Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807022295/ng2251sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807022295/ng2251Isup2.hkl |
CCDC reference: 650669
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (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
For related literature, see: Balamurugan et al. (2004); Knoblauch et al. (1999); Solomon et al. (1992).
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.
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).
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).
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.
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] |
[Cu(C20H20N4O2S4)] | F(000) = 1108 |
Mr = 540.23 | Dx = 1.593 Mg m−3 |
Orthorhombic, Iba2 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: I 2 -2c | Cell parameters from 516 reflections |
a = 11.634 (2) Å | θ = 3.1–19.6° |
b = 12.983 (2) Å | µ = 1.37 mm−1 |
c = 14.908 (3) Å | T = 293 K |
V = 2251.8 (7) Å3 | Block, blue |
Z = 4 | 0.2 × 0.15 × 0.1 mm |
Bruker SMART CCD area-detector diffractometer | 1985 independent reflections |
Radiation source: fine-focus sealed tube | 1557 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.051 |
φ and ω scans | θmax = 25.0°, θmin = 2.4° |
Absorption correction: multi-scan (SADABS; Bruker, 2000) | h = −12→13 |
Tmin = 0.782, Tmax = 0.872 | k = −12→15 |
5393 measured reflections | l = −17→17 |
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)] = 0.042 | H-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 reflections | Δρmax = 0.56 e Å−3 |
142 parameters | Δρmin = −0.59 e Å−3 |
1 restraint | Absolute structure: Flack (1983), from 942 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: −0.03 (2) |
[Cu(C20H20N4O2S4)] | V = 2251.8 (7) Å3 |
Mr = 540.23 | Z = 4 |
Orthorhombic, Iba2 | Mo Kα radiation |
a = 11.634 (2) Å | µ = 1.37 mm−1 |
b = 12.983 (2) Å | T = 293 K |
c = 14.908 (3) Å | 0.2 × 0.15 × 0.1 mm |
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 = 0.872 | Rint = 0.051 |
5393 measured reflections |
R[F2 > 2σ(F2)] = 0.042 | H-atom parameters constrained |
wR(F2) = 0.061 | Δρmax = 0.56 e Å−3 |
S = 0.99 | Δρmin = −0.59 e Å−3 |
1985 reflections | Absolute structure: Flack (1983), from 942 Friedel pairs |
142 parameters | Absolute structure parameter: −0.03 (2) |
1 restraint |
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. |
x | y | z | Uiso*/Ueq | ||
Cu1 | 0.5000 | 1.0000 | 0.68635 (6) | 0.0349 (2) | |
N1 | 0.5939 (3) | 0.8681 (3) | 0.6945 (3) | 0.0355 (9) | |
N2 | 0.6911 (3) | 0.8713 (3) | 0.7513 (2) | 0.0368 (10) | |
O1 | 0.4892 (3) | 0.8974 (2) | 0.5277 (2) | 0.0491 (9) | |
C7 | 0.4388 (4) | 0.8036 (4) | 0.5383 (3) | 0.0378 (12) | |
C6 | 0.3541 (4) | 0.7662 (4) | 0.4830 (3) | 0.0476 (15) | |
H6 | 0.3259 | 0.8068 | 0.4366 | 0.057* | |
C5 | 0.3112 (5) | 0.6691 (5) | 0.4963 (4) | 0.0570 (16) | |
H5 | 0.2510 | 0.6457 | 0.4606 | 0.068* | |
C4 | 0.3548 (5) | 0.6071 (4) | 0.5603 (4) | 0.0600 (18) | |
H4 | 0.3261 | 0.5408 | 0.5676 | 0.072* | |
C3 | 0.4430 (5) | 0.6425 (4) | 0.6154 (4) | 0.0531 (16) | |
H3 | 0.4745 | 0.5989 | 0.6584 | 0.064* | |
C2 | 0.4845 (5) | 0.7431 (3) | 0.6066 (3) | 0.0392 (13) | |
C1 | 0.5741 (4) | 0.7768 (3) | 0.6668 (3) | 0.0401 (13) | |
H1 | 0.6233 | 0.7258 | 0.6880 | 0.048* | |
C10 | 0.4623 (4) | 0.9540 (3) | 0.4493 (4) | 0.0472 (15) | |
H10A | 0.3821 | 0.9745 | 0.4498 | 0.057* | |
H10B | 0.4762 | 0.9126 | 0.3962 | 0.057* | |
S1 | 0.66889 (11) | 1.07741 (9) | 0.72688 (11) | 0.0513 (4) | |
S2 | 0.85065 (12) | 0.97951 (11) | 0.83033 (10) | 0.0638 (5) | |
C8 | 0.7281 (4) | 0.9633 (4) | 0.7652 (3) | 0.0441 (14) | |
C9 | 0.8979 (4) | 0.8506 (4) | 0.8538 (4) | 0.0684 (19) | |
H9A | 0.8364 | 0.8032 | 0.8422 | 0.103* | |
H9B | 0.9205 | 0.8457 | 0.9156 | 0.103* | |
H9C | 0.9623 | 0.8341 | 0.8161 | 0.103* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.0355 (5) | 0.0335 (4) | 0.0357 (4) | −0.0002 (4) | 0.000 | 0.000 |
N1 | 0.032 (2) | 0.034 (2) | 0.041 (3) | −0.0024 (16) | −0.001 (2) | −0.005 (2) |
N2 | 0.032 (2) | 0.044 (3) | 0.034 (3) | 0.0000 (19) | −0.0069 (19) | 0.004 (2) |
O1 | 0.066 (3) | 0.035 (2) | 0.047 (2) | −0.0108 (18) | −0.023 (2) | 0.0052 (17) |
C7 | 0.041 (3) | 0.028 (3) | 0.045 (3) | −0.004 (2) | 0.002 (3) | −0.001 (3) |
C6 | 0.053 (4) | 0.037 (4) | 0.053 (4) | −0.006 (3) | −0.008 (3) | −0.004 (3) |
C5 | 0.052 (4) | 0.059 (4) | 0.060 (4) | −0.009 (3) | −0.010 (3) | −0.009 (3) |
C4 | 0.070 (5) | 0.050 (4) | 0.060 (4) | −0.025 (3) | 0.008 (4) | −0.013 (3) |
C3 | 0.072 (4) | 0.037 (3) | 0.050 (4) | −0.006 (3) | 0.005 (3) | 0.002 (3) |
C2 | 0.045 (3) | 0.032 (3) | 0.041 (3) | −0.002 (3) | 0.004 (3) | −0.005 (2) |
C1 | 0.041 (3) | 0.042 (3) | 0.038 (4) | 0.005 (2) | 0.003 (3) | 0.005 (3) |
C10 | 0.069 (4) | 0.047 (3) | 0.026 (3) | 0.000 (2) | −0.007 (3) | −0.002 (3) |
S1 | 0.0401 (7) | 0.0390 (7) | 0.0746 (10) | −0.0035 (6) | −0.0068 (8) | −0.0048 (8) |
S2 | 0.0411 (9) | 0.0754 (12) | 0.0749 (11) | −0.0001 (7) | −0.0160 (8) | −0.0220 (9) |
C8 | 0.038 (3) | 0.055 (4) | 0.039 (3) | −0.001 (3) | 0.006 (3) | −0.011 (3) |
C9 | 0.047 (4) | 0.088 (5) | 0.070 (5) | 0.011 (3) | −0.010 (3) | 0.014 (4) |
Cu1—N1i | 2.035 (3) | C4—C3 | 1.392 (7) |
Cu1—N1 | 2.035 (3) | C4—H4 | 0.9300 |
Cu1—S1i | 2.2882 (13) | C3—C2 | 1.398 (6) |
Cu1—S1 | 2.2882 (13) | C3—H3 | 0.9300 |
N1—C1 | 1.276 (5) | C2—C1 | 1.444 (6) |
N1—N2 | 1.413 (4) | C1—H1 | 0.9300 |
N2—C8 | 1.287 (5) | C10—C10i | 1.482 (8) |
O1—C7 | 1.361 (5) | C10—H10A | 0.9700 |
O1—C10 | 1.416 (5) | C10—H10B | 0.9700 |
C7—C6 | 1.373 (6) | S1—C8 | 1.731 (5) |
C7—C2 | 1.392 (6) | S2—C8 | 1.738 (5) |
C6—C5 | 1.370 (7) | S2—C9 | 1.796 (5) |
C6—H6 | 0.9300 | C9—H9A | 0.9600 |
C5—C4 | 1.348 (7) | C9—H9B | 0.9600 |
C5—H5 | 0.9300 | C9—H9C | 0.9600 |
N1i—Cu1—N1 | 173.2 (2) | C2—C3—H3 | 119.8 |
N1i—Cu1—S1i | 83.85 (10) | C7—C2—C3 | 117.6 (5) |
N1—Cu1—S1i | 94.34 (10) | C7—C2—C1 | 124.0 (4) |
N1i—Cu1—S1 | 94.34 (10) | C3—C2—C1 | 118.3 (5) |
N1—Cu1—S1 | 83.85 (10) | N1—C1—C2 | 127.8 (4) |
S1i—Cu1—S1 | 149.38 (9) | N1—C1—H1 | 116.1 |
C1—N1—N2 | 111.4 (4) | C2—C1—H1 | 116.1 |
C1—N1—Cu1 | 131.7 (3) | O1—C10—C10i | 106.7 (3) |
N2—N1—Cu1 | 116.1 (3) | O1—C10—H10A | 110.4 |
C8—N2—N1 | 113.1 (4) | C10i—C10—H10A | 110.4 |
C7—O1—C10 | 117.8 (4) | O1—C10—H10B | 110.4 |
O1—C7—C6 | 123.7 (5) | C10i—C10—H10B | 110.4 |
O1—C7—C2 | 115.2 (4) | H10A—C10—H10B | 108.6 |
C6—C7—C2 | 120.9 (5) | C8—S1—Cu1 | 93.03 (17) |
C5—C6—C7 | 120.0 (5) | C8—S2—C9 | 104.3 (2) |
C5—C6—H6 | 120.0 | N2—C8—S1 | 127.5 (4) |
C7—C6—H6 | 120.0 | N2—C8—S2 | 118.5 (4) |
C4—C5—C6 | 121.0 (6) | S1—C8—S2 | 114.0 (3) |
C4—C5—H5 | 119.5 | S2—C9—H9A | 109.5 |
C6—C5—H5 | 119.5 | S2—C9—H9B | 109.5 |
C5—C4—C3 | 119.9 (5) | H9A—C9—H9B | 109.5 |
C5—C4—H4 | 120.0 | S2—C9—H9C | 109.5 |
C3—C4—H4 | 120.0 | H9A—C9—H9C | 109.5 |
C4—C3—C2 | 120.5 (5) | H9B—C9—H9C | 109.5 |
C4—C3—H3 | 119.8 |
Symmetry code: (i) −x+1, −y+2, z. |
Experimental details
Crystal data | |
Chemical formula | [Cu(C20H20N4O2S4)] |
Mr | 540.23 |
Crystal system, space group | Orthorhombic, Iba2 |
Temperature (K) | 293 |
a, b, c (Å) | 11.634 (2), 12.983 (2), 14.908 (3) |
V (Å3) | 2251.8 (7) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.37 |
Crystal size (mm) | 0.2 × 0.15 × 0.1 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector |
Absorption correction | Multi-scan (SADABS; Bruker, 2000) |
Tmin, Tmax | 0.782, 0.872 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5393, 1985, 1557 |
Rint | 0.051 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.042, 0.061, 0.99 |
No. of reflections | 1985 |
No. of parameters | 142 |
No. of restraints | 1 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.56, −0.59 |
Absolute structure | Flack (1983), from 942 Friedel pairs |
Absolute structure parameter | −0.03 (2) |
Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SAINT, SHELXTL (Bruker, 2000), SHELXTL.
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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.