catena-Poly[1,1′-dimethyl-4,4′-(ethane-1,2-di­yl)dipyridinium [lead(II)-tri-μ-iodido-lead(II)-tri-μ-iodido]]

Xu, G.; He, X.

doi:10.1107/S160053681102006X

metal-organic compounds

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ISSN: 2056-9890

Volume 67| Part 7| July 2011| Page m847

doi:10.1107/S160053681102006X

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catena-Poly[1,1′-dimethyl-4,4′-(ethane-1,2-diyl)dipyridinium [lead(II)-tri-μ-iodido-lead(II)-tri-μ-iodido]]

Guohai Xu ^a ^* and Xiyun He ^a

^aKey Laboratory of Jiangxi University for Functional Materials Chemistry, Department of Chemistry and Life Science, Gannan Normal University, Ganzhou, Jiangxi 341000, People's Republic of China
^*Correspondence e-mail: xugh308@126.com

(Received 20 May 2011; accepted 26 May 2011; online 4 June 2011)

The title compound, {(C₁₄H₁₈N₂)[Pb₂I₆]}_n, consists of discrete 1,1′-dimethyl-4,4′-(ethane-1,2-diyl)dipyridinium cations and one-dimensional [Pb₂I₆]_n anions. The organic cation has an inversion center at the mid-point of the ethane C—C bond. In the anion, the Pb^II atom is coordinated by six I atoms in a distorted octahedral geometry. The I atoms bridge the Pb^II atoms into a polymeric chain running along [001]. These inorganic chains are separated by the isolated organic cations.

Related literature

For general background to the applications of metal halides, see: Jin et al. (2011 ); Manjunatha et al. (2011 ). For bond-length data, see: Lemmerer & Billing (2006 ).

Experimental

Crystal data

(C₁₄H₁₈N₂)[Pb₂I₆]
M_r = 1390.08
Monoclinic, P 2₁ /c
a = 10.120 (6) Å
b = 17.575 (10) Å
c = 8.025 (4) Å
β = 101.239 (10)°
V = 1399.9 (13) Å³
Z = 2
Mo Kα radiation
μ = 18.63 mm⁻¹
T = 296 K
0.25 × 0.20 × 0.19 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ) T_min = 0.016, T_max = 0.030
22768 measured reflections
3425 independent reflections
2838 reflections with I > 2σ(I)
R_int = 0.038

Refinement

R[F² > 2σ(F²)] = 0.022
wR(F²) = 0.046
S = 1.02
3425 reflections
109 parameters
H-atom parameters constrained
Δρ_max = 0.79 e Å⁻³
Δρ_min = −1.16 e Å⁻³

Table 1
Selected bond lengths (Å)

Pb1—I1	3.2296 (13)
Pb1—I1ⁱ	3.2214 (13)
Pb1—I2	3.2311 (11)
Pb1—I2ⁱⁱ	3.1724 (11)
Pb1—I3	3.2435 (12)
Pb1—I3ⁱⁱ	3.2073 (12)
Symmetry codes: (i) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (ii) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053681102006X/hy2435sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053681102006X/hy2435Isup2.hkl

checkCIF report

Comment top

Organic–inorganic hybrid materials offer an important opportunity to combine useful properties of inorganic and organic systems within a single molecular-scale composite (Manjunatha et al., 2011). As a member of this family, there continues to be interest in the study on the design and synthesis of novel metal halides due to their potential applications in the fields of optics and electrical conductivity, as well as their structural diversity (Jin et al., 2011). In this contribution, we use 1,1'-dimethyl-4,4'-(ethane-1,2-diyl)dipyridinium dichloride as an organic ligand, generating an organic-inorganic hybrid, which is reported here.

The title compound consists of discrete 1,1'-dimethyl-4,4'-(ethane-1,2-diyl)dipyridinium cations and one-dimensional ploymeric anions, [Pb₂I₆]_n. The organic cation has an inversion center at the middle of the ethane C—C bond. In the anion, the Pb^II atom is coordinated by six iodide atoms in a distorted octahedral geometry (Fig. 1). The Pb—I bond lengths lie in a normal range (Table 1) (Lemmerer & Billing, 2006). The iodide atoms bridge the Pb^II atoms, forming polymeric chains running along [0 0 1]. These inorganic chains are separated by the isolated organic cations.

Related literature top

For general background to the applications of metal halides, see: Jin et al. (2011); Manjunatha et al. (2011). For bond-length data, see: Lemmerer & Billing (2006).

Experimental top

A mixture of 1,1'-dimethyl-4,4'-(ethane-1,2-diyl)dipyridinium dichloride (0.1 mmol, 0.030 g), KI (0.6 mmol, 0.10 g) and Pb(NO₃)₂ (0.2 mmol, 0.0662 g) in distilled water (12 ml) was placed in a Teflon-lined stainless steel vessel, heated to 423 K for 4 d and then cooled to room temperature over 12 h. Black block crystals were obtained after five months by slow evaporation of the solvent (yield: 62% based on Pb).

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. The structure of the title compound. Displacement ellipsoids are drawn at the 30% probability level. [Symmetry codes: (i) 1-x, -y, 1-z; (ii) x, 1/2-y, -1/2+z; (iii) x, 1/2-y, 1/2+z; (iv) x, y, 1+z.]

catena-Poly[1,1'-dimethyl-4,4'-(ethane-1,2-diyl)dipyridinium [lead(II)-tri-µ-iodido-lead(II)-tri-µ-iodido]] top

Crystal data top

(C₁₄H₁₈N₂)[Pb₂I₆]	F(000) = 1196
M_r = 1390.08	D_x = 3.298 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3425 reflections
a = 10.120 (6) Å	θ = 1.0–28.2°
b = 17.575 (10) Å	µ = 18.63 mm⁻¹
c = 8.025 (4) Å	T = 296 K
β = 101.239 (10)°	Block, black
V = 1399.9 (13) Å³	0.25 × 0.20 × 0.19 mm
Z = 2

Data collection top

Bruker APEXII CCD diffractometer	3425 independent reflections
Radiation source: fine-focus sealed tube	2838 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.038
ϕ and ω scans	θ_max = 28.2°, θ_min = 2.6°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −13→13
T_min = 0.016, T_max = 0.030	k = −23→23
22768 measured reflections	l = −10→10

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)] = 0.022	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.046	H-atom parameters constrained
S = 1.02	w = 1/[σ²(F_o²) + (0.0121P)² + 2.6844P] where P = (F_o² + 2F_c²)/3
3425 reflections	(Δ/σ)_max = 0.002
109 parameters	Δρ_max = 0.79 e Å⁻³
0 restraints	Δρ_min = −1.16 e Å⁻³

Crystal data top

(C₁₄H₁₈N₂)[Pb₂I₆]	V = 1399.9 (13) Å³
M_r = 1390.08	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 10.120 (6) Å	µ = 18.63 mm⁻¹
b = 17.575 (10) Å	T = 296 K
c = 8.025 (4) Å	0.25 × 0.20 × 0.19 mm
β = 101.239 (10)°

Data collection top

Bruker APEXII CCD diffractometer	3425 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2001)	2838 reflections with I > 2σ(I)
T_min = 0.016, T_max = 0.030	R_int = 0.038
22768 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.022	0 restraints
wR(F²) = 0.046	H-atom parameters constrained
S = 1.02	Δρ_max = 0.79 e Å⁻³
3425 reflections	Δρ_min = −1.16 e Å⁻³
109 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
C1	0.3721 (5)	0.0444 (3)	0.6192 (6)	0.0475 (11)
C2	0.4292 (6)	0.1058 (4)	0.7117 (8)	0.0714 (17)
H2	0.5030	0.1300	0.6817	0.086*
C3	0.3793 (6)	0.1318 (4)	0.8467 (8)	0.0678 (16)
H3	0.4190	0.1734	0.9084	0.081*
C4	0.2127 (5)	0.0402 (3)	0.7986 (7)	0.0542 (13)
H4	0.1365	0.0184	0.8274	0.065*
C5	0.2599 (5)	0.0132 (3)	0.6641 (7)	0.0495 (12)
H5	0.2158	−0.0269	0.6011	0.059*
C6	0.2247 (6)	0.1251 (4)	1.0451 (8)	0.0715 (17)
H6A	0.1488	0.0950	1.0604	0.107*
H6B	0.1983	0.1775	1.0303	0.107*
H6C	0.2955	0.1202	1.1433	0.107*
C7	0.4287 (5)	0.0148 (3)	0.4740 (6)	0.0538 (12)
H7A	0.4275	0.0552	0.3913	0.065*
H7B	0.3715	−0.0259	0.4194	0.065*
N1	0.2741 (4)	0.0979 (2)	0.8906 (5)	0.0521 (10)
I1	0.84206 (3)	0.106359 (17)	0.85470 (4)	0.04934 (8)
I2	1.04264 (4)	0.16980 (2)	0.40344 (5)	0.06218 (11)
I3	0.60383 (3)	0.190241 (18)	0.29726 (4)	0.04830 (8)
Pb1	0.835213 (18)	0.251424 (10)	0.60612 (2)	0.04107 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.043 (3)	0.050 (3)	0.047 (3)	−0.010 (2)	0.003 (2)	0.003 (2)
C2	0.060 (3)	0.092 (4)	0.068 (4)	−0.031 (3)	0.027 (3)	−0.018 (3)
C3	0.059 (3)	0.084 (4)	0.064 (4)	−0.027 (3)	0.019 (3)	−0.027 (3)
C4	0.041 (3)	0.052 (3)	0.072 (4)	−0.003 (2)	0.016 (3)	0.009 (3)
C5	0.043 (3)	0.040 (2)	0.067 (3)	−0.0040 (19)	0.012 (2)	0.000 (2)
C6	0.054 (3)	0.102 (5)	0.061 (4)	0.011 (3)	0.019 (3)	−0.008 (3)
C7	0.053 (3)	0.064 (3)	0.044 (3)	−0.017 (2)	0.008 (2)	−0.004 (2)
N1	0.045 (2)	0.063 (3)	0.048 (3)	0.0076 (19)	0.0089 (19)	0.003 (2)
I1	0.05674 (19)	0.04184 (15)	0.04717 (19)	−0.00310 (13)	0.00453 (14)	−0.00125 (13)
I2	0.0597 (2)	0.0799 (2)	0.0471 (2)	0.02966 (18)	0.01069 (16)	0.00598 (17)
I3	0.04488 (17)	0.05507 (18)	0.04462 (18)	−0.00848 (13)	0.00792 (13)	0.00162 (14)
Pb1	0.04505 (10)	0.04862 (10)	0.02984 (9)	−0.00104 (7)	0.00803 (7)	−0.00048 (7)

Geometric parameters (Å, º) top

C1—C5	1.371 (6)	C6—H6A	0.9600
C1—C2	1.372 (7)	C6—H6B	0.9600
C1—C7	1.489 (7)	C6—H6C	0.9600
C2—C3	1.361 (8)	C7—C7ⁱ	1.514 (10)
C2—H2	0.9300	C7—H7A	0.9700
C3—N1	1.326 (7)	C7—H7B	0.9700
C3—H3	0.9300	Pb1—I1	3.2296 (13)
C4—N1	1.334 (6)	Pb1—I1ⁱⁱ	3.2214 (13)
C4—C5	1.349 (7)	Pb1—I2	3.2311 (11)
C4—H4	0.9300	Pb1—I2ⁱⁱⁱ	3.1724 (11)
C5—H5	0.9300	Pb1—I3	3.2435 (12)
C6—N1	1.502 (7)	Pb1—I3ⁱⁱⁱ	3.2073 (12)

C5—C1—C2	117.1 (5)	C1—C7—H7B	108.9
C5—C1—C7	122.1 (4)	C7ⁱ—C7—H7B	108.9
C2—C1—C7	120.8 (4)	H7A—C7—H7B	107.7
C3—C2—C1	120.8 (5)	C3—N1—C4	120.4 (5)
C3—C2—H2	119.6	C3—N1—C6	119.3 (5)
C1—C2—H2	119.6	C4—N1—C6	120.3 (4)
N1—C3—C2	120.2 (5)	Pb1ⁱⁱⁱ—I1—Pb1	76.93 (4)
N1—C3—H3	119.9	Pb1ⁱⁱ—I2—Pb1	77.60 (4)
C2—C3—H3	119.9	Pb1ⁱⁱ—I3—Pb1	76.93 (4)
N1—C4—C5	120.7 (5)	I2ⁱⁱⁱ—Pb1—I3ⁱⁱⁱ	86.47 (4)
N1—C4—H4	119.6	I2ⁱⁱⁱ—Pb1—I1ⁱⁱ	92.33 (4)
C5—C4—H4	119.6	I3ⁱⁱⁱ—Pb1—I1ⁱⁱ	99.11 (3)
C4—C5—C1	120.7 (5)	I2ⁱⁱⁱ—Pb1—I1	87.05 (4)
C4—C5—H5	119.6	I3ⁱⁱⁱ—Pb1—I1	83.49 (3)
C1—C5—H5	119.6	I1ⁱⁱ—Pb1—I1	177.283 (13)
N1—C6—H6A	109.5	I2ⁱⁱⁱ—Pb1—I2	99.95 (4)
N1—C6—H6B	109.5	I3ⁱⁱⁱ—Pb1—I2	171.539 (12)
H6A—C6—H6B	109.5	I1ⁱⁱ—Pb1—I2	86.20 (3)
N1—C6—H6C	109.5	I1—Pb1—I2	91.30 (1)
H6A—C6—H6C	109.5	I2ⁱⁱⁱ—Pb1—I3	173.097 (12)
H6B—C6—H6C	109.5	I3ⁱⁱⁱ—Pb1—I3	89.19 (4)
C1—C7—C7ⁱ	113.3 (5)	I1ⁱⁱ—Pb1—I3	83.05 (3)
C1—C7—H7A	108.9	I1—Pb1—I3	97.80 (1)
C7ⁱ—C7—H7A	108.9	I2—Pb1—I3	84.91 (1)

C5—C1—C2—C3	3.0 (9)	Pb1ⁱⁱⁱ—I1—Pb1—I2ⁱⁱⁱ	41.42 (2)
C7—C1—C2—C3	−178.5 (6)	Pb1ⁱⁱⁱ—I1—Pb1—I3ⁱⁱⁱ	−45.363 (18)
C1—C2—C3—N1	−0.1 (10)	Pb1ⁱⁱⁱ—I1—Pb1—I2	141.321 (18)
N1—C4—C5—C1	0.1 (8)	Pb1ⁱⁱⁱ—I1—Pb1—I3	−133.64 (2)
C2—C1—C5—C4	−3.0 (8)	Pb1ⁱⁱ—I2—Pb1—I2ⁱⁱⁱ	−133.01 (3)
C7—C1—C5—C4	178.6 (5)	Pb1ⁱⁱ—I2—Pb1—I1ⁱⁱ	−41.307 (16)
C5—C1—C7—C7ⁱ	−118.8 (6)	Pb1ⁱⁱ—I2—Pb1—I1	139.759 (16)
C2—C1—C7—C7ⁱ	62.9 (8)	Pb1ⁱⁱ—I2—Pb1—I3	42.04 (2)
C2—C3—N1—C4	−3.0 (9)	Pb1ⁱⁱ—I3—Pb1—I3ⁱⁱⁱ	144.45 (2)
C2—C3—N1—C6	177.1 (6)	Pb1ⁱⁱ—I3—Pb1—I1ⁱⁱ	45.168 (14)
C5—C4—N1—C3	3.0 (8)	Pb1ⁱⁱ—I3—Pb1—I1	−132.231 (15)
C5—C4—N1—C6	−177.1 (5)	Pb1ⁱⁱ—I3—Pb1—I2	−41.62 (2)

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

Experimental details

Crystal data
Chemical formula	(C₁₄H₁₈N₂)[Pb₂I₆]
M_r	1390.08
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	10.120 (6), 17.575 (10), 8.025 (4)
β (°)	101.239 (10)
V (Å³)	1399.9 (13)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	18.63
Crystal size (mm)	0.25 × 0.20 × 0.19

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2001)
T_min, T_max	0.016, 0.030
No. of measured, independent and observed [I > 2σ(I)] reflections	22768, 3425, 2838
R_int	0.038
(sin θ/λ)_max (Å⁻¹)	0.664

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.022, 0.046, 1.02
No. of reflections	3425
No. of parameters	109
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.79, −1.16

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXTL (Sheldrick, 2008).

Selected bond lengths (Å) top

Pb1—I1	3.2296 (13)	Pb1—I2ⁱⁱ	3.1724 (11)
Pb1—I1ⁱ	3.2214 (13)	Pb1—I3	3.2435 (12)
Pb1—I2	3.2311 (11)	Pb1—I3ⁱⁱ	3.2073 (12)

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

Acknowledgements

This work was supported by the NSF of Jiangxi Province (grant No. 2010GQH0022) and the Development Program of Science and Technology of the Education Department of Jiangxi Province (grant No. GJJ10716).

References

Bruker (2001). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Jin, J., Jia, M.-J., Peng, Y., Yu, J.-H. & Xu, J.-Q. (2011). CrystEngComm, 13, 2942–2947. Web of Science CSD CrossRef CAS Google Scholar
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Manjunatha, M. N., Ziaulla, M., Sankolli, R., Begum, N. S. & Nagasundara, K. R. (2011). Acta Cryst. E67, m578. Web of Science CSD CrossRef IUCr Journals Google Scholar
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