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The title mononuclear complex, [Cu(NCS)2(C10H10N4)], is located on a twofold rotation axis. The CuII ion assumes a tetra­hedrally distorted square-planar coordination geometry. Two thio­cyanate (NCS) anions and two N atoms from pyridine (py) rings coordinate in a cis manner to the CuII ion with a dihedral angle of 26.29 (16) Å between the Cu/Npy/Npy and Cu/NNCS/NNCS planes. There is a π–π stacking inter­action between neighbouring pyridine rings [with a centroid–centroid distance of 3.7302 (14) Å and an interplanar distance of 3.311 Å] and N—H...N, N—H...S and C—H...N hydrogen bonds.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807029030/bt2392sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807029030/bt2392Isup2.hkl
Contains datablock I

CCDC reference: 654789

Key indicators

  • Single-crystal X-ray study
  • T = 298 K
  • Mean [sigma](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

Comment top

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.

Related literature top

For the crystal structures of related complexes, see: Rice et al. (2002); Shi et al. (2006a,b).

Experimental top

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.

Refinement top

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.

Structure description top

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).

Computing details top

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.

Figures top
[Figure 1] Fig. 1. Complex structure of (I) showing the atom numbering scheme with thermal ellipsoids drawn at the 30% probability level. [Symmetry codes: (i) -x, y, -z + 3/2].
[Figure 2] Fig. 2. Packing diagram with hydrogen bonds shown as dashed lines.
(3,3'-Diamino-2,2'-bipyridine-κ2N,N')bis(thiocyanato-κN)copper(II) top
Crystal data top
[Cu(NCS)2(C10H10N4)]F(000) = 740
Mr = 365.92Dx = 1.731 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 1907 reflections
a = 8.8127 (18) Åθ = 2.7–27.3°
b = 14.991 (3) ŵ = 1.85 mm1
c = 10.627 (2) ÅT = 298 K
β = 90.738 (3)°Block, green
V = 1403.8 (5) Å30.38 × 0.36 × 0.30 mm
Z = 4
Data collection top
Bruker SMART APEX CCD
diffractometer
1450 independent reflections
Radiation source: fine-focus sealed tube1285 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.019
φ and ω scansθmax = 26.5°, θmin = 2.7°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
h = 118
Tmin = 0.539, Tmax = 0.606k = 1718
3905 measured reflectionsl = 1213
Refinement top
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) = 0.088H-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 parametersΔρmax = 0.34 e Å3
0 restraintsΔρmin = 0.18 e Å3
Crystal data top
[Cu(NCS)2(C10H10N4)]V = 1403.8 (5) Å3
Mr = 365.92Z = 4
Monoclinic, C2/cMo Kα radiation
a = 8.8127 (18) ŵ = 1.85 mm1
b = 14.991 (3) ÅT = 298 K
c = 10.627 (2) Å0.38 × 0.36 × 0.30 mm
β = 90.738 (3)°
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 = 0.606Rint = 0.019
3905 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0330 restraints
wR(F2) = 0.088H-atom parameters constrained
S = 1.05Δρmax = 0.34 e Å3
1450 reflectionsΔρmin = 0.18 e Å3
96 parameters
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
xyzUiso*/Ueq
Cu10.00000.39730 (3)0.75000.04805 (18)
S10.21601 (8)0.62017 (5)1.00428 (7)0.0497 (2)
N10.1402 (2)0.29769 (13)0.78613 (17)0.0366 (4)
C20.3693 (3)0.2373 (2)0.8676 (2)0.0464 (6)
H20.47110.24500.88930.056*
N20.1172 (3)0.48687 (15)0.8415 (2)0.0509 (5)
C60.1577 (3)0.54235 (16)0.9084 (2)0.0381 (5)
N30.0829 (3)0.06250 (16)0.8619 (3)0.0636 (7)
H3A0.13300.02070.89920.076*
H3B0.01010.05390.83950.076*
C50.0762 (2)0.21557 (15)0.78060 (19)0.0339 (5)
C10.2826 (3)0.30898 (18)0.8271 (2)0.0443 (6)
H10.32430.36600.82840.053*
C40.1515 (3)0.14310 (16)0.8380 (2)0.0418 (5)
C30.3032 (3)0.15565 (18)0.8753 (2)0.0462 (6)
H30.35930.10750.90560.055*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.0534 (3)0.0320 (2)0.0580 (3)0.0000.0273 (2)0.000
S10.0562 (4)0.0435 (4)0.0492 (4)0.0030 (3)0.0126 (3)0.0086 (3)
N10.0383 (10)0.0386 (10)0.0328 (9)0.0013 (8)0.0093 (8)0.0003 (8)
C20.0357 (13)0.0640 (18)0.0394 (14)0.0077 (11)0.0046 (10)0.0025 (12)
N20.0589 (13)0.0373 (11)0.0560 (13)0.0041 (10)0.0179 (10)0.0018 (10)
C60.0373 (12)0.0350 (12)0.0419 (13)0.0011 (9)0.0067 (10)0.0059 (10)
N30.0594 (15)0.0423 (13)0.0888 (19)0.0083 (11)0.0059 (13)0.0216 (12)
C50.0377 (12)0.0354 (12)0.0283 (10)0.0011 (9)0.0031 (9)0.0015 (9)
C10.0416 (13)0.0500 (15)0.0410 (13)0.0047 (10)0.0076 (10)0.0001 (11)
C40.0469 (13)0.0386 (13)0.0399 (12)0.0074 (10)0.0011 (10)0.0002 (10)
C30.0451 (14)0.0535 (15)0.0401 (13)0.0184 (12)0.0009 (10)0.0017 (11)
Geometric parameters (Å, º) top
Cu1—N21.947 (2)N2—C61.147 (3)
Cu1—N2i1.947 (2)N3—C41.376 (3)
Cu1—N1i1.9728 (19)N3—H3A0.8600
Cu1—N11.9728 (19)N3—H3B0.8600
S1—C61.628 (3)C5—C41.408 (3)
N1—C11.333 (3)C5—C5i1.484 (4)
N1—C51.355 (3)C1—H10.9300
C2—C31.359 (4)C4—C31.402 (3)
C2—C11.384 (4)C3—H30.9300
C2—H20.9300
N2—Cu1—N2i92.80 (13)C4—N3—H3B120.0
N2—Cu1—N1i161.13 (9)H3A—N3—H3B120.0
N2i—Cu1—N1i95.61 (9)N1—C5—C4119.24 (19)
N2—Cu1—N195.61 (9)N1—C5—C5i113.13 (12)
N2i—Cu1—N1161.13 (9)C4—C5—C5i127.48 (14)
N1i—Cu1—N181.60 (11)N1—C1—C2121.1 (2)
C1—N1—C5121.3 (2)N1—C1—H1119.4
C1—N1—Cu1123.49 (17)C2—C1—H1119.4
C5—N1—Cu1114.82 (14)N3—C4—C3119.0 (2)
C3—C2—C1118.8 (2)N3—C4—C5123.5 (2)
C3—C2—H2120.6C3—C4—C5117.5 (2)
C1—C2—H2120.6C2—C3—C4120.8 (2)
C6—N2—Cu1165.4 (2)C2—C3—H3119.6
N2—C6—S1179.3 (2)C4—C3—H3119.6
C4—N3—H3A120.0
N2—Cu1—N1—C116.6 (2)Cu1—N1—C5—C5i13.7 (3)
N2i—Cu1—N1—C199.5 (3)C5—N1—C1—C21.2 (3)
N1i—Cu1—N1—C1177.8 (2)Cu1—N1—C1—C2170.89 (18)
N2—Cu1—N1—C5155.98 (16)C3—C2—C1—N15.5 (4)
N2i—Cu1—N1—C588.0 (3)N1—C5—C4—N3165.2 (2)
N1i—Cu1—N1—C55.21 (11)C5i—C5—C4—N310.0 (4)
N2i—Cu1—N2—C671.6 (8)N1—C5—C4—C313.0 (3)
N1i—Cu1—N2—C644.8 (10)C5i—C5—C4—C3171.8 (3)
N1—Cu1—N2—C6125.3 (8)C1—C2—C3—C42.6 (4)
C1—N1—C5—C410.6 (3)N3—C4—C3—C2171.8 (2)
Cu1—N1—C5—C4162.18 (16)C5—C4—C3—C26.5 (3)
C1—N1—C5—C5i173.6 (2)
Symmetry code: (i) x, y, z+3/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N3—H3A···S1ii0.862.693.550 (2)174
N3—H3B···N3i0.862.232.775 (4)121
C1—H1···N20.932.583.044 (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)]
Mr365.92
Crystal system, space groupMonoclinic, C2/c
Temperature (K)298
a, b, c (Å)8.8127 (18), 14.991 (3), 10.627 (2)
β (°) 90.738 (3)
V3)1403.8 (5)
Z4
Radiation typeMo Kα
µ (mm1)1.85
Crystal size (mm)0.38 × 0.36 × 0.30
Data collection
DiffractometerBruker SMART APEX CCD
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.539, 0.606
No. of measured, independent and
observed [I > 2σ(I)] reflections
3905, 1450, 1285
Rint0.019
(sin θ/λ)max1)0.628
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.033, 0.088, 1.05
No. of reflections1450
No. of parameters96
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.34, 0.18

Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SAINT, SHELXTL (Bruker, 2001), SHELXTL.

Selected geometric parameters (Å, º) top
Cu1—N21.947 (2)Cu1—N11.9728 (19)
N2—Cu1—N2i92.80 (13)N2—Cu1—N195.61 (9)
N2—Cu1—N1i161.13 (9)N1i—Cu1—N181.60 (11)
Symmetry code: (i) x, y, z+3/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N3—H3A···S1ii0.862.693.550 (2)174.3
N3—H3B···N3i0.862.232.775 (4)121
C1—H1···N20.932.583.044 (4)112
Symmetry codes: (i) x, y, z+3/2; (ii) x+1/2, y+1/2, z+2.
 

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