Bis­[(S)-β-phenethyl­ammonium] tri­bromo­plumbate(II)

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.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](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

---

S1. Comment

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.

S2. Experimental

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%.

S3. Refinement

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.

Computing details

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).

Figures

	Fig. 1. View of (I), with ellipsoids drawn at the 50% probability level.
	Fig. 2. Packing diagram of (I), viewed along the b axis.
	Fig. 3. Packing diagram of (I), viewed along the a axis.

(I)

Crystal data

(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) Å^3	Plate, colourless
Z = 4	0.22 × 0.16 × 0.03 mm

Data collection

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

Refinement on F^2	w = 1/[σ^2(Fo^2) + (0.0222P)^2] where P = (Fo^2 + 2Fc^2)/3
Least-squares matrix: full	(Δ/σ)max = 0.001
R[F^2 > 2σ(F^2)] = 0.033	Δρmax = 1.21 e Å^−3
wR(F^2) = 0.065	Δρmin = −0.71 e Å^−3
S = 1.01	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/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

Special details

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 (Ų)

	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 (Ų)

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

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—Br3^i	2.8981 (14)
C6—H6	0.93	Pb1—Br2^i	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—Pb1^ii	2.9880 (15)
C7—C8	1.530 (12)	Br3—Pb1^ii	2.8981 (14)
C7—N1	1.532 (10)	Pb1—Br1^i	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—Br3^i	88.80 (3)
C2—C1—C6	120	Br1—Pb1—Br2^i	84.84 (4)
C2—C1—C7	117.6 (5)	Br3^i—Pb1—Br2^i	93.49 (5)
C6—C1—C7	122.4 (5)	Br1—Pb1—Br2	82.86 (4)
C1—C2—C4	120	Br3^i—Pb1—Br2	88.28 (5)
C1—C2—H2	120	Br2^i—Pb1—Br2	167.54 (2)
C4—C2—H2	120	Br1—Pb1—Br3	77.21 (3)
C1—C7—C8	115.2 (7)	Br3^i—Pb1—Br3	165.20 (2)
C1—C7—N1	108.7 (6)	Br2^i—Pb1—Br3	90.07 (5)
C8—C7—N1	106.9 (7)	Br2—Pb1—Br3	85.25 (5)
C1—C7—H7	108.6	Pb1^ii—Br2—Pb1	82.58 (5)
C8—C7—H7	108.6	Pb1^ii—Br3—Pb1	80.81 (5)
N1—C7—H7	108.6	Br1—Pb1—Br1^i	154.83 (3)
C7—C8—H8A	109.5	Br3^i—Pb1—Br1^i	75.56 (4)
C3—C6—C1—C7	177.3 (6)	Br3^i—Pb1—Br2—Pb1^ii	137.23 (3)
C7—C1—C2—C4	−177.4 (6)	Br2^i—Pb1—Br2—Pb1^ii	38.80 (10)
C2—C1—C7—C8	−142.7 (6)	Br3—Pb1—Br2—Pb1^ii	−29.45 (3)
C6—C1—C7—C8	39.9 (9)	Br1—Pb1—Br3—Pb1^ii	−53.14 (3)
C2—C1—C7—N1	97.4 (6)	Br3^i—Pb1—Br3—Pb1^ii	−33.78 (8)
C6—C1—C7—N1	−80.0 (7)	Br2^i—Pb1—Br3—Pb1^ii	−137.83 (3)
Br1—Pb1—Br2—Pb1^ii	48.23 (2)	Br2—Pb1—Br3—Pb1^ii	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)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···Br2^iii	0.89	2.76	3.452 (7)	136
N1—H1A···Br3^iv	0.89	2.88	3.567 (7)	135
N1—H1B···Br1^iv	0.89	2.68	3.532 (7)	162
N1—H1C···Br3^v	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.