along [010] direction. H atoms have been omitted for clarity.

poly[(diethylenetriamine)tetra-µ-iodido-dilead(II)] top

Crystal data top

[Pb₂I₄(C₄H₁₃N₃)]	F(000) = 1736
M_r = 1025.15	D_x = 3.910 Mg m⁻³
Orthorhombic, Pnma	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2n	Cell parameters from 25 reflections
a = 17.034 (6) Å	θ = 10.7–13.8°
b = 9.218 (3) Å	µ = 26.38 mm⁻¹
c = 11.092 (4) Å	T = 293 K
V = 1741.6 (10) Å³	Needle, yellow
Z = 4	0.2 × 0.05 × 0.05 mm

Data collection top

Enraf–Nonius CAD-4 diffractometer	1202 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.045
Graphite monochromator	θ_max = 27.0°, θ_min = 2.2°
Non–profiled ω/2θ scans	h = −1→21
Absorption correction: ψ scan (North et al., 1968)	k = −11→3
T_min = 0.095, T_max = 0.268	l = −1→14
2906 measured reflections	2 standard reflections every 120 min
1998 independent reflections	intensity decay: 5%

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)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.099	H-atom parameters constrained
S = 1.00	w = 1/[σ²(F_o²) + (0.0394P)²] where P = (F_o² + 2F_c²)/3
1998 reflections	(Δ/σ)_max < 0.001
67 parameters	Δρ_max = 1.57 e Å⁻³
0 restraints	Δρ_min = −1.58 e Å⁻³

Crystal data top

[Pb₂I₄(C₄H₁₃N₃)]	V = 1741.6 (10) Å³
M_r = 1025.15	Z = 4
Orthorhombic, Pnma	Mo Kα radiation
a = 17.034 (6) Å	µ = 26.38 mm⁻¹
b = 9.218 (3) Å	T = 293 K
c = 11.092 (4) Å	0.2 × 0.05 × 0.05 mm

Data collection top

Enraf–Nonius CAD-4 diffractometer	1202 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.045
T_min = 0.095, T_max = 0.268	2 standard reflections every 120 min
2906 measured reflections	intensity decay: 5%
1998 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.040	0 restraints
wR(F²) = 0.099	H-atom parameters constrained
S = 1.00	Δρ_max = 1.57 e Å⁻³
1998 reflections	Δρ_min = −1.58 e Å⁻³
67 parameters

Special details top

Experimental. Number of psi-scan sets used was 4 Theta correction was applied. Averaged transmission function was used. No Fourier smoothing was applied (North et al.,1968).

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
Pb1	0.49490 (3)	0.2500	0.49379 (7)	0.0376 (2)
Pb2	0.23035 (4)	0.2500	0.86880 (7)	0.0361 (2)
I1	0.32678 (7)	0.2500	0.61874 (12)	0.0482 (4)
I2	0.66724 (7)	0.2500	0.36339 (11)	0.0441 (3)
I3	0.43945 (5)	−0.00127 (10)	0.31479 (9)	0.0458 (3)
N1	0.2835 (7)	−0.0102 (10)	0.8986 (11)	0.049 (3)
H1A	0.2469	−0.0639	0.9365	0.059*
H1B	0.2922	−0.0506	0.8260	0.059*
N2	0.3598 (9)	0.2500	0.9763 (17)	0.055 (5)
H2	0.3467	0.2500	1.0558	0.066*
C2	0.4032 (8)	0.113 (2)	0.9595 (18)	0.079 (6)
H2C	0.4281	0.1143	0.8807	0.094*
H2D	0.4445	0.1075	1.0195	0.094*
C1	0.3559 (10)	−0.0133 (16)	0.9684 (18)	0.076 (6)
H1C	0.3426	−0.0282	1.0525	0.091*
H1D	0.3867	−0.0961	0.9425	0.091*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Pb1	0.0375 (4)	0.0355 (4)	0.0399 (4)	0.000	0.0008 (3)	0.000
Pb2	0.0285 (3)	0.0402 (4)	0.0397 (4)	0.000	0.0006 (3)	0.000
I1	0.0465 (7)	0.0557 (8)	0.0425 (8)	0.000	0.0098 (7)	0.000
I2	0.0429 (7)	0.0507 (8)	0.0388 (7)	0.000	0.0023 (6)	0.000
I3	0.0484 (5)	0.0472 (6)	0.0419 (5)	−0.0063 (4)	−0.0028 (4)	−0.0008 (5)
N1	0.060 (7)	0.025 (6)	0.062 (9)	0.006 (5)	0.010 (6)	0.001 (6)
N2	0.043 (8)	0.062 (12)	0.059 (12)	0.000	−0.015 (9)	0.000
C2	0.048 (9)	0.084 (14)	0.103 (16)	0.013 (10)	−0.007 (10)	0.011 (13)
C1	0.088 (12)	0.043 (10)	0.096 (16)	0.017 (9)	−0.023 (12)	0.001 (11)

Geometric parameters (Å, º) top

Pb1—I1	3.1816 (17)	N1—H1A	0.9000
Pb1—I3	3.1936 (13)	N1—H1B	0.9000
Pb1—I2	3.2725 (16)	N2—C2	1.476 (18)
Pb1—I3ⁱ	3.3190 (13)	N2—H2	0.9100
Pb2—N2	2.506 (15)	C2—C1	1.42 (2)
Pb2—N1	2.585 (10)	C2—H2C	0.9700
Pb2—I2ⁱⁱ	3.1591 (18)	C2—H2D	0.9700
Pb2—I1	3.2236 (17)	C1—H1C	0.9700
Pb2—I3ⁱⁱⁱ	3.7392 (17)	C1—H1D	0.9700
N1—C1	1.457 (19)

I1—Pb1—I3	90.26 (3)	Pb1^ix—I3—Pb2^viii	74.61 (2)
I3—Pb1—I3^iv	92.98 (5)	Pb1—I1—Pb2	146.46 (5)
I1—Pb1—I2	179.59 (4)	Pb2^x—I2—Pb1	83.66 (4)
I3—Pb1—I2	89.46 (3)	Pb1—I3—Pb1^ix	90.21 (4)
I1—Pb1—I3ⁱ	91.41 (3)	C1—N1—Pb2	112.5 (8)
I3—Pb1—I3ⁱ	176.76 (3)	C1—N1—H1A	109.1
I3^iv—Pb1—I3ⁱ	89.79 (4)	Pb2—N1—H1A	109.1
I2—Pb1—I3ⁱ	88.88 (3)	C1—N1—H1B	109.1
I3—Pb1—I3^v	89.79 (4)	Pb2—N1—H1B	109.1
I3^iv—Pb1—I3^v	176.76 (3)	H1A—N1—H1B	107.8
I3ⁱ—Pb1—I3^v	87.39 (4)	C2—N2—C2^iv	117.7 (17)
N2—Pb2—N1	68.4 (3)	C2—N2—Pb2	112.4 (9)
N1^iv—Pb2—N1	136.3 (5)	C2—N2—H2	104.2
N2—Pb2—I2ⁱⁱ	81.5 (4)	Pb2—N2—H2	104.2
N1—Pb2—I2ⁱⁱ	89.9 (3)	C1—C2—N2	114.1 (12)
N2—Pb2—I1	87.8 (4)	C1—C2—H2C	108.7
N1—Pb2—I1	86.1 (3)	N2—C2—H2C	108.7
I2ⁱⁱ—Pb2—I1	169.26 (4)	C1—C2—H2D	108.7
I3ⁱⁱⁱ—Pb2—N1	73.9 (3)	N2—C2—H2D	108.7
I1—Pb2—I3ⁱⁱⁱ	104.85 (3)	H2C—C2—H2D	107.6
I3ⁱⁱⁱ—Pb2—N2	139.17 (15)	C2—C1—N1	115.4 (13)
I3ⁱⁱⁱ—Pb2—I3^vi	75.64 (2)	C2—C1—H1C	108.4
I2^vii—Pb2—I3ⁱⁱⁱ	83.54 (3)	N1—C1—H1C	108.4
I3^vi—Pb2—N1	149.3 (3)	C2—C1—H1D	108.4
I3^vi—Pb2—N1^iv	73.8 (3)	N1—C1—H1D	108.4
Pb1—I3—Pb2^viii	125.02 (3)	H1C—C1—H1D	107.5

C1—N1—N2—C2	25.1 (14)

Symmetry codes: (i) −x+1, y+1/2, −z+1; (ii) x−1/2, y, −z+3/2; (iii) −x+1/2, −y, z+1/2; (iv) x, −y+1/2, z; (v) −x+1, −y, −z+1; (vi) −x+1/2, y+1/2, z+1/2; (vii) x−1/2, −y+1/2, −z+3/2; (viii) −x+1/2, −y, z−1/2; (ix) −x+1, y−1/2, −z+1; (x) x+1/2, y, −z+3/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···I1ⁱⁱⁱ	0.90	2.93	3.791 (12)	160
N1—H1B···I2^v	0.90	2.88	3.746 (12)	163
N2—H2···I2ⁱⁱ	0.91	3.19	3.731 (17)	121

Symmetry codes: (ii) x−1/2, y, −z+3/2; (iii) −x+1/2, −y, z+1/2; (v) −x+1, −y, −z+1.

Experimental details

Crystal data
Chemical formula	[Pb₂I₄(C₄H₁₃N₃)]
M_r	1025.15
Crystal system, space group	Orthorhombic, Pnma
Temperature (K)	293
a, b, c (Å)	17.034 (6), 9.218 (3), 11.092 (4)
V (Å³)	1741.6 (10)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	26.38
Crystal size (mm)	0.2 × 0.05 × 0.05

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.095, 0.268
No. of measured, independent and observed [I > 2σ(I)] reflections	2906, 1998, 1202
R_int	0.045
(sin θ/λ)_max (Å⁻¹)	0.638

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.099, 1.00
No. of reflections	1998
No. of parameters	67
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.57, −1.58

Computer programs: CAD-4 EXPRESS (Duisenberg, 1992; Macíček & Yordanov, 1992), XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2003) and DIAMOND (Brandenburg, 2006).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···I1ⁱ	0.90	2.93	3.791 (12)	160.0
N1—H1B···I2ⁱⁱ	0.90	2.88	3.746 (12)	163.4
N2—H2···I2ⁱⁱⁱ	0.91	3.19	3.731 (17)	120.5

Symmetry codes: (i) −x+1/2, −y, z+1/2; (ii) −x+1, −y, −z+1; (iii) x−1/2, y, −z+3/2.

References

Brandenburg, K. (2006). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Duisenberg, A. J. M. (1992). J. Appl. Cryst. 25, 92–96. CrossRef CAS Web of Science IUCr Journals Google Scholar
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Krautscheild, K., Lode, C., Vielsack, F. & Vollmer, H. (2001). J. Chem. Soc. Dalton Trans. pp. 1099–1104.. Google Scholar
Lode, C. & Krautscheild, H. (2001). Z. Anorg. Allg. Chem. 627 1454–1458. CrossRef CAS Google Scholar
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doi:10.1107/S1600536808013913

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

The one-dimensional organic inorganic hybrid compound poly[(di­ethyl­ene­tri­amine)tetra-μ-iodido-dilead(II)]

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

References

metal-organic compounds

The one-dimensional organic inorganic hybrid compound poly[(diethylenetriamine)tetra-μ-iodido-dilead(II)]