

Supporting information
![]() | Crystallographic Information File (CIF) https://doi.org/10.1107/S160053681101422X/bt5517sup1.cif |
![]() | Structure factor file (CIF format) https://doi.org/10.1107/S160053681101422X/bt5517Isup2.hkl |
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean
(C-C) = 0.004 Å
- R factor = 0.049
- wR factor = 0.122
- Data-to-parameter ratio = 16.1
checkCIF/PLATON results
No syntax errors found
Alert level B PLAT910_ALERT_3_B Missing # of FCF Reflections Below Th(Min) ..... 11
Alert level C PLAT241_ALERT_2_C Check High Ueq as Compared to Neighbors for S1 PLAT241_ALERT_2_C Check High Ueq as Compared to Neighbors for O2 PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L= 0.600 9 PLAT912_ALERT_4_C Missing # of FCF Reflections Above STh/L= 0.600 247 PLAT913_ALERT_3_C Missing # of Very Strong Reflections in FCF .... 5
Alert level G PLAT128_ALERT_4_G Alternate Setting of Space-group P21/c ....... P21/n PLAT180_ALERT_4_G Check Cell Rounding: # of Values Ending with 0 = 3 PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature 293 K PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature 293 K
0 ALERT level A = Most likely a serious problem - resolve or explain 1 ALERT level B = A potentially serious problem, consider carefully 5 ALERT level C = Check. Ensure it is not caused by an omission or oversight 4 ALERT level G = General information/check it is not something unexpected 2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 2 ALERT type 2 Indicator that the structure model may be wrong or deficient 3 ALERT type 3 Indicator that the structure quality may be low 3 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
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.
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.
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.
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).
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).
[Cu(C20H17N2O2S)2] | F(000) = 1580 |
Mr = 762.37 | Dx = 1.387 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 22283 reflections |
a = 18.8390 (3) Å | θ = 2.9–26.7° |
b = 10.8730 (2) Å | µ = 0.76 mm−1 |
c = 19.6200 (3) Å | T = 293 K |
β = 114.748 (1)° | Prism, blue |
V = 3649.79 (10) Å3 | 0.49 × 0.44 × 0.39 mm |
Z = 4 |
Nonius KappaCCD area-detector diffractometer | 7413 independent reflections |
Radiation source: Enraf–Nonius FR590 | 6761 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.027 |
Detector resolution: 9 pixels mm-1 | θmax = 26.7°, θmin = 3.0° |
CCD rotation images, thick slices scans | h = −23→23 |
Absorption correction: gaussian (Coppens et al., 1965) | k = −13→13 |
Tmin = 0.779, Tmax = 0.886 | l = −24→24 |
21982 measured reflections |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.049 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.122 | H-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 parameters | Δρmax = 0.23 e Å−3 |
0 restraints | Δρmin = −0.39 e Å−3 |
[Cu(C20H17N2O2S)2] | V = 3649.79 (10) Å3 |
Mr = 762.37 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 18.8390 (3) Å | µ = 0.76 mm−1 |
b = 10.8730 (2) Å | T = 293 K |
c = 19.6200 (3) Å | 0.49 × 0.44 × 0.39 mm |
β = 114.748 (1)° |
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 = 0.886 | Rint = 0.027 |
21982 measured reflections |
R[F2 > 2σ(F2)] = 0.049 | 0 restraints |
wR(F2) = 0.122 | H-atom parameters constrained |
S = 1.07 | Δρmax = 0.23 e Å−3 |
7413 reflections | Δρmin = −0.39 e Å−3 |
460 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
Cu | 0.508045 (16) | 0.07839 (3) | 0.297423 (16) | 0.04477 (11) | |
S2 | 0.59888 (4) | 0.07792 (6) | 0.25262 (4) | 0.05644 (19) | |
S1 | 0.53343 (5) | 0.27665 (7) | 0.32023 (5) | 0.0707 (2) | |
O1 | 0.45058 (10) | 0.06749 (15) | 0.35857 (10) | 0.0493 (4) | |
O2 | 0.46288 (11) | −0.07565 (18) | 0.25155 (12) | 0.0641 (5) | |
O3 | 0.39877 (11) | −0.02783 (16) | 0.45314 (11) | 0.0570 (4) | |
O4 | 0.35836 (12) | −0.2514 (2) | 0.18813 (13) | 0.0763 (6) | |
N1 | 0.44597 (11) | 0.26752 (17) | 0.40284 (11) | 0.0424 (4) | |
N2 | 0.47257 (11) | 0.45499 (18) | 0.36697 (11) | 0.0429 (4) | |
N3 | 0.53966 (11) | −0.14815 (18) | 0.19153 (11) | 0.0447 (4) | |
N4 | 0.65912 (11) | −0.09441 (17) | 0.19891 (11) | 0.0425 (4) | |
C1 | 0.43832 (12) | 0.1451 (2) | 0.39995 (12) | 0.0395 (5) | |
C2 | 0.47889 (13) | 0.3315 (2) | 0.36579 (13) | 0.0420 (5) | |
C3 | 0.40694 (13) | 0.0971 (2) | 0.45135 (13) | 0.0415 (5) | |
C4 | 0.38350 (16) | 0.1503 (3) | 0.50008 (15) | 0.0574 (7) | |
H4 | 0.3837 | 0.234 | 0.51 | 0.069* | |
C5 | 0.35819 (19) | 0.0537 (3) | 0.53378 (17) | 0.0668 (8) | |
H5 | 0.338 | 0.0618 | 0.5695 | 0.08* | |
C6 | 0.36918 (17) | −0.0499 (3) | 0.50399 (17) | 0.0626 (7) | |
H6 | 0.358 | −0.1279 | 0.5165 | 0.075* | |
C7 | 0.43616 (13) | 0.5172 (2) | 0.41091 (12) | 0.0422 (5) | |
H7A | 0.4716 | 0.58 | 0.4417 | 0.051* | |
H7B | 0.4291 | 0.4577 | 0.4444 | 0.051* | |
C8 | 0.35843 (13) | 0.5760 (2) | 0.36437 (12) | 0.0414 (5) | |
C9 | 0.29283 (14) | 0.5045 (3) | 0.32657 (14) | 0.0545 (6) | |
H9 | 0.2976 | 0.4193 | 0.3272 | 0.065* | |
C10 | 0.22047 (16) | 0.5575 (3) | 0.28797 (17) | 0.0673 (8) | |
H10 | 0.1768 | 0.5086 | 0.2627 | 0.081* | |
C11 | 0.21354 (17) | 0.6836 (3) | 0.28721 (16) | 0.0685 (8) | |
H11 | 0.1648 | 0.72 | 0.2616 | 0.082* | |
C12 | 0.27814 (18) | 0.7558 (3) | 0.32403 (17) | 0.0681 (8) | |
H12 | 0.2732 | 0.8409 | 0.3231 | 0.082* | |
C13 | 0.35041 (16) | 0.7019 (2) | 0.36246 (15) | 0.0540 (6) | |
H13 | 0.3941 | 0.7512 | 0.3873 | 0.065* | |
C14 | 0.50761 (15) | 0.5373 (2) | 0.33057 (14) | 0.0495 (6) | |
H14A | 0.4777 | 0.6131 | 0.3175 | 0.059* | |
H14B | 0.5031 | 0.4993 | 0.2842 | 0.059* | |
C15 | 0.59256 (15) | 0.5687 (2) | 0.37715 (14) | 0.0465 (5) | |
C16 | 0.63705 (15) | 0.5165 (2) | 0.44601 (14) | 0.0533 (6) | |
H16 | 0.615 | 0.4577 | 0.4658 | 0.064* | |
C17 | 0.71447 (18) | 0.5511 (3) | 0.48607 (18) | 0.0709 (8) | |
H17 | 0.7439 | 0.516 | 0.5327 | 0.085* | |
C18 | 0.7477 (2) | 0.6370 (4) | 0.4571 (2) | 0.0827 (10) | |
H18 | 0.7994 | 0.6608 | 0.4842 | 0.099* | |
C19 | 0.7043 (2) | 0.6874 (3) | 0.3881 (2) | 0.0791 (10) | |
H19 | 0.727 | 0.7445 | 0.368 | 0.095* | |
C20 | 0.62787 (18) | 0.6542 (3) | 0.34867 (18) | 0.0621 (7) | |
H20 | 0.599 | 0.6895 | 0.302 | 0.075* | |
C21 | 0.47872 (13) | −0.1453 (2) | 0.20874 (13) | 0.0441 (5) | |
C22 | 0.59750 (13) | −0.0648 (2) | 0.21315 (12) | 0.0405 (5) | |
C23 | 0.42344 (14) | −0.2456 (2) | 0.17448 (13) | 0.0491 (6) | |
C24 | 0.42619 (19) | −0.3425 (3) | 0.13331 (16) | 0.0645 (7) | |
H24 | 0.4649 | −0.3597 | 0.1169 | 0.077* | |
C25 | 0.3587 (2) | −0.4131 (3) | 0.1198 (2) | 0.0890 (11) | |
H25 | 0.3443 | −0.4861 | 0.0927 | 0.107* | |
C26 | 0.3200 (2) | −0.3554 (4) | 0.1530 (2) | 0.0917 (12) | |
H26 | 0.2728 | −0.3822 | 0.1524 | 0.11* | |
C27 | 0.66466 (15) | −0.2122 (2) | 0.16429 (13) | 0.0476 (6) | |
H27A | 0.628 | −0.2702 | 0.1693 | 0.057* | |
H27B | 0.7168 | −0.2456 | 0.191 | 0.057* | |
C28 | 0.64762 (15) | −0.1988 (2) | 0.08239 (14) | 0.0484 (6) | |
C29 | 0.57841 (18) | −0.1499 (3) | 0.03292 (17) | 0.0744 (9) | |
H29 | 0.5418 | −0.1239 | 0.0501 | 0.089* | |
C30 | 0.5620 (2) | −0.1384 (4) | −0.04314 (18) | 0.0916 (11) | |
H30 | 0.5149 | −0.104 | −0.0762 | 0.11* | |
C31 | 0.6151 (2) | −0.1776 (4) | −0.06883 (19) | 0.0873 (11) | |
H31 | 0.6042 | −0.1704 | −0.1195 | 0.105* | |
C32 | 0.6840 (2) | −0.2271 (3) | −0.02047 (19) | 0.0816 (10) | |
H32 | 0.7201 | −0.2543 | −0.0381 | 0.098* | |
C33 | 0.70071 (19) | −0.2372 (3) | 0.05522 (17) | 0.0648 (7) | |
H33 | 0.7483 | −0.2703 | 0.0881 | 0.078* | |
C34 | 0.72555 (14) | −0.0120 (2) | 0.21270 (13) | 0.0453 (5) | |
H34A | 0.7097 | 0.0719 | 0.2159 | 0.054* | |
H34B | 0.7394 | −0.0166 | 0.1704 | 0.054* | |
C35 | 0.79670 (14) | −0.0422 (2) | 0.28359 (14) | 0.0452 (5) | |
C36 | 0.79724 (17) | −0.0283 (3) | 0.35352 (16) | 0.0621 (7) | |
H36 | 0.7525 | −0.0007 | 0.3577 | 0.074* | |
C37 | 0.8635 (2) | −0.0550 (3) | 0.41754 (18) | 0.0785 (9) | |
H37 | 0.8628 | −0.0459 | 0.4644 | 0.094* | |
C38 | 0.9302 (2) | −0.0947 (3) | 0.4126 (2) | 0.0787 (9) | |
H38 | 0.9748 | −0.1119 | 0.4558 | 0.094* | |
C39 | 0.93044 (19) | −0.1087 (4) | 0.3436 (2) | 0.0822 (10) | |
H39 | 0.9754 | −0.136 | 0.3397 | 0.099* | |
C40 | 0.86415 (17) | −0.0825 (3) | 0.27935 (18) | 0.0648 (8) | |
H40 | 0.865 | −0.0922 | 0.2326 | 0.078* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu | 0.04319 (18) | 0.04824 (19) | 0.04929 (19) | 0.00021 (12) | 0.02570 (14) | −0.01030 (13) |
S2 | 0.0615 (4) | 0.0452 (4) | 0.0818 (5) | −0.0050 (3) | 0.0489 (4) | −0.0158 (3) |
S1 | 0.0980 (6) | 0.0474 (4) | 0.1073 (6) | −0.0094 (4) | 0.0828 (5) | −0.0144 (4) |
O1 | 0.0552 (10) | 0.0469 (9) | 0.0563 (10) | −0.0054 (7) | 0.0336 (8) | −0.0133 (8) |
O2 | 0.0590 (11) | 0.0696 (13) | 0.0804 (13) | −0.0178 (9) | 0.0454 (10) | −0.0342 (10) |
O3 | 0.0683 (11) | 0.0439 (9) | 0.0703 (12) | −0.0069 (8) | 0.0403 (10) | −0.0053 (9) |
O4 | 0.0626 (12) | 0.0881 (16) | 0.0874 (15) | −0.0211 (11) | 0.0405 (11) | −0.0213 (12) |
N1 | 0.0440 (10) | 0.0412 (10) | 0.0481 (10) | 0.0014 (8) | 0.0252 (9) | −0.0018 (9) |
N2 | 0.0474 (11) | 0.0409 (10) | 0.0433 (10) | 0.0041 (8) | 0.0218 (9) | 0.0028 (8) |
N3 | 0.0473 (11) | 0.0462 (11) | 0.0446 (10) | −0.0001 (9) | 0.0233 (9) | −0.0041 (9) |
N4 | 0.0487 (11) | 0.0396 (10) | 0.0472 (11) | 0.0025 (8) | 0.0279 (9) | −0.0029 (8) |
C1 | 0.0328 (11) | 0.0457 (13) | 0.0402 (11) | 0.0035 (9) | 0.0154 (9) | −0.0033 (10) |
C2 | 0.0432 (12) | 0.0420 (12) | 0.0429 (12) | 0.0009 (9) | 0.0202 (10) | −0.0027 (10) |
C3 | 0.0412 (12) | 0.0375 (12) | 0.0477 (12) | −0.0010 (9) | 0.0204 (10) | −0.0025 (10) |
C4 | 0.0742 (18) | 0.0493 (14) | 0.0653 (16) | 0.0050 (13) | 0.0456 (15) | −0.0022 (13) |
C5 | 0.080 (2) | 0.073 (2) | 0.0662 (18) | 0.0004 (15) | 0.0490 (16) | 0.0085 (15) |
C6 | 0.0674 (18) | 0.0558 (16) | 0.0739 (19) | −0.0076 (13) | 0.0389 (15) | 0.0094 (14) |
C7 | 0.0445 (12) | 0.0419 (12) | 0.0371 (11) | 0.0055 (10) | 0.0140 (10) | −0.0031 (10) |
C8 | 0.0432 (12) | 0.0443 (13) | 0.0358 (11) | 0.0047 (10) | 0.0157 (10) | −0.0013 (9) |
C9 | 0.0476 (14) | 0.0512 (15) | 0.0579 (15) | 0.0003 (11) | 0.0153 (12) | −0.0010 (12) |
C10 | 0.0427 (14) | 0.083 (2) | 0.0657 (18) | −0.0004 (14) | 0.0126 (13) | 0.0011 (16) |
C11 | 0.0495 (16) | 0.090 (2) | 0.0579 (16) | 0.0248 (15) | 0.0144 (13) | 0.0093 (16) |
C12 | 0.075 (2) | 0.0539 (16) | 0.0663 (18) | 0.0252 (15) | 0.0209 (15) | 0.0085 (14) |
C13 | 0.0550 (15) | 0.0451 (14) | 0.0536 (14) | 0.0078 (11) | 0.0145 (12) | −0.0023 (12) |
C14 | 0.0591 (15) | 0.0446 (13) | 0.0481 (13) | 0.0048 (11) | 0.0258 (12) | 0.0084 (11) |
C15 | 0.0572 (14) | 0.0372 (12) | 0.0530 (14) | 0.0043 (10) | 0.0309 (12) | −0.0026 (10) |
C16 | 0.0573 (15) | 0.0509 (15) | 0.0557 (14) | 0.0048 (12) | 0.0277 (13) | −0.0016 (12) |
C17 | 0.0568 (17) | 0.080 (2) | 0.0663 (18) | 0.0095 (15) | 0.0166 (15) | −0.0163 (16) |
C18 | 0.0609 (19) | 0.083 (2) | 0.113 (3) | −0.0150 (17) | 0.045 (2) | −0.037 (2) |
C19 | 0.085 (2) | 0.0617 (19) | 0.115 (3) | −0.0185 (17) | 0.066 (2) | −0.0185 (19) |
C20 | 0.079 (2) | 0.0470 (15) | 0.0763 (18) | −0.0002 (13) | 0.0483 (16) | 0.0032 (13) |
C21 | 0.0447 (12) | 0.0476 (13) | 0.0416 (12) | −0.0001 (10) | 0.0198 (10) | −0.0043 (10) |
C22 | 0.0472 (12) | 0.0414 (12) | 0.0390 (11) | 0.0047 (10) | 0.0240 (10) | 0.0021 (9) |
C23 | 0.0489 (14) | 0.0550 (15) | 0.0448 (13) | −0.0050 (11) | 0.0210 (11) | −0.0044 (11) |
C24 | 0.082 (2) | 0.0624 (17) | 0.0602 (16) | −0.0189 (15) | 0.0406 (15) | −0.0195 (14) |
C25 | 0.111 (3) | 0.082 (2) | 0.072 (2) | −0.044 (2) | 0.037 (2) | −0.0325 (18) |
C26 | 0.076 (2) | 0.110 (3) | 0.088 (2) | −0.046 (2) | 0.032 (2) | −0.019 (2) |
C27 | 0.0567 (14) | 0.0395 (12) | 0.0550 (14) | 0.0068 (10) | 0.0316 (12) | −0.0018 (11) |
C28 | 0.0561 (14) | 0.0446 (13) | 0.0512 (13) | −0.0004 (11) | 0.0290 (12) | −0.0095 (11) |
C29 | 0.0671 (19) | 0.098 (2) | 0.0580 (17) | 0.0151 (17) | 0.0262 (15) | −0.0092 (17) |
C30 | 0.084 (2) | 0.122 (3) | 0.0528 (18) | 0.013 (2) | 0.0128 (17) | −0.0080 (19) |
C31 | 0.112 (3) | 0.101 (3) | 0.0537 (17) | −0.017 (2) | 0.040 (2) | −0.0148 (18) |
C32 | 0.104 (3) | 0.093 (2) | 0.074 (2) | −0.003 (2) | 0.062 (2) | −0.0129 (19) |
C33 | 0.0751 (19) | 0.0673 (18) | 0.0683 (17) | 0.0095 (15) | 0.0461 (15) | 0.0000 (14) |
C34 | 0.0550 (14) | 0.0404 (12) | 0.0544 (13) | −0.0022 (10) | 0.0366 (12) | −0.0017 (11) |
C35 | 0.0531 (14) | 0.0383 (12) | 0.0527 (13) | −0.0045 (10) | 0.0305 (12) | −0.0040 (10) |
C36 | 0.0674 (17) | 0.0714 (18) | 0.0568 (15) | 0.0016 (14) | 0.0353 (14) | −0.0061 (14) |
C37 | 0.086 (2) | 0.095 (3) | 0.0522 (17) | 0.0030 (19) | 0.0257 (17) | −0.0060 (16) |
C38 | 0.069 (2) | 0.076 (2) | 0.071 (2) | 0.0052 (16) | 0.0100 (17) | −0.0041 (16) |
C39 | 0.0589 (19) | 0.097 (3) | 0.087 (2) | 0.0159 (17) | 0.0274 (18) | −0.005 (2) |
C40 | 0.0599 (17) | 0.079 (2) | 0.0643 (17) | 0.0119 (14) | 0.0345 (15) | −0.0024 (14) |
Cu—O1 | 1.9269 (16) | C15—C16 | 1.379 (4) |
Cu—S1 | 2.2128 (8) | C15—C20 | 1.389 (4) |
O1—C1 | 1.257 (3) | C16—C17 | 1.388 (4) |
N1—C1 | 1.338 (3) | C16—H16 | 0.93 |
Cu—O2 | 1.9230 (18) | C17—C18 | 1.373 (5) |
Cu—S2 | 2.2272 (7) | C17—H17 | 0.93 |
S1—C2 | 1.726 (2) | C18—C19 | 1.369 (5) |
S2—C22 | 1.730 (2) | C18—H18 | 0.93 |
O2—C21 | 1.256 (3) | C19—C20 | 1.367 (5) |
O3—C6 | 1.353 (3) | C19—H19 | 0.93 |
O3—C3 | 1.369 (3) | C20—H20 | 0.93 |
O4—C23 | 1.362 (3) | C21—C23 | 1.462 (3) |
O4—C26 | 1.364 (4) | C23—C24 | 1.342 (4) |
N1—C2 | 1.332 (3) | C24—C25 | 1.412 (4) |
N2—C2 | 1.349 (3) | C24—H24 | 0.93 |
N2—C14 | 1.463 (3) | C25—C26 | 1.322 (5) |
N2—C7 | 1.472 (3) | C25—H25 | 0.93 |
N3—C21 | 1.326 (3) | C26—H26 | 0.93 |
N3—C22 | 1.342 (3) | C27—C28 | 1.508 (3) |
N4—C22 | 1.342 (3) | C27—H27A | 0.97 |
N4—C34 | 1.470 (3) | C27—H27B | 0.97 |
N4—C27 | 1.474 (3) | C28—C29 | 1.366 (4) |
C1—C3 | 1.462 (3) | C28—C33 | 1.380 (4) |
C3—C4 | 1.341 (3) | C29—C30 | 1.397 (4) |
C4—C5 | 1.425 (4) | C29—H29 | 0.93 |
C4—H4 | 0.93 | C30—C31 | 1.364 (5) |
C5—C6 | 1.325 (4) | C30—H30 | 0.93 |
C5—H5 | 0.93 | C31—C32 | 1.358 (5) |
C6—H6 | 0.93 | C31—H31 | 0.93 |
C7—C8 | 1.506 (3) | C32—C33 | 1.388 (4) |
C7—H7A | 0.97 | C32—H32 | 0.93 |
C7—H7B | 0.97 | C33—H33 | 0.93 |
C8—C13 | 1.376 (3) | C34—C35 | 1.509 (3) |
C8—C9 | 1.384 (3) | C34—H34A | 0.97 |
C9—C10 | 1.379 (4) | C34—H34B | 0.97 |
C9—H9 | 0.93 | C35—C40 | 1.379 (4) |
C10—C11 | 1.376 (4) | C35—C36 | 1.376 (3) |
C10—H10 | 0.93 | C36—C37 | 1.381 (4) |
C11—C12 | 1.372 (4) | C36—H36 | 0.93 |
C11—H11 | 0.93 | C37—C38 | 1.370 (5) |
C12—C13 | 1.380 (4) | C37—H37 | 0.93 |
C12—H12 | 0.93 | C38—C39 | 1.365 (5) |
C13—H13 | 0.93 | C38—H38 | 0.93 |
C14—C15 | 1.513 (4) | C39—C40 | 1.382 (5) |
C14—H14A | 0.97 | C39—H39 | 0.93 |
C14—H14B | 0.97 | C40—H40 | 0.93 |
O2—Cu—O1 | 89.08 (7) | C16—C17—H17 | 119.9 |
O2—Cu—S1 | 163.52 (7) | C19—C18—C17 | 119.6 (3) |
O1—Cu—S1 | 93.68 (5) | C19—C18—H18 | 120.2 |
O2—Cu—S2 | 94.35 (5) | C17—C18—H18 | 120.2 |
O1—Cu—S2 | 166.02 (6) | C18—C19—C20 | 120.4 (3) |
S1—Cu—S2 | 86.86 (2) | C18—C19—H19 | 119.8 |
C22—S2—Cu | 107.99 (8) | C20—C19—H19 | 119.8 |
C2—S1—Cu | 108.45 (8) | C19—C20—C15 | 121.1 (3) |
C1—O1—Cu | 131.58 (15) | C19—C20—H20 | 119.4 |
C21—O2—Cu | 130.97 (16) | C15—C20—H20 | 119.4 |
C6—O3—C3 | 106.3 (2) | O2—C21—N3 | 131.1 (2) |
C23—O4—C26 | 105.7 (2) | O2—C21—C23 | 115.7 (2) |
C2—N1—C1 | 124.29 (19) | N3—C21—C23 | 113.0 (2) |
C2—N2—C14 | 122.62 (19) | N3—C22—N4 | 115.52 (19) |
C2—N2—C7 | 122.24 (19) | N3—C22—S2 | 127.25 (17) |
C14—N2—C7 | 114.91 (19) | N4—C22—S2 | 117.15 (17) |
C21—N3—C22 | 125.4 (2) | C24—C23—O4 | 110.3 (2) |
C22—N4—C34 | 124.03 (19) | C24—C23—C21 | 131.5 (2) |
C22—N4—C27 | 122.60 (19) | O4—C23—C21 | 118.1 (2) |
C34—N4—C27 | 113.32 (18) | C23—C24—C25 | 106.4 (3) |
O1—C1—N1 | 130.5 (2) | C23—C24—H24 | 126.8 |
O1—C1—C3 | 116.3 (2) | C25—C24—H24 | 126.8 |
N1—C1—C3 | 113.16 (19) | C26—C25—C24 | 106.8 (3) |
N1—C2—N2 | 116.5 (2) | C26—C25—H25 | 126.6 |
N1—C2—S1 | 128.01 (18) | C24—C25—H25 | 126.6 |
N2—C2—S1 | 115.40 (17) | C25—C26—O4 | 110.9 (3) |
C4—C3—O3 | 109.6 (2) | C25—C26—H26 | 124.5 |
C4—C3—C1 | 133.4 (2) | O4—C26—H26 | 124.5 |
O3—C3—C1 | 116.99 (19) | N4—C27—C28 | 112.5 (2) |
C3—C4—C5 | 106.7 (2) | N4—C27—H27A | 109.1 |
C3—C4—H4 | 126.7 | C28—C27—H27A | 109.1 |
C5—C4—H4 | 126.7 | N4—C27—H27B | 109.1 |
C6—C5—C4 | 106.1 (2) | C28—C27—H27B | 109.1 |
C6—C5—H5 | 126.9 | H27A—C27—H27B | 107.8 |
C4—C5—H5 | 126.9 | C29—C28—C33 | 118.3 (3) |
C5—C6—O3 | 111.3 (2) | C29—C28—C27 | 120.6 (2) |
C5—C6—H6 | 124.4 | C33—C28—C27 | 121.1 (2) |
O3—C6—H6 | 124.4 | C28—C29—C30 | 120.8 (3) |
N2—C7—C8 | 114.41 (18) | C28—C29—H29 | 119.6 |
N2—C7—H7A | 108.7 | C30—C29—H29 | 119.6 |
C8—C7—H7A | 108.7 | C31—C30—C29 | 119.9 (3) |
N2—C7—H7B | 108.7 | C31—C30—H30 | 120.1 |
C8—C7—H7B | 108.7 | C29—C30—H30 | 120.1 |
H7A—C7—H7B | 107.6 | C32—C31—C30 | 120.0 (3) |
C13—C8—C9 | 118.8 (2) | C32—C31—H31 | 120 |
C13—C8—C7 | 120.5 (2) | C30—C31—H31 | 120 |
C9—C8—C7 | 120.6 (2) | C31—C32—C33 | 120.1 (3) |
C10—C9—C8 | 121.0 (3) | C31—C32—H32 | 120 |
C10—C9—H9 | 119.5 | C33—C32—H32 | 120 |
C8—C9—H9 | 119.5 | C28—C33—C32 | 120.9 (3) |
C11—C10—C9 | 119.4 (3) | C28—C33—H33 | 119.6 |
C11—C10—H10 | 120.3 | C32—C33—H33 | 119.6 |
C9—C10—H10 | 120.3 | N4—C34—C35 | 113.34 (19) |
C12—C11—C10 | 120.3 (3) | N4—C34—H34A | 108.9 |
C12—C11—H11 | 119.8 | C35—C34—H34A | 108.9 |
C10—C11—H11 | 119.8 | N4—C34—H34B | 108.9 |
C11—C12—C13 | 119.9 (3) | C35—C34—H34B | 108.9 |
C11—C12—H12 | 120 | H34A—C34—H34B | 107.7 |
C13—C12—H12 | 120 | C40—C35—C36 | 118.2 (3) |
C12—C13—C8 | 120.6 (3) | C40—C35—C34 | 119.9 (2) |
C12—C13—H13 | 119.7 | C36—C35—C34 | 121.9 (2) |
C8—C13—H13 | 119.7 | C35—C36—C37 | 120.7 (3) |
N2—C14—C15 | 115.0 (2) | C35—C36—H36 | 119.6 |
N2—C14—H14A | 108.5 | C37—C36—H36 | 119.6 |
C15—C14—H14A | 108.5 | C38—C37—C36 | 120.5 (3) |
N2—C14—H14B | 108.5 | C38—C37—H37 | 119.7 |
C15—C14—H14B | 108.5 | C36—C37—H37 | 119.7 |
H14A—C14—H14B | 107.5 | C39—C38—C37 | 119.3 (3) |
C16—C15—C20 | 118.2 (3) | C39—C38—H38 | 120.3 |
C16—C15—C14 | 123.7 (2) | C37—C38—H38 | 120.3 |
C20—C15—C14 | 118.1 (2) | C38—C39—C40 | 120.3 (3) |
C15—C16—C17 | 120.5 (3) | C38—C39—H39 | 119.9 |
C15—C16—H16 | 119.8 | C40—C39—H39 | 119.9 |
C17—C16—H16 | 119.8 | C35—C40—C39 | 120.9 (3) |
C18—C17—C16 | 120.2 (3) | C35—C40—H40 | 119.5 |
C18—C17—H17 | 119.9 | C39—C40—H40 | 119.5 |
O2—Cu—S2—C22 | −9.59 (11) | C15—C16—C17—C18 | −0.6 (4) |
O1—Cu—S2—C22 | 94.2 (2) | C16—C17—C18—C19 | −0.7 (5) |
S1—Cu—S2—C22 | −173.12 (9) | C17—C18—C19—C20 | 1.1 (5) |
O2—Cu—S1—C2 | 89.5 (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—C19 | 179.6 (3) |
O2—Cu—O1—C1 | −168.3 (2) | Cu—O2—C21—N3 | 13.8 (4) |
S1—Cu—O1—C1 | −4.5 (2) | Cu—O2—C21—C23 | −170.15 (19) |
S2—Cu—O1—C1 | 87.3 (3) | C22—N3—C21—O2 | −6.4 (4) |
O1—Cu—O2—C21 | −169.5 (3) | C22—N3—C21—C23 | 177.5 (2) |
S1—Cu—O2—C21 | 90.5 (3) | C21—N3—C22—N4 | 170.6 (2) |
S2—Cu—O2—C21 | −3.1 (3) | C21—N3—C22—S2 | −12.8 (4) |
Cu—O1—C1—N1 | 16.9 (4) | C34—N4—C22—N3 | 175.0 (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—C3 | 174.5 (2) | C27—N4—C22—S2 | −179.00 (17) |
C1—N1—C2—N2 | 171.5 (2) | Cu—S2—C22—N3 | 18.8 (2) |
C1—N1—C2—S1 | −12.3 (3) | Cu—S2—C22—N4 | −164.70 (15) |
C14—N2—C2—N1 | 178.3 (2) | C26—O4—C23—C24 | −0.7 (3) |
C7—N2—C2—N1 | 4.1 (3) | C26—O4—C23—C21 | −177.1 (3) |
C14—N2—C2—S1 | 1.6 (3) | O2—C21—C23—C24 | −172.0 (3) |
C7—N2—C2—S1 | −172.62 (16) | N3—C21—C23—C24 | 4.8 (4) |
Cu—S1—C2—N1 | 19.6 (2) | O2—C21—C23—O4 | 3.4 (4) |
Cu—S1—C2—N2 | −164.11 (15) | N3—C21—C23—O4 | −179.8 (2) |
C6—O3—C3—C4 | 0.4 (3) | O4—C23—C24—C25 | 0.4 (4) |
C6—O3—C3—C1 | 180.0 (2) | C21—C23—C24—C25 | 176.1 (3) |
O1—C1—C3—C4 | −176.3 (3) | C23—C24—C25—C26 | 0.1 (4) |
N1—C1—C3—C4 | 0.8 (4) | C24—C25—C26—O4 | −0.5 (5) |
O1—C1—C3—O3 | 4.2 (3) | C23—O4—C26—C25 | 0.8 (4) |
N1—C1—C3—O3 | −178.7 (2) | C22—N4—C27—C28 | 103.0 (3) |
O3—C3—C4—C5 | −0.8 (3) | C34—N4—C27—C28 | −74.3 (3) |
C1—C3—C4—C5 | 179.7 (3) | N4—C27—C28—C29 | −56.7 (3) |
C3—C4—C5—C6 | 0.9 (3) | N4—C27—C28—C33 | 124.3 (3) |
C4—C5—C6—O3 | −0.7 (4) | C33—C28—C29—C30 | −0.3 (5) |
C3—O3—C6—C5 | 0.2 (3) | C27—C28—C29—C30 | −179.4 (3) |
C2—N2—C7—C8 | −109.9 (2) | C28—C29—C30—C31 | 0.7 (6) |
C14—N2—C7—C8 | 75.5 (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—C9 | 71.2 (3) | C29—C28—C33—C32 | −0.4 (5) |
C13—C8—C9—C10 | −0.4 (4) | C27—C28—C33—C32 | 178.6 (3) |
C7—C8—C9—C10 | 175.6 (2) | C31—C32—C33—C28 | 0.8 (5) |
C8—C9—C10—C11 | −0.1 (4) | C22—N4—C34—C35 | 101.4 (3) |
C9—C10—C11—C12 | 0.5 (5) | C27—N4—C34—C35 | −81.2 (2) |
C10—C11—C12—C13 | −0.4 (5) | N4—C34—C35—C40 | 114.7 (3) |
C11—C12—C13—C8 | −0.1 (4) | N4—C34—C35—C36 | −66.7 (3) |
C9—C8—C13—C12 | 0.5 (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—C38 | 0.6 (5) |
C7—N2—C14—C15 | 89.9 (2) | C36—C37—C38—C39 | −0.5 (6) |
N2—C14—C15—C16 | 5.7 (3) | C37—C38—C39—C40 | 0.3 (6) |
N2—C14—C15—C20 | −174.8 (2) | C36—C35—C40—C39 | 0.2 (5) |
C20—C15—C16—C17 | 1.4 (4) | C34—C35—C40—C39 | 178.9 (3) |
C14—C15—C16—C17 | −179.1 (2) | C38—C39—C40—C35 | −0.2 (5) |
Experimental details
Crystal data | |
Chemical formula | [Cu(C20H17N2O2S)2] |
Mr | 762.37 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 293 |
a, b, c (Å) | 18.8390 (3), 10.8730 (2), 19.6200 (3) |
β (°) | 114.748 (1) |
V (Å3) | 3649.79 (10) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.76 |
Crystal size (mm) | 0.49 × 0.44 × 0.39 |
Data collection | |
Diffractometer | Nonius KappaCCD area-detector |
Absorption correction | Gaussian (Coppens et al., 1965) |
Tmin, Tmax | 0.779, 0.886 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 21982, 7413, 6761 |
Rint | 0.027 |
(sin θ/λ)max (Å−1) | 0.631 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.049, 0.122, 1.07 |
No. of reflections | 7413 |
No. of parameters | 460 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.23, −0.39 |
Computer programs: COLLECT (Enraf–Nonius, 2000), DENZO and SCALEPACK (Otwinowski & Minor, 1997); SORTAV (Blessing, 1987, 1989), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997) and Mercury (Macrae et al., 2006), WinGX (Farrugia, 1999).
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.