Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807028735/at2326sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807028735/at2326Isup2.hkl |
CCDC reference: 1249794
Key indicators
- Single-crystal X-ray study
- T = 273 K
- Mean (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
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.
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).
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).
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.
[Zn(NCS)2(C4H4N2)4] | F(000) = 1024 |
Mr = 501.90 | Dx = 1.379 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2yc | Cell parameters from 2205 reflections |
a = 11.251 (4) Å | θ = 2.3–23.7° |
b = 14.224 (3) Å | µ = 1.21 mm−1 |
c = 15.108 (3) Å | T = 273 K |
β = 91.002 (3)° | Block, colourless |
V = 2417.4 (12) Å3 | 0.26 × 0.16 × 0.07 mm |
Z = 4 |
Bruker APEXII area-detector diffractometer | 2360 independent reflections |
Radiation source: fine-focus sealed tube | 1660 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.033 |
φ and ω scans | θmax = 26.1°, θmin = 2.3° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −13→13 |
Tmin = 0.746, Tmax = 0.919 | k = −17→17 |
7726 measured reflections | l = −18→18 |
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)] = 0.048 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.149 | H-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 parameters | Δρmax = 0.52 e Å−3 |
0 restraints | Δρmin = −0.41 e Å−3 |
[Zn(NCS)2(C4H4N2)4] | V = 2417.4 (12) Å3 |
Mr = 501.90 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 11.251 (4) Å | µ = 1.21 mm−1 |
b = 14.224 (3) Å | T = 273 K |
c = 15.108 (3) Å | 0.26 × 0.16 × 0.07 mm |
β = 91.002 (3)° |
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 = 0.919 | Rint = 0.033 |
7726 measured reflections |
R[F2 > 2σ(F2)] = 0.048 | 0 restraints |
wR(F2) = 0.149 | H-atom parameters constrained |
S = 1.07 | Δρmax = 0.52 e Å−3 |
2360 reflections | Δρmin = −0.41 e Å−3 |
143 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
Zn1 | 0.0000 | 0.35957 (4) | 0.7500 | 0.0524 (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) | |
N2 | 0.0000 | 0.2158 (3) | 0.7500 | 0.0497 (9) | |
N3 | 0.1069 (3) | 0.36039 (18) | 0.87475 (19) | 0.0499 (7) | |
N4 | 0.0000 | 0.5059 (3) | 0.7500 | 0.0514 (9) | |
N5 | 0.0000 | 0.6954 (4) | 0.7500 | 0.123 (2) | |
N6 | 0.2532 (6) | 0.3886 (4) | 1.0273 (4) | 0.1200 (18) | |
N7 | 0.0000 | 0.0258 (4) | 0.7500 | 0.1020 (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 | −0.0697 | 0.2019 | 0.8695 | 0.069* | |
C3 | −0.0429 (4) | 0.0755 (3) | 0.8239 (3) | 0.0734 (11) | |
H3 | −0.0713 | 0.0437 | 0.8730 | 0.088* | |
C4 | 0.2265 (3) | 0.3412 (3) | 0.8754 (3) | 0.0679 (11) | |
H4 | 0.2596 | 0.3185 | 0.8236 | 0.081* | |
C5 | 0.3013 (4) | 0.3537 (3) | 0.9492 (4) | 0.0855 (14) | |
H5 | 0.3817 | 0.3391 | 0.9464 | 0.103* | |
C6 | 0.1316 (5) | 0.4057 (4) | 1.0276 (3) | 0.1073 (19) | |
H6 | 0.0963 | 0.4273 | 1.0790 | 0.129* | |
C7 | 0.0628 (4) | 0.3910 (4) | 0.9524 (3) | 0.0834 (14) | |
H7 | −0.0183 | 0.4028 | 0.9552 | 0.100* | |
C8 | 0.0984 (3) | 0.5539 (3) | 0.7766 (3) | 0.0637 (10) | |
H8 | 0.1664 | 0.5205 | 0.7930 | 0.076* | |
C9 | 0.1009 (5) | 0.6459 (3) | 0.7797 (4) | 0.0893 (16) | |
H9 | 0.1677 | 0.6776 | 0.8011 | 0.107* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Zn1 | 0.0475 (4) | 0.0526 (4) | 0.0574 (4) | 0.000 | 0.0112 (2) | 0.000 |
S1 | 0.0758 (8) | 0.1068 (10) | 0.1135 (11) | 0.0011 (7) | 0.0562 (8) | 0.0004 (8) |
N1 | 0.0467 (17) | 0.0619 (19) | 0.0639 (18) | 0.0016 (13) | 0.0145 (14) | −0.0005 (14) |
N2 | 0.047 (2) | 0.048 (2) | 0.054 (2) | 0.000 | 0.0012 (17) | 0.000 |
N3 | 0.0494 (16) | 0.0447 (15) | 0.0558 (17) | 0.0002 (12) | 0.0025 (12) | −0.0005 (12) |
N4 | 0.048 (2) | 0.041 (2) | 0.065 (2) | 0.000 | 0.0032 (18) | 0.000 |
N5 | 0.118 (6) | 0.060 (4) | 0.190 (7) | 0.000 | −0.015 (5) | 0.000 |
N6 | 0.146 (5) | 0.101 (3) | 0.111 (4) | 0.000 (3) | −0.042 (4) | −0.012 (3) |
N7 | 0.117 (5) | 0.068 (4) | 0.120 (5) | 0.000 | −0.012 (4) | 0.000 |
C1 | 0.0470 (19) | 0.0447 (18) | 0.056 (2) | 0.0052 (14) | 0.0084 (15) | −0.0006 (14) |
C2 | 0.063 (2) | 0.051 (2) | 0.059 (2) | −0.0027 (17) | 0.0039 (17) | 0.0061 (17) |
C3 | 0.092 (3) | 0.056 (2) | 0.072 (3) | −0.009 (2) | −0.001 (2) | 0.012 (2) |
C4 | 0.056 (2) | 0.075 (3) | 0.073 (3) | 0.0110 (19) | 0.0022 (19) | 0.012 (2) |
C5 | 0.056 (3) | 0.095 (4) | 0.105 (4) | −0.003 (2) | −0.015 (2) | 0.022 (3) |
C6 | 0.093 (4) | 0.149 (5) | 0.079 (3) | 0.034 (4) | −0.022 (3) | −0.040 (3) |
C7 | 0.069 (3) | 0.114 (4) | 0.067 (3) | 0.024 (3) | −0.007 (2) | −0.026 (3) |
C8 | 0.053 (2) | 0.051 (2) | 0.087 (3) | −0.0043 (17) | −0.0042 (19) | 0.0028 (19) |
C9 | 0.071 (3) | 0.052 (3) | 0.144 (5) | −0.008 (2) | −0.022 (3) | 0.000 (3) |
Zn1—N1 | 2.109 (3) | N6—C6 | 1.390 (7) |
Zn1—N2 | 2.046 (4) | N6—C5 | 1.398 (8) |
Zn1—N3 | 2.218 (3) | N7—C3i | 1.414 (5) |
Zn1—N4 | 2.081 (4) | N7—C3 | 1.414 (5) |
Zn1—N1i | 2.109 (3) | C2—C3 | 1.320 (5) |
Zn1—N3i | 2.218 (3) | C2—H2 | 0.9300 |
S1—C1 | 1.669 (4) | C3—H3 | 0.9300 |
N1—C1 | 1.202 (5) | C4—C5 | 1.396 (6) |
N2—C2i | 1.363 (4) | C4—H4 | 0.9300 |
N2—C2 | 1.363 (4) | C5—H5 | 0.9300 |
N3—C7 | 1.353 (5) | C6—C7 | 1.379 (6) |
N3—C4 | 1.373 (5) | C6—H6 | 0.9300 |
N4—C8i | 1.356 (4) | C7—H7 | 0.9300 |
N4—C8 | 1.356 (4) | C8—C9 | 1.310 (5) |
N5—C9i | 1.402 (6) | C8—H8 | 0.9300 |
N5—C9 | 1.402 (6) | C9—H9 | 0.9300 |
N1—Zn1—N2 | 91.21 (8) | C3i—N7—C3 | 120.0 (5) |
N1—Zn1—N3 | 89.97 (11) | N1—C1—S1 | 179.7 (3) |
N1—Zn1—N4 | 88.79 (8) | C3—C2—N2 | 121.5 (4) |
N2—Zn1—N3 | 90.30 (7) | C3—C2—H2 | 119.2 |
N2—Zn1—N4 | 180.00 (1) | N2—C2—H2 | 119.2 |
N3—Zn1—N4 | 89.70 (7) | C2—C3—N7 | 118.2 (4) |
N2—Zn1—N1i | 91.21 (8) | C2—C3—H3 | 120.9 |
N4—Zn1—N1i | 88.79 (8) | N7—C3—H3 | 120.9 |
N1—Zn1—N1i | 177.59 (16) | N3—C4—C5 | 123.9 (4) |
N2—Zn1—N3i | 90.30 (7) | N3—C4—H4 | 118.1 |
N4—Zn1—N3i | 89.70 (7) | C5—C4—H4 | 118.1 |
N1—Zn1—N3i | 90.02 (12) | C4—C5—N6 | 118.8 (5) |
N1i—Zn1—N3i | 89.96 (11) | C4—C5—H5 | 120.6 |
N1i—Zn1—N3 | 90.02 (12) | N6—C5—H5 | 120.6 |
N3i—Zn1—N3 | 179.40 (14) | C7—C6—N6 | 120.6 (5) |
C1—N1—Zn1 | 176.4 (3) | C7—C6—H6 | 119.7 |
C2i—N2—C2 | 120.5 (4) | N6—C6—H6 | 119.7 |
C2i—N2—Zn1 | 119.7 (2) | N3—C7—C6 | 123.7 (4) |
C2—N2—Zn1 | 119.7 (2) | N3—C7—H7 | 118.2 |
C7—N3—C4 | 115.6 (3) | C6—C7—H7 | 118.2 |
C7—N3—Zn1 | 122.5 (3) | C9—C8—N4 | 122.0 (4) |
C4—N3—Zn1 | 121.4 (2) | C9—C8—H8 | 119.0 |
C8i—N4—C8 | 119.5 (4) | N4—C8—H8 | 119.0 |
C8i—N4—Zn1 | 120.3 (2) | C8—C9—N5 | 118.3 (4) |
C8—N4—Zn1 | 120.3 (2) | C8—C9—H9 | 120.9 |
C9i—N5—C9 | 119.8 (6) | N5—C9—H9 | 120.9 |
C6—N6—C5 | 117.4 (4) |
Symmetry code: (i) −x, y, −z+3/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
C4—H4···N1i | 0.93 | 2.56 | 3.108 (5) | 118 |
C7—H7···N1 | 0.93 | 2.57 | 3.150 (5) | 121 |
C2—H2···N1 | 0.93 | 2.58 | 3.058 (5) | 112 |
Symmetry code: (i) −x, y, −z+3/2. |
Experimental details
Crystal data | |
Chemical formula | [Zn(NCS)2(C4H4N2)4] |
Mr | 501.90 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 273 |
a, b, c (Å) | 11.251 (4), 14.224 (3), 15.108 (3) |
β (°) | 91.002 (3) |
V (Å3) | 2417.4 (12) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.21 |
Crystal size (mm) | 0.26 × 0.16 × 0.07 |
Data collection | |
Diffractometer | Bruker APEXII area-detector |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.746, 0.919 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7726, 2360, 1660 |
Rint | 0.033 |
(sin θ/λ)max (Å−1) | 0.618 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.048, 0.149, 1.07 |
No. of reflections | 2360 |
No. of parameters | 143 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.52, −0.41 |
Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Siemens, 1996), SHELXTL.
D—H···A | D—H | H···A | D···A | D—H···A |
C4—H4···N1i | 0.93 | 2.56 | 3.108 (5) | 118 |
C7—H7···N1 | 0.93 | 2.57 | 3.150 (5) | 121 |
C2—H2···N1 | 0.93 | 2.58 | 3.058 (5) | 112 |
Symmetry code: (i) −x, y, −z+3/2. |
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.