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Acta Crystallogr Sect E Struct Rep Online. 2010 February 1; 66(Pt 2): m217.
Published online 2010 January 30. doi:  10.1107/S1600536810001431
PMCID: PMC2979958

Poly[(μ2-3,6-di-4-pyridyl-1,2,4,5-tetra­zine)(μ2-thio­cyanato)copper(I)]

Abstract

The title compound, [Cu(NCS)(C12H8N6)]n, is a self-assembled two-dimensional metal–organic network. The Cu atom is linked by two N atoms from two 3,6-di-4-pyridyl-1,2,4,5-tetra­zine ligands and by the N and S atoms from two thio­cyanate ligands in a distorted tetra­hedral environment. The Cu atom and the thio­cyanate ligand occupy a crystallographic mirror plane m, and a crystallographic inversion centre is in the middle of the tetra­zine ring, generating the zigzag fashion of the two-dimensional network. The infinite –Cu—SCN—Cu—SCN– chain is due to translational symmetry along the a axis. These chains are further connected through the 3,6-di-4-pyridyl-1,2,4,5-tetra­zine ligands that bridge the CuI centers, generating a two-dimensional network. There are π—π stacking inter­actions between the pyridine and tetra­zine rings (perpendicular distances of 3.357 and 3.418 Å), with a centroid–centroid distance of 3.6785 (16) Å.

Related literature

For compounds with related architectures, see: Oxtoby et al. (2003 [triangle]); Dinolfo et al. (2004 [triangle]); Hsu et al. (2006 [triangle]); Xue et al. (2008 [triangle]); Withersby et al. (1997 [triangle], 2000 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-66-0m217-scheme1.jpg

Experimental

Crystal data

  • [Cu(NCS)(C12H8N6)]
  • M r = 357.88
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-0m217-efi2.jpg
  • a = 5.8640 (12) Å
  • b = 18.510 (4) Å
  • c = 6.3993 (13) Å
  • β = 104.42 (3)°
  • V = 672.7 (2) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 1.79 mm−1
  • T = 250 K
  • 0.20 × 0.20 × 0.20 mm

Data collection

  • Rigaku Mercury diffractometer
  • Absorption correction: multi-scan (ABSCOR; Higashi, 1995 [triangle]) T min = 0.445, T max = 0.738
  • 3288 measured reflections
  • 1373 independent reflections
  • 1304 reflections with I > 2σ(I)
  • R int = 0.018

Refinement

  • R[F 2 > 2σ(F 2)] = 0.033
  • wR(F 2) = 0.069
  • S = 1.11
  • 1373 reflections
  • 106 parameters
  • H-atom parameters constrained
  • Δρmax = 0.48 e Å−3
  • Δρmin = −0.36 e Å−3

Data collection: CrystalClear (Rigaku, 2008 [triangle]); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXL97.

Table 1
Selected bond lengths (Å)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810001431/si2230sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810001431/si2230Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

This work was supported by the National Natural Science Foundation of China (No. 50472048).

supplementary crystallographic information

Comment

The coordination polymers that based on metal halides and N-donor ligands are one of the most important and promising fields in magnetism, nonlinear optics, electronics, catalysis and molecular topologies (Oxtoby et al., 2003; Hsu et al., 2006), the title compound is an example.

Many different coordination modes' polymers can be obtained by 3,6-di-4-pyridyl-1,2,4,5-tetrazine ligands because it can connect two different metal cations, and the Cu atom in CuSCN can be linked by linear spacer ligands into sheets (Dinolfo et al., 2004; Hsu et al., 2006). We obtained a two-dimensional metal-organic compound as the title complex, C13H8CuN7S (Fig. 1), whose structure contains single [CuSCN] ribbons as a characteristic motif. The asymmetric unit of the title compound consist of a half 3,6-di-4-pyridyl-1,2,4,5-tetrazine ligand, half a copper(I) and one SCN . group. Each Cu atom connected by three N atoms and one S atom, give rise to a distorted tetrahedron (Table 1). The layers can be described as formed by two types of perpendicular zigzag like chains crossing at the CuI centers. Chains of the first type run along the b-axis and have 3,6-di-4-pyridyl-1,2,4,5-tetrazine as a bridging ligand, while the second type extend along the a-axis containing bridging thiocyanate ligands. The structure is stabilized through π—π stacking interactions which can be imagined in Figure 2, with perpendicular distances between pyridine and tetrazine rings of 3.357 Å [symmetry code for Cg2tetrazine: x, y, -1 + z), and of 3.418 Å [symmetry code for Cg1pyridine: x, y, 1 + z); the Cg1···Cg2 distance is 3.6785 (16) Å. Cg1 and Cg2 are the centroids of rings (N1, C1, C3, C2, C6, C5) and (N3, C4, N4, N3iv, C4iv, N4iv), symmetry code iv = -1 - x, -y, 1 - z.

Experimental

CuSCN (12.2 mg) and NH4SCN(1.4 mg) were added into 2.5 ml DMF and the solution were stirred for 10 min at room temperature until became clarification. Then, the resulting solution was subsequently filterated to a tube, then 2.5 ml solution of i.-pron and 3,6-di-4-pyridyl-1,2,4,5-tetrazine added to afford a black filtrate. Many prismatic black crystals were obtained a few weeks later.

Refinement

H atoms were positioned geometrically and refined as a riding model, with Uiso(H) = 1.2Ueq (pyridyl C atoms). The C—H bond lengths are 0.93 Å.

Figures

Fig. 1.
A section of the two-dimensional structure of the title complex, with atom labels and 30% probability displacement ellipsoids. H atoms have been omitted. [symmetry codes: i = -1 + x, y, z; ii = 1 + x, y, z; iii = x, 1/2 - y, z; iv = -1 - x, -y, 1 - z.] ...
Fig. 2.
The unit cell packing diagram.

Crystal data

[Cu(NCS)(C12H8N6)]F(000) = 360
Mr = 357.88Dx = 1.767 Mg m3
Monoclinic, P21/mMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybCell parameters from 2914 reflections
a = 5.8640 (12) Åθ = 3.3–28.9°
b = 18.510 (4) ŵ = 1.79 mm1
c = 6.3993 (13) ÅT = 250 K
β = 104.42 (3)°Prism, black
V = 672.7 (2) Å30.20 × 0.20 × 0.20 mm
Z = 2

Data collection

Rigaku Mercury diffractometer1373 independent reflections
Radiation source: fine-focus sealed tube1304 reflections with I > 2σ(I)
graphiteRint = 0.018
Detector resolution: 28.5714 pixels mm-1θmax = 26.4°, θmin = 3.3°
dtprofit.ref scansh = −7→5
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)k = −22→20
Tmin = 0.445, Tmax = 0.738l = −8→7
3288 measured reflections

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.033Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.069H-atom parameters constrained
S = 1.11w = 1/[σ2(Fo2) + (0.0163P)2 + 0.7211P] where P = (Fo2 + 2Fc2)/3
1373 reflections(Δ/σ)max < 0.001
106 parametersΔρmax = 0.48 e Å3
0 restraintsΔρmin = −0.36 e Å3

Special details

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)

xyzUiso*/Ueq
Cu1−0.50890 (7)0.2500−0.44195 (7)0.03870 (15)
S1−0.83431 (16)0.2500−0.71812 (15)0.0502 (3)
N1−0.5137 (3)0.16473 (11)−0.2265 (3)0.0379 (5)
N2−1.2068 (5)0.2500−0.5169 (5)0.0454 (7)
N3−0.7033 (4)0.00418 (13)0.3425 (3)0.0465 (5)
N4−0.3006 (4)0.03426 (13)0.4828 (3)0.0467 (5)
C1−0.7064 (4)0.12996 (14)−0.2042 (4)0.0407 (6)
H1A−0.84410.1346−0.31310.049*
C2−0.5081 (4)0.07992 (13)0.1348 (4)0.0351 (5)
C3−0.7118 (4)0.08763 (14)−0.0286 (4)0.0407 (6)
H3A−0.85000.0646−0.01980.049*
C4−0.5051 (4)0.03705 (13)0.3302 (4)0.0373 (5)
C5−0.3166 (5)0.15430 (15)−0.0716 (4)0.0436 (6)
H5A−0.17890.1761−0.08710.052*
C6−0.3058 (4)0.11312 (14)0.1092 (4)0.0417 (6)
H6A−0.16430.10770.21290.050*
C7−1.0503 (6)0.2500−0.5953 (5)0.0374 (8)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Cu10.0309 (2)0.0500 (3)0.0350 (2)0.0000.00798 (17)0.000
S10.0272 (4)0.0901 (8)0.0326 (5)0.0000.0059 (3)0.000
N10.0372 (11)0.0403 (11)0.0357 (11)0.0029 (9)0.0079 (9)0.0063 (9)
N20.0297 (15)0.057 (2)0.0506 (19)0.0000.0111 (14)0.000
N30.0462 (13)0.0554 (14)0.0363 (11)−0.0009 (11)0.0070 (9)0.0117 (10)
N40.0458 (13)0.0558 (14)0.0369 (11)−0.0005 (11)0.0075 (10)0.0097 (10)
C10.0349 (13)0.0462 (14)0.0386 (13)0.0031 (11)0.0047 (10)0.0071 (11)
C20.0429 (13)0.0324 (12)0.0305 (11)0.0032 (10)0.0101 (10)−0.0016 (10)
C30.0353 (12)0.0444 (14)0.0432 (14)0.0002 (11)0.0112 (11)0.0081 (11)
C40.0430 (14)0.0361 (13)0.0334 (12)0.0040 (11)0.0105 (10)−0.0004 (10)
C50.0376 (13)0.0484 (15)0.0426 (14)−0.0044 (12)0.0060 (11)0.0072 (12)
C60.0391 (13)0.0483 (15)0.0340 (13)−0.0009 (11)0.0024 (10)0.0035 (11)
C70.0297 (17)0.046 (2)0.0330 (17)0.0000.0008 (14)0.000

Geometric parameters (Å, °)

Cu1—N2i1.948 (3)N4—N3iv1.321 (3)
Cu1—N1ii2.100 (2)N4—C41.346 (3)
Cu1—N12.100 (2)C1—C31.377 (3)
Cu1—S12.2550 (13)C1—H1A0.9300
S1—C71.648 (4)C2—C61.381 (3)
N1—C51.336 (3)C2—C31.385 (3)
N1—C11.339 (3)C2—C41.477 (3)
N2—C71.150 (4)C3—H3A0.9300
N2—Cu1iii1.948 (3)C5—C61.374 (3)
N3—N4iv1.321 (3)C5—H5A0.9300
N3—C41.332 (3)C6—H6A0.9300
N2i—Cu1—N1ii108.87 (8)C6—C2—C3118.0 (2)
N2i—Cu1—N1108.87 (8)C6—C2—C4120.7 (2)
N1ii—Cu1—N197.43 (11)C3—C2—C4121.4 (2)
N2i—Cu1—S1116.81 (10)C1—C3—C2119.0 (2)
N1ii—Cu1—S1111.55 (6)C1—C3—H3A120.5
N1—Cu1—S1111.55 (6)C2—C3—H3A120.5
C7—S1—Cu1103.11 (12)N3—C4—N4125.0 (2)
C5—N1—C1116.6 (2)N3—C4—C2118.0 (2)
C5—N1—Cu1116.43 (17)N4—C4—C2117.1 (2)
C1—N1—Cu1125.52 (16)N1—C5—C6123.7 (2)
C7—N2—Cu1iii168.8 (3)N1—C5—H5A118.1
N4iv—N3—C4117.7 (2)C6—C5—H5A118.1
N3iv—N4—C4117.3 (2)C5—C6—C2119.1 (2)
N1—C1—C3123.5 (2)C5—C6—H6A120.5
N1—C1—H1A118.2C2—C6—H6A120.5
C3—C1—H1A118.2N2—C7—S1177.5 (3)

Symmetry codes: (i) x+1, y, z; (ii) x, −y+1/2, z; (iii) x−1, y, z; (iv) −x−1, −y, −z+1.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: SI2230).

References

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Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography