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

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

doi:10.1107/S1600536810003879

metal-organic compounds

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ISSN: 2056-9890

Volume 66| Part 3| March 2010| Page m261

doi:10.1107/S1600536810003879

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

Alireza Azhdari Tehrani,^a Bahareh Mir Mohammad Sadegh ^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 3 January 2010; accepted 1 February 2010; online 6 February 2010)

In the polymeric title compound, [HgCl₂(C₅H₅N₃O)₂]_n, the Hg^II atom (site symmetry $[\overline{1}]$ ) adopts a distorted trans-HgN₂Cl₄ octahedral coordination geometry. In the crystal, adjacent mercury ions are bridged by pairs of chloride ions, generating infinite [100] chains, and N—H⋯O and N—H⋯(N,N) hydrogen bonds help to consolidate the packing.

Related literature

For related structures, see: Cati & Stoeckli-Evans (2004 ); Hausmann & Brooker (2004 ); Mir Mohammad Sadegh et al. (2010 ); Miyazaki et al. (2007 ).

Experimental

Crystal data

[HgCl₂(C₅H₅N₃O)₂]
M_r = 517.73
Triclinic, $[P \overline 1]$
a = 3.8451 (8) Å
b = 6.4170 (13) Å
c = 14.854 (3) Å
α = 101.14 (3)°
β = 92.53 (3)°
γ = 94.69 (3)°
V = 357.73 (13) Å³
Z = 1
Mo Kα radiation
μ = 11.14 mm⁻¹
T = 298 K
0.48 × 0.15 × 0.06 mm

Data collection

Stoe IPDS II diffractometer
Absorption correction: numerical [optically, by X-RED and XSHAPE (Stoe & Cie, 2005 )] T_min = 0.150, T_max = 0.515
4201 measured reflections
1887 independent reflections
1880 reflections with I > 2σ(I)
R_int = 0.096

Refinement

R[F² > 2σ(F²)] = 0.054
wR(F²) = 0.144
S = 1.08
1887 reflections
97 parameters
H-atom parameters constrained
Δρ_max = 3.25 e Å⁻³
Δρ_min = −3.75 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

Hg1—N2	2.661 (7)
Hg1—Cl1ⁱ	2.970 (2)
Hg1—Cl1	2.375 (2)

Hg1—Cl1—Hg1ⁱⁱ	91.31 (7)
Symmetry codes: (i) x-1, y, z; (ii) x+1, y, z.

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3A⋯O1ⁱⁱⁱ	0.86	2.01	2.864 (12)	176
N3—H3B⋯N1	0.86	2.40	2.758 (12)	105
N3—H3B⋯N1^iv	0.86	2.54	3.198 (12)	134
Symmetry codes: (iii) -x+2, -y, -z+1; (iv) -x+1, -y+1, -z+1.

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

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810003879/hb5301sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810003879/hb5301Isup2.hkl

checkCIF report

Comment top

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 and 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 Cl atoms. The bridging function of chloro atoms leads to a one-dimensional chain structure. The Hg—Cl 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 related structures, see: Cati & Stoeckli-Evans (2004); Hausmann & Brooker (2004); Mir Mohammad Sadegh et al. (2010); Miyazaki et al. (2007).

Experimental top

A solution of pyrazineamide (0.246 g, 2.0 mmol) in methanol (10 ml) was added to a solution of HgCl₂ (0.272 g, 1.0 mmol) in methanol (5 ml) at room temperature. Colourless plates of (I) were obtained by slow evaporation from methanolic solution after one week (yield; 0.359 g, 69.3%).

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: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

	Fig. 1. The molecular staucture with displacement ellipsoids drawn at 30% probability level.
	Fig. 2. A packing diagram of (I) in b-directrion. Hydrogen bonds are shown as dashed lines.

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

Crystal data top

[HgCl₂(C₅H₅N₃O)₂]	Z = 1
M_r = 517.73	F(000) = 242
Triclinic, P1	D_x = 2.403 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 3.8451 (8) Å	Cell parameters from 976 reflections
b = 6.4170 (13) Å	θ = 3.3–29.1°
c = 14.854 (3) Å	µ = 11.14 mm⁻¹
α = 101.14 (3)°	T = 298 K
β = 92.53 (3)°	Plate, colourless
γ = 94.69 (3)°	0.48 × 0.15 × 0.06 mm
V = 357.73 (13) Å³

Data collection top

Stoe IPDS II diffractometer	1880 reflections with I > 2σ(I)
ω scans	R_int = 0.096
Absorption correction: numerical [optically, by X-RED and X-SHAPE (Stoe & Cie, 2005)]	θ_max = 29.1°, θ_min = 3.3°
T_min = 0.150, T_max = 0.515	h = −5→4
4201 measured reflections	k = −8→8
1887 independent reflections	l = −20→20

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.054	w = 1/[σ²(F_o²) + (0.110P)² + 0.204P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.144	(Δ/σ)_max < 0.001
S = 1.08	Δρ_max = 3.25 e Å⁻³
1887 reflections	Δρ_min = −3.75 e Å⁻³
97 parameters

Crystal data top

[HgCl₂(C₅H₅N₃O)₂]	γ = 94.69 (3)°
M_r = 517.73	V = 357.73 (13) Å³
Triclinic, P1	Z = 1
a = 3.8451 (8) Å	Mo Kα radiation
b = 6.4170 (13) Å	µ = 11.14 mm⁻¹
c = 14.854 (3) Å	T = 298 K
α = 101.14 (3)°	0.48 × 0.15 × 0.06 mm
β = 92.53 (3)°

Data collection top

Stoe IPDS II diffractometer	1887 independent reflections
Absorption correction: numerical [optically, by X-RED and X-SHAPE (Stoe & Cie, 2005)]	1880 reflections with I > 2σ(I)
T_min = 0.150, T_max = 0.515	R_int = 0.096
4201 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.054	0 restraints
wR(F²) = 0.144	H-atom parameters constrained
S = 1.08	Δρ_max = 3.25 e Å⁻³
1887 reflections	Δρ_min = −3.75 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	0.397 (3)	0.5265 (12)	0.2863 (6)	0.0431 (16)
H1	0.3077	0.6583	0.3014	0.052*
C2	0.400 (3)	0.4268 (13)	0.1935 (6)	0.0431 (16)
H2	0.3177	0.4953	0.1482	0.052*
C3	0.632 (2)	0.1435 (13)	0.2363 (6)	0.0391 (14)
H3	0.7083	0.008	0.2215	0.047*
C4	0.639 (2)	0.2438 (11)	0.3279 (5)	0.0341 (12)
C5	0.793 (2)	0.1365 (12)	0.3999 (6)	0.0385 (14)
N1	0.520 (2)	0.4354 (11)	0.3536 (5)	0.0429 (14)
N2	0.519 (2)	0.2350 (11)	0.1690 (5)	0.0412 (13)
N3	0.784 (3)	0.2340 (13)	0.4863 (6)	0.0516 (19)
H3A	0.8724	0.1795	0.5296	0.062*
H3B	0.6888	0.352	0.4994	0.062*
O1	0.924 (3)	−0.0327 (12)	0.3755 (5)	0.0539 (18)
Cl1	0.8689 (6)	−0.2371 (3)	0.05218 (16)	0.0444 (4)
Hg1	0.5	0	0	0.03963 (18)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.054 (4)	0.036 (3)	0.041 (4)	0.016 (3)	−0.005 (3)	0.007 (3)
C2	0.056 (4)	0.042 (3)	0.034 (4)	0.011 (3)	0.000 (3)	0.012 (3)
C3	0.046 (4)	0.042 (3)	0.029 (3)	0.016 (3)	0.001 (3)	0.004 (2)
C4	0.038 (3)	0.036 (3)	0.029 (3)	0.009 (2)	−0.001 (3)	0.006 (2)
C5	0.045 (4)	0.040 (3)	0.030 (3)	0.006 (3)	−0.004 (3)	0.008 (2)
N1	0.052 (4)	0.038 (3)	0.038 (3)	0.012 (2)	−0.001 (3)	0.003 (2)
N2	0.049 (4)	0.045 (3)	0.031 (3)	0.014 (2)	−0.001 (3)	0.007 (2)
N3	0.077 (6)	0.045 (3)	0.035 (3)	0.032 (3)	−0.003 (3)	0.003 (3)
O1	0.084 (5)	0.047 (3)	0.033 (3)	0.033 (3)	0.001 (3)	0.004 (2)
Cl1	0.0448 (9)	0.0477 (9)	0.0434 (10)	0.0146 (7)	0.0022 (8)	0.0114 (7)
Hg1	0.0397 (2)	0.0505 (3)	0.0305 (2)	0.01765 (14)	−0.00015 (15)	0.00733 (15)

Geometric parameters (Å, º) top

C1—N1	1.340 (12)	C5—N3	1.318 (11)
C1—C2	1.404 (12)	N3—H3A	0.86
C1—H1	0.93	N3—H3B	0.86
C2—N2	1.338 (11)	Cl1—Hg1ⁱ	2.970 (2)
C2—H2	0.93	Hg1—Cl1ⁱⁱ	2.375 (2)
C3—N2	1.327 (11)	Hg1—N2ⁱⁱ	2.661 (7)
C3—C4	1.387 (10)	Hg1—Cl1ⁱⁱⁱ	2.970 (2)
C3—H3	0.93	Hg1—N2	2.661 (7)
C4—N1	1.338 (10)	Hg1—Cl1^iv	2.970 (2)
C4—C5	1.506 (11)	Hg1—Cl1	2.375 (2)
C5—O1	1.232 (11)

N1—C1—C2	121.3 (7)	C5—N3—H3A	120
N1—C1—H1	119.4	C5—N3—H3B	120
C2—C1—H1	119.4	H3A—N3—H3B	120
N2—C2—C1	121.3 (8)	Hg1—Cl1—Hg1ⁱ	91.31 (7)
N2—C2—H2	119.4	Cl1ⁱⁱ—Hg1—Cl1	180.0
C1—C2—H2	119.4	Cl1ⁱⁱ—Hg1—N2	89.49 (17)
N2—C3—C4	122.0 (7)	Cl1—Hg1—N2	90.51 (17)
N2—C3—H3	119	Cl1ⁱⁱ—Hg1—N2ⁱⁱ	90.51 (17)
C4—C3—H3	119	Cl1—Hg1—N2ⁱⁱ	89.49 (17)
N1—C4—C3	121.7 (8)	N2—Hg1—N2ⁱⁱ	180.0
N1—C4—C5	119.3 (7)	Cl1ⁱⁱ—Hg1—Cl1ⁱⁱⁱ	91.31 (7)
C3—C4—C5	118.9 (7)	Cl1—Hg1—Cl1ⁱⁱⁱ	88.69 (7)
O1—C5—N3	124.0 (8)	N2—Hg1—Cl1ⁱⁱⁱ	94.05 (18)
O1—C5—C4	119.1 (7)	N2ⁱⁱ—Hg1—Cl1ⁱⁱⁱ	85.95 (18)
N3—C5—C4	116.9 (7)	Cl1ⁱⁱ—Hg1—Cl1^iv	88.69 (7)
C4—N1—C1	116.7 (7)	Cl1—Hg1—Cl1^iv	91.31 (7)
C3—N2—C2	117.0 (7)	N2—Hg1—Cl1^iv	85.95 (18)
C3—N2—Hg1	116.0 (5)	N2ⁱⁱ—Hg1—Cl1^iv	94.05 (18)
C2—N2—Hg1	126.8 (6)	Cl1ⁱⁱⁱ—Hg1—Cl1^iv	180.0

N1—C1—C2—N2	1.5 (15)	C1—C2—N2—Hg1	174.2 (7)
N2—C3—C4—N1	2.4 (13)	Hg1ⁱ—Cl1—Hg1—N2	−94.04 (18)
N2—C3—C4—C5	−175.8 (8)	Hg1ⁱ—Cl1—Hg1—N2ⁱⁱ	85.96 (18)
N1—C4—C5—O1	−174.9 (9)	Hg1ⁱ—Cl1—Hg1—Cl1ⁱⁱⁱ	0
C3—C4—C5—O1	3.3 (12)	Hg1ⁱ—Cl1—Hg1—Cl1^iv	180
N1—C4—C5—N3	4.0 (12)	C3—N2—Hg1—Cl1ⁱⁱ	163.8 (6)
C3—C4—C5—N3	−177.8 (9)	C2—N2—Hg1—Cl1ⁱⁱ	−10.0 (8)
C3—C4—N1—C1	−0.5 (12)	C3—N2—Hg1—Cl1	−16.2 (6)
C5—C4—N1—C1	177.7 (8)	C2—N2—Hg1—Cl1	170.0 (8)
C2—C1—N1—C4	−1.4 (13)	C3—N2—Hg1—Cl1ⁱⁱⁱ	−104.9 (6)
C4—C3—N2—C2	−2.3 (13)	C2—N2—Hg1—Cl1ⁱⁱⁱ	81.3 (8)
C4—C3—N2—Hg1	−176.7 (6)	C3—N2—Hg1—Cl1^iv	75.1 (6)
C1—C2—N2—C3	0.4 (13)	C2—N2—Hg1—Cl1^iv	−98.7 (8)

Symmetry codes: (i) x+1, y, z; (ii) −x+1, −y, −z; (iii) −x+2, −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	2.01	2.864 (12)	176
N3—H3B···N1	0.86	2.40	2.758 (12)	105
N3—H3B···N1^vi	0.86	2.54	3.198 (12)	134

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

Experimental details

Crystal data
Chemical formula	[HgCl₂(C₅H₅N₃O)₂]
M_r	517.73
Crystal system, space group	Triclinic, P1
Temperature (K)	298
a, b, c (Å)	3.8451 (8), 6.4170 (13), 14.854 (3)
α, β, γ (°)	101.14 (3), 92.53 (3), 94.69 (3)
V (Å³)	357.73 (13)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	11.14
Crystal size (mm)	0.48 × 0.15 × 0.06

Data collection
Diffractometer	Stoe IPDS II diffractometer
Absorption correction	Numerical [optically, by X-RED and X-SHAPE (Stoe & Cie, 2005)]
T_min, T_max	0.150, 0.515
No. of measured, independent and observed [I > 2σ(I)] reflections	4201, 1887, 1880
R_int	0.096
(sin θ/λ)_max (Å⁻¹)	0.684

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.054, 0.144, 1.08
No. of reflections	1887
No. of parameters	97
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	3.25, −3.75

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

Selected geometric parameters (Å, º) top

Hg1—N2	2.661 (7)	Hg1—Cl1	2.375 (2)
Hg1—Cl1ⁱ	2.970 (2)

Hg1—Cl1—Hg1ⁱⁱ	91.31 (7)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3A···O1ⁱⁱⁱ	0.86	2.01	2.864 (12)	176
N3—H3B···N1	0.86	2.40	2.758 (12)	105
N3—H3B···N1^iv	0.86	2.54	3.198 (12)	134

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

Acknowledgements

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

References

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