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Acta Cryst. (2007). E63, m2141    [ doi:10.1107/S1600536807033181 ]

Bis(2,2'-bipyridyl-[kappa]2N,N')bis(isothiocyanato-[kappa]N)copper(II)

H. Zhong, X.-M. Yang, Q.-Y. Luo and Y.-P. Xu

Abstract top

In the molecule of the title compound, [Cu(NCS)2(C10H8N2)2], the CuII atom is six-coordinated by the four N atoms of two 2,2'-bipyridyl ligands and the two N atoms of two thiocyanate ligands, in a distorted octahedral arrangement. In the crystal structure, intramolecular C-H...N and intermolecular C-H...S hydrogen bonds and [pi]-[pi] stacking interactions, with a centroid-centroid distance of 3.573 (2) Å, lead to a supramolecular network structure.

Comment top

The crystal structure of bis[(2,2'-bipyridyl-κ2N,N')bis(thiocyanato-κN)] nickel(II), (II), has previously been reported (Zhong et al., 2007). The crystal structure determination of the title compound, (I), has been carried out in order to elucidate the molecular conformation and to compare it with that of (II).

In the molecule of (I) (Fig. 1), the ligand bond lengths and angles are within normal ranges (Allen et al., 1987). The six-coordinate environment of the Cu atom is completed by the four N atoms of two 2,2'-bipyridyl ligands and two N atoms of two SCN- ligands, in a distorted octahedral arrangement (Table 1). The Cu—N bonds [average 2.156 (4) Å] of the 2,2'-bipyridyl ligands are somewhat longer than the Cu—N bonds [average 2.073 (2) Å] for the SCN- ligands. The two 2,2'-bipyridyl ligands are nearly perpendicular to each other, with a dihedral angle of 105.7 (4) °, as in (II).

In the crystal structure, intramolecular C—H···N and intermolecular C—H···S hydrogen bonds and π-π stacking interactions, with a centroid-centroid distance of 3.573 (2) Å [symmetry code: 2 - x, 1 - y, -z] lead to a supramolecular network structure (Fig. 2), as in (II).

The both compounds, (I) and (II), are isostructural.

Related literature top

For a related structure, see: Zhong et al. (2007). For bond-length data, see: Allen et al. (1987).

Experimental top

Crystals of the title compound were synthesized using hydrothermal method in a 23 ml Teflon-lined Parr bomb. Copper dinitrate hexahydrate (88.7 mg, 0.3 mmol), 2,2'-bipyridyl (93.6 mg, 0.6 mmol), potassium thiocyanate (58.4 mg, 0.6 mmol) and distilled water (4 g) were placed into the bomb and sealed. The bomb was then heated under autogenous pressure up to 423 K over the course of 7 d and allowed to cool at room temperature for 24 h. Upon opening the bomb, a clear colorless solution was decanted from small blue crystals. These crystals were washed with distilled water followed by ethanol, and allowed to air-dry at room temperature.

Refinement top

H atoms were positioned geometrically, with C—H = 0.93 Å, and constrained to ride on their parent atoms, with Uiso(H) = 1.2Ueq(C).

Computing details top

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Siemens, 1996); software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. The molecular structure of the title molecule, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
[Figure 2] Fig. 2. A packing diagram of (I). Hydrogen bonds are shown as dashed lines.
Bis(2,2'-bipyridyl-k2N,N')bis (isothiocyanato-kN)copper(II) top
Crystal data top
[Cu(NCS)2(C10H8N2)2]F(000) = 2008
Mr = 492.07Dx = 1.505 Mg m−3
Orthorhombic, PbcaMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2abCell parameters from 11573 reflections
a = 15.981 (4) Åθ = 2.4–27.2°
b = 15.997 (2) ŵ = 1.22 mm−1
c = 16.9947 (18) ÅT = 273 K
V = 4344.7 (13) Å3Block, blue
Z = 80.36 × 0.34 × 0.22 mm
Data collection top
Bruker SMART CCD area-detector
diffractometer		4708 independent reflections
Radiation source: fine-focus sealed tube3481 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.023
φ and ω scansθmax = 27.0°, θmin = 2.2°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −20→20
Tmin = 0.661, Tmax = 0.768k = −20→20
28695 measured reflectionsl = −21→21
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)] = 0.045Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.159H-atom parameters constrained
S = 1.02 w = 1/[σ2(Fo2) + (0.1098P)2 + 0.816P]
where P = (Fo2 + 2Fc2)/3
4708 reflections(Δ/σ)max = 0.001
280 parametersΔρmax = 0.48 e Å−3
0 restraintsΔρmin = −0.88 e Å−3
Crystal data top
[Cu(NCS)2(C10H8N2)2]V = 4344.7 (13) Å3
Mr = 492.07Z = 8
Orthorhombic, PbcaMo Kα radiation
a = 15.981 (4) ŵ = 1.22 mm−1
b = 15.997 (2) ÅT = 273 K
c = 16.9947 (18) Å0.36 × 0.34 × 0.22 mm
Data collection top
Bruker SMART CCD area-detector
diffractometer		4708 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		3481 reflections with I > 2σ(I)
Tmin = 0.661, Tmax = 0.768Rint = 0.023
28695 measured reflectionsθmax = 27.0°
Refinement top
R[F2 > 2σ(F2)] = 0.045H-atom parameters constrained
wR(F2) = 0.159Δρmax = 0.48 e Å−3
S = 1.02Δρmin = −0.88 e Å−3
4708 reflectionsAbsolute structure: ?
280 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
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
Cu10.70224 (2)0.38400 (2)−0.000711 (17)0.04902 (16)
S10.57516 (6)0.51149 (7)−0.22514 (5)0.0814 (3)
S20.51121 (6)0.22560 (5)0.15952 (5)0.0732 (3)
N10.62899 (16)0.44609 (15)−0.08263 (15)0.0641 (6)
N20.60959 (15)0.31786 (15)0.05761 (16)0.0599 (6)
N30.80970 (13)0.46127 (13)−0.02964 (14)0.0476 (5)
N40.69877 (12)0.48310 (13)0.08362 (13)0.0476 (5)
N50.72280 (12)0.28371 (12)−0.08243 (12)0.0455 (5)
N60.79904 (12)0.30930 (14)0.05457 (13)0.0480 (5)
C10.60600 (16)0.47314 (16)−0.14211 (18)0.0523 (6)
C20.56808 (15)0.28035 (15)0.09985 (16)0.0474 (6)
C30.86341 (18)0.4456 (2)−0.08797 (16)0.0633 (7)
H30.85480.3983−0.11880.076*
C40.9306 (2)0.4959 (2)−0.1045 (2)0.0783 (10)
H40.96670.4837−0.14590.094*
C50.9426 (2)0.5644 (2)−0.0580 (2)0.0803 (10)
H50.98720.6003−0.06790.096*
C60.8892 (2)0.5806 (2)0.00314 (18)0.0670 (8)
H60.89720.62710.03500.080*
C70.82324 (17)0.52678 (16)0.01687 (16)0.0489 (6)
C80.76310 (15)0.53800 (15)0.08204 (15)0.0469 (5)
C90.77042 (19)0.5995 (2)0.13901 (18)0.0636 (7)
H90.81580.63590.13820.076*
C100.7112 (2)0.6067 (2)0.1961 (2)0.0753 (9)
H100.71670.64710.23510.090*
C110.6435 (2)0.5541 (2)0.19573 (18)0.0716 (8)
H110.60090.55990.23260.086*
C120.64040 (18)0.49203 (18)0.13903 (17)0.0584 (7)
H120.59560.45490.13960.070*
C130.67722 (17)0.26890 (17)−0.14712 (17)0.0547 (6)
H130.63730.3082−0.16190.066*
C140.6864 (2)0.1988 (2)−0.19262 (19)0.0666 (8)
H140.65310.1902−0.23680.080*
C150.7460 (2)0.1416 (2)−0.1711 (2)0.0729 (9)
H150.75370.0933−0.20070.087*
C160.79439 (19)0.15602 (19)−0.1056 (2)0.0669 (8)
H160.83560.1179−0.09110.080*
C170.78159 (15)0.22705 (16)−0.06151 (16)0.0493 (6)
C180.82897 (16)0.24607 (18)0.01153 (16)0.0500 (6)
C190.89974 (18)0.2015 (2)0.0339 (2)0.0700 (8)
H190.92050.15870.00240.084*
C200.93845 (19)0.2220 (2)0.1038 (3)0.0847 (11)
H200.98580.19290.12000.102*
C210.9068 (2)0.2862 (2)0.1499 (2)0.0757 (10)
H210.93160.30030.19760.091*
C220.83809 (19)0.32779 (19)0.12268 (17)0.0613 (7)
H220.81700.37140.15290.074*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.0490 (2)0.0480 (2)0.0500 (3)−0.00325 (13)0.00051 (12)−0.00126 (12)
S10.0734 (5)0.1012 (7)0.0696 (6)−0.0093 (5)−0.0232 (4)0.0129 (5)
S20.0793 (5)0.0683 (5)0.0719 (5)−0.0118 (4)0.0254 (4)0.0008 (4)
N10.0711 (15)0.0507 (13)0.0704 (16)0.0035 (11)−0.0179 (13)0.0021 (12)
N20.0540 (12)0.0548 (13)0.0709 (15)−0.0063 (10)0.0088 (12)−0.0043 (11)
N30.0499 (11)0.0492 (11)0.0436 (11)−0.0075 (9)0.0025 (9)0.0016 (9)
N40.0483 (11)0.0467 (11)0.0479 (12)−0.0038 (8)0.0015 (9)−0.0044 (9)
N50.0459 (10)0.0440 (11)0.0466 (12)−0.0006 (8)0.0016 (9)−0.0013 (8)
N60.0457 (11)0.0521 (11)0.0461 (12)−0.0047 (9)−0.0010 (9)0.0048 (9)
C10.0456 (12)0.0452 (13)0.0662 (17)0.0010 (10)−0.0073 (12)−0.0093 (12)
C20.0421 (11)0.0446 (12)0.0553 (15)−0.0001 (10)0.0035 (11)−0.0088 (11)
C30.0641 (16)0.0734 (18)0.0525 (16)−0.0135 (14)0.0119 (13)−0.0047 (14)
C40.0653 (18)0.107 (3)0.0622 (19)−0.0238 (18)0.0212 (15)−0.0014 (18)
C50.0658 (19)0.089 (2)0.086 (2)−0.0310 (18)0.0113 (17)0.0048 (19)
C60.0610 (18)0.0634 (19)0.077 (2)−0.0193 (15)−0.0002 (14)−0.0054 (14)
C70.0467 (13)0.0478 (14)0.0521 (14)−0.0040 (11)−0.0053 (11)0.0039 (11)
C80.0475 (12)0.0454 (13)0.0478 (14)−0.0009 (10)−0.0080 (10)−0.0010 (10)
C90.0632 (16)0.0641 (17)0.0634 (18)−0.0092 (14)−0.0088 (15)−0.0126 (14)
C100.088 (2)0.079 (2)0.0594 (19)−0.0027 (17)−0.0027 (16)−0.0273 (17)
C110.077 (2)0.082 (2)0.0558 (17)−0.0038 (17)0.0122 (15)−0.0174 (15)
C120.0619 (15)0.0589 (15)0.0543 (16)−0.0038 (13)0.0100 (13)−0.0064 (12)
C130.0552 (14)0.0554 (15)0.0534 (16)−0.0037 (12)−0.0015 (12)−0.0039 (12)
C140.0797 (19)0.0658 (18)0.0542 (17)−0.0080 (15)0.0005 (15)−0.0129 (14)
C150.091 (2)0.0601 (18)0.068 (2)0.0047 (17)0.0143 (18)−0.0178 (15)
C160.0740 (19)0.0532 (16)0.073 (2)0.0134 (14)0.0085 (15)−0.0066 (14)
C170.0483 (12)0.0502 (14)0.0495 (15)0.0000 (10)0.0095 (11)0.0004 (11)
C180.0391 (12)0.0528 (14)0.0582 (16)−0.0020 (11)0.0057 (11)0.0104 (12)
C190.0486 (15)0.0728 (19)0.089 (2)0.0112 (14)0.0035 (16)0.0164 (17)
C200.0504 (16)0.095 (3)0.109 (3)0.0042 (16)−0.0205 (18)0.028 (2)
C210.0671 (19)0.083 (2)0.077 (2)−0.0152 (17)−0.0257 (17)0.0176 (18)
C220.0678 (17)0.0612 (16)0.0548 (16)−0.0096 (14)−0.0100 (14)0.0090 (13)
Geometric parameters (Å, º) top
Cu1—N12.073 (2)C7—C81.477 (4)
Cu1—N22.072 (2)C8—C91.386 (4)
Cu1—N32.172 (2)C9—C101.360 (5)
Cu1—N42.138 (2)C9—H90.9300
Cu1—N52.147 (2)C10—C111.372 (5)
Cu1—N62.169 (2)C10—H100.9300
S1—C11.616 (3)C11—C121.384 (4)
S2—C21.619 (3)C11—H110.9300
N1—C11.159 (4)C12—H120.9300
N2—C21.147 (3)C13—C141.370 (4)
N3—C71.330 (3)C13—H130.9300
N3—C31.335 (4)C14—C151.371 (5)
N4—C121.333 (3)C14—H140.9300
N4—C81.352 (3)C15—C161.375 (5)
N5—C131.340 (3)C15—H150.9300
N5—C171.353 (3)C16—C171.376 (4)
N6—C181.337 (4)C16—H160.9300
N6—C221.348 (4)C17—C181.486 (4)
C3—C41.371 (4)C18—C191.390 (4)
C3—H30.9300C19—C201.379 (5)
C4—C51.365 (5)C19—H190.9300
C4—H40.9300C20—C211.387 (5)
C5—C61.370 (5)C20—H200.9300
C5—H50.9300C21—C221.366 (4)
C6—C71.380 (4)C21—H210.9300
C6—H60.9300C22—H220.9300
N1—Cu1—N299.34 (11)N4—C8—C9120.8 (2)
N1—Cu1—N391.25 (9)N4—C8—C7115.5 (2)
N1—Cu1—N494.60 (9)C9—C8—C7123.7 (2)
N1—Cu1—N590.57 (9)C10—C9—C8120.0 (3)
N1—Cu1—N6163.33 (9)C10—C9—H9120.0
N2—Cu1—N3164.51 (10)C8—C9—H9120.0
N2—Cu1—N492.26 (9)C9—C10—C11119.6 (3)
N2—Cu1—N592.13 (9)C9—C10—H10120.2
N2—Cu1—N691.21 (9)C11—C10—H10120.2
N3—Cu1—N475.54 (8)C10—C11—C12118.1 (3)
N3—Cu1—N599.08 (8)C10—C11—H11120.9
N3—Cu1—N681.24 (8)C12—C11—H11120.9
N4—Cu1—N5172.59 (8)N4—C12—C11122.9 (3)
N4—Cu1—N697.86 (8)N4—C12—H12118.5
N5—Cu1—N676.08 (8)C11—C12—H12118.5
C1—N1—Cu1160.7 (2)N5—C13—C14123.4 (3)
C2—N2—Cu1168.4 (2)N5—C13—H13118.3
C7—N3—C3119.0 (2)C14—C13—H13118.3
C7—N3—Cu1116.26 (18)C13—C14—C15118.0 (3)
C3—N3—Cu1124.71 (19)C13—C14—H14121.0
C12—N4—C8118.4 (2)C15—C14—H14121.0
C12—N4—Cu1124.83 (18)C16—C15—C14119.6 (3)
C8—N4—Cu1116.65 (16)C16—C15—H15120.2
C13—N5—C17118.3 (2)C14—C15—H15120.2
C13—N5—Cu1125.43 (17)C15—C16—C17119.7 (3)
C17—N5—Cu1115.91 (17)C15—C16—H16120.1
C18—N6—C22118.1 (2)C17—C16—H16120.1
C18—N6—Cu1115.79 (18)N5—C17—C16120.9 (3)
C22—N6—Cu1125.5 (2)N5—C17—C18115.9 (2)
N1—C1—S1179.2 (3)C16—C17—C18123.2 (3)
N2—C2—S2178.6 (2)N6—C18—C19122.0 (3)
N3—C3—C4123.1 (3)N6—C18—C17115.5 (2)
N3—C3—H3118.5C19—C18—C17122.5 (3)
C4—C3—H3118.5C20—C19—C18118.5 (3)
C5—C4—C3117.6 (3)C20—C19—H19120.7
C5—C4—H4121.2C18—C19—H19120.7
C3—C4—H4121.2C19—C20—C21120.0 (3)
C4—C5—C6120.2 (3)C19—C20—H20120.0
C4—C5—H5119.9C21—C20—H20120.0
C6—C5—H5119.9C22—C21—C20117.5 (3)
C5—C6—C7119.1 (3)C22—C21—H21121.2
C5—C6—H6120.4C20—C21—H21121.2
C7—C6—H6120.4N6—C22—C21123.8 (3)
N3—C7—C6121.0 (3)N6—C22—H22118.1
N3—C7—C8115.8 (2)C21—C22—H22118.1
C6—C7—C8123.2 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C13—H13···N10.932.593.135 (4)118
C12—H12···N20.932.613.150 (4)117
C4—H4···S1i0.932.833.712 (3)159
Symmetry code: (i) x+1/2, y, −z−1/2.
Selected geometric parameters (Å, º) top
Cu1—N12.073 (2)Cu1—N42.138 (2)
Cu1—N22.072 (2)Cu1—N52.147 (2)
Cu1—N32.172 (2)Cu1—N62.169 (2)
N1—Cu1—N299.34 (11)N2—Cu1—N691.21 (9)
N1—Cu1—N391.25 (9)N3—Cu1—N475.54 (8)
N1—Cu1—N494.60 (9)N3—Cu1—N599.08 (8)
N1—Cu1—N590.57 (9)N3—Cu1—N681.24 (8)
N1—Cu1—N6163.33 (9)N4—Cu1—N5172.59 (8)
N2—Cu1—N3164.51 (10)N4—Cu1—N697.86 (8)
N2—Cu1—N492.26 (9)N5—Cu1—N676.08 (8)
N2—Cu1—N592.13 (9)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C13—H13···N10.932.593.135 (4)118
C12—H12···N20.932.613.150 (4)117
C4—H4···S1i0.932.833.712 (3)159
Symmetry code: (i) x+1/2, y, −z−1/2.
Acknowledgements top

This work was supported by the Science and Technology Bureau of Jian, Jiangxi Province of China (grant No. 20052827).

references
References top

Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19.

Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.

Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.

Siemens (1996). SMART, SAINT and SHELXTL. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA.

Zhong, H., Yang, X.-M., Luo, Q.-Y. & Xu, Y.-P. (2007). Acta Cryst. E63, m2062–?.