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

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

doi:10.1107/S1600536808040312

metal-organic compounds

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Bis[4-(dimethylamino)pyridinium] 3.75-bromido-0.25-chloridodiphenylplumbate(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 24 November 2008; accepted 1 December 2008; online 6 December 2008)

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, P 2₁ /n
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 ) 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[F² > 2σ(F²)] = 0.022
wR(F²) = 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

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)

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/S1600536808040312/hb2863sup1.cif

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

checkCIF report

Related literature top

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

Experimental top

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).

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. 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).

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

Crystal data top

(C₇H₁₁N)₂[PbBr_3.75(C₆H₅)₂Cl_0.25]	F(000) = 867
M_r = 916.27	D_x = 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 top

Bruker SMART APEX CCD diffractometer	3327 independent reflections
Radiation source: fine-focus sealed tube	2909 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.028
ω scans	θ_max = 27.5°, θ_min = 2.4°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −12→12
T_min = 0.351, T_max = 0.405	k = −15→18
10028 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)] = 0.022	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(F_o²) + (0.0227P)² + 0.2619P] where P = (F_o² + 2F_c²)/3
3327 reflections	(Δ/σ)_max = 0.001
166 parameters	Δρ_max = 0.77 e Å⁻³
1 restraint	Δρ_min = −0.52 e Å⁻³

Crystal data top

(C₇H₁₁N)₂[PbBr_3.75(C₆H₅)₂Cl_0.25]	V = 1447.88 (5) Å³
M_r = 916.27	Z = 2
Monoclinic, P2₁/n	Mo Kα radiation
a = 9.5010 (2) Å	µ = 11.05 mm⁻¹
b = 13.8916 (3) Å	T = 100 K
c = 10.9851 (2) Å	0.12 × 0.11 × 0.10 mm
β = 92.996 (1)°

Data collection top

Bruker SMART APEX CCD diffractometer	3327 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2909 reflections with I > 2σ(I)
T_min = 0.351, T_max = 0.405	R_int = 0.028
10028 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.022	1 restraint
wR(F²) = 0.048	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	Δρ_max = 0.77 e Å⁻³
3327 reflections	Δρ_min = −0.52 e Å⁻³
166 parameters

Special details top

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) top

	x	y	z	U_iso*/U_eq	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 (Å²) top

	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, º) top

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

Experimental details

Crystal data
Chemical formula	(C₇H₁₁N)₂[PbBr_3.75(C₆H₅)₂Cl_0.25]
M_r	916.27
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	100
a, b, c (Å)	9.5010 (2), 13.8916 (3), 10.9851 (2)
β (°)	92.996 (1)
V (Å³)	1447.88 (5)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	11.05
Crystal size (mm)	0.12 × 0.11 × 0.10

Data collection
Diffractometer	Bruker SMART APEX CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.351, 0.405
No. of measured, independent and observed [I > 2σ(I)] reflections	10028, 3327, 2909
R_int	0.028
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.022, 0.048, 1.02
No. of reflections	3327
No. of parameters	166
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.77, −0.52

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	2.184 (3)	Pb1—Br2	2.8885 (3)
Pb1—Br1	2.8523 (3)

Hydrogen-bond geometry (Å, º) top

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)

Acknowledgements

We thank the University of Malaya for funding this study (grant No. FS339/2008A) 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
Lo, K. M. & Ng, S. W. (2008). Acta Cryst. E64, m1222. Web of Science CrossRef IUCr Journals 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

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

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

metal-organic compounds

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