catena-Poly[[(2,9-dimethyl-1,10-phenanthroline-κ² N,N′)lead(II)]-di-μ-bromido]

Abstract

In the title compound, [PbBr₂(C₁₄H₁₂N₂)]_n, the Pb^II atom lies on a twofold rotation axis. The N-heterocycle-chelated Pb^II atom exists in a distorted octa­hedral geometry owing to two long Pb⋯Br inter­actions [2.9562 (5) and 3.2594 (5) Å]. These result in a zigzag chain running along the c axis. The lone pair is stereochemically inactive.

Related literature  

For the lead(II) bromide–1,10-phenanthroline homolog, see: Bowmaker et al. (1996 ▶).

Experimental  

Crystal data  

• [PbBr₂(C₁₄H₁₂N₂)]

• M _r = 575.27

• Monoclinic,

• a = 18.3852 (13) Å

• b = 11.8312 (5) Å

• c = 7.4609 (5) Å

• β = 112.346 (8)°

• V = 1501.02 (16) ų

• Z = 4

• Mo Kα radiation

• μ = 16.55 mm⁻¹

• T = 100 K

• 0.15 × 0.15 × 0.05 mm

Data collection  

• Agilent SuperNova Dual diffractometer with an Atlas detector

• Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012 ▶) T _min = 0.190, T _max = 0.492

• 4947 measured reflections

• 1734 independent reflections

• 1620 reflections with I > 2σ(I)

• R _int = 0.032

Refinement  

• R[F ² > 2σ(F ²)] = 0.026

• wR(F ²) = 0.058

• S = 1.01

• 1734 reflections

• 88 parameters

• H-atom parameters constrained

• Δρ_max = 1.43 e Å⁻³

• Δρ_min = −1.45 e Å⁻³

Data collection: CrysAlis PRO (Agilent, 2012 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; 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, 2010 ▶).

Supplementary Material

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

supplementary crystallographic information

Comment

The N-heterocycle chelated Pb^II atom in PbBr₂(C₁₄H₁₂N₂) exists in a slightly distorted octahedral geometry with Pb···Br distances of 2.9562 (5)Å and 3.2594 (5)Å. The result are zigzag chains running along the c-axis of the monoclinic unit cell. The Pb centre lies on a twofold rotation axis. The lack of stereochemical activity can be attributed to crowding from the methyl substituents of the N-heterocycle (Bowmaker et al., 1996).

Experimental

Lead(II) bromide (0.37 g, 1 mmol) and 2,9-dimethyl-1,10-phenanthroline (1/5, 1 mmol) were loaded in a convection tube; the tube was filled with methanol and kept at 333 K. Colorless crystals were collected from the side arm after several days.

Refinement

H-atoms were placed in calculated positions [C–H 0.95 to 0.98 Å, U_iso(H) 1.2 to 1.5U_eq(C)] and were included in the refinement in the riding model approximation.

The final difference Fourier map had a peak at 0.82 Å and a hole at 1.01 Å from Pb1.

Figures

Fig. 1.

Anisotropic displacement ellipsoid plot (Barbour, 2001) of PbBr2(C14H12N2) at the 70% probability level; hydrogen atoms are drawn as spheres of arbitrary radius; symmetry-related atoms are not labeled. Adjacent molecules are linked by a weak Pb···Br bond, which is denoted as a dashed line.

Crystal data

[PbBr2(C14H12N2)]	F(000) = 1048
Mr = 575.27	Dx = 2.546 Mg m−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 2739 reflections
a = 18.3852 (13) Å	θ = 2.4–27.5°
b = 11.8312 (5) Å	µ = 16.55 mm−1
c = 7.4609 (5) Å	T = 100 K
β = 112.346 (8)°	Prism, colorless
V = 1501.02 (16) Å3	0.15 × 0.15 × 0.05 mm
Z = 4

Data collection

Agilent SuperNova Dual diffractometer with an Atlas detector	1734 independent reflections
Radiation source: SuperNova (Mo) X-ray Source	1620 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.032
Detector resolution: 10.4041 pixels mm-1	θmax = 27.6°, θmin = 2.4°
ω scan	h = −22→23
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012)	k = −15→11
Tmin = 0.190, Tmax = 0.492	l = −8→9
4947 measured reflections

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)] = 0.026	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.058	H-atom parameters constrained
S = 1.01	w = 1/[σ2(Fo2) + (0.0298P)2] where P = (Fo2 + 2Fc2)/3
1734 reflections	(Δ/σ)max = 0.001
88 parameters	Δρmax = 1.43 e Å−3
0 restraints	Δρmin = −1.45 e Å−3

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

	x	y	z	Uiso*/Ueq
Pb1	0.5000	0.399831 (16)	0.2500	0.01318 (9)
Br1	0.40287 (3)	0.38883 (3)	0.48715 (6)	0.01909 (12)
N1	0.5735 (2)	0.2162 (3)	0.3998 (5)	0.0138 (7)
C1	0.6822 (3)	0.3265 (4)	0.6184 (6)	0.0261 (11)
H1A	0.6768	0.3765	0.5092	0.039*
H1B	0.7381	0.3151	0.6972	0.039*
H1C	0.6563	0.3610	0.6980	0.039*
C2	0.6450 (3)	0.2162 (4)	0.5439 (6)	0.0183 (9)
C3	0.6839 (3)	0.1139 (4)	0.6216 (7)	0.0241 (11)
H3	0.7345	0.1152	0.7230	0.029*
C4	0.6485 (3)	0.0134 (4)	0.5503 (6)	0.0250 (11)
H4	0.6743	−0.0554	0.6030	0.030*
C5	0.5748 (3)	0.0111 (3)	0.4008 (6)	0.0206 (10)
C6	0.5374 (3)	0.1159 (3)	0.3270 (6)	0.0141 (9)
C7	0.5352 (4)	−0.0932 (3)	0.3218 (7)	0.0257 (12)
H7	0.5598	−0.1631	0.3730	0.031*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
Pb1	0.01465 (15)	0.01085 (12)	0.01436 (13)	0.000	0.00588 (10)	0.000
Br1	0.0217 (3)	0.0169 (2)	0.0212 (2)	−0.00258 (17)	0.0109 (2)	−0.00127 (15)
N1	0.014 (2)	0.0143 (16)	0.0136 (16)	0.0002 (15)	0.0052 (15)	−0.0005 (13)
C1	0.016 (3)	0.035 (3)	0.021 (2)	−0.004 (2)	0.001 (2)	−0.0017 (19)
C2	0.016 (3)	0.026 (2)	0.0156 (19)	−0.0006 (19)	0.0089 (19)	0.0041 (17)
C3	0.014 (3)	0.034 (3)	0.023 (2)	0.009 (2)	0.005 (2)	0.0105 (18)
C4	0.032 (3)	0.024 (2)	0.024 (2)	0.013 (2)	0.017 (2)	0.0115 (19)
C5	0.028 (3)	0.017 (2)	0.024 (2)	0.0061 (19)	0.018 (2)	0.0055 (17)
C6	0.020 (3)	0.0131 (19)	0.0137 (19)	0.0009 (16)	0.011 (2)	0.0008 (14)
C7	0.045 (4)	0.011 (2)	0.032 (3)	0.0033 (19)	0.028 (3)	0.0029 (16)

Geometric parameters (Å, º)

Pb1—N1i	2.578 (3)	C2—C3	1.413 (6)
Pb1—N1	2.578 (3)	C3—C4	1.362 (7)
Pb1—Br1i	2.9562 (5)	C3—H3	0.9500
Pb1—Br1	2.9562 (5)	C4—C5	1.390 (7)
Pb1—Br1ii	3.2594 (5)	C4—H4	0.9500
N1—C2	1.345 (6)	C5—C6	1.423 (5)
N1—C6	1.368 (5)	C5—C7	1.440 (6)
C1—C2	1.481 (6)	C6—C6i	1.417 (9)
C1—H1A	0.9800	C7—C7i	1.330 (12)
C1—H1B	0.9800	C7—H7	0.9500
C1—H1C	0.9800
N1i—Pb1—N1	65.15 (16)	N1—C2—C3	121.1 (4)
N1i—Pb1—Br1i	92.27 (7)	N1—C2—C1	118.1 (4)
N1—Pb1—Br1i	83.46 (7)	C3—C2—C1	120.8 (4)
N1i—Pb1—Br1	83.46 (7)	C4—C3—C2	119.6 (5)
N1—Pb1—Br1	92.27 (7)	C4—C3—H3	120.2
Br1i—Pb1—Br1	174.955 (16)	C2—C3—H3	120.2
N1i—Pb1—Br1ii	169.82 (7)	C3—C4—C5	120.4 (4)
N1—Pb1—Br1ii	107.98 (8)	C3—C4—H4	119.8
Br1i—Pb1—Br1ii	94.383 (13)	C5—C4—H4	119.8
Br1—Pb1—Br1ii	89.490 (13)	C4—C5—C6	118.3 (4)
C2—N1—C6	119.7 (4)	C4—C5—C7	122.1 (4)
C2—N1—Pb1	122.6 (3)	C6—C5—C7	119.6 (5)
C6—N1—Pb1	117.6 (3)	N1—C6—C6i	119.8 (2)
C2—C1—H1A	109.5	N1—C6—C5	120.8 (4)
C2—C1—H1B	109.5	C6i—C6—C5	119.4 (3)
H1A—C1—H1B	109.5	C7i—C7—C5	121.0 (3)
C2—C1—H1C	109.5	C7i—C7—H7	119.5
H1A—C1—H1C	109.5	C5—C7—H7	119.5
H1B—C1—H1C	109.5
N1i—Pb1—N1—C2	179.5 (4)	C2—C3—C4—C5	0.5 (7)
Br1i—Pb1—N1—C2	83.9 (3)	C3—C4—C5—C6	−0.8 (7)
Br1—Pb1—N1—C2	−98.8 (3)	C3—C4—C5—C7	−179.8 (4)
Br1ii—Pb1—N1—C2	−8.6 (3)	C2—N1—C6—C6i	−179.0 (4)
N1i—Pb1—N1—C6	−0.2 (2)	Pb1—N1—C6—C6i	0.7 (6)
Br1i—Pb1—N1—C6	−95.8 (3)	C2—N1—C6—C5	−0.5 (6)
Br1—Pb1—N1—C6	81.5 (3)	Pb1—N1—C6—C5	179.2 (3)
Br1ii—Pb1—N1—C6	171.7 (3)	C4—C5—C6—N1	0.8 (6)
C6—N1—C2—C3	0.2 (6)	C7—C5—C6—N1	179.8 (4)
Pb1—N1—C2—C3	−179.5 (3)	C4—C5—C6—C6i	179.2 (5)
C6—N1—C2—C1	179.8 (4)	C7—C5—C6—C6i	−1.7 (7)
Pb1—N1—C2—C1	0.1 (5)	C4—C5—C7—C7i	−179.7 (5)
N1—C2—C3—C4	−0.3 (7)	C6—C5—C7—C7i	1.3 (8)
C1—C2—C3—C4	−179.8 (4)

Symmetry codes: (i) −x+1, y, −z+1/2; (ii) −x+1, −y+1, −z+1.