supplementary materials
(3,3'-Diamino-2,2'-bipyridine-![[kappa]](/logos/entities/kappa_rmgif.gif)
2N,N')bis(thiocyanato-N)copper(II)
Cu(ClO4)2·6H2O (0.0637 g, 0.172 mmol) and NaSCN (0.0139 g, 0.172 mmol) were dissoved in 5 ml H2O, respectively, and stirred for a few minutes. The solution was poured into 5 ml acetonitrile solution containing 3,3'-diamino-2,2'-bipyridine (0.0160 g, 0.0860 mmol), and the mixed solution was stirred for a few minutes. The green single crystals were obtained after the solution had been allowed to stand at room temperature for two weeks. The IR peaks at 1640 cm−1, 1566 cm−1, 1465 cm−1 and 1383 cm−1 may be attributed to the stretching vibrations of the C=C, C=N and NH2 groups, whereas strong and sharp peak at 2090 cm−1 obviously is from the stretching vibration of thiocyanate group.
All H atoms were placed in calculated positions, and refined as riding, with C—H = 0.93 Å, Uiso(H) = 1.2eq(C) for pyridine ring; N—H = 0.86 Å, Uiso(H) = 1.2 (N) for amino group.
Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Bruker, 2001); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
(3,3'-Diamino-2,2'-bipyridine-
κ2N,
N')bis(thiocyanato-
κN)copper(II)
top
Crystal data top
| [Cu(NCS)2(C10H10N4)] | F000 = 740 |
| Mr = 365.92 | Dx = 1.731 Mg m−3 |
| Monoclinic, C2/c | Mo Kα radiation
λ = 0.71073 Å |
| Hall symbol: -C 2yc | Cell parameters from 1907 reflections |
| a = 8.8127 (18) Å | θ = 2.7–27.3º |
| b = 14.991 (3) Å | µ = 1.85 mm−1 |
| c = 10.627 (2) Å | T = 298 (2) K |
| β = 90.738 (3)º | Block, green |
| V = 1403.8 (5) Å3 | 0.38 × 0.36 × 0.30 mm |
| Z = 4 | |
Data collection top
Bruker SMART APEX CCD
diffractometer | 1450 independent reflections |
| Radiation source: fine-focus sealed tube | 1285 reflections with I > 2σ(I) |
| Monochromator: graphite | Rint = 0.019 |
| T = 298(2) K | θmax = 26.5º |
| φ and ω scans | θmin = 2.7º |
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996) | h = −11→8 |
| Tmin = 0.539, Tmax = 0.606 | k = −17→18 |
| 3905 measured reflections | l = −12→13 |
Refinement top
| 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)] = 0.033 | H-atom parameters constrained |
| wR(F2) = 0.088 | w = 1/[σ2(Fo2) + (0.0466P)2 + 1.0653P]
where P = (Fo2 + 2Fc2)/3 |
| S = 1.05 | (Δ/σ)max = 0.001 |
| 1450 reflections | Δρmax = 0.34 e Å−3 |
| 96 parameters | Δρmin = −0.18 e Å−3 |
| Primary atom site location: structure-invariant direct methods | Extinction correction: none |
Crystal data top
| [Cu(NCS)2(C10H10N4)] | V = 1403.8 (5) Å3 |
| Mr = 365.92 | Z = 4 |
| Monoclinic, C2/c | Mo Kα |
| a = 8.8127 (18) Å | µ = 1.85 mm−1 |
| b = 14.991 (3) Å | T = 298 (2) K |
| c = 10.627 (2) Å | 0.38 × 0.36 × 0.30 mm |
| β = 90.738 (3)º | |
Data collection top
Bruker SMART APEX CCD
diffractometer | 1450 independent reflections |
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996) | 1285 reflections with I > 2σ(I) |
| Tmin = 0.539, Tmax = 0.606 | Rint = 0.019 |
| 3905 measured reflections | |
Refinement top
| R[F2 > 2σ(F2)] = 0.033 | 96 parameters |
| wR(F2) = 0.088 | H-atom parameters constrained |
| S = 1.05 | Δρmax = 0.34 e Å−3 |
| 1450 reflections | Δρmin = −0.18 e Å−3 |
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| | x | y | z | Uiso*/Ueq | |
| Cu1 | 0.0000 | 0.39730 (3) | 0.7500 | 0.04805 (18) | |
| S1 | 0.21601 (8) | 0.62017 (5) | 1.00428 (7) | 0.0497 (2) | |
| N1 | 0.1402 (2) | 0.29769 (13) | 0.78613 (17) | 0.0366 (4) | |
| C2 | 0.3693 (3) | 0.2373 (2) | 0.8676 (2) | 0.0464 (6) | |
| H2 | 0.4711 | 0.2450 | 0.8893 | 0.056* | |
| N2 | 0.1172 (3) | 0.48687 (15) | 0.8415 (2) | 0.0509 (5) | |
| C6 | 0.1577 (3) | 0.54235 (16) | 0.9084 (2) | 0.0381 (5) | |
| N3 | 0.0829 (3) | 0.06250 (16) | 0.8619 (3) | 0.0636 (7) | |
| H3A | 0.1330 | 0.0207 | 0.8992 | 0.076* | |
| H3B | −0.0101 | 0.0539 | 0.8395 | 0.076* | |
| C5 | 0.0762 (2) | 0.21557 (15) | 0.78060 (19) | 0.0339 (5) | |
| C1 | 0.2826 (3) | 0.30898 (18) | 0.8271 (2) | 0.0443 (6) | |
| H1 | 0.3243 | 0.3660 | 0.8284 | 0.053* | |
| C4 | 0.1515 (3) | 0.14310 (16) | 0.8380 (2) | 0.0418 (5) | |
| C3 | 0.3032 (3) | 0.15565 (18) | 0.8753 (2) | 0.0462 (6) | |
| H3 | 0.3593 | 0.1075 | 0.9056 | 0.055* | |
Atomic displacement parameters (Å2) top| | U11 | U22 | U33 | U12 | U13 | U23 |
| Cu1 | 0.0534 (3) | 0.0320 (2) | 0.0580 (3) | 0.000 | −0.0273 (2) | 0.000 |
| S1 | 0.0562 (4) | 0.0435 (4) | 0.0492 (4) | −0.0030 (3) | −0.0126 (3) | −0.0086 (3) |
| N1 | 0.0383 (10) | 0.0386 (10) | 0.0328 (9) | 0.0013 (8) | −0.0093 (8) | 0.0003 (8) |
| C2 | 0.0357 (13) | 0.0640 (18) | 0.0394 (14) | 0.0077 (11) | −0.0046 (10) | −0.0025 (12) |
| N2 | 0.0589 (13) | 0.0373 (11) | 0.0560 (13) | −0.0041 (10) | −0.0179 (10) | −0.0018 (10) |
| C6 | 0.0373 (12) | 0.0350 (12) | 0.0419 (13) | 0.0011 (9) | −0.0067 (10) | 0.0059 (10) |
| N3 | 0.0594 (15) | 0.0423 (13) | 0.0888 (19) | 0.0083 (11) | −0.0059 (13) | 0.0216 (12) |
| C5 | 0.0377 (12) | 0.0354 (12) | 0.0283 (10) | 0.0011 (9) | −0.0031 (9) | −0.0015 (9) |
| C1 | 0.0416 (13) | 0.0500 (15) | 0.0410 (13) | −0.0047 (10) | −0.0076 (10) | −0.0001 (11) |
| C4 | 0.0469 (13) | 0.0386 (13) | 0.0399 (12) | 0.0074 (10) | 0.0011 (10) | −0.0002 (10) |
| C3 | 0.0451 (14) | 0.0535 (15) | 0.0401 (13) | 0.0184 (12) | 0.0009 (10) | 0.0017 (11) |
Geometric parameters (Å, °) top
| Cu1—N2 | 1.947 (2) | N2—C6 | 1.147 (3) |
| Cu1—N2i | 1.947 (2) | N3—C4 | 1.376 (3) |
| Cu1—N1i | 1.9728 (19) | N3—H3A | 0.8600 |
| Cu1—N1 | 1.9728 (19) | N3—H3B | 0.8600 |
| S1—C6 | 1.628 (3) | C5—C4 | 1.408 (3) |
| N1—C1 | 1.333 (3) | C5—C5i | 1.484 (4) |
| N1—C5 | 1.355 (3) | C1—H1 | 0.9300 |
| C2—C3 | 1.359 (4) | C4—C3 | 1.402 (3) |
| C2—C1 | 1.384 (4) | C3—H3 | 0.9300 |
| C2—H2 | 0.9300 | | |
| | | |
| N2—Cu1—N2i | 92.80 (13) | C4—N3—H3B | 120.0 |
| N2—Cu1—N1i | 161.13 (9) | H3A—N3—H3B | 120.0 |
| N2i—Cu1—N1i | 95.61 (9) | N1—C5—C4 | 119.24 (19) |
| N2—Cu1—N1 | 95.61 (9) | N1—C5—C5i | 113.13 (12) |
| N2i—Cu1—N1 | 161.13 (9) | C4—C5—C5i | 127.48 (14) |
| N1i—Cu1—N1 | 81.60 (11) | N1—C1—C2 | 121.1 (2) |
| C1—N1—C5 | 121.3 (2) | N1—C1—H1 | 119.4 |
| C1—N1—Cu1 | 123.49 (17) | C2—C1—H1 | 119.4 |
| C5—N1—Cu1 | 114.82 (14) | N3—C4—C3 | 119.0 (2) |
| C3—C2—C1 | 118.8 (2) | N3—C4—C5 | 123.5 (2) |
| C3—C2—H2 | 120.6 | C3—C4—C5 | 117.5 (2) |
| C1—C2—H2 | 120.6 | C2—C3—C4 | 120.8 (2) |
| C6—N2—Cu1 | 165.4 (2) | C2—C3—H3 | 119.6 |
| N2—C6—S1 | 179.3 (2) | C4—C3—H3 | 119.6 |
| C4—N3—H3A | 120.0 | | |
| | | |
| N2—Cu1—N1—C1 | −16.6 (2) | Cu1—N1—C5—C5i | 13.7 (3) |
| N2i—Cu1—N1—C1 | 99.5 (3) | C5—N1—C1—C2 | −1.2 (3) |
| N1i—Cu1—N1—C1 | −177.8 (2) | Cu1—N1—C1—C2 | 170.89 (18) |
| N2—Cu1—N1—C5 | 155.98 (16) | C3—C2—C1—N1 | −5.5 (4) |
| N2i—Cu1—N1—C5 | −88.0 (3) | N1—C5—C4—N3 | 165.2 (2) |
| N1i—Cu1—N1—C5 | −5.21 (11) | C5i—C5—C4—N3 | −10.0 (4) |
| N2i—Cu1—N2—C6 | 71.6 (8) | N1—C5—C4—C3 | −13.0 (3) |
| N1i—Cu1—N2—C6 | −44.8 (10) | C5i—C5—C4—C3 | 171.8 (3) |
| N1—Cu1—N2—C6 | −125.3 (8) | C1—C2—C3—C4 | 2.6 (4) |
| C1—N1—C5—C4 | 10.6 (3) | N3—C4—C3—C2 | −171.8 (2) |
| Cu1—N1—C5—C4 | −162.18 (16) | C5—C4—C3—C2 | 6.5 (3) |
| C1—N1—C5—C5i | −173.6 (2) | | |
| Symmetry codes: (i) −x, y, −z+3/2. |
Hydrogen-bond geometry (Å, °) top
| D—H···A | D—H | H···A | D···A | D—H···A |
| N3—H3A···S1ii | 0.86 | 2.69 | 3.550 (2) | 174 |
| N3—H3B···N3i | 0.86 | 2.23 | 2.775 (4) | 121 |
| C1—H1···N2 | 0.93 | 2.58 | 3.044 (4) | 112 |
| Symmetry codes: (ii) −x+1/2, −y+1/2, −z+2; (i) −x, y, −z+3/2. |
Table 1
Selected geometric parameters (Å, °) top| Cu1—N2 | 1.947 (2) | Cu1—N1 | 1.9728 (19) |
| | | |
| N2—Cu1—N2i | 92.80 (13) | N2—Cu1—N1 | 95.61 (9) |
| N2—Cu1—N1i | 161.13 (9) | N1i—Cu1—N1 | 81.60 (11) |
| Symmetry codes: (i) −x, y, −z+3/2. |
Table 2
Hydrogen-bond geometry (Å, °) top
| D—H···A | D—H | H···A | D···A | D—H···A |
| N3—H3A···S1ii | 0.86 | 2.69 | 3.550 (2) | 174 |
| N3—H3B···N3i | 0.86 | 2.23 | 2.775 (4) | 121 |
| C1—H1···N2 | 0.93 | 2.58 | 3.044 (4) | 112 |
| Symmetry codes: (ii) −x+1/2, −y+1/2, −z+2; (i) −x, y, −z+3/2. |
The authors thank the Natural Science Foundation of Shandong Province of China (grant No. Y2005B25).
Bruker (1997). SMART (Version 5.6) and SAINT (Version 5.A06). Bruker AXS Inc., Madison, Wisconsin, USA.
Bruker (2001). SHELXTL (Version 6.12). Bruker AXS Inc., Madison, Wisconsin, USA.
Rice, C. R., Onions, S., Vidal, N., Wallis, J. D., Senna, M. C., Pilkington, M. & Stoeckli-Evans, H. (2002). Eur. J. Inorg. Chem. pp. 1985–1997.
Sheldrick, G. M. (1996). SADABS (Version 2.10). University of Göttingen, Germany.
Shi, J.-M., Chen, J.-N. & Liu, L.-D. (2006a). Acta Cryst. E62, m2151–m2152.
Shi, J.-M., Chen, J.-N. & Liu, L.-D. (2006b). Acta Cryst. E62, m2094–m2095.
![[pi]](/logos/entities/pi_rmgif.gif)
-
N, N-H![[Figure 1]](./bt2392fig1thm.gif)
![[Figure 2]](./bt2392fig2thm.gif)
As a derivative of 2,2'-bipyridine 3,3'-diamino-2,'2-bipyridine may function as a useful chelating multi-dentate ligand, and a few complexes dealing with this ligand have been published (Rice et al., 2002; Shi et al., 2006a; Shi et al., 2006b), in which there are two mono-nuclear CuII complexes. Here we report another CuII mono-nuclear complex (Fig. 1).
Fig. 1 shows the asymmetric unit with the CuII atom in a four-coordinate geometry. The Cu/N1/N1i plane is tilted with respect to the CuN2N2i plane by a dihedral angle of 26.29 (16)°. The bond angles at the Cu atom (Table 1) also show the extent of the distortion of the coordinated geometry from square planar. In the uncoordinated 3,3'-diamino-2,'2-bipyridine all non-hydrogen atoms are located in a plane and two amino groups are in trans-configuration, whereas in the title compound the dihedral angle between the two pyridine ring planes is 22.15 (7)°. There is a π-π stacking interaction between adjacent pyridine rings, with a centroid···centroid distance of 3.7302 (14)Å and an interplanar distance of 3.311 Å [symmetry code: 1/2 - X, 1/2 - Y, 2 - Z]. In addition, there are intra- and intermolecular hydrogen bonds.