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

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.

Key indicators

• Single-crystal X-ray study
• T = 296 K
• Mean [sigma](C-C) = 0.020 Å
• R factor = 0.047
• wR factor = 0.082
• Data-to-parameter ratio = 19.7

checkCIF/PLATON results

No syntax errors found



Alert level C
RINTA01_ALERT_3_C  The value of Rint is greater than 0.12
            Rint given   0.156
PLAT026_ALERT_3_C Ratio Observed / Unique Reflections too Low ....         43 Perc.
PLAT213_ALERT_2_C Atom C7              has ADP max/min Ratio .....        3.2 prola
PLAT234_ALERT_4_C Large Hirshfeld Difference C3     --  C4      ..       0.20 Ang.
PLAT234_ALERT_4_C Large Hirshfeld Difference C15    --  C16     ..       0.20 Ang.
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for         C6
PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor ....        2.4
PLAT334_ALERT_2_C Small Average Benzene  C-C Dist. C11    -C16           1.37 Ang.
PLAT342_ALERT_3_C Low Bond Precision on  C-C Bonds ...............     0.0199 Ang
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.600          2

Alert level G
PLAT004_ALERT_5_G Info: Polymeric Structure Found with Dimension .          1
PLAT005_ALERT_5_G No _iucr_refine_instructions_details in CIF ....          ?
PLAT194_ALERT_1_G Missing _cell_measurement_reflns_used datum ....          ?
PLAT195_ALERT_1_G Missing _cell_measurement_theta_max   datum ....          ?
PLAT196_ALERT_1_G Missing _cell_measurement_theta_min   datum ....          ?
PLAT233_ALERT_4_G Hirshfeld (M-X Solvent)    Pb1    --  I3      ..        6.3 su
PLAT233_ALERT_4_G Hirshfeld (M-X Solvent)    Pb1    --  I2_b    ..       11.2 su
PLAT764_ALERT_4_G Overcomplete CIF Bond List Detected (Rep/Expd) .       1.11 Ratio
PLAT794_ALERT_5_G Note: Tentative Bond Valency for Pb1     (II)          2.07
PLAT961_ALERT_5_G Dataset Contains no Negative Intensities .......          !

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
  10 ALERT level C = Check. Ensure it is not caused by an omission or oversight
  10 ALERT level G = General information/check it is not something unexpected

   3 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   4 ALERT type 2 Indicator that the structure model may be wrong or deficient
   4 ALERT type 3 Indicator that the structure quality may be low
   5 ALERT type 4 Improvement, methodology, query or suggestion
   4 ALERT type 5 Informative message, check

---

S1. Comment

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

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).

S2. Experimental

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%.

S3. Refinement

H atoms were placed to the bonded parent atoms in geometrically idealized positions and refined as riding atoms, with U_iso(H) = 1.2U_eq(C).

Computing details

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

	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]]

Crystal data

(C16H12FN2)[PbI3]	Z = 8
Mr = 839.17	F(000) = 2976
Orthorhombic, Pbca	Dx = 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) Å^3	0.04 × 0.02 × 0.01 mm

Data collection

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

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.082	H-atom parameters constrained
S = 0.96	w = 1/[σ^2(Fo^2) + (0.0158P)^2] where P = (Fo^2 + 2Fc^2)/3
4090 reflections	(Δ/σ)max = 0.001
208 parameters	Δρmax = 0.96 e Å^−3
0 restraints	Δρmin = −0.95 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

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—I3^i	3.1935 (12)	C5—C6	1.323 (17)
Pb1—I2	3.1938 (11)	C5—H5	0.9300
Pb1—I1^i	3.2102 (11)	C6—C7	1.440 (18)
Pb1—I2^i	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—Pb1^ii	3.2102 (11)	C8—C9	1.399 (18)
I2—Pb1^ii	3.2339 (11)	C8—H8	0.9300
I3—Pb1^ii	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)
I3^i—Pb1—I2	94.65 (3)	C6—C5—H5	119.4
I3^i—Pb1—I1^i	84.55 (3)	C4—C5—H5	119.4
I2—Pb1—I1^i	90.95 (3)	C5—C6—C7	121.4 (15)
I3^i—Pb1—I2^i	89.13 (3)	C5—C6—H6	119.3
I2—Pb1—I2^i	175.06 (4)	C7—C6—H6	119.3
I1^i—Pb1—I2^i	86.24 (3)	C8—C7—C6	120.0 (14)
I3^i—Pb1—I3	96.66 (3)	C8—C7—H7	120.0
I2—Pb1—I3	89.01 (3)	C6—C7—H7	120.0
I1^i—Pb1—I3	178.79 (3)	C7—C8—C9	120.0 (14)
I2^i—Pb1—I3	93.71 (3)	C7—C8—H8	120.0
I3^i—Pb1—I1	179.26 (3)	C9—C8—H8	120.0
I2—Pb1—I1	85.80 (3)	N1—C9—C8	121.5 (14)
I1^i—Pb1—I1	96.03 (3)	N1—C9—C4	117.6 (14)
I2^i—Pb1—I1	90.45 (3)	C8—C9—C4	120.8 (15)
I3—Pb1—I1	82.76 (3)	N2—C10—C11	118.4 (12)
Pb1^ii—I1—Pb1	75.16 (2)	N2—C10—H10	120.8
Pb1—I2—Pb1^ii	75.97 (2)	C11—C10—H10	120.8
Pb1^ii—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.