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

Lo, K.M.; Ng, S.W.

doi:10.1107/S1600536808027530

metal-organic compounds

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Volume 64| Part 10| October 2008| Page m1222

doi:10.1107/S1600536808027530

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

Kong Mun Lo ^a and Seik Weng Ng ^a ^*

^aDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: seikweng@um.edu.my

(Received 8 August 2008; accepted 27 August 2008; online 6 September 2008)

The Pb^IV 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.

Related literature

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

Experimental

Crystal data

(C₇H₁₁N₂)₂[PbBr₄(C₆H₅)₂]
M_r = 927.39
Monoclinic, P 2₁ /n
a = 9.4994 (8) Å
b = 13.882 (1) Å
c = 10.991 (1) Å
β = 92.998 (1)°
V = 1447.3 (2) Å³
Z = 2
Mo Kα radiation
μ = 11.37 mm⁻¹
T = 100 (2) K
0.22 × 0.08 × 0.06 mm

Data collection

Bruker SMART APEX diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.246, T_max = 0.549 (expected range = 0.226–0.505)
8227 measured reflections
3309 independent reflections
2879 reflections with I > 2σ(I)
R_int = 0.029

Refinement

R[F² > 2σ(F²)] = 0.029
wR(F²) = 0.074
S = 1.03
3309 reflections
162 parameters
H-atom parameters constrained
Δρ_max = 1.21 e Å⁻³
Δρ_min = −1.70 e Å⁻³

Table 1
Selected bond lengths (Å)

Pb1—C1	2.190 (5)
Pb1—Br1	2.8516 (5)
Pb1—Br2	2.8897 (5)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2n⋯Br1	0.88	2.52	3.254 (4)	142

Data collection: APEX2 (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; 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 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808027530/im2080sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808027530/im2080Isup2.hkl

checkCIF report

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.

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

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
M_r = 927.39	D_x = 2.128 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 3449 reflections
a = 9.4994 (8) Å	θ = 2.3–28.3°
b = 13.882 (1) Å	µ = 11.37 mm⁻¹
c = 10.991 (1) Å	T = 100 K
β = 92.998 (1)°	Prism, colorless
V = 1447.3 (2) Å³	0.22 × 0.08 × 0.06 mm
Z = 2

Data collection top

Bruker SMART APEX diffractometer	3309 independent reflections
Radiation source: fine-focus sealed tube	2879 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.029
ω scans	θ_max = 27.5°, θ_min = 2.4°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −12→12
T_min = 0.246, T_max = 0.549	k = −17→18
8227 measured reflections	l = −14→14

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.029	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.074	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.0374P)² + 3.9748P] where P = (F_o² + 2F_c²)/3
3309 reflections	(Δ/σ)_max = 0.001
162 parameters	Δρ_max = 1.21 e Å⁻³
0 restraints	Δρ_min = −1.70 e Å⁻³

Crystal data top

(C₇H₁₁N₂)₂[PbBr₄(C₆H₅)₂]	V = 1447.3 (2) Å³
M_r = 927.39	Z = 2
Monoclinic, P2₁/n	Mo Kα radiation
a = 9.4994 (8) Å	µ = 11.37 mm⁻¹
b = 13.882 (1) Å	T = 100 K
c = 10.991 (1) Å	0.22 × 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)
T_min = 0.246, T_max = 0.549	R_int = 0.029
8227 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.029	0 restraints
wR(F²) = 0.074	H-atom parameters constrained
S = 1.03	Δρ_max = 1.21 e Å⁻³
3309 reflections	Δρ_min = −1.70 e Å⁻³
162 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Pb1	0.5000	0.5000	0.5000	0.00948 (8)
Br1	0.55832 (5)	0.61261 (3)	0.29156 (5)	0.01773 (12)
Br2	0.76243 (5)	0.40245 (3)	0.46044 (4)	0.01405 (11)
N1	1.1998 (4)	0.5912 (3)	−0.0112 (4)	0.0149 (8)
N2	0.8888 (4)	0.5868 (3)	0.2341 (4)	0.0195 (9)
H2n	0.8188	0.5819	0.2831	0.023*
C1	0.6145 (5)	0.6028 (3)	0.6196 (4)	0.0122 (9)
C2	0.5516 (5)	0.6319 (3)	0.7245 (4)	0.0138 (9)
H2	0.4624	0.6071	0.7443	0.017*
C3	0.6230 (5)	0.6988 (3)	0.8006 (4)	0.0171 (10)
H3	0.5821	0.7202	0.8728	0.021*
C4	0.7539 (5)	0.7339 (3)	0.7703 (4)	0.0163 (10)
H4	0.8019	0.7795	0.8219	0.020*
C5	0.8145 (5)	0.7028 (3)	0.6654 (4)	0.0161 (10)
H5	0.9041	0.7269	0.6455	0.019*
C6	0.7450 (5)	0.6367 (3)	0.5894 (4)	0.0136 (9)
H6	0.7864	0.6150	0.5175	0.016*
C7	0.8774 (5)	0.6473 (4)	0.1383 (5)	0.0209 (11)
H7	0.7961	0.6869	0.1276	0.025*
C8	0.9792 (5)	0.6529 (3)	0.0567 (5)	0.0162 (10)
H8	0.9691	0.6961	−0.0102	0.019*
C9	1.1018 (5)	0.5936 (3)	0.0715 (4)	0.0115 (9)
C10	1.1123 (5)	0.5358 (4)	0.1782 (4)	0.0164 (10)
H10	1.1945	0.4981	0.1952	0.020*
C11	1.0064 (5)	0.5337 (4)	0.2559 (5)	0.0189 (10)
H11	1.0150	0.4944	0.3266	0.023*
C12	1.1934 (6)	0.6536 (4)	−0.1184 (5)	0.0235 (12)
H12A	1.0949	0.6696	−0.1405	0.035*
H12B	1.2346	0.6201	−0.1865	0.035*
H12C	1.2463	0.7129	−0.1001	0.035*
C13	1.3293 (5)	0.5345 (4)	0.0087 (5)	0.0195 (10)
H13A	1.3939	0.5682	0.0667	0.029*
H13B	1.3744	0.5264	−0.0688	0.029*
H13C	1.3061	0.4712	0.0416	0.029*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Pb1	0.01089 (12)	0.01025 (12)	0.00716 (12)	−0.00156 (9)	−0.00091 (8)	−0.00108 (9)
Br1	0.0182 (2)	0.0185 (2)	0.0164 (2)	0.00011 (18)	0.00039 (19)	0.00211 (19)
Br2	0.0142 (2)	0.0158 (2)	0.0120 (2)	0.00186 (17)	−0.00032 (18)	−0.00038 (17)
N1	0.018 (2)	0.0146 (19)	0.012 (2)	0.0033 (16)	0.0018 (17)	0.0019 (16)
N2	0.018 (2)	0.025 (2)	0.016 (2)	−0.0001 (18)	0.0063 (18)	−0.0024 (18)
C1	0.014 (2)	0.011 (2)	0.011 (2)	−0.0021 (17)	−0.0035 (18)	0.0002 (17)
C2	0.015 (2)	0.013 (2)	0.014 (2)	0.0022 (18)	0.0000 (19)	0.0002 (18)
C3	0.022 (2)	0.018 (2)	0.011 (2)	0.003 (2)	−0.003 (2)	−0.0025 (19)
C4	0.023 (3)	0.009 (2)	0.016 (3)	−0.0022 (19)	−0.008 (2)	−0.0004 (18)
C5	0.016 (2)	0.016 (2)	0.016 (2)	−0.0037 (19)	−0.004 (2)	0.0035 (19)
C6	0.020 (2)	0.015 (2)	0.005 (2)	−0.0030 (19)	−0.0028 (18)	0.0005 (18)
C7	0.016 (2)	0.021 (3)	0.025 (3)	0.006 (2)	−0.005 (2)	−0.005 (2)
C8	0.019 (2)	0.016 (2)	0.013 (2)	0.0049 (19)	−0.002 (2)	0.0004 (19)
C9	0.013 (2)	0.011 (2)	0.011 (2)	−0.0004 (17)	−0.0021 (18)	−0.0026 (17)
C10	0.018 (2)	0.019 (2)	0.012 (2)	−0.001 (2)	−0.003 (2)	0.000 (2)
C11	0.019 (2)	0.023 (2)	0.015 (3)	−0.001 (2)	−0.001 (2)	−0.001 (2)
C12	0.030 (3)	0.023 (3)	0.018 (3)	0.004 (2)	0.003 (2)	0.008 (2)
C13	0.013 (2)	0.027 (3)	0.018 (3)	0.005 (2)	0.000 (2)	−0.003 (2)

Geometric parameters (Å, º) top

Pb1—C1	2.190 (5)	C4—H4	0.9500
Pb1—C1ⁱ	2.190 (5)	C5—C6	1.385 (6)
Pb1—Br1	2.8516 (5)	C5—H5	0.9500
Pb1—Br1ⁱ	2.8516 (5)	C6—H6	0.9500
Pb1—Br2ⁱ	2.8897 (5)	C7—C8	1.356 (7)
Pb1—Br2	2.8897 (5)	C7—H7	0.9500
N1—C9	1.335 (6)	C8—C9	1.428 (6)
N1—C13	1.467 (6)	C8—H8	0.9500
N1—C12	1.461 (6)	C9—C10	1.420 (7)
N2—C7	1.347 (7)	C10—C11	1.353 (7)
N2—C11	1.349 (7)	C10—H10	0.9500
N2—H2n	0.8800	C11—H11	0.9500
C1—C6	1.383 (6)	C12—H12A	0.9800
C1—C2	1.386 (6)	C12—H12B	0.9800
C2—C3	1.401 (7)	C12—H12C	0.9800
C2—H2	0.9500	C13—H13A	0.9800
C3—C4	1.392 (7)	C13—H13B	0.9800
C3—H3	0.9500	C13—H13C	0.9800
C4—C5	1.384 (7)

C1—Pb1—C1ⁱ	180.00 (17)	C6—C5—C4	120.2 (4)
C1—Pb1—Br1	90.79 (12)	C6—C5—H5	119.9
C1ⁱ—Pb1—Br1	89.21 (12)	C4—C5—H5	119.9
C1—Pb1—Br1ⁱ	89.21 (12)	C1—C6—C5	119.1 (4)
C1ⁱ—Pb1—Br1ⁱ	90.79 (12)	C1—C6—H6	120.4
Br1—Pb1—Br1ⁱ	180.000 (16)	C5—C6—H6	120.4
C1—Pb1—Br2ⁱ	90.55 (12)	C8—C7—N2	121.5 (5)
C1ⁱ—Pb1—Br2ⁱ	89.45 (12)	C8—C7—H7	119.3
Br1—Pb1—Br2ⁱ	93.978 (14)	N2—C7—H7	119.3
Br1ⁱ—Pb1—Br2ⁱ	86.022 (14)	C7—C8—C9	119.8 (5)
C1—Pb1—Br2	89.45 (12)	C7—C8—H8	120.1
C1ⁱ—Pb1—Br2	90.55 (12)	C9—C8—H8	120.1
Br1—Pb1—Br2	86.022 (14)	N1—C9—C10	121.8 (4)
Br1ⁱ—Pb1—Br2	93.978 (14)	N1—C9—C8	122.0 (4)
Br2ⁱ—Pb1—Br2	180.0	C10—C9—C8	116.2 (4)
C9—N1—C13	121.4 (4)	C11—C10—C9	120.7 (5)
C9—N1—C12	122.2 (4)	C11—C10—H10	119.7
C13—N1—C12	115.9 (4)	C9—C10—H10	119.7
C7—N2—C11	120.7 (4)	C10—C11—N2	120.8 (5)
C7—N2—H2n	119.6	C10—C11—H11	119.6
C11—N2—H2n	119.6	N2—C11—H11	119.6
C6—C1—C2	122.1 (4)	N1—C12—H12A	109.5
C6—C1—Pb1	120.1 (3)	N1—C12—H12B	109.5
C2—C1—Pb1	117.8 (3)	H12A—C12—H12B	109.5
C1—C2—C3	118.2 (4)	N1—C12—H12C	109.5
C1—C2—H2	120.9	H12A—C12—H12C	109.5
C3—C2—H2	120.9	H12B—C12—H12C	109.5
C4—C3—C2	120.0 (4)	N1—C13—H13A	109.5
C4—C3—H3	120.0	N1—C13—H13B	109.5
C2—C3—H3	120.0	H13A—C13—H13B	109.5
C5—C4—C3	120.4 (4)	N1—C13—H13C	109.5
C5—C4—H4	119.8	H13A—C13—H13C	109.5
C3—C4—H4	119.8	H13B—C13—H13C	109.5

Br1—Pb1—C1—C6	−46.0 (4)	Pb1—C1—C6—C5	179.0 (3)
Br1ⁱ—Pb1—C1—C6	134.0 (4)	C4—C5—C6—C1	0.2 (7)
Br2ⁱ—Pb1—C1—C6	−140.0 (4)	C11—N2—C7—C8	3.9 (8)
Br2—Pb1—C1—C6	40.0 (4)	N2—C7—C8—C9	0.1 (8)
Br1—Pb1—C1—C2	133.8 (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—C2	39.9 (3)	C13—N1—C9—C8	176.2 (4)
Br2—Pb1—C1—C2	−140.1 (3)	C12—N1—C9—C8	4.2 (7)
C6—C1—C2—C3	0.9 (7)	C7—C8—C9—N1	174.8 (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—C11	4.0 (7)
C3—C4—C5—C6	0.3 (7)	C9—C10—C11—N2	−0.3 (8)
C2—C1—C6—C5	−0.8 (7)	C7—N2—C11—C10	−3.8 (8)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2n···Br1	0.88	2.52	3.254 (4)	142

Experimental details

Crystal data
Chemical formula	(C₇H₁₁N₂)₂[PbBr₄(C₆H₅)₂]
M_r	927.39
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	100
a, b, c (Å)	9.4994 (8), 13.882 (1), 10.991 (1)
β (°)	92.998 (1)
V (Å³)	1447.3 (2)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	11.37
Crystal size (mm)	0.22 × 0.08 × 0.06

Data collection
Diffractometer	Bruker SMART APEX diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.246, 0.549
No. of measured, independent and observed [I > 2σ(I)] reflections	8227, 3309, 2879
R_int	0.029
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.029, 0.074, 1.03
No. of reflections	3309
No. of parameters	162
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.21, −1.70

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2008).

Selected bond lengths (Å) top

Pb1—C1	2.190 (5)	Pb1—Br2	2.8897 (5)
Pb1—Br1	2.8516 (5)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2n···Br1	0.88	2.52	3.254 (4)	142

Acknowledgements

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

References

Barbour, L. J. (2001). J. Supramol. Chem. 1, 189–191. CrossRef CAS Google Scholar
Bruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Westrip, S. P. (2008). publCIF. In preparation. Google Scholar
Yap, Q. L., Lo, K. M. & Ng, S. W. (2008). Acta Cryst. E64, m696. Web of Science CSD CrossRef IUCr Journals Google Scholar