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Acta Crystallogr Sect E Struct Rep Online. 2009 January 1; 65(Pt 1): m13.
Published online 2008 December 6. doi:  10.1107/S1600536808040312
PMCID: PMC2967864

Bis[4-(dimethyl­amino)pyridinium] 3.75-bromido-0.25-chloridodiphenyl­plumbate(IV)

Abstract

The PbIV atom of the plumbate dianion in the title compound, (C7H11N)2[Pb(Br3.75Cl0.25)(C6H5)2], lies on a centre of inversion in a tetra­gonally compressed octa­hedral geometry. One of the attached Br atoms is disordered with respect to a Cl atom in a 7:1 ratio. The disordered halogen atom is an N—H(...)(Br/Cl) hydrogen-bond acceptor for the cation.

Related literature

For the structure of the isostructural compound bis­(4-di­methyl­amino­pyridinium) tetra­bromidodiphenyl­plumbate(IV), see: Lo & Ng (2008 [triangle]).

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Object name is e-65-00m13-scheme1.jpg

Experimental

Crystal data

  • (C7H11N)2[Pb(Br3.75Cl0.25)(C6H5)2]
  • M r = 916.27
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-00m13-efi1.jpg
  • a = 9.5010 (2) Å
  • b = 13.8916 (3) Å
  • c = 10.9851 (2) Å
  • β = 92.996 (1)°
  • V = 1447.88 (5) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 11.05 mm−1
  • T = 100 (2) K
  • 0.12 × 0.11 × 0.10 mm

Data collection

  • Bruker SMART APEX CCD diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 1996 [triangle]) T min = 0.351, T max = 0.405 (expected range = 0.287–0.331)
  • 10028 measured reflections
  • 3327 independent reflections
  • 2909 reflections with I > 2σ(I)
  • R int = 0.028

Refinement

  • R[F 2 > 2σ(F 2)] = 0.022
  • wR(F 2) = 0.048
  • S = 1.02
  • 3327 reflections
  • 166 parameters
  • 1 restraint
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.77 e Å−3
  • Δρmin = −0.52 e Å−3

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

Table 1
Selected bond lengths (Å)
Table 2
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808040312/hb2863sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808040312/hb2863Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

We thank the University of Malaya for funding this study (grant No. FS339/2008A) for the purchase of the diffractometer.

supplementary crystallographic information

Experimental

Diphenyllead dichloride (1.3 g, 3 mmol) and 4-dimethylaminopyridine hydrobromide perbromide (1.1 g, 3 mmol) were heated in chloroform (100 ml) for an hour. The filtered solution when allowed to evaporate yielded large colorless crystals of (I).

Refinement

The carbon-bound H-atoms were placed in calculated positions (C—H = 0.95–0.98 Å) and refined as riding with Uiso(H) = 1.2 to 1.5Ueq(C). The ammonium H atom was located in a difference Fourier map, and was refined with a distance constraint of N—H = 0.88 (1) Å; its Uiso value was refined.

The two independent halogen atoms were initially refined as full-occupancy Br atoms; however, the difference Fourier map had a deep hole near one of the two. When this atom was allowed to refine as a mixture of bromine and chlorine, the refinement converged, and it gave the Br:Cl ratio as 0.88:0.12. The ratio was subsequently fixed as 0.875:0.125. Attempts to model the Br and Cl atoms on separate sites were not successful.

The published (C7H11N)2[PbBr4(C6H5)2] structure (Lo & Ng, 2008) does not contain any chlorine as the compound was synthesized by the cleavage of tetraphenyllead by 4-aminomethylpyridine hydrobromide perbromide.

Figures

Fig. 1.
View of the molecular structure of (I) at the 70% probability level. H atoms are drawn as spheres of arbitrary radius. Unlabelled atoms in the anion are generated by the symmetry operation (1 - x, 1 - y, 1 - z).

Crystal data

(C7H11N)2[PbBr3.75(C6H5)2Cl0.25]F(000) = 867
Mr = 916.27Dx = 2.102 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 4255 reflections
a = 9.5010 (2) Åθ = 2.4–28.4°
b = 13.8916 (3) ŵ = 11.05 mm1
c = 10.9851 (2) ÅT = 100 K
β = 92.996 (1)°Faceted block, colourless
V = 1447.88 (5) Å30.12 × 0.11 × 0.10 mm
Z = 2

Data collection

Bruker SMART APEX CCD diffractometer3327 independent reflections
Radiation source: fine-focus sealed tube2909 reflections with I > 2σ(I)
graphiteRint = 0.028
ω scansθmax = 27.5°, θmin = 2.4°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)h = −12→12
Tmin = 0.351, Tmax = 0.405k = −15→18
10028 measured reflectionsl = −14→14

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.022Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.048H atoms treated by a mixture of independent and constrained refinement
S = 1.02w = 1/[σ2(Fo2) + (0.0227P)2 + 0.2619P] where P = (Fo2 + 2Fc2)/3
3327 reflections(Δ/σ)max = 0.001
166 parametersΔρmax = 0.77 e Å3
1 restraintΔρmin = −0.52 e Å3

Special details

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)

xyzUiso*/UeqOcc. (<1)
Pb10.50000.50000.50000.01182 (5)
Br10.55819 (4)0.61268 (2)0.29147 (3)0.01476 (8)0.875
Br20.76221 (3)0.40251 (2)0.46037 (3)0.01660 (8)
Cl10.55819 (4)0.61268 (2)0.29147 (3)0.01476 (8)0.125
N10.8894 (3)0.5871 (2)0.2345 (3)0.0224 (7)
H10.815 (3)0.582 (3)0.277 (3)0.042 (13)*
N21.1998 (3)0.59111 (19)−0.0113 (2)0.0173 (6)
C10.6143 (3)0.6021 (2)0.6197 (3)0.0138 (6)
C20.7445 (3)0.6367 (2)0.5890 (3)0.0152 (7)
H20.78560.61560.51670.018*
C30.8144 (4)0.7030 (2)0.6660 (3)0.0198 (7)
H30.90400.72710.64650.024*
C40.7533 (4)0.7336 (2)0.7709 (3)0.0191 (7)
H40.80090.77900.82290.023*
C50.6228 (4)0.6982 (2)0.8003 (3)0.0204 (7)
H50.58140.71940.87240.024*
C60.5527 (4)0.6321 (2)0.7248 (3)0.0163 (7)
H60.46350.60760.74480.020*
C71.0060 (4)0.5338 (3)0.2555 (3)0.0208 (7)
H71.01410.49410.32600.025*
C81.1124 (4)0.5356 (2)0.1781 (3)0.0189 (7)
H81.19450.49800.19530.023*
C91.1019 (3)0.5933 (2)0.0715 (3)0.0146 (7)
C100.9798 (4)0.6523 (2)0.0576 (3)0.0189 (7)
H100.97010.6959−0.00890.023*
C110.8778 (4)0.6469 (2)0.1382 (3)0.0220 (8)
H110.79620.68600.12670.026*
C121.3282 (4)0.5343 (3)0.0091 (3)0.0225 (7)
H12A1.30340.46830.03130.034*
H12B1.38720.56320.07520.034*
H12C1.38030.5332−0.06560.034*
C131.1938 (4)0.6535 (3)−0.1175 (3)0.0267 (8)
H13A1.09520.6658−0.14340.040*
H13B1.24140.6222−0.18400.040*
H13C1.24090.7146−0.09700.040*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Pb10.01154 (9)0.01443 (9)0.00939 (8)−0.00187 (6)−0.00034 (6)−0.00126 (6)
Br10.01359 (18)0.01750 (17)0.01320 (16)0.00047 (13)0.00073 (13)0.00243 (12)
Br20.01506 (17)0.02009 (17)0.01462 (16)0.00203 (12)0.00038 (12)−0.00043 (12)
Cl10.01359 (18)0.01750 (17)0.01320 (16)0.00047 (13)0.00073 (13)0.00243 (12)
N10.0161 (17)0.0309 (17)0.0206 (16)−0.0016 (13)0.0056 (12)−0.0050 (13)
N20.0201 (16)0.0158 (14)0.0162 (14)0.0043 (11)0.0029 (11)0.0024 (11)
C10.0133 (17)0.0130 (16)0.0146 (16)−0.0008 (12)−0.0031 (12)0.0003 (12)
C20.0157 (17)0.0171 (16)0.0127 (16)0.0016 (13)−0.0020 (12)0.0004 (12)
C30.0186 (19)0.0201 (18)0.0204 (18)−0.0036 (14)−0.0008 (14)0.0032 (13)
C40.024 (2)0.0171 (18)0.0156 (17)−0.0024 (14)−0.0081 (14)−0.0015 (13)
C50.029 (2)0.0191 (18)0.0133 (16)−0.0003 (14)−0.0015 (14)−0.0027 (13)
C60.0147 (18)0.0197 (17)0.0143 (16)0.0007 (13)−0.0017 (13)0.0031 (13)
C70.022 (2)0.0252 (18)0.0149 (17)−0.0029 (15)0.0004 (14)−0.0010 (14)
C80.0188 (18)0.0211 (17)0.0170 (17)0.0021 (14)0.0014 (13)−0.0004 (13)
C90.0158 (17)0.0164 (16)0.0113 (15)−0.0013 (12)−0.0011 (12)−0.0051 (12)
C100.0213 (19)0.0171 (17)0.0183 (18)0.0024 (14)−0.0009 (14)−0.0008 (13)
C110.0188 (19)0.0229 (19)0.0242 (19)0.0047 (14)−0.0015 (14)−0.0052 (14)
C120.0190 (19)0.0306 (19)0.0180 (18)0.0059 (15)0.0027 (14)0.0008 (15)
C130.032 (2)0.028 (2)0.0203 (19)0.0065 (16)0.0057 (16)0.0057 (15)

Geometric parameters (Å, °)

Pb1—C1i2.184 (3)C4—C51.388 (5)
Pb1—C12.184 (3)C4—H40.9500
Pb1—Br12.8523 (3)C5—C61.385 (4)
Pb1—Cl1i2.8523 (3)C5—H50.9500
Pb1—Br1i2.8523 (3)C6—H60.9500
Pb1—Br22.8885 (3)C7—C81.355 (4)
Pb1—Br2i2.8885 (3)C7—H70.9500
N1—C71.342 (5)C8—C91.419 (4)
N1—C111.345 (5)C8—H80.9500
N1—H10.87 (1)C9—C101.421 (4)
N2—C91.335 (4)C10—C111.348 (5)
N2—C131.452 (4)C10—H100.9500
N2—C121.461 (4)C11—H110.9500
C1—C61.385 (4)C12—H12A0.9800
C1—C21.385 (4)C12—H12B0.9800
C2—C31.395 (4)C12—H12C0.9800
C2—H20.9500C13—H13A0.9800
C3—C41.383 (4)C13—H13B0.9800
C3—H30.9500C13—H13C0.9800
C1i—Pb1—C1180.00 (12)C3—C4—C5120.2 (3)
C1i—Pb1—Br189.09 (8)C3—C4—H4119.9
C1—Pb1—Br190.91 (8)C5—C4—H4119.9
C1i—Pb1—Cl1i90.91 (8)C6—C5—C4120.2 (3)
C1—Pb1—Cl1i89.09 (8)C6—C5—H5119.9
Br1—Pb1—Cl1i180.0C4—C5—H5119.9
C1i—Pb1—Br1i90.91 (8)C5—C6—C1119.2 (3)
C1—Pb1—Br1i89.09 (8)C5—C6—H6120.4
Br1—Pb1—Br1i180.0C1—C6—H6120.4
Cl1i—Pb1—Br1i0.000 (17)N1—C7—C8121.2 (3)
C1i—Pb1—Br290.60 (8)N1—C7—H7119.4
C1—Pb1—Br289.40 (8)C8—C7—H7119.4
Br1—Pb1—Br286.065 (9)C7—C8—C9120.4 (3)
Cl1i—Pb1—Br293.935 (9)C7—C8—H8119.8
Br1i—Pb1—Br293.935 (9)C9—C8—H8119.8
C1i—Pb1—Br2i89.40 (8)N2—C9—C8121.9 (3)
C1—Pb1—Br2i90.60 (8)N2—C9—C10122.3 (3)
Br1—Pb1—Br2i93.935 (9)C8—C9—C10115.9 (3)
Cl1i—Pb1—Br2i86.065 (9)C11—C10—C9120.5 (3)
Br1i—Pb1—Br2i86.065 (9)C11—C10—H10119.7
Br2—Pb1—Br2i180.0C9—C10—H10119.7
C7—N1—C11120.6 (3)N1—C11—C10121.2 (3)
C7—N1—H1124 (3)N1—C11—H11119.4
C11—N1—H1116 (3)C10—C11—H11119.4
C9—N2—C13122.3 (3)N2—C12—H12A109.5
C9—N2—C12120.9 (3)N2—C12—H12B109.5
C13—N2—C12116.3 (3)H12A—C12—H12B109.5
C6—C1—C2121.3 (3)N2—C12—H12C109.5
C6—C1—Pb1118.6 (2)H12A—C12—H12C109.5
C2—C1—Pb1120.1 (2)H12B—C12—H12C109.5
C1—C2—C3119.0 (3)N2—C13—H13A109.5
C1—C2—H2120.5N2—C13—H13B109.5
C3—C2—H2120.5H13A—C13—H13B109.5
C4—C3—C2120.1 (3)N2—C13—H13C109.5
C4—C3—H3120.0H13A—C13—H13C109.5
C2—C3—H3120.0H13B—C13—H13C109.5
Br1—Pb1—C1—C6133.5 (2)C4—C5—C6—C1−0.2 (5)
Cl1i—Pb1—C1—C6−46.5 (2)C2—C1—C6—C50.2 (5)
Br1i—Pb1—C1—C6−46.5 (2)Pb1—C1—C6—C5−178.8 (2)
Br2—Pb1—C1—C6−140.4 (2)C11—N1—C7—C8−2.8 (5)
Br2i—Pb1—C1—C639.6 (2)N1—C7—C8—C9−0.8 (5)
Br1—Pb1—C1—C2−45.5 (2)C13—N2—C9—C8−176.7 (3)
Cl1i—Pb1—C1—C2134.5 (2)C12—N2—C9—C8−4.9 (5)
Br1i—Pb1—C1—C2134.5 (2)C13—N2—C9—C104.3 (5)
Br2—Pb1—C1—C240.6 (2)C12—N2—C9—C10176.2 (3)
Br2i—Pb1—C1—C2−139.4 (2)C7—C8—C9—N2−174.7 (3)
C6—C1—C2—C30.0 (5)C7—C8—C9—C104.3 (5)
Pb1—C1—C2—C3179.0 (2)N2—C9—C10—C11174.6 (3)
C1—C2—C3—C4−0.3 (5)C8—C9—C10—C11−4.4 (5)
C2—C3—C4—C50.3 (5)C7—N1—C11—C102.6 (5)
C3—C4—C5—C6−0.1 (5)C9—C10—C11—N11.1 (5)

Symmetry codes: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N1—H1···Br10.87 (1)2.49 (2)3.260 (3)148 (4)

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HB2863).

References

  • Barbour, L. J. (2001). J. Supramol. Chem.1, 189–191.
  • Bruker (2007). APEX2 and SAINT Bruker AXS Inc., Madison, Wisconsin, USA.
  • Lo, K. M. & Ng, S. W. (2008). Acta Cryst. E64, m1222. [PMC free article] [PubMed]
  • Sheldrick, G. M. (1996). SADABS University of Göttingen, Germany.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Westrip, S. P. (2008). publCIF In preparation.

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