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Acta Cryst. (2011). E67, m621    [ doi:10.1107/S160053681101422X ]

cis-Bis[1,1-dibenzyl-3-(furan-2-ylcarbonyl)thioureato-[kappa]2O,S]copper(II)

H. Pérez, C. C. P. da Silva, A. M. Plutín, C. A. de Simone and J. Ellena

Abstract top

In the title compound, [Cu(C20H17N2O2S)2], the CuII atom is coordinated by the S and O atoms of two 1,1-dibenzyl-3-(furan-2-ylcarbonyl)thioureate ligands in a distorted square-planar geometry. The two O and two S atoms are mutually cis to each other. The Cu-S and Cu-O bond lengths lie within the ranges of those found in related structures. The dihedral angle between the planes of the two chelating rings is 26.15 (6)°.

Comment top

N-acyl-N',N'-disubstituted thioureas have attracted the attention of researches over the last three decades with regard to coordination behaviour towards transition metals (Arslan et al., 2003). During complex formation, the ligand is deprotonated, which results in a neutral complex with a six-membered ring chelating the metal ion.

In the crystal structure of the title complex, the two furoylthiourea molecules adopt a cis conformation, bonded to the central CuII ion as shown in Fig. 1. The complex coordination geometry is a distorted square-plane as reflected by angles O1—Cu—S2 [166.02 (6)°] and O2—Cu—S1 [163.52 (7)°]. The distance of Cu atom from the best plane through the coordination sphere is 0.2486 (1) Å. The chelate ring systems, Cu–O1–C1–N1–C2–S1 and Cu–O2–C21–N3–C22–S2, are nearly planar with the largest deviations from the best plane being -0.118 (1) Å for C2 and 0.114 (2) Å for C22, respectively. The dihedral angle of 26.15 (6)° between these chelate planes indicates a strong distortion from square planar towards tetrahedral geometry. By comparison, the corresponding O—Ni—S angles and dihedral angle for the NiII analog (Pérez et al., 2011) are 169.66 (5)°, 170.09 (6)° and 20.33 (6)°, respectively. As a result, the square-planar coordination geometry of the title molecule is more distorted. The Cu—S and Cu—O bond lengths lie within the range of those found in the related structures (Gomes et al., 2007, Binzet et al., 2006). The bond lengths of the thiocarbonyl and carbonyl bonds are longer than the average for C═S (1.68 Å) and C═O (1.20 Å) in thioureas, while the C—N bonds in the chelate rings are all shorter than the average for C—N single bond of about 1.48 Å. This indicates extensive electronic delocalization within the complex rings. Fig. 2 shows the arrangement of the complex molecules in the unit cell.

Related literature top

For general background, see: Arslan et al. (2003). For synthesis details, see: Nagasawa & Mitsunobu (1981). For related structures, see: Binzet et al. (2006); Gomes et al. (2007); Pérez et al. (2011).

Experimental top

The 1,1-dibenzyl-3-[(furan-2-yl)-carbonyl]thiourea ligand was prepared using the standard procedure previously reported in the literature (Nagasawa & Mitsunobu, 1981) by the reaction of furoyl chloride with KSCN in anhydrous acetone, and then condensation with dibenzylamine. To an ethanol solution (30 ml) containing the ligand (0.70 g, 2 mmol) was added an ethanol solution of Cu(CH3COO)2.H2O (0.20 g, 1 mmol). The solution was stirred at room temperature for 2 h, and at once a solution of NaOH (1 N) was added to adjust pH to the neutral value. The mixture was filtered and the filtrate was evaporated under reduced pressure to give a green solid, which was washed with acetone. Single crystals were obtained by slow evaporation of a chloroform/dichloromethane solution (1:1, v/v) of the complex.

Refinement top

H atoms were positioned geometrically and refined as riding atoms, with C—H = 0.93 Å and Uiso(H) = 1.2Ueq(C) for aromatic, and C—H = 0.97 Å and 1.5Ueq(C) for methylene.

Computing details top

Data collection: COLLECT (Enraf–Nonius, 2000); cell refinement: SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO and SCALEPACK (Otwinowski & Minor, 1997); SORTAV (Blessing, 1987, 1989); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and Mercury (Macrae et al., 2006); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top
[Figure 1] Fig. 1. The molecular structure of title compound. Displacement ellipsoids are drawn at the 50% probability level.
[Figure 2] Fig. 2. Crystal packing of title complex, viewed along [010]. H atoms have been omitted for clarity.
cis-Bis[1,1-dibenzyl-3-(furan-2-ylcarbonyl)thioureato- κ2O,S]copper(II) top
Crystal data top
[Cu(C20H17N2O2S)2]F(000) = 1580
Mr = 762.37Dx = 1.387 Mg m−3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 22283 reflections
a = 18.8390 (3) Åθ = 2.9–26.7°
b = 10.8730 (2) ŵ = 0.76 mm−1
c = 19.6200 (3) ÅT = 293 K
β = 114.748 (1)°Prism, blue
V = 3649.79 (10) Å30.49 × 0.44 × 0.39 mm
Z = 4
Data collection top
Nonius KappaCCD area-detector
diffractometer		7413 independent reflections
Radiation source: Enraf–Nonius FR5906761 reflections with I > 2σ(I)
graphiteRint = 0.027
Detector resolution: 9 pixels mm-1θmax = 26.7°, θmin = 3.0°
CCD rotation images, thick slices scansh = −23→23
Absorption correction: gaussian
(Coppens et al., 1965)		k = −13→13
Tmin = 0.779, Tmax = 0.886l = −24→24
21982 measured reflections
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)] = 0.049Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.122H-atom parameters constrained
S = 1.07 w = 1/[σ2(Fo2) + (0.0633P)2 + 1.1325P]
where P = (Fo2 + 2Fc2)/3
7413 reflections(Δ/σ)max = 0.001
460 parametersΔρmax = 0.23 e Å−3
0 restraintsΔρmin = −0.39 e Å−3
Crystal data top
[Cu(C20H17N2O2S)2]V = 3649.79 (10) Å3
Mr = 762.37Z = 4
Monoclinic, P21/nMo Kα radiation
a = 18.8390 (3) ŵ = 0.76 mm−1
b = 10.8730 (2) ÅT = 293 K
c = 19.6200 (3) Å0.49 × 0.44 × 0.39 mm
β = 114.748 (1)°
Data collection top
Nonius KappaCCD area-detector
diffractometer		7413 independent reflections
Absorption correction: gaussian
(Coppens et al., 1965)		6761 reflections with I > 2σ(I)
Tmin = 0.779, Tmax = 0.886Rint = 0.027
21982 measured reflectionsθmax = 26.7°
Refinement top
R[F2 > 2σ(F2)] = 0.049H-atom parameters constrained
wR(F2) = 0.122Δρmax = 0.23 e Å−3
S = 1.07Δρmin = −0.39 e Å−3
7413 reflectionsAbsolute structure: ?
460 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
Special details top

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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
Cu0.508045 (16)0.07839 (3)0.297423 (16)0.04477 (11)
S20.59888 (4)0.07792 (6)0.25262 (4)0.05644 (19)
S10.53343 (5)0.27665 (7)0.32023 (5)0.0707 (2)
O10.45058 (10)0.06749 (15)0.35857 (10)0.0493 (4)
O20.46288 (11)−0.07565 (18)0.25155 (12)0.0641 (5)
O30.39877 (11)−0.02783 (16)0.45314 (11)0.0570 (4)
O40.35836 (12)−0.2514 (2)0.18813 (13)0.0763 (6)
N10.44597 (11)0.26752 (17)0.40284 (11)0.0424 (4)
N20.47257 (11)0.45499 (18)0.36697 (11)0.0429 (4)
N30.53966 (11)−0.14815 (18)0.19153 (11)0.0447 (4)
N40.65912 (11)−0.09441 (17)0.19891 (11)0.0425 (4)
C10.43832 (12)0.1451 (2)0.39995 (12)0.0395 (5)
C20.47889 (13)0.3315 (2)0.36579 (13)0.0420 (5)
C30.40694 (13)0.0971 (2)0.45135 (13)0.0415 (5)
C40.38350 (16)0.1503 (3)0.50008 (15)0.0574 (7)
H40.38370.2340.510.069*
C50.35819 (19)0.0537 (3)0.53378 (17)0.0668 (8)
H50.3380.06180.56950.08*
C60.36918 (17)−0.0499 (3)0.50399 (17)0.0626 (7)
H60.358−0.12790.51650.075*
C70.43616 (13)0.5172 (2)0.41091 (12)0.0422 (5)
H7A0.47160.580.44170.051*
H7B0.42910.45770.44440.051*
C80.35843 (13)0.5760 (2)0.36437 (12)0.0414 (5)
C90.29283 (14)0.5045 (3)0.32657 (14)0.0545 (6)
H90.29760.41930.32720.065*
C100.22047 (16)0.5575 (3)0.28797 (17)0.0673 (8)
H100.17680.50860.26270.081*
C110.21354 (17)0.6836 (3)0.28721 (16)0.0685 (8)
H110.16480.720.26160.082*
C120.27814 (18)0.7558 (3)0.32403 (17)0.0681 (8)
H120.27320.84090.32310.082*
C130.35041 (16)0.7019 (2)0.36246 (15)0.0540 (6)
H130.39410.75120.38730.065*
C140.50761 (15)0.5373 (2)0.33057 (14)0.0495 (6)
H14A0.47770.61310.31750.059*
H14B0.50310.49930.28420.059*
C150.59256 (15)0.5687 (2)0.37715 (14)0.0465 (5)
C160.63705 (15)0.5165 (2)0.44601 (14)0.0533 (6)
H160.6150.45770.46580.064*
C170.71447 (18)0.5511 (3)0.48607 (18)0.0709 (8)
H170.74390.5160.53270.085*
C180.7477 (2)0.6370 (4)0.4571 (2)0.0827 (10)
H180.79940.66080.48420.099*
C190.7043 (2)0.6874 (3)0.3881 (2)0.0791 (10)
H190.7270.74450.3680.095*
C200.62787 (18)0.6542 (3)0.34867 (18)0.0621 (7)
H200.5990.68950.3020.075*
C210.47872 (13)−0.1453 (2)0.20874 (13)0.0441 (5)
C220.59750 (13)−0.0648 (2)0.21315 (12)0.0405 (5)
C230.42344 (14)−0.2456 (2)0.17448 (13)0.0491 (6)
C240.42619 (19)−0.3425 (3)0.13331 (16)0.0645 (7)
H240.4649−0.35970.11690.077*
C250.3587 (2)−0.4131 (3)0.1198 (2)0.0890 (11)
H250.3443−0.48610.09270.107*
C260.3200 (2)−0.3554 (4)0.1530 (2)0.0917 (12)
H260.2728−0.38220.15240.11*
C270.66466 (15)−0.2122 (2)0.16429 (13)0.0476 (6)
H27A0.628−0.27020.16930.057*
H27B0.7168−0.24560.1910.057*
C280.64762 (15)−0.1988 (2)0.08239 (14)0.0484 (6)
C290.57841 (18)−0.1499 (3)0.03292 (17)0.0744 (9)
H290.5418−0.12390.05010.089*
C300.5620 (2)−0.1384 (4)−0.04314 (18)0.0916 (11)
H300.5149−0.104−0.07620.11*
C310.6151 (2)−0.1776 (4)−0.06883 (19)0.0873 (11)
H310.6042−0.1704−0.11950.105*
C320.6840 (2)−0.2271 (3)−0.02047 (19)0.0816 (10)
H320.7201−0.2543−0.03810.098*
C330.70071 (19)−0.2372 (3)0.05522 (17)0.0648 (7)
H330.7483−0.27030.08810.078*
C340.72555 (14)−0.0120 (2)0.21270 (13)0.0453 (5)
H34A0.70970.07190.21590.054*
H34B0.7394−0.01660.17040.054*
C350.79670 (14)−0.0422 (2)0.28359 (14)0.0452 (5)
C360.79724 (17)−0.0283 (3)0.35352 (16)0.0621 (7)
H360.7525−0.00070.35770.074*
C370.8635 (2)−0.0550 (3)0.41754 (18)0.0785 (9)
H370.8628−0.04590.46440.094*
C380.9302 (2)−0.0947 (3)0.4126 (2)0.0787 (9)
H380.9748−0.11190.45580.094*
C390.93044 (19)−0.1087 (4)0.3436 (2)0.0822 (10)
H390.9754−0.1360.33970.099*
C400.86415 (17)−0.0825 (3)0.27935 (18)0.0648 (8)
H400.865−0.09220.23260.078*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu0.04319 (18)0.04824 (19)0.04929 (19)0.00021 (12)0.02570 (14)−0.01030 (13)
S20.0615 (4)0.0452 (4)0.0818 (5)−0.0050 (3)0.0489 (4)−0.0158 (3)
S10.0980 (6)0.0474 (4)0.1073 (6)−0.0094 (4)0.0828 (5)−0.0144 (4)
O10.0552 (10)0.0469 (9)0.0563 (10)−0.0054 (7)0.0336 (8)−0.0133 (8)
O20.0590 (11)0.0696 (13)0.0804 (13)−0.0178 (9)0.0454 (10)−0.0342 (10)
O30.0683 (11)0.0439 (9)0.0703 (12)−0.0069 (8)0.0403 (10)−0.0053 (9)
O40.0626 (12)0.0881 (16)0.0874 (15)−0.0211 (11)0.0405 (11)−0.0213 (12)
N10.0440 (10)0.0412 (10)0.0481 (10)0.0014 (8)0.0252 (9)−0.0018 (9)
N20.0474 (11)0.0409 (10)0.0433 (10)0.0041 (8)0.0218 (9)0.0028 (8)
N30.0473 (11)0.0462 (11)0.0446 (10)−0.0001 (9)0.0233 (9)−0.0041 (9)
N40.0487 (11)0.0396 (10)0.0472 (11)0.0025 (8)0.0279 (9)−0.0029 (8)
C10.0328 (11)0.0457 (13)0.0402 (11)0.0035 (9)0.0154 (9)−0.0033 (10)
C20.0432 (12)0.0420 (12)0.0429 (12)0.0009 (9)0.0202 (10)−0.0027 (10)
C30.0412 (12)0.0375 (12)0.0477 (12)−0.0010 (9)0.0204 (10)−0.0025 (10)
C40.0742 (18)0.0493 (14)0.0653 (16)0.0050 (13)0.0456 (15)−0.0022 (13)
C50.080 (2)0.073 (2)0.0662 (18)0.0004 (15)0.0490 (16)0.0085 (15)
C60.0674 (18)0.0558 (16)0.0739 (19)−0.0076 (13)0.0389 (15)0.0094 (14)
C70.0445 (12)0.0419 (12)0.0371 (11)0.0055 (10)0.0140 (10)−0.0031 (10)
C80.0432 (12)0.0443 (13)0.0358 (11)0.0047 (10)0.0157 (10)−0.0013 (9)
C90.0476 (14)0.0512 (15)0.0579 (15)0.0003 (11)0.0153 (12)−0.0010 (12)
C100.0427 (14)0.083 (2)0.0657 (18)−0.0004 (14)0.0126 (13)0.0011 (16)
C110.0495 (16)0.090 (2)0.0579 (16)0.0248 (15)0.0144 (13)0.0093 (16)
C120.075 (2)0.0539 (16)0.0663 (18)0.0252 (15)0.0209 (15)0.0085 (14)
C130.0550 (15)0.0451 (14)0.0536 (14)0.0078 (11)0.0145 (12)−0.0023 (12)
C140.0591 (15)0.0446 (13)0.0481 (13)0.0048 (11)0.0258 (12)0.0084 (11)
C150.0572 (14)0.0372 (12)0.0530 (14)0.0043 (10)0.0309 (12)−0.0026 (10)
C160.0573 (15)0.0509 (15)0.0557 (14)0.0048 (12)0.0277 (13)−0.0016 (12)
C170.0568 (17)0.080 (2)0.0663 (18)0.0095 (15)0.0166 (15)−0.0163 (16)
C180.0609 (19)0.083 (2)0.113 (3)−0.0150 (17)0.045 (2)−0.037 (2)
C190.085 (2)0.0617 (19)0.115 (3)−0.0185 (17)0.066 (2)−0.0185 (19)
C200.079 (2)0.0470 (15)0.0763 (18)−0.0002 (13)0.0483 (16)0.0032 (13)
C210.0447 (12)0.0476 (13)0.0416 (12)−0.0001 (10)0.0198 (10)−0.0043 (10)
C220.0472 (12)0.0414 (12)0.0390 (11)0.0047 (10)0.0240 (10)0.0021 (9)
C230.0489 (14)0.0550 (15)0.0448 (13)−0.0050 (11)0.0210 (11)−0.0044 (11)
C240.082 (2)0.0624 (17)0.0602 (16)−0.0189 (15)0.0406 (15)−0.0195 (14)
C250.111 (3)0.082 (2)0.072 (2)−0.044 (2)0.037 (2)−0.0325 (18)
C260.076 (2)0.110 (3)0.088 (2)−0.046 (2)0.032 (2)−0.019 (2)
C270.0567 (14)0.0395 (12)0.0550 (14)0.0068 (10)0.0316 (12)−0.0018 (11)
C280.0561 (14)0.0446 (13)0.0512 (13)−0.0004 (11)0.0290 (12)−0.0095 (11)
C290.0671 (19)0.098 (2)0.0580 (17)0.0151 (17)0.0262 (15)−0.0092 (17)
C300.084 (2)0.122 (3)0.0528 (18)0.013 (2)0.0128 (17)−0.0080 (19)
C310.112 (3)0.101 (3)0.0537 (17)−0.017 (2)0.040 (2)−0.0148 (18)
C320.104 (3)0.093 (2)0.074 (2)−0.003 (2)0.062 (2)−0.0129 (19)
C330.0751 (19)0.0673 (18)0.0683 (17)0.0095 (15)0.0461 (15)0.0000 (14)
C340.0550 (14)0.0404 (12)0.0544 (13)−0.0022 (10)0.0366 (12)−0.0017 (11)
C350.0531 (14)0.0383 (12)0.0527 (13)−0.0045 (10)0.0305 (12)−0.0040 (10)
C360.0674 (17)0.0714 (18)0.0568 (15)0.0016 (14)0.0353 (14)−0.0061 (14)
C370.086 (2)0.095 (3)0.0522 (17)0.0030 (19)0.0257 (17)−0.0060 (16)
C380.069 (2)0.076 (2)0.071 (2)0.0052 (16)0.0100 (17)−0.0041 (16)
C390.0589 (19)0.097 (3)0.087 (2)0.0159 (17)0.0274 (18)−0.005 (2)
C400.0599 (17)0.079 (2)0.0643 (17)0.0119 (14)0.0345 (15)−0.0024 (14)
Geometric parameters (Å, °) top
Cu—O11.9269 (16)C15—C161.379 (4)
Cu—S12.2128 (8)C15—C201.389 (4)
O1—C11.257 (3)C16—C171.388 (4)
N1—C11.338 (3)C16—H160.93
Cu—O21.9230 (18)C17—C181.373 (5)
Cu—S22.2272 (7)C17—H170.93
S1—C21.726 (2)C18—C191.369 (5)
S2—C221.730 (2)C18—H180.93
O2—C211.256 (3)C19—C201.367 (5)
O3—C61.353 (3)C19—H190.93
O3—C31.369 (3)C20—H200.93
O4—C231.362 (3)C21—C231.462 (3)
O4—C261.364 (4)C23—C241.342 (4)
N1—C21.332 (3)C24—C251.412 (4)
N2—C21.349 (3)C24—H240.93
N2—C141.463 (3)C25—C261.322 (5)
N2—C71.472 (3)C25—H250.93
N3—C211.326 (3)C26—H260.93
N3—C221.342 (3)C27—C281.508 (3)
N4—C221.342 (3)C27—H27A0.97
N4—C341.470 (3)C27—H27B0.97
N4—C271.474 (3)C28—C291.366 (4)
C1—C31.462 (3)C28—C331.380 (4)
C3—C41.341 (3)C29—C301.397 (4)
C4—C51.425 (4)C29—H290.93
C4—H40.93C30—C311.364 (5)
C5—C61.325 (4)C30—H300.93
C5—H50.93C31—C321.358 (5)
C6—H60.93C31—H310.93
C7—C81.506 (3)C32—C331.388 (4)
C7—H7A0.97C32—H320.93
C7—H7B0.97C33—H330.93
C8—C131.376 (3)C34—C351.509 (3)
C8—C91.384 (3)C34—H34A0.97
C9—C101.379 (4)C34—H34B0.97
C9—H90.93C35—C401.379 (4)
C10—C111.376 (4)C35—C361.376 (3)
C10—H100.93C36—C371.381 (4)
C11—C121.372 (4)C36—H360.93
C11—H110.93C37—C381.370 (5)
C12—C131.380 (4)C37—H370.93
C12—H120.93C38—C391.365 (5)
C13—H130.93C38—H380.93
C14—C151.513 (4)C39—C401.382 (5)
C14—H14A0.97C39—H390.93
C14—H14B0.97C40—H400.93
O2—Cu—O189.08 (7)C16—C17—H17119.9
O2—Cu—S1163.52 (7)C19—C18—C17119.6 (3)
O1—Cu—S193.68 (5)C19—C18—H18120.2
O2—Cu—S294.35 (5)C17—C18—H18120.2
O1—Cu—S2166.02 (6)C18—C19—C20120.4 (3)
S1—Cu—S286.86 (2)C18—C19—H19119.8
C22—S2—Cu107.99 (8)C20—C19—H19119.8
C2—S1—Cu108.45 (8)C19—C20—C15121.1 (3)
C1—O1—Cu131.58 (15)C19—C20—H20119.4
C21—O2—Cu130.97 (16)C15—C20—H20119.4
C6—O3—C3106.3 (2)O2—C21—N3131.1 (2)
C23—O4—C26105.7 (2)O2—C21—C23115.7 (2)
C2—N1—C1124.29 (19)N3—C21—C23113.0 (2)
C2—N2—C14122.62 (19)N3—C22—N4115.52 (19)
C2—N2—C7122.24 (19)N3—C22—S2127.25 (17)
C14—N2—C7114.91 (19)N4—C22—S2117.15 (17)
C21—N3—C22125.4 (2)C24—C23—O4110.3 (2)
C22—N4—C34124.03 (19)C24—C23—C21131.5 (2)
C22—N4—C27122.60 (19)O4—C23—C21118.1 (2)
C34—N4—C27113.32 (18)C23—C24—C25106.4 (3)
O1—C1—N1130.5 (2)C23—C24—H24126.8
O1—C1—C3116.3 (2)C25—C24—H24126.8
N1—C1—C3113.16 (19)C26—C25—C24106.8 (3)
N1—C2—N2116.5 (2)C26—C25—H25126.6
N1—C2—S1128.01 (18)C24—C25—H25126.6
N2—C2—S1115.40 (17)C25—C26—O4110.9 (3)
C4—C3—O3109.6 (2)C25—C26—H26124.5
C4—C3—C1133.4 (2)O4—C26—H26124.5
O3—C3—C1116.99 (19)N4—C27—C28112.5 (2)
C3—C4—C5106.7 (2)N4—C27—H27A109.1
C3—C4—H4126.7C28—C27—H27A109.1
C5—C4—H4126.7N4—C27—H27B109.1
C6—C5—C4106.1 (2)C28—C27—H27B109.1
C6—C5—H5126.9H27A—C27—H27B107.8
C4—C5—H5126.9C29—C28—C33118.3 (3)
C5—C6—O3111.3 (2)C29—C28—C27120.6 (2)
C5—C6—H6124.4C33—C28—C27121.1 (2)
O3—C6—H6124.4C28—C29—C30120.8 (3)
N2—C7—C8114.41 (18)C28—C29—H29119.6
N2—C7—H7A108.7C30—C29—H29119.6
C8—C7—H7A108.7C31—C30—C29119.9 (3)
N2—C7—H7B108.7C31—C30—H30120.1
C8—C7—H7B108.7C29—C30—H30120.1
H7A—C7—H7B107.6C32—C31—C30120.0 (3)
C13—C8—C9118.8 (2)C32—C31—H31120
C13—C8—C7120.5 (2)C30—C31—H31120
C9—C8—C7120.6 (2)C31—C32—C33120.1 (3)
C10—C9—C8121.0 (3)C31—C32—H32120
C10—C9—H9119.5C33—C32—H32120
C8—C9—H9119.5C28—C33—C32120.9 (3)
C11—C10—C9119.4 (3)C28—C33—H33119.6
C11—C10—H10120.3C32—C33—H33119.6
C9—C10—H10120.3N4—C34—C35113.34 (19)
C12—C11—C10120.3 (3)N4—C34—H34A108.9
C12—C11—H11119.8C35—C34—H34A108.9
C10—C11—H11119.8N4—C34—H34B108.9
C11—C12—C13119.9 (3)C35—C34—H34B108.9
C11—C12—H12120H34A—C34—H34B107.7
C13—C12—H12120C40—C35—C36118.2 (3)
C12—C13—C8120.6 (3)C40—C35—C34119.9 (2)
C12—C13—H13119.7C36—C35—C34121.9 (2)
C8—C13—H13119.7C35—C36—C37120.7 (3)
N2—C14—C15115.0 (2)C35—C36—H36119.6
N2—C14—H14A108.5C37—C36—H36119.6
C15—C14—H14A108.5C38—C37—C36120.5 (3)
N2—C14—H14B108.5C38—C37—H37119.7
C15—C14—H14B108.5C36—C37—H37119.7
H14A—C14—H14B107.5C39—C38—C37119.3 (3)
C16—C15—C20118.2 (3)C39—C38—H38120.3
C16—C15—C14123.7 (2)C37—C38—H38120.3
C20—C15—C14118.1 (2)C38—C39—C40120.3 (3)
C15—C16—C17120.5 (3)C38—C39—H39119.9
C15—C16—H16119.8C40—C39—H39119.9
C17—C16—H16119.8C35—C40—C39120.9 (3)
C18—C17—C16120.2 (3)C35—C40—H40119.5
C18—C17—H17119.9C39—C40—H40119.5
O2—Cu—S2—C22−9.59 (11)C15—C16—C17—C18−0.6 (4)
O1—Cu—S2—C2294.2 (2)C16—C17—C18—C19−0.7 (5)
S1—Cu—S2—C22−173.12 (9)C17—C18—C19—C201.1 (5)
O2—Cu—S1—C289.5 (2)C18—C19—C20—C15−0.3 (5)
O1—Cu—S1—C2−9.81 (11)C16—C15—C20—C19−0.9 (4)
S2—Cu—S1—C2−175.82 (9)C14—C15—C20—C19179.6 (3)
O2—Cu—O1—C1−168.3 (2)Cu—O2—C21—N313.8 (4)
S1—Cu—O1—C1−4.5 (2)Cu—O2—C21—C23−170.15 (19)
S2—Cu—O1—C187.3 (3)C22—N3—C21—O2−6.4 (4)
O1—Cu—O2—C21−169.5 (3)C22—N3—C21—C23177.5 (2)
S1—Cu—O2—C2190.5 (3)C21—N3—C22—N4170.6 (2)
S2—Cu—O2—C21−3.1 (3)C21—N3—C22—S2−12.8 (4)
Cu—O1—C1—N116.9 (4)C34—N4—C22—N3175.0 (2)
Cu—O1—C1—C3−166.58 (16)C27—N4—C22—N3−2.1 (3)
C2—N1—C1—O1−8.8 (4)C34—N4—C22—S2−1.9 (3)
C2—N1—C1—C3174.5 (2)C27—N4—C22—S2−179.00 (17)
C1—N1—C2—N2171.5 (2)Cu—S2—C22—N318.8 (2)
C1—N1—C2—S1−12.3 (3)Cu—S2—C22—N4−164.70 (15)
C14—N2—C2—N1178.3 (2)C26—O4—C23—C24−0.7 (3)
C7—N2—C2—N14.1 (3)C26—O4—C23—C21−177.1 (3)
C14—N2—C2—S11.6 (3)O2—C21—C23—C24−172.0 (3)
C7—N2—C2—S1−172.62 (16)N3—C21—C23—C244.8 (4)
Cu—S1—C2—N119.6 (2)O2—C21—C23—O43.4 (4)
Cu—S1—C2—N2−164.11 (15)N3—C21—C23—O4−179.8 (2)
C6—O3—C3—C40.4 (3)O4—C23—C24—C250.4 (4)
C6—O3—C3—C1180.0 (2)C21—C23—C24—C25176.1 (3)
O1—C1—C3—C4−176.3 (3)C23—C24—C25—C260.1 (4)
N1—C1—C3—C40.8 (4)C24—C25—C26—O4−0.5 (5)
O1—C1—C3—O34.2 (3)C23—O4—C26—C250.8 (4)
N1—C1—C3—O3−178.7 (2)C22—N4—C27—C28103.0 (3)
O3—C3—C4—C5−0.8 (3)C34—N4—C27—C28−74.3 (3)
C1—C3—C4—C5179.7 (3)N4—C27—C28—C29−56.7 (3)
C3—C4—C5—C60.9 (3)N4—C27—C28—C33124.3 (3)
C4—C5—C6—O3−0.7 (4)C33—C28—C29—C30−0.3 (5)
C3—O3—C6—C50.2 (3)C27—C28—C29—C30−179.4 (3)
C2—N2—C7—C8−109.9 (2)C28—C29—C30—C310.7 (6)
C14—N2—C7—C875.5 (3)C29—C30—C31—C32−0.4 (6)
N2—C7—C8—C13−112.8 (3)C30—C31—C32—C33−0.4 (6)
N2—C7—C8—C971.2 (3)C29—C28—C33—C32−0.4 (5)
C13—C8—C9—C10−0.4 (4)C27—C28—C33—C32178.6 (3)
C7—C8—C9—C10175.6 (2)C31—C32—C33—C280.8 (5)
C8—C9—C10—C11−0.1 (4)C22—N4—C34—C35101.4 (3)
C9—C10—C11—C120.5 (5)C27—N4—C34—C35−81.2 (2)
C10—C11—C12—C13−0.4 (5)N4—C34—C35—C40114.7 (3)
C11—C12—C13—C8−0.1 (4)N4—C34—C35—C36−66.7 (3)
C9—C8—C13—C120.5 (4)C40—C35—C36—C37−0.5 (4)
C7—C8—C13—C12−175.5 (2)C34—C35—C36—C37−179.1 (3)
C2—N2—C14—C15−84.6 (3)C35—C36—C37—C380.6 (5)
C7—N2—C14—C1589.9 (2)C36—C37—C38—C39−0.5 (6)
N2—C14—C15—C165.7 (3)C37—C38—C39—C400.3 (6)
N2—C14—C15—C20−174.8 (2)C36—C35—C40—C390.2 (5)
C20—C15—C16—C171.4 (4)C34—C35—C40—C39178.9 (3)
C14—C15—C16—C17−179.1 (2)C38—C39—C40—C35−0.2 (5)
Acknowledgements top

The authors thank the Grupo de Cristalografia, IFSC, USP, Brazil, for allowing the X-ray data collection. The authors acknowledge financial support from PhD Cooperative Program - ICTP/CLAF.

references
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