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

Abstract

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,

• a = 10.120 (6) Å

• b = 17.575 (10) Å

• c = 8.025 (4) Å

• β = 101.239 (10)°

• V = 1399.9 (13) ų

• 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[F ² > 2σ(F ²)] = 0.022

• wR(F ²) = 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

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.

Supplementary Material

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

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) ; (ii) .

supplementary crystallographic information

Comment

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.

Experimental

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

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 U_iso(H) = 1.2(1.5 for methyl)U_eq(C).

Figures

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.]

Crystal data

(C14H18N2)[Pb2I6]	F(000) = 1196
Mr = 1390.08	Dx = 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

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

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)] = 0.022	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.046	H-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 parameters	Δρmax = 0.79 e Å−3
0 restraints	Δρmin = −1.16 e Å−3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	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, °)

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.