The title compound, (C6H5C2H4NH3)2[PbI4], crystallizes as an organic–inorganic hybrid-perovskite, with Pb located on a centre of inversion. As such, it consists of layers of tilted corner-sharing iodoplumbate octahedra, parallel to the bc plane. Adjacent inorganic layers are separated by organic 1-phenylethylammonium layers. The individual organic cations are linked to the inorganic layer by hydrogen bonds, and to adjacent cations by π–π interactions.
Supporting information
CCDC reference: 200737
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.008 Å
- R factor = 0.024
- wR factor = 0.057
- Data-to-parameter ratio = 27.6
checkCIF results
No syntax errors found
ADDSYM reports no extra symmetry
General Notes
FORMU_01 There is a discrepancy between the atom counts in the
_chemical_formula_sum and _chemical_formula_moiety. This is
usually due to the moiety formula being in the wrong format.
Atom count from _chemical_formula_sum: C16 H24 I4 N2 Pb1
Atom count from _chemical_formula_moiety:C160 H240 N20
Data collection: SMART-NT (Bruker, 1998); cell refinement: SAINT-Plus (Bruker, 1999); data reduction: XPREP (Bruker, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and DIAMOND (Brandenburg, 1999); software used to prepare material for publication: WinGX (Farrugia, 1999) and PLATON (Spek, 2002).
Bis(1-phenylethylammonium)Tetraiodoplumbate(II)
top
Crystal data top
(C8H12N)2[PbI4] | F(000) = 856 |
Mr = 959.16 | Dx = 2.676 Mg m−3 |
Monoclinic, P21/a | Melting point = 165–168 K |
Hall symbol: -P 2yab | Mo Kα radiation, λ = 0.71073 Å |
a = 8.7935 (11) Å | Cell parameters from 870 reflections |
b = 9.3913 (11) Å | θ = 3.0–28.2° |
c = 14.6428 (18) Å | µ = 12.27 mm−1 |
β = 100.093 (2)° | T = 293 K |
V = 1190.5 (3) Å3 | Rhomboid, orange |
Z = 2 | 0.3 × 0.26 × 0.2 mm |
Data collection top
Bruker SMART CCD area-detector diffractometer | 2950 independent reflections |
Radiation source: fine-focus sealed tube | 2580 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.039 |
φ and ω scans | θmax = 28.3°, θmin = 1.4° |
Absorption correction: numerical (XPREP; Bruker, 1999) | h = −11→11 |
Tmin = 0.072, Tmax = 0.161 | k = −9→12 |
8011 measured reflections | l = −18→19 |
Refinement top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.024 | H-atom parameters constrained |
wR(F2) = 0.057 | w = 1/[σ2(Fo2) + (0.0229P)2 + 0.4657P] where P = (Fo2 + 2Fc2)/3 |
S = 1.05 | (Δ/σ)max = 0.006 |
2950 reflections | Δρmax = 0.83 e Å−3 |
107 parameters | Δρmin = −0.52 e Å−3 |
0 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.00101 (9) |
Special details top
Experimental. Numerical integration absroption corrections based on indexed crystal faces were
applied using the XPREP routine (Bruker, 1999) |
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 | Uiso*/Ueq | |
C1 | 0.5275 (6) | 0.9595 (7) | 0.2491 (4) | 0.0549 (13) | |
H1 | 0.4266 | 0.9129 | 0.2335 | 0.066* | |
C2 | 0.5922 (6) | 0.9284 (6) | 0.3509 (3) | 0.0487 (12) | |
C3 | 0.7301 (7) | 0.9928 (5) | 0.3970 (4) | 0.0523 (13) | |
H3 | 0.787 | 1.0522 | 0.3649 | 0.063* | |
C4 | 0.7787 (6) | 0.9662 (6) | 0.4900 (4) | 0.0518 (12) | |
H4 | 0.8693 | 1.0071 | 0.5214 | 0.062* | |
C5 | 0.6927 (6) | 0.8793 (6) | 0.5356 (4) | 0.0537 (12) | |
H5 | 0.7253 | 0.8616 | 0.5985 | 0.064* | |
C6 | 0.5606 (7) | 0.8180 (6) | 0.4911 (4) | 0.0563 (13) | |
H6 | 0.5042 | 0.7589 | 0.5236 | 0.068* | |
C7 | 0.5103 (6) | 0.8422 (6) | 0.3999 (4) | 0.0563 (13) | |
H7 | 0.4193 | 0.7999 | 0.3703 | 0.068* | |
C8 | 0.5062 (8) | 1.1141 (7) | 0.2261 (4) | 0.0757 (19) | |
H8A | 0.4648 | 1.1246 | 0.1613 | 0.114* | |
H8B | 0.604 | 1.1619 | 0.2401 | 0.114* | |
H8C | 0.436 | 1.1552 | 0.2621 | 0.114* | |
I1 | 0.19412 (3) | 0.30343 (3) | −0.00066 (2) | 0.04323 (9) | |
I2 | 0.54813 (4) | 0.52588 (3) | 0.220390 (19) | 0.04376 (9) | |
Pb | 0.5 | 0.5 | 0 | 0.03565 (8) | |
N1 | 0.6330 (5) | 0.8960 (5) | 0.1876 (3) | 0.0491 (10) | |
HNA | 0.6473 | 0.8038 | 0.2005 | 0.059* | |
HNB | 0.7237 | 0.9407 | 0.1981 | 0.059* | |
HNC | 0.5898 | 0.9063 | 0.1283 | 0.059* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1 | 0.046 (3) | 0.065 (3) | 0.055 (3) | 0.005 (3) | 0.014 (2) | 0.004 (3) |
C2 | 0.050 (3) | 0.052 (3) | 0.043 (2) | 0.015 (2) | 0.008 (2) | −0.009 (2) |
C3 | 0.058 (3) | 0.052 (3) | 0.051 (3) | 0.007 (2) | 0.022 (2) | −0.001 (2) |
C4 | 0.042 (3) | 0.056 (3) | 0.056 (3) | −0.001 (2) | 0.007 (2) | −0.008 (2) |
C5 | 0.063 (3) | 0.051 (3) | 0.047 (3) | 0.012 (3) | 0.011 (2) | −0.003 (2) |
C6 | 0.062 (3) | 0.043 (3) | 0.067 (3) | −0.003 (2) | 0.018 (3) | −0.001 (2) |
C7 | 0.052 (3) | 0.049 (3) | 0.068 (3) | 0.000 (2) | 0.010 (3) | −0.011 (3) |
C8 | 0.100 (5) | 0.064 (4) | 0.068 (4) | 0.027 (4) | 0.028 (3) | 0.020 (3) |
I1 | 0.03643 (16) | 0.04865 (19) | 0.04418 (16) | −0.00984 (12) | 0.00588 (11) | −0.00068 (12) |
I2 | 0.04740 (18) | 0.04987 (18) | 0.03303 (15) | 0.00212 (13) | 0.00435 (12) | −0.00037 (12) |
Pb | 0.03496 (13) | 0.04045 (13) | 0.03161 (12) | −0.00200 (9) | 0.00605 (9) | −0.00309 (9) |
N1 | 0.048 (2) | 0.057 (3) | 0.041 (2) | 0.0059 (19) | 0.0057 (17) | −0.0068 (19) |
Geometric parameters (Å, º) top
C1—C8 | 1.495 (8) | C7—H7 | 0.93 |
C1—N1 | 1.523 (6) | C8—H8A | 0.96 |
C1—C2 | 1.528 (7) | C8—H8B | 0.96 |
C1—H1 | 0.98 | C8—H8C | 0.96 |
C2—C7 | 1.368 (7) | I1—Pb | 3.2609 (4) |
C2—C3 | 1.416 (8) | I1—Pbi | 3.3227 (4) |
C3—C4 | 1.377 (8) | I2—Pb | 3.1896 (5) |
C3—H3 | 0.93 | Pb—I2ii | 3.1896 (5) |
C4—C5 | 1.364 (7) | Pb—I1ii | 3.2609 (4) |
C4—H4 | 0.93 | Pb—I1iii | 3.3227 (4) |
C5—C6 | 1.356 (8) | Pb—I1iv | 3.3227 (4) |
C5—H5 | 0.93 | N1—HNA | 0.89 |
C6—C7 | 1.349 (7) | N1—HNB | 0.89 |
C6—H6 | 0.93 | N1—HNC | 0.89 |
| | | |
C8—C1—N1 | 108.2 (4) | H8A—C8—H8B | 109.5 |
C8—C1—C2 | 114.6 (5) | C1—C8—H8C | 109.5 |
N1—C1—C2 | 109.9 (4) | H8A—C8—H8C | 109.5 |
C8—C1—H1 | 108 | H8B—C8—H8C | 109.5 |
N1—C1—H1 | 108 | Pb—I1—Pbi | 155.425 (11) |
C2—C1—H1 | 108 | I2ii—Pb—I2 | 180.000 (12) |
C7—C2—C3 | 119.2 (5) | I2ii—Pb—I1 | 89.469 (8) |
C7—C2—C1 | 119.0 (5) | I2—Pb—I1 | 90.531 (8) |
C3—C2—C1 | 121.6 (5) | I2ii—Pb—I1ii | 90.531 (8) |
C4—C3—C2 | 119.0 (5) | I2—Pb—I1ii | 89.469 (8) |
C4—C3—H3 | 120.5 | I1—Pb—I1ii | 180 |
C2—C3—H3 | 120.5 | I2ii—Pb—I1iii | 95.230 (8) |
C5—C4—C3 | 119.3 (5) | I2—Pb—I1iii | 84.770 (8) |
C5—C4—H4 | 120.3 | I1—Pb—I1iii | 93.532 (9) |
C3—C4—H4 | 120.3 | I1ii—Pb—I1iii | 86.468 (9) |
C6—C5—C4 | 121.3 (5) | I2ii—Pb—I1iv | 84.770 (8) |
C6—C5—H5 | 119.3 | I2—Pb—I1iv | 95.230 (8) |
C4—C5—H5 | 119.3 | I1—Pb—I1iv | 86.468 (9) |
C7—C6—C5 | 120.6 (5) | I1ii—Pb—I1iv | 93.532 (9) |
C7—C6—H6 | 119.7 | I1iii—Pb—I1iv | 180.000 (10) |
C5—C6—H6 | 119.7 | C1—N1—HNA | 109.5 |
C6—C7—C2 | 120.5 (5) | C1—N1—HNB | 109.5 |
C6—C7—H7 | 119.8 | HNA—N1—HNB | 109.5 |
C2—C7—H7 | 119.8 | C1—N1—HNC | 109.5 |
C1—C8—H8A | 109.5 | HNA—N1—HNC | 109.5 |
C1—C8—H8B | 109.5 | HNB—N1—HNC | 109.5 |
| | | |
C8—C1—C2—C7 | 123.1 (6) | C4—C5—C6—C7 | −0.2 (8) |
N1—C1—C2—C7 | −114.8 (5) | C5—C6—C7—C2 | 0.3 (8) |
C8—C1—C2—C3 | −53.3 (7) | C3—C2—C7—C6 | −0.4 (8) |
N1—C1—C2—C3 | 68.9 (6) | C1—C2—C7—C6 | −176.8 (5) |
C7—C2—C3—C4 | 0.4 (7) | Pbi—I1—Pb—I2ii | 85.71 (2) |
C1—C2—C3—C4 | 176.8 (5) | Pbi—I1—Pb—I2 | −94.29 (2) |
C2—C3—C4—C5 | −0.4 (8) | Pbi—I1—Pb—I1iii | −179.08 (3) |
C3—C4—C5—C6 | 0.3 (8) | Pbi—I1—Pb—I1iv | 0.92 (3) |
Symmetry codes: (i) −x+1/2, y−1/2, −z; (ii) −x+1, −y+1, −z; (iii) −x+1/2, y+1/2, −z; (iv) x+1/2, −y+1/2, z. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—HNA···I2 | 0.89 | 2.78 | 3.605 (4) | 154 |
N1—HNB···I2v | 0.89 | 2.83 | 3.671 (4) | 158 |
N1—HNC···I1iii | 0.89 | 3.00 | 3.710 (4) | 138 |
Symmetry codes: (iii) −x+1/2, y+1/2, −z; (v) x+1/2, −y+3/2, z. |