1-Amino­pyridinium triiodidoplumbate(II)

Yu, S.-S.; Xian, H.; Duan, H.-B.

doi:10.1107/S1600536810036263

metal-organic compounds

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ISSN: 2056-9890

Volume 66| Part 10| October 2010| Page m1259

doi:10.1107/S1600536810036263

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1-Aminopyridinium triiodidoplumbate(II)

Shan-Shan Yu,^a Hua Xian ^a and Hai-Bao Duan ^a ^*

^aDepartment of Chemistry, Nanjing Xiaozhuang College, Nanjing 210017, People's Republic of China
^*Correspondence e-mail: duanhaibao4660@163.com

(Received 21 August 2010; accepted 9 September 2010; online 15 September 2010)

The title complex, (C₅H₇N₂)[PbI₃], consists of a 1-aminopyridinium cation, disordered about a mirror plane, and a [PbI₃]⁻ anion. The Pb²⁺ ion (site symmetry $[\overline{1}]$ ) is surrounded by six I atoms in a slightly distorted octahedral coordination. The PbI₆ octahedra share faces, building up _∞¹[PbI_6/2] chains running along [010]. The cations are situated between the chains. Coulombic attractions and van der Waals interactions between the inorganic and organic components are mainly responsible for the cohesion of the structure.

Related literature

For background to hybrid materials, see: Rogow et al. (2010 ); Thirumurugan & Rao (2008 ). For structures with lead halide building blocks, see: Li et al. (2008 ); Zhang et al. (2008 ).

Experimental

Crystal data

(C₅H₇N₂)[PbI₃]
M_r = 683.03
Orthorhombic, P n m a
a = 15.0417 (19) Å
b = 8.1316 (10) Å
c = 10.5625 (14) Å
V = 1291.9 (3) Å³
Z = 4
Mo Kα radiation
μ = 20.18 mm⁻¹
T = 296 K
0.6 × 0.2 × 0.1 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2000 ) T_min = 0.011, T_max = 0.133
10792 measured reflections
1607 independent reflections
1263 reflections with I > 2σ(I)
R_int = 0.036

Refinement

R[F² > 2σ(F²)] = 0.025
wR(F²) = 0.056
S = 1.11
1607 reflections
61 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.86 e Å⁻³
Δρ_min = −1.05 e Å⁻³

Table 1
Selected bond lengths (Å)

Pb1—I3	3.2301 (5)
Pb1—I1	3.2303 (5)
Pb1—I2	3.2412 (5)

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); 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/S1600536810036263/wm2395sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810036263/wm2395Isup2.hkl

checkCIF report

Comment top

Inorganic metal-halide building-blocks have received special attention with respect to the construction of inorganic-organic hybrid materials (Rogow et al., 2010; Thirumurugan et al., 2008). Among these materials octahedral building blocks of lead halides are frequently found and numerous crystal structures, from one-dimensional chains to three-dimensional frameworks (Li et al., 2008; Zhang et al., 2008), were observed. Herein we report the crystal structure of the title compound, (C₅H₇N₂)[PbI₃] (I).

Compound (I) crystallizes with one [PbI₃]^- anion and one 1-aminopyridinium cation in the asymmetric unit (Fig. 1). The cation is disordered about a mirror plane. The Pb²⁺ cation is coordinated by six iodide anions in a slightly distorted octahedral coordination geometry. The PbI₆ octahedra share faces, resulting in anionic chains running along [010]. As show in Fig. 2., the straight inorganic chains are embedded in cationic stacks. Besides Coulomb attractions, only weak van der Waals interactions between the inorganic and organic components exist.

Related literature top

For background to hybrid materials, see: Rogow et al. (2010); Thirumurugan & Rao (2008). For structures with lead halide building blocks, see: Li et al. (2008); Zhang et al. (2008).

Experimental top

A mixture of PbI₂ (922 mg, 2.0 mmol) and 1-aminopyridinium iodide (190 mg, 2.0 mmol) in a molar ratio of 1:1 in DMF was slowly evaporated to produce orange needle-shaped crystals.

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); 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. Part of the structure of (I), showing the atom-numbering scheme and displacement ellipsoids at the 30% probability level. Atom C3 and N1 are positionally disordered. H atoms have been omitted for clyrity. [Symmetry code: A x, 0.5 - y, z.]
	Fig. 2. The alignment of inorganic and organic components in the crystals of l along [010].

1-Aminopyridinium triiodidoplumbate(II) top

Crystal data top

(C₅H₇N₂)[PbI₃]	Z = 4
M_r = 683.03	F(000) = 1168
Orthorhombic, Pnma	D_x = 3.512 Mg m⁻³
Hall symbol: -P 2ac 2n	Mo Kα radiation, λ = 0.71073 Å
a = 15.0417 (19) Å	µ = 20.18 mm⁻¹
b = 8.1316 (10) Å	T = 296 K
c = 10.5625 (14) Å	Needle, orange
V = 1291.9 (3) Å³	0.6 × 0.2 × 0.1 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	1607 independent reflections
Radiation source: fine-focus sealed tube	1263 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.036
phi and ω scans	θ_max = 27.6°, θ_min = 2.4°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −19→19
T_min = 0.011, T_max = 0.133	k = −10→10
10792 measured reflections	l = −13→13

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)] = 0.025	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.056	H-atom parameters constrained
S = 1.11	w = 1/[σ²(F_o²) + (0.016P)² + 2.8133P] where P = (F_o² + 2F_c²)/3
1607 reflections	(Δ/σ)_max = 0.001
61 parameters	Δρ_max = 0.86 e Å⁻³
1 restraint	Δρ_min = −1.05 e Å⁻³

Crystal data top

(C₅H₇N₂)[PbI₃]	V = 1291.9 (3) Å³
M_r = 683.03	Z = 4
Orthorhombic, Pnma	Mo Kα radiation
a = 15.0417 (19) Å	µ = 20.18 mm⁻¹
b = 8.1316 (10) Å	T = 296 K
c = 10.5625 (14) Å	0.6 × 0.2 × 0.1 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	1607 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2000)	1263 reflections with I > 2σ(I)
T_min = 0.011, T_max = 0.133	R_int = 0.036
10792 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.025	1 restraint
wR(F²) = 0.056	H-atom parameters constrained
S = 1.11	Δρ_max = 0.86 e Å⁻³
1607 reflections	Δρ_min = −1.05 e Å⁻³
61 parameters

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s 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	Occ. (<1)
Pb1	0.5000	0.5000	0.5000	0.05028 (11)
I1	0.66188 (4)	0.2500	0.44218 (7)	0.06995 (19)
I2	0.45861 (4)	0.2500	0.73162 (5)	0.05961 (16)
I3	0.38187 (5)	0.2500	0.33215 (6)	0.06837 (19)
C1	0.0996 (6)	0.1682 (10)	0.4247 (8)	0.100 (3)
H1	0.0708	0.1100	0.3609	0.120*
C2	0.1419 (7)	0.0883 (12)	0.5186 (9)	0.103 (3)
H2	0.1424	−0.0261	0.5197	0.123*
C3	0.1824 (5)	0.1708 (11)	0.6087 (7)	0.100 (3)	0.50
H3	0.2114	0.1142	0.6731	0.120*	0.50
N1	0.1824 (5)	0.1708 (11)	0.6087 (7)	0.100 (3)	0.50
N2	0.2230 (10)	0.132 (2)	0.7177 (16)	0.121 (5)	0.50
H2A	0.2415	0.2091	0.7672	0.146*	0.50
H2B	0.2307	0.0310	0.7382	0.146*	0.50

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Pb1	0.0585 (2)	0.03787 (16)	0.05448 (19)	0.00017 (13)	0.00130 (15)	−0.00097 (14)
I1	0.0549 (3)	0.0611 (4)	0.0938 (5)	0.000	0.0189 (3)	0.000
I2	0.0727 (4)	0.0575 (3)	0.0486 (3)	0.000	0.0023 (3)	0.000
I3	0.0753 (4)	0.0603 (4)	0.0696 (4)	0.000	−0.0268 (3)	0.000
C1	0.120 (7)	0.100 (6)	0.081 (5)	−0.001 (5)	−0.015 (5)	−0.010 (5)
C2	0.104 (7)	0.089 (6)	0.114 (8)	−0.005 (5)	0.008 (6)	0.004 (6)
C3	0.064 (4)	0.162 (9)	0.074 (5)	0.010 (4)	0.010 (3)	0.026 (5)
N1	0.064 (4)	0.162 (9)	0.074 (5)	0.010 (4)	0.010 (3)	0.026 (5)
N2	0.111 (11)	0.121 (12)	0.133 (13)	0.004 (10)	−0.004 (11)	0.029 (11)

Geometric parameters (Å, º) top

Pb1—I3ⁱ	3.2301 (5)	C1—C1ⁱⁱⁱ	1.331 (16)
Pb1—I3	3.2301 (5)	C1—C2	1.345 (12)
Pb1—I1	3.2303 (5)	C1—H1	0.9300
Pb1—I1ⁱ	3.2303 (5)	C2—C3	1.315 (11)
Pb1—I2	3.2412 (5)	C2—H2	0.9300
Pb1—I2ⁱ	3.2412 (5)	C3—C3ⁱⁱⁱ	1.288 (18)
I1—Pb1ⁱⁱ	3.2303 (5)	C3—H3	0.9300
I2—Pb1ⁱⁱ	3.2412 (5)	N2—H2A	0.8600
I3—Pb1ⁱⁱ	3.2301 (5)	N2—H2B	0.8600

I3ⁱ—Pb1—I3	180.0	I2—Pb1—I2ⁱ	180.0
I3ⁱ—Pb1—I1	94.886 (17)	Pb1ⁱⁱ—I1—Pb1	78.000 (17)
I3—Pb1—I1	85.114 (17)	Pb1ⁱⁱ—I2—Pb1	77.688 (16)
I3ⁱ—Pb1—I1ⁱ	85.114 (17)	Pb1—I3—Pb1ⁱⁱ	78.007 (16)
I3—Pb1—I1ⁱ	94.886 (17)	C1ⁱⁱⁱ—C1—C2	118.9 (6)
I1—Pb1—I1ⁱ	180.0	C1ⁱⁱⁱ—C1—H1	120.6
I3ⁱ—Pb1—I2	94.940 (16)	C2—C1—H1	120.6
I3—Pb1—I2	85.060 (16)	C3—C2—C1	120.4 (9)
I1—Pb1—I2	83.844 (15)	C3—C2—H2	119.8
I1ⁱ—Pb1—I2	96.156 (15)	C1—C2—H2	119.8
I3ⁱ—Pb1—I2ⁱ	85.060 (16)	C3ⁱⁱⁱ—C3—C2	120.7 (6)
I3—Pb1—I2ⁱ	94.940 (16)	C3ⁱⁱⁱ—C3—H3	119.7
I1—Pb1—I2ⁱ	96.156 (15)	C2—C3—H3	119.7
I1ⁱ—Pb1—I2ⁱ	83.844 (15)	H2A—N2—H2B	120.0

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

Experimental details

Crystal data
Chemical formula	(C₅H₇N₂)[PbI₃]
M_r	683.03
Crystal system, space group	Orthorhombic, Pnma
Temperature (K)	296
a, b, c (Å)	15.0417 (19), 8.1316 (10), 10.5625 (14)
V (Å³)	1291.9 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	20.18
Crystal size (mm)	0.6 × 0.2 × 0.1

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2000)
T_min, T_max	0.011, 0.133
No. of measured, independent and observed [I > 2σ(I)] reflections	10792, 1607, 1263
R_int	0.036
(sin θ/λ)_max (Å⁻¹)	0.652

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.025, 0.056, 1.11
No. of reflections	1607
No. of parameters	61
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.86, −1.05

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXTL (Sheldrick, 2008).

Selected bond lengths (Å) top

Pb1—I3	3.2301 (5)	Pb1—I2	3.2412 (5)
Pb1—I1	3.2303 (5)

Acknowledgements

The authors thank the Science and Technology Department of Jiangsu Province for financial support (grant No 10774076).

References

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