Bis(2,2'-bipyridine-κN,N')(thio-cyanato-κN)copper(II) perchlorate.

The asymmetric unit of title compound, [Cu(NCS)(C(10)H(8)N(2))(2)]ClO(4), contains a bis-(2,2'-bipyridine)(isothio-cyanato)copper(II) cation and a perchlorate anion. In the cation, the Cu(2+) ion is coordinated by four N atoms from two bidentate 2,2'-bipyridine mol-ecules and an N atom from an isothio-cyanate anion, resulting in a distorted CuN(5) pyramidal configuration. The crystal structure is stabilized by weak inter-molecular C-H⋯O and C-H⋯S hydrogen bonds, and weak π-π inter-actions 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.

Related literature

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

Crystal data

[Cu(NCS)(C10H8N2)2]ClO4

M = 533.46

Monoclinic,

a = 15.151 (2) Å

b = 8.9518 (13) Å

c = 19.0409 (17) Å

β = 120.306 (7)°

V = 2229.6 (5) Å3

Z = 4

Mo Kα radiation

μ = 1.23 mm−1

T = 293 K

0.21 × 0.15 × 0.13 mm

Data collection

Bruker SMART CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 2001 ▶) T min = 0.782, T max = 0.856

10831 measured reflections

3917 independent reflections

2370 reflections with I > 2σ(I)

R int = 0.043

Refinement

R[F 2 > 2σ(F 2)] = 0.049

wR(F 2) = 0.116

S = 1.03

3917 reflections

335 parameters

44 restraints

H-atom parameters constrained

Δρmax = 0.60 e Å−3

Δρmin = −0.82 e Å−3

Data collection: SMART (Bruker, 2001 ▶); cell refinement: SAINT-Plus (Bruker, 2001 ▶); data reduction: SAINT-Plus; 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.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809031067/at2856sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809031067/at2856Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

[Cu(NCS)(C10H8N2)2]ClO4	F(000) = 1084
Mr = 533.46	Dx = 1.589 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2091 reflections
a = 15.151 (2) Å	θ = 2.5–20.5°
b = 8.9518 (13) Å	µ = 1.23 mm−1
c = 19.0409 (17) Å	T = 293 K
β = 120.306 (7)°	Block, green
V = 2229.6 (5) Å3	0.21 × 0.15 × 0.13 mm
Z = 4

Bruker SMART CCD area-detector diffractometer	3917 independent reflections
Radiation source: fine-focus sealed tube	2370 reflections with I > 2σ(I)
graphite	Rint = 0.043
φ and ω scans	θmax = 25.1°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 2001)	h = −9→18
Tmin = 0.782, Tmax = 0.856	k = −10→10
10831 measured reflections	l = −22→20

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)] = 0.049	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.116	H-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 parameters	Δρmax = 0.60 e Å−3
44 restraints	Δρmin = −0.82 e Å−3

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	Occ. (<1)
Cu1	0.28304 (4)	0.52479 (6)	0.58542 (3)	0.0504 (2)
S1	0.21213 (11)	0.09251 (15)	0.69020 (9)	0.0736 (4)
N1	0.4011 (3)	0.4415 (4)	0.5796 (2)	0.0489 (10)
N2	0.3811 (3)	0.7044 (4)	0.6288 (2)	0.0478 (9)
N3	0.1728 (3)	0.5378 (4)	0.4610 (2)	0.0475 (9)
N4	0.1701 (3)	0.6262 (4)	0.5907 (2)	0.0488 (9)
N5	0.2680 (3)	0.3429 (5)	0.6365 (3)	0.0659 (12)
C1	0.4060 (4)	0.3036 (5)	0.5556 (3)	0.0588 (13)
H1A	0.3494	0.2416	0.5375	0.071*
C2	0.4912 (4)	0.2495 (6)	0.5565 (3)	0.0637 (14)
H2A	0.4918	0.1535	0.5381	0.076*
C3	0.5754 (4)	0.3400 (6)	0.5852 (3)	0.0657 (14)
H3A	0.6348	0.3055	0.5875	0.079*
C4	0.5712 (4)	0.4814 (5)	0.6103 (3)	0.0576 (13)
H4A	0.6278	0.5439	0.6300	0.069*
C5	0.4828 (3)	0.5312 (5)	0.6062 (3)	0.0453 (11)
C6	0.4705 (3)	0.6823 (5)	0.6308 (3)	0.0456 (11)
C7	0.5427 (4)	0.7926 (5)	0.6539 (3)	0.0552 (13)
H7A	0.6031	0.7753	0.6537	0.066*
C8	0.5246 (4)	0.9294 (6)	0.6772 (3)	0.0651 (14)
H8A	0.5732	1.0050	0.6941	0.078*
C9	0.4346 (4)	0.9526 (5)	0.6753 (3)	0.0666 (14)
H9A	0.4209	1.0440	0.6911	0.080*
C10	0.3643 (4)	0.8385 (5)	0.6498 (3)	0.0584 (13)
H10A	0.3021	0.8559	0.6471	0.070*
C11	0.1745 (4)	0.4783 (5)	0.3972 (3)	0.0570 (13)
H11A	0.2310	0.4217	0.4067	0.068*
C12	0.0976 (4)	0.4968 (5)	0.3191 (3)	0.0642 (14)
H12A	0.1007	0.4517	0.2764	0.077*
C13	0.0156 (4)	0.5828 (6)	0.3046 (3)	0.0702 (15)
H13A	−0.0374	0.5987	0.2516	0.084*
C14	0.0126 (4)	0.6453 (5)	0.3689 (3)	0.0617 (14)
H14A	−0.0424	0.7049	0.3600	0.074*
C15	0.0910 (3)	0.6196 (5)	0.4464 (3)	0.0462 (11)
C16	0.0909 (3)	0.6708 (5)	0.5202 (3)	0.0467 (11)
C17	0.0122 (4)	0.7529 (6)	0.5185 (3)	0.0660 (15)
H17A	−0.0420	0.7867	0.4694	0.079*
C18	0.0157 (4)	0.7834 (6)	0.5909 (4)	0.0721 (16)
H18A	−0.0365	0.8384	0.5908	0.087*
C19	0.0945 (4)	0.7339 (5)	0.6616 (4)	0.0675 (15)
H19A	0.0970	0.7527	0.7107	0.081*
C20	0.1706 (4)	0.6553 (5)	0.6597 (3)	0.0612 (14)
H20A	0.2250	0.6206	0.7085	0.073*
C21	0.2448 (3)	0.2379 (5)	0.6594 (3)	0.0514 (12)
Cl1	0.24431 (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
O1	0.1870 (7)	0.9781 (12)	0.4423 (6)	0.0755 (10)	0.34
O2	0.2143 (8)	0.8817 (10)	0.3404 (6)	0.0728 (10)	0.34
O3	0.3518 (6)	0.9693 (14)	0.4598 (7)	0.0730 (10)	0.34
O4	0.2356 (9)	1.1359 (8)	0.3709 (6)	0.0730 (10)	0.34

	U11	U22	U33	U12	U13	U23
Cu1	0.0461 (4)	0.0518 (4)	0.0585 (4)	0.0054 (3)	0.0303 (3)	0.0020 (3)
S1	0.0721 (10)	0.0594 (9)	0.1024 (12)	0.0078 (7)	0.0536 (9)	0.0197 (8)
N1	0.049 (2)	0.045 (2)	0.057 (2)	0.0044 (19)	0.030 (2)	−0.0022 (19)
N2	0.047 (2)	0.043 (2)	0.056 (3)	0.0038 (18)	0.028 (2)	−0.0002 (19)
N3	0.046 (2)	0.052 (2)	0.051 (2)	0.0014 (19)	0.029 (2)	0.0017 (19)
N4	0.047 (2)	0.054 (2)	0.054 (3)	0.0036 (19)	0.032 (2)	0.001 (2)
N5	0.058 (3)	0.068 (3)	0.077 (3)	0.003 (2)	0.038 (3)	0.009 (2)
C1	0.063 (3)	0.048 (3)	0.071 (4)	0.004 (3)	0.038 (3)	−0.003 (3)
C2	0.071 (4)	0.054 (3)	0.074 (4)	0.018 (3)	0.042 (3)	0.001 (3)
C3	0.057 (4)	0.073 (4)	0.075 (4)	0.020 (3)	0.039 (3)	0.002 (3)
C4	0.043 (3)	0.066 (3)	0.064 (3)	0.006 (2)	0.027 (3)	0.000 (3)
C5	0.040 (3)	0.049 (3)	0.047 (3)	0.004 (2)	0.022 (2)	0.003 (2)
C6	0.041 (3)	0.051 (3)	0.039 (3)	0.004 (2)	0.016 (2)	0.004 (2)
C7	0.042 (3)	0.058 (3)	0.063 (3)	−0.003 (2)	0.024 (3)	−0.003 (3)
C8	0.052 (3)	0.056 (3)	0.075 (4)	−0.007 (3)	0.023 (3)	−0.003 (3)
C9	0.077 (4)	0.050 (3)	0.065 (4)	0.005 (3)	0.031 (3)	−0.009 (3)
C10	0.056 (3)	0.053 (3)	0.071 (4)	0.006 (3)	0.036 (3)	−0.002 (3)
C11	0.059 (3)	0.065 (3)	0.061 (3)	0.002 (3)	0.040 (3)	0.000 (3)
C12	0.070 (4)	0.078 (4)	0.057 (4)	−0.012 (3)	0.041 (3)	−0.008 (3)
C13	0.056 (4)	0.090 (4)	0.057 (4)	−0.013 (3)	0.022 (3)	0.007 (3)
C14	0.048 (3)	0.072 (4)	0.061 (4)	0.005 (3)	0.024 (3)	0.006 (3)
C15	0.044 (3)	0.042 (3)	0.056 (3)	−0.001 (2)	0.028 (3)	0.002 (2)
C16	0.037 (3)	0.047 (3)	0.058 (3)	−0.001 (2)	0.026 (3)	−0.002 (2)
C17	0.049 (3)	0.072 (4)	0.075 (4)	0.013 (3)	0.030 (3)	0.004 (3)
C18	0.063 (4)	0.070 (4)	0.103 (5)	0.004 (3)	0.057 (4)	−0.014 (4)
C19	0.075 (4)	0.065 (4)	0.085 (4)	−0.009 (3)	0.057 (4)	−0.013 (3)
C20	0.063 (3)	0.069 (3)	0.060 (3)	0.000 (3)	0.037 (3)	−0.002 (3)
C21	0.040 (3)	0.053 (3)	0.064 (3)	0.010 (2)	0.029 (3)	0.001 (3)
Cl1	0.0573 (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)
O1	0.0592 (14)	0.0735 (14)	0.0817 (15)	0.0063 (13)	0.0267 (13)	−0.0106 (13)
O2	0.0582 (14)	0.0710 (14)	0.0786 (15)	0.0059 (13)	0.0266 (13)	−0.0119 (13)
O3	0.0569 (13)	0.0713 (14)	0.0797 (15)	0.0063 (13)	0.0263 (13)	−0.0118 (13)
O4	0.0577 (13)	0.0715 (14)	0.0796 (15)	0.0058 (13)	0.0270 (13)	−0.0097 (13)

Cu1—N5	1.968 (4)	C11—C12	1.360 (7)
Cu1—N4	1.985 (3)	C11—H11A	0.9300
Cu1—N1	1.992 (4)	C12—C13	1.365 (6)
Cu1—N2	2.058 (4)	C12—H12A	0.9300
Cu1—N3	2.102 (4)	C13—C14	1.369 (6)
S1—C21	1.605 (5)	C13—H13A	0.9300
N1—C1	1.331 (5)	C14—C15	1.368 (6)
N1—C5	1.342 (5)	C14—H14A	0.9300
N2—C10	1.331 (5)	C15—C16	1.478 (6)
N2—C6	1.349 (5)	C16—C17	1.387 (6)
N3—C11	1.339 (5)	C17—C18	1.380 (7)
N3—C15	1.342 (5)	C17—H17A	0.9300
N4—C16	1.332 (5)	C18—C19	1.347 (7)
N4—C20	1.335 (5)	C18—H18A	0.9300
N5—C21	1.163 (5)	C19—C20	1.368 (6)
C1—C2	1.371 (6)	C19—H19A	0.9300
C1—H1A	0.9300	C20—H20A	0.9300
C2—C3	1.371 (6)	Cl1—O1'	1.374 (5)
C2—H2A	0.9300	Cl1—O2	1.395 (7)
C3—C4	1.366 (6)	Cl1—O2'	1.403 (5)
C3—H3A	0.9300	Cl1—O3'	1.409 (5)
C4—C5	1.376 (6)	Cl1—O1	1.419 (6)
C4—H4A	0.9300	Cl1—O4	1.437 (7)
C5—C6	1.473 (6)	Cl1—O3	1.442 (7)
C6—C7	1.372 (6)	Cl1—O4'	1.446 (6)
C7—C8	1.377 (6)	O1'—O4	1.180 (11)
C7—H7A	0.9300	O1'—O1	1.385 (11)
C8—C9	1.362 (7)	O2'—O2	0.927 (11)
C8—H8A	0.9300	O2'—O1	1.701 (11)
C9—C10	1.375 (6)	O3'—O3	0.638 (17)
C9—H9A	0.9300	O4'—O4	1.429 (12)
C10—H10A	0.9300	O4'—O2	1.553 (12)
N5—Cu1—N4	92.02 (16)	N3—C15—C16	114.5 (4)
N5—Cu1—N1	92.83 (16)	C14—C15—C16	123.8 (4)
N4—Cu1—N1	174.75 (15)	N4—C16—C17	120.5 (4)
N5—Cu1—N2	133.48 (16)	N4—C16—C15	115.7 (4)
N4—Cu1—N2	95.11 (14)	C17—C16—C15	123.7 (5)
N1—Cu1—N2	80.08 (15)	C18—C17—C16	118.9 (5)
N5—Cu1—N3	112.25 (16)	C18—C17—H17A	120.6
N4—Cu1—N3	79.43 (15)	C16—C17—H17A	120.6
N1—Cu1—N3	100.55 (14)	C19—C18—C17	120.1 (5)
N2—Cu1—N3	114.25 (14)	C19—C18—H18A	119.9
C1—N1—C5	119.0 (4)	C17—C18—H18A	119.9
C1—N1—Cu1	125.0 (3)	C18—C19—C20	118.5 (5)
C5—N1—Cu1	116.0 (3)	C18—C19—H19A	120.8
C10—N2—C6	117.8 (4)	C20—C19—H19A	120.8
C10—N2—Cu1	128.0 (3)	N4—C20—C19	122.7 (5)
C6—N2—Cu1	114.1 (3)	N4—C20—H20A	118.7
C11—N3—C15	117.8 (4)	C19—C20—H20A	118.7
C11—N3—Cu1	129.2 (3)	N5—C21—S1	179.5 (6)
C15—N3—Cu1	112.9 (3)	O1'—Cl1—O2	131.4 (6)
C16—N4—C20	119.3 (4)	O1'—Cl1—O2'	111.6 (5)
C16—N4—Cu1	116.5 (3)	O2—Cl1—O2'	38.7 (5)
C20—N4—Cu1	124.2 (3)	O1'—Cl1—O3'	112.2 (5)
C21—N5—Cu1	170.6 (4)	O2—Cl1—O3'	114.9 (6)
N1—C1—C2	122.6 (5)	O2'—Cl1—O3'	110.8 (5)
N1—C1—H1A	118.7	O1'—Cl1—O1	59.4 (5)
C2—C1—H1A	118.7	O2—Cl1—O1	112.8 (6)
C1—C2—C3	118.5 (5)	O2'—Cl1—O1	74.1 (5)
C1—C2—H2A	120.7	O3'—Cl1—O1	85.6 (5)
C3—C2—H2A	120.7	O1'—Cl1—O4	49.6 (5)
C4—C3—C2	119.2 (5)	O2—Cl1—O4	110.7 (6)
C4—C3—H3A	120.4	O2'—Cl1—O4	128.0 (6)
C2—C3—H3A	120.4	O3'—Cl1—O4	121.2 (6)
C3—C4—C5	119.8 (5)	O1—Cl1—O4	108.9 (5)
C3—C4—H4A	120.1	O1'—Cl1—O3	118.5 (7)
C5—C4—H4A	120.1	O2—Cl1—O3	109.2 (6)
N1—C5—C4	120.9 (4)	O2'—Cl1—O3	123.4 (7)
N1—C5—C6	115.4 (4)	O3'—Cl1—O3	25.8 (7)
C4—C5—C6	123.8 (4)	O1—Cl1—O3	110.4 (6)
N2—C6—C7	122.0 (4)	O4—Cl1—O3	104.5 (6)
N2—C6—C5	114.3 (4)	O1'—Cl1—O4'	108.5 (5)
C7—C6—C5	123.6 (4)	O2—Cl1—O4'	66.3 (6)
C6—C7—C8	119.2 (4)	O2'—Cl1—O4'	104.0 (5)
C6—C7—H7A	120.4	O3'—Cl1—O4'	109.4 (5)
C8—C7—H7A	120.4	O1—Cl1—O4'	164.2 (6)
C9—C8—C7	119.1 (5)	O4—Cl1—O4'	59.4 (5)
C9—C8—H8A	120.4	O3—Cl1—O4'	84.0 (7)
C7—C8—H8A	120.4	O4—O1'—Cl1	68.0 (4)
C8—C9—C10	118.8 (5)	O4—O1'—O1	129.8 (6)
C8—C9—H9A	120.6	Cl1—O1'—O1	61.9 (4)
C10—C9—H9A	120.6	O2—O2'—Cl1	70.2 (6)
N2—C10—C9	123.0 (5)	O2—O2'—O1	123.5 (7)
N2—C10—H10A	118.5	Cl1—O2'—O1	53.4 (3)
C9—C10—H10A	118.5	O3—O3'—Cl1	80.0 (9)
N3—C11—C12	123.1 (5)	O4—O4'—Cl1	60.0 (4)
N3—C11—H11A	118.4	O4—O4'—O2	102.7 (6)
C12—C11—H11A	118.4	Cl1—O4'—O2	55.3 (4)
C11—C12—C13	118.7 (5)	O1'—O1—Cl1	58.7 (4)
C11—C12—H12A	120.7	O1'—O1—O2'	95.7 (6)
C13—C12—H12A	120.7	Cl1—O1—O2'	52.5 (3)
C12—C13—C14	119.2 (5)	O2'—O2—Cl1	71.1 (6)
C12—C13—H13A	120.4	O2'—O2—O4'	127.8 (8)
C14—C13—H13A	120.4	Cl1—O2—O4'	58.4 (4)
C15—C14—C13	119.6 (5)	O3'—O3—Cl1	74.2 (9)
C15—C14—H14A	120.2	O1'—O4—O4'	122.4 (7)
C13—C14—H14A	120.2	O1'—O4—Cl1	62.4 (4)
N3—C15—C14	121.6 (4)	O4'—O4—Cl1	60.6 (4)

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7A···O4'i	0.93	2.55	3.176 (15)	125
C10—H10A···S1ii	0.93	2.85	3.587 (6)	137
C18—H18A···O1'iii	0.93	2.45	3.335 (13)	159

Table 1

Selected geometric parameters (Å, °)

Cu1—N5	1.968 (4)
Cu1—N4	1.985 (3)
Cu1—N1	1.992 (4)
Cu1—N2	2.058 (4)
Cu1—N3	2.102 (4)

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C7—H7A⋯O4′i	0.93	2.55	3.176 (15)	125
C10—H10A⋯S1ii	0.93	2.85	3.587 (6)	137
C18—H18A⋯O1′iii	0.93	2.45	3.335 (13)	159

Symmetry codes: (i) ; (ii) ; (iii) .