Recently, with the prevalence of `perovskite fever', organic–inorganic hybrid perovskites (OHPs) have attracted intense attention due to their remarkable structural variability and highly tunable properties. In particular, the optical and electrical properties of organic–inorganic hybrid lead halides are typical of the OHP family. Besides, although three-dimensional hybrid perovskites, such as [CH3NH3]PbX3 (X = Cl, Br or I), have been reported, the development of new organic–inorganic hybrid semiconductors is still an area in urgent need of exploration. Here, an organic–inorganic hybrid lead halide perovskite is reported, namely poly[(2-azaniumylethyl)trimethylphosphanium [tetra-μ-bromido-plumbate(II)]], {(C5H16NP)[PbBr4]}n, in which an organic cation is embedded in inorganic two-dimensional (2D) mesh layers to produce a sandwich structure. This unique sandwich 2D hybrid perovskite material shows an indirect band gap of ∼2.700 eV. The properties of this compound as a semiconductor are demonstrated by a series of optical characterizations and indicate potential applications for optical devices.
Supporting information
CCDC reference: 1883687
Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: DIAMOND (Brandenburg & Putz, 2005); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015).
Poly[(2-azaniumylethyl)trimethylphosphanium [tetra-µ-bromido-plumbate(II)]]
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Crystal data top
(C5H16NP)[PbBr4] | F(000) = 580 |
Mr = 647.99 | Dx = 2.980 Mg m−3 |
Monoclinic, P21 | Mo Kα radiation, λ = 0.71073 Å |
a = 6.0127 (12) Å | Cell parameters from 2927 reflections |
b = 12.056 (2) Å | θ = 3.4–27.5° |
c = 9.962 (2) Å | µ = 22.82 mm−1 |
β = 90.43 (3)° | T = 293 K |
V = 722.1 (2) Å3 | Prism, colourless |
Z = 2 | 0.20 × 0.20 × 0.20 mm |
Data collection top
Rigaku SCXmini diffractometer | 2927 reflections with I > 2σ(I) |
Detector resolution: 13.6612 pixels mm-1 | Rint = 0.050 |
CCD_Profile_fitting scans | θmax = 27.5°, θmin = 3.4° |
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005) | h = −7→7 |
Tmin = 0.761, Tmax = 0.797 | k = −14→15 |
5045 measured reflections | l = −11→12 |
3093 independent reflections | |
Refinement top
Refinement on F2 | H-atom parameters constrained |
Least-squares matrix: full | w = 1/[σ2(Fo2) + (0.0192P)2 + 1.5138P] where P = (Fo2 + 2Fc2)/3 |
R[F2 > 2σ(F2)] = 0.037 | (Δ/σ)max = 0.001 |
wR(F2) = 0.083 | Δρmax = 1.62 e Å−3 |
S = 1.10 | Δρmin = −1.80 e Å−3 |
3093 reflections | Extinction correction: SHELXL2014 (Sheldrick, 2015), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
115 parameters | Extinction coefficient: 0.0255 (9) |
2 restraints | Absolute structure: Refined as an inversion twin. |
Hydrogen site location: inferred from neighbouring sites | Absolute structure parameter: 0.501 (17) |
Special details top
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell esds are taken
into account individually in the estimation of esds in distances, angles
and torsion angles; correlations between esds in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell esds is used for estimating esds involving l.s. planes. |
Refinement. Refined as a 2-component inversion twin |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Pb1 | 0.99441 (8) | 0.47547 (5) | 1.01083 (5) | 0.01630 (18) | |
Br2 | 0.9858 (3) | 0.22134 (17) | 1.04342 (17) | 0.0348 (4) | |
Br3 | 0.9976 (3) | 0.40750 (16) | 0.72279 (16) | 0.0314 (4) | |
Br4 | 0.9586 (3) | 0.50865 (16) | 1.30396 (17) | 0.0406 (6) | |
P1 | 0.5945 (6) | 0.2047 (4) | 0.4259 (4) | 0.0216 (9) | |
Br1 | 0.5008 (2) | 0.4928 (3) | 0.99230 (18) | 0.0355 (7) | |
C3 | 0.490 (3) | 0.2820 (19) | 0.289 (2) | 0.046 (6) | |
H3A | 0.5859 | 0.3441 | 0.2725 | 0.070* | |
H3B | 0.3433 | 0.3081 | 0.3091 | 0.070* | |
H3C | 0.4844 | 0.2357 | 0.2105 | 0.070* | |
C4 | 0.504 (3) | 0.2613 (12) | 0.5792 (17) | 0.025 (4) | |
H4A | 0.5755 | 0.3327 | 0.5922 | 0.030* | |
H4B | 0.3450 | 0.2743 | 0.5731 | 0.030* | |
C1 | 0.506 (3) | 0.0669 (16) | 0.407 (2) | 0.048 (6) | |
H1A | 0.3563 | 0.0598 | 0.4385 | 0.073* | |
H1B | 0.6020 | 0.0189 | 0.4574 | 0.073* | |
H1C | 0.5109 | 0.0468 | 0.3135 | 0.073* | |
C5 | 0.551 (3) | 0.1901 (15) | 0.7009 (16) | 0.033 (4) | |
H5A | 0.4845 | 0.1175 | 0.6874 | 0.039* | |
H5B | 0.7099 | 0.1802 | 0.7109 | 0.039* | |
N1 | 0.463 (3) | 0.2386 (14) | 0.8236 (14) | 0.047 (5) | |
H1D | 0.5500 | 0.2941 | 0.8502 | 0.071* | |
H1E | 0.4580 | 0.1871 | 0.8876 | 0.071* | |
H1F | 0.3260 | 0.2642 | 0.8081 | 0.071* | |
C2 | 0.888 (2) | 0.2065 (16) | 0.4267 (16) | 0.031 (4) | |
H2A | 0.9430 | 0.1617 | 0.4994 | 0.046* | |
H2B | 0.9397 | 0.2814 | 0.4379 | 0.046* | |
H2C | 0.9417 | 0.1776 | 0.3432 | 0.046* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Pb1 | 0.0116 (3) | 0.0198 (3) | 0.0176 (3) | −0.0001 (2) | 0.00187 (18) | −0.0012 (3) |
Br2 | 0.0516 (11) | 0.0196 (7) | 0.0332 (9) | 0.0005 (9) | 0.0074 (8) | 0.0007 (9) |
Br3 | 0.0330 (10) | 0.0420 (9) | 0.0192 (8) | 0.0051 (8) | −0.0024 (7) | −0.0049 (7) |
Br4 | 0.0507 (12) | 0.0502 (12) | 0.0211 (9) | −0.0198 (9) | 0.0067 (8) | −0.0090 (7) |
P1 | 0.0174 (19) | 0.025 (2) | 0.022 (2) | 0.0001 (18) | 0.0033 (16) | −0.0007 (16) |
Br1 | 0.0111 (7) | 0.0474 (19) | 0.0480 (10) | 0.0018 (8) | −0.0007 (7) | −0.0085 (9) |
C3 | 0.019 (9) | 0.083 (15) | 0.037 (12) | 0.006 (10) | −0.001 (9) | 0.030 (11) |
C4 | 0.025 (9) | 0.024 (8) | 0.025 (9) | −0.004 (7) | 0.009 (8) | −0.003 (6) |
C1 | 0.045 (13) | 0.040 (10) | 0.060 (14) | −0.016 (10) | 0.019 (11) | −0.026 (11) |
C5 | 0.028 (9) | 0.044 (11) | 0.027 (10) | 0.008 (9) | 0.012 (8) | −0.010 (8) |
N1 | 0.069 (12) | 0.049 (10) | 0.023 (8) | 0.030 (9) | −0.006 (8) | −0.002 (7) |
C2 | 0.017 (7) | 0.048 (10) | 0.027 (9) | −0.010 (8) | 0.008 (7) | 0.004 (8) |
Geometric parameters (Å, º) top
Pb1—Br4 | 2.9568 (18) | Br2—Pb1iii | 3.016 (2) |
Pb1—Br1 | 2.9798 (15) | P1—C1 | 1.754 (18) |
Pb1—Br3 | 2.9844 (17) | P1—C4 | 1.763 (16) |
Pb1—Br2i | 3.016 (2) | P1—C3 | 1.764 (17) |
Pb1—Br1ii | 3.0587 (16) | P1—C2 | 1.766 (14) |
Pb1—Br2 | 3.082 (2) | Br1—Pb1iv | 3.0587 (15) |
C4—C5 | 1.510 (17) | C5—N1 | 1.46 (2) |
| | | |
Br4—Pb1—Br1 | 88.39 (6) | N1—C5—C4 | 112.2 (14) |
Br4—Pb1—Br3 | 171.02 (6) | Br4—Pb1—Br2i | 92.71 (5) |
Br1—Pb1—Br3 | 88.47 (6) | Br1—Pb1—Br2i | 87.76 (7) |
Br4—Pb1—Br2 | 91.67 (5) | Br3—Pb1—Br2i | 95.57 (5) |
Br1—Pb1—Br2 | 93.35 (7) | Br4—Pb1—Br1ii | 97.48 (6) |
Br3—Pb1—Br2 | 80.13 (5) | Br1—Pb1—Br1ii | 169.41 (10) |
C1—P1—C4 | 111.5 (9) | Br3—Pb1—Br1ii | 86.96 (6) |
C1—P1—C3 | 108.0 (12) | Br2i—Pb1—Br1ii | 83.19 (7) |
C4—P1—C3 | 110.9 (9) | Br2i—Pb1—Br2 | 175.51 (2) |
C1—P1—C2 | 108.3 (9) | Br1ii—Pb1—Br2 | 95.26 (7) |
C4—P1—C2 | 107.9 (8) | Pb1iii—Br2—Pb1 | 163.28 (6) |
C3—P1—C2 | 110.3 (8) | Pb1—Br1—Pb1iv | 169.41 (10) |
C5—C4—P1 | 114.8 (11) | | |
Symmetry codes: (i) −x+2, y+1/2, −z+2; (ii) x+1, y, z; (iii) −x+2, y−1/2, −z+2; (iv) x−1, y, z. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C2—H2C···Br2v | 0.96 | 3.05 | 3.871 (16) | 145 |
C2—H2B···Br4v | 0.96 | 3.05 | 3.866 (19) | 144 |
C2—H2A···Br4iii | 0.96 | 2.75 | 3.702 (18) | 170 |
N1—H1F···Br3iv | 0.89 | 2.75 | 3.596 (15) | 159 |
N1—H1E···Br1vi | 0.89 | 2.64 | 3.491 (16) | 160 |
N1—H1D···Br1 | 0.89 | 2.80 | 3.502 (16) | 137 |
C5—H5B···Br4iii | 0.97 | 2.88 | 3.674 (17) | 140 |
C5—H5A···Br4vi | 0.97 | 2.97 | 3.762 (19) | 140 |
C1—H1C···Br1vii | 0.96 | 3.12 | 4.07 (2) | 176 |
C4—H4B···Br3iv | 0.97 | 3.04 | 3.806 (17) | 137 |
C4—H4A···Br3 | 0.97 | 2.98 | 3.728 (18) | 135 |
C3—H3A···Br4v | 0.96 | 3.01 | 3.93 (2) | 161 |
Symmetry codes: (iii) −x+2, y−1/2, −z+2; (iv) x−1, y, z; (v) x, y, z−1; (vi) −x+1, y−1/2, −z+2; (vii) −x+1, y−1/2, −z+1. |