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

Abstract

The Pb^IV atom of the plumbate dianion in the title compound, (C₇H₁₁N)₂[Pb(Br_3.75Cl_0.25)(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 ▶).

Experimental

Crystal data

• (C₇H₁₁N)₂[Pb(Br_3.75Cl_0.25)(C₆H₅)₂]

• M _r = 916.27

• Monoclinic,

• a = 9.5010 (2) Å

• b = 13.8916 (3) Å

• c = 10.9851 (2) Å

• β = 92.996 (1)°

• V = 1447.88 (5) ų

• 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 ▶) 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

• Δρ_max = 0.77 e Å⁻³

• Δρ_min = −0.52 e Å⁻³

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 ▶).

Supplementary Material

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

Table 1. Selected bond lengths (Å).

X = Br, Cl.

Pb1—C1	2.184 (3)
Pb1—X1	2.8523 (3)
Pb1—Br2	2.8885 (3)

Table 2. Hydrogen-bond geometry (Å, °).

X = Br, Cl.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯X1	0.87 (1)	2.49 (2)	3.260 (3)	148 (4)

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 U_iso(H) = 1.2 to 1.5U_eq(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 U_iso 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 = 916.27	Dx = 2.102 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 4255 reflections
a = 9.5010 (2) Å	θ = 2.4–28.4°
b = 13.8916 (3) Å	µ = 11.05 mm−1
c = 10.9851 (2) Å	T = 100 K
β = 92.996 (1)°	Faceted block, colourless
V = 1447.88 (5) Å3	0.12 × 0.11 × 0.10 mm
Z = 2

Data collection

Bruker SMART APEX CCD diffractometer	3327 independent reflections
Radiation source: fine-focus sealed tube	2909 reflections with I > 2σ(I)
graphite	Rint = 0.028
ω scans	θmax = 27.5°, θmin = 2.4°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −12→12
Tmin = 0.351, Tmax = 0.405	k = −15→18
10028 measured reflections	l = −14→14

Refinement

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)] = 0.022	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.048	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ2(Fo2) + (0.0227P)2 + 0.2619P] where P = (Fo2 + 2Fc2)/3
3327 reflections	(Δ/σ)max = 0.001
166 parameters	Δρmax = 0.77 e Å−3
1 restraint	Δρmin = −0.52 e Å−3

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 (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
Pb1	0.5000	0.5000	0.5000	0.01182 (5)
Br1	0.55819 (4)	0.61268 (2)	0.29147 (3)	0.01476 (8)	0.875
Br2	0.76221 (3)	0.40251 (2)	0.46037 (3)	0.01660 (8)
Cl1	0.55819 (4)	0.61268 (2)	0.29147 (3)	0.01476 (8)	0.125
N1	0.8894 (3)	0.5871 (2)	0.2345 (3)	0.0224 (7)
H1	0.815 (3)	0.582 (3)	0.277 (3)	0.042 (13)*
N2	1.1998 (3)	0.59111 (19)	−0.0113 (2)	0.0173 (6)
C1	0.6143 (3)	0.6021 (2)	0.6197 (3)	0.0138 (6)
C2	0.7445 (3)	0.6367 (2)	0.5890 (3)	0.0152 (7)
H2	0.7856	0.6156	0.5167	0.018*
C3	0.8144 (4)	0.7030 (2)	0.6660 (3)	0.0198 (7)
H3	0.9040	0.7271	0.6465	0.024*
C4	0.7533 (4)	0.7336 (2)	0.7709 (3)	0.0191 (7)
H4	0.8009	0.7790	0.8229	0.023*
C5	0.6228 (4)	0.6982 (2)	0.8003 (3)	0.0204 (7)
H5	0.5814	0.7194	0.8724	0.024*
C6	0.5527 (4)	0.6321 (2)	0.7248 (3)	0.0163 (7)
H6	0.4635	0.6076	0.7448	0.020*
C7	1.0060 (4)	0.5338 (3)	0.2555 (3)	0.0208 (7)
H7	1.0141	0.4941	0.3260	0.025*
C8	1.1124 (4)	0.5356 (2)	0.1781 (3)	0.0189 (7)
H8	1.1945	0.4980	0.1953	0.023*
C9	1.1019 (3)	0.5933 (2)	0.0715 (3)	0.0146 (7)
C10	0.9798 (4)	0.6523 (2)	0.0576 (3)	0.0189 (7)
H10	0.9701	0.6959	−0.0089	0.023*
C11	0.8778 (4)	0.6469 (2)	0.1382 (3)	0.0220 (8)
H11	0.7962	0.6860	0.1267	0.026*
C12	1.3282 (4)	0.5343 (3)	0.0091 (3)	0.0225 (7)
H12A	1.3034	0.4683	0.0313	0.034*
H12B	1.3872	0.5632	0.0752	0.034*
H12C	1.3803	0.5332	−0.0656	0.034*
C13	1.1938 (4)	0.6535 (3)	−0.1175 (3)	0.0267 (8)
H13A	1.0952	0.6658	−0.1434	0.040*
H13B	1.2414	0.6222	−0.1840	0.040*
H13C	1.2409	0.7146	−0.0970	0.040*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
Pb1	0.01154 (9)	0.01443 (9)	0.00939 (8)	−0.00187 (6)	−0.00034 (6)	−0.00126 (6)
Br1	0.01359 (18)	0.01750 (17)	0.01320 (16)	0.00047 (13)	0.00073 (13)	0.00243 (12)
Br2	0.01506 (17)	0.02009 (17)	0.01462 (16)	0.00203 (12)	0.00038 (12)	−0.00043 (12)
Cl1	0.01359 (18)	0.01750 (17)	0.01320 (16)	0.00047 (13)	0.00073 (13)	0.00243 (12)
N1	0.0161 (17)	0.0309 (17)	0.0206 (16)	−0.0016 (13)	0.0056 (12)	−0.0050 (13)
N2	0.0201 (16)	0.0158 (14)	0.0162 (14)	0.0043 (11)	0.0029 (11)	0.0024 (11)
C1	0.0133 (17)	0.0130 (16)	0.0146 (16)	−0.0008 (12)	−0.0031 (12)	0.0003 (12)
C2	0.0157 (17)	0.0171 (16)	0.0127 (16)	0.0016 (13)	−0.0020 (12)	0.0004 (12)
C3	0.0186 (19)	0.0201 (18)	0.0204 (18)	−0.0036 (14)	−0.0008 (14)	0.0032 (13)
C4	0.024 (2)	0.0171 (18)	0.0156 (17)	−0.0024 (14)	−0.0081 (14)	−0.0015 (13)
C5	0.029 (2)	0.0191 (18)	0.0133 (16)	−0.0003 (14)	−0.0015 (14)	−0.0027 (13)
C6	0.0147 (18)	0.0197 (17)	0.0143 (16)	0.0007 (13)	−0.0017 (13)	0.0031 (13)
C7	0.022 (2)	0.0252 (18)	0.0149 (17)	−0.0029 (15)	0.0004 (14)	−0.0010 (14)
C8	0.0188 (18)	0.0211 (17)	0.0170 (17)	0.0021 (14)	0.0014 (13)	−0.0004 (13)
C9	0.0158 (17)	0.0164 (16)	0.0113 (15)	−0.0013 (12)	−0.0011 (12)	−0.0051 (12)
C10	0.0213 (19)	0.0171 (17)	0.0183 (18)	0.0024 (14)	−0.0009 (14)	−0.0008 (13)
C11	0.0188 (19)	0.0229 (19)	0.0242 (19)	0.0047 (14)	−0.0015 (14)	−0.0052 (14)
C12	0.0190 (19)	0.0306 (19)	0.0180 (18)	0.0059 (15)	0.0027 (14)	0.0008 (15)
C13	0.032 (2)	0.028 (2)	0.0203 (19)	0.0065 (16)	0.0057 (16)	0.0057 (15)

Geometric parameters (Å, °)

Pb1—C1i	2.184 (3)	C4—C5	1.388 (5)
Pb1—C1	2.184 (3)	C4—H4	0.9500
Pb1—Br1	2.8523 (3)	C5—C6	1.385 (4)
Pb1—Cl1i	2.8523 (3)	C5—H5	0.9500
Pb1—Br1i	2.8523 (3)	C6—H6	0.9500
Pb1—Br2	2.8885 (3)	C7—C8	1.355 (4)
Pb1—Br2i	2.8885 (3)	C7—H7	0.9500
N1—C7	1.342 (5)	C8—C9	1.419 (4)
N1—C11	1.345 (5)	C8—H8	0.9500
N1—H1	0.87 (1)	C9—C10	1.421 (4)
N2—C9	1.335 (4)	C10—C11	1.348 (5)
N2—C13	1.452 (4)	C10—H10	0.9500
N2—C12	1.461 (4)	C11—H11	0.9500
C1—C6	1.385 (4)	C12—H12A	0.9800
C1—C2	1.385 (4)	C12—H12B	0.9800
C2—C3	1.395 (4)	C12—H12C	0.9800
C2—H2	0.9500	C13—H13A	0.9800
C3—C4	1.383 (4)	C13—H13B	0.9800
C3—H3	0.9500	C13—H13C	0.9800
C1i—Pb1—C1	180.00 (12)	C3—C4—C5	120.2 (3)
C1i—Pb1—Br1	89.09 (8)	C3—C4—H4	119.9
C1—Pb1—Br1	90.91 (8)	C5—C4—H4	119.9
C1i—Pb1—Cl1i	90.91 (8)	C6—C5—C4	120.2 (3)
C1—Pb1—Cl1i	89.09 (8)	C6—C5—H5	119.9
Br1—Pb1—Cl1i	180.0	C4—C5—H5	119.9
C1i—Pb1—Br1i	90.91 (8)	C5—C6—C1	119.2 (3)
C1—Pb1—Br1i	89.09 (8)	C5—C6—H6	120.4
Br1—Pb1—Br1i	180.0	C1—C6—H6	120.4
Cl1i—Pb1—Br1i	0.000 (17)	N1—C7—C8	121.2 (3)
C1i—Pb1—Br2	90.60 (8)	N1—C7—H7	119.4
C1—Pb1—Br2	89.40 (8)	C8—C7—H7	119.4
Br1—Pb1—Br2	86.065 (9)	C7—C8—C9	120.4 (3)
Cl1i—Pb1—Br2	93.935 (9)	C7—C8—H8	119.8
Br1i—Pb1—Br2	93.935 (9)	C9—C8—H8	119.8
C1i—Pb1—Br2i	89.40 (8)	N2—C9—C8	121.9 (3)
C1—Pb1—Br2i	90.60 (8)	N2—C9—C10	122.3 (3)
Br1—Pb1—Br2i	93.935 (9)	C8—C9—C10	115.9 (3)
Cl1i—Pb1—Br2i	86.065 (9)	C11—C10—C9	120.5 (3)
Br1i—Pb1—Br2i	86.065 (9)	C11—C10—H10	119.7
Br2—Pb1—Br2i	180.0	C9—C10—H10	119.7
C7—N1—C11	120.6 (3)	N1—C11—C10	121.2 (3)
C7—N1—H1	124 (3)	N1—C11—H11	119.4
C11—N1—H1	116 (3)	C10—C11—H11	119.4
C9—N2—C13	122.3 (3)	N2—C12—H12A	109.5
C9—N2—C12	120.9 (3)	N2—C12—H12B	109.5
C13—N2—C12	116.3 (3)	H12A—C12—H12B	109.5
C6—C1—C2	121.3 (3)	N2—C12—H12C	109.5
C6—C1—Pb1	118.6 (2)	H12A—C12—H12C	109.5
C2—C1—Pb1	120.1 (2)	H12B—C12—H12C	109.5
C1—C2—C3	119.0 (3)	N2—C13—H13A	109.5
C1—C2—H2	120.5	N2—C13—H13B	109.5
C3—C2—H2	120.5	H13A—C13—H13B	109.5
C4—C3—C2	120.1 (3)	N2—C13—H13C	109.5
C4—C3—H3	120.0	H13A—C13—H13C	109.5
C2—C3—H3	120.0	H13B—C13—H13C	109.5
Br1—Pb1—C1—C6	133.5 (2)	C4—C5—C6—C1	−0.2 (5)
Cl1i—Pb1—C1—C6	−46.5 (2)	C2—C1—C6—C5	0.2 (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—C6	39.6 (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—C2	134.5 (2)	C12—N2—C9—C8	−4.9 (5)
Br1i—Pb1—C1—C2	134.5 (2)	C13—N2—C9—C10	4.3 (5)
Br2—Pb1—C1—C2	40.6 (2)	C12—N2—C9—C10	176.2 (3)
Br2i—Pb1—C1—C2	−139.4 (2)	C7—C8—C9—N2	−174.7 (3)
C6—C1—C2—C3	0.0 (5)	C7—C8—C9—C10	4.3 (5)
Pb1—C1—C2—C3	179.0 (2)	N2—C9—C10—C11	174.6 (3)
C1—C2—C3—C4	−0.3 (5)	C8—C9—C10—C11	−4.4 (5)
C2—C3—C4—C5	0.3 (5)	C7—N1—C11—C10	2.6 (5)
C3—C4—C5—C6	−0.1 (5)	C9—C10—C11—N1	1.1 (5)

Symmetry codes: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···Br1	0.87 (1)	2.49 (2)	3.260 (3)	148 (4)