(2,2′-Bipyridine-κ² N,N′)iodido(pyrrol­idine-1-dithio­carboxyl­ato-κ² S,S′)copper(II)

Abstract

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,

• a = 6.606 (3) Å

• b = 16.212 (8) Å

• c = 16.405 (8) Å

• β = 98.399 (10)°

• V = 1738.3 (15) ų

• 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[F ² > 2σ(F ²)] = 0.034

• wR(F ²) = 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.

Supplementary Material

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

supplementary crystallographic information

Comment

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).

Experimental

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).

Refinement

H atoms were positioned geometrically and refined as riding atoms, with C—H = 0.93 (aromatic) or 0.97 Å (pyrrolidinyl), U_iso(H) = 1.2U_eq(C).

Figures

Fig. 1.

The molecular structure of (I) with 30% probability displacement ellipsoids (arbitrary spheres for H atoms).

Crystal data

[Cu(C5H8NS2)I(C10H8N2)]	F000 = 964
Mr = 492.87	Dx = 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 = 2.5–27.5º
b = 16.212 (8) Å	µ = 3.27 mm−1
c = 16.405 (8) Å	T = 293 (2) K
β = 98.399 (10)º	Prism, black
V = 1738.3 (15) Å3	0.20 × 0.20 × 0.10 mm
Z = 4

Data collection

Rigaku Mercury CCD diffractometer	3983 independent reflections
Radiation source: Sealed Tube	3326 reflections with I > 2σ(I)
Monochromator: Graphite Monochromator	Rint = 0.029
T = 293(2) K	θmax = 27.5º
ω scans	θmin = 2.5º
Absorption correction: multi-scan(CrystalClear; Rigaku, 2000)	h = −8→8
Tmin = 0.722, Tmax = 1.000	k = −20→21
13239 measured reflections	l = −21→20

Refinement

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.034	H-atom parameters constrained
wR(F2) = 0.085	w = 1/[σ2(Fo2) + (0.041P)2 + 0.011P] where P = (Fo2 + 2Fc2)/3
S = 1.07	(Δ/σ)max = 0.001
3983 reflections	Δρmax = 0.54 e Å−3
199 parameters	Δρmin = −0.63 e Å−3
Primary atom site location: structure-invariant direct methods	Extinction correction: none

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	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, °)

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