(2,2′-Bipyridine-κ2N,N′)iodido(pyrrol­idine-1-dithio­carboxyl­ato-κ2S,S′)copper(II)

Fan, L.-Q.; Wu, J.-H.

doi:10.1107/S1600536808008945

metal-organic compounds

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Volume 64| Part 5| May 2008| Page m639

doi:10.1107/S1600536808008945

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(2,2′-Bipyridine-κ²N,N′)iodido(pyrrolidine-1-dithiocarboxylato-κ²S,S′)copper(II)

Le-Qing Fan ^a ^* and Ji-Huai Wu ^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 1 April 2008; accepted 2 April 2008; online 10 April 2008)

In the title compound, [Cu(C₅H₈NS₂)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 pyrrolidine-1-dithiocarboxylate ligand in a distorted square-pyramidal environment.

Related literature

For related literature, see: Englhardt et al. (1998 ); Fernández et al. (2000 ); Koh et al. (2003 ); Noro et al. (2000 ); Yaghi et al. (1998 ).

Experimental

Crystal data

[Cu(C₅H₈NS₂)I(C₁₀H₈N₂)]
M_r = 492.87
Monoclinic, P 2₁ /c
a = 6.606 (3) Å
b = 16.212 (8) Å
c = 16.405 (8) Å
β = 98.399 (10)°
V = 1738.3 (15) Å³
Z = 4
Mo Kα radiation
μ = 3.27 mm⁻¹
T = 293 (2) K
0.20 × 0.20 × 0.10 mm

Data collection

Rigaku Mercury CCD diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2000 ) T_min = 0.722, T_max = 1.000 (expected range = 0.521–0.721)
13239 measured reflections
3983 independent reflections
3326 reflections with I > 2σ(I)
R_int = 0.029

Refinement

R[F² > 2σ(F²)] = 0.034
wR(F²) = 0.085
S = 1.07
3983 reflections
199 parameters
H-atom parameters constrained
Δρ_max = 0.54 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/S1600536808008945/at2555sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808008945/at2555Isup2.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). Dialkyldithiocarbamates anions, which are typical sulfur ligands, acting as monodentate, bidentate or bridging ligands, are often chosen for the preparation of a considerable structural variety of complexes (Englhardt et al., 1998; Fernández et al., 2000; Koh, et al., 2003). We report here the crystal structure of the title copper(II) complex, (I), contanining a pyrrolidine-1-dithiocarboxylate 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 pyrrolidine-1-dithiocarboxylate ligand in the basal plane (Table 1).

Related literature top

For related literature, see: Englhardt et al. (1998); 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), NaS₂CNC₄H₈.2H₂O (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) with 30% probability displacement ellipsoids (arbitrary spheres for H atoms).

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

Crystal data top

[Cu(C₅H₈NS₂)I(C₁₀H₈N₂)]	F(000) = 964
M_r = 492.87	D_x = 1.883 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1823 reflections
a = 6.606 (3) Å	θ = 2.5–27.5°
b = 16.212 (8) Å	µ = 3.27 mm⁻¹
c = 16.405 (8) Å	T = 293 K
β = 98.399 (10)°	Prism, black
V = 1738.3 (15) Å³	0.20 × 0.20 × 0.10 mm
Z = 4

Data collection top

Rigaku Mercury CCD diffractometer	3983 independent reflections
Radiation source: Sealed Tube	3326 reflections with I > 2σ(I)
Graphite Monochromator monochromator	R_int = 0.029
ω scans	θ_max = 27.5°, θ_min = 2.5°
Absorption correction: multi-scan (CrystalClear; Rigaku, 2000)	h = −8→8
T_min = 0.722, T_max = 1.000	k = −20→21
13239 measured reflections	l = −21→20

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)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.085	H-atom parameters constrained
S = 1.07	w = 1/[σ²(F_o²) + (0.041P)² + 0.011P] where P = (F_o² + 2F_c²)/3
3983 reflections	(Δ/σ)_max = 0.001
199 parameters	Δρ_max = 0.54 e Å⁻³
0 restraints	Δρ_min = −0.63 e Å⁻³

Crystal data top

[Cu(C₅H₈NS₂)I(C₁₀H₈N₂)]	V = 1738.3 (15) Å³
M_r = 492.87	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 6.606 (3) Å	µ = 3.27 mm⁻¹
b = 16.212 (8) Å	T = 293 K
c = 16.405 (8) Å	0.20 × 0.20 × 0.10 mm
β = 98.399 (10)°

Data collection top

Rigaku Mercury CCD diffractometer	3983 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2000)	3326 reflections with I > 2σ(I)
T_min = 0.722, T_max = 1.000	R_int = 0.029
13239 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.034	0 restraints
wR(F²) = 0.085	H-atom parameters constrained
S = 1.07	Δρ_max = 0.54 e Å⁻³
3983 reflections	Δρ_min = −0.63 e Å⁻³
199 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	0.47246 (6)	0.43996 (2)	0.34106 (3)	0.03678 (12)
I1	0.22688 (4)	0.387568 (15)	0.190445 (15)	0.04821 (10)
S1	0.37645 (15)	0.34944 (6)	0.43793 (6)	0.0475 (2)
S2	0.74152 (13)	0.34585 (6)	0.36071 (6)	0.0419 (2)
N1	0.6415 (4)	0.22460 (17)	0.45729 (17)	0.0400 (7)
N2	0.3012 (4)	0.53917 (17)	0.36333 (17)	0.0383 (6)
N3	0.6083 (4)	0.52693 (16)	0.28057 (17)	0.0368 (6)
C1	0.5952 (5)	0.2977 (2)	0.4244 (2)	0.0364 (7)
C2	0.5177 (6)	0.1803 (2)	0.5103 (2)	0.0485 (9)
H2A	0.3908	0.1609	0.4789	0.058*
H2B	0.4865	0.2152	0.5548	0.058*
C3	0.6532 (9)	0.1087 (3)	0.5431 (4)	0.0826 (16)
H3A	0.7337	0.1227	0.5955	0.099*
H3B	0.5716	0.0603	0.5504	0.099*
C4	0.7884 (8)	0.0936 (3)	0.4791 (3)	0.0711 (13)
H4A	0.7235	0.0559	0.4373	0.085*
H4B	0.9180	0.0701	0.5039	0.085*
C5	0.8212 (6)	0.1769 (2)	0.4417 (3)	0.0512 (10)
H5A	0.9469	0.2021	0.4682	0.061*
H5B	0.8262	0.1721	0.3831	0.061*
C6	0.1427 (6)	0.5395 (2)	0.4055 (2)	0.0497 (9)
H6A	0.1079	0.4906	0.4297	0.060*
C7	0.0283 (7)	0.6094 (3)	0.4148 (2)	0.0549 (11)
H7A	−0.0793	0.6080	0.4455	0.066*
C8	0.0778 (6)	0.6805 (3)	0.3777 (2)	0.0549 (11)
H8A	0.0025	0.7283	0.3822	0.066*
C9	0.2389 (6)	0.6810 (2)	0.3336 (2)	0.0501 (9)
H9A	0.2730	0.7291	0.3079	0.060*
C10	0.3503 (5)	0.60970 (19)	0.3277 (2)	0.0369 (7)
C11	0.5251 (5)	0.60319 (19)	0.2813 (2)	0.0351 (7)
C12	0.6013 (6)	0.6680 (2)	0.2401 (2)	0.0458 (9)
H12A	0.5432	0.7202	0.2411	0.055*
C13	0.7627 (6)	0.6551 (3)	0.1978 (2)	0.0522 (10)
H13A	0.8167	0.6986	0.1708	0.063*
C14	0.8441 (6)	0.5771 (2)	0.1955 (2)	0.0497 (9)
H14A	0.9515	0.5667	0.1661	0.060*
C15	0.7631 (5)	0.5149 (2)	0.2378 (2)	0.0428 (8)
H15A	0.8183	0.4622	0.2365	0.051*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0405 (2)	0.0267 (2)	0.0451 (2)	0.00447 (16)	0.01283 (19)	0.00300 (16)
I1	0.04930 (17)	0.04100 (16)	0.05259 (17)	−0.00012 (10)	0.00166 (12)	−0.00718 (10)
S1	0.0485 (5)	0.0420 (5)	0.0574 (6)	0.0155 (4)	0.0255 (5)	0.0126 (4)
S2	0.0394 (5)	0.0381 (5)	0.0508 (5)	0.0054 (4)	0.0154 (4)	0.0079 (4)
N1	0.0428 (16)	0.0355 (16)	0.0437 (16)	0.0073 (12)	0.0125 (13)	0.0047 (12)
N2	0.0435 (16)	0.0343 (15)	0.0379 (15)	0.0081 (12)	0.0084 (13)	0.0008 (11)
N3	0.0400 (15)	0.0280 (14)	0.0430 (15)	0.0001 (11)	0.0076 (13)	−0.0002 (11)
C1	0.0398 (17)	0.0344 (18)	0.0357 (17)	0.0029 (14)	0.0081 (15)	−0.0011 (13)
C2	0.053 (2)	0.045 (2)	0.049 (2)	0.0033 (17)	0.0125 (18)	0.0156 (16)
C3	0.094 (4)	0.052 (3)	0.107 (4)	0.018 (3)	0.030 (3)	0.031 (3)
C4	0.095 (4)	0.038 (2)	0.083 (3)	0.020 (2)	0.021 (3)	0.009 (2)
C5	0.049 (2)	0.046 (2)	0.061 (2)	0.0199 (17)	0.0170 (19)	0.0053 (18)
C6	0.054 (2)	0.050 (2)	0.048 (2)	0.0113 (18)	0.0144 (18)	0.0037 (17)
C7	0.055 (2)	0.065 (3)	0.047 (2)	0.022 (2)	0.0126 (19)	−0.0027 (18)
C8	0.061 (2)	0.048 (2)	0.054 (2)	0.023 (2)	0.001 (2)	−0.0090 (18)
C9	0.063 (2)	0.034 (2)	0.049 (2)	0.0139 (17)	−0.0024 (19)	−0.0033 (16)
C10	0.0429 (18)	0.0295 (17)	0.0362 (17)	0.0049 (13)	−0.0008 (15)	−0.0031 (13)
C11	0.0372 (17)	0.0292 (17)	0.0363 (17)	−0.0012 (13)	−0.0031 (14)	0.0011 (13)
C12	0.051 (2)	0.0270 (18)	0.057 (2)	0.0008 (15)	0.0004 (19)	0.0038 (15)
C13	0.054 (2)	0.044 (2)	0.059 (2)	−0.0094 (18)	0.010 (2)	0.0128 (17)
C14	0.052 (2)	0.048 (2)	0.052 (2)	−0.0051 (18)	0.0155 (18)	0.0043 (17)
C15	0.0446 (19)	0.037 (2)	0.049 (2)	−0.0012 (15)	0.0147 (17)	−0.0015 (15)

Geometric parameters (Å, º) top

Cu1—N3	2.010 (3)	C4—H4A	0.9700
Cu1—N2	2.030 (3)	C4—H4B	0.9700
Cu1—S1	2.3185 (12)	C5—H5A	0.9700
Cu1—S2	2.3289 (13)	C5—H5B	0.9700
Cu1—I1	2.8789 (11)	C6—C7	1.382 (5)
S1—C1	1.713 (3)	C6—H6A	0.9300
S2—C1	1.712 (3)	C7—C8	1.365 (6)
N1—C1	1.319 (4)	C7—H7A	0.9300
N1—C2	1.466 (4)	C8—C9	1.371 (6)
N1—C5	1.471 (4)	C8—H8A	0.9300
N2—C6	1.337 (5)	C9—C10	1.381 (5)
N2—C10	1.345 (4)	C9—H9A	0.9300
N3—C15	1.336 (4)	C10—C11	1.476 (5)
N3—C11	1.354 (4)	C11—C12	1.384 (5)
C2—C3	1.516 (5)	C12—C13	1.371 (5)
C2—H2A	0.9700	C12—H12A	0.9300
C2—H2B	0.9700	C13—C14	1.377 (6)
C3—C4	1.495 (7)	C13—H13A	0.9300
C3—H3A	0.9700	C14—C15	1.375 (5)
C3—H3B	0.9700	C14—H14A	0.9300
C4—C5	1.511 (5)	C15—H15A	0.9300

N3—Cu1—N2	80.44 (12)	C3—C4—H4B	110.5
N3—Cu1—S1	165.74 (8)	C5—C4—H4B	110.5
N2—Cu1—S1	99.36 (9)	H4A—C4—H4B	108.7
N3—Cu1—S2	98.11 (9)	N1—C5—C4	103.4 (3)
N2—Cu1—S2	158.17 (8)	N1—C5—H5A	111.1
S1—Cu1—S2	76.71 (4)	C4—C5—H5A	111.1
N3—Cu1—I1	91.12 (8)	N1—C5—H5B	111.1
N2—Cu1—I1	97.42 (8)	C4—C5—H5B	111.1
S1—Cu1—I1	103.02 (4)	H5A—C5—H5B	109.0
S2—Cu1—I1	104.39 (4)	N2—C6—C7	122.9 (4)
C1—S1—Cu1	84.31 (12)	N2—C6—H6A	118.6
C1—S2—Cu1	84.01 (12)	C7—C6—H6A	118.6
C1—N1—C2	124.5 (3)	C8—C7—C6	118.2 (4)
C1—N1—C5	123.1 (3)	C8—C7—H7A	120.9
C2—N1—C5	112.3 (3)	C6—C7—H7A	120.9
C6—N2—C10	118.6 (3)	C7—C8—C9	119.7 (4)
C6—N2—Cu1	126.6 (3)	C7—C8—H8A	120.2
C10—N2—Cu1	114.8 (2)	C9—C8—H8A	120.2
C15—N3—C11	118.7 (3)	C8—C9—C10	119.7 (4)
C15—N3—Cu1	126.0 (2)	C8—C9—H9A	120.2
C11—N3—Cu1	115.1 (2)	C10—C9—H9A	120.2
N1—C1—S2	122.8 (3)	N2—C10—C9	121.0 (4)
N1—C1—S1	122.4 (3)	N2—C10—C11	114.8 (3)
S2—C1—S1	114.70 (19)	C9—C10—C11	124.1 (3)
N1—C2—C3	103.5 (3)	N3—C11—C12	120.8 (3)
N1—C2—H2A	111.1	N3—C11—C10	114.8 (3)
C3—C2—H2A	111.1	C12—C11—C10	124.4 (3)
N1—C2—H2B	111.1	C13—C12—C11	119.8 (3)
C3—C2—H2B	111.1	C13—C12—H12A	120.1
H2A—C2—H2B	109.0	C11—C12—H12A	120.1
C4—C3—C2	105.0 (4)	C12—C13—C14	119.3 (4)
C4—C3—H3A	110.8	C12—C13—H13A	120.3
C2—C3—H3A	110.8	C14—C13—H13A	120.3
C4—C3—H3B	110.8	C15—C14—C13	118.5 (4)
C2—C3—H3B	110.8	C15—C14—H14A	120.7
H3A—C3—H3B	108.8	C13—C14—H14A	120.7
C3—C4—C5	105.9 (4)	N3—C15—C14	122.8 (4)
C3—C4—H4A	110.5	N3—C15—H15A	118.6
C5—C4—H4A	110.5	C14—C15—H15A	118.6

Experimental details

Crystal data
Chemical formula	[Cu(C₅H₈NS₂)I(C₁₀H₈N₂)]
M_r	492.87
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	6.606 (3), 16.212 (8), 16.405 (8)
β (°)	98.399 (10)
V (Å³)	1738.3 (15)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	3.27
Crystal size (mm)	0.20 × 0.20 × 0.10

Data collection
Diffractometer	Rigaku Mercury CCD diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2000)
T_min, T_max	0.722, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	13239, 3983, 3326
R_int	0.029
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.034, 0.085, 1.07
No. of reflections	3983
No. of parameters	199
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.54, −0.63

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

Acknowledgements

This work was supported financially by the National Natural Science Foundation of China (Nos. 50572030, 50372022), the Research Fund of Huaqiao University (No. 06BS216) and the Young Talent Fund of Fujian Province (2007 F3060).

References

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