catena-Poly[[bis­(pyrazine-2-carbox­amide-κN4)mercury(II)]-di-μ-bromido]

Mir Mohammad Sadegh, B.; Azhdari Tehrani, A.; Khavasi, H.R.

doi:10.1107/S1600536810001182

metal-organic compounds

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ISSN: 2056-9890

Volume 66| Part 2| February 2010| Page m158

https://doi.org/10.1107/S1600536810001182

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catena-Poly[[bis(pyrazine-2-carboxamide-κN⁴)mercury(II)]-di-μ-bromido]

Bahareh Mir Mohammad Sadegh,^a Alireza Azhdari Tehrani ^a and Hamid Reza Khavasi ^a ^*

^aDepartment of Chemistry, Shahid Beheshti University, G. C., Evin, Tehran 1983963113, Iran
^*Correspondence e-mail: h-khavasi@sbu.ac.ir

(Received 1 January 2010; accepted 10 January 2010; online 16 January 2010)

In the crystal structure of the title compound, [HgBr₂(C₅H₅N₃O)₂]_n, the Hg^II cation is located on an inversion center and is coordinated by two N atoms from the pyrazine rings and four bridging Br⁻ anions in a distorted octahedral geometry. The Br⁻ anions bridge the Hg^II cations with significantly different Hg—Br bond distances of 2.4775 (8) and 3.1122 (8) Å, forming polymeric chains running along the a axis. Intermolecular N—H⋯O and N—H⋯N hydrogen bonds are effective in the stabilization of the crystal structure.

Related literature

For metal-binding properties of pyridine and pyrazine ligands, see: Sasan et al. (2008 ); Khavasi et al. (2009 ); Petro & Mukherjee (1999 ); Sigh & Mukherjee (2005 ). For the coordination modes of pyrazineamide, see: Hausmann & Brooker (2004 ); Cati & Stoeckli-Evans (2004 ); Miyazaki et al. (2007 ).

Experimental

Crystal data

[HgBr₂(C₅H₅N₃O)₂]
M_r = 606.63
Triclinic, $[P \overline 1]$
a = 3.9628 (5) Å
b = 6.5162 (9) Å
c = 15.0388 (19) Å
α = 101.783 (10)°
β = 93.418 (11)°
γ = 95.214 (11)°
V = 377.36 (9) Å³
Z = 1
Mo Kα radiation
μ = 15.50 mm⁻¹
T = 298 K
0.50 × 0.06 × 0.03 mm

Data collection

Stoe IPDS II diffractometer
Absorption correction: multi-scan (X-RED and X-SHAPE; Stoe & Cie, 2005 ) T_min = 0.345, T_max = 0.630
4311 measured reflections
2002 independent reflections
1933 reflections with I > 2σ(I)
R_int = 0.144

Refinement

R[F² > 2σ(F²)] = 0.065
wR(F²) = 0.173
S = 1.11
2002 reflections
97 parameters
H-atom parameters constrained
Δρ_max = 3.93 e Å⁻³
Δρ_min = −5.48 e Å⁻³

Table 1
Selected bond lengths (Å)

Hg1—Br1	2.4775 (8)
Hg1—Br1ⁱ	3.1122 (8)
Hg1—N2	2.758 (6)
Symmetry code: (i) x-1, y, z.

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3A⋯O1ⁱⁱ	0.86	2.02	2.881 (11)	174
N3—H3B⋯N1ⁱⁱⁱ	0.86	2.53	3.214 (11)	137
Symmetry codes: (ii) -x+2, -y, -z+2; (iii) -x+1, -y+1, -z+2.

Data collection: X-AREA (Stoe & Cie, 2005); cell refinement: X-AREA; data reduction: X-AREA; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536810001182/xu2716sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810001182/xu2716Isup2.hkl

checkCIF report

Comment top

A large variety of pyridine and pyrazine amide ligands have been synthesized for investigating their metal-binding properties (Sasan et al., 2008; Khavasi et al., 2009; Petro & Mukherjee, 1999; Sigh & Mukherjee, 2005). The coordination chemistry of parazineamides is rich. Examples of coordination via the pyrazine N atoms, the carbonyl O atoms and the amide N atoms of the ligand in a non-, mono-, or bis-deprotonated form are known (Hausmann & Brooker, 2004; Cati & Stoeckli-Evans, 2004; Miyazaki et al., 2007) and metal complexes of the ligands have been used extensively to mimic the properties of biologically active systems. Here we synthesized the title compound, (I), and report here its crystal structure.

The asymmetric unit of the title compound, (I), contains one half-molecule (Fig. 1). The Hg^II atom is six-coordinated in a distorted octahedral configuration by two N atoms from pyrazine amides and four bridging Br atoms. The bridging function of bromo atoms leads to a one-dimensional chain structure. The Hg—Br and Hg—N bond lengths and angles (Table 1) are within normal ranges. In the crystal structure (Fig. 2), intermolecular N—H···O and N—H···N hydrogen bonds (Table 2) result in the formation of a supramolecular structure, in which they may be effective in the stabilization of the structure.

Related literature top

For metal-binding properties of pyridine and pyrazine ligands, see: Sasan et al. (2008); Khavasi et al. (2009); Petro & Mukherjee (1999); Sigh & Mukherjee (2005). For the coordination modes of pyrazineamide, see: Hausmann & Brooker (2004); Cati & Stoeckli-Evans (2004); Miyazaki et al. (2007).

Experimental top

For the preparation of the title compound, a solution of pyrazineamide (0.246 g, 2.0 mmol) in methanol (10 ml) was added to a solution of HgBr₂ (0.360 g, 1.0 mmol) in methanol (5 ml) at room temperature. The suitable crystals for X-ray analysis were obtained by slow evaporation from methanolic solution after one week (yield 0.500 g, 82.5%).

Structure description top

For metal-binding properties of pyridine and pyrazine ligands, see: Sasan et al. (2008); Khavasi et al. (2009); Petro & Mukherjee (1999); Sigh & Mukherjee (2005). For the coordination modes of pyrazineamide, see: Hausmann & Brooker (2004); Cati & Stoeckli-Evans (2004); Miyazaki et al. (2007).

Computing details top

Data collection: X-AREA (Stoe & Cie, 2005); cell refinement: X-AREA (Stoe & Cie, 2005); data reduction: X-AREA (Stoe & Cie, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

	Fig. 1. The molecular structure with the atom-numbering scheme. Displacement ellipsoids are drawn at 30% probability level.
	Fig. 2. A packing diagram of (I). Hydrogen bonds are shown as dashed lines.

catena-Poly[[bis(pyrazine-2-carboxamide-κN⁴)mercury(II)]-di-µ-bromido] top

Crystal data top

[HgBr₂(C₅H₅N₃O)₂]	Z = 1
M_r = 606.63	F(000) = 278
Triclinic, P1	D_x = 2.669 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 3.9628 (5) Å	Cell parameters from 765 reflections
b = 6.5162 (9) Å	θ = 3.2–29.1°
c = 15.0388 (19) Å	µ = 15.50 mm⁻¹
α = 101.783 (10)°	T = 298 K
β = 93.418 (11)°	Needle, colorless
γ = 95.214 (11)°	0.5 × 0.06 × 0.03 mm
V = 377.36 (9) Å³

Data collection top

Stoe IPDS II diffractometer	1933 reflections with I > 2σ(I)
rotation method scans	R_int = 0.144
Absorption correction: multi-scan (X-RED and X-SHAPE; Stoe & Cie, 2005)	θ_max = 29.1°, θ_min = 3.2°
T_min = 0.345, T_max = 0.630	h = −5→5
4311 measured reflections	k = −8→8
2002 independent reflections	l = −20→20

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.065	w = 1/[σ²(F_o²) + (0.1262P)²] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.173	(Δ/σ)_max < 0.001
S = 1.11	Δρ_max = 3.93 e Å⁻³
2002 reflections	Δρ_min = −5.48 e Å⁻³
97 parameters

Crystal data top

[HgBr₂(C₅H₅N₃O)₂]	γ = 95.214 (11)°
M_r = 606.63	V = 377.36 (9) Å³
Triclinic, P1	Z = 1
a = 3.9628 (5) Å	Mo Kα radiation
b = 6.5162 (9) Å	µ = 15.50 mm⁻¹
c = 15.0388 (19) Å	T = 298 K
α = 101.783 (10)°	0.5 × 0.06 × 0.03 mm
β = 93.418 (11)°

Data collection top

Stoe IPDS II diffractometer	2002 independent reflections
Absorption correction: multi-scan (X-RED and X-SHAPE; Stoe & Cie, 2005)	1933 reflections with I > 2σ(I)
T_min = 0.345, T_max = 0.630	R_int = 0.144
4311 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.065	0 restraints
wR(F²) = 0.173	H-atom parameters constrained
S = 1.11	Δρ_max = 3.93 e Å⁻³
2002 reflections	Δρ_min = −5.48 e Å⁻³
97 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
C1	0.402 (2)	0.5193 (13)	0.7914 (6)	0.0456 (17)
H1	0.3215	0.6506	0.8064	0.055*
C2	0.400 (2)	0.4210 (13)	0.7010 (6)	0.0444 (16)
H2	0.3156	0.4876	0.6566	0.053*
C3	0.629 (2)	0.1448 (13)	0.7407 (5)	0.0414 (15)
H3	0.7049	0.0123	0.7252	0.05*
C4	0.638 (2)	0.2438 (14)	0.8329 (6)	0.0381 (15)
C5	0.790 (2)	0.1363 (13)	0.9029 (5)	0.0413 (15)
N1	0.519 (2)	0.4278 (10)	0.8588 (5)	0.0420 (14)
N2	0.5148 (18)	0.2350 (10)	0.6752 (4)	0.0422 (13)
N3	0.779 (2)	0.2309 (12)	0.9885 (5)	0.0525 (17)
H3A	0.8633	0.1766	1.0313	0.063*
H3B	0.6883	0.3471	1.0017	0.063*
O1	0.914 (2)	−0.0290 (12)	0.8783 (5)	0.0577 (19)
Hg1	0.5	0	0.5	0.0390 (2)
Br1	0.86218 (19)	−0.24778 (12)	0.55380 (6)	0.0394 (2)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.065 (5)	0.036 (3)	0.038 (4)	0.015 (3)	−0.006 (3)	0.011 (3)
C2	0.055 (4)	0.042 (4)	0.037 (3)	0.004 (3)	−0.009 (3)	0.014 (3)
C3	0.056 (4)	0.039 (3)	0.030 (3)	0.013 (3)	−0.006 (3)	0.006 (3)
C4	0.048 (4)	0.037 (3)	0.028 (3)	0.006 (3)	−0.005 (3)	0.004 (3)
C5	0.055 (4)	0.041 (4)	0.029 (3)	0.011 (3)	−0.002 (3)	0.009 (3)
N1	0.062 (4)	0.031 (3)	0.032 (3)	0.007 (3)	−0.007 (3)	0.007 (2)
N2	0.057 (3)	0.040 (3)	0.029 (3)	0.007 (3)	−0.007 (2)	0.010 (2)
N3	0.085 (5)	0.045 (3)	0.030 (3)	0.023 (4)	−0.005 (3)	0.009 (3)
O1	0.095 (6)	0.049 (3)	0.031 (3)	0.032 (4)	−0.005 (3)	0.007 (2)
Hg1	0.0387 (3)	0.0433 (3)	0.0380 (3)	0.01479 (17)	−0.00149 (16)	0.01255 (19)
Br1	0.0390 (4)	0.0374 (4)	0.0453 (5)	0.0116 (3)	0.0000 (3)	0.0146 (3)

Geometric parameters (Å, º) top

C1—N1	1.356 (10)	C5—O1	1.224 (11)
C1—C2	1.378 (12)	C5—N3	1.313 (10)
C1—H1	0.93	N3—H3A	0.86
C2—N2	1.325 (11)	N3—H3B	0.86
C2—H2	0.93	Hg1—Br1	2.4775 (8)
C3—N2	1.323 (9)	Hg1—Br1ⁱ	2.4775 (8)
C3—C4	1.402 (11)	Hg1—Br1ⁱⁱ	3.1122 (8)
C3—H3	0.93	Hg1—Br1ⁱⁱⁱ	3.1122 (8)
C4—N1	1.321 (12)	Hg1—N2	2.758 (6)
C4—C5	1.505 (12)	Hg1—N2ⁱ	2.758 (6)

N1—C1—C2	121.2 (8)	N3—C5—C4	116.1 (8)
N1—C1—H1	119.4	C4—N1—C1	116.5 (7)
C2—C1—H1	119.4	C3—N2—C2	116.8 (7)
N2—C2—C1	122.2 (7)	C5—N3—H3A	120
N2—C2—H2	118.9	C5—N3—H3B	120
C1—C2—H2	118.9	H3A—N3—H3B	120
N2—C3—C4	121.7 (8)	Br1—Hg1—Br1ⁱ	180.00 (4)
N2—C3—H3	119.1	Br1—Hg1—Br1ⁱⁱ	90.44 (2)
C4—C3—H3	119.1	Br1ⁱ—Hg1—Br1ⁱⁱ	89.56 (2)
N1—C4—C3	121.5 (8)	Br1—Hg1—Br1ⁱⁱⁱ	89.56 (2)
N1—C4—C5	120.1 (7)	Br1ⁱ—Hg1—Br1ⁱⁱⁱ	90.44 (2)
C3—C4—C5	118.4 (8)	Br1ⁱⁱ—Hg1—Br1ⁱⁱⁱ	180.000 (17)
O1—C5—N3	124.2 (8)	Hg1—Br1—Hg1^iv	89.56 (2)
O1—C5—C4	119.7 (7)

N1—C1—C2—N2	−0.7 (15)	C3—C4—C5—N3	−177.2 (9)
N2—C3—C4—N1	2.9 (14)	C3—C4—N1—C1	−2.6 (12)
N2—C3—C4—C5	−176.4 (8)	C5—C4—N1—C1	176.7 (9)
N1—C4—C5—O1	−176.4 (8)	C2—C1—N1—C4	1.6 (13)
C3—C4—C5—O1	3.0 (14)	C4—C3—N2—C2	−1.9 (12)
N1—C4—C5—N3	3.4 (13)	C1—C2—N2—C3	0.8 (13)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3A···O1^v	0.86	2.02	2.881 (11)	174
N3—H3B···N1^vi	0.86	2.53	3.214 (11)	137

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

Experimental details

Crystal data
Chemical formula	[HgBr₂(C₅H₅N₃O)₂]
M_r	606.63
Crystal system, space group	Triclinic, P1
Temperature (K)	298
a, b, c (Å)	3.9628 (5), 6.5162 (9), 15.0388 (19)
α, β, γ (°)	101.783 (10), 93.418 (11), 95.214 (11)
V (Å³)	377.36 (9)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	15.50
Crystal size (mm)	0.5 × 0.06 × 0.03

Data collection
Diffractometer	Stoe IPDS II
Absorption correction	Multi-scan (X-RED and X-SHAPE; Stoe & Cie, 2005)
T_min, T_max	0.345, 0.630
No. of measured, independent and observed [I > 2σ(I)] reflections	4311, 2002, 1933
R_int	0.144
(sin θ/λ)_max (Å⁻¹)	0.685

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.065, 0.173, 1.11
No. of reflections	2002
No. of parameters	97
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	3.93, −5.48

Computer programs: X-AREA (Stoe & Cie, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).

Selected bond lengths (Å) top

Hg1—Br1	2.4775 (8)	Hg1—N2	2.758 (6)
Hg1—Br1ⁱ	3.1122 (8)

Symmetry code: (i) x−1, y, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3A···O1ⁱⁱ	0.86	2.0200	2.881 (11)	174.00
N3—H3B···N1ⁱⁱⁱ	0.86	2.5300	3.214 (11)	137.00

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

Acknowledgements

The authors wish to acknowledge Shahid Beheshti University, G·C., for financial support.

References

Cati, D. S. & Stoeckli-Evans, H. (2004). Acta Cryst. E60, m177–m179. Web of Science CSD CrossRef IUCr Journals Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838. CrossRef CAS IUCr Journals Google Scholar
Hausmann, J. & Brooker, S. (2004). Chem. Commun. pp. 1530–1531. Web of Science CSD CrossRef Google Scholar
Khavasi, H. R., Sasan, K., Pirouzmand, M. & Ebrahimi, S. N. (2009). Inorg. Chem. 48, 5593–5595. Web of Science CSD CrossRef PubMed CAS Google Scholar
Miyazaki, S., Ohkubo, K., Kojima, T. & Fukuzumi, S. (2007). Angew. Chem. Int. Ed. 46, 905–908. Web of Science CSD CrossRef CAS Google Scholar
Petro, A. K. & Mukherjee, R. (1999). Inorg. Chem. 38, 1388–1393. Google Scholar
Sasan, K., Khavasi, H. R. & Davari, M. D. (2008). Monatsh. Chem. 139, 773–780. Web of Science CSD CrossRef CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sigh, A. K. & Mukherjee, R. (2005). Dalton Trans. pp. 2886–2891. Google Scholar
Stoe & Cie (2005). X-AREA, X-RED and X-SHAPE. Stoe & Cie, Darmstadt, Germany. Google Scholar