The title compound, [(S)-C6H5C2H4NH3][PbBr3], crystallizes as an organic–inorganic hybrid. As such, the structure consists of extended chains of [PbBr3]− units running along the a axis. Each Pb atom is octahedrally coordinated by six bromides, arranged as chains of face-sharing octahedra. These inorganic chains are separated by the isolated organic cations.
Supporting information
CCDC reference: 214796
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.010 Å
- R factor = 0.033
- wR factor = 0.065
- Data-to-parameter ratio = 27.5
checkCIF results
No syntax errors found
ADDSYM reports no extra symmetry
Alert Level C:
PLAT_732 Alert C Angle Calc 85.25(2), Rep 85.25(5) .... 2.50 su-Ratio
BR2 -PB1 -BR3 1.555 1.555 1.555
General Notes
REFLT_03
From the CIF: _diffrn_reflns_theta_max 28.28
From the CIF: _reflns_number_total 3268
Count of symmetry unique reflns 1914
Completeness (_total/calc) 170.74%
TEST3: Check Friedels for noncentro structure
Estimate of Friedel pairs measured 1354
Fraction of Friedel pairs measured 0.707
Are heavy atom types Z>Si present yes
Please check that the estimate of the number of Friedel pairs is
correct. If it is not, please give the correct count in the
_publ_section_exptl_refinement section of the submitted CIF.
0 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
1 Alert Level C = Please check
Crystals of ((S)—C6H5C2H4NH3)[PbBr3] where grown at room temperature by first dissolving 0.204 g PbBr2 (0.556 mmol) in 5 ml HBr and 5 ml of ethanol. Then, 0.120 g of (S) - C6H5C2H4NH2(l) (0.990 mmol) was added drop wise. The needle shaped, colourless crystals where harvested after seven days. A crystal suitable for X-Ray diffraction studies was selected and studied. Analysis calculated for C8H12N1PbBr3: C 16.89, H 2.13, N 2.46%; found: C 16.95, H 2.20, N 2.43%.
All H atoms were refined in idealized positions in the riding model approximation and with their isotropic displacement parameters fixed to 1.2 of the equivalent isotropic displacement parameter of the atom to which they are bonded.
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).
Crystal data top
(C8H12N)[PbBr3] | F(000) = 1016 |
Mr = 569.11 | Dx = 2.843 Mg m−3 |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71069 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 840 reflections |
a = 7.930 (5) Å | θ = 7.8–55.7° |
b = 8.147 (5) Å | µ = 21.67 mm−1 |
c = 20.580 (5) Å | T = 293 K |
V = 1329.6 (12) Å3 | Plate, colourless |
Z = 4 | 0.22 × 0.16 × 0.03 mm |
Data collection top
Bruker CCD area-detector diffractometer | 2587 reflections with I > 2σ(I) |
ϕ and ω scans | Rint = 0.062 |
Absorption correction: integration (XPREP; Bruker, 1999) | θmax = 28.3°, θmin = 2.0° |
Tmin = 0.056, Tmax = 0.485 | h = −10→6 |
9328 measured reflections | k = −10→10 |
3268 independent reflections | l = −27→26 |
Refinement top
Refinement on F2 | w = 1/[σ2(Fo2) + (0.0222P)2] where P = (Fo2 + 2Fc2)/3 |
Least-squares matrix: full | (Δ/σ)max = 0.001 |
R[F2 > 2σ(F2)] = 0.033 | Δρmax = 1.21 e Å−3 |
wR(F2) = 0.065 | Δρmin = −0.71 e Å−3 |
S = 1.01 | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
3268 reflections | Extinction coefficient: 0.0118 (3) |
119 parameters | Absolute structure: Flack (1983) |
0 restraints | Absolute structure parameter: −0.032 (12) |
H-atom parameters constrained | |
Crystal data top
(C8H12N)[PbBr3] | V = 1329.6 (12) Å3 |
Mr = 569.11 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 7.930 (5) Å | µ = 21.67 mm−1 |
b = 8.147 (5) Å | T = 293 K |
c = 20.580 (5) Å | 0.22 × 0.16 × 0.03 mm |
Data collection top
Bruker CCD area-detector diffractometer | 3268 independent reflections |
Absorption correction: integration (XPREP; Bruker, 1999) | 2587 reflections with I > 2σ(I) |
Tmin = 0.056, Tmax = 0.485 | Rint = 0.062 |
9328 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.033 | H-atom parameters constrained |
wR(F2) = 0.065 | Δρmax = 1.21 e Å−3 |
S = 1.01 | Δρmin = −0.71 e Å−3 |
3268 reflections | Absolute structure: Flack (1983) |
119 parameters | Absolute structure parameter: −0.032 (12) |
0 restraints | |
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
C4 | 0.6191 (8) | 0.0836 (7) | 0.7740 (3) | 0.063 (3) | |
H4 | 0.5516 | −0.0055 | 0.785 | 0.076* | |
C5 | 0.6153 (8) | 0.2253 (8) | 0.8115 (2) | 0.060 (3) | |
H5 | 0.5453 | 0.2311 | 0.8477 | 0.072* | |
C3 | 0.7163 (9) | 0.3584 (7) | 0.7950 (3) | 0.063 (3) | |
H3 | 0.7137 | 0.4533 | 0.8202 | 0.076* | |
C6 | 0.8210 (7) | 0.3498 (6) | 0.7410 (3) | 0.056 (3) | |
H6 | 0.8885 | 0.4389 | 0.73 | 0.067* | |
C1 | 0.8248 (6) | 0.2081 (7) | 0.7034 (2) | 0.038 (2) | |
C2 | 0.7238 (8) | 0.0750 (6) | 0.7199 (3) | 0.059 (3) | |
H2 | 0.7264 | −0.0199 | 0.6948 | 0.07* | |
C7 | 0.9286 (10) | 0.1945 (10) | 0.6435 (4) | 0.038 (2) | |
H7 | 0.942 | 0.078 | 0.6328 | 0.045* | |
C8 | 1.1036 (11) | 0.2730 (14) | 0.6476 (5) | 0.069 (3) | |
H8A | 1.1618 | 0.2575 | 0.6071 | 0.103* | |
H8B | 1.1667 | 0.2225 | 0.682 | 0.103* | |
H8C | 1.0922 | 0.3883 | 0.6561 | 0.103* | |
N1 | 0.8352 (8) | 0.2793 (8) | 0.5877 (3) | 0.0433 (18) | |
H1A | 0.8953 | 0.27 | 0.5513 | 0.065* | |
H1B | 0.8209 | 0.3849 | 0.5971 | 0.065* | |
H1C | 0.735 | 0.232 | 0.5821 | 0.065* | |
Pb1 | 0.79006 (4) | 0.24316 (4) | 0.98767 (2) | 0.03691 (11) | |
Br2 | 0.51410 (11) | −0.01730 (10) | 0.96931 (5) | 0.0410 (2) | |
Br3 | 0.49616 (11) | 0.50666 (10) | 0.95114 (4) | 0.0383 (2) | |
Br1 | 0.62355 (11) | 0.29255 (10) | 1.10925 (4) | 0.0409 (2) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C4 | 0.074 (7) | 0.051 (6) | 0.064 (7) | −0.020 (6) | 0.008 (7) | −0.003 (6) |
C5 | 0.074 (6) | 0.069 (7) | 0.035 (5) | 0.009 (7) | 0.001 (5) | 0.001 (5) |
C3 | 0.097 (9) | 0.043 (6) | 0.050 (6) | −0.011 (6) | 0.016 (7) | −0.011 (5) |
C6 | 0.071 (7) | 0.041 (5) | 0.055 (6) | −0.010 (5) | 0.011 (6) | −0.002 (5) |
C1 | 0.043 (5) | 0.040 (5) | 0.032 (4) | 0.004 (4) | −0.006 (4) | −0.001 (4) |
C2 | 0.073 (7) | 0.052 (6) | 0.052 (6) | −0.007 (6) | 0.003 (6) | −0.004 (5) |
C7 | 0.036 (5) | 0.032 (4) | 0.045 (5) | 0.013 (4) | 0.001 (4) | 0.002 (4) |
C8 | 0.043 (5) | 0.084 (8) | 0.079 (7) | 0.012 (6) | −0.008 (5) | 0.005 (7) |
N1 | 0.047 (4) | 0.042 (4) | 0.040 (4) | −0.001 (3) | −0.003 (3) | −0.003 (3) |
Pb1 | 0.03070 (15) | 0.03236 (17) | 0.04768 (19) | −0.00020 (16) | 0.00014 (15) | −0.00010 (18) |
Br2 | 0.0374 (5) | 0.0291 (4) | 0.0565 (6) | 0.0002 (4) | −0.0081 (5) | −0.0019 (4) |
Br3 | 0.0372 (5) | 0.0317 (4) | 0.0458 (5) | −0.0008 (4) | −0.0022 (4) | 0.0024 (4) |
Br1 | 0.0441 (5) | 0.0364 (5) | 0.0422 (5) | 0.0008 (4) | 0.0017 (4) | 0.0025 (4) |
Geometric parameters (Å, º) top
C4—C5 | 1.39 | C8—H8A | 0.96 |
C4—C2 | 1.39 | C8—H8B | 0.96 |
C4—H4 | 0.93 | C8—H8C | 0.96 |
C5—C3 | 1.39 | N1—H1A | 0.89 |
C5—H5 | 0.93 | N1—H1B | 0.89 |
C3—C6 | 1.39 | N1—H1C | 0.89 |
C3—H3 | 0.93 | Pb1—Br1 | 2.8576 (11) |
C6—C1 | 1.39 | Pb1—Br3i | 2.8981 (14) |
C6—H6 | 0.93 | Pb1—Br2i | 2.9880 (15) |
C1—C2 | 1.39 | Pb1—Br2 | 3.0716 (16) |
C1—C7 | 1.487 (9) | Pb1—Br3 | 3.2566 (16) |
C2—H2 | 0.93 | Br2—Pb1ii | 2.9880 (15) |
C7—C8 | 1.530 (12) | Br3—Pb1ii | 2.8981 (14) |
C7—N1 | 1.532 (10) | Pb1—Br1i | 3.3253 (17) |
C7—H7 | 0.98 | | |
| | | |
C5—C4—C2 | 120 | C7—C8—H8B | 109.5 |
C5—C4—H4 | 120 | H8A—C8—H8B | 109.5 |
C2—C4—H4 | 120 | C7—C8—H8C | 109.5 |
C4—C5—C3 | 120 | H8A—C8—H8C | 109.5 |
C4—C5—H5 | 120 | H8B—C8—H8C | 109.5 |
C3—C5—H5 | 120 | C7—N1—H1A | 109.5 |
C5—C3—C6 | 120 | C7—N1—H1B | 109.5 |
C5—C3—H3 | 120 | H1A—N1—H1B | 109.5 |
C6—C3—H3 | 120 | C7—N1—H1C | 109.5 |
C1—C6—C3 | 120 | H1A—N1—H1C | 109.5 |
C1—C6—H6 | 120 | H1B—N1—H1C | 109.5 |
C3—C6—H6 | 120 | Br1—Pb1—Br3i | 88.80 (3) |
C2—C1—C6 | 120 | Br1—Pb1—Br2i | 84.84 (4) |
C2—C1—C7 | 117.6 (5) | Br3i—Pb1—Br2i | 93.49 (5) |
C6—C1—C7 | 122.4 (5) | Br1—Pb1—Br2 | 82.86 (4) |
C1—C2—C4 | 120 | Br3i—Pb1—Br2 | 88.28 (5) |
C1—C2—H2 | 120 | Br2i—Pb1—Br2 | 167.54 (2) |
C4—C2—H2 | 120 | Br1—Pb1—Br3 | 77.21 (3) |
C1—C7—C8 | 115.2 (7) | Br3i—Pb1—Br3 | 165.20 (2) |
C1—C7—N1 | 108.7 (6) | Br2i—Pb1—Br3 | 90.07 (5) |
C8—C7—N1 | 106.9 (7) | Br2—Pb1—Br3 | 85.25 (5) |
C1—C7—H7 | 108.6 | Pb1ii—Br2—Pb1 | 82.58 (5) |
C8—C7—H7 | 108.6 | Pb1ii—Br3—Pb1 | 80.81 (5) |
N1—C7—H7 | 108.6 | Br1—Pb1—Br1i | 154.83 (3) |
C7—C8—H8A | 109.5 | Br3i—Pb1—Br1i | 75.56 (4) |
| | | |
C3—C6—C1—C7 | 177.3 (6) | Br3i—Pb1—Br2—Pb1ii | 137.23 (3) |
C7—C1—C2—C4 | −177.4 (6) | Br2i—Pb1—Br2—Pb1ii | 38.80 (10) |
C2—C1—C7—C8 | −142.7 (6) | Br3—Pb1—Br2—Pb1ii | −29.45 (3) |
C6—C1—C7—C8 | 39.9 (9) | Br1—Pb1—Br3—Pb1ii | −53.14 (3) |
C2—C1—C7—N1 | 97.4 (6) | Br3i—Pb1—Br3—Pb1ii | −33.78 (8) |
C6—C1—C7—N1 | −80.0 (7) | Br2i—Pb1—Br3—Pb1ii | −137.83 (3) |
Br1—Pb1—Br2—Pb1ii | 48.23 (2) | Br2—Pb1—Br3—Pb1ii | 30.61 (3) |
Symmetry codes: (i) x+1/2, −y+1/2, −z+2; (ii) x−1/2, −y+1/2, −z+2. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···Br2iii | 0.89 | 2.76 | 3.452 (7) | 136 |
N1—H1A···Br3iv | 0.89 | 2.88 | 3.567 (7) | 135 |
N1—H1B···Br1iv | 0.89 | 2.68 | 3.532 (7) | 162 |
N1—H1C···Br3v | 0.89 | 2.68 | 3.532 (7) | 160 |
Symmetry codes: (iii) −x+3/2, −y, z−1/2; (iv) −x+3/2, −y+1, z−1/2; (v) −x+1, y−1/2, −z+3/2. |
Experimental details
Crystal data |
Chemical formula | (C8H12N)[PbBr3] |
Mr | 569.11 |
Crystal system, space group | Orthorhombic, P212121 |
Temperature (K) | 293 |
a, b, c (Å) | 7.930 (5), 8.147 (5), 20.580 (5) |
V (Å3) | 1329.6 (12) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 21.67 |
Crystal size (mm) | 0.22 × 0.16 × 0.03 |
|
Data collection |
Diffractometer | Bruker CCD area-detector diffractometer |
Absorption correction | Integration (XPREP; Bruker, 1999) |
Tmin, Tmax | 0.056, 0.485 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 9328, 3268, 2587 |
Rint | 0.062 |
(sin θ/λ)max (Å−1) | 0.667 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.033, 0.065, 1.01 |
No. of reflections | 3268 |
No. of parameters | 119 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 1.21, −0.71 |
Absolute structure | Flack (1983) |
Absolute structure parameter | −0.032 (12) |
Selected geometric parameters (Å, º) topPb1—Br1 | 2.8576 (11) | Pb1—Br3 | 3.2566 (16) |
Pb1—Br3i | 2.8981 (14) | Br2—Pb1ii | 2.9880 (15) |
Pb1—Br2i | 2.9880 (15) | Br3—Pb1ii | 2.8981 (14) |
Pb1—Br2 | 3.0716 (16) | Pb1—Br1i | 3.3253 (17) |
| | | |
Br1—Pb1—Br3i | 88.80 (3) | Br3i—Pb1—Br3 | 165.20 (2) |
Br1—Pb1—Br2i | 84.84 (4) | Br2i—Pb1—Br3 | 90.07 (5) |
Br3i—Pb1—Br2i | 93.49 (5) | Br2—Pb1—Br3 | 85.25 (5) |
Br1—Pb1—Br2 | 82.86 (4) | Pb1ii—Br2—Pb1 | 82.58 (5) |
Br3i—Pb1—Br2 | 88.28 (5) | Pb1ii—Br3—Pb1 | 80.81 (5) |
Br2i—Pb1—Br2 | 167.54 (2) | Br1—Pb1—Br1i | 154.83 (3) |
Br1—Pb1—Br3 | 77.21 (3) | Br3i—Pb1—Br1i | 75.56 (4) |
Symmetry codes: (i) x+1/2, −y+1/2, −z+2; (ii) x−1/2, −y+1/2, −z+2. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···Br2iii | 0.89 | 2.76 | 3.452 (7) | 136 |
N1—H1A···Br3iv | 0.89 | 2.88 | 3.567 (7) | 135 |
N1—H1B···Br1iv | 0.89 | 2.68 | 3.532 (7) | 162 |
N1—H1C···Br3v | 0.89 | 2.68 | 3.532 (7) | 160 |
Symmetry codes: (iii) −x+3/2, −y, z−1/2; (iv) −x+3/2, −y+1, z−1/2; (v) −x+1, y−1/2, −z+3/2. |
In recent years, a significant number of organic–inorganic hybrid materials based on metal halide units have been prepared and studied; for reviews, see Papavassiliou (1997) and Mitzi (2001). Haloplumbates, in particular, have demonstrated a propensity for forming a great variety of crystalline structures by self-assembling from suitable solution mixtures. It has been shown that their structures can vary considerably, ranging from systems based on isolated molecules to ones containing extended chains as in [Me4N][PbI3] (Contreras et al., 1983) and right up to two- or three-dimensional networks (Mitzi, 1999). For systems containing extended chains, the extended chains may be formed by one, two or three bridging halides. Very few examples of the latter, also described in terms of face-sharing octahedra, involving bromide are known, for example, [Et4N][PbBr3] and [Bu4N][PbBr3] (Vanek et al., 1992). A search of the Cambridge Structural Database (Allen, 2002) with amines yielded only one similiar case involving bromide, [PhMe3N]4[Pb3Br10] (Wiest, 1999), consisting of face-sharing trimeric [Pb3Br10] units connected by sharing a vertex.
Having previously reported the structure of organic-inorganic hybrid perovskite containing a racemic mixture of the cation 1-phenylethylammonium (Billing, 2002), we present here the room temperature structure of the title compound, ((S)—C6H5C2H4NH3)[PbBr3] (I). This is the first report of an inorganic-organic hybrid with only a single enantiomer of a chiral amine as the counter ion.
Fig. 1 shows the asymmetric unit of the title compound with its atomic numbering scheme. The Bromide Br(1) is axial and Br(2) and Br(3) are equatorial. The inorganic chains of distorted face-sharing octahedra orientated along the a axis, separated by isolated amides, are clearly visible in the packing diagrams (Fig. 2 and Fig. 3). Within the chain, the shared face consists of two equatorial and one axial bromide. The octahedra are severely distorted with all lead bromide distances different, ranging from 2.8576 (11) Å to 3.3253 (17) Å (Table 1). The bond angles between cis ligands vary from 75.56 (4)° to 93.49 (5)° and trans angles from 154.83 (3)° to167.54 (2)°.
There is extensive hydrogen bonding, with the large ionic radius of bromine enabling contact with four different hydrogen atoms (Table 2). The hydrogen bonds are similar in lenth to the average lengths reported by Steiner (1998) for hydrogen bonds involving halide ions. The bifurcated Br(2)···H(1 A)···Br(3) distances are 2.76 Å and 2.88 Å, whereas the lengths in the simpler Br···H(1B) and Br···H(1 C) are both 2.68 Å. Within the organic section, adjacent aromatic rings are separated by a centroid-to-centroid distance of 5.373 Å, which is probably too large to be considered in terms of π-stacking interactions.