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Di­chloridobis(pyrazine-2-carboxamide-κN4)zinc(II)

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

(Received 26 March 2012; accepted 30 March 2012; online 4 April 2012)

In the crystal of the title compound, [ZnCl2(C5H5N3O)2], the mol­ecule has m symmetry, with the ZnII cation and Cl anions located on the mirror plane. The ZnII cation is coordinated by two Cl anions and two pyrazine-2-carboxamide ligands in a distorted ZnCl2N2 tetra­hedral geometry. The two pyrazine rings are nearly perpendicular to each other [dihedral angle = 86.61 (10)°]. Inter­molecular N—H⋯O and N—H⋯N hydrogen bonds and weak C—H⋯O inter­actions stabilize the crystal packing.

Related literature

For related structures, see: Abu-Youssef et al. (2006[Abu-Youssef, M. A. M., Escuer, A. & Langer, V. (2006). Eur. J. Inorg. Chem. pp. 3177-3184.]); Azhdari Tehrani et al. (2010[Azhdari Tehrani, A., Mir Mohammad Sadegh, B. & Khavasi, H. R. (2010). Acta Cryst. E66, m261.]); Goher & Mautner (2000[Goher, M. A. S. & Mautner, F. A. (2000). Polyhedron, 19, 601-606.]); Kristiansson (2002[Kristiansson, O. (2002). Acta Cryst. E58, m130-m132.]); Mir Mohammad Sadegh et al. (2010[Mir Mohammad Sadegh, B., Azhdari Tehrani, A. & Khavasi, H. R. (2010). Acta Cryst. E66, m158.]); Munakata et al. (1997[Munakata, M., Wu, L. P., Sowa, T. K., Maekawa, M., Moriwaki, K. & Kitagawa, S. (1997). Inorg. Chem. 36, 5416-5418.]); Pacigova et al. (2008[Pacigova, S., Gyepes, R., Tatiersky, J. & Sivak, M. (2008). Dalton Trans. pp. 121-130.]).

[Scheme 1]

Experimental

Crystal data
  • [ZnCl2(C5H5N3O)2]

  • Mr = 382.53

  • Monoclinic, P 21 /m

  • a = 5.4296 (5) Å

  • b = 19.7629 (14) Å

  • c = 6.8396 (5) Å

  • β = 105.131 (7)°

  • V = 708.48 (10) Å3

  • Z = 2

  • Mo Kα radiation

  • μ = 2.12 mm−1

  • T = 298 K

  • 0.40 × 0.06 × 0.05 mm

Data collection
  • Bruker APEXII CCD area-detector' diffractometer

  • Absorption correction: multi-scan (SADABS; Bruker, 2001[Bruker (2001). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]) Tmin = 0.881, Tmax = 0.902

  • 5777 measured reflections

  • 1441 independent reflections

  • 1064 reflections with I > 2σ(I)

  • Rint = 0.085

Refinement
  • R[F2 > 2σ(F2)] = 0.045

  • wR(F2) = 0.093

  • S = 0.97

  • 1441 reflections

  • 100 parameters

  • H-atom parameters constrained

  • Δρmax = 0.78 e Å−3

  • Δρmin = −0.65 e Å−3

Table 1
Selected bond lengths (Å)

Zn1—N1 2.085 (3)
Zn1—Cl1 2.1945 (16)
Zn1—Cl2 2.1888 (16)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
N3—H3B⋯O1i 0.86 2.02 2.875 (5) 175
N3—H3C⋯N2ii 0.86 2.61 3.205 (5) 128
C3—H3⋯O1iii 0.93 2.44 3.357 (5) 170
Symmetry codes: (i) -x+1, -y+1, -z; (ii) -x+2, -y+1, -z+1; (iii) x+1, y, z+1.

Data collection: APEX2 (Bruker, 2007[Bruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2007[Bruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information


Comment top

Pyrazine-2-carboxamide (pzc), is a good ligand, and a few complexes with pzc have been prepared, such as that of mercury (Azhdari Tehrani et al., 2010; Mir Mohammad Sadegh et al., 2010), vanadium (Pacigova et al., 2008), manganese (Abu-Youssef et al., 2006) and copper (Kristiansson, 2002; Munakata et al., 1997; Goher & Mautner, 2000). Here, we report the synthesis and structure of the title compound.

The asymmetric unit of the title compound, (Fig. 1), contains one ZnII atom, two Cl atoms and one pyrazine-2-carboxamide ligand. The ZnII atom is four-coordinated in a distorted tetrahedral configuration by two N atoms from two pyrazine-2-carboxamide ligands and two terminal Cl atoms. The Zn—Cl and Zn—N bond lengths and angles are collected in Table 1.

In the crystal structure, intermolecular N—H···O, N—H···N and C—H···O hydrogen bonds (Table 2, Fig. 2) may stabilize the structure.

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 ZnCl2 (0.13 g, 1.0 mmol) in methanol (10 ml) and the resulting colorless solution was stirred for 15 min at room temperature. This solution was left to evaporate slowly at room temperature. After one week, colorless plate crystals of the title compound were isolated (yield 0.30 g, 78.4%).

Refinement top

All H atoms were positioned geometrically, with C—H = 0.93 and N—H = 0.86 Å, and constrained to ride on their parent atoms with Uiso(H) = 1.2Ueq(C,N).

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] 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,1/2 - y,z].
[Figure 2] Fig. 2. Unit-cell packing diagram for title molecule. Hydrogen bonds are shown as dashed lines
Dichloridobis(pyrazine-2-carboxamide-κN4)zinc(II) top
Crystal data top
[ZnCl2(C5H5N3O)2]F(000) = 384
Mr = 382.53Dx = 1.793 Mg m3
Monoclinic, P21/mMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybCell parameters from 5777 reflections
a = 5.4296 (5) Åθ = 2.1–26.0°
b = 19.7629 (14) ŵ = 2.12 mm1
c = 6.8396 (5) ÅT = 298 K
β = 105.131 (7)°Plate, colorless
V = 708.48 (10) Å30.40 × 0.06 × 0.05 mm
Z = 2
Data collection top
Bruker APEXII CCD area-detector'
diffractometer
1441 independent reflections
Radiation source: fine-focus sealed tube1064 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.085
ω scansθmax = 26.0°, θmin = 2.1°
Absorption correction: multi-scan
(SADABS; Bruker, 2001)
h = 66
Tmin = 0.881, Tmax = 0.902k = 2124
5777 measured reflectionsl = 88
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.045Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.093H-atom parameters constrained
S = 0.97 w = 1/[σ2(Fo2) + (0.0467P)2]
where P = (Fo2 + 2Fc2)/3
1441 reflections(Δ/σ)max = 0.003
100 parametersΔρmax = 0.78 e Å3
0 restraintsΔρmin = 0.65 e Å3
Crystal data top
[ZnCl2(C5H5N3O)2]V = 708.48 (10) Å3
Mr = 382.53Z = 2
Monoclinic, P21/mMo Kα radiation
a = 5.4296 (5) ŵ = 2.12 mm1
b = 19.7629 (14) ÅT = 298 K
c = 6.8396 (5) Å0.40 × 0.06 × 0.05 mm
β = 105.131 (7)°
Data collection top
Bruker APEXII CCD area-detector'
diffractometer
1441 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2001)
1064 reflections with I > 2σ(I)
Tmin = 0.881, Tmax = 0.902Rint = 0.085
5777 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0450 restraints
wR(F2) = 0.093H-atom parameters constrained
S = 0.97Δρmax = 0.78 e Å3
1441 reflectionsΔρmin = 0.65 e Å3
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
xyzUiso*/Ueq
C10.3963 (7)0.3616 (2)0.4810 (6)0.0307 (9)
H10.25830.35120.37240.037*
C20.6226 (8)0.3464 (2)0.8085 (6)0.0364 (10)
H20.64350.32620.93470.044*
C30.8016 (8)0.3930 (2)0.7802 (6)0.0391 (10)
H30.94280.40220.88730.047*
C40.5722 (7)0.4094 (2)0.4563 (6)0.0310 (8)
C50.5370 (8)0.4445 (2)0.2579 (6)0.0366 (9)
N10.4213 (6)0.33021 (16)0.6574 (5)0.0312 (7)
N20.7776 (6)0.42473 (18)0.6048 (5)0.0366 (8)
N30.7336 (7)0.4801 (2)0.2331 (6)0.0535 (11)
H3B0.72100.50220.12260.064*
H3C0.87360.48120.32760.064*
O10.3309 (6)0.44069 (17)0.1293 (4)0.0506 (8)
Zn10.18582 (12)0.25000.69002 (10)0.0304 (2)
Cl10.1855 (3)0.25001.0108 (2)0.0480 (4)
Cl20.1427 (3)0.25000.4244 (2)0.0416 (4)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0264 (19)0.030 (2)0.034 (2)0.0008 (16)0.0050 (17)0.0030 (17)
C20.040 (2)0.038 (2)0.028 (2)0.0004 (18)0.0041 (18)0.0030 (18)
C30.036 (2)0.046 (3)0.030 (2)0.0092 (19)0.0004 (18)0.0013 (19)
C40.0278 (19)0.030 (2)0.034 (2)0.0010 (16)0.0063 (16)0.0002 (17)
C50.041 (2)0.031 (2)0.036 (2)0.0065 (18)0.0050 (19)0.0002 (18)
N10.0300 (16)0.0295 (18)0.0341 (19)0.0027 (14)0.0081 (14)0.0011 (14)
N20.0325 (18)0.037 (2)0.037 (2)0.0053 (14)0.0032 (15)0.0011 (15)
N30.041 (2)0.073 (3)0.042 (2)0.0229 (19)0.0026 (17)0.017 (2)
O10.0432 (17)0.058 (2)0.0413 (18)0.0198 (15)0.0053 (15)0.0173 (16)
Zn10.0290 (3)0.0313 (4)0.0329 (4)0.0000.0114 (3)0.000
Cl10.0570 (10)0.0575 (11)0.0328 (8)0.0000.0174 (7)0.000
Cl20.0303 (7)0.0525 (10)0.0408 (8)0.0000.0069 (6)0.000
Geometric parameters (Å, º) top
C1—N11.332 (5)C5—O11.232 (5)
C1—C41.384 (5)C5—N31.326 (5)
C1—H10.9300N1—Zn12.085 (3)
C2—N11.333 (5)N3—H3B0.8600
C2—C31.388 (6)N3—H3C0.8600
C2—H20.9300Zn1—N12.085 (3)
C3—N21.330 (5)Zn1—N1i2.085 (3)
C3—H30.9300Zn1—Cl12.1945 (16)
C4—N21.333 (5)Zn1—Cl22.1888 (16)
C4—C51.491 (6)
N1—C1—C4121.2 (4)N3—C5—C4116.6 (4)
N1—C1—H1119.4C1—N1—C2117.4 (3)
C4—C1—H1119.4C1—N1—Zn1122.1 (3)
N1—C2—C3120.9 (4)C2—N1—Zn1120.1 (3)
N1—C2—H2119.6C3—N2—C4116.4 (3)
C3—C2—H2119.6C5—N3—H3B120.0
N2—C3—C2122.1 (4)C5—N3—H3C120.0
N2—C3—H3118.9H3B—N3—H3C120.0
C2—C3—H3118.9N1—Zn1—N1i99.00 (18)
N2—C4—C1121.9 (4)N1—Zn1—Cl2107.51 (10)
N2—C4—C5118.1 (3)N1i—Zn1—Cl2107.51 (10)
C1—C4—C5120.0 (3)N1—Zn1—Cl1105.53 (9)
O1—C5—N3123.5 (4)N1i—Zn1—Cl1105.53 (9)
O1—C5—C4119.9 (4)Cl2—Zn1—Cl1128.07 (6)
N1—C2—C3—N21.9 (7)C3—C2—N1—Zn1170.7 (3)
N1—C1—C4—N22.1 (6)C2—C3—N2—C40.2 (6)
N1—C1—C4—C5179.0 (4)C1—C4—N2—C31.7 (6)
N2—C4—C5—O1167.5 (4)C5—C4—N2—C3179.4 (4)
C1—C4—C5—O113.5 (6)C1—N1—Zn1—N1i96.5 (3)
N2—C4—C5—N310.8 (6)C2—N1—Zn1—N1i75.5 (3)
C1—C4—C5—N3168.2 (4)C1—N1—Zn1—Cl215.2 (3)
C4—C1—N1—C20.3 (6)C2—N1—Zn1—Cl2172.9 (3)
C4—C1—N1—Zn1172.5 (3)C1—N1—Zn1—Cl1154.6 (3)
C3—C2—N1—C11.5 (6)C2—N1—Zn1—Cl133.5 (3)
Symmetry code: (i) x, y+1/2, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N3—H3B···O1ii0.862.022.875 (5)175
N3—H3C···N2iii0.862.613.205 (5)128
C3—H3···O1iv0.932.443.357 (5)170
Symmetry codes: (ii) x+1, y+1, z; (iii) x+2, y+1, z+1; (iv) x+1, y, z+1.

Experimental details

Crystal data
Chemical formula[ZnCl2(C5H5N3O)2]
Mr382.53
Crystal system, space groupMonoclinic, P21/m
Temperature (K)298
a, b, c (Å)5.4296 (5), 19.7629 (14), 6.8396 (5)
β (°) 105.131 (7)
V3)708.48 (10)
Z2
Radiation typeMo Kα
µ (mm1)2.12
Crystal size (mm)0.40 × 0.06 × 0.05
Data collection
DiffractometerBruker APEXII CCD area-detector'
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 2001)
Tmin, Tmax0.881, 0.902
No. of measured, independent and
observed [I > 2σ(I)] reflections
5777, 1441, 1064
Rint0.085
(sin θ/λ)max1)0.617
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.045, 0.093, 0.97
No. of reflections1441
No. of parameters100
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.78, 0.65

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

Selected bond lengths (Å) top
Zn1—N12.085 (3)Zn1—Cl22.1888 (16)
Zn1—Cl12.1945 (16)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N3—H3B···O1i0.862.022.875 (5)175.00
N3—H3C···N2ii0.862.613.205 (5)128.00
C3—H3···O1iii0.932.443.357 (5)170.00
Symmetry codes: (i) x+1, y+1, z; (ii) x+2, y+1, z+1; (iii) x+1, y, z+1.
 

Acknowledgements

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

References

First citationAbu-Youssef, M. A. M., Escuer, A. & Langer, V. (2006). Eur. J. Inorg. Chem. pp. 3177–3184.  Google Scholar
First citationAzhdari Tehrani, A., Mir Mohammad Sadegh, B. & Khavasi, H. R. (2010). Acta Cryst. E66, m261.  Web of Science CSD CrossRef IUCr Journals Google Scholar
First citationBruker (2001). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
First citationBruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
First citationGoher, M. A. S. & Mautner, F. A. (2000). Polyhedron, 19, 601–606.  Web of Science CSD CrossRef CAS Google Scholar
First citationKristiansson, O. (2002). Acta Cryst. E58, m130–m132.  Web of Science CSD CrossRef IUCr Journals Google Scholar
First citationMir Mohammad Sadegh, B., Azhdari Tehrani, A. & Khavasi, H. R. (2010). Acta Cryst. E66, m158.  Web of Science CSD CrossRef IUCr Journals Google Scholar
First citationMunakata, M., Wu, L. P., Sowa, T. K., Maekawa, M., Moriwaki, K. & Kitagawa, S. (1997). Inorg. Chem. 36, 5416–5418.  CSD CrossRef CAS Web of Science Google Scholar
First citationPacigova, S., Gyepes, R., Tatiersky, J. & Sivak, M. (2008). Dalton Trans. pp. 121–130.  Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar

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