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

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

doi:10.1107/S1600536812013888

metal-organic compounds

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ISSN: 2056-9890

Volume 68| Part 5| May 2012| Page m546

doi:10.1107/S1600536812013888

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

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 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 Zn^II cation and Cl⁻ anions located on the mirror plane. The Zn^II 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 ); 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

[ZnCl₂(C₅H₅N₃O)₂]
M_r = 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 ) T_min = 0.881, T_max = 0.902
5777 measured reflections
1441 independent reflections
1064 reflections with I > 2σ(I)
R_int = 0.085

Refinement

R[F² > 2σ(F²)] = 0.045
wR(F²) = 0.093
S = 0.97
1441 reflections
100 parameters
H-atom parameters constrained
Δρ_max = 0.78 e Å⁻³
Δρ_min = −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	D⋯A	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 ); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812013888/xu5500sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812013888/xu5500Isup2.hkl

checkCIF report

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 Zn^II atom, two Cl 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 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%).

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

	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].
	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
M_r = 382.53	D_x = 1.793 Mg m⁻³
Monoclinic, P2₁/m	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yb	Cell parameters from 5777 reflections
a = 5.4296 (5) Å	θ = 2.1–26.0°
b = 19.7629 (14) Å	µ = 2.12 mm⁻¹
c = 6.8396 (5) Å	T = 298 K
β = 105.131 (7)°	Plate, colorless
V = 708.48 (10) Å³	0.40 × 0.06 × 0.05 mm
Z = 2

Data collection top

Bruker APEXII CCD area-detector' diffractometer	1441 independent reflections
Radiation source: fine-focus sealed tube	1064 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.085
ω scans	θ_max = 26.0°, θ_min = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −6→6
T_min = 0.881, T_max = 0.902	k = −21→24
5777 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)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.093	H-atom parameters constrained
S = 0.97	w = 1/[σ²(F_o²) + (0.0467P)²] where P = (F_o² + 2F_c²)/3
1441 reflections	(Δ/σ)_max = 0.003
100 parameters	Δρ_max = 0.78 e Å⁻³
0 restraints	Δρ_min = −0.65 e Å⁻³

Crystal data top

[ZnCl₂(C₅H₅N₃O)₂]	V = 708.48 (10) Å³
M_r = 382.53	Z = 2
Monoclinic, P2₁/m	Mo Kα radiation
a = 5.4296 (5) Å	µ = 2.12 mm⁻¹
b = 19.7629 (14) Å	T = 298 K
c = 6.8396 (5) Å	0.40 × 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)
T_min = 0.881, T_max = 0.902	R_int = 0.085
5777 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.045	0 restraints
wR(F²) = 0.093	H-atom parameters constrained
S = 0.97	Δρ_max = 0.78 e Å⁻³
1441 reflections	Δρ_min = −0.65 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	0.3963 (7)	0.3616 (2)	0.4810 (6)	0.0307 (9)
H1	0.2583	0.3512	0.3724	0.037*
C2	0.6226 (8)	0.3464 (2)	0.8085 (6)	0.0364 (10)
H2	0.6435	0.3262	0.9347	0.044*
C3	0.8016 (8)	0.3930 (2)	0.7802 (6)	0.0391 (10)
H3	0.9428	0.4022	0.8873	0.047*
C4	0.5722 (7)	0.4094 (2)	0.4563 (6)	0.0310 (8)
C5	0.5370 (8)	0.4445 (2)	0.2579 (6)	0.0366 (9)
N1	0.4213 (6)	0.33021 (16)	0.6574 (5)	0.0312 (7)
N2	0.7776 (6)	0.42473 (18)	0.6048 (5)	0.0366 (8)
N3	0.7336 (7)	0.4801 (2)	0.2331 (6)	0.0535 (11)
H3B	0.7210	0.5022	0.1226	0.064*
H3C	0.8736	0.4812	0.3276	0.064*
O1	0.3309 (6)	0.44069 (17)	0.1293 (4)	0.0506 (8)
Zn1	0.18582 (12)	0.2500	0.69002 (10)	0.0304 (2)
Cl1	0.1855 (3)	0.2500	1.0108 (2)	0.0480 (4)
Cl2	−0.1427 (3)	0.2500	0.4244 (2)	0.0416 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0264 (19)	0.030 (2)	0.034 (2)	−0.0008 (16)	0.0050 (17)	0.0030 (17)
C2	0.040 (2)	0.038 (2)	0.028 (2)	−0.0004 (18)	0.0041 (18)	0.0030 (18)
C3	0.036 (2)	0.046 (3)	0.030 (2)	−0.0092 (19)	−0.0004 (18)	0.0013 (19)
C4	0.0278 (19)	0.030 (2)	0.034 (2)	−0.0010 (16)	0.0063 (16)	−0.0002 (17)
C5	0.041 (2)	0.031 (2)	0.036 (2)	−0.0065 (18)	0.0050 (19)	0.0002 (18)
N1	0.0300 (16)	0.0295 (18)	0.0341 (19)	−0.0027 (14)	0.0081 (14)	−0.0011 (14)
N2	0.0325 (18)	0.037 (2)	0.037 (2)	−0.0053 (14)	0.0032 (15)	−0.0011 (15)
N3	0.041 (2)	0.073 (3)	0.042 (2)	−0.0229 (19)	0.0026 (17)	0.017 (2)
O1	0.0432 (17)	0.058 (2)	0.0413 (18)	−0.0198 (15)	−0.0053 (15)	0.0173 (16)
Zn1	0.0290 (3)	0.0313 (4)	0.0329 (4)	0.000	0.0114 (3)	0.000
Cl1	0.0570 (10)	0.0575 (11)	0.0328 (8)	0.000	0.0174 (7)	0.000
Cl2	0.0303 (7)	0.0525 (10)	0.0408 (8)	0.000	0.0069 (6)	0.000

Geometric parameters (Å, º) top

C1—N1	1.332 (5)	C5—O1	1.232 (5)
C1—C4	1.384 (5)	C5—N3	1.326 (5)
C1—H1	0.9300	N1—Zn1	2.085 (3)
C2—N1	1.333 (5)	N3—H3B	0.8600
C2—C3	1.388 (6)	N3—H3C	0.8600
C2—H2	0.9300	Zn1—N1	2.085 (3)
C3—N2	1.330 (5)	Zn1—N1ⁱ	2.085 (3)
C3—H3	0.9300	Zn1—Cl1	2.1945 (16)
C4—N2	1.333 (5)	Zn1—Cl2	2.1888 (16)
C4—C5	1.491 (6)

N1—C1—C4	121.2 (4)	N3—C5—C4	116.6 (4)
N1—C1—H1	119.4	C1—N1—C2	117.4 (3)
C4—C1—H1	119.4	C1—N1—Zn1	122.1 (3)
N1—C2—C3	120.9 (4)	C2—N1—Zn1	120.1 (3)
N1—C2—H2	119.6	C3—N2—C4	116.4 (3)
C3—C2—H2	119.6	C5—N3—H3B	120.0
N2—C3—C2	122.1 (4)	C5—N3—H3C	120.0
N2—C3—H3	118.9	H3B—N3—H3C	120.0
C2—C3—H3	118.9	N1—Zn1—N1ⁱ	99.00 (18)
N2—C4—C1	121.9 (4)	N1—Zn1—Cl2	107.51 (10)
N2—C4—C5	118.1 (3)	N1ⁱ—Zn1—Cl2	107.51 (10)
C1—C4—C5	120.0 (3)	N1—Zn1—Cl1	105.53 (9)
O1—C5—N3	123.5 (4)	N1ⁱ—Zn1—Cl1	105.53 (9)
O1—C5—C4	119.9 (4)	Cl2—Zn1—Cl1	128.07 (6)

N1—C2—C3—N2	1.9 (7)	C3—C2—N1—Zn1	170.7 (3)
N1—C1—C4—N2	2.1 (6)	C2—C3—N2—C4	−0.2 (6)
N1—C1—C4—C5	−179.0 (4)	C1—C4—N2—C3	−1.7 (6)
N2—C4—C5—O1	−167.5 (4)	C5—C4—N2—C3	179.4 (4)
C1—C4—C5—O1	13.5 (6)	C1—N1—Zn1—N1ⁱ	96.5 (3)
N2—C4—C5—N3	10.8 (6)	C2—N1—Zn1—N1ⁱ	−75.5 (3)
C1—C4—C5—N3	−168.2 (4)	C1—N1—Zn1—Cl2	−15.2 (3)
C4—C1—N1—C2	−0.3 (6)	C2—N1—Zn1—Cl2	172.9 (3)
C4—C1—N1—Zn1	−172.5 (3)	C1—N1—Zn1—Cl1	−154.6 (3)
C3—C2—N1—C1	−1.5 (6)	C2—N1—Zn1—Cl1	33.5 (3)

Symmetry code: (i) x, −y+1/2, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3B···O1ⁱⁱ	0.86	2.02	2.875 (5)	175
N3—H3C···N2ⁱⁱⁱ	0.86	2.61	3.205 (5)	128
C3—H3···O1^iv	0.93	2.44	3.357 (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]
M_r	382.53
Crystal system, space group	Monoclinic, P2₁/m
Temperature (K)	298
a, b, c (Å)	5.4296 (5), 19.7629 (14), 6.8396 (5)
β (°)	105.131 (7)
V (Å³)	708.48 (10)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	2.12
Crystal size (mm)	0.40 × 0.06 × 0.05

Data collection
Diffractometer	Bruker APEXII CCD area-detector' diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2001)
T_min, T_max	0.881, 0.902
No. of measured, independent and observed [I > 2σ(I)] reflections	5777, 1441, 1064
R_int	0.085
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.045, 0.093, 0.97
No. of reflections	1441
No. of parameters	100
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.78, −0.65

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

Selected bond lengths (Å) top

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3B···O1ⁱ	0.86	2.02	2.875 (5)	175.00
N3—H3C···N2ⁱⁱ	0.86	2.61	3.205 (5)	128.00
C3—H3···O1ⁱⁱⁱ	0.93	2.44	3.357 (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

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