Acta Cryst. (2009). E65, m1488-m1489 [ doi:10.1107/S1600536809044717 ]
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2N3,N3')(thiocyanato-N)copper(II) chlorideIn the title salt, [Cu(NCS)(C6H6N4)2]Cl, the CuII atom adopts a five-coordinated square-pyramidal geometry consisting of an N atom from a thiocyanate anion and four N atoms from two chealting biimidazole ligands. The thiocyanate ligand occupies the axial position and is, like the CuII centre, located on a mirror plane. The cation and anion are linked into a linear chain by N-H
S and N-HCl hydrogen bonds.
All chemicals were of reagent grade, were commercially available and were used without further purification. CuCl (0.099 g, 0.10 mmol) dissloved in 10.0 ml of ethanol solution was added to 10.0 ml of ethanol solution of H2biim (0.0134 g, 0.10 mmol) with stirring. Half an hour later, KSCN (0.0195 g, 0.20 mmol) was slowly added above the mixture. Black green crystal of [Cu(biim)2(SCN)]Cl were separated from the mother liquor by slow evaporation at room temperature after two weeks.
H atoms attached to C and N(biimidazole) atoms of (I) were placed in geometrically idealized positions with Csp2—H = 0.93Å and N—H=0.86Å and constrained to ride on their parent atoms.
Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL/PC (Sheldrick, 2008); software used to prepare material for publication: publCIF (Westrip, 2009).
![[Figure 1]](./ng2677fig1thm.gif)
| Fig. 1. A view of the structure of (I) with displacement ellipsoids drawn at the 30% probability level. Symmetrical code (i) 2 - x, y, z |
![[Figure 2]](./ng2677fig2thm.gif)
| Fig. 2. The packing view in (I). Cu (Light cyan); Cl (green); S (yellow); N (blue); C (gray) |
| [Cu(NCS)(C6H6N4)2]Cl | F(000) = 860 |
| Mr = 425.37 | Dx = 1.800 Mg m−3 |
| Orthorhombic, Cmc21 | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: C 2c -2 | Cell parameters from 4272 reflections |
| a = 12.900 (5) Å | θ = 2.1–26.6° |
| b = 9.442 (4) Å | µ = 1.71 mm−1 |
| c = 12.888 (5) Å | T = 298 K |
| V = 1569.8 (11) Å3 | Block, green |
| Z = 4 | 0.10 × 0.10 × 0.10 mm |
| Bruker SMART CCD area-detector diffractometer | 1291 independent reflections |
| Radiation source: fine-focus sealed tube | 1254 reflections with I > 2σ(I) |
| graphite | Rint = 0.046 |
| ω scans | θmax = 25.0°, θmin = 3.1° |
| Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −14→15 |
| Tmin = 0.610, Tmax = 0.847 | k = −11→10 |
| 3518 measured reflections | l = −13→15 |
| Refinement on F2 | Secondary atom site location: difference Fourier map |
| Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
| R[F2 > 2σ(F2)] = 0.047 | H-atom parameters constrained |
| wR(F2) = 0.096 | w = 1/[σ2(Fo2) + (0.0005P)2 + 5.3473P] where P = (Fo2 + 2Fc2)/3 |
| S = 1.20 | (Δ/σ)max < 0.001 |
| 1291 reflections | Δρmax = 0.45 e Å−3 |
| 121 parameters | Δρmin = −0.45 e Å−3 |
| 1 restraint | Absolute structure: Flack (1983), 539 Friedel pairs |
| Primary atom site location: structure-invariant direct methods | Flack parameter: 0.06 (3) |
| [Cu(NCS)(C6H6N4)2]Cl | V = 1569.8 (11) Å3 |
| Mr = 425.37 | Z = 4 |
| Orthorhombic, Cmc21 | Mo Kα radiation |
| a = 12.900 (5) Å | µ = 1.71 mm−1 |
| b = 9.442 (4) Å | T = 298 K |
| c = 12.888 (5) Å | 0.10 × 0.10 × 0.10 mm |
| Bruker SMART CCD area-detector diffractometer | 1291 independent reflections |
| Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 1254 reflections with I > 2σ(I) |
| Tmin = 0.610, Tmax = 0.847 | Rint = 0.046 |
| 3518 measured reflections | θmax = 25.0° |
| R[F2 > 2σ(F2)] = 0.047 | H-atom parameters constrained |
| wR(F2) = 0.096 | Δρmax = 0.45 e Å−3 |
| S = 1.20 | Δρmin = −0.45 e Å−3 |
| 1291 reflections | Absolute structure: Flack (1983), 539 Friedel pairs |
| 121 parameters | Flack parameter: 0.06 (3) |
| 1 restraint |
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 | ||
| Cu1 | 0.5000 | 0.39548 (11) | 0.38462 (9) | 0.0307 (3) | |
| S1 | 0.5000 | 0.7886 (3) | 0.1136 (2) | 0.0476 (7) | |
| N1 | 0.6167 (3) | 0.4872 (6) | 0.4638 (4) | 0.0317 (12) | |
| N2 | 0.7857 (4) | 0.4990 (6) | 0.4874 (4) | 0.0316 (13) | |
| H2A | 0.8509 | 0.4821 | 0.4808 | 0.038* | |
| N3 | 0.3808 (4) | 0.2803 (5) | 0.3256 (4) | 0.0294 (12) | |
| N4 | 0.2133 (4) | 0.2519 (6) | 0.3172 (4) | 0.0333 (13) | |
| H4 | 0.1484 | 0.2647 | 0.3294 | 0.040* | |
| N5 | 0.5000 | 0.5634 (10) | 0.2506 (7) | 0.044 (2) | |
| C1 | 0.6381 (5) | 0.5905 (6) | 0.5367 (5) | 0.0321 (15) | |
| H1 | 0.5893 | 0.6466 | 0.5703 | 0.039* | |
| C2 | 0.7418 (5) | 0.5963 (8) | 0.5509 (6) | 0.0369 (18) | |
| H2 | 0.7767 | 0.6563 | 0.5962 | 0.044* | |
| C3 | 0.7087 (4) | 0.4344 (7) | 0.4372 (5) | 0.0302 (15) | |
| C4 | 0.2915 (4) | 0.3246 (6) | 0.3605 (4) | 0.0248 (14) | |
| C5 | 0.3575 (5) | 0.1711 (8) | 0.2579 (5) | 0.0359 (16) | |
| H5 | 0.4062 | 0.1168 | 0.2225 | 0.043* | |
| C6 | 0.2537 (5) | 0.1550 (10) | 0.2509 (6) | 0.0345 (18) | |
| H6 | 0.2176 | 0.0911 | 0.2094 | 0.041* | |
| C7 | 0.5000 | 0.6548 (10) | 0.1940 (8) | 0.034 (2) | |
| Cl1 | 0.0000 | 0.3818 (3) | 0.4227 (2) | 0.0501 (8) |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Cu1 | 0.0153 (5) | 0.0344 (6) | 0.0425 (6) | 0.000 | 0.000 | −0.0068 (6) |
| S1 | 0.0303 (13) | 0.0513 (17) | 0.0612 (19) | 0.000 | 0.000 | 0.0124 (14) |
| N1 | 0.019 (2) | 0.039 (3) | 0.037 (3) | 0.004 (2) | 0.004 (2) | 0.007 (3) |
| N2 | 0.015 (2) | 0.033 (3) | 0.047 (4) | 0.001 (2) | −0.002 (2) | −0.004 (3) |
| N3 | 0.019 (2) | 0.033 (3) | 0.036 (3) | −0.005 (2) | −0.002 (2) | −0.005 (2) |
| N4 | 0.021 (3) | 0.037 (3) | 0.042 (3) | −0.001 (2) | −0.005 (2) | 0.002 (3) |
| N5 | 0.031 (4) | 0.055 (6) | 0.046 (6) | 0.000 | 0.000 | −0.006 (4) |
| C1 | 0.032 (3) | 0.025 (4) | 0.040 (4) | −0.003 (3) | 0.003 (3) | −0.004 (3) |
| C2 | 0.037 (4) | 0.041 (5) | 0.033 (4) | −0.005 (3) | −0.001 (3) | −0.002 (4) |
| C3 | 0.021 (3) | 0.035 (4) | 0.035 (4) | 0.003 (3) | 0.002 (3) | 0.003 (3) |
| C4 | 0.018 (3) | 0.032 (3) | 0.024 (4) | −0.003 (2) | −0.002 (2) | 0.010 (3) |
| C5 | 0.022 (3) | 0.043 (4) | 0.042 (4) | 0.001 (3) | 0.005 (3) | −0.001 (3) |
| C6 | 0.026 (4) | 0.039 (4) | 0.038 (4) | −0.010 (3) | 0.001 (3) | −0.004 (3) |
| C7 | 0.021 (4) | 0.026 (5) | 0.054 (7) | 0.000 | 0.000 | 0.006 (5) |
| Cl1 | 0.0206 (11) | 0.0479 (15) | 0.082 (2) | 0.000 | 0.000 | −0.0179 (14) |
| Cu1—N1 | 2.014 (6) | N4—C4 | 1.342 (7) |
| Cu1—N1i | 2.014 (6) | N4—C6 | 1.356 (10) |
| Cu1—N3 | 2.031 (5) | N4—H4 | 0.8600 |
| Cu1—N3i | 2.031 (5) | N5—C7 | 1.130 (13) |
| Cu1—N5 | 2.344 (10) | C1—C2 | 1.351 (9) |
| S1—C7 | 1.634 (11) | C1—H1 | 0.9300 |
| N1—C3 | 1.332 (7) | C2—H2 | 0.9300 |
| N1—C1 | 1.382 (8) | C3—C4i | 1.432 (8) |
| N2—C3 | 1.333 (8) | C4—C3i | 1.432 (8) |
| N2—C2 | 1.354 (9) | C5—C6 | 1.352 (9) |
| N2—H2A | 0.8600 | C5—H5 | 0.9300 |
| N3—C4 | 1.305 (7) | C6—H6 | 0.9300 |
| N3—C5 | 1.383 (8) | ||
| N1—Cu1—N1i | 96.7 (3) | C6—N4—H4 | 125.7 |
| N1—Cu1—N3 | 170.3 (2) | C7—N5—Cu1 | 172.8 (8) |
| N1i—Cu1—N3 | 81.62 (18) | C2—C1—N1 | 108.6 (6) |
| N1—Cu1—N3i | 81.62 (18) | C2—C1—H1 | 125.7 |
| N1i—Cu1—N3i | 170.3 (2) | N1—C1—H1 | 125.7 |
| N3—Cu1—N3i | 98.4 (3) | C1—C2—N2 | 107.8 (7) |
| N1—Cu1—N5 | 94.7 (2) | C1—C2—H2 | 126.1 |
| N1i—Cu1—N5 | 94.7 (2) | N2—C2—H2 | 126.1 |
| N3—Cu1—N5 | 95.0 (2) | N1—C3—N2 | 111.6 (6) |
| N3i—Cu1—N5 | 95.0 (2) | N1—C3—C4i | 116.5 (6) |
| C3—N1—C1 | 105.1 (5) | N2—C3—C4i | 131.9 (6) |
| C3—N1—Cu1 | 112.0 (5) | N3—C4—N4 | 110.9 (5) |
| C1—N1—Cu1 | 142.9 (4) | N3—C4—C3i | 118.2 (5) |
| C3—N2—C2 | 106.9 (5) | N4—C4—C3i | 131.0 (6) |
| C3—N2—H2A | 126.5 | C6—C5—N3 | 110.0 (7) |
| C2—N2—H2A | 126.5 | C6—C5—H5 | 125.0 |
| C4—N3—C5 | 105.3 (5) | N3—C5—H5 | 125.0 |
| C4—N3—Cu1 | 111.5 (4) | C5—C6—N4 | 105.2 (7) |
| C5—N3—Cu1 | 143.1 (4) | C5—C6—H6 | 127.4 |
| C4—N4—C6 | 108.6 (5) | N4—C6—H6 | 127.4 |
| C4—N4—H4 | 125.7 | N5—C7—S1 | 179.1 (10) |
| N1i—Cu1—N1—C3 | 172.7 (3) | C1—N1—C3—N2 | −0.8 (7) |
| N3i—Cu1—N1—C3 | 2.3 (4) | Cu1—N1—C3—N2 | 177.9 (4) |
| N5—Cu1—N1—C3 | −92.0 (5) | C1—N1—C3—C4i | −179.4 (5) |
| N1i—Cu1—N1—C1 | −9.4 (9) | Cu1—N1—C3—C4i | −0.6 (7) |
| N3i—Cu1—N1—C1 | −179.7 (7) | C2—N2—C3—N1 | 1.1 (8) |
| N5—Cu1—N1—C1 | 85.9 (7) | C2—N2—C3—C4i | 179.4 (6) |
| N1i—Cu1—N3—C4 | 3.8 (4) | C5—N3—C4—N4 | −1.3 (7) |
| N3i—Cu1—N3—C4 | 173.9 (3) | Cu1—N3—C4—N4 | 177.1 (4) |
| N5—Cu1—N3—C4 | −90.3 (4) | C5—N3—C4—C3i | 177.0 (5) |
| N1i—Cu1—N3—C5 | −178.8 (8) | Cu1—N3—C4—C3i | −4.6 (6) |
| N3i—Cu1—N3—C5 | −8.6 (9) | C6—N4—C4—N3 | 0.2 (8) |
| N5—Cu1—N3—C5 | 87.1 (7) | C6—N4—C4—C3i | −177.8 (7) |
| C3—N1—C1—C2 | 0.2 (7) | C4—N3—C5—C6 | 2.0 (8) |
| Cu1—N1—C1—C2 | −177.8 (6) | Cu1—N3—C5—C6 | −175.5 (6) |
| N1—C1—C2—N2 | 0.5 (8) | N3—C5—C6—N4 | −1.9 (9) |
| C3—N2—C2—C1 | −1.0 (8) | C4—N4—C6—C5 | 1.1 (9) |
| Symmetry codes: (i) −x+1, y, z. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N2—H2A···Cl1ii | 0.86 | 2.27 | 3.092 (5) | 160 |
| N4—H4···Cl1 | 0.86 | 2.52 | 3.305 (6) | 153 |
| N2—H2A···S1iii | 0.86 | 3.36 | 3.782 (6) | 113 |
| N4—H4···S1iv | 0.86 | 3.38 | 3.818 (6) | 114 |
| Symmetry codes: (ii) x+1, y, z; (iii) −x+3/2, −y+3/2, z+1/2; (iv) x−1/2, y−1/2, z. |
| Cu1—N1 | 2.014 (6) | Cu1—N5 | 2.344 (10) |
| Cu1—N3 | 2.031 (5) | ||
| N1—Cu1—N1i | 96.7 (3) | N1—Cu1—N5 | 94.7 (2) |
| N1—Cu1—N3 | 170.3 (2) | N3—Cu1—N5 | 95.0 (2) |
| N1i—Cu1—N3 | 81.62 (18) |
| Symmetry codes: (i) −x+1, y, z. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N2—H2A···Cl1ii | 0.86 | 2.27 | 3.092 (5) | 160 |
| N4—H4···Cl1 | 0.86 | 2.52 | 3.305 (6) | 153 |
| N2—H2A···S1iii | 0.86 | 3.36 | 3.782 (6) | 113 |
| N4—H4···S1iv | 0.86 | 3.38 | 3.818 (6) | 114 |
| Symmetry codes: (ii) x+1, y, z; (iii) −x+3/2, −y+3/2, z+1/2; (iv) x−1/2, y−1/2, z. |
The authors acknowledge financial support from the National Natural Science Foundation of China (grant No. 20471033), the Natural Science Foundation of Shanxi Province (grant No. 20051013) and the Overseas Returned Scholar Foundation of Shanxi Province in 2008.
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The neutral molecule 2,2'-biimidazole (H2biim) and its monoanionic derivative(Hbiim-) is a particular organic target for construction of hybrid materials. Its molecular moieties possess a double property, namely they can be coordinated to metal centres and can act as a donor in hydrogen bonding interactions (Tadokoro et al., 2000). The thiocyanate is a versatile briding ligand (Ribas et al., 1998), we think that the self-assembly of these ligand with metal ions should yield structure fascinating compounds. Thus, the title compound (I) was synthesized and its crystal structure is reported here.
The X-ray crystallographic analysis shows that the crystal structure of (I) consists of [Cu(NCS)(biim)2]+ cation and Cl- anions(Fig 1). Cu(II) ion adopts a five coordinated square pyramidal geometry consisting of a nitrogen atom(N5) from thiocyanato anion and four nitrogen atoms (N1, N1i, N3 and N3i) from two coordinating biimidazole ligands. Four nitrogen atoms of two chelating H2biim ligands form the basal plane of the pyramid and the apical position is occupied by the thiocyanate ligand which is coordinated in the axial position through the nitrogen atom. Bond distances of the Cu—N1 and Cu—N3(biim) [2.014 (6) and 2.031 (5) Å](Table 1) are shorter than the apical Cu1—N5(SCN-) distance[2.344 (10) Å]. These distances lie in the range reported for biimidazole-Cu complexes (Govor et al.,2008). The chelating H2biim ligands are almost planar and dihedral angle of two biimidazole plane is 6.32°. Meanwhile, In the crystal,molecules are linked by hydrogen bond interaction (N—H···Cl) forming the three-dimensional architecture(Fig 2).