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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 π–π 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.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807028735/at2326sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807028735/at2326Isup2.hkl
Contains datablock I

CCDC reference: 1249794

Key indicators

  • Single-crystal X-ray study
  • T = 273 K
  • Mean [sigma](C-C) = 0.007 Å
  • R factor = 0.048
  • wR factor = 0.149
  • Data-to-parameter ratio = 16.5

checkCIF/PLATON results

No syntax errors found



Alert level B PLAT230_ALERT_2_B Hirshfeld Test Diff for N6 - C6 .. 10.99 su
Alert level C PLAT230_ALERT_2_C Hirshfeld Test Diff for N5 - C9 .. 5.03 su PLAT230_ALERT_2_C Hirshfeld Test Diff for N7 - C3 .. 5.56 su PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X) Zn1 - N3 .. 5.20 su PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X) Zn1 - N4 .. 5.80 su PLAT241_ALERT_2_C Check High Ueq as Compared to Neighbors for N6 PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for N3 PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C1 PLAT341_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ... 7
Alert level G PLAT794_ALERT_5_G Check Predicted Bond Valency for Zn1 (2) 2.01
0 ALERT level A = In general: serious problem 1 ALERT level B = Potentially serious problem 8 ALERT level C = Check and explain 1 ALERT level G = General alerts; check 0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 8 ALERT type 2 Indicator that the structure model may be wrong or deficient 1 ALERT type 3 Indicator that the structure quality may be low 0 ALERT type 4 Improvement, methodology, query or suggestion 1 ALERT type 5 Informative message, check

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).

Structure description 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.

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

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 m3
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 mm1
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 = 1313
Tmin = 0.746, Tmax = 0.919k = 1717
7726 measured reflectionsl = 1818
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 Å3
0 restraintsΔρmin = 0.41 e Å3
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 mm1
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 reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0480 restraints
wR(F2) = 0.149H-atom parameters constrained
S = 1.07Δρmax = 0.52 e Å3
2360 reflectionsΔρmin = 0.41 e Å3
143 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
Zn10.00000.35957 (4)0.75000.0524 (2)
S10.36272 (12)0.36690 (10)0.93388 (11)0.0980 (5)
N10.1575 (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)
C10.2434 (3)0.3642 (2)0.8698 (2)0.0491 (8)
C20.0416 (3)0.1682 (3)0.8214 (2)0.0577 (9)
H20.06970.20190.86950.069*
C30.0429 (4)0.0755 (3)0.8239 (3)0.0734 (11)
H30.07130.04370.87300.088*
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)
H70.01830.40280.95520.100*
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)0.0000.015 (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)0.0000.012 (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.

Experimental details

Crystal data
Chemical formula[Zn(NCS)2(C4H4N2)4]
Mr501.90
Crystal system, space groupMonoclinic, C2/c
Temperature (K)273
a, b, c (Å)11.251 (4), 14.224 (3), 15.108 (3)
β (°) 91.002 (3)
V3)2417.4 (12)
Z4
Radiation typeMo Kα
µ (mm1)1.21
Crystal size (mm)0.26 × 0.16 × 0.07
Data collection
DiffractometerBruker APEXII area-detector
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.746, 0.919
No. of measured, independent and
observed [I > 2σ(I)] reflections
7726, 2360, 1660
Rint0.033
(sin θ/λ)max1)0.618
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.048, 0.149, 1.07
No. of reflections2360
No. of parameters143
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.52, 0.41

Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Siemens, 1996), SHELXTL.

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.
 

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