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Acta Cryst. (2008). E64, m1249    [ doi:10.1107/S1600536808028213 ]

Iodido(1,10-phenanthroline-[kappa]2N,N')(piperine-1-carbodithioato-[kappa]2S,S')copper(II)

L.-Q. Fan

Abstract top

In the title compound, [Cu(C6H10NS2)I(C12H8N2)], the CuII 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.

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 CuII complex (Fig. 1). The CuII 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).

Refinement top

H atoms were positioned geometrically and refined as riding atoms, with C—H = 0.93 (aromatic) or 0.97 Å (piperidyl), Uiso(H) = 1.2Ueq(C).

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
[Figure 1] 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
Mr = 530.91Dx = 1.843 Mg m−3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 4118 reflections
a = 6.408 (4) Åθ = 3.3–27.5°
b = 17.11 (1) ŵ = 2.98 mm−1
c = 18.400 (9) ÅT = 293 K
β = 108.42 (2)°Prism, black
V = 1914 (2) Å30.40 × 0.08 × 0.03 mm
Z = 4
Data collection top
Rigaku Mercury CCD
diffractometer		4236 independent reflections
Radiation source: Sealed Tube3298 reflections with I > 2σ(I)
Graphite MonochromatorRint = 0.069
ω scansθmax = 27.5°, θmin = 2.3°
Absorption correction: multi-scan
(CrystalClear; Rigaku,2000)		h = −8→8
Tmin = 0.751, Tmax = 0.915k = −22→22
14752 measured reflectionsl = −23→23
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.063Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.166H-atom parameters constrained
S = 1.09 w = 1/[σ2(Fo2) + (0.0831P)2 + 0.6436P]
where P = (Fo2 + 2Fc2)/3
4236 reflections(Δ/σ)max < 0.001
226 parametersΔρmax = 1.41 e Å−3
0 restraintsΔρmin = −1.52 e Å−3
Crystal data top
[Cu(C6H10NS2)I(C12H8N2)]V = 1914 (2) Å3
Mr = 530.91Z = 4
Monoclinic, P21/cMo Kα radiation
a = 6.408 (4) ŵ = 2.98 mm−1
b = 17.11 (1) ÅT = 293 K
c = 18.400 (9) Å0.40 × 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)
Tmin = 0.751, Tmax = 0.915Rint = 0.069
14752 measured reflectionsθmax = 27.5°
Refinement top
R[F2 > 2σ(F2)] = 0.063H-atom parameters constrained
wR(F2) = 0.166Δρmax = 1.41 e Å−3
S = 1.09Δρmin = −1.52 e Å−3
4236 reflectionsAbsolute structure: ?
226 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
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
xyzUiso*/Ueq
Cu10.45983 (13)0.35695 (5)0.41693 (4)0.0396 (2)
I10.22830 (8)0.21581 (3)0.35611 (3)0.04846 (19)
S10.2502 (3)0.45295 (13)0.33902 (11)0.0603 (6)
S20.6695 (3)0.39466 (10)0.34223 (9)0.0399 (4)
N10.4499 (9)0.5001 (3)0.2390 (3)0.0405 (12)
N20.3528 (9)0.3678 (3)0.5106 (3)0.0351 (11)
N30.6887 (9)0.2896 (3)0.4912 (3)0.0361 (12)
C10.4559 (11)0.4560 (3)0.2983 (3)0.0362 (14)
C20.2686 (13)0.5527 (4)0.2018 (4)0.0539 (19)
H2A0.32430.60540.20160.065*
H2B0.16440.55330.23030.065*
C30.1534 (13)0.5263 (4)0.1201 (4)0.0532 (18)
H3A0.04100.56410.09470.064*
H3B0.08190.47650.12070.064*
C40.3171 (14)0.5182 (5)0.0754 (4)0.062 (2)
H4A0.24300.49660.02510.074*
H4B0.37350.56940.06850.074*
C50.5064 (13)0.4654 (5)0.1179 (4)0.059 (2)
H5A0.61410.46370.09090.071*
H5B0.45220.41270.11970.071*
C60.6142 (12)0.4953 (4)0.1989 (4)0.0492 (17)
H6A0.73170.46020.22620.059*
H6B0.67740.54650.19730.059*
C70.1837 (11)0.4078 (3)0.5183 (4)0.0411 (15)
H7A0.10030.43860.47780.049*
C80.1278 (12)0.4048 (4)0.5863 (4)0.0472 (17)
H8A0.00980.43400.59050.057*
C90.2441 (12)0.3598 (4)0.6453 (4)0.0436 (16)
H9A0.20490.35680.68980.052*
C100.4269 (12)0.3172 (4)0.6389 (4)0.0399 (15)
C110.4745 (10)0.3239 (3)0.5700 (3)0.0328 (13)
C120.5573 (13)0.2666 (4)0.6979 (4)0.0483 (17)
H12A0.52350.26070.74320.058*
C130.7278 (13)0.2278 (4)0.6880 (4)0.0478 (17)
H13A0.81310.19630.72750.057*
C140.7832 (11)0.2334 (4)0.6183 (4)0.0416 (15)
C150.6546 (11)0.2818 (3)0.5602 (4)0.0343 (13)
C160.9566 (13)0.1938 (4)0.6047 (4)0.0488 (17)
H16A1.04930.16250.64260.059*
C170.9907 (12)0.2009 (4)0.5348 (4)0.0463 (16)
H17A1.10350.17340.52460.056*
C180.8542 (11)0.2500 (4)0.4793 (4)0.0408 (14)
H18A0.87950.25520.43250.049*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.0419 (5)0.0493 (5)0.0317 (4)0.0084 (3)0.0172 (4)0.0075 (3)
I10.0453 (3)0.0554 (3)0.0486 (3)−0.0062 (2)0.0204 (2)−0.01413 (19)
S10.0582 (13)0.0803 (13)0.0535 (11)0.0306 (10)0.0335 (10)0.0285 (10)
S20.0402 (9)0.0471 (9)0.0349 (8)0.0043 (7)0.0155 (7)0.0071 (6)
N10.046 (3)0.046 (3)0.032 (3)0.005 (2)0.015 (3)0.011 (2)
N20.038 (3)0.038 (3)0.028 (3)0.000 (2)0.010 (2)−0.001 (2)
N30.035 (3)0.043 (3)0.032 (3)0.001 (2)0.012 (2)0.000 (2)
C10.042 (4)0.039 (3)0.027 (3)0.001 (3)0.010 (3)0.001 (2)
C20.068 (5)0.045 (4)0.042 (4)0.014 (4)0.010 (4)0.009 (3)
C30.055 (5)0.041 (4)0.052 (4)0.003 (3)−0.001 (4)0.004 (3)
C40.071 (6)0.076 (5)0.030 (4)0.002 (4)0.002 (4)−0.001 (3)
C50.058 (5)0.079 (5)0.045 (4)0.009 (4)0.022 (4)0.005 (4)
C60.045 (4)0.060 (4)0.041 (4)0.001 (3)0.011 (3)0.018 (3)
C70.046 (4)0.038 (3)0.044 (4)0.010 (3)0.021 (3)0.001 (3)
C80.051 (4)0.050 (4)0.051 (4)0.001 (3)0.029 (4)−0.007 (3)
C90.058 (5)0.042 (3)0.037 (4)−0.010 (3)0.023 (4)−0.011 (3)
C100.046 (4)0.044 (3)0.034 (3)−0.009 (3)0.019 (3)−0.003 (3)
C110.036 (4)0.032 (3)0.029 (3)−0.009 (2)0.008 (3)0.000 (2)
C120.059 (5)0.056 (4)0.031 (3)−0.009 (3)0.016 (3)0.001 (3)
C130.055 (5)0.050 (4)0.034 (4)−0.008 (3)0.006 (3)0.008 (3)
C140.039 (4)0.041 (3)0.040 (4)−0.005 (3)0.006 (3)0.005 (3)
C150.037 (4)0.033 (3)0.033 (3)−0.001 (2)0.012 (3)−0.001 (2)
C160.049 (5)0.040 (3)0.052 (4)0.003 (3)0.010 (4)0.006 (3)
C170.034 (4)0.046 (4)0.058 (5)0.006 (3)0.012 (3)−0.003 (3)
C180.035 (4)0.046 (3)0.043 (4)0.002 (3)0.014 (3)−0.002 (3)
Geometric parameters (Å, °) top
Cu1—N32.020 (5)C5—H5A0.9700
Cu1—N22.055 (5)C5—H5B0.9700
Cu1—S22.2972 (19)C6—H6A0.9700
Cu1—S12.311 (2)C6—H6B0.9700
Cu1—I12.8694 (16)C7—C81.408 (8)
S1—C11.711 (6)C7—H7A0.9300
S2—C11.711 (7)C8—C91.348 (10)
N1—C11.317 (7)C8—H8A0.9300
N1—C21.457 (9)C9—C101.416 (10)
N1—C61.466 (8)C9—H9A0.9300
N2—C71.326 (8)C10—C111.398 (8)
N2—C111.353 (8)C10—C121.433 (10)
N3—C181.334 (8)C11—C151.419 (9)
N3—C151.361 (7)C12—C131.339 (11)
C2—C31.520 (10)C12—H12A0.9300
C2—H2A0.9700C13—C141.438 (10)
C2—H2B0.9700C13—H13A0.9300
C3—C41.530 (11)C14—C161.391 (10)
C3—H3A0.9700C14—C151.397 (9)
C3—H3B0.9700C16—C171.376 (10)
C4—C51.517 (11)C16—H16A0.9300
C4—H4A0.9700C17—C181.395 (10)
C4—H4B0.9700C17—H17A0.9300
C5—C61.520 (10)C18—H18A0.9300
N3—Cu1—N281.2 (2)C4—C5—H5B109.6
N3—Cu1—S297.36 (16)C6—C5—H5B109.6
N2—Cu1—S2152.84 (15)H5A—C5—H5B108.1
N3—Cu1—S1168.73 (16)N1—C6—C5109.6 (6)
N2—Cu1—S199.97 (15)N1—C6—H6A109.7
S2—Cu1—S176.38 (7)C5—C6—H6A109.7
N3—Cu1—I187.66 (15)N1—C6—H6B109.7
N2—Cu1—I197.75 (14)C5—C6—H6B109.7
S2—Cu1—I1109.33 (6)H6A—C6—H6B108.2
S1—Cu1—I1103.21 (8)N2—C7—C8121.5 (6)
C1—S1—Cu185.2 (2)N2—C7—H7A119.3
C1—S2—Cu185.6 (2)C8—C7—H7A119.3
C1—N1—C2123.5 (6)C9—C8—C7120.4 (6)
C1—N1—C6123.1 (5)C9—C8—H8A119.8
C2—N1—C6113.1 (5)C7—C8—H8A119.8
C7—N2—C11118.8 (5)C8—C9—C10119.2 (6)
C7—N2—Cu1129.5 (4)C8—C9—H9A120.4
C11—N2—Cu1111.6 (4)C10—C9—H9A120.4
C18—N3—C15118.3 (6)C11—C10—C9117.2 (6)
C18—N3—Cu1128.6 (4)C11—C10—C12119.6 (6)
C15—N3—Cu1113.0 (4)C9—C10—C12123.2 (6)
N1—C1—S1123.8 (5)N2—C11—C10122.9 (6)
N1—C1—S2123.5 (5)N2—C11—C15117.6 (5)
S1—C1—S2112.7 (3)C10—C11—C15119.6 (6)
N1—C2—C3110.3 (6)C13—C12—C10120.1 (6)
N1—C2—H2A109.6C13—C12—H12A120.0
C3—C2—H2A109.6C10—C12—H12A120.0
N1—C2—H2B109.6C12—C13—C14122.1 (7)
C3—C2—H2B109.6C12—C13—H13A119.0
H2A—C2—H2B108.1C14—C13—H13A119.0
C2—C3—C4111.0 (7)C16—C14—C15117.5 (6)
C2—C3—H3A109.4C16—C14—C13124.4 (7)
C4—C3—H3A109.4C15—C14—C13118.0 (7)
C2—C3—H3B109.4N3—C15—C14122.8 (6)
C4—C3—H3B109.4N3—C15—C11116.5 (5)
H3A—C3—H3B108.0C14—C15—C11120.6 (6)
C5—C4—C3110.5 (6)C17—C16—C14119.8 (7)
C5—C4—H4A109.6C17—C16—H16A120.1
C3—C4—H4A109.6C14—C16—H16A120.1
C5—C4—H4B109.6C16—C17—C18119.3 (6)
C3—C4—H4B109.6C16—C17—H17A120.4
H4A—C4—H4B108.1C18—C17—H17A120.4
C4—C5—C6110.3 (6)N3—C18—C17122.2 (6)
C4—C5—H5A109.6N3—C18—H18A118.9
C6—C5—H5A109.6C17—C18—H18A118.9
Acknowledgements top

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
References top

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