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Acta Cryst. (2007). E63, m1908    [ doi:10.1107/S1600536807028735 ]

Tetrakis(pyrazine-[kappa]N)bis(thiocyanato-[kappa]N)zinc(II)

T. Liu and Z.-P. Xie

Abstract top

In the molecule of the title complex, [Zn(NCS)2(C4H4N2)4], the ZnII atom is bonded in a distorted octahedral arrangement composed of two N atoms of two thiocyanate and four N atoms of four pyrazine ligands. A crystallographic twofold rotation axis passes through the Zn atom and the N atoms of two trans-pyrazine rings. In the crystal structure, nonclassical hydrogen bonds and weak [pi]-[pi] stacking interactions, with a centroid-centroid distance of 3.3119 (6) Å (symmetry code: 1-x, 2-y, 1-z), result in the formation of a supramolecular network structure.

Comment top

The crystal structure of Tetrakis(pyrazine-N)bis(thiocyanato-N)manganese(II), (II), has previously been reported (Liu & Xie, 2007). The crystal structure determination of the title compound, (I), has been carried out in order to elucidate the molecular conformation and to compare it with that of (II). We report herein the crystal structure of (I).

In the molecule of (I), (Fig. 1) the ligand bond lengths and angles are within normal ranges (Allen et al., 1987). The two N atoms of two SCN- and four N atoms of four pyrazine ligands are coordinated to the Zn atom, in a distorted octahedral arrangement (Table 1). A crystallographic twofold rotation axis passes through the Zn atom, and the N and para-N atoms of two trans pyrazine rings. The planar pyrazine rings A (N3/N6/C4—C7), B (N2/N7/C2A/C3A/C2—C3) and C (N4/N5/C8A/C9A/C8—C9) are nearly perpendicular to each other, with dihedral angles of A/B = 87.3 (5), A/C = 109.5 (3) and B/C = 86.6 (4)°, as in (II).

In the crystal structure, the non-classica hydrogen bonds and the weak π-π stacking interactions, involving the pyrazine rings of adjacent pyrazine ligands with centroid-centroid distance of 3.3119 (6) Å [symmetry code: 1 - x, 2 - y, 1 - z], cause to the formation of a supramolecular network structure (Fig. 2), as in (II).

The both compounds, (I) and (II), are isostructural.

Related literature top

For a related structure, see: Liu & Xie (2007). For bond-length data, see: Allen et al. (1987).

Experimental top

Crystals of the title compound were synthesized using hydrothermal method in a Teflon-lined Parr bomb (23 ml), which was then sealed. Zinc dinitrate hexahydrate (59.4 mg, 0.2 mmol), potassium thiocyanate (38.9 mg, 0.4 mmol), pyrazine (1.5 ml), and distilled water (2 g) were placed into the bomb and sealed. The bomb was heated under autogenous pressure for 7 d at 423 K and allowed to cool at room temperature for 24 h. Upon opening the bomb, a clear colourless solution was decanted from small colourless crystals. These crystals were washed with distilled water followed by ethanol, and allowed to air-dry at room temperature.

Refinement top

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

Computing details top

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Siemens, 1996); software used to prepare material for publication: SHELXTL.

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 code (A): - x, y, 3/2 - z].
[Figure 2] Fig. 2. A packing diagram for (I). Hydrogen bonds are shown as dashed lines.
Tetrakis(pyrazine-κN)bis(thiocyanato-κN)zinc(II) top
Crystal data top
[Zn(NCS)2(C4H4N2)4]F(000) = 1024
Mr = 501.90Dx = 1.379 Mg m−3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 2205 reflections
a = 11.251 (4) Åθ = 2.3–23.7°
b = 14.224 (3) ŵ = 1.21 mm−1
c = 15.108 (3) ÅT = 273 K
β = 91.002 (3)°Block, colourless
V = 2417.4 (12) Å30.26 × 0.16 × 0.07 mm
Z = 4
Data collection top
Bruker APEXII area-detector
diffractometer		2360 independent reflections
Radiation source: fine-focus sealed tube1660 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.033
φ and ω scansθmax = 26.1°, θmin = 2.3°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −13→13
Tmin = 0.746, Tmax = 0.919k = −17→17
7726 measured reflectionsl = −18→18
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)] = 0.048Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.149H-atom parameters constrained
S = 1.07 w = 1/[σ2(Fo2) + (0.0742P)2 + 1.8799P]
where P = (Fo2 + 2Fc2)/3
2360 reflections(Δ/σ)max < 0.001
143 parametersΔρmax = 0.52 e Å−3
0 restraintsΔρmin = −0.41 e Å−3
Crystal data top
[Zn(NCS)2(C4H4N2)4]V = 2417.4 (12) Å3
Mr = 501.90Z = 4
Monoclinic, C2/cMo Kα radiation
a = 11.251 (4) ŵ = 1.21 mm−1
b = 14.224 (3) ÅT = 273 K
c = 15.108 (3) Å0.26 × 0.16 × 0.07 mm
β = 91.002 (3)°
Data collection top
Bruker APEXII area-detector
diffractometer		2360 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		1660 reflections with I > 2σ(I)
Tmin = 0.746, Tmax = 0.919Rint = 0.033
7726 measured reflectionsθmax = 26.1°
Refinement top
R[F2 > 2σ(F2)] = 0.048H-atom parameters constrained
wR(F2) = 0.149Δρmax = 0.52 e Å−3
S = 1.07Δρmin = −0.41 e Å−3
2360 reflectionsAbsolute structure: ?
143 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
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
Zn10.00000.35957 (4)0.75000.0524 (2)
S1−0.36272 (12)0.36690 (10)0.93388 (11)0.0980 (5)
N1−0.1575 (3)0.3627 (2)0.8237 (2)0.0573 (8)
N20.00000.2158 (3)0.75000.0497 (9)
N30.1069 (3)0.36039 (18)0.87475 (19)0.0499 (7)
N40.00000.5059 (3)0.75000.0514 (9)
N50.00000.6954 (4)0.75000.123 (2)
N60.2532 (6)0.3886 (4)1.0273 (4)0.1200 (18)
N70.00000.0258 (4)0.75000.1020 (19)
C1−0.2434 (3)0.3642 (2)0.8698 (2)0.0491 (8)
C2−0.0416 (3)0.1682 (3)0.8214 (2)0.0577 (9)
H2−0.06970.20190.86950.069*
C3−0.0429 (4)0.0755 (3)0.8239 (3)0.0734 (11)
H3−0.07130.04370.87300.088*
C40.2265 (3)0.3412 (3)0.8754 (3)0.0679 (11)
H40.25960.31850.82360.081*
C50.3013 (4)0.3537 (3)0.9492 (4)0.0855 (14)
H50.38170.33910.94640.103*
C60.1316 (5)0.4057 (4)1.0276 (3)0.1073 (19)
H60.09630.42731.07900.129*
C70.0628 (4)0.3910 (4)0.9524 (3)0.0834 (14)
H7−0.01830.40280.95520.100*
C80.0984 (3)0.5539 (3)0.7766 (3)0.0637 (10)
H80.16640.52050.79300.076*
C90.1009 (5)0.6459 (3)0.7797 (4)0.0893 (16)
H90.16770.67760.80110.107*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Zn10.0475 (4)0.0526 (4)0.0574 (4)0.0000.0112 (2)0.000
S10.0758 (8)0.1068 (10)0.1135 (11)0.0011 (7)0.0562 (8)0.0004 (8)
N10.0467 (17)0.0619 (19)0.0639 (18)0.0016 (13)0.0145 (14)−0.0005 (14)
N20.047 (2)0.048 (2)0.054 (2)0.0000.0012 (17)0.000
N30.0494 (16)0.0447 (15)0.0558 (17)0.0002 (12)0.0025 (12)−0.0005 (12)
N40.048 (2)0.041 (2)0.065 (2)0.0000.0032 (18)0.000
N50.118 (6)0.060 (4)0.190 (7)0.000−0.015 (5)0.000
N60.146 (5)0.101 (3)0.111 (4)0.000 (3)−0.042 (4)−0.012 (3)
N70.117 (5)0.068 (4)0.120 (5)0.000−0.012 (4)0.000
C10.0470 (19)0.0447 (18)0.056 (2)0.0052 (14)0.0084 (15)−0.0006 (14)
C20.063 (2)0.051 (2)0.059 (2)−0.0027 (17)0.0039 (17)0.0061 (17)
C30.092 (3)0.056 (2)0.072 (3)−0.009 (2)−0.001 (2)0.012 (2)
C40.056 (2)0.075 (3)0.073 (3)0.0110 (19)0.0022 (19)0.012 (2)
C50.056 (3)0.095 (4)0.105 (4)−0.003 (2)−0.015 (2)0.022 (3)
C60.093 (4)0.149 (5)0.079 (3)0.034 (4)−0.022 (3)−0.040 (3)
C70.069 (3)0.114 (4)0.067 (3)0.024 (3)−0.007 (2)−0.026 (3)
C80.053 (2)0.051 (2)0.087 (3)−0.0043 (17)−0.0042 (19)0.0028 (19)
C90.071 (3)0.052 (3)0.144 (5)−0.008 (2)−0.022 (3)0.000 (3)
Geometric parameters (Å, º) top
Zn1—N12.109 (3)N6—C61.390 (7)
Zn1—N22.046 (4)N6—C51.398 (8)
Zn1—N32.218 (3)N7—C3i1.414 (5)
Zn1—N42.081 (4)N7—C31.414 (5)
Zn1—N1i2.109 (3)C2—C31.320 (5)
Zn1—N3i2.218 (3)C2—H20.9300
S1—C11.669 (4)C3—H30.9300
N1—C11.202 (5)C4—C51.396 (6)
N2—C2i1.363 (4)C4—H40.9300
N2—C21.363 (4)C5—H50.9300
N3—C71.353 (5)C6—C71.379 (6)
N3—C41.373 (5)C6—H60.9300
N4—C8i1.356 (4)C7—H70.9300
N4—C81.356 (4)C8—C91.310 (5)
N5—C9i1.402 (6)C8—H80.9300
N5—C91.402 (6)C9—H90.9300
N1—Zn1—N291.21 (8)C3i—N7—C3120.0 (5)
N1—Zn1—N389.97 (11)N1—C1—S1179.7 (3)
N1—Zn1—N488.79 (8)C3—C2—N2121.5 (4)
N2—Zn1—N390.30 (7)C3—C2—H2119.2
N2—Zn1—N4180.00 (1)N2—C2—H2119.2
N3—Zn1—N489.70 (7)C2—C3—N7118.2 (4)
N2—Zn1—N1i91.21 (8)C2—C3—H3120.9
N4—Zn1—N1i88.79 (8)N7—C3—H3120.9
N1—Zn1—N1i177.59 (16)N3—C4—C5123.9 (4)
N2—Zn1—N3i90.30 (7)N3—C4—H4118.1
N4—Zn1—N3i89.70 (7)C5—C4—H4118.1
N1—Zn1—N3i90.02 (12)C4—C5—N6118.8 (5)
N1i—Zn1—N3i89.96 (11)C4—C5—H5120.6
N1i—Zn1—N390.02 (12)N6—C5—H5120.6
N3i—Zn1—N3179.40 (14)C7—C6—N6120.6 (5)
C1—N1—Zn1176.4 (3)C7—C6—H6119.7
C2i—N2—C2120.5 (4)N6—C6—H6119.7
C2i—N2—Zn1119.7 (2)N3—C7—C6123.7 (4)
C2—N2—Zn1119.7 (2)N3—C7—H7118.2
C7—N3—C4115.6 (3)C6—C7—H7118.2
C7—N3—Zn1122.5 (3)C9—C8—N4122.0 (4)
C4—N3—Zn1121.4 (2)C9—C8—H8119.0
C8i—N4—C8119.5 (4)N4—C8—H8119.0
C8i—N4—Zn1120.3 (2)C8—C9—N5118.3 (4)
C8—N4—Zn1120.3 (2)C8—C9—H9120.9
C9i—N5—C9119.8 (6)N5—C9—H9120.9
C6—N6—C5117.4 (4)
Symmetry code: (i) −x, y, −z+3/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C4—H4···N1i0.932.563.108 (5)118
C7—H7···N10.932.573.150 (5)121
C2—H2···N10.932.583.058 (5)112
Symmetry code: (i) −x, y, −z+3/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C4—H4···N1i0.932.563.108 (5)118
C7—H7···N10.932.573.150 (5)121
C2—H2···N10.932.583.058 (5)112
Symmetry code: (i) −x, y, −z+3/2.
Acknowledgements top

This work was supported by the Science and Technology Bureau of Jian, Jiangxi Province of China (grant No. 20052817).

references
References top

Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19.

Liu, T. & Xie, Z.-P. (2007). Acta Cryst. E63, m1820–?.

Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.

Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.

Siemens (1996). SMART, SAINT and SHELXTL. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA. [SMART does not match APEXII diffractometer given above. Please provide correct reference for software used]