Iodido(1,10-phenanthroline-κ2N,N′)(piperine-1-carbodithioato-κ2S,S′)copper(II)

Fan, L.-Q.

doi:10.1107/S1600536808028213

metal-organic compounds

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Volume 64| Part 10| October 2008| Page m1249

doi:10.1107/S1600536808028213

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Iodido(1,10-phenanthroline-κ²N,N′)(piperine-1-carbodithioato-κ²S,S′)copper(II)

Le-Qing Fan ^a ^*

^aInstitute of Materials Physical Chemistry, and 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 30 August 2008; accepted 3 September 2008; online 6 September 2008)

In the title compound, [Cu(C₆H₁₀NS₂)I(C₁₂H₈N₂)], the Cu^II ion is coordinated by one iodide ion, two N atoms of the phenanthroline ligand and two S atoms from the piperidyldithiocarbamate 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(C₆H₁₀NS₂)I(C₁₂H₈N₂)]
M_r = 530.91
Monoclinic, P 2₁ /c
a = 6.408 (4) Å
b = 17.11 (1) Å
c = 18.400 (9) Å
β = 108.42 (2)°
V = 1914 (2) Å³
Z = 4
Mo Kα radiation
μ = 2.98 mm⁻¹
T = 293 (2) K
0.40 × 0.08 × 0.03 mm

Data collection

Rigaku Mercury CCD diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku,2000 ) T_min = 0.751, T_max = 0.915
14752 measured reflections
4236 independent reflections
3298 reflections with I > 2σ(I)
R_int = 0.069

Refinement

R[F² > 2σ(F²)] = 0.063
wR(F²) = 0.166
S = 1.09
4236 reflections
226 parameters
H-atom parameters constrained
Δρ_max = 1.41 e Å⁻³
Δρ_min = −1.52 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/S1600536808028213/im2082sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808028213/im2082Isup2.hkl

checkCIF report

Comment top

Research concerning 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 a considerable structural variety of complexes (Englhardt et al., 1998; Fernández et al., 2000; Koh et al., 2003). I report here the crystal structure of the title copper(II) complex, (I), contanining 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 phenanthroline ligand and two S atoms from the piperidyldithiocarbamate 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), NaS₂CNC₅H₁₀.2H₂O (0.09 g, 0.4 mmol), 1,10-phenanthroline (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).

Iodido(1,10-phenanthroline-κ²N,N')(piperine-1-carbodithioato- κ²S,S')copper(II) top

Crystal data top

[Cu(C₆H₁₀NS₂)I(C₁₂H₈N₂)]	F(000) = 1044
M_r = 530.91	D_x = 1.843 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 4118 reflections
a = 6.408 (4) Å	θ = 3.3–27.5°
b = 17.11 (1) Å	µ = 2.98 mm⁻¹
c = 18.400 (9) Å	T = 293 K
β = 108.42 (2)°	Prism, black
V = 1914 (2) Å³	0.40 × 0.08 × 0.03 mm
Z = 4

Data collection top

Rigaku Mercury CCD diffractometer	4236 independent reflections
Radiation source: Sealed Tube	3298 reflections with I > 2σ(I)
Graphite Monochromator monochromator	R_int = 0.069
ω scans	θ_max = 27.5°, θ_min = 2.3°
Absorption correction: multi-scan (CrystalClear; Rigaku,2000)	h = −8→8
T_min = 0.751, T_max = 0.915	k = −22→22
14752 measured reflections	l = −23→23

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)] = 0.063	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.166	H-atom parameters constrained
S = 1.09	w = 1/[σ²(F_o²) + (0.0831P)² + 0.6436P] where P = (F_o² + 2F_c²)/3
4236 reflections	(Δ/σ)_max < 0.001
226 parameters	Δρ_max = 1.41 e Å⁻³
0 restraints	Δρ_min = −1.52 e Å⁻³

Crystal data top

[Cu(C₆H₁₀NS₂)I(C₁₂H₈N₂)]	V = 1914 (2) Å³
M_r = 530.91	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 6.408 (4) Å	µ = 2.98 mm⁻¹
b = 17.11 (1) Å	T = 293 K
c = 18.400 (9) Å	0.40 × 0.08 × 0.03 mm
β = 108.42 (2)°

Data collection top

Rigaku Mercury CCD diffractometer	4236 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku,2000)	3298 reflections with I > 2σ(I)
T_min = 0.751, T_max = 0.915	R_int = 0.069
14752 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.063	0 restraints
wR(F²) = 0.166	H-atom parameters constrained
S = 1.09	Δρ_max = 1.41 e Å⁻³
4236 reflections	Δρ_min = −1.52 e Å⁻³
226 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	0.45983 (13)	0.35695 (5)	0.41693 (4)	0.0396 (2)
I1	0.22830 (8)	0.21581 (3)	0.35611 (3)	0.04846 (19)
S1	0.2502 (3)	0.45295 (13)	0.33902 (11)	0.0603 (6)
S2	0.6695 (3)	0.39466 (10)	0.34223 (9)	0.0399 (4)
N1	0.4499 (9)	0.5001 (3)	0.2390 (3)	0.0405 (12)
N2	0.3528 (9)	0.3678 (3)	0.5106 (3)	0.0351 (11)
N3	0.6887 (9)	0.2896 (3)	0.4912 (3)	0.0361 (12)
C1	0.4559 (11)	0.4560 (3)	0.2983 (3)	0.0362 (14)
C2	0.2686 (13)	0.5527 (4)	0.2018 (4)	0.0539 (19)
H2A	0.3243	0.6054	0.2016	0.065*
H2B	0.1644	0.5533	0.2303	0.065*
C3	0.1534 (13)	0.5263 (4)	0.1201 (4)	0.0532 (18)
H3A	0.0410	0.5641	0.0947	0.064*
H3B	0.0819	0.4765	0.1207	0.064*
C4	0.3171 (14)	0.5182 (5)	0.0754 (4)	0.062 (2)
H4A	0.2430	0.4966	0.0251	0.074*
H4B	0.3735	0.5694	0.0685	0.074*
C5	0.5064 (13)	0.4654 (5)	0.1179 (4)	0.059 (2)
H5A	0.6141	0.4637	0.0909	0.071*
H5B	0.4522	0.4127	0.1197	0.071*
C6	0.6142 (12)	0.4953 (4)	0.1989 (4)	0.0492 (17)
H6A	0.7317	0.4602	0.2262	0.059*
H6B	0.6774	0.5465	0.1973	0.059*
C7	0.1837 (11)	0.4078 (3)	0.5183 (4)	0.0411 (15)
H7A	0.1003	0.4386	0.4778	0.049*
C8	0.1278 (12)	0.4048 (4)	0.5863 (4)	0.0472 (17)
H8A	0.0098	0.4340	0.5905	0.057*
C9	0.2441 (12)	0.3598 (4)	0.6453 (4)	0.0436 (16)
H9A	0.2049	0.3568	0.6898	0.052*
C10	0.4269 (12)	0.3172 (4)	0.6389 (4)	0.0399 (15)
C11	0.4745 (10)	0.3239 (3)	0.5700 (3)	0.0328 (13)
C12	0.5573 (13)	0.2666 (4)	0.6979 (4)	0.0483 (17)
H12A	0.5235	0.2607	0.7432	0.058*
C13	0.7278 (13)	0.2278 (4)	0.6880 (4)	0.0478 (17)
H13A	0.8131	0.1963	0.7275	0.057*
C14	0.7832 (11)	0.2334 (4)	0.6183 (4)	0.0416 (15)
C15	0.6546 (11)	0.2818 (3)	0.5602 (4)	0.0343 (13)
C16	0.9566 (13)	0.1938 (4)	0.6047 (4)	0.0488 (17)
H16A	1.0493	0.1625	0.6426	0.059*
C17	0.9907 (12)	0.2009 (4)	0.5348 (4)	0.0463 (16)
H17A	1.1035	0.1734	0.5246	0.056*
C18	0.8542 (11)	0.2500 (4)	0.4793 (4)	0.0408 (14)
H18A	0.8795	0.2552	0.4325	0.049*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0419 (5)	0.0493 (5)	0.0317 (4)	0.0084 (3)	0.0172 (4)	0.0075 (3)
I1	0.0453 (3)	0.0554 (3)	0.0486 (3)	−0.0062 (2)	0.0204 (2)	−0.01413 (19)
S1	0.0582 (13)	0.0803 (13)	0.0535 (11)	0.0306 (10)	0.0335 (10)	0.0285 (10)
S2	0.0402 (9)	0.0471 (9)	0.0349 (8)	0.0043 (7)	0.0155 (7)	0.0071 (6)
N1	0.046 (3)	0.046 (3)	0.032 (3)	0.005 (2)	0.015 (3)	0.011 (2)
N2	0.038 (3)	0.038 (3)	0.028 (3)	0.000 (2)	0.010 (2)	−0.001 (2)
N3	0.035 (3)	0.043 (3)	0.032 (3)	0.001 (2)	0.012 (2)	0.000 (2)
C1	0.042 (4)	0.039 (3)	0.027 (3)	0.001 (3)	0.010 (3)	0.001 (2)
C2	0.068 (5)	0.045 (4)	0.042 (4)	0.014 (4)	0.010 (4)	0.009 (3)
C3	0.055 (5)	0.041 (4)	0.052 (4)	0.003 (3)	−0.001 (4)	0.004 (3)
C4	0.071 (6)	0.076 (5)	0.030 (4)	0.002 (4)	0.002 (4)	−0.001 (3)
C5	0.058 (5)	0.079 (5)	0.045 (4)	0.009 (4)	0.022 (4)	0.005 (4)
C6	0.045 (4)	0.060 (4)	0.041 (4)	0.001 (3)	0.011 (3)	0.018 (3)
C7	0.046 (4)	0.038 (3)	0.044 (4)	0.010 (3)	0.021 (3)	0.001 (3)
C8	0.051 (4)	0.050 (4)	0.051 (4)	0.001 (3)	0.029 (4)	−0.007 (3)
C9	0.058 (5)	0.042 (3)	0.037 (4)	−0.010 (3)	0.023 (4)	−0.011 (3)
C10	0.046 (4)	0.044 (3)	0.034 (3)	−0.009 (3)	0.019 (3)	−0.003 (3)
C11	0.036 (4)	0.032 (3)	0.029 (3)	−0.009 (2)	0.008 (3)	0.000 (2)
C12	0.059 (5)	0.056 (4)	0.031 (3)	−0.009 (3)	0.016 (3)	0.001 (3)
C13	0.055 (5)	0.050 (4)	0.034 (4)	−0.008 (3)	0.006 (3)	0.008 (3)
C14	0.039 (4)	0.041 (3)	0.040 (4)	−0.005 (3)	0.006 (3)	0.005 (3)
C15	0.037 (4)	0.033 (3)	0.033 (3)	−0.001 (2)	0.012 (3)	−0.001 (2)
C16	0.049 (5)	0.040 (3)	0.052 (4)	0.003 (3)	0.010 (4)	0.006 (3)
C17	0.034 (4)	0.046 (4)	0.058 (5)	0.006 (3)	0.012 (3)	−0.003 (3)
C18	0.035 (4)	0.046 (3)	0.043 (4)	0.002 (3)	0.014 (3)	−0.002 (3)

Geometric parameters (Å, º) top

Cu1—N3	2.020 (5)	C5—H5A	0.9700
Cu1—N2	2.055 (5)	C5—H5B	0.9700
Cu1—S2	2.2972 (19)	C6—H6A	0.9700
Cu1—S1	2.311 (2)	C6—H6B	0.9700
Cu1—I1	2.8694 (16)	C7—C8	1.408 (8)
S1—C1	1.711 (6)	C7—H7A	0.9300
S2—C1	1.711 (7)	C8—C9	1.348 (10)
N1—C1	1.317 (7)	C8—H8A	0.9300
N1—C2	1.457 (9)	C9—C10	1.416 (10)
N1—C6	1.466 (8)	C9—H9A	0.9300
N2—C7	1.326 (8)	C10—C11	1.398 (8)
N2—C11	1.353 (8)	C10—C12	1.433 (10)
N3—C18	1.334 (8)	C11—C15	1.419 (9)
N3—C15	1.361 (7)	C12—C13	1.339 (11)
C2—C3	1.520 (10)	C12—H12A	0.9300
C2—H2A	0.9700	C13—C14	1.438 (10)
C2—H2B	0.9700	C13—H13A	0.9300
C3—C4	1.530 (11)	C14—C16	1.391 (10)
C3—H3A	0.9700	C14—C15	1.397 (9)
C3—H3B	0.9700	C16—C17	1.376 (10)
C4—C5	1.517 (11)	C16—H16A	0.9300
C4—H4A	0.9700	C17—C18	1.395 (10)
C4—H4B	0.9700	C17—H17A	0.9300
C5—C6	1.520 (10)	C18—H18A	0.9300

N3—Cu1—N2	81.2 (2)	C4—C5—H5B	109.6
N3—Cu1—S2	97.36 (16)	C6—C5—H5B	109.6
N2—Cu1—S2	152.84 (15)	H5A—C5—H5B	108.1
N3—Cu1—S1	168.73 (16)	N1—C6—C5	109.6 (6)
N2—Cu1—S1	99.97 (15)	N1—C6—H6A	109.7
S2—Cu1—S1	76.38 (7)	C5—C6—H6A	109.7
N3—Cu1—I1	87.66 (15)	N1—C6—H6B	109.7
N2—Cu1—I1	97.75 (14)	C5—C6—H6B	109.7
S2—Cu1—I1	109.33 (6)	H6A—C6—H6B	108.2
S1—Cu1—I1	103.21 (8)	N2—C7—C8	121.5 (6)
C1—S1—Cu1	85.2 (2)	N2—C7—H7A	119.3
C1—S2—Cu1	85.6 (2)	C8—C7—H7A	119.3
C1—N1—C2	123.5 (6)	C9—C8—C7	120.4 (6)
C1—N1—C6	123.1 (5)	C9—C8—H8A	119.8
C2—N1—C6	113.1 (5)	C7—C8—H8A	119.8
C7—N2—C11	118.8 (5)	C8—C9—C10	119.2 (6)
C7—N2—Cu1	129.5 (4)	C8—C9—H9A	120.4
C11—N2—Cu1	111.6 (4)	C10—C9—H9A	120.4
C18—N3—C15	118.3 (6)	C11—C10—C9	117.2 (6)
C18—N3—Cu1	128.6 (4)	C11—C10—C12	119.6 (6)
C15—N3—Cu1	113.0 (4)	C9—C10—C12	123.2 (6)
N1—C1—S1	123.8 (5)	N2—C11—C10	122.9 (6)
N1—C1—S2	123.5 (5)	N2—C11—C15	117.6 (5)
S1—C1—S2	112.7 (3)	C10—C11—C15	119.6 (6)
N1—C2—C3	110.3 (6)	C13—C12—C10	120.1 (6)
N1—C2—H2A	109.6	C13—C12—H12A	120.0
C3—C2—H2A	109.6	C10—C12—H12A	120.0
N1—C2—H2B	109.6	C12—C13—C14	122.1 (7)
C3—C2—H2B	109.6	C12—C13—H13A	119.0
H2A—C2—H2B	108.1	C14—C13—H13A	119.0
C2—C3—C4	111.0 (7)	C16—C14—C15	117.5 (6)
C2—C3—H3A	109.4	C16—C14—C13	124.4 (7)
C4—C3—H3A	109.4	C15—C14—C13	118.0 (7)
C2—C3—H3B	109.4	N3—C15—C14	122.8 (6)
C4—C3—H3B	109.4	N3—C15—C11	116.5 (5)
H3A—C3—H3B	108.0	C14—C15—C11	120.6 (6)
C5—C4—C3	110.5 (6)	C17—C16—C14	119.8 (7)
C5—C4—H4A	109.6	C17—C16—H16A	120.1
C3—C4—H4A	109.6	C14—C16—H16A	120.1
C5—C4—H4B	109.6	C16—C17—C18	119.3 (6)
C3—C4—H4B	109.6	C16—C17—H17A	120.4
H4A—C4—H4B	108.1	C18—C17—H17A	120.4
C4—C5—C6	110.3 (6)	N3—C18—C17	122.2 (6)
C4—C5—H5A	109.6	N3—C18—H18A	118.9
C6—C5—H5A	109.6	C17—C18—H18A	118.9

Experimental details

Crystal data
Chemical formula	[Cu(C₆H₁₀NS₂)I(C₁₂H₈N₂)]
M_r	530.91
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	6.408 (4), 17.11 (1), 18.400 (9)
β (°)	108.42 (2)
V (Å³)	1914 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	2.98
Crystal size (mm)	0.40 × 0.08 × 0.03

Data collection
Diffractometer	Rigaku Mercury CCD diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku,2000)
T_min, T_max	0.751, 0.915
No. of measured, independent and observed [I > 2σ(I)] reflections	14752, 4236, 3298
R_int	0.069
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.063, 0.166, 1.09
No. of reflections	4236
No. of parameters	226
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.41, −1.52

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. 2007F3060).

References

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