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

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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]]

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 PbII atom is coordinated by six I atoms in a distorted octa­hedral geometry. The I atoms bridge the PbII 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[Jin, J., Jia, M.-J., Peng, Y., Yu, J.-H. & Xu, J.-Q. (2011). CrystEngComm, 13, 2942-2947.]); Manjunatha et al. (2011[Manjunatha, M. N., Ziaulla, M., Sankolli, R., Begum, N. S. & Nagasundara, K. R. (2011). Acta Cryst. E67, m578.]). For bond-length data, see: Lemmerer & Billing (2006[Lemmerer, A. & Billing, D. G. (2006). Acta Cryst. E62, m904-m906.]).

[Scheme 1]

Experimental

Crystal data
  • (C14H18N2)[Pb2I6]

  • Mr = 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[Bruker (2001). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]) Tmin = 0.016, Tmax = 0.030

  • 22768 measured reflections

  • 3425 independent reflections

  • 2838 reflections with I > 2σ(I)

  • Rint = 0.038

Refinement
  • R[F2 > 2σ(F2)] = 0.022

  • wR(F2) = 0.046

  • S = 1.02

  • 3425 reflections

  • 109 parameters

  • H-atom parameters constrained

  • Δρmax = 0.79 e Å−3

  • Δρmin = −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[Bruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2007[Bruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information


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 PbII 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 PbII 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).

Refinement top

H atoms were positioned geometrically and refined as riding atoms, with C—H = 0.93 (CH), 0.97 (CH2) and 0.96 (CH3) Å and Uiso(H) = 1.2(1.5 for methyl)Ueq(C).

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
[Figure 1] 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
Mr = 1390.08Dx = 3.298 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 3425 reflections
a = 10.120 (6) Åθ = 1.0–28.2°
b = 17.575 (10) ŵ = 18.63 mm1
c = 8.025 (4) ÅT = 296 K
β = 101.239 (10)°Block, black
V = 1399.9 (13) Å30.25 × 0.20 × 0.19 mm
Z = 2
Data collection top
Bruker APEXII CCD
diffractometer
3425 independent reflections
Radiation source: fine-focus sealed tube2838 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.038
ϕ and ω scansθmax = 28.2°, θmin = 2.6°
Absorption correction: multi-scan
(SADABS; Bruker, 2001)
h = 1313
Tmin = 0.016, Tmax = 0.030k = 2323
22768 measured reflectionsl = 1010
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.022Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.046H-atom parameters constrained
S = 1.02 w = 1/[σ2(Fo2) + (0.0121P)2 + 2.6844P]
where P = (Fo2 + 2Fc2)/3
3425 reflections(Δ/σ)max = 0.002
109 parametersΔρmax = 0.79 e Å3
0 restraintsΔρmin = 1.16 e Å3
Crystal data top
(C14H18N2)[Pb2I6]V = 1399.9 (13) Å3
Mr = 1390.08Z = 2
Monoclinic, P21/cMo Kα radiation
a = 10.120 (6) ŵ = 18.63 mm1
b = 17.575 (10) ÅT = 296 K
c = 8.025 (4) Å0.25 × 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)
Tmin = 0.016, Tmax = 0.030Rint = 0.038
22768 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0220 restraints
wR(F2) = 0.046H-atom parameters constrained
S = 1.02Δρmax = 0.79 e Å3
3425 reflectionsΔρmin = 1.16 e Å3
109 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C10.3721 (5)0.0444 (3)0.6192 (6)0.0475 (11)
C20.4292 (6)0.1058 (4)0.7117 (8)0.0714 (17)
H20.50300.13000.68170.086*
C30.3793 (6)0.1318 (4)0.8467 (8)0.0678 (16)
H30.41900.17340.90840.081*
C40.2127 (5)0.0402 (3)0.7986 (7)0.0542 (13)
H40.13650.01840.82740.065*
C50.2599 (5)0.0132 (3)0.6641 (7)0.0495 (12)
H50.21580.02690.60110.059*
C60.2247 (6)0.1251 (4)1.0451 (8)0.0715 (17)
H6A0.14880.09501.06040.107*
H6B0.19830.17751.03030.107*
H6C0.29550.12021.14330.107*
C70.4287 (5)0.0148 (3)0.4740 (6)0.0538 (12)
H7A0.42750.05520.39130.065*
H7B0.37150.02590.41940.065*
N10.2741 (4)0.0979 (2)0.8906 (5)0.0521 (10)
I10.84206 (3)0.106359 (17)0.85470 (4)0.04934 (8)
I21.04264 (4)0.16980 (2)0.40344 (5)0.06218 (11)
I30.60383 (3)0.190241 (18)0.29726 (4)0.04830 (8)
Pb10.835213 (18)0.251424 (10)0.60612 (2)0.04107 (5)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.043 (3)0.050 (3)0.047 (3)0.010 (2)0.003 (2)0.003 (2)
C20.060 (3)0.092 (4)0.068 (4)0.031 (3)0.027 (3)0.018 (3)
C30.059 (3)0.084 (4)0.064 (4)0.027 (3)0.019 (3)0.027 (3)
C40.041 (3)0.052 (3)0.072 (4)0.003 (2)0.016 (3)0.009 (3)
C50.043 (3)0.040 (2)0.067 (3)0.0040 (19)0.012 (2)0.000 (2)
C60.054 (3)0.102 (5)0.061 (4)0.011 (3)0.019 (3)0.008 (3)
C70.053 (3)0.064 (3)0.044 (3)0.017 (2)0.008 (2)0.004 (2)
N10.045 (2)0.063 (3)0.048 (3)0.0076 (19)0.0089 (19)0.003 (2)
I10.05674 (19)0.04184 (15)0.04717 (19)0.00310 (13)0.00453 (14)0.00125 (13)
I20.0597 (2)0.0799 (2)0.0471 (2)0.02966 (18)0.01069 (16)0.00598 (17)
I30.04488 (17)0.05507 (18)0.04462 (18)0.00848 (13)0.00792 (13)0.00162 (14)
Pb10.04505 (10)0.04862 (10)0.02984 (9)0.00104 (7)0.00803 (7)0.00048 (7)
Geometric parameters (Å, º) top
C1—C51.371 (6)C6—H6A0.9600
C1—C21.372 (7)C6—H6B0.9600
C1—C71.489 (7)C6—H6C0.9600
C2—C31.361 (8)C7—C7i1.514 (10)
C2—H20.9300C7—H7A0.9700
C3—N11.326 (7)C7—H7B0.9700
C3—H30.9300Pb1—I13.2296 (13)
C4—N11.334 (6)Pb1—I1ii3.2214 (13)
C4—C51.349 (7)Pb1—I23.2311 (11)
C4—H40.9300Pb1—I2iii3.1724 (11)
C5—H50.9300Pb1—I33.2435 (12)
C6—N11.502 (7)Pb1—I3iii3.2073 (12)
C5—C1—C2117.1 (5)C1—C7—H7B108.9
C5—C1—C7122.1 (4)C7i—C7—H7B108.9
C2—C1—C7120.8 (4)H7A—C7—H7B107.7
C3—C2—C1120.8 (5)C3—N1—C4120.4 (5)
C3—C2—H2119.6C3—N1—C6119.3 (5)
C1—C2—H2119.6C4—N1—C6120.3 (4)
N1—C3—C2120.2 (5)Pb1iii—I1—Pb176.93 (4)
N1—C3—H3119.9Pb1ii—I2—Pb177.60 (4)
C2—C3—H3119.9Pb1ii—I3—Pb176.93 (4)
N1—C4—C5120.7 (5)I2iii—Pb1—I3iii86.47 (4)
N1—C4—H4119.6I2iii—Pb1—I1ii92.33 (4)
C5—C4—H4119.6I3iii—Pb1—I1ii99.11 (3)
C4—C5—C1120.7 (5)I2iii—Pb1—I187.05 (4)
C4—C5—H5119.6I3iii—Pb1—I183.49 (3)
C1—C5—H5119.6I1ii—Pb1—I1177.283 (13)
N1—C6—H6A109.5I2iii—Pb1—I299.95 (4)
N1—C6—H6B109.5I3iii—Pb1—I2171.539 (12)
H6A—C6—H6B109.5I1ii—Pb1—I286.20 (3)
N1—C6—H6C109.5I1—Pb1—I291.30 (1)
H6A—C6—H6C109.5I2iii—Pb1—I3173.097 (12)
H6B—C6—H6C109.5I3iii—Pb1—I389.19 (4)
C1—C7—C7i113.3 (5)I1ii—Pb1—I383.05 (3)
C1—C7—H7A108.9I1—Pb1—I397.80 (1)
C7i—C7—H7A108.9I2—Pb1—I384.91 (1)
C5—C1—C2—C33.0 (9)Pb1iii—I1—Pb1—I2iii41.42 (2)
C7—C1—C2—C3178.5 (6)Pb1iii—I1—Pb1—I3iii45.363 (18)
C1—C2—C3—N10.1 (10)Pb1iii—I1—Pb1—I2141.321 (18)
N1—C4—C5—C10.1 (8)Pb1iii—I1—Pb1—I3133.64 (2)
C2—C1—C5—C43.0 (8)Pb1ii—I2—Pb1—I2iii133.01 (3)
C7—C1—C5—C4178.6 (5)Pb1ii—I2—Pb1—I1ii41.307 (16)
C5—C1—C7—C7i118.8 (6)Pb1ii—I2—Pb1—I1139.759 (16)
C2—C1—C7—C7i62.9 (8)Pb1ii—I2—Pb1—I342.04 (2)
C2—C3—N1—C43.0 (9)Pb1ii—I3—Pb1—I3iii144.45 (2)
C2—C3—N1—C6177.1 (6)Pb1ii—I3—Pb1—I1ii45.168 (14)
C5—C4—N1—C33.0 (8)Pb1ii—I3—Pb1—I1132.231 (15)
C5—C4—N1—C6177.1 (5)Pb1ii—I3—Pb1—I241.62 (2)
Symmetry codes: (i) x+1, y, z+1; (ii) x, y+1/2, z1/2; (iii) x, y+1/2, z+1/2.

Experimental details

Crystal data
Chemical formula(C14H18N2)[Pb2I6]
Mr1390.08
Crystal system, space groupMonoclinic, P21/c
Temperature (K)296
a, b, c (Å)10.120 (6), 17.575 (10), 8.025 (4)
β (°) 101.239 (10)
V3)1399.9 (13)
Z2
Radiation typeMo Kα
µ (mm1)18.63
Crystal size (mm)0.25 × 0.20 × 0.19
Data collection
DiffractometerBruker APEXII CCD
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 2001)
Tmin, Tmax0.016, 0.030
No. of measured, independent and
observed [I > 2σ(I)] reflections
22768, 3425, 2838
Rint0.038
(sin θ/λ)max1)0.664
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.022, 0.046, 1.02
No. of reflections3425
No. of parameters109
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.79, 1.16

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

Selected bond lengths (Å) top
Pb1—I13.2296 (13)Pb1—I2ii3.1724 (11)
Pb1—I1i3.2214 (13)Pb1—I33.2435 (12)
Pb1—I23.2311 (11)Pb1—I3ii3.2073 (12)
Symmetry codes: (i) x, y+1/2, z1/2; (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

First citationBruker (2001). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.
First citationBruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.
First citationJin, J., Jia, M.-J., Peng, Y., Yu, J.-H. & Xu, J.-Q. (2011). CrystEngComm, 13, 2942–2947.  Web of Science CSD CrossRef CAS
First citationLemmerer, A. & Billing, D. G. (2006). Acta Cryst. E62, m904–m906.  Web of Science CSD CrossRef IUCr Journals
First citationManjunatha, M. N., Ziaulla, M., Sankolli, R., Begum, N. S. & Nagasundara, K. R. (2011). Acta Cryst. E67, m578.  Web of Science CSD CrossRef IUCr Journals
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals

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