Poly[aqua-μ-bromido-(μ2-5-methyl­pyrazine-2-carboxyl­ato-κ4N1,O2:O2,O2′)lead(II)]

Yang, P.; Liu, Y.; Li, H.Y.; Ding, B.

doi:10.1107/S1600536812033776

metal-organic compounds

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ISSN: 2056-9890

Volume 68| Part 9| September 2012| Page m1139

doi:10.1107/S1600536812033776

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Poly[aqua-μ-bromido-(μ₂-5-methylpyrazine-2-carboxylato-κ⁴N¹,O²:O²,O^2′)lead(II)]

Pan Yang,^a Yan Liu,^a Hua Yun Li ^a and Bin Ding ^a ^*

^aTianjin Key Laboratory of Structure and Performance of Functional Molecules, Tianjin Normal University, Tianjin 300071, People's Republic of China
^*Correspondence e-mail: qsdingbin@yahoo.com.cn

(Received 22 July 2012; accepted 27 July 2012; online 1 August 2012)

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, P 2₁ /c
a = 7.5493 (10) Å
b = 6.6775 (9) Å
c = 19.335 (3) Å
β = 92.884 (2)°
V = 973.5 (2) Å³
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[F² > 2σ(F²)] = 0.033
wR(F²) = 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

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) -x+1, -y, -z+2; (ii) x, y-1, z.

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).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536812033776/ng5284sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812033776/ng5284Isup2.hkl

checkCIF report

Related literature top

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

Experimental top

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.

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: DIAMOND (Brandenburg, 1999); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

	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).

Poly[aqua-µ-bromido-(µ₂-5-methylpyrazine-2-carboxylato- κ⁴N¹,O²:O²,O^2')lead(II)] top

Crystal data top

[PbBr(C₆H₅N₂O₂)(H₂O)]	F(000) = 792
M_r = 442.24	D_x = 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 top

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

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.033	w = 1/[σ²(F_o²) + (0.0596P)²] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.091	(Δ/σ)_max = 0.032
S = 1.05	Δρ_max = 2.26 e Å⁻³
1904 reflections	Δρ_min = −2.20 e Å⁻³
120 parameters

Crystal data top

[PbBr(C₆H₅N₂O₂)(H₂O)]	V = 973.5 (2) Å³
M_r = 442.24	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 7.5493 (10) Å	µ = 21.41 mm⁻¹
b = 6.6775 (9) Å	T = 296 K
c = 19.335 (3) Å	0.15 × 0.14 × 0.13 mm
β = 92.884 (2)°

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	1904 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1747 reflections with I > 2σ(I)
T_min = 0.142, T_max = 0.167	R_int = 0.039
5123 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.033	0 restraints
wR(F²) = 0.091	H-atom parameters constrained
S = 1.05	Δρ_max = 2.26 e Å⁻³
1904 reflections	Δρ_min = −2.20 e Å⁻³
120 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.

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 (Å²) top

	x	y	z	U_iso*/U_eq
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 (Å²) top

	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) top

Pb1—O1ⁱ	2.531 (5)	N1—C1	1.334 (8)
Pb1—O1	2.572 (5)	N1—Pb1^iv	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—Pb1^iv	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—Pb1^iv	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—Pb1^iv	121.4 (4)	O1—C5—C1	117.0 (5)
C5—O1—Pb1	98.7 (4)	C3—C6—H6A	109.5
Pb1^iv—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—Pb1^iv	125.1 (4)

O1ⁱ—Pb1—Br1—Pb1ⁱⁱⁱ	13.5 (3)	Pb1^iv—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)	Pb1^iv—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—Pb1^iv	43.5 (3)	Pb1^iv—O1—C5—O2	−162.2 (6)
N1ⁱ—Pb1—O1—Pb1^iv	−17.9 (3)	Pb1—O1—C5—O2	10.0 (8)
O3—Pb1—O1—Pb1^iv	145.9 (4)	Pb1^iv—O1—C5—C1	18.3 (8)
Br1—Pb1—O1—Pb1^iv	−110.4 (3)	Pb1—O1—C5—C1	−169.5 (5)
Br1ⁱⁱ—Pb1—O1—Pb1^iv	−39.1 (5)	N1—C1—C5—O2	−179.9 (6)
C4—N1—C1—C2	−1.5 (9)	C2—C1—C5—O2	−0.7 (10)
Pb1^iv—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) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3A···N2^v	0.85	1.97	2.816 (9)	173
O3—H3B···Br1^vi	0.85	2.56	3.378 (6)	161

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

Experimental details

Crystal data
Chemical formula	[PbBr(C₆H₅N₂O₂)(H₂O)]
M_r	442.24
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	7.5493 (10), 6.6775 (9), 19.335 (3)
β (°)	92.884 (2)
V (Å³)	973.5 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	21.41
Crystal size (mm)	0.15 × 0.14 × 0.13

Data collection
Diffractometer	Bruker SMART APEX CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.142, 0.167
No. of measured, independent and observed [I > 2σ(I)] reflections	5123, 1904, 1747
R_int	0.039
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.033, 0.091, 1.05
No. of reflections	1904
No. of parameters	120
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	2.26, −2.20

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg, 1999), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3A···N2ⁱ	0.85	1.97	2.816 (9)	173.1
O3—H3B···Br1ⁱⁱ	0.85	2.56	3.378 (6)	161.3

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

Acknowledgements

This present work was supported by the Tianjin Educational Committee (20090504) and Tianjin Normal University (1E0402B).

References

Brandenburg, K. (1999). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Bruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
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Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
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