Buy article online - an online subscription or single-article purchase is required to access this article.
Download citation
Download citation
link to html
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.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807022295/ng2251sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807022295/ng2251Isup2.hkl
Contains datablock I

CCDC reference: 650669

Key indicators

  • Single-crystal X-ray study
  • T = 293 K
  • Mean [sigma](C-C) = 0.007 Å
  • R factor = 0.042
  • wR factor = 0.061
  • Data-to-parameter ratio = 14.0

checkCIF/PLATON results

No syntax errors found



Alert level C PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical . ? PLAT341_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ... 7
Alert level G REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is correct. If it is not, please give the correct count in the _publ_section_exptl_refinement section of the submitted CIF. From the CIF: _diffrn_reflns_theta_max 25.00 From the CIF: _reflns_number_total 1985 Count of symmetry unique reflns 1043 Completeness (_total/calc) 190.32% TEST3: Check Friedels for noncentro structure Estimate of Friedel pairs measured 942 Fraction of Friedel pairs measured 0.903 Are heavy atom types Z>Si present yes PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature 293 K PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature . 293 K PLAT794_ALERT_5_G Check Predicted Bond Valency for Cu1 (2) 1.99 PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 1
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 2 ALERT level C = Check and explain 5 ALERT level G = General alerts; check 3 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 0 ALERT type 2 Indicator that the structure model may be wrong or deficient 2 ALERT type 3 Indicator that the structure quality may be low 1 ALERT type 4 Improvement, methodology, query or suggestion 1 ALERT type 5 Informative message, check

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).

Structure description 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.

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

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 m3
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 mm1
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)
Graphite monochromatorRint = 0.051
φ and ω scansθmax = 25.0°, θmin = 2.4°
Absorption correction: multi-scan
(SADABS; Bruker, 2000)
h = 1213
Tmin = 0.782, Tmax = 0.872k = 1215
5393 measured reflectionsl = 1717
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 Å3
142 parametersΔρmin = 0.59 e Å3
1 restraintAbsolute structure: Flack (1983), from 942 Friedel pairs
Primary atom site location: structure-invariant direct methodsAbsolute structure 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 mm1
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 reflections
Refinement top
R[F2 > 2σ(F2)] = 0.042H-atom parameters constrained
wR(F2) = 0.061Δρmax = 0.56 e Å3
S = 0.99Δρmin = 0.59 e Å3
1985 reflectionsAbsolute structure: Flack (1983), from 942 Friedel pairs
142 parametersAbsolute structure 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, º) 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 code: (i) x+1, y+2, z.

Experimental details

Crystal data
Chemical formula[Cu(C20H20N4O2S4)]
Mr540.23
Crystal system, space groupOrthorhombic, Iba2
Temperature (K)293
a, b, c (Å)11.634 (2), 12.983 (2), 14.908 (3)
V3)2251.8 (7)
Z4
Radiation typeMo Kα
µ (mm1)1.37
Crystal size (mm)0.2 × 0.15 × 0.1
Data collection
DiffractometerBruker SMART CCD area-detector
Absorption correctionMulti-scan
(SADABS; Bruker, 2000)
Tmin, Tmax0.782, 0.872
No. of measured, independent and
observed [I > 2σ(I)] reflections
5393, 1985, 1557
Rint0.051
(sin θ/λ)max1)0.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.042, 0.061, 0.99
No. of reflections1985
No. of parameters142
No. of restraints1
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.56, 0.59
Absolute structureFlack (1983), from 942 Friedel pairs
Absolute structure parameter0.03 (2)

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SAINT, SHELXTL (Bruker, 2000), SHELXTL.

 

Subscribe to Acta Crystallographica Section E: Crystallographic Communications

The full text of this article is available to subscribers to the journal.

If you have already registered and are using a computer listed in your registration details, please email support@iucr.org for assistance.

Buy online

You may purchase this article in PDF and/or HTML formats. For purchasers in the European Community who do not have a VAT number, VAT will be added at the local rate. Payments to the IUCr are handled by WorldPay, who will accept payment by credit card in several currencies. To purchase the article, please complete the form below (fields marked * are required), and then click on `Continue'.
E-mail address* 
Repeat e-mail address* 
(for error checking) 

Format*   PDF (US $40)
   HTML (US $40)
   PDF+HTML (US $50)
In order for VAT to be shown for your country javascript needs to be enabled.

VAT number 
(non-UK EC countries only) 
Country* 
 

Terms and conditions of use
Contact us

Follow Acta Cryst. E
Sign up for e-alerts
Follow Acta Cryst. on Twitter
Follow us on facebook
Sign up for RSS feeds