Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807029030/bt2392sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807029030/bt2392Isup2.hkl |
CCDC reference: 654789
Key indicators
- Single-crystal X-ray study
- T = 298 K
- Mean (C-C) = 0.004 Å
- R factor = 0.033
- wR factor = 0.088
- Data-to-parameter ratio = 15.1
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT062_ALERT_4_C Rescale T(min) & T(max) by ..................... 0.95 PLAT230_ALERT_2_C Hirshfeld Test Diff for S1 - C6 .. 6.16 su PLAT416_ALERT_2_C Short Intra D-H..H-D H3B .. H3B .. 1.91 Ang.
Alert level G ABSTM02_ALERT_3_G When printed, the submitted absorption T values will be replaced by the scaled T values. Since the ratio of scaled T's is identical to the ratio of reported T values, the scaling does not imply a change to the absorption corrections used in the study. Ratio of Tmax expected/reported 0.946 Tmax scaled 0.573 Tmin scaled 0.510 PLAT794_ALERT_5_G Check Predicted Bond Valency for Cu1 (1) 1.22
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 3 ALERT level C = Check and explain 2 ALERT level G = General alerts; check 0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 2 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 1 ALERT type 4 Improvement, methodology, query or suggestion 1 ALERT type 5 Informative message, check
For the crystal structures of related complexes, see: Rice et al. (2002); Shi et al. (2006a,b).
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.
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.
For the crystal structures of related complexes, see: Rice et al. (2002); Shi et al. (2006a,b).
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.
[Cu(NCS)2(C10H10N4)] | F(000) = 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 = 2.7–27.3° |
b = 14.991 (3) Å | µ = 1.85 mm−1 |
c = 10.627 (2) Å | T = 298 K |
β = 90.738 (3)° | Block, green |
V = 1403.8 (5) Å3 | 0.38 × 0.36 × 0.30 mm |
Z = 4 |
Bruker SMART APEX CCD diffractometer | 1450 independent reflections |
Radiation source: fine-focus sealed tube | 1285 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.019 |
φ and ω scans | θmax = 26.5°, θmin = 2.7° |
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 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)] = 0.033 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.088 | H-atom parameters constrained |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0466P)2 + 1.0653P] where P = (Fo2 + 2Fc2)/3 |
1450 reflections | (Δ/σ)max = 0.001 |
96 parameters | Δρmax = 0.34 e Å−3 |
0 restraints | Δρmin = −0.18 e Å−3 |
[Cu(NCS)2(C10H10N4)] | V = 1403.8 (5) Å3 |
Mr = 365.92 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 8.8127 (18) Å | µ = 1.85 mm−1 |
b = 14.991 (3) Å | T = 298 K |
c = 10.627 (2) Å | 0.38 × 0.36 × 0.30 mm |
β = 90.738 (3)° |
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 |
R[F2 > 2σ(F2)] = 0.033 | 0 restraints |
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 |
96 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 | ||
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* |
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) |
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 code: (i) −x, y, −z+3/2. |
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: (i) −x, y, −z+3/2; (ii) −x+1/2, −y+1/2, −z+2. |
Experimental details
Crystal data | |
Chemical formula | [Cu(NCS)2(C10H10N4)] |
Mr | 365.92 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 298 |
a, b, c (Å) | 8.8127 (18), 14.991 (3), 10.627 (2) |
β (°) | 90.738 (3) |
V (Å3) | 1403.8 (5) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.85 |
Crystal size (mm) | 0.38 × 0.36 × 0.30 |
Data collection | |
Diffractometer | Bruker SMART APEX CCD |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.539, 0.606 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3905, 1450, 1285 |
Rint | 0.019 |
(sin θ/λ)max (Å−1) | 0.628 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.033, 0.088, 1.05 |
No. of reflections | 1450 |
No. of parameters | 96 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.34, −0.18 |
Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SAINT, SHELXTL (Bruker, 2001), SHELXTL.
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 code: (i) −x, y, −z+3/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H3A···S1ii | 0.86 | 2.69 | 3.550 (2) | 174.3 |
N3—H3B···N3i | 0.86 | 2.23 | 2.775 (4) | 121 |
C1—H1···N2 | 0.93 | 2.58 | 3.044 (4) | 112 |
Symmetry codes: (i) −x, y, −z+3/2; (ii) −x+1/2, −y+1/2, −z+2. |
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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.