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

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.

Key indicators

• Single-crystal X-ray study
• T = 100 K
• Mean [sigma](C-C) = 0.006 Å
• R factor = 0.029
• wR factor = 0.075
• Data-to-parameter ratio = 20.4

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT232_ALERT_2_B Hirshfeld Test Diff (M-X)  Pb1    --  Br1     ..      30.52 su

Alert level C
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X)  Pb1    --  Br2     ..       5.26 su
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT062_ALERT_4_C Rescale T(min) & T(max) by .....................       0.92
PLAT180_ALERT_4_C Check Cell Rounding: # of Values Ending with 0 =          3
PLAT716_ALERT_1_C H...A   Unknown or Inconsistent Label ..........    H2<I>N<

Alert level G
ABSTM02_ALERT_3_G  When printed, the submitted absorption T values will be
            replaced by the scaled T values. Since the ratio of scaled T's
            is identical to the ratio of reported T values, the scaling
            does not imply a change to the absorption corrections used in
            the study.
            Ratio of Tmax expected/reported      0.921
            Tmax scaled      0.505 Tmin scaled      0.226

   0 ALERT level A = In general: serious problem
   1 ALERT level B = Potentially serious problem
   5 ALERT level C = Check and explain
   1 ALERT level G = General alerts; check

   2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   2 ALERT type 2 Indicator that the structure model may be wrong or deficient
   1 ALERT type 3 Indicator that the structure quality may be low
   2 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

---

S1. Comment

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

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

S2. Experimental

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.

S3. Refinement

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 1.5U_eq(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

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

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)

Crystal data

(C7H11N2)2[PbBr4(C6H5)2]	F(000) = 876
Mr = 927.39	Dx = 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) Å^3	0.22 × 0.08 × 0.06 mm
Z = 2

Data collection

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

Refinement

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

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

Pb1—C1	2.190 (5)	C4—H4	0.9500
Pb1—C1^i	2.190 (5)	C5—C6	1.385 (6)
Pb1—Br1	2.8516 (5)	C5—H5	0.9500
Pb1—Br1^i	2.8516 (5)	C6—H6	0.9500
Pb1—Br2^i	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—C1^i	180.00 (17)	C6—C5—C4	120.2 (4)
C1—Pb1—Br1	90.79 (12)	C6—C5—H5	119.9
C1^i—Pb1—Br1	89.21 (12)	C4—C5—H5	119.9
C1—Pb1—Br1^i	89.21 (12)	C1—C6—C5	119.1 (4)
C1^i—Pb1—Br1^i	90.79 (12)	C1—C6—H6	120.4
Br1—Pb1—Br1^i	180.000 (16)	C5—C6—H6	120.4
C1—Pb1—Br2^i	90.55 (12)	C8—C7—N2	121.5 (5)
C1^i—Pb1—Br2^i	89.45 (12)	C8—C7—H7	119.3
Br1—Pb1—Br2^i	93.978 (14)	N2—C7—H7	119.3
Br1^i—Pb1—Br2^i	86.022 (14)	C7—C8—C9	119.8 (5)
C1—Pb1—Br2	89.45 (12)	C7—C8—H8	120.1
C1^i—Pb1—Br2	90.55 (12)	C9—C8—H8	120.1
Br1—Pb1—Br2	86.022 (14)	N1—C9—C10	121.8 (4)
Br1^i—Pb1—Br2	93.978 (14)	N1—C9—C8	122.0 (4)
Br2^i—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)
Br1^i—Pb1—C1—C6	134.0 (4)	C4—C5—C6—C1	0.2 (7)
Br2^i—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)
Br1^i—Pb1—C1—C2	−46.2 (3)	C12—N1—C9—C10	−177.1 (5)
Br2^i—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)

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