Dibromidobis(pyrazine-2-carboxamide-κN4)zinc

Shirvan, S.A.; Haydari Dezfuli, S.

doi:10.1107/S1600536812013335

metal-organic compounds

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ISSN: 2056-9890

Volume 68| Part 4| April 2012| Page m527

doi:10.1107/S1600536812013335

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Dibromidobis(pyrazine-2-carboxamide-κN⁴)zinc

Sadif A. Shirvan ^a ^* and Sara Haydari Dezfuli ^a

^aDepartment of Chemistry, Omidieh Branch, Islamic Azad University, Omidieh, Iran
^*Correspondence e-mail: sadif.shirvan1@gmail.com

(Received 27 March 2012; accepted 27 March 2012; online 31 March 2012)

The title complex, [ZnBr₂(C₅H₅N₃O)₂], shows crystallographic mirror symmetry with the Zn atom and the two bromine ligands located on the mirror plane. The Zn atom is four-coordinated in a distorted tetrahedral fashion by two N atoms from two pyrazine-2-carboxamide ligands and two Br atoms. Only one of the amino H atoms is involved in an N—H⋯O hydrogen bond. The crystal packing is further stabilized by weak N—H⋯N and C—H⋯O interactions.

Related literature

For related structures, see: Abu-Youssef et al. (2006 ); Azhdari Tehrani et al. (2010 ); Goher & Mautner (2000 ); Kristiansson (2002 ); Mir Mohammad Sadegh et al. (2010 ); Munakata et al. (1997 ); Pacigova et al. (2008 ).

Experimental

Crystal data

[ZnBr₂(C₅H₅N₃O)₂]
M_r = 471.43
Monoclinic, P 2₁ /m
a = 5.6042 (4) Å
b = 19.5147 (19) Å
c = 7.0656 (5) Å
β = 106.835 (5)°
V = 739.61 (10) Å³
Z = 2
Mo Kα radiation
μ = 7.08 mm⁻¹
T = 298 K
0.25 × 0.24 × 0.20 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2007 ) T_min = 0.205, T_max = 0.250
3935 measured reflections
1495 independent reflections
1247 reflections with I > 2σ(I)
R_int = 0.053

Refinement

R[F² > 2σ(F²)] = 0.046
wR(F²) = 0.111
S = 1.10
1495 reflections
100 parameters
H-atom parameters constrained
Δρ_max = 0.77 e Å⁻³
Δρ_min = −1.19 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3B⋯O1ⁱ	0.86	2.01	2.869 (7)	175
N3—H3C⋯N2	0.86	2.38	2.732 (7)	105
N3—H3C⋯N2ⁱⁱ	0.86	2.54	3.182 (7)	132
C3—H3⋯O1ⁱⁱⁱ	0.93	2.49	3.414 (7)	172
Symmetry codes: (i) -x+1, -y+1, -z+3; (ii) -x, -y+1, -z+2; (iii) x-1, y, z-1.

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: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812013335/bt5863sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812013335/bt5863Isup2.hkl

checkCIF report

Comment top

A few complexes of pyrazine-2-carboxamide (pzc) have been prepared, such as that of mercury (Azhdari Tehrani et al., 2010; Mir Mohammad Sadegh et al., 2010) and vanadium (Pacigova et al., 2008), manganese (Abu-Youssef et al., 2006) and copper (Kristiansson, 2002; Munakata et al., 1997; Goher & Mautner, 2000).

The asymmetric unit of the title compound, (Fig. 1), contains one Zn^II atom, two Br atoms and one pyrazine-2-carboxamide ligand. The Zn^II atom is four-coordinated in a distorted tetrahedral configuration by two N atoms from two pyrazine-2-carboxamide ligands and two terminal Br atoms.

Only one of the amino H atoms is involved in a N—H···O hydrogen bond. The crystal packing is further stabilized by weak N—H···N and C—H···O interactions.

Related literature top

For related structures, see: Abu-Youssef et al. (2006); Azhdari Tehrani et al. (2010); Goher & Mautner (2000); Kristiansson (2002); Mir Mohammad Sadegh et al. (2010); Munakata et al. (1997); Pacigova et al. (2008).

Experimental top

A solution of pyrazine-2-carboxamide (0.25 g, 2.0 mmol) in methanol (10 ml) was added to a solution of ZnBr₂ (0.23 g, 1.0 mmol) in methanol (10 ml) and the resulting colourless solution was stirred for 15 min at room temperature. This solution was left to evaporate slowly at room temperature. After one week, colourless block shaped crystals of the title compound were isolated (yield 0.38 g, 80.6%).

Structure description top

Only one of the amino H atoms is involved in a N—H···O hydrogen bond. The crystal packing is further stabilized by weak N—H···N and C—H···O interactions.

For related structures, see: Abu-Youssef et al. (2006); Azhdari Tehrani et al. (2010); Goher & Mautner (2000); Kristiansson (2002); Mir Mohammad Sadegh et al. (2010); Munakata et al. (1997); Pacigova et al. (2008).

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: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title molecule, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. [Symmetry codes: (a) x,3/2 - y,z].
	Fig. 2. Unit-cell packing diagram for title molecule. Hydrogen bonds are shown as dashed lines.

Dibromidobis(pyrazine-2-carboxamide-κN⁴)zinc top

Crystal data top

[ZnBr₂(C₅H₅N₃O)₂]	F(000) = 456
M_r = 471.43	D_x = 2.117 Mg m⁻³
Monoclinic, P2₁/m	Mo Kα radiation, λ = 0.71073 Å
a = 5.6042 (4) Å	Cell parameters from 3935 reflections
b = 19.5147 (19) Å	θ = 3.0–26.0°
c = 7.0656 (5) Å	µ = 7.08 mm⁻¹
β = 106.835 (5)°	T = 298 K
V = 739.61 (10) Å³	Block, colorless
Z = 2	0.25 × 0.24 × 0.20 mm

Data collection top

Bruker APEXII CCD area-detector diffractometer	1495 independent reflections
Radiation source: fine-focus sealed tube	1247 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.053
ω scans	θ_max = 26.0°, θ_min = 3.0°
Absorption correction: multi-scan (SADABS; Bruker, 2007)	h = −6→6
T_min = 0.205, T_max = 0.250	k = −21→24
3935 measured reflections	l = −8→8

Refinement top

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)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.111	H-atom parameters constrained
S = 1.10	w = 1/[σ²(F_o²) + (0.0663P)²] where P = (F_o² + 2F_c²)/3
1495 reflections	(Δ/σ)_max = 0.003
100 parameters	Δρ_max = 0.77 e Å⁻³
0 restraints	Δρ_min = −1.19 e Å⁻³

Crystal data top

[ZnBr₂(C₅H₅N₃O)₂]	V = 739.61 (10) Å³
M_r = 471.43	Z = 2
Monoclinic, P2₁/m	Mo Kα radiation
a = 5.6042 (4) Å	µ = 7.08 mm⁻¹
b = 19.5147 (19) Å	T = 298 K
c = 7.0656 (5) Å	0.25 × 0.24 × 0.20 mm
β = 106.835 (5)°

Data collection top

Bruker APEXII CCD area-detector diffractometer	1495 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2007)	1247 reflections with I > 2σ(I)
T_min = 0.205, T_max = 0.250	R_int = 0.053
3935 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.046	0 restraints
wR(F²) = 0.111	H-atom parameters constrained
S = 1.10	Δρ_max = 0.77 e Å⁻³
1495 reflections	Δρ_min = −1.19 e Å⁻³
100 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
C1	0.5931 (9)	0.6363 (3)	1.0284 (7)	0.0268 (10)
H1	0.7306	0.6466	1.1350	0.032*
C2	0.3658 (9)	0.6512 (3)	0.7068 (8)	0.0322 (11)
H2	0.3429	0.6717	0.5839	0.039*
C3	0.1931 (10)	0.6034 (3)	0.7302 (8)	0.0360 (12)
H3	0.0550	0.5936	0.6237	0.043*
C4	0.4230 (9)	0.5883 (3)	1.0503 (7)	0.0264 (10)
C5	0.4616 (10)	0.5526 (3)	1.2446 (8)	0.0320 (11)
N1	0.5632 (7)	0.6684 (2)	0.8557 (6)	0.0256 (9)
N2	0.2205 (7)	0.5714 (2)	0.9018 (7)	0.0334 (10)
N3	0.2721 (10)	0.5171 (3)	1.2679 (8)	0.0532 (15)
H3B	0.2850	0.4963	1.3778	0.064*
H3C	0.1355	0.5147	1.1732	0.064*
O1	0.6621 (7)	0.5585 (2)	1.3724 (6)	0.0469 (11)
Zn1	0.79117 (14)	0.7500	0.82766 (12)	0.0244 (2)
Br1	0.79321 (15)	0.7500	0.49867 (12)	0.0392 (2)
Br2	1.13911 (12)	0.7500	1.10460 (11)	0.0351 (2)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.025 (2)	0.029 (3)	0.023 (2)	−0.0022 (18)	0.0017 (19)	0.001 (2)
C2	0.035 (3)	0.035 (3)	0.023 (3)	−0.001 (2)	0.002 (2)	0.002 (2)
C3	0.033 (3)	0.043 (3)	0.026 (3)	−0.011 (2)	−0.001 (2)	0.003 (2)
C4	0.025 (2)	0.026 (2)	0.027 (3)	−0.0027 (19)	0.0062 (19)	0.001 (2)
C5	0.036 (3)	0.032 (3)	0.026 (3)	−0.009 (2)	0.006 (2)	0.001 (2)
N1	0.0247 (18)	0.028 (2)	0.024 (2)	−0.0028 (17)	0.0075 (16)	−0.0010 (17)
N2	0.027 (2)	0.037 (3)	0.033 (2)	−0.0069 (18)	0.0033 (18)	0.001 (2)
N3	0.044 (3)	0.074 (4)	0.034 (3)	−0.028 (3)	0.000 (2)	0.017 (3)
O1	0.043 (2)	0.055 (3)	0.032 (2)	−0.0183 (19)	−0.0068 (17)	0.0147 (19)
Zn1	0.0224 (4)	0.0275 (4)	0.0247 (4)	0.000	0.0088 (3)	0.000
Br1	0.0424 (4)	0.0536 (5)	0.0242 (4)	0.000	0.0138 (3)	0.000
Br2	0.0222 (4)	0.0511 (5)	0.0302 (4)	0.000	0.0049 (3)	0.000

Geometric parameters (Å, º) top

C1—N1	1.338 (6)	C4—C5	1.499 (7)
C1—C4	1.377 (7)	C5—O1	1.226 (6)
C1—H1	0.9300	C5—N3	1.317 (7)
C2—N1	1.331 (7)	N1—Zn1	2.086 (4)
C2—C3	1.388 (8)	N3—H3B	0.8600
C2—H2	0.9300	N3—H3C	0.8600
C3—N2	1.333 (7)	Zn1—N1ⁱ	2.086 (4)
C3—H3	0.9300	Zn1—Br1	2.3278 (11)
C4—N2	1.345 (6)	Zn1—Br2	2.3283 (11)

N1—C1—C4	120.8 (5)	N3—C5—C4	116.8 (5)
N1—C1—H1	119.6	C2—N1—C1	117.3 (4)
C4—C1—H1	119.6	C2—N1—Zn1	120.6 (4)
N1—C2—C3	121.6 (5)	C1—N1—Zn1	121.7 (3)
N1—C2—H2	119.2	C3—N2—C4	116.3 (4)
C3—C2—H2	119.2	C5—N3—H3B	120.0
N2—C3—C2	121.6 (5)	C5—N3—H3C	120.0
N2—C3—H3	119.2	H3B—N3—H3C	120.0
C2—C3—H3	119.2	N1—Zn1—N1ⁱ	99.5 (2)
N2—C4—C1	122.4 (5)	N1—Zn1—Br1	105.96 (12)
N2—C4—C5	117.7 (4)	N1ⁱ—Zn1—Br1	105.96 (12)
C1—C4—C5	119.9 (4)	N1—Zn1—Br2	107.88 (12)
O1—C5—N3	123.9 (5)	N1ⁱ—Zn1—Br2	107.88 (12)
O1—C5—C4	119.3 (5)	Br1—Zn1—Br2	126.45 (4)

N1—C2—C3—N2	−1.7 (9)	C4—C1—N1—Zn1	172.0 (4)
N1—C1—C4—N2	−0.1 (8)	C2—C3—N2—C4	0.5 (8)
N1—C1—C4—C5	179.4 (5)	C1—C4—N2—C3	0.4 (8)
N2—C4—C5—O1	168.4 (5)	C5—C4—N2—C3	−179.2 (5)
C1—C4—C5—O1	−11.2 (8)	C2—N1—Zn1—N1ⁱ	75.8 (4)
N2—C4—C5—N3	−12.6 (8)	C1—N1—Zn1—N1ⁱ	−97.0 (4)
C1—C4—C5—N3	167.8 (5)	C2—N1—Zn1—Br1	−33.9 (4)
C3—C2—N1—C1	1.9 (8)	C1—N1—Zn1—Br1	153.3 (4)
C3—C2—N1—Zn1	−171.2 (4)	C2—N1—Zn1—Br2	−171.8 (4)
C4—C1—N1—C2	−1.0 (7)	C1—N1—Zn1—Br2	15.4 (4)

Symmetry code: (i) x, −y+3/2, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3B···O1ⁱⁱ	0.86	2.01	2.869 (7)	175
N3—H3C···N2	0.86	2.38	2.732 (7)	105
N3—H3C···N2ⁱⁱⁱ	0.86	2.54	3.182 (7)	132
C3—H3···O1^iv	0.93	2.49	3.414 (7)	172

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

Experimental details

Crystal data
Chemical formula	[ZnBr₂(C₅H₅N₃O)₂]
M_r	471.43
Crystal system, space group	Monoclinic, P2₁/m
Temperature (K)	298
a, b, c (Å)	5.6042 (4), 19.5147 (19), 7.0656 (5)
β (°)	106.835 (5)
V (Å³)	739.61 (10)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	7.08
Crystal size (mm)	0.25 × 0.24 × 0.20

Data collection
Diffractometer	Bruker APEXII CCD area-detector
Absorption correction	Multi-scan (SADABS; Bruker, 2007)
T_min, T_max	0.205, 0.250
No. of measured, independent and observed [I > 2σ(I)] reflections	3935, 1495, 1247
R_int	0.053
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.046, 0.111, 1.10
No. of reflections	1495
No. of parameters	100
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.77, −1.19

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3B···O1ⁱ	0.8600	2.0100	2.869 (7)	175.00
N3—H3C···N2	0.8600	2.3800	2.732 (7)	105.00
N3—H3C···N2ⁱⁱ	0.8600	2.5400	3.182 (7)	132.00
C3—H3···O1ⁱⁱⁱ	0.9300	2.4900	3.414 (7)	172.00

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

Acknowledgements

We are grateful to the Islamic Azad University, Omidieh Branch for financial support.

References

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