Poly[aqua-μ-bromido-(μ₂-5-methyl­pyrazine-2-carboxyl­ato-κ⁴ N ¹,O ²:O ²,O ^2′)lead(II)]

Abstract

In the title coordination polymer, [PbBr(C₆H₅N₂O₂)(H₂O)]_n, the Pb^II atom is coordinated by one pyrazine N atom, two bridging Br atoms, a water mol­ecule and three carboxyl­ate O atoms. Bridging by the two anions generates a layer structure parallel to (001); the layers are linked by O—H⋯N and O—H⋯Br hydrogen bonds, forming a three-dimensional network. The lone pair is stereochemically active, resulting in a Ψ-dodeca­hedral coordination environment for Pb^II.

Related literature  

For background, see: Ding et al. (2009 ▶).

Experimental  

Crystal data  

• [PbBr(C₆H₅N₂O₂)(H₂O)]

• M _r = 442.24

• Monoclinic,

• a = 7.5493 (10) Å

• b = 6.6775 (9) Å

• c = 19.335 (3) Å

• β = 92.884 (2)°

• V = 973.5 (2) ų

• Z = 4

• Mo Kα radiation

• μ = 21.41 mm⁻¹

• T = 296 K

• 0.15 × 0.14 × 0.13 mm

Data collection  

• Bruker SMART APEX CCD area-detector diffractometer

• Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.142, T _max = 0.167

• 5123 measured reflections

• 1904 independent reflections

• 1747 reflections with I > 2σ(I)

• R _int = 0.039

Refinement  

• R[F ² > 2σ(F ²)] = 0.033

• wR(F ²) = 0.091

• S = 1.05

• 1904 reflections

• 120 parameters

• H-atom parameters constrained

• Δρ_max = 2.26 e Å⁻³

• Δρ_min = −2.20 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: DIAMOND (Brandenburg, 1999 ▶); software used to prepare material for publication: publCIF (Westrip, 2010) ▶.

Supplementary Material

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

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3A⋯N2i	0.85	1.97	2.816 (9)	173
O3—H3B⋯Br1ii	0.85	2.56	3.378 (6)	161

Symmetry codes: (i) ; (ii) .

supplementary crystallographic information

Experimental

Lead(II) bromide (73.4 mg, 0.2 mmol), 5-pyrazine-2-carboxylic acid (27.6 mg, 0.2 mmol) and water (15 ml) were sealed in a 25 ml Teflon-lined steel vessel. The mixture was heated heated to 393 K for 5 days . The autoclave was cooled to room temperature at a rate of 10 K h^-1. Yellow block-shaped crystals were obtained in 60% yield based on Pb.

Refinement

H atoms were placed in calculated positions as riding atoms attached to non-riding atoms with O—H es of 0.85 Å and C–H 0.93 to 0.96 Å, and with U_iso(H) = 1.2 to 1.5U_eq(O,C). The final difference Fourier map had a peak in the vicinity of Pb and a hole in the vicinty of the same atom.

Figures

Fig. 1.

ORTEP plot of a portion of the polymeric structure drawn at 30% probability displacement ellipsoids. Symmetry codes: i: -x + 1, y - 1/2, -z + 3/2; ii: -x, y - 1/2, -z + 3/2.

Fig. 2.

Layer structures.

Fig. 3.

Three-dimensional supramolecular structure. Dashed lines represent O—H···N and weak O—H···Br hydrogen bonds.

Fig. 4.

Ψ-Dodecahedral geometry of lead(II).

Crystal data

[PbBr(C6H5N2O2)(H2O)]	F(000) = 792
Mr = 442.24	Dx = 3.018 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3510 reflections
a = 7.5493 (10) Å	θ = 3.3–28.2°
b = 6.6775 (9) Å	µ = 21.41 mm−1
c = 19.335 (3) Å	T = 296 K
β = 92.884 (2)°	Block, colourless
V = 973.5 (2) Å3	0.15 × 0.14 × 0.13 mm
Z = 4

Data collection

Bruker SMART APEX CCD area-detector diffractometer	1904 independent reflections
Radiation source: fine-focus sealed tube	1747 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.039
phi and ω scans	θmax = 26.0°, θmin = 3.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −9→5
Tmin = 0.142, Tmax = 0.167	k = −8→8
5123 measured reflections	l = −23→22

Refinement

Refinement on F2	0 restraints
Least-squares matrix: full	H-atom parameters constrained
R[F2 > 2σ(F2)] = 0.033	w = 1/[σ2(Fo2) + (0.0596P)2] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.091	(Δ/σ)max = 0.032
S = 1.05	Δρmax = 2.26 e Å−3
1904 reflections	Δρmin = −2.20 e Å−3
120 parameters

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.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	Uiso*/Ueq
Pb1	0.29327 (3)	−0.20899 (3)	0.782606 (12)	0.02328 (17)
Br1	0.00888 (10)	0.08548 (11)	0.80760 (4)	0.0386 (2)
O1	0.5113 (7)	0.0867 (8)	0.7933 (3)	0.0351 (12)
O2	0.4664 (8)	−0.0254 (8)	0.8984 (3)	0.0427 (13)
O3	0.2211 (10)	−0.5006 (9)	0.8682 (3)	0.067 (2)
H3A	0.2481	−0.4963	0.9114	0.100*
H3B	0.1828	−0.6189	0.8608	0.100*
N1	0.6818 (7)	0.4165 (8)	0.8455 (3)	0.0274 (12)
N2	0.7181 (8)	0.4728 (9)	0.9872 (3)	0.0322 (13)
C1	0.6189 (9)	0.2822 (9)	0.8890 (4)	0.0245 (15)
C2	0.6373 (10)	0.3105 (10)	0.9598 (4)	0.0302 (16)
H2	0.5925	0.2146	0.9891	0.036*
C3	0.7783 (9)	0.6113 (9)	0.9431 (4)	0.0298 (15)
C4	0.7588 (9)	0.5805 (9)	0.8721 (4)	0.0285 (15)
H4	0.8006	0.6771	0.8423	0.034*
C5	0.5250 (9)	0.0994 (10)	0.8587 (4)	0.0280 (15)
C6	0.8627 (14)	0.7958 (11)	0.9749 (6)	0.049 (2)
H6A	0.7859	0.8517	1.0079	0.073*
H6B	0.8818	0.8924	0.9392	0.073*
H6C	0.9743	0.7609	0.9977	0.073*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
Pb1	0.0230 (2)	0.0234 (2)	0.0233 (2)	−0.00092 (7)	0.00028 (12)	0.00041 (8)
Br1	0.0362 (4)	0.0338 (4)	0.0451 (5)	0.0095 (3)	−0.0054 (3)	0.0001 (3)
O1	0.036 (3)	0.042 (3)	0.027 (3)	−0.017 (2)	−0.005 (2)	−0.004 (2)
O2	0.056 (4)	0.038 (3)	0.034 (3)	−0.015 (2)	−0.002 (2)	0.009 (2)
O3	0.119 (7)	0.049 (4)	0.031 (3)	−0.039 (4)	−0.019 (3)	0.008 (3)
N1	0.028 (3)	0.026 (3)	0.028 (3)	−0.001 (2)	−0.001 (2)	−0.002 (2)
N2	0.040 (4)	0.030 (3)	0.026 (3)	−0.004 (2)	−0.001 (2)	−0.005 (2)
C1	0.021 (3)	0.026 (4)	0.027 (4)	0.000 (2)	−0.002 (3)	0.000 (3)
C2	0.031 (4)	0.031 (4)	0.029 (4)	−0.001 (3)	0.003 (3)	0.001 (3)
C3	0.030 (4)	0.024 (3)	0.035 (4)	0.000 (3)	−0.003 (3)	−0.003 (3)
C4	0.031 (4)	0.023 (3)	0.031 (4)	−0.002 (3)	0.001 (3)	−0.001 (3)
C5	0.025 (3)	0.030 (3)	0.029 (4)	−0.006 (3)	0.003 (3)	−0.003 (3)
C6	0.059 (6)	0.033 (5)	0.055 (6)	−0.011 (3)	0.004 (5)	−0.008 (4)

Geometric parameters (Å, º)

Pb1—O1i	2.531 (5)	N1—C1	1.334 (8)
Pb1—O1	2.572 (5)	N1—Pb1iv	2.631 (5)
Pb1—N1i	2.631 (6)	N2—C2	1.340 (9)
Pb1—O3	2.631 (6)	N2—C3	1.353 (9)
Pb1—Br1	2.9688 (8)	C1—C2	1.381 (11)
Pb1—Br1ii	3.1190 (9)	C1—C5	1.514 (9)
Br1—Pb1iii	3.1190 (9)	C2—H2	0.9300
O1—C5	1.268 (8)	C3—C4	1.388 (10)
O1—Pb1iv	2.531 (5)	C3—C6	1.504 (10)
O2—C5	1.230 (8)	C4—H4	0.9300
O3—H3A	0.8501	C6—H6A	0.9600
O3—H3B	0.8510	C6—H6B	0.9600
N1—C4	1.331 (9)	C6—H6C	0.9600
O1i—Pb1—O1	94.06 (8)	C1—N1—Pb1iv	115.1 (4)
O1i—Pb1—N1i	63.56 (16)	C2—N2—C3	117.6 (6)
O1—Pb1—N1i	75.81 (17)	N1—C1—C2	120.8 (6)
O1i—Pb1—O3	96.4 (2)	N1—C1—C5	118.2 (6)
O1—Pb1—O3	132.06 (18)	C2—C1—C5	121.0 (6)
N1i—Pb1—O3	148.79 (18)	N2—C2—C1	121.6 (6)
O1i—Pb1—Br1	153.98 (12)	N2—C2—H2	119.2
O1—Pb1—Br1	86.76 (12)	C1—C2—H2	119.2
N1i—Pb1—Br1	91.65 (12)	N2—C3—C4	120.0 (6)
O3—Pb1—Br1	102.33 (18)	N2—C3—C6	116.8 (7)
O1i—Pb1—Br1ii	82.54 (13)	C4—C3—C6	123.2 (7)
O1—Pb1—Br1ii	146.05 (12)	N1—C4—C3	121.8 (6)
N1i—Pb1—Br1ii	72.46 (13)	N1—C4—H4	119.1
O3—Pb1—Br1ii	81.80 (15)	C3—C4—H4	119.1
Br1—Pb1—Br1ii	82.410 (17)	O2—C5—O1	124.3 (6)
Pb1—Br1—Pb1iii	135.64 (3)	O2—C5—C1	118.7 (6)
C5—O1—Pb1iv	121.4 (4)	O1—C5—C1	117.0 (5)
C5—O1—Pb1	98.7 (4)	C3—C6—H6A	109.5
Pb1iv—O1—Pb1	139.2 (2)	C3—C6—H6B	109.5
Pb1—O3—H3A	123.1	H6A—C6—H6B	109.5
Pb1—O3—H3B	131.3	C3—C6—H6C	109.5
H3A—O3—H3B	105.1	H6A—C6—H6C	109.5
C4—N1—C1	118.2 (6)	H6B—C6—H6C	109.5
C4—N1—Pb1iv	125.1 (4)
O1i—Pb1—Br1—Pb1iii	13.5 (3)	Pb1iv—N1—C1—C5	−15.9 (7)
O1—Pb1—Br1—Pb1iii	106.16 (12)	C3—N2—C2—C1	1.4 (10)
N1i—Pb1—Br1—Pb1iii	30.47 (13)	N1—C1—C2—N2	0.1 (11)
O3—Pb1—Br1—Pb1iii	−121.43 (15)	C5—C1—C2—N2	−179.1 (6)
Br1ii—Pb1—Br1—Pb1iii	−41.59 (4)	C2—N2—C3—C4	−1.4 (10)
O1i—Pb1—O1—C5	−126.3 (4)	C2—N2—C3—C6	177.8 (7)
N1i—Pb1—O1—C5	172.3 (4)	C1—N1—C4—C3	1.6 (10)
O3—Pb1—O1—C5	−23.9 (5)	Pb1iv—N1—C4—C3	−163.3 (5)
Br1—Pb1—O1—C5	79.8 (4)	N2—C3—C4—N1	−0.1 (10)
Br1ii—Pb1—O1—C5	151.1 (3)	C6—C3—C4—N1	−179.3 (7)
O1i—Pb1—O1—Pb1iv	43.5 (3)	Pb1iv—O1—C5—O2	−162.2 (6)
N1i—Pb1—O1—Pb1iv	−17.9 (3)	Pb1—O1—C5—O2	10.0 (8)
O3—Pb1—O1—Pb1iv	145.9 (4)	Pb1iv—O1—C5—C1	18.3 (8)
Br1—Pb1—O1—Pb1iv	−110.4 (3)	Pb1—O1—C5—C1	−169.5 (5)
Br1ii—Pb1—O1—Pb1iv	−39.1 (5)	N1—C1—C5—O2	−179.9 (6)
C4—N1—C1—C2	−1.5 (9)	C2—C1—C5—O2	−0.7 (10)
Pb1iv—N1—C1—C2	164.8 (5)	N1—C1—C5—O1	−0.4 (9)
C4—N1—C1—C5	177.7 (6)	C2—C1—C5—O1	178.8 (6)

Symmetry codes: (i) −x+1, y−1/2, −z+3/2; (ii) −x, y−1/2, −z+3/2; (iii) −x, y+1/2, −z+3/2; (iv) −x+1, y+1/2, −z+3/2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3A···N2v	0.85	1.97	2.816 (9)	173
O3—H3B···Br1vi	0.85	2.56	3.378 (6)	161

Symmetry codes: (v) −x+1, −y, −z+2; (vi) x, y−1, z.