(2,2′-Bipyridine-κ2N,N′)iodido(piperidine-1-carbodithio­ato-κ2S,S′)copper(II)

Fan, L.-Q.

doi:10.1107/S1600536808039901

metal-organic compounds

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Volume 65| Part 1| January 2009| Page m6

doi:10.1107/S1600536808039901

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(2,2′-Bipyridine-κ²N,N′)iodido(piperidine-1-carbodithioato-κ²S,S′)copper(II)

Le-Qing Fan ^a ^*

^aInstitute of Materials Physical Chemistry and The Key Laboratory for Functional Materials of Fujian Higher Education, Huaqiao University, Quanzhou, Fujian 362021, People's Republic of China
^*Correspondence e-mail: lqfan@hqu.edu.cn

(Received 14 November 2008; accepted 27 November 2008; online 3 December 2008)

In the title compound, [Cu(C₆H₁₀NS₂)I(C₁₀H₈N₂)], the Cu^II ion is coordinated by one iodide ion, two N atoms of the bipyridine ligand and two S atoms from the piperidinecarbodithioate ligand in a distorted square-pyramidal environment. π–π stacking interactions, with centroid–centroid distances of 3.643 (4) Å, between pyridyl rings of the bipyridyl ligands of neighbouring molecules lead to chains propagating parallel to the a axis.

Related literature

For background to transition metal complexes, see: Engelhardt et al. (1988 ); Fernández et al. (2000 ); Koh et al. (2003 ); Noro et al. (2000 ); Yaghi et al. (1998 ).

Experimental

Crystal data

[Cu(C₆H₁₀NS₂)I(C₁₀H₈N₂)]
M_r = 506.89
Monoclinic, P 2₁ /c
a = 6.532 (3) Å
b = 16.859 (7) Å
c = 17.578 (7) Å
β = 108.047 (14)°
V = 1840.5 (14) Å³
Z = 4
Mo Kα radiation
μ = 3.09 mm⁻¹
T = 293 (2) K
0.45 × 0.08 × 0.05 mm

Data collection

Rigaku Mercury CCD diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2000 ) T_min = 0.751, T_max = 1.000 (expected range = 0.643–0.857)
13746 measured reflections
3946 independent reflections
3389 reflections with I > 2σ(I)
R_int = 0.036

Refinement

R[F² > 2σ(F²)] = 0.047
wR(F²) = 0.108
S = 1.08
3946 reflections
208 parameters
H-atom parameters constrained
Δρ_max = 0.52 e Å⁻³
Δρ_min = −0.63 e Å⁻³

Data collection: CrystalClear (Rigaku, 2000); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808039901/ez2153sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808039901/ez2153Isup2.hkl

checkCIF report

Comment top

Research into transition metal complexes has been rapidly expanding because of their fascinating structural diversity, as well as their potential applications as functional materials and enzymes (Noro et al., 2000; Yaghi et al., 1998). Dialkyldithiocarbamate anions, which are typical sulfur ligands, acting as monodentate, bidentate or bridging ligands, are often chosen for the preparation of complexes with a considerable structural variety (Engelhardt et al., 1988; Fernández et al., 2000; Koh et al., 2003). I report here the crystal structure of the title copper(II) complex, (I), containing a piperidyldithiocarbamate ligand.

The crystal structure of (I) is built of discrete molecules of the Cu^II complex (Fig. 1). The Cu^II ion is five-coordinated in a distorted square-pyramidal environment by one I atom in the apical position, two N atoms from the bipyridine ligand and two S atoms from the piperidyldithiocarbamate ligand in the basal plane (Table 1).

There is a π-π stacking interaction between the pyridyl rings R1 [N(2)/C(7)–C(11)] and R2 [N3/C(12)–C(16)] with a centroid-to-centroid distance of 3.643 (4) Å. These face-to-face interactions result in the complexes assembling into chains.

Related literature top

For background to transition metal complexes, see: Engelhardt et al. (1988); Fernández et al. (2000); Koh et al. (2003); Noro et al. (2000); Yaghi et al. (1998).

Experimental top

A mixture of Cu(Ac)₂.H₂O (0.08 g, 0.4 mmol), NaS₂CNC₅H₁₀.2H₂O (0.09 g, 0.4 mmol), 2,2'-bipyridine (0.06 g 0.4 mmol) and NaI.2H₂O (0.07 g, 0.4 mmol) was stirred in DMF (15 ml). 2-PrOH was diffused into the resulting solution, yielding single crystals of (I).

Computing details top

Data collection: CrystalClear (Rigaku, 2000); cell refinement: CrystalClear (Rigaku, 2000); data reduction: CrystalClear (Rigaku, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of (I), showing the atom-labelling scheme, with 30% probability displacement ellipsoids.

(2,2'-Bipyridine-κ²N,N')iodido(piperidine-1- carbodithioato-κ²S,S')copper(II) top

Crystal data top

[Cu(C₆H₁₀NS₂)I(C₁₀H₈N₂)]	F(000) = 996
M_r = 506.89	D_x = 1.829 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3988 reflections
a = 6.532 (3) Å	θ = 3.3–27.5°
b = 16.859 (7) Å	µ = 3.09 mm⁻¹
c = 17.578 (7) Å	T = 293 K
β = 108.047 (14)°	Prism, black
V = 1840.5 (14) Å³	0.45 × 0.08 × 0.05 mm
Z = 4

Data collection top

Rigaku Mercury CCD diffractometer	3946 independent reflections
Radiation source: Sealed Tube	3389 reflections with I > 2σ(I)
Graphite Monochromator monochromator	R_int = 0.036
ω scans	θ_max = 27.5°, θ_min = 2.4°
Absorption correction: multi-scan (CrystalClear; Rigaku,2000)	h = −8→6
T_min = 0.751, T_max = 1.000	k = −21→21
13746 measured reflections	l = −22→22

Refinement top

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)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.108	H-atom parameters constrained
S = 1.09	w = 1/[σ²(F_o²) + (0.043P)² + 2.8277P] where P = (F_o² + 2F_c²)/3
3946 reflections	(Δ/σ)_max = 0.001
208 parameters	Δρ_max = 0.52 e Å⁻³
0 restraints	Δρ_min = −0.63 e Å⁻³

Crystal data top

[Cu(C₆H₁₀NS₂)I(C₁₀H₈N₂)]	V = 1840.5 (14) Å³
M_r = 506.89	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 6.532 (3) Å	µ = 3.09 mm⁻¹
b = 16.859 (7) Å	T = 293 K
c = 17.578 (7) Å	0.45 × 0.08 × 0.05 mm
β = 108.047 (14)°

Data collection top

Rigaku Mercury CCD diffractometer	3946 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku,2000)	3389 reflections with I > 2σ(I)
T_min = 0.751, T_max = 1.000	R_int = 0.036
13746 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.047	0 restraints
wR(F²) = 0.108	H-atom parameters constrained
S = 1.09	Δρ_max = 0.52 e Å⁻³
3946 reflections	Δρ_min = −0.63 e Å⁻³
208 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

	x	y	z	U_iso*/U_eq
Cu1	0.43714 (10)	0.66212 (3)	0.42086 (3)	0.04099 (17)
I1	0.19321 (6)	0.80141 (2)	0.36188 (2)	0.05420 (14)
S1	0.6396 (2)	0.64039 (8)	0.33518 (8)	0.0502 (3)
S2	0.2619 (3)	0.55763 (9)	0.34096 (8)	0.0586 (4)
N1	0.4731 (7)	0.5184 (2)	0.2378 (2)	0.0423 (9)
N2	0.6611 (7)	0.7232 (2)	0.5076 (2)	0.0401 (9)
N3	0.3271 (7)	0.6421 (2)	0.5154 (2)	0.0420 (9)
C1	0.4607 (8)	0.5651 (3)	0.2965 (3)	0.0386 (10)
C2	0.6306 (8)	0.5319 (3)	0.1943 (3)	0.0496 (12)
H2A	0.7044	0.4828	0.1907	0.059*
H2B	0.7370	0.5706	0.2225	0.059*
C3	0.5104 (9)	0.5620 (3)	0.1113 (3)	0.0556 (14)
H3A	0.6106	0.5693	0.0811	0.067*
H3B	0.4459	0.6130	0.1154	0.067*
C4	0.3347 (10)	0.5035 (4)	0.0674 (3)	0.0620 (15)
H4A	0.2530	0.5255	0.0160	0.074*
H4B	0.4004	0.4544	0.0578	0.074*
C5	0.1852 (9)	0.4865 (3)	0.1159 (3)	0.0533 (13)
H5A	0.1057	0.5342	0.1194	0.064*
H5B	0.0822	0.4461	0.0891	0.064*
C6	0.3075 (9)	0.4585 (3)	0.1993 (3)	0.0499 (13)
H6A	0.2094	0.4515	0.2304	0.060*
H6B	0.3757	0.4079	0.1966	0.060*
C7	0.8254 (8)	0.7641 (3)	0.4972 (3)	0.0464 (12)
H7A	0.8406	0.7663	0.4464	0.056*
C8	0.9733 (9)	0.8031 (3)	0.5591 (3)	0.0537 (13)
H8A	1.0845	0.8323	0.5503	0.064*
C9	0.9520 (10)	0.7979 (3)	0.6347 (4)	0.0615 (16)
H9A	1.0515	0.8226	0.6777	0.074*
C10	0.7829 (9)	0.7558 (3)	0.6462 (3)	0.0553 (14)
H10A	0.7675	0.7519	0.6969	0.066*
C11	0.6367 (8)	0.7197 (3)	0.5814 (3)	0.0430 (11)
C12	0.4453 (9)	0.6746 (3)	0.5851 (3)	0.0417 (11)
C13	0.3853 (10)	0.6676 (3)	0.6542 (3)	0.0528 (13)
H13A	0.4662	0.6917	0.7016	0.063*
C14	0.2037 (10)	0.6243 (3)	0.6510 (3)	0.0587 (15)
H14A	0.1636	0.6173	0.6970	0.070*
C15	0.0828 (10)	0.5918 (3)	0.5800 (4)	0.0614 (16)
H15A	−0.0417	0.5634	0.5769	0.074*
C16	0.1483 (9)	0.6016 (3)	0.5129 (3)	0.0515 (13)
H16A	0.0661	0.5794	0.4646	0.062*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0480 (4)	0.0472 (3)	0.0298 (3)	−0.0078 (3)	0.0150 (3)	−0.0058 (2)
I1	0.0605 (3)	0.0538 (2)	0.0489 (2)	0.00754 (16)	0.01783 (18)	0.01277 (15)
S1	0.0491 (8)	0.0629 (8)	0.0430 (6)	−0.0169 (6)	0.0207 (6)	−0.0195 (6)
S2	0.0670 (10)	0.0688 (8)	0.0495 (7)	−0.0287 (7)	0.0322 (7)	−0.0201 (6)
N1	0.043 (3)	0.048 (2)	0.0346 (19)	−0.0025 (18)	0.0103 (18)	−0.0079 (16)
N2	0.043 (3)	0.0428 (19)	0.0308 (18)	0.0023 (17)	0.0068 (17)	−0.0013 (15)
N3	0.057 (3)	0.0387 (19)	0.0343 (19)	0.0032 (18)	0.0195 (18)	0.0019 (15)
C1	0.044 (3)	0.040 (2)	0.031 (2)	−0.002 (2)	0.011 (2)	−0.0012 (17)
C2	0.043 (3)	0.062 (3)	0.042 (3)	−0.001 (2)	0.011 (2)	−0.017 (2)
C3	0.060 (4)	0.066 (3)	0.042 (3)	−0.010 (3)	0.019 (3)	−0.003 (2)
C4	0.069 (4)	0.070 (4)	0.038 (3)	−0.011 (3)	0.003 (3)	−0.004 (3)
C5	0.056 (4)	0.045 (3)	0.047 (3)	−0.010 (2)	−0.001 (3)	−0.001 (2)
C6	0.065 (4)	0.040 (2)	0.042 (3)	−0.012 (2)	0.013 (2)	−0.007 (2)
C7	0.047 (3)	0.048 (3)	0.044 (3)	−0.005 (2)	0.013 (2)	−0.002 (2)
C8	0.048 (3)	0.048 (3)	0.058 (3)	−0.002 (2)	0.005 (3)	−0.008 (2)
C9	0.060 (4)	0.053 (3)	0.054 (3)	0.001 (3)	−0.008 (3)	−0.019 (3)
C10	0.067 (4)	0.052 (3)	0.037 (3)	0.012 (3)	0.003 (3)	−0.007 (2)
C11	0.050 (3)	0.044 (2)	0.030 (2)	0.014 (2)	0.006 (2)	−0.0001 (18)
C12	0.058 (3)	0.042 (2)	0.027 (2)	0.012 (2)	0.016 (2)	0.0019 (17)
C13	0.071 (4)	0.054 (3)	0.037 (3)	0.017 (3)	0.022 (3)	0.010 (2)
C14	0.085 (5)	0.058 (3)	0.046 (3)	0.021 (3)	0.038 (3)	0.013 (2)
C15	0.082 (4)	0.046 (3)	0.073 (4)	0.007 (3)	0.048 (3)	0.006 (3)
C16	0.067 (4)	0.045 (3)	0.052 (3)	−0.004 (2)	0.033 (3)	−0.004 (2)

Geometric parameters (Å, º) top

Cu1—N3	2.033 (4)	C5—C6	1.510 (7)
Cu1—N2	2.035 (4)	C5—H5A	0.9700
Cu1—S1	2.3205 (15)	C5—H5B	0.9700
Cu1—S2	2.3218 (15)	C6—H6A	0.9700
Cu1—I1	2.8470 (11)	C6—H6B	0.9700
S1—C1	1.717 (5)	C7—C8	1.379 (7)
S2—C1	1.716 (5)	C7—H7A	0.9300
N1—C1	1.320 (6)	C8—C9	1.380 (8)
N1—C2	1.476 (6)	C8—H8A	0.9300
N1—C6	1.482 (6)	C9—C10	1.379 (9)
N2—C7	1.335 (6)	C9—H9A	0.9300
N2—C11	1.357 (6)	C10—C11	1.380 (7)
N3—C16	1.342 (6)	C10—H10A	0.9300
N3—C12	1.345 (6)	C11—C12	1.481 (7)
C2—C3	1.514 (7)	C12—C13	1.392 (6)
C2—H2A	0.9700	C13—C14	1.380 (8)
C2—H2B	0.9700	C13—H13A	0.9300
C3—C4	1.529 (7)	C14—C15	1.369 (8)
C3—H3A	0.9700	C14—H14A	0.9300
C3—H3B	0.9700	C15—C16	1.384 (7)
C4—C5	1.511 (8)	C15—H15A	0.9300
C4—H4A	0.9700	C16—H16A	0.9300
C4—H4B	0.9700

N3—Cu1—N2	79.95 (16)	C6—C5—C4	111.5 (5)
N3—Cu1—S1	157.11 (12)	C6—C5—H5A	109.3
N2—Cu1—S1	98.30 (12)	C4—C5—H5A	109.3
N3—Cu1—S2	97.80 (12)	C6—C5—H5B	109.3
N2—Cu1—S2	160.43 (12)	C4—C5—H5B	109.3
S1—Cu1—S2	76.17 (5)	H5A—C5—H5B	108.0
N3—Cu1—I1	97.76 (11)	N1—C6—C5	108.8 (4)
N2—Cu1—I1	92.69 (11)	N1—C6—H6A	109.9
S1—Cu1—I1	105.13 (5)	C5—C6—H6A	109.9
S2—Cu1—I1	106.86 (6)	N1—C6—H6B	109.9
C1—S1—Cu1	85.37 (16)	C5—C6—H6B	109.9
C1—S2—Cu1	85.37 (16)	H6A—C6—H6B	108.3
C1—N1—C2	122.3 (4)	N2—C7—C8	122.3 (5)
C1—N1—C6	123.4 (4)	N2—C7—H7A	118.8
C2—N1—C6	113.3 (4)	C8—C7—H7A	118.8
C7—N2—C11	119.4 (4)	C7—C8—C9	118.3 (6)
C7—N2—Cu1	125.5 (3)	C7—C8—H8A	120.8
C11—N2—Cu1	115.1 (3)	C9—C8—H8A	120.8
C16—N3—C12	119.0 (4)	C10—C9—C8	119.9 (5)
C16—N3—Cu1	125.6 (3)	C10—C9—H9A	120.1
C12—N3—Cu1	115.4 (3)	C8—C9—H9A	120.1
N1—C1—S2	123.5 (4)	C9—C10—C11	119.2 (5)
N1—C1—S1	123.5 (4)	C9—C10—H10A	120.4
S2—C1—S1	113.1 (2)	C11—C10—H10A	120.4
N1—C2—C3	108.3 (4)	N2—C11—C10	120.9 (5)
N1—C2—H2A	110.0	N2—C11—C12	114.5 (4)
C3—C2—H2A	110.0	C10—C11—C12	124.7 (5)
N1—C2—H2B	110.0	N3—C12—C13	121.5 (5)
C3—C2—H2B	110.0	N3—C12—C11	115.1 (4)
H2A—C2—H2B	108.4	C13—C12—C11	123.4 (5)
C2—C3—C4	110.8 (4)	C14—C13—C12	118.7 (5)
C2—C3—H3A	109.5	C14—C13—H13A	120.6
C4—C3—H3A	109.5	C12—C13—H13A	120.6
C2—C3—H3B	109.5	C15—C14—C13	119.6 (5)
C4—C3—H3B	109.5	C15—C14—H14A	120.2
H3A—C3—H3B	108.1	C13—C14—H14A	120.2
C5—C4—C3	110.6 (4)	C14—C15—C16	119.1 (6)
C5—C4—H4A	109.5	C14—C15—H15A	120.4
C3—C4—H4A	109.5	C16—C15—H15A	120.4
C5—C4—H4B	109.5	N3—C16—C15	121.9 (5)
C3—C4—H4B	109.5	N3—C16—H16A	119.1
H4A—C4—H4B	108.1	C15—C16—H16A	119.1

Experimental details

Crystal data
Chemical formula	[Cu(C₆H₁₀NS₂)I(C₁₀H₈N₂)]
M_r	506.89
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	6.532 (3), 16.859 (7), 17.578 (7)
β (°)	108.047 (14)
V (Å³)	1840.5 (14)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	3.09
Crystal size (mm)	0.45 × 0.08 × 0.05

Data collection
Diffractometer	Rigaku Mercury CCD diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku,2000)
T_min, T_max	0.751, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	13746, 3946, 3389
R_int	0.036
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.047, 0.108, 1.09
No. of reflections	3946
No. of parameters	208
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.52, −0.63

Computer programs: CrystalClear (Rigaku, 2000), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Acknowledgements

This work was supported financially by the Research Fund of Huaqiao University (No. 06BS216) and the Young Talent Fund of Fujian Province (No. 2007 F3060).

References

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