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Acta Cryst. (2009). E65, m1061    [ doi:10.1107/S1600536809031067 ]

Bis(2,2'-bipyridine-[kappa]2N,N')(thiocyanato-[kappa]N)copper(II) perchlorate

Q. Li, D. Zhang, C.-L. Chen and L. Yan

Abstract top

The asymmetric unit of title compound, [Cu(NCS)(C10H8N2)2]ClO4, contains a bis(2,2'-bipyridine)(isothiocyanato)copper(II) cation and a perchlorate anion. In the cation, the Cu2+ ion is coordinated by four N atoms from two bidentate 2,2'-bipyridine molecules and an N atom from an isothiocyanate anion, resulting in a distorted CuN5 pyramidal configuration. The crystal structure is stabilized by weak intermolecular C-H...O and C-H...S hydrogen bonds, and weak [pi]-[pi] interactions between 2,2'-bipyridine rings [centroid-centroid distance = 3.908 (4) Å]. The perchlorate counteranion is disordered over two positions in a 0.66:0.34 ratio.

Comment top

Recently, more attentions have been paid to metal-organic coordination compounds (MOCPs) due to their potenial applications in catalysis, nonlinear optics, gas absorption, luminescene and magnetism (Maspoch et al. 2007, Kitagawa & Matsuda 2007). In the field of coordination chemistry, dual-ligand or multidentate ligands are usually engaged in the costruction of MOCPs, among which N,N-bidentate ligands (such as 2,2'-bipyridine) is familiar chelate ligand. Herein, we report the structure of the title compound (I) containing organic dual ligands.

The title compound (I) consists of one [Cu(C10H8N2)2(SCN)]+ complex cations, one disordered [ClO4]- anion (Fig.1). In the molecular structure, the Cu2+ centre is coordinated by five N atoms, among which four N atoms come from two bidentate 2,2'-bipyridine molecule and another one N atom from an isothiocyanato anion. The environment of the Cu2+ cation is in a distorted pyramidal geometry with Cu–N bond lengths ranging from 1.968 (4) to 2.102 (4) Å (Table 1).

In addition, the crystal structure is stability by weak intermolecular C—H···O and C—H···S hydrogen bonds (Table 2), and weak π-π interactions between 2,2'-bipyridine rings with centroid-to centroid distance of 3.908 (4) Å.

Related literature top

For the potenial applications of metal-organic coordination compounds in catalysis, non-linear optics, gas absorption, luminescene and magnetism, see: Kitagawa & Matsuda (2007); Maspoch et al. (2007).

Experimental top

2,2'-Bipyridine (1 mol, 0.16 g) was suspended in 20 ml

ethanol solution, to which Cu(ClO4).2H2O (0.5 mmol, 0.19 g) was added, and then KSCN (0.5 mmol, 0.5 g) were added to the mixture. It was stirred under reflux for 4 h. The solution was cooled and filtered, and the filtrate was kept at the room temperature. After ten days, green blocks of (I) were obtained.

Refinement top

H atoms were treated as riding, with C—H distances of 0.93 Å, and were refined as riding with Uiso(H) = 1.2Ueq(C).

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: PLATON (Spek, 2009).

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level. Hydrogen atoms are omitted for clarity.
Bis(2,2'-bipyridine-κ2N,N')(thiocyanato-κN)copper(II) perchlorate top
Crystal data top
[Cu(NCS)(C10H8N2)2]ClO4F(000) = 1084
Mr = 533.46Dx = 1.589 Mg m−3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 2091 reflections
a = 15.151 (2) Åθ = 2.5–20.5°
b = 8.9518 (13) ŵ = 1.23 mm−1
c = 19.0409 (17) ÅT = 293 K
β = 120.306 (7)°Block, green
V = 2229.6 (5) Å30.21 × 0.15 × 0.13 mm
Z = 4
Data collection top
Bruker SMART CCD area-detector
diffractometer		3917 independent reflections
Radiation source: fine-focus sealed tube2370 reflections with I > 2σ(I)
graphiteRint = 0.043
φ and ω scansθmax = 25.1°, θmin = 2.2°
Absorption correction: multi-scan
(SADABS; Sheldrick, 2001)		h = −9→18
Tmin = 0.782, Tmax = 0.856k = −10→10
10831 measured reflectionsl = −22→20
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)] = 0.049Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.116H-atom parameters constrained
S = 1.03 w = 1/[σ2(Fo2) + (0.0453P)2]
where P = (Fo2 + 2Fc2)/3
3917 reflections(Δ/σ)max < 0.001
335 parametersΔρmax = 0.60 e Å−3
44 restraintsΔρmin = −0.82 e Å−3
Crystal data top
[Cu(NCS)(C10H8N2)2]ClO4V = 2229.6 (5) Å3
Mr = 533.46Z = 4
Monoclinic, P21/cMo Kα radiation
a = 15.151 (2) ŵ = 1.23 mm−1
b = 8.9518 (13) ÅT = 293 K
c = 19.0409 (17) Å0.21 × 0.15 × 0.13 mm
β = 120.306 (7)°
Data collection top
Bruker SMART CCD area-detector
diffractometer		3917 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2001)		2370 reflections with I > 2σ(I)
Tmin = 0.782, Tmax = 0.856Rint = 0.043
10831 measured reflectionsθmax = 25.1°
Refinement top
R[F2 > 2σ(F2)] = 0.049H-atom parameters constrained
wR(F2) = 0.116Δρmax = 0.60 e Å−3
S = 1.03Δρmin = −0.82 e Å−3
3917 reflectionsAbsolute structure: ?
335 parametersFlack parameter: ?
44 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*/UeqOcc. (<1)
Cu10.28304 (4)0.52479 (6)0.58542 (3)0.0504 (2)
S10.21213 (11)0.09251 (15)0.69020 (9)0.0736 (4)
N10.4011 (3)0.4415 (4)0.5796 (2)0.0489 (10)
N20.3811 (3)0.7044 (4)0.6288 (2)0.0478 (9)
N30.1728 (3)0.5378 (4)0.4610 (2)0.0475 (9)
N40.1701 (3)0.6262 (4)0.5907 (2)0.0488 (9)
N50.2680 (3)0.3429 (5)0.6365 (3)0.0659 (12)
C10.4060 (4)0.3036 (5)0.5556 (3)0.0588 (13)
H1A0.34940.24160.53750.071*
C20.4912 (4)0.2495 (6)0.5565 (3)0.0637 (14)
H2A0.49180.15350.53810.076*
C30.5754 (4)0.3400 (6)0.5852 (3)0.0657 (14)
H3A0.63480.30550.58750.079*
C40.5712 (4)0.4814 (5)0.6103 (3)0.0576 (13)
H4A0.62780.54390.63000.069*
C50.4828 (3)0.5312 (5)0.6062 (3)0.0453 (11)
C60.4705 (3)0.6823 (5)0.6308 (3)0.0456 (11)
C70.5427 (4)0.7926 (5)0.6539 (3)0.0552 (13)
H7A0.60310.77530.65370.066*
C80.5246 (4)0.9294 (6)0.6772 (3)0.0651 (14)
H8A0.57321.00500.69410.078*
C90.4346 (4)0.9526 (5)0.6753 (3)0.0666 (14)
H9A0.42091.04400.69110.080*
C100.3643 (4)0.8385 (5)0.6498 (3)0.0584 (13)
H10A0.30210.85590.64710.070*
C110.1745 (4)0.4783 (5)0.3972 (3)0.0570 (13)
H11A0.23100.42170.40670.068*
C120.0976 (4)0.4968 (5)0.3191 (3)0.0642 (14)
H12A0.10070.45170.27640.077*
C130.0156 (4)0.5828 (6)0.3046 (3)0.0702 (15)
H13A−0.03740.59870.25160.084*
C140.0126 (4)0.6453 (5)0.3689 (3)0.0617 (14)
H14A−0.04240.70490.36000.074*
C150.0910 (3)0.6196 (5)0.4464 (3)0.0462 (11)
C160.0909 (3)0.6708 (5)0.5202 (3)0.0467 (11)
C170.0122 (4)0.7529 (6)0.5185 (3)0.0660 (15)
H17A−0.04200.78670.46940.079*
C180.0157 (4)0.7834 (6)0.5909 (4)0.0721 (16)
H18A−0.03650.83840.59080.087*
C190.0945 (4)0.7339 (5)0.6616 (4)0.0675 (15)
H19A0.09700.75270.71070.081*
C200.1706 (4)0.6553 (5)0.6597 (3)0.0612 (14)
H20A0.22500.62060.70850.073*
C210.2448 (3)0.2379 (5)0.6594 (3)0.0514 (12)
Cl10.24431 (10)0.98729 (15)0.40224 (9)0.0726 (4)
O1'0.1951 (6)1.1109 (9)0.4087 (6)0.190 (5)0.66
O2'0.1768 (7)0.8670 (8)0.3661 (5)0.193 (5)0.66
O3'0.3286 (6)0.9451 (11)0.4777 (4)0.177 (5)0.66
O4'0.2788 (8)1.0206 (15)0.3457 (6)0.268 (7)0.66
O10.1870 (7)0.9781 (12)0.4423 (6)0.0755 (10)0.34
O20.2143 (8)0.8817 (10)0.3404 (6)0.0728 (10)0.34
O30.3518 (6)0.9693 (14)0.4598 (7)0.0730 (10)0.34
O40.2356 (9)1.1359 (8)0.3709 (6)0.0730 (10)0.34
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.0461 (4)0.0518 (4)0.0585 (4)0.0054 (3)0.0303 (3)0.0020 (3)
S10.0721 (10)0.0594 (9)0.1024 (12)0.0078 (7)0.0536 (9)0.0197 (8)
N10.049 (2)0.045 (2)0.057 (2)0.0044 (19)0.030 (2)−0.0022 (19)
N20.047 (2)0.043 (2)0.056 (3)0.0038 (18)0.028 (2)−0.0002 (19)
N30.046 (2)0.052 (2)0.051 (2)0.0014 (19)0.029 (2)0.0017 (19)
N40.047 (2)0.054 (2)0.054 (3)0.0036 (19)0.032 (2)0.001 (2)
N50.058 (3)0.068 (3)0.077 (3)0.003 (2)0.038 (3)0.009 (2)
C10.063 (3)0.048 (3)0.071 (4)0.004 (3)0.038 (3)−0.003 (3)
C20.071 (4)0.054 (3)0.074 (4)0.018 (3)0.042 (3)0.001 (3)
C30.057 (4)0.073 (4)0.075 (4)0.020 (3)0.039 (3)0.002 (3)
C40.043 (3)0.066 (3)0.064 (3)0.006 (2)0.027 (3)0.000 (3)
C50.040 (3)0.049 (3)0.047 (3)0.004 (2)0.022 (2)0.003 (2)
C60.041 (3)0.051 (3)0.039 (3)0.004 (2)0.016 (2)0.004 (2)
C70.042 (3)0.058 (3)0.063 (3)−0.003 (2)0.024 (3)−0.003 (3)
C80.052 (3)0.056 (3)0.075 (4)−0.007 (3)0.023 (3)−0.003 (3)
C90.077 (4)0.050 (3)0.065 (4)0.005 (3)0.031 (3)−0.009 (3)
C100.056 (3)0.053 (3)0.071 (4)0.006 (3)0.036 (3)−0.002 (3)
C110.059 (3)0.065 (3)0.061 (3)0.002 (3)0.040 (3)0.000 (3)
C120.070 (4)0.078 (4)0.057 (4)−0.012 (3)0.041 (3)−0.008 (3)
C130.056 (4)0.090 (4)0.057 (4)−0.013 (3)0.022 (3)0.007 (3)
C140.048 (3)0.072 (4)0.061 (4)0.005 (3)0.024 (3)0.006 (3)
C150.044 (3)0.042 (3)0.056 (3)−0.001 (2)0.028 (3)0.002 (2)
C160.037 (3)0.047 (3)0.058 (3)−0.001 (2)0.026 (3)−0.002 (2)
C170.049 (3)0.072 (4)0.075 (4)0.013 (3)0.030 (3)0.004 (3)
C180.063 (4)0.070 (4)0.103 (5)0.004 (3)0.057 (4)−0.014 (4)
C190.075 (4)0.065 (4)0.085 (4)−0.009 (3)0.057 (4)−0.013 (3)
C200.063 (3)0.069 (3)0.060 (3)0.000 (3)0.037 (3)−0.002 (3)
C210.040 (3)0.053 (3)0.064 (3)0.010 (2)0.029 (3)0.001 (3)
Cl10.0573 (8)0.0714 (9)0.0791 (10)0.0056 (7)0.0270 (8)−0.0106 (7)
O1'0.128 (7)0.134 (7)0.300 (13)0.047 (6)0.102 (8)−0.069 (7)
O2'0.201 (10)0.176 (8)0.174 (9)−0.140 (8)0.072 (7)−0.028 (7)
O3'0.183 (9)0.215 (10)0.062 (5)0.082 (8)0.008 (6)0.001 (5)
O4'0.224 (13)0.41 (2)0.259 (14)−0.040 (12)0.189 (13)0.037 (12)
O10.0592 (14)0.0735 (14)0.0817 (15)0.0063 (13)0.0267 (13)−0.0106 (13)
O20.0582 (14)0.0710 (14)0.0786 (15)0.0059 (13)0.0266 (13)−0.0119 (13)
O30.0569 (13)0.0713 (14)0.0797 (15)0.0063 (13)0.0263 (13)−0.0118 (13)
O40.0577 (13)0.0715 (14)0.0796 (15)0.0058 (13)0.0270 (13)−0.0097 (13)
Geometric parameters (Å, °) top
Cu1—N51.968 (4)C11—C121.360 (7)
Cu1—N41.985 (3)C11—H11A0.9300
Cu1—N11.992 (4)C12—C131.365 (6)
Cu1—N22.058 (4)C12—H12A0.9300
Cu1—N32.102 (4)C13—C141.369 (6)
S1—C211.605 (5)C13—H13A0.9300
N1—C11.331 (5)C14—C151.368 (6)
N1—C51.342 (5)C14—H14A0.9300
N2—C101.331 (5)C15—C161.478 (6)
N2—C61.349 (5)C16—C171.387 (6)
N3—C111.339 (5)C17—C181.380 (7)
N3—C151.342 (5)C17—H17A0.9300
N4—C161.332 (5)C18—C191.347 (7)
N4—C201.335 (5)C18—H18A0.9300
N5—C211.163 (5)C19—C201.368 (6)
C1—C21.371 (6)C19—H19A0.9300
C1—H1A0.9300C20—H20A0.9300
C2—C31.371 (6)Cl1—O1'1.374 (5)
C2—H2A0.9300Cl1—O21.395 (7)
C3—C41.366 (6)Cl1—O2'1.403 (5)
C3—H3A0.9300Cl1—O3'1.409 (5)
C4—C51.376 (6)Cl1—O11.419 (6)
C4—H4A0.9300Cl1—O41.437 (7)
C5—C61.473 (6)Cl1—O31.442 (7)
C6—C71.372 (6)Cl1—O4'1.446 (6)
C7—C81.377 (6)O1'—O41.180 (11)
C7—H7A0.9300O1'—O11.385 (11)
C8—C91.362 (7)O2'—O20.927 (11)
C8—H8A0.9300O2'—O11.701 (11)
C9—C101.375 (6)O3'—O30.638 (17)
C9—H9A0.9300O4'—O41.429 (12)
C10—H10A0.9300O4'—O21.553 (12)
N5—Cu1—N492.02 (16)N3—C15—C16114.5 (4)
N5—Cu1—N192.83 (16)C14—C15—C16123.8 (4)
N4—Cu1—N1174.75 (15)N4—C16—C17120.5 (4)
N5—Cu1—N2133.48 (16)N4—C16—C15115.7 (4)
N4—Cu1—N295.11 (14)C17—C16—C15123.7 (5)
N1—Cu1—N280.08 (15)C18—C17—C16118.9 (5)
N5—Cu1—N3112.25 (16)C18—C17—H17A120.6
N4—Cu1—N379.43 (15)C16—C17—H17A120.6
N1—Cu1—N3100.55 (14)C19—C18—C17120.1 (5)
N2—Cu1—N3114.25 (14)C19—C18—H18A119.9
C1—N1—C5119.0 (4)C17—C18—H18A119.9
C1—N1—Cu1125.0 (3)C18—C19—C20118.5 (5)
C5—N1—Cu1116.0 (3)C18—C19—H19A120.8
C10—N2—C6117.8 (4)C20—C19—H19A120.8
C10—N2—Cu1128.0 (3)N4—C20—C19122.7 (5)
C6—N2—Cu1114.1 (3)N4—C20—H20A118.7
C11—N3—C15117.8 (4)C19—C20—H20A118.7
C11—N3—Cu1129.2 (3)N5—C21—S1179.5 (6)
C15—N3—Cu1112.9 (3)O1'—Cl1—O2131.4 (6)
C16—N4—C20119.3 (4)O1'—Cl1—O2'111.6 (5)
C16—N4—Cu1116.5 (3)O2—Cl1—O2'38.7 (5)
C20—N4—Cu1124.2 (3)O1'—Cl1—O3'112.2 (5)
C21—N5—Cu1170.6 (4)O2—Cl1—O3'114.9 (6)
N1—C1—C2122.6 (5)O2'—Cl1—O3'110.8 (5)
N1—C1—H1A118.7O1'—Cl1—O159.4 (5)
C2—C1—H1A118.7O2—Cl1—O1112.8 (6)
C1—C2—C3118.5 (5)O2'—Cl1—O174.1 (5)
C1—C2—H2A120.7O3'—Cl1—O185.6 (5)
C3—C2—H2A120.7O1'—Cl1—O449.6 (5)
C4—C3—C2119.2 (5)O2—Cl1—O4110.7 (6)
C4—C3—H3A120.4O2'—Cl1—O4128.0 (6)
C2—C3—H3A120.4O3'—Cl1—O4121.2 (6)
C3—C4—C5119.8 (5)O1—Cl1—O4108.9 (5)
C3—C4—H4A120.1O1'—Cl1—O3118.5 (7)
C5—C4—H4A120.1O2—Cl1—O3109.2 (6)
N1—C5—C4120.9 (4)O2'—Cl1—O3123.4 (7)
N1—C5—C6115.4 (4)O3'—Cl1—O325.8 (7)
C4—C5—C6123.8 (4)O1—Cl1—O3110.4 (6)
N2—C6—C7122.0 (4)O4—Cl1—O3104.5 (6)
N2—C6—C5114.3 (4)O1'—Cl1—O4'108.5 (5)
C7—C6—C5123.6 (4)O2—Cl1—O4'66.3 (6)
C6—C7—C8119.2 (4)O2'—Cl1—O4'104.0 (5)
C6—C7—H7A120.4O3'—Cl1—O4'109.4 (5)
C8—C7—H7A120.4O1—Cl1—O4'164.2 (6)
C9—C8—C7119.1 (5)O4—Cl1—O4'59.4 (5)
C9—C8—H8A120.4O3—Cl1—O4'84.0 (7)
C7—C8—H8A120.4O4—O1'—Cl168.0 (4)
C8—C9—C10118.8 (5)O4—O1'—O1129.8 (6)
C8—C9—H9A120.6Cl1—O1'—O161.9 (4)
C10—C9—H9A120.6O2—O2'—Cl170.2 (6)
N2—C10—C9123.0 (5)O2—O2'—O1123.5 (7)
N2—C10—H10A118.5Cl1—O2'—O153.4 (3)
C9—C10—H10A118.5O3—O3'—Cl180.0 (9)
N3—C11—C12123.1 (5)O4—O4'—Cl160.0 (4)
N3—C11—H11A118.4O4—O4'—O2102.7 (6)
C12—C11—H11A118.4Cl1—O4'—O255.3 (4)
C11—C12—C13118.7 (5)O1'—O1—Cl158.7 (4)
C11—C12—H12A120.7O1'—O1—O2'95.7 (6)
C13—C12—H12A120.7Cl1—O1—O2'52.5 (3)
C12—C13—C14119.2 (5)O2'—O2—Cl171.1 (6)
C12—C13—H13A120.4O2'—O2—O4'127.8 (8)
C14—C13—H13A120.4Cl1—O2—O4'58.4 (4)
C15—C14—C13119.6 (5)O3'—O3—Cl174.2 (9)
C15—C14—H14A120.2O1'—O4—O4'122.4 (7)
C13—C14—H14A120.2O1'—O4—Cl162.4 (4)
N3—C15—C14121.6 (4)O4'—O4—Cl160.6 (4)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C7—H7A···O4'i0.932.553.176 (15)125
C10—H10A···S1ii0.932.853.587 (6)137
C18—H18A···O1'iii0.932.453.335 (13)159
Symmetry codes: (i) −x+1, −y+2, −z+1; (ii) x, y+1, z; (iii) −x, −y+2, −z+1.
Table 1
Selected geometric parameters (Å, °) top
Cu1—N51.968 (4)Cu1—N22.058 (4)
Cu1—N41.985 (3)Cu1—N32.102 (4)
Cu1—N11.992 (4)
N5—Cu1—N492.02 (16)N1—Cu1—N280.08 (15)
N5—Cu1—N192.83 (16)N5—Cu1—N3112.25 (16)
N4—Cu1—N1174.75 (15)N4—Cu1—N379.43 (15)
N5—Cu1—N2133.48 (16)N1—Cu1—N3100.55 (14)
N4—Cu1—N295.11 (14)N2—Cu1—N3114.25 (14)
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C7—H7A···O4'i0.932.553.176 (15)125
C10—H10A···S1ii0.932.853.587 (6)137
C18—H18A···O1'iii0.932.453.335 (13)159
Symmetry codes: (i) −x+1, −y+2, −z+1; (ii) x, y+1, z; (iii) −x, −y+2, −z+1.
references
References top

Bruker (2001). SAINT-Plus and SMART. Bruker AXS Inc., Madison, Wisconsin, USA.

Kitagawa, S. & Matsuda, R. (2007). Coord. Chem. Rev. 251, 2490–2509.

Maspoch, D., Ruiz-Molina, D. & Veciana, J. (2007). Chem. Soc. Rev. 36, 770–818.

Sheldrick, G. M. (2001). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Spek, A. L. (2009). Acta Cryst. D65, 148–155.