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Acta Cryst. (2007). E63, m1653    [ doi:10.1107/S1600536807022295 ]

{Dimethyl [2,2'-(ethane-1,2-diyldioxy)bis(benzylidenehydrazono)]bis(dithioformato)-[kappa]4S,N,N',S'}copper(II)

G.-Q. Mei and K.-L. Huang

Abstract top

The Cu atom in the title complex, [Cu(C20H20N4O2S4)], lies on a crystallographic twofold rotation axis and exists in a distorted square-planar coordination geometry. The geometry is distorted towards octahedral owing to the interactions of the ether O atoms.

Comment top

Blue copper centers in Type I proteins are involved in electron transfer process such as photosynthesis, nitrogen fixation and lignin degradation (Solomon et al.,1992). Investigations of the coordination chemistry of [CuN2S2] complexes revolve around the development of mimics for blue copper centers (Balamurugan et al., 2004). Few [CuN2S2] complexes and their crystal structures have been reported (Knoblauch et al.,1999). In (I), the ethane-1,2-bis((2-oxybenzylidene)hydrazono)(methylthio)methanethiolato dianion, like a pair of plipers, clamps the Cu atom through N and S atom to render a square-planar geometry at the metal. The two ether oxygen atoms are weakly involved [Cu···O 2.718 (2) Å] and their proximity distorts the geometry. The central ion deviates 0.363 (1) Å from the least-square plane.

Related literature top

For related literature, see: Balamurugan et al. (2004); Knoblauch et al. (1999); Solomon et al. (1992).

Experimental top

To a DMF solution (20 ml) of ethane-1,2-bis[(2-oxybenzylidene)hydrazono](methylthio)methanethiol (1 mmol), a methanolic solution (15 ml) of Cu2(ClO4).6H2O (1 mmol) was added. Blue block-shaped crystals were obtained by diffusion of Et2O into the mother liquour over one week.

Refinement top

The carbon-bound H atoms were generated geometrically (C–H 0.93 to 0.97 Å) and were included in the refinement in the riding model approximation, with U(H) set to 1.2Ueq(C).

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Bruker, 2000); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. Molecular structure of (I), with displacement ellipsoids drawn at the 30% probability level. H atoms have been omitted. [Symmetry codes: (i) 1 - x, 2 - y,z]
{Dimethyl [2,2'-(ethane-1,2-diyldioxy)bis(benzylidenehydrazono)]bis(dithioformato)- κ4S,N,N',S'}copper(II) top
Crystal data top
[Cu(C20H20N4O2S4)]F(000) = 1108
Mr = 540.23Dx = 1.593 Mg m−3
Orthorhombic, Iba2Mo Kα radiation, λ = 0.71073 Å
Hall symbol: I 2 -2cCell parameters from 516 reflections
a = 11.634 (2) Åθ = 3.1–19.6°
b = 12.983 (2) ŵ = 1.37 mm−1
c = 14.908 (3) ÅT = 293 K
V = 2251.8 (7) Å3Block, blue
Z = 40.2 × 0.15 × 0.1 mm
Data collection top
Bruker SMART CCD area-detector
diffractometer		1985 independent reflections
Radiation source: fine-focus sealed tube1557 reflections with I > 2σ(I)
graphiteRint = 0.051
φ and ω scansθmax = 25.0°, θmin = 2.4°
Absorption correction: multi-scan
(SADABS; Bruker, 2000)		h = −12→13
Tmin = 0.782, Tmax = 0.872k = −12→15
5393 measured reflectionsl = −17→17
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.042H-atom parameters constrained
wR(F2) = 0.061 w = 1/[σ2(Fo2) + (0.005P)2]
where P = (Fo2 + 2Fc2)/3
S = 0.99(Δ/σ)max < 0.001
1985 reflectionsΔρmax = 0.56 e Å−3
142 parametersΔρmin = −0.59 e Å−3
1 restraintAbsolute structure: Flack (1983), from 942 Friedel pairs
Primary atom site location: structure-invariant direct methodsFlack parameter: −0.03 (2)
Crystal data top
[Cu(C20H20N4O2S4)]V = 2251.8 (7) Å3
Mr = 540.23Z = 4
Orthorhombic, Iba2Mo Kα radiation
a = 11.634 (2) ŵ = 1.37 mm−1
b = 12.983 (2) ÅT = 293 K
c = 14.908 (3) Å0.2 × 0.15 × 0.1 mm
Data collection top
Bruker SMART CCD area-detector
diffractometer		1985 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2000)		1557 reflections with I > 2σ(I)
Tmin = 0.782, Tmax = 0.872Rint = 0.051
5393 measured reflectionsθmax = 25.0°
Refinement top
R[F2 > 2σ(F2)] = 0.042H-atom parameters constrained
wR(F2) = 0.061Δρmax = 0.56 e Å−3
S = 0.99Δρmin = −0.59 e Å−3
1985 reflectionsAbsolute structure: Flack (1983), from 942 Friedel pairs
142 parametersFlack parameter: −0.03 (2)
1 restraint
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
Cu10.50001.00000.68635 (6)0.0349 (2)
N10.5939 (3)0.8681 (3)0.6945 (3)0.0355 (9)
N20.6911 (3)0.8713 (3)0.7513 (2)0.0368 (10)
O10.4892 (3)0.8974 (2)0.5277 (2)0.0491 (9)
C70.4388 (4)0.8036 (4)0.5383 (3)0.0378 (12)
C60.3541 (4)0.7662 (4)0.4830 (3)0.0476 (15)
H60.32590.80680.43660.057*
C50.3112 (5)0.6691 (5)0.4963 (4)0.0570 (16)
H50.25100.64570.46060.068*
C40.3548 (5)0.6071 (4)0.5603 (4)0.0600 (18)
H40.32610.54080.56760.072*
C30.4430 (5)0.6425 (4)0.6154 (4)0.0531 (16)
H30.47450.59890.65840.064*
C20.4845 (5)0.7431 (3)0.6066 (3)0.0392 (13)
C10.5741 (4)0.7768 (3)0.6668 (3)0.0401 (13)
H10.62330.72580.68800.048*
C100.4623 (4)0.9540 (3)0.4493 (4)0.0472 (15)
H10A0.38210.97450.44980.057*
H10B0.47620.91260.39620.057*
S10.66889 (11)1.07741 (9)0.72688 (11)0.0513 (4)
S20.85065 (12)0.97951 (11)0.83033 (10)0.0638 (5)
C80.7281 (4)0.9633 (4)0.7652 (3)0.0441 (14)
C90.8979 (4)0.8506 (4)0.8538 (4)0.0684 (19)
H9A0.83640.80320.84220.103*
H9B0.92050.84570.91560.103*
H9C0.96230.83410.81610.103*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.0355 (5)0.0335 (4)0.0357 (4)−0.0002 (4)0.0000.000
N10.032 (2)0.034 (2)0.041 (3)−0.0024 (16)−0.001 (2)−0.005 (2)
N20.032 (2)0.044 (3)0.034 (3)0.0000 (19)−0.0069 (19)0.004 (2)
O10.066 (3)0.035 (2)0.047 (2)−0.0108 (18)−0.023 (2)0.0052 (17)
C70.041 (3)0.028 (3)0.045 (3)−0.004 (2)0.002 (3)−0.001 (3)
C60.053 (4)0.037 (4)0.053 (4)−0.006 (3)−0.008 (3)−0.004 (3)
C50.052 (4)0.059 (4)0.060 (4)−0.009 (3)−0.010 (3)−0.009 (3)
C40.070 (5)0.050 (4)0.060 (4)−0.025 (3)0.008 (4)−0.013 (3)
C30.072 (4)0.037 (3)0.050 (4)−0.006 (3)0.005 (3)0.002 (3)
C20.045 (3)0.032 (3)0.041 (3)−0.002 (3)0.004 (3)−0.005 (2)
C10.041 (3)0.042 (3)0.038 (4)0.005 (2)0.003 (3)0.005 (3)
C100.069 (4)0.047 (3)0.026 (3)0.000 (2)−0.007 (3)−0.002 (3)
S10.0401 (7)0.0390 (7)0.0746 (10)−0.0035 (6)−0.0068 (8)−0.0048 (8)
S20.0411 (9)0.0754 (12)0.0749 (11)−0.0001 (7)−0.0160 (8)−0.0220 (9)
C80.038 (3)0.055 (4)0.039 (3)−0.001 (3)0.006 (3)−0.011 (3)
C90.047 (4)0.088 (5)0.070 (5)0.011 (3)−0.010 (3)0.014 (4)
Geometric parameters (Å, °) top
Cu1—N1i2.035 (3)C4—C31.392 (7)
Cu1—N12.035 (3)C4—H40.9300
Cu1—S1i2.2882 (13)C3—C21.398 (6)
Cu1—S12.2882 (13)C3—H30.9300
N1—C11.276 (5)C2—C11.444 (6)
N1—N21.413 (4)C1—H10.9300
N2—C81.287 (5)C10—C10i1.482 (8)
O1—C71.361 (5)C10—H10A0.9700
O1—C101.416 (5)C10—H10B0.9700
C7—C61.373 (6)S1—C81.731 (5)
C7—C21.392 (6)S2—C81.738 (5)
C6—C51.370 (7)S2—C91.796 (5)
C6—H60.9300C9—H9A0.9600
C5—C41.348 (7)C9—H9B0.9600
C5—H50.9300C9—H9C0.9600
N1i—Cu1—N1173.2 (2)C2—C3—H3119.8
N1i—Cu1—S1i83.85 (10)C7—C2—C3117.6 (5)
N1—Cu1—S1i94.34 (10)C7—C2—C1124.0 (4)
N1i—Cu1—S194.34 (10)C3—C2—C1118.3 (5)
N1—Cu1—S183.85 (10)N1—C1—C2127.8 (4)
S1i—Cu1—S1149.38 (9)N1—C1—H1116.1
C1—N1—N2111.4 (4)C2—C1—H1116.1
C1—N1—Cu1131.7 (3)O1—C10—C10i106.7 (3)
N2—N1—Cu1116.1 (3)O1—C10—H10A110.4
C8—N2—N1113.1 (4)C10i—C10—H10A110.4
C7—O1—C10117.8 (4)O1—C10—H10B110.4
O1—C7—C6123.7 (5)C10i—C10—H10B110.4
O1—C7—C2115.2 (4)H10A—C10—H10B108.6
C6—C7—C2120.9 (5)C8—S1—Cu193.03 (17)
C5—C6—C7120.0 (5)C8—S2—C9104.3 (2)
C5—C6—H6120.0N2—C8—S1127.5 (4)
C7—C6—H6120.0N2—C8—S2118.5 (4)
C4—C5—C6121.0 (6)S1—C8—S2114.0 (3)
C4—C5—H5119.5S2—C9—H9A109.5
C6—C5—H5119.5S2—C9—H9B109.5
C5—C4—C3119.9 (5)H9A—C9—H9B109.5
C5—C4—H4120.0S2—C9—H9C109.5
C3—C4—H4120.0H9A—C9—H9C109.5
C4—C3—C2120.5 (5)H9B—C9—H9C109.5
C4—C3—H3119.8
Symmetry codes: (i) −x+1, −y+2, z.
Acknowledgements top

This work was supported by the Technical Project of the Department of Education of Jiangxi Province.

references
References top

Balamurugan, R., Palaniandavar, M., Gopalan, R. S. & Kulkarni, G. U. (2004). Inorg. Chim. Acta, 357, 919–930.

Bruker (2000). SAINT, SMART and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.

Flack, H. D. (1983). Acta Cryst. A39, 876–881.

Knoblauch, S., Hartl, F., Stufkens, D. J. & Hennig, H. (1999). Eur. J. Inorg. Chem. pp. 303–312.

Solomon, E. I., Baldwin, M. J. & Lowery, M. D. (1992). Chem. Rev. 92, 521–542.