catena-Poly[1-[(2-fluoro­benzyl­idene)amino]­quinolinium [plumbate(II)-tri-μ-iodido]]

Zhao, H.-R.

doi:10.1107/S1600536811051853

metal-organic compounds

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Volume 68| Part 1| January 2012| Page m19

doi:10.1107/S1600536811051853

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catena-Poly[1-[(2-fluorobenzylidene)amino]quinolinium [plumbate(II)-tri-μ-iodido]]

Hai-Rong Zhao ^a ^*

^aSchool of Biochemical and Environmental Engineering, Nanjing Xiaozhuang College, Nanjing 210017, People's Republic of China
^*Correspondence e-mail: zhaohairong5@yahoo.com.cn

(Received 28 October 2011; accepted 1 December 2011; online 7 December 2011)

The title complex, {(C₁₆H₁₂FN₂)[PbI₃]}_n, consists of 1-[(2-fluorobenzylidene)amino]quinolinium cations and a polymeric PbI₃⁻ anion formed by face-sharing PbI₆ octahedra. These octahedra form straight and regular infinite chains along the b axis. In the asymmetric unit, one cation and one anionic [PbI₃]⁻ fragment are observed in general positions. Polymeric chains are produced by the glide plane perpendicular to the a axis.

Related literature

For second-order non-linear optical (NLO) properties, pyroelectricity, ferroelectricity and triboluminescence of inorganic-organic hybrid materials, see: Guloy et al. (2001 ); Horiuchi et al. (2010 ); Chen et al. (2001 ). For related structures, see: Bi et al. (2008 ); Zhang et al. (2006 ); Duan et al. (2011 ); Zhao et al. (2010 ).

Experimental

Crystal data

(C₁₆H₁₂FN₂)[PbI₃]
M_r = 839.17
Orthorhombic, P b c a
a = 20.888 (4) Å
b = 7.9112 (15) Å
c = 25.197 (5) Å
V = 4163.8 (14) Å³
Z = 8
Mo Kα radiation
μ = 12.56 mm⁻¹
T = 296 K
0.04 × 0.02 × 0.01 mm

Data collection

Siemens SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2002 ) T_min = 0.747, T_max = 0.882
30847 measured reflections
4090 independent reflections
1770 reflections with I > 2σ(I)
R_int = 0.156

Refinement

R[F² > 2σ(F²)] = 0.047
wR(F²) = 0.082
S = 0.96
4090 reflections
208 parameters
H-atom parameters constrained
Δρ_max = 0.96 e Å⁻³
Δρ_min = −0.95 e Å⁻³

Data collection: SMART (Siemens, 1996 ); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811051853/im2337sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811051853/im2337Isup2.hkl

checkCIF report

Comment top

Inorganic-organic hybrid materials have attracted intense interest in recent years, owing to their technologically important physical properties from optics to electronics, such as second-order nonlinear optical (NLO) properties, (Guloy et al., 2001) pyroelectricity, ferroelectricity (Horiuchi et al., 2010) and triboluminescence (Chen et al., 2001).

Inorganic metal-halide building blocks exhibiting [MX₆]^4-/^3- fragments (M = Sn²⁺, Pb²⁺, Bi³⁺, Sb³⁺; X = F^-, Cl^-, Br^-, I^-) have received special attention in the construction of inorganic-organic hybrid materials (Zhang et al., 2006; Bi et al., 2008). Herein we report the crystal structure of the title compound (I) (Figure 1).

The title compound crystallizes in the orthorhombic space group Pbca with an asymmetric unit containing one anionic PbI₃ fragment together with one Schiff base cation. The polymeric anion [PbI₃]_n^n- possesses slightly distorted PbI₆ octahedra which are linked to polymeric chains by symmetry related atoms (symmetry code 1/2 - x, 1/2 + y, z). Bond lengths and angles are in good agreement with the other structurally characterized compounds with the same anion (Zhao et al., 2010; Duan et al., 2011)

Related literature top

For second-order non-linear optical (NLO) properties, pyroelectricity, ferroelectricity and triboluminescence of inorganic-organic hybrid materials, see: Guloy et al. (2001); Horiuchi et al. (2010); Chen et al. (2001). For related structures, see: Bi et al. (2008); Zhang et al. (2006); Duan et al. (2011); Zhao et al. (2010).

Experimental top

A mixture of PbI₂ (461.3 mg, 1.0 mmol) and 1-(2-fluorobenzylideneamino)-quinolinium iodide (377.9 mg, 1.0 mmol) in a 1:1 molar ratio in DMF was slowly evaporated to produce orange-red needle-shaped crystals. The yield of the compound (1) was 67%.

Computing details top

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT (Siemens, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. Molecular structure of the cation showing displacement ellipsoids at the 30% probability level.
	Fig. 2. Cut-out of the polymeric polyanion consisting of face-sharing PbI₆ octahedra showing displacement ellipsoids at the 30% probability level.

catena-Poly[1-[(2-fluorobenzylidene)amino]quinolinium [plumbate(II)-tri-µ-iodido]] top

Crystal data top

(C₁₆H₁₂FN₂)[PbI₃]	Z = 8
M_r = 839.17	F(000) = 2976
Orthorhombic, Pbca	D_x = 2.677 Mg m⁻³
Hall symbol: -P 2ac 2ab	Mo Kα radiation, λ = 0.71073 Å
a = 20.888 (4) Å	µ = 12.56 mm⁻¹
b = 7.9112 (15) Å	T = 296 K
c = 25.197 (5) Å	Neddle, orange-red
V = 4163.8 (14) Å³	0.04 × 0.02 × 0.01 mm

Data collection top

Siemens SMART CCD area-detector diffractometer	4090 independent reflections
Radiation source: fine-focus sealed tube	1770 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.156
phi and ω scans	θ_max = 26.0°, θ_min = 1.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 2002)	h = −25→25
T_min = 0.747, T_max = 0.882	k = −9→9
30847 measured reflections	l = −31→31

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)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.082	H-atom parameters constrained
S = 0.96	w = 1/[σ²(F_o²) + (0.0158P)²] where P = (F_o² + 2F_c²)/3
4090 reflections	(Δ/σ)_max = 0.001
208 parameters	Δρ_max = 0.96 e Å⁻³
0 restraints	Δρ_min = −0.95 e Å⁻³

Crystal data top

(C₁₆H₁₂FN₂)[PbI₃]	V = 4163.8 (14) Å³
M_r = 839.17	Z = 8
Orthorhombic, Pbca	Mo Kα radiation
a = 20.888 (4) Å	µ = 12.56 mm⁻¹
b = 7.9112 (15) Å	T = 296 K
c = 25.197 (5) Å	0.04 × 0.02 × 0.01 mm

Data collection top

Siemens SMART CCD area-detector diffractometer	4090 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2002)	1770 reflections with I > 2σ(I)
T_min = 0.747, T_max = 0.882	R_int = 0.156
30847 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.047	0 restraints
wR(F²) = 0.082	H-atom parameters constrained
S = 0.96	Δρ_max = 0.96 e Å⁻³
4090 reflections	Δρ_min = −0.95 e Å⁻³
208 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
C12	−0.1124 (8)	0.409 (2)	0.2967 (6)	0.073 (5)
Pb1	0.24868 (3)	0.30676 (6)	0.394853 (19)	0.04686 (15)
I1	0.31600 (4)	0.05236 (13)	0.48094 (3)	0.0538 (3)
I2	0.12891 (4)	0.05643 (12)	0.40030 (4)	0.0583 (3)
I3	0.31533 (4)	0.05436 (13)	0.30998 (3)	0.0596 (3)
F1	−0.1508 (4)	0.4781 (12)	0.2589 (4)	0.111 (4)
N1	0.0224 (5)	0.2690 (14)	0.1530 (4)	0.049 (3)
N2	0.0119 (5)	0.2585 (14)	0.2088 (4)	0.058 (3)
C1	−0.0187 (7)	0.2012 (17)	0.1191 (5)	0.060 (4)
H1	−0.0562	0.1525	0.1318	0.073*
C2	−0.0062 (7)	0.2018 (18)	0.0630 (6)	0.071 (5)
H2	−0.0359	0.1579	0.0392	0.086*
C3	0.0503 (7)	0.2683 (18)	0.0453 (6)	0.064 (4)
H3	0.0597	0.2675	0.0093	0.077*
C4	0.0927 (7)	0.336 (2)	0.0803 (7)	0.070 (5)
C5	0.1517 (7)	0.408 (2)	0.0643 (6)	0.090 (6)
H5	0.1622	0.4115	0.0284	0.108*
C6	0.1922 (7)	0.471 (2)	0.0994 (6)	0.112 (7)
H6	0.2299	0.5216	0.0877	0.134*
C7	0.1793 (7)	0.464 (2)	0.1555 (6)	0.097 (6)
H7	0.2087	0.5072	0.1796	0.117*
C8	0.1249 (7)	0.394 (2)	0.1730 (6)	0.080 (5)
H8	0.1170	0.3871	0.2092	0.096*
C9	0.0800 (7)	0.3326 (18)	0.1367 (6)	0.055 (4)
C10	−0.0397 (6)	0.3288 (15)	0.2223 (5)	0.043 (3)
H10	−0.0665	0.3773	0.1971	0.052*
C11	−0.0565 (7)	0.3323 (17)	0.2785 (5)	0.051 (4)
C13	−0.1289 (7)	0.421 (2)	0.3469 (6)	0.080 (5)
H13	−0.1660	0.4788	0.3563	0.096*
C14	−0.0916 (9)	0.350 (2)	0.3848 (7)	0.096 (6)
H14	−0.1040	0.3526	0.4202	0.115*
C15	−0.0353 (8)	0.274 (2)	0.3700 (6)	0.083 (6)
H15	−0.0097	0.2252	0.3959	0.099*
C16	−0.0158 (7)	0.2680 (18)	0.3182 (6)	0.065 (4)
H16	0.0238	0.2220	0.3093	0.078*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C12	0.076 (12)	0.102 (14)	0.042 (10)	0.015 (11)	−0.003 (9)	−0.037 (10)
Pb1	0.0469 (3)	0.0437 (3)	0.0499 (3)	−0.0005 (2)	−0.0006 (4)	−0.0024 (3)
I1	0.0494 (6)	0.0675 (6)	0.0444 (5)	−0.0033 (6)	−0.0076 (4)	−0.0005 (5)
I2	0.0422 (5)	0.0616 (6)	0.0710 (6)	−0.0023 (5)	−0.0070 (5)	−0.0082 (6)
I3	0.0676 (6)	0.0681 (6)	0.0432 (5)	−0.0080 (6)	0.0125 (5)	−0.0060 (6)
F1	0.067 (7)	0.161 (10)	0.104 (8)	0.055 (6)	0.000 (6)	−0.021 (7)
N1	0.046 (8)	0.065 (9)	0.035 (8)	0.004 (7)	−0.006 (6)	−0.009 (6)
N2	0.050 (8)	0.080 (9)	0.043 (8)	0.009 (6)	0.010 (6)	−0.005 (6)
C1	0.052 (10)	0.071 (11)	0.059 (11)	0.007 (8)	−0.001 (8)	−0.019 (8)
C2	0.037 (10)	0.117 (15)	0.060 (11)	0.014 (10)	−0.023 (8)	−0.021 (10)
C3	0.044 (10)	0.088 (12)	0.061 (11)	−0.013 (9)	−0.002 (8)	−0.015 (9)
C4	0.039 (10)	0.085 (13)	0.087 (13)	0.008 (9)	0.016 (9)	−0.004 (10)
C5	0.034 (9)	0.190 (19)	0.046 (9)	−0.021 (11)	0.002 (7)	−0.037 (11)
C6	0.059 (11)	0.21 (2)	0.062 (11)	−0.040 (12)	0.019 (10)	−0.037 (13)
C7	0.023 (8)	0.20 (2)	0.066 (11)	−0.017 (11)	0.003 (7)	−0.045 (12)
C8	0.052 (11)	0.124 (16)	0.064 (11)	−0.005 (10)	0.008 (9)	−0.012 (10)
C9	0.043 (10)	0.067 (11)	0.057 (11)	−0.004 (8)	0.013 (8)	−0.013 (9)
C10	0.057 (10)	0.046 (9)	0.027 (8)	0.006 (7)	−0.014 (7)	0.000 (6)
C11	0.044 (9)	0.065 (10)	0.042 (9)	0.001 (8)	0.007 (7)	−0.005 (7)
C13	0.035 (9)	0.134 (15)	0.072 (12)	0.023 (11)	0.016 (8)	−0.017 (12)
C14	0.089 (15)	0.123 (16)	0.077 (15)	0.019 (12)	0.020 (12)	−0.018 (12)
C15	0.071 (14)	0.109 (15)	0.068 (13)	0.014 (11)	−0.011 (10)	0.010 (11)
C16	0.065 (12)	0.095 (13)	0.036 (9)	0.017 (9)	0.005 (9)	−0.004 (9)

Geometric parameters (Å, º) top

C12—C13	1.313 (17)	C3—H3	0.9300
C12—F1	1.359 (16)	C4—C5	1.418 (18)
C12—C11	1.397 (17)	C4—C9	1.446 (18)
Pb1—I3ⁱ	3.1935 (12)	C5—C6	1.323 (17)
Pb1—I2	3.1938 (11)	C5—H5	0.9300
Pb1—I1ⁱ	3.2102 (11)	C6—C7	1.440 (18)
Pb1—I2ⁱ	3.2339 (11)	C6—H6	0.9300
Pb1—I3	3.2402 (11)	C7—C8	1.335 (18)
Pb1—I1	3.2761 (11)	C7—H7	0.9300
I1—Pb1ⁱⁱ	3.2102 (11)	C8—C9	1.399 (18)
I2—Pb1ⁱⁱ	3.2339 (11)	C8—H8	0.9300
I3—Pb1ⁱⁱ	3.1935 (11)	C10—C11	1.457 (16)
N1—C1	1.324 (14)	C10—H10	0.9300
N1—C9	1.366 (15)	C11—C16	1.407 (17)
N1—N2	1.427 (13)	C13—C14	1.355 (19)
N2—C10	1.260 (14)	C13—H13	0.9300
C1—C2	1.437 (17)	C14—C15	1.373 (19)
C1—H1	0.9300	C14—H14	0.9300
C2—C3	1.366 (17)	C15—C16	1.368 (17)
C2—H2	0.9300	C15—H15	0.9300
C3—C4	1.358 (18)	C16—H16	0.9300

C13—C12—F1	119.5 (15)	C3—C4—C9	120.7 (15)
C13—C12—C11	124.6 (16)	C5—C4—C9	116.5 (15)
F1—C12—C11	115.9 (13)	C6—C5—C4	121.3 (15)
I3ⁱ—Pb1—I2	94.65 (3)	C6—C5—H5	119.4
I3ⁱ—Pb1—I1ⁱ	84.55 (3)	C4—C5—H5	119.4
I2—Pb1—I1ⁱ	90.95 (3)	C5—C6—C7	121.4 (15)
I3ⁱ—Pb1—I2ⁱ	89.13 (3)	C5—C6—H6	119.3
I2—Pb1—I2ⁱ	175.06 (4)	C7—C6—H6	119.3
I1ⁱ—Pb1—I2ⁱ	86.24 (3)	C8—C7—C6	120.0 (14)
I3ⁱ—Pb1—I3	96.66 (3)	C8—C7—H7	120.0
I2—Pb1—I3	89.01 (3)	C6—C7—H7	120.0
I1ⁱ—Pb1—I3	178.79 (3)	C7—C8—C9	120.0 (14)
I2ⁱ—Pb1—I3	93.71 (3)	C7—C8—H8	120.0
I3ⁱ—Pb1—I1	179.26 (3)	C9—C8—H8	120.0
I2—Pb1—I1	85.80 (3)	N1—C9—C8	121.5 (14)
I1ⁱ—Pb1—I1	96.03 (3)	N1—C9—C4	117.6 (14)
I2ⁱ—Pb1—I1	90.45 (3)	C8—C9—C4	120.8 (15)
I3—Pb1—I1	82.76 (3)	N2—C10—C11	118.4 (12)
Pb1ⁱⁱ—I1—Pb1	75.16 (2)	N2—C10—H10	120.8
Pb1—I2—Pb1ⁱⁱ	75.97 (2)	C11—C10—H10	120.8
Pb1ⁱⁱ—I3—Pb1	75.88 (2)	C16—C11—C12	115.4 (13)
C1—N1—C9	121.7 (13)	C16—C11—C10	122.6 (13)
C1—N1—N2	120.8 (12)	C12—C11—C10	121.9 (13)
C9—N1—N2	117.0 (12)	C12—C13—C14	119.9 (16)
C10—N2—N1	111.8 (11)	C12—C13—H13	120.1
N1—C1—C2	121.0 (14)	C14—C13—H13	120.1
N1—C1—H1	119.5	C13—C14—C15	118.9 (17)
C2—C1—H1	119.5	C13—C14—H14	120.6
C3—C2—C1	118.6 (13)	C15—C14—H14	120.6
C3—C2—H2	120.7	C16—C15—C14	122.0 (16)
C1—C2—H2	120.7	C16—C15—H15	119.0
C4—C3—C2	120.2 (15)	C14—C15—H15	119.0
C4—C3—H3	119.9	C15—C16—C11	119.1 (14)
C2—C3—H3	119.9	C15—C16—H16	120.5
C3—C4—C5	122.9 (16)	C11—C16—H16	120.5

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

Experimental details

Crystal data
Chemical formula	(C₁₆H₁₂FN₂)[PbI₃]
M_r	839.17
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	296
a, b, c (Å)	20.888 (4), 7.9112 (15), 25.197 (5)
V (Å³)	4163.8 (14)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	12.56
Crystal size (mm)	0.04 × 0.02 × 0.01

Data collection
Diffractometer	Siemens SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2002)
T_min, T_max	0.747, 0.882
No. of measured, independent and observed [I > 2σ(I)] reflections	30847, 4090, 1770
R_int	0.156
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.047, 0.082, 0.96
No. of reflections	4090
No. of parameters	208
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.96, −0.95

Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Acknowledgements

The authors thank the Natural Science Foundation of China for financial support (grant No. 21002096).

References

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