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Acta Cryst. (2008). E64, m1222    [ doi:10.1107/S1600536808027530 ]

Bis[4-(dimethylamino)pyridinium] tetrabromidodiphenylplumbate(IV)

K. M. Lo and S. W. Ng

Abstract top

The PbIV atom of the anion of the title salt, (C7H11N2)2[PbBr4(C6H5)2], is situated on a crystallographic center of inversion and exhibits a tetragonally compressed octahedral coordination. One of the two independent Br atoms acts as a hydrogen-bond acceptor towards the NH group of the cation.

Comment top

In an earlier study, the tin-alkyl and one tin-aryl bond of an alkyltriphenyltin compound could be cleaved by 4-dimethylaminopyridine hydrobromide perbromide to form bis(4-dimethylaminopyridinium) tetrabromidodiphenylstannate (Yap et al., 2008). In the present study, the organic reagent similarly cleaves two lead-carbon bonds to afford the corresponding plumbate (Scheme I, Fig. 1). The two compounds are isostructural.

Related literature top

For the structure of isostructural bis(4-dimethylaminopyridinium) tetrabromidodiphenylstannate, see: Yap et al. (2008).

Experimental top

Tetraphenyllead (1.55 g, 3 mmol) and 4-dimethylaminopyridinium hydrobromide perbromide (1.1 g, 3 mmol) were heated in chloroform (100 ml) for 3 h. The filtered solution when allowed to evaporate yielded large colorless crystals.

Refinement top

Carbon-bound H-atoms were placed in calculated positions (C—H 0.95 to 0.98 Å) and were included in the refinement in the riding model approximation, with U(H) set to 1.2 to 1.5Ueq(C). The ammonium H atom was similarly constrained (N–H 0.88 Å).

The difference Fourier map had large peaks/deep holes near the lead atom.

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2008).

Figures top
[Figure 1] Fig. 1. Thermal ellipsoid plot (Barbour, 2001) plot of (C7H11N)2 [PbBr4(C6H5)2] at the 70% probability level. Hydrogen atoms are drawn as spheres of arbitrary radius.
Bis[4-(dimethylamino)pyridinium] tetrabromidodiphenylplumbate(IV) top
Crystal data top
(C7H11N2)2[PbBr4(C6H5)2]F(000) = 876
Mr = 927.39Dx = 2.128 Mg m−3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 3449 reflections
a = 9.4994 (8) Åθ = 2.3–28.3°
b = 13.882 (1) ŵ = 11.37 mm−1
c = 10.991 (1) ÅT = 100 K
β = 92.998 (1)°Prism, colorless
V = 1447.3 (2) Å30.22 × 0.08 × 0.06 mm
Z = 2
Data collection top
Bruker SMART APEX
diffractometer		3309 independent reflections
Radiation source: fine-focus sealed tube2879 reflections with I > 2σ(I)
graphiteRint = 0.029
ω scansθmax = 27.5°, θmin = 2.4°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −12→12
Tmin = 0.246, Tmax = 0.549k = −17→18
8227 measured reflectionsl = −14→14
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.029Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.074H-atom parameters constrained
S = 1.03 w = 1/[σ2(Fo2) + (0.0374P)2 + 3.9748P]
where P = (Fo2 + 2Fc2)/3
3309 reflections(Δ/σ)max = 0.001
162 parametersΔρmax = 1.21 e Å−3
0 restraintsΔρmin = −1.70 e Å−3
Crystal data top
(C7H11N2)2[PbBr4(C6H5)2]V = 1447.3 (2) Å3
Mr = 927.39Z = 2
Monoclinic, P21/nMo Kα radiation
a = 9.4994 (8) ŵ = 11.37 mm−1
b = 13.882 (1) ÅT = 100 K
c = 10.991 (1) Å0.22 × 0.08 × 0.06 mm
β = 92.998 (1)°
Data collection top
Bruker SMART APEX
diffractometer		3309 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		2879 reflections with I > 2σ(I)
Tmin = 0.246, Tmax = 0.549Rint = 0.029
8227 measured reflectionsθmax = 27.5°
Refinement top
R[F2 > 2σ(F2)] = 0.029H-atom parameters constrained
wR(F2) = 0.074Δρmax = 1.21 e Å−3
S = 1.03Δρmin = −1.70 e Å−3
3309 reflectionsAbsolute structure: ?
162 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Pb10.50000.50000.50000.00948 (8)
Br10.55832 (5)0.61261 (3)0.29156 (5)0.01773 (12)
Br20.76243 (5)0.40245 (3)0.46044 (4)0.01405 (11)
N11.1998 (4)0.5912 (3)−0.0112 (4)0.0149 (8)
N20.8888 (4)0.5868 (3)0.2341 (4)0.0195 (9)
H2n0.81880.58190.28310.023*
C10.6145 (5)0.6028 (3)0.6196 (4)0.0122 (9)
C20.5516 (5)0.6319 (3)0.7245 (4)0.0138 (9)
H20.46240.60710.74430.017*
C30.6230 (5)0.6988 (3)0.8006 (4)0.0171 (10)
H30.58210.72020.87280.021*
C40.7539 (5)0.7339 (3)0.7703 (4)0.0163 (10)
H40.80190.77950.82190.020*
C50.8145 (5)0.7028 (3)0.6654 (4)0.0161 (10)
H50.90410.72690.64550.019*
C60.7450 (5)0.6367 (3)0.5894 (4)0.0136 (9)
H60.78640.61500.51750.016*
C70.8774 (5)0.6473 (4)0.1383 (5)0.0209 (11)
H70.79610.68690.12760.025*
C80.9792 (5)0.6529 (3)0.0567 (5)0.0162 (10)
H80.96910.6961−0.01020.019*
C91.1018 (5)0.5936 (3)0.0715 (4)0.0115 (9)
C101.1123 (5)0.5358 (4)0.1782 (4)0.0164 (10)
H101.19450.49810.19520.020*
C111.0064 (5)0.5337 (4)0.2559 (5)0.0189 (10)
H111.01500.49440.32660.023*
C121.1934 (6)0.6536 (4)−0.1184 (5)0.0235 (12)
H12A1.09490.6696−0.14050.035*
H12B1.23460.6201−0.18650.035*
H12C1.24630.7129−0.10010.035*
C131.3293 (5)0.5345 (4)0.0087 (5)0.0195 (10)
H13A1.39390.56820.06670.029*
H13B1.37440.5264−0.06880.029*
H13C1.30610.47120.04160.029*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Pb10.01089 (12)0.01025 (12)0.00716 (12)−0.00156 (9)−0.00091 (8)−0.00108 (9)
Br10.0182 (2)0.0185 (2)0.0164 (2)0.00011 (18)0.00039 (19)0.00211 (19)
Br20.0142 (2)0.0158 (2)0.0120 (2)0.00186 (17)−0.00032 (18)−0.00038 (17)
N10.018 (2)0.0146 (19)0.012 (2)0.0033 (16)0.0018 (17)0.0019 (16)
N20.018 (2)0.025 (2)0.016 (2)−0.0001 (18)0.0063 (18)−0.0024 (18)
C10.014 (2)0.011 (2)0.011 (2)−0.0021 (17)−0.0035 (18)0.0002 (17)
C20.015 (2)0.013 (2)0.014 (2)0.0022 (18)0.0000 (19)0.0002 (18)
C30.022 (2)0.018 (2)0.011 (2)0.003 (2)−0.003 (2)−0.0025 (19)
C40.023 (3)0.009 (2)0.016 (3)−0.0022 (19)−0.008 (2)−0.0004 (18)
C50.016 (2)0.016 (2)0.016 (2)−0.0037 (19)−0.004 (2)0.0035 (19)
C60.020 (2)0.015 (2)0.005 (2)−0.0030 (19)−0.0028 (18)0.0005 (18)
C70.016 (2)0.021 (3)0.025 (3)0.006 (2)−0.005 (2)−0.005 (2)
C80.019 (2)0.016 (2)0.013 (2)0.0049 (19)−0.002 (2)0.0004 (19)
C90.013 (2)0.011 (2)0.011 (2)−0.0004 (17)−0.0021 (18)−0.0026 (17)
C100.018 (2)0.019 (2)0.012 (2)−0.001 (2)−0.003 (2)0.000 (2)
C110.019 (2)0.023 (2)0.015 (3)−0.001 (2)−0.001 (2)−0.001 (2)
C120.030 (3)0.023 (3)0.018 (3)0.004 (2)0.003 (2)0.008 (2)
C130.013 (2)0.027 (3)0.018 (3)0.005 (2)0.000 (2)−0.003 (2)
Geometric parameters (Å, °) top
Pb1—C12.190 (5)C4—H40.9500
Pb1—C1i2.190 (5)C5—C61.385 (6)
Pb1—Br12.8516 (5)C5—H50.9500
Pb1—Br1i2.8516 (5)C6—H60.9500
Pb1—Br2i2.8897 (5)C7—C81.356 (7)
Pb1—Br22.8897 (5)C7—H70.9500
N1—C91.335 (6)C8—C91.428 (6)
N1—C131.467 (6)C8—H80.9500
N1—C121.461 (6)C9—C101.420 (7)
N2—C71.347 (7)C10—C111.353 (7)
N2—C111.349 (7)C10—H100.9500
N2—H2n0.8800C11—H110.9500
C1—C61.383 (6)C12—H12A0.9800
C1—C21.386 (6)C12—H12B0.9800
C2—C31.401 (7)C12—H12C0.9800
C2—H20.9500C13—H13A0.9800
C3—C41.392 (7)C13—H13B0.9800
C3—H30.9500C13—H13C0.9800
C4—C51.384 (7)
C1—Pb1—C1i180.00 (17)C6—C5—C4120.2 (4)
C1—Pb1—Br190.79 (12)C6—C5—H5119.9
C1i—Pb1—Br189.21 (12)C4—C5—H5119.9
C1—Pb1—Br1i89.21 (12)C1—C6—C5119.1 (4)
C1i—Pb1—Br1i90.79 (12)C1—C6—H6120.4
Br1—Pb1—Br1i180.000 (16)C5—C6—H6120.4
C1—Pb1—Br2i90.55 (12)C8—C7—N2121.5 (5)
C1i—Pb1—Br2i89.45 (12)C8—C7—H7119.3
Br1—Pb1—Br2i93.978 (14)N2—C7—H7119.3
Br1i—Pb1—Br2i86.022 (14)C7—C8—C9119.8 (5)
C1—Pb1—Br289.45 (12)C7—C8—H8120.1
C1i—Pb1—Br290.55 (12)C9—C8—H8120.1
Br1—Pb1—Br286.022 (14)N1—C9—C10121.8 (4)
Br1i—Pb1—Br293.978 (14)N1—C9—C8122.0 (4)
Br2i—Pb1—Br2180.0C10—C9—C8116.2 (4)
C9—N1—C13121.4 (4)C11—C10—C9120.7 (5)
C9—N1—C12122.2 (4)C11—C10—H10119.7
C13—N1—C12115.9 (4)C9—C10—H10119.7
C7—N2—C11120.7 (4)C10—C11—N2120.8 (5)
C7—N2—H2n119.6C10—C11—H11119.6
C11—N2—H2n119.6N2—C11—H11119.6
C6—C1—C2122.1 (4)N1—C12—H12A109.5
C6—C1—Pb1120.1 (3)N1—C12—H12B109.5
C2—C1—Pb1117.8 (3)H12A—C12—H12B109.5
C1—C2—C3118.2 (4)N1—C12—H12C109.5
C1—C2—H2120.9H12A—C12—H12C109.5
C3—C2—H2120.9H12B—C12—H12C109.5
C4—C3—C2120.0 (4)N1—C13—H13A109.5
C4—C3—H3120.0N1—C13—H13B109.5
C2—C3—H3120.0H13A—C13—H13B109.5
C5—C4—C3120.4 (4)N1—C13—H13C109.5
C5—C4—H4119.8H13A—C13—H13C109.5
C3—C4—H4119.8H13B—C13—H13C109.5
Br1—Pb1—C1—C6−46.0 (4)Pb1—C1—C6—C5179.0 (3)
Br1i—Pb1—C1—C6134.0 (4)C4—C5—C6—C10.2 (7)
Br2i—Pb1—C1—C6−140.0 (4)C11—N2—C7—C83.9 (8)
Br2—Pb1—C1—C640.0 (4)N2—C7—C8—C90.1 (8)
Br1—Pb1—C1—C2133.8 (3)C13—N1—C9—C10−5.1 (7)
Br1i—Pb1—C1—C2−46.2 (3)C12—N1—C9—C10−177.1 (5)
Br2i—Pb1—C1—C239.9 (3)C13—N1—C9—C8176.2 (4)
Br2—Pb1—C1—C2−140.1 (3)C12—N1—C9—C84.2 (7)
C6—C1—C2—C30.9 (7)C7—C8—C9—N1174.8 (5)
Pb1—C1—C2—C3−179.0 (3)C7—C8—C9—C10−3.9 (7)
C1—C2—C3—C4−0.3 (7)N1—C9—C10—C11−174.7 (5)
C2—C3—C4—C5−0.2 (7)C8—C9—C10—C114.0 (7)
C3—C4—C5—C60.3 (7)C9—C10—C11—N2−0.3 (8)
C2—C1—C6—C5−0.8 (7)C7—N2—C11—C10−3.8 (8)
Symmetry codes: (i) −x+1, −y+1, −z+1.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N2—H2n···Br10.882.523.254 (4)142
Table 1
Selected geometric parameters (Å) top
Pb1—C12.190 (5)Pb1—Br22.8897 (5)
Pb1—Br12.8516 (5)
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N2—H2n···Br10.882.523.254 (4)142
Acknowledgements top

We thank the University of Malaya for funding this study (SF022155/2007 A) and also for the purchase of the diffractometer.

references
References top

Barbour, L. J. (2001). J. Supramol. Chem. 1, 189–191.

Bruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.

Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Westrip, S. P. (2008). publCIF. In preparation.

Yap, Q. L., Lo, K. M. & Ng, S. W. (2008). Acta Cryst. E64, m696.