Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270111052036/fn3087sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270111052036/fn3087Isup4.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270111052036/fn3087IIsup5.hkl |
CCDC references: 866741; 866742
For related literature, see: Dennehy et al. (2007, 2009); García-Vázquez, Souza-Pedrares, Carabel, Romero & Souza (2005); López-Torres, Mendiola & Pastor (2006); Ruan & Shi (2007).
[Cu4(tsac)4(CH3CN)2].2CH3CN, (I), was synthesized as reported previously (Dennehy et al., 2007). [Cu2(tsac)2(Sbim)2(CH3CN)], (II), was synthesized by dropwise addition of a red solution of [Cu4(tsac)4(CH3CN)2].2CH3CN (10 mg, 0.04 mmol of Cu+) in CH3CN (5 ml) to another solution of 2-mercaptobenzimidazole (6 mg, 0.04 mmol) in CH3CN (4 ml) with mechanical stirring. The solution turned orange. After a day of slow evaporation of the solvent, red crystals of (II) suitable for X-ray diffraction studies were obtained. The crystals were washed with diethyl ether and were air stable. Compound (II) was synthesized employing different molar ratios of (I) and Sbim (Cu:Sbim = 1:1, 1:4, 1:10) in CH3CN solutions. When the molar ratio was 1:1 to 1:4, crystals of the title compounds were obtained as unique products. When the Cu:Sbim ratio was 1:10, a very few thin orange needles of (II) were obtained. Analysis, calculated for C30H23Cu2N7O4S6: C 41.6, H 2.6, N 11.3%; found: C 41.6, H 2.3, N 11.3%. IR spectra were obtained in KBr dispersion and in Nujol mulls, and showed no differences in the vibrational bands. The IR spectra of this complex confirm the presence of two different thiosaccharinate anions. Selected anion bands, KBr (cm-1): 1394 (w)/1355 (s), 1258 (s), 1234/1222 (w), 1149 (vs), 1118 (m), 1022 (vw)/1008 (m), 837 (m)/822 (m), 622 (w). The UV–Vis spectra of the solid complex presents broad bands (200/214/245 and 298/310 nm) that are assigned to transitions in the phenyl groups and in the thiocarbonilic bonds within the ligands.
For (I), the H atoms were positioned geometrically and treated as riding, with C—H = 0.93–0.96 Å and N—H = 0.86 Å. H atoms bonded to tertiary C atoms were refined with Uiso(H) = 1.2Ueq(C), while for the methyl groups Uiso(H) = 1.5Ueq(C). The anisotropic displacement ellipsoid of atom S1D displays a marked elongation in the normal direction to both the S—C and S—Cu bonds. This can be related to the motion of the corresponding Sbim molecule, which coordinates to Cu via only one bond through atom S1D. The highest residual electron-density peak is located 0.79 Å from atom S1D.
In the case of (II), refinement proceeded in a similar manner. The main difference arises in the treatment of the disordered Sbim(D) molecule, which was refined in two orientations. The atomic displacements for Sbim(D) were refined isotropically because of the proximity between atoms belonging to the two disordered positions. Anisotropic treatment of the atomic displacement did not provide better statistics considering the increase of variables in the refinement. Finally, the distance between the closest atoms in the Sbim(D) molecule were restrained to the average distance of the rest of the Sbim molecules in the complex. The C7—N1 and C7—N2 distances were restrained to 1.33 Å and the N1—N2 distance was restrained to 2.145 Å. The position of the highest residual electron-density peak is located 2.44 Å from atom H4DA.
For both compounds, data collection: CrysAlis PRO (Oxford Diffraction, 2009); cell refinement: CrysAlis PRO (Oxford Diffraction, 2009); data reduction: CrysAlis PRO (Oxford Diffraction, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: Mercury [Version 1.4.2 (Build 2); Macrae et al., 2008]; software used to prepare material for publication: PLATON (Spek, 2009).
[Cu2(C7H4NO2S2)2(C7H6N2S)2(C2H3N)] | Z = 2 |
Mr = 865.01 | F(000) = 876 |
Triclinic, P1 | Dx = 1.715 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 8.0466 (1) Å | Cell parameters from 34323 reflections |
b = 13.8150 (2) Å | θ = 3.6–29.0° |
c = 15.3621 (2) Å | µ = 1.69 mm−1 |
α = 87.739 (1)° | T = 293 K |
β = 89.480 (1)° | Plate, orange |
γ = 79.033 (1)° | 0.30 × 0.20 × 0.10 mm |
V = 1675.21 (4) Å3 |
Oxford Xcalibur Eos Gemini diffractometer | 8285 independent reflections |
Radiation source: Enhance (Mo) X-ray Source | 5570 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.046 |
Detector resolution: 16.1158 pixels mm-1 | θmax = 29.1°, θmin = 3.6° |
ω scans, thick slices | h = −10→10 |
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009) | k = −18→18 |
Tmin = 0.716, Tmax = 0.801 | l = −20→20 |
97442 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)] = 0.036 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.118 | H-atom parameters constrained |
S = 1.10 | w = 1/[σ2(Fo2) + (0.0557P)2 + 0.8876P] where P = (Fo2 + 2Fc2)/3 |
8285 reflections | (Δ/σ)max < 0.001 |
443 parameters | Δρmax = 0.50 e Å−3 |
0 restraints | Δρmin = −0.65 e Å−3 |
0 constraints |
[Cu2(C7H4NO2S2)2(C7H6N2S)2(C2H3N)] | γ = 79.033 (1)° |
Mr = 865.01 | V = 1675.21 (4) Å3 |
Triclinic, P1 | Z = 2 |
a = 8.0466 (1) Å | Mo Kα radiation |
b = 13.8150 (2) Å | µ = 1.69 mm−1 |
c = 15.3621 (2) Å | T = 293 K |
α = 87.739 (1)° | 0.30 × 0.20 × 0.10 mm |
β = 89.480 (1)° |
Oxford Xcalibur Eos Gemini diffractometer | 8285 independent reflections |
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009) | 5570 reflections with I > 2σ(I) |
Tmin = 0.716, Tmax = 0.801 | Rint = 0.046 |
97442 measured reflections |
R[F2 > 2σ(F2)] = 0.036 | 0 restraints |
wR(F2) = 0.118 | H-atom parameters constrained |
S = 1.10 | Δρmax = 0.50 e Å−3 |
8285 reflections | Δρmin = −0.65 e Å−3 |
443 parameters |
Experimental. CrysAlisPro, Oxford Diffraction Ltd., Version 1.171.33.66 (release 28-04-2010 CrysAlis171 .NET) (compiled Apr 28 2010,14:27:37) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm. |
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 | ||
Cu1 | 0.67554 (5) | 0.61946 (3) | 0.39313 (3) | 0.04144 (12) | |
Cu2 | 0.53872 (6) | 0.74039 (3) | 0.26582 (3) | 0.05018 (14) | |
S1B | 0.58063 (11) | 0.72928 (6) | 0.49776 (5) | 0.0396 (2) | |
S2A | 0.64788 (10) | 0.31860 (6) | 0.22573 (6) | 0.0405 (2) | |
S2B | 0.29075 (10) | 0.92876 (6) | 0.32946 (5) | 0.03420 (18) | |
S1A | 0.42920 (11) | 0.58106 (6) | 0.32965 (5) | 0.03798 (19) | |
S1C | 0.83493 (11) | 0.70616 (6) | 0.29731 (6) | 0.0413 (2) | |
N1B | 0.4306 (3) | 0.82974 (17) | 0.35820 (15) | 0.0318 (6) | |
C7B | 0.4556 (4) | 0.8228 (2) | 0.44401 (19) | 0.0293 (6) | |
O1B | 0.3684 (3) | 0.99138 (16) | 0.27139 (14) | 0.0458 (6) | |
N1A | 0.6375 (3) | 0.4325 (2) | 0.25543 (18) | 0.0392 (6) | |
N1D | 0.3392 (5) | 0.8356 (2) | −0.01325 (18) | 0.0535 (8) | |
H1DA | 0.3478 | 0.7844 | −0.0442 | 0.064* | |
C1B | 0.2627 (4) | 0.9753 (2) | 0.43408 (19) | 0.0327 (6) | |
N1C | 0.8893 (3) | 0.54599 (19) | 0.19383 (16) | 0.0344 (6) | |
H1C | 0.7978 | 0.5259 | 0.2084 | 0.041* | |
C7C | 0.9355 (4) | 0.6266 (2) | 0.2226 (2) | 0.0347 (7) | |
O1A | 0.6731 (4) | 0.3143 (2) | 0.13315 (18) | 0.0601 (7) | |
C7A | 0.4871 (4) | 0.4680 (2) | 0.28895 (19) | 0.0321 (6) | |
C6B | 0.3604 (4) | 0.9079 (2) | 0.49073 (19) | 0.0308 (6) | |
O2B | 0.1414 (3) | 0.9013 (2) | 0.29776 (17) | 0.0548 (7) | |
N2C | 1.0826 (3) | 0.6351 (2) | 0.18357 (19) | 0.0412 (6) | |
H2CA | 1.1360 | 0.6826 | 0.1904 | 0.049* | |
C7D | 0.3908 (5) | 0.8345 (3) | 0.0698 (2) | 0.0459 (9) | |
C3A | 0.1899 (5) | 0.2473 (3) | 0.2725 (2) | 0.0447 (8) | |
H3A | 0.1276 | 0.1976 | 0.2669 | 0.054* | |
O2A | 0.7673 (3) | 0.25142 (19) | 0.2784 (2) | 0.0603 (7) | |
C6A | 0.3665 (4) | 0.3980 (2) | 0.28957 (19) | 0.0318 (6) | |
C2B | 0.1632 (4) | 1.0609 (2) | 0.4620 (2) | 0.0433 (8) | |
H2B | 0.0985 | 1.1059 | 0.4232 | 0.052* | |
C4A | 0.1140 (4) | 0.3352 (3) | 0.3084 (2) | 0.0446 (8) | |
H4A | 0.0013 | 0.3436 | 0.3258 | 0.053* | |
C5B | 0.3598 (4) | 0.9250 (2) | 0.5785 (2) | 0.0392 (7) | |
H5B | 0.4245 | 0.8800 | 0.6173 | 0.047* | |
C5C | 1.0257 (5) | 0.4124 (3) | 0.0933 (2) | 0.0442 (8) | |
H5C | 0.9423 | 0.3742 | 0.0969 | 0.053* | |
C3B | 0.1636 (5) | 1.0772 (2) | 0.5505 (2) | 0.0442 (8) | |
H3B | 0.0974 | 1.1340 | 0.5716 | 0.053* | |
C6C | 1.0107 (4) | 0.4991 (2) | 0.1367 (2) | 0.0351 (7) | |
C5A | 0.2018 (4) | 0.4109 (2) | 0.3189 (2) | 0.0375 (7) | |
H5A | 0.1511 | 0.4687 | 0.3451 | 0.045* | |
N2D | 0.3557 (4) | 0.9281 (2) | 0.09472 (18) | 0.0476 (7) | |
H2DA | 0.3773 | 0.9470 | 0.1454 | 0.057* | |
C1A | 0.4399 (4) | 0.3100 (2) | 0.2535 (2) | 0.0340 (7) | |
C4B | 0.2605 (5) | 1.0107 (2) | 0.6075 (2) | 0.0442 (8) | |
H4B | 0.2591 | 1.0236 | 0.6665 | 0.053* | |
C1C | 1.1356 (4) | 0.5558 (3) | 0.1307 (2) | 0.0398 (7) | |
C2A | 0.3574 (4) | 0.2318 (2) | 0.2446 (2) | 0.0394 (7) | |
H2A | 0.4106 | 0.1726 | 0.2215 | 0.047* | |
C4C | 1.1697 (5) | 0.3850 (3) | 0.0443 (2) | 0.0527 (9) | |
H4C | 1.1841 | 0.3268 | 0.0143 | 0.063* | |
C1D | 0.2705 (5) | 0.9307 (3) | −0.0420 (2) | 0.0510 (9) | |
C6D | 0.2796 (5) | 0.9902 (3) | 0.0273 (2) | 0.0484 (9) | |
C2D | 0.1985 (6) | 0.9682 (3) | −0.1200 (3) | 0.0682 (13) | |
H2D | 0.1906 | 0.9277 | −0.1661 | 0.082* | |
C3C | 1.2937 (5) | 0.4420 (3) | 0.0386 (3) | 0.0597 (11) | |
H3C | 1.3897 | 0.4208 | 0.0052 | 0.072* | |
C5D | 0.2200 (7) | 1.0907 (3) | 0.0208 (3) | 0.0706 (13) | |
H5D | 0.2270 | 1.1311 | 0.0671 | 0.085* | |
C2C | 1.2794 (5) | 0.5281 (3) | 0.0806 (3) | 0.0568 (10) | |
H2C | 1.3624 | 0.5666 | 0.0759 | 0.068* | |
C4D | 0.1494 (8) | 1.1283 (3) | −0.0581 (3) | 0.0889 (17) | |
H4D | 0.1081 | 1.1957 | −0.0650 | 0.107* | |
C3D | 0.1386 (7) | 1.0684 (4) | −0.1267 (3) | 0.0810 (16) | |
H3D | 0.0896 | 1.0963 | −0.1786 | 0.097* | |
S1D | 0.47787 (18) | 0.73062 (7) | 0.12689 (6) | 0.0683 (3) | |
N1S | 0.7954 (4) | 0.4923 (2) | 0.4425 (2) | 0.0484 (7) | |
C1S | 0.8343 (4) | 0.4153 (3) | 0.4720 (2) | 0.0424 (8) | |
C2S | 0.8855 (5) | 0.3149 (3) | 0.5064 (3) | 0.0598 (11) | |
H2S1 | 0.8348 | 0.2714 | 0.4725 | 0.090* | |
H2S2 | 0.8492 | 0.3108 | 0.5659 | 0.090* | |
H2S3 | 1.0065 | 0.2961 | 0.5035 | 0.090* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.0497 (3) | 0.0292 (2) | 0.0422 (2) | 0.00143 (17) | −0.00238 (19) | −0.00406 (16) |
Cu2 | 0.0598 (3) | 0.0529 (3) | 0.0304 (2) | 0.0106 (2) | −0.00513 (19) | −0.01216 (18) |
S1B | 0.0538 (5) | 0.0308 (4) | 0.0294 (4) | 0.0042 (3) | −0.0064 (4) | −0.0019 (3) |
S2A | 0.0360 (4) | 0.0404 (4) | 0.0497 (5) | −0.0156 (4) | 0.0087 (4) | −0.0183 (4) |
S2B | 0.0419 (4) | 0.0321 (4) | 0.0259 (4) | 0.0007 (3) | −0.0061 (3) | −0.0040 (3) |
S1A | 0.0396 (4) | 0.0331 (4) | 0.0421 (4) | −0.0077 (3) | 0.0011 (3) | −0.0073 (3) |
S1C | 0.0443 (5) | 0.0393 (4) | 0.0426 (5) | −0.0125 (4) | 0.0018 (4) | −0.0072 (3) |
N1B | 0.0408 (15) | 0.0268 (12) | 0.0258 (12) | 0.0000 (10) | −0.0041 (11) | −0.0051 (10) |
C7B | 0.0340 (16) | 0.0256 (13) | 0.0285 (14) | −0.0055 (12) | −0.0033 (12) | −0.0046 (11) |
O1B | 0.0725 (17) | 0.0356 (12) | 0.0278 (11) | −0.0063 (11) | −0.0005 (11) | −0.0003 (9) |
N1A | 0.0407 (16) | 0.0397 (15) | 0.0433 (15) | −0.0206 (12) | 0.0120 (12) | −0.0148 (12) |
N1D | 0.093 (3) | 0.0424 (16) | 0.0292 (15) | −0.0208 (16) | −0.0111 (15) | −0.0082 (12) |
C1B | 0.0399 (17) | 0.0297 (14) | 0.0283 (15) | −0.0060 (13) | 0.0000 (13) | −0.0037 (12) |
N1C | 0.0295 (13) | 0.0407 (14) | 0.0351 (14) | −0.0123 (11) | 0.0041 (11) | −0.0013 (11) |
C7C | 0.0320 (16) | 0.0412 (17) | 0.0321 (16) | −0.0106 (13) | −0.0027 (13) | 0.0028 (13) |
O1A | 0.0662 (18) | 0.0663 (17) | 0.0571 (16) | −0.0315 (14) | 0.0236 (14) | −0.0321 (14) |
C7A | 0.0375 (17) | 0.0346 (15) | 0.0263 (14) | −0.0121 (13) | −0.0008 (13) | −0.0030 (12) |
C6B | 0.0360 (17) | 0.0277 (14) | 0.0292 (15) | −0.0061 (12) | 0.0009 (12) | −0.0068 (11) |
O2B | 0.0464 (15) | 0.0697 (17) | 0.0473 (15) | −0.0052 (13) | −0.0145 (12) | −0.0146 (13) |
N2C | 0.0349 (15) | 0.0439 (16) | 0.0484 (17) | −0.0165 (12) | 0.0025 (13) | 0.0005 (13) |
C7D | 0.074 (3) | 0.0426 (19) | 0.0247 (16) | −0.0194 (17) | −0.0024 (16) | −0.0044 (13) |
C3A | 0.048 (2) | 0.051 (2) | 0.0421 (19) | −0.0297 (17) | −0.0109 (16) | 0.0084 (16) |
O2A | 0.0364 (14) | 0.0490 (15) | 0.096 (2) | −0.0073 (11) | −0.0033 (14) | −0.0096 (14) |
C6A | 0.0331 (16) | 0.0358 (16) | 0.0276 (15) | −0.0100 (13) | −0.0045 (12) | 0.0012 (12) |
C2B | 0.052 (2) | 0.0331 (16) | 0.0400 (18) | 0.0053 (14) | −0.0006 (15) | −0.0013 (14) |
C4A | 0.0335 (18) | 0.062 (2) | 0.0410 (19) | −0.0178 (16) | −0.0055 (15) | 0.0082 (16) |
C5B | 0.049 (2) | 0.0357 (16) | 0.0309 (16) | −0.0017 (14) | −0.0046 (14) | −0.0028 (13) |
C5C | 0.050 (2) | 0.0472 (19) | 0.0375 (18) | −0.0137 (16) | 0.0054 (15) | −0.0018 (15) |
C3B | 0.057 (2) | 0.0310 (16) | 0.0417 (19) | 0.0010 (15) | 0.0064 (16) | −0.0095 (14) |
C6C | 0.0330 (17) | 0.0407 (17) | 0.0311 (16) | −0.0069 (13) | 0.0032 (13) | 0.0042 (13) |
C5A | 0.0342 (17) | 0.0435 (18) | 0.0348 (17) | −0.0081 (14) | −0.0019 (14) | 0.0017 (14) |
N2D | 0.079 (2) | 0.0379 (15) | 0.0285 (14) | −0.0163 (15) | −0.0094 (14) | −0.0047 (11) |
C1A | 0.0314 (16) | 0.0378 (16) | 0.0352 (16) | −0.0125 (13) | −0.0039 (13) | −0.0009 (13) |
C4B | 0.060 (2) | 0.0444 (19) | 0.0280 (16) | −0.0075 (16) | 0.0046 (15) | −0.0125 (14) |
C1C | 0.0346 (17) | 0.0458 (18) | 0.0397 (18) | −0.0108 (14) | 0.0033 (14) | 0.0039 (14) |
C2A | 0.0423 (19) | 0.0393 (17) | 0.0404 (18) | −0.0169 (15) | −0.0054 (15) | −0.0005 (14) |
C4C | 0.058 (2) | 0.053 (2) | 0.044 (2) | −0.0025 (18) | 0.0070 (18) | −0.0067 (17) |
C1D | 0.073 (3) | 0.048 (2) | 0.0374 (19) | −0.0261 (19) | −0.0116 (18) | 0.0009 (16) |
C6D | 0.074 (3) | 0.0459 (19) | 0.0282 (16) | −0.0186 (18) | −0.0102 (17) | 0.0009 (14) |
C2D | 0.110 (4) | 0.066 (3) | 0.034 (2) | −0.031 (3) | −0.023 (2) | 0.0048 (18) |
C3C | 0.049 (2) | 0.072 (3) | 0.056 (2) | −0.005 (2) | 0.0179 (19) | −0.008 (2) |
C5D | 0.117 (4) | 0.046 (2) | 0.051 (2) | −0.019 (2) | −0.025 (3) | −0.0038 (18) |
C2C | 0.041 (2) | 0.071 (3) | 0.062 (3) | −0.0200 (19) | 0.0142 (18) | −0.002 (2) |
C4D | 0.141 (5) | 0.050 (3) | 0.075 (3) | −0.017 (3) | −0.042 (3) | 0.013 (2) |
C3D | 0.124 (4) | 0.069 (3) | 0.054 (3) | −0.031 (3) | −0.041 (3) | 0.016 (2) |
S1D | 0.1312 (11) | 0.0366 (5) | 0.0328 (5) | −0.0027 (6) | −0.0185 (6) | −0.0076 (4) |
N1S | 0.0521 (18) | 0.0406 (16) | 0.0467 (17) | 0.0055 (13) | −0.0024 (14) | −0.0006 (13) |
C1S | 0.0385 (18) | 0.0402 (18) | 0.0448 (19) | 0.0022 (14) | −0.0035 (15) | −0.0033 (15) |
C2S | 0.065 (3) | 0.042 (2) | 0.065 (3) | 0.0068 (18) | 0.005 (2) | 0.0107 (18) |
Cu1—N1S | 1.964 (3) | C6A—C5A | 1.377 (4) |
Cu1—S1B | 2.2799 (9) | C6A—C1A | 1.381 (4) |
Cu1—S1A | 2.3743 (9) | C2B—C3B | 1.386 (5) |
Cu1—S1C | 2.3785 (10) | C2B—H2B | 0.9300 |
Cu1—Cu2 | 2.6285 (6) | C4A—C5A | 1.384 (5) |
Cu2—N1B | 2.000 (2) | C4A—H4A | 0.9300 |
Cu2—S1D | 2.2091 (10) | C5B—C4B | 1.383 (4) |
Cu2—S1C | 2.3901 (10) | C5B—H5B | 0.9300 |
Cu2—S1A | 2.6711 (10) | C5C—C4C | 1.375 (5) |
S1B—C7B | 1.673 (3) | C5C—C6C | 1.379 (5) |
S2A—O2A | 1.433 (3) | C5C—H5C | 0.9300 |
S2A—O1A | 1.437 (3) | C3B—C4B | 1.377 (5) |
S2A—N1A | 1.642 (3) | C3B—H3B | 0.9300 |
S2A—C1A | 1.748 (3) | C6C—C1C | 1.388 (5) |
S2B—O2B | 1.423 (3) | C5A—H5A | 0.9300 |
S2B—O1B | 1.438 (2) | N2D—C6D | 1.389 (4) |
S2B—N1B | 1.646 (2) | N2D—H2DA | 0.8600 |
S2B—C1B | 1.751 (3) | C1A—C2A | 1.384 (4) |
S1A—C7A | 1.687 (3) | C4B—H4B | 0.9300 |
S1C—C7C | 1.710 (3) | C1C—C2C | 1.384 (5) |
N1B—C7B | 1.332 (4) | C2A—H2A | 0.9300 |
C7B—C6B | 1.483 (4) | C4C—C3C | 1.384 (6) |
N1A—C7A | 1.324 (4) | C4C—H4C | 0.9300 |
N1D—C7D | 1.345 (4) | C1D—C2D | 1.375 (5) |
N1D—C1D | 1.381 (5) | C1D—C6D | 1.381 (5) |
N1D—H1DA | 0.8600 | C6D—C5D | 1.380 (5) |
C1B—C2B | 1.378 (4) | C2D—C3D | 1.376 (6) |
C1B—C6B | 1.383 (4) | C2D—H2D | 0.9300 |
N1C—C7C | 1.331 (4) | C3C—C2C | 1.360 (6) |
N1C—C6C | 1.390 (4) | C3C—H3C | 0.9300 |
N1C—H1C | 0.8600 | C5D—C4D | 1.382 (6) |
C7C—N2C | 1.345 (4) | C5D—H5D | 0.9300 |
C7A—C6A | 1.494 (4) | C2C—H2C | 0.9300 |
C6B—C5B | 1.378 (4) | C4D—C3D | 1.379 (7) |
N2C—C1C | 1.388 (4) | C4D—H4D | 0.9300 |
N2C—H2CA | 0.8600 | C3D—H3D | 0.9300 |
C7D—N2D | 1.339 (4) | N1S—C1S | 1.128 (4) |
C7D—S1D | 1.688 (4) | C1S—C2S | 1.449 (5) |
C3A—C4A | 1.385 (5) | C2S—H2S1 | 0.9600 |
C3A—C2A | 1.390 (5) | C2S—H2S2 | 0.9600 |
C3A—H3A | 0.9300 | C2S—H2S3 | 0.9600 |
N1S—Cu1—S1B | 112.41 (9) | C5A—C6A—C7A | 129.5 (3) |
N1S—Cu1—S1A | 103.95 (10) | C1A—C6A—C7A | 110.9 (3) |
S1B—Cu1—S1A | 105.73 (3) | C1B—C2B—C3B | 117.1 (3) |
N1S—Cu1—S1C | 116.16 (10) | C1B—C2B—H2B | 121.5 |
S1B—Cu1—S1C | 104.04 (3) | C3B—C2B—H2B | 121.5 |
S1A—Cu1—S1C | 114.30 (3) | C5A—C4A—C3A | 121.5 (3) |
N1S—Cu1—Cu2 | 154.15 (9) | C5A—C4A—H4A | 119.2 |
S1B—Cu1—Cu2 | 93.28 (2) | C3A—C4A—H4A | 119.2 |
S1A—Cu1—Cu2 | 64.31 (3) | C6B—C5B—C4B | 118.3 (3) |
S1C—Cu1—Cu2 | 56.76 (3) | C6B—C5B—H5B | 120.8 |
N1B—Cu2—S1D | 132.11 (8) | C4B—C5B—H5B | 120.8 |
N1B—Cu2—S1C | 105.88 (8) | C4C—C5C—C6C | 117.0 (3) |
S1D—Cu2—S1C | 114.20 (5) | C4C—C5C—H5C | 121.5 |
N1B—Cu2—Cu1 | 86.83 (7) | C6C—C5C—H5C | 121.5 |
S1D—Cu2—Cu1 | 137.19 (3) | C4B—C3B—C2B | 121.2 (3) |
S1C—Cu2—Cu1 | 56.34 (2) | C4B—C3B—H3B | 119.4 |
N1B—Cu2—S1A | 95.33 (8) | C2B—C3B—H3B | 119.4 |
S1D—Cu2—S1A | 99.20 (4) | C5C—C6C—C1C | 121.2 (3) |
S1C—Cu2—S1A | 104.02 (3) | C5C—C6C—N1C | 132.4 (3) |
Cu1—Cu2—S1A | 53.23 (2) | C1C—C6C—N1C | 106.3 (3) |
C7B—S1B—Cu1 | 104.36 (10) | C6A—C5A—C4A | 118.1 (3) |
O2A—S2A—O1A | 116.16 (18) | C6A—C5A—H5A | 121.0 |
O2A—S2A—N1A | 110.71 (16) | C4A—C5A—H5A | 121.0 |
O1A—S2A—N1A | 109.42 (16) | C7D—N2D—C6D | 110.5 (3) |
O2A—S2A—C1A | 111.23 (16) | C7D—N2D—H2DA | 124.8 |
O1A—S2A—C1A | 110.93 (16) | C6D—N2D—H2DA | 124.8 |
N1A—S2A—C1A | 96.68 (14) | C6A—C1A—C2A | 123.8 (3) |
O2B—S2B—O1B | 115.58 (15) | C6A—C1A—S2A | 107.2 (2) |
O2B—S2B—N1B | 110.19 (15) | C2A—C1A—S2A | 129.0 (3) |
O1B—S2B—N1B | 109.61 (14) | C3B—C4B—C5B | 121.1 (3) |
O2B—S2B—C1B | 112.12 (16) | C3B—C4B—H4B | 119.5 |
O1B—S2B—C1B | 111.82 (14) | C5B—C4B—H4B | 119.5 |
N1B—S2B—C1B | 95.73 (13) | C2C—C1C—C6C | 121.4 (3) |
C7A—S1A—Cu1 | 106.49 (11) | C2C—C1C—N2C | 132.6 (3) |
C7A—S1A—Cu2 | 123.48 (11) | C6C—C1C—N2C | 106.0 (3) |
Cu1—S1A—Cu2 | 62.47 (2) | C1A—C2A—C3A | 115.7 (3) |
C7C—S1C—Cu1 | 108.83 (11) | C1A—C2A—H2A | 122.1 |
C7C—S1C—Cu2 | 108.56 (11) | C3A—C2A—H2A | 122.1 |
Cu1—S1C—Cu2 | 66.90 (3) | C5C—C4C—C3C | 121.5 (4) |
C7B—N1B—S2B | 111.6 (2) | C5C—C4C—H4C | 119.2 |
C7B—N1B—Cu2 | 129.40 (19) | C3C—C4C—H4C | 119.2 |
S2B—N1B—Cu2 | 118.97 (13) | C2D—C1D—C6D | 121.7 (4) |
N1B—C7B—C6B | 113.5 (2) | C2D—C1D—N1D | 131.9 (4) |
N1B—C7B—S1B | 125.4 (2) | C6D—C1D—N1D | 106.4 (3) |
C6B—C7B—S1B | 121.1 (2) | C5D—C6D—C1D | 121.5 (3) |
C7A—N1A—S2A | 110.8 (2) | C5D—C6D—N2D | 132.5 (3) |
C7D—N1D—C1D | 110.5 (3) | C1D—C6D—N2D | 106.0 (3) |
C7D—N1D—H1DA | 124.8 | C1D—C2D—C3D | 117.0 (4) |
C1D—N1D—H1DA | 124.8 | C1D—C2D—H2D | 121.5 |
C2B—C1B—C6B | 122.3 (3) | C3D—C2D—H2D | 121.5 |
C2B—C1B—S2B | 130.1 (2) | C2C—C3C—C4C | 121.9 (4) |
C6B—C1B—S2B | 107.6 (2) | C2C—C3C—H3C | 119.0 |
C7C—N1C—C6C | 110.0 (3) | C4C—C3C—H3C | 119.0 |
C7C—N1C—H1C | 125.0 | C6D—C5D—C4D | 116.6 (4) |
C6C—N1C—H1C | 125.0 | C6D—C5D—H5D | 121.7 |
N1C—C7C—N2C | 107.7 (3) | C4D—C5D—H5D | 121.7 |
N1C—C7C—S1C | 128.2 (2) | C3C—C2C—C1C | 117.0 (4) |
N2C—C7C—S1C | 124.2 (2) | C3C—C2C—H2C | 121.5 |
N1A—C7A—C6A | 114.3 (3) | C1C—C2C—H2C | 121.5 |
N1A—C7A—S1A | 125.1 (2) | C3D—C4D—C5D | 121.7 (4) |
C6A—C7A—S1A | 120.6 (2) | C3D—C4D—H4D | 119.1 |
C5B—C6B—C1B | 120.1 (3) | C5D—C4D—H4D | 119.1 |
C5B—C6B—C7B | 128.5 (3) | C2D—C3D—C4D | 121.5 (4) |
C1B—C6B—C7B | 111.4 (3) | C2D—C3D—H3D | 119.3 |
C7C—N2C—C1C | 110.0 (3) | C4D—C3D—H3D | 119.3 |
C7C—N2C—H2CA | 125.0 | C7D—S1D—Cu2 | 118.95 (12) |
C1C—N2C—H2CA | 125.0 | C1S—N1S—Cu1 | 166.9 (3) |
N2D—C7D—N1D | 106.7 (3) | N1S—C1S—C2S | 177.6 (4) |
N2D—C7D—S1D | 129.8 (3) | C1S—C2S—H2S1 | 109.5 |
N1D—C7D—S1D | 123.6 (3) | C1S—C2S—H2S2 | 109.5 |
C4A—C3A—C2A | 121.3 (3) | H2S1—C2S—H2S2 | 109.5 |
C4A—C3A—H3A | 119.4 | C1S—C2S—H2S3 | 109.5 |
C2A—C3A—H3A | 119.4 | H2S1—C2S—H2S3 | 109.5 |
C5A—C6A—C1A | 119.6 (3) | H2S2—C2S—H2S3 | 109.5 |
D—H···A | D—H | H···A | D···A | D—H···A |
N1D—H1DA···O1Ai | 0.86 | 2.00 | 2.841 (4) | 167 |
N1C—H1C···N1A | 0.86 | 2.10 | 2.918 (4) | 160 |
N2D—H2DA···O1B | 0.86 | 2.05 | 2.893 (4) | 166 |
Symmetry code: (i) −x+1, −y+1, −z. |
[Cu2(C7H4NO2S2)2(C7H6N2S)3] | F(000) = 1976 |
Mr = 974.14 | Dx = 1.613 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 2072 reflections |
a = 13.2395 (12) Å | θ = 3.7–29.0° |
b = 10.2731 (10) Å | µ = 1.48 mm−1 |
c = 29.536 (15) Å | T = 293 K |
β = 93.135 (16)° | Needle, red |
V = 4011 (2) Å3 | 0.25 × 0.15 × 0.10 mm |
Z = 4 |
Oxford Xcalibur Eos Gemini diffractometer | 8812 independent reflections |
Radiation source: Enhance (Mo) X-ray Source | 4863 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.066 |
Detector resolution: 16.1158 pixels mm-1 | θmax = 27.5°, θmin = 3.7° |
ω scans, thick slices | h = −17→17 |
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009) | k = −7→13 |
Tmin = 0.814, Tmax = 0.867 | l = −34→38 |
18885 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)] = 0.067 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.154 | H-atom parameters constrained |
S = 1.01 | w = 1/[σ2(Fo2) + (0.0565P)2 + 0.3051P] where P = (Fo2 + 2Fc2)/3 |
8812 reflections | (Δ/σ)max < 0.001 |
587 parameters | Δρmax = 0.78 e Å−3 |
317 restraints | Δρmin = −0.39 e Å−3 |
0 constraints |
[Cu2(C7H4NO2S2)2(C7H6N2S)3] | V = 4011 (2) Å3 |
Mr = 974.14 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 13.2395 (12) Å | µ = 1.48 mm−1 |
b = 10.2731 (10) Å | T = 293 K |
c = 29.536 (15) Å | 0.25 × 0.15 × 0.10 mm |
β = 93.135 (16)° |
Oxford Xcalibur Eos Gemini diffractometer | 8812 independent reflections |
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009) | 4863 reflections with I > 2σ(I) |
Tmin = 0.814, Tmax = 0.867 | Rint = 0.066 |
18885 measured reflections |
R[F2 > 2σ(F2)] = 0.067 | 317 restraints |
wR(F2) = 0.154 | H-atom parameters constrained |
S = 1.01 | Δρmax = 0.78 e Å−3 |
8812 reflections | Δρmin = −0.39 e Å−3 |
587 parameters |
Experimental. CrysAlisPro, Oxford Diffraction Ltd., Version 1.171.33.66 (release 28-04-2010 CrysAlis171 .NET) (compiled Apr 28 2010,14:27:37) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm. |
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 | Occ. (<1) | |
Cu1 | 0.45898 (5) | 0.29325 (7) | 0.06351 (2) | 0.0462 (2) | |
Cu2 | 0.29961 (5) | 0.19343 (7) | 0.09829 (2) | 0.0477 (2) | |
S2A | 0.16473 (11) | 0.53028 (13) | −0.02790 (4) | 0.0388 (3) | |
S1A | 0.33525 (11) | 0.43466 (13) | 0.08724 (4) | 0.0407 (3) | |
N1A | 0.2332 (3) | 0.4332 (4) | 0.00611 (12) | 0.0356 (10) | |
O2A | 0.2242 (3) | 0.5729 (4) | −0.06449 (11) | 0.0550 (11) | |
O1A | 0.0702 (3) | 0.4702 (3) | −0.04161 (12) | 0.0507 (10) | |
C1A | 0.1518 (4) | 0.6578 (5) | 0.01085 (16) | 0.0342 (12) | |
C2A | 0.1034 (4) | 0.7758 (5) | 0.00591 (18) | 0.0430 (13) | |
H2A | 0.0652 | 0.7965 | −0.0205 | 0.052* | |
C5A | 0.2208 (4) | 0.7131 (5) | 0.08459 (16) | 0.0416 (13) | |
H5A | 0.2596 | 0.6930 | 0.1109 | 0.050* | |
C6A | 0.2109 (4) | 0.6253 (5) | 0.04947 (15) | 0.0322 (11) | |
C7A | 0.2575 (4) | 0.4936 (5) | 0.04479 (15) | 0.0329 (12) | |
S2B | 0.34219 (12) | 0.06820 (15) | 0.19724 (4) | 0.0486 (4) | |
O1B | 0.3195 (4) | −0.0613 (4) | 0.18141 (14) | 0.0730 (13) | |
O2B | 0.2613 (3) | 0.1388 (5) | 0.21697 (12) | 0.0668 (13) | |
S1B | 0.55635 (11) | 0.26931 (15) | 0.13012 (4) | 0.0468 (4) | |
N1B | 0.3876 (3) | 0.1568 (4) | 0.15603 (12) | 0.0378 (10) | |
C1B | 0.4531 (4) | 0.0747 (5) | 0.23276 (16) | 0.0438 (14) | |
C2B | 0.4724 (6) | 0.0209 (6) | 0.27513 (19) | 0.0658 (19) | |
H2B | 0.4240 | −0.0290 | 0.2888 | 0.079* | |
C3B | 0.5659 (7) | 0.0436 (7) | 0.2964 (2) | 0.078 (2) | |
H3B | 0.5813 | 0.0094 | 0.3252 | 0.093* | |
C4B | 0.6364 (6) | 0.1164 (7) | 0.2755 (2) | 0.079 (2) | |
H4B | 0.6991 | 0.1315 | 0.2903 | 0.095* | |
C5B | 0.6161 (5) | 0.1683 (6) | 0.23212 (19) | 0.0637 (18) | |
H5B | 0.6645 | 0.2167 | 0.2179 | 0.076* | |
C6B | 0.5227 (5) | 0.1459 (5) | 0.21125 (16) | 0.0424 (14) | |
C7B | 0.4833 (4) | 0.1897 (5) | 0.16545 (15) | 0.0373 (13) | |
S1C | 0.39098 (11) | 0.07216 (13) | 0.04742 (4) | 0.0424 (4) | |
N2C | 0.3124 (3) | −0.0420 (4) | −0.02884 (13) | 0.0413 (11) | |
H2C | 0.3498 | −0.1101 | −0.0255 | 0.050* | |
N1C | 0.2506 (3) | 0.1494 (4) | −0.01819 (13) | 0.0412 (11) | |
H1C | 0.2407 | 0.2252 | −0.0069 | 0.049* | |
C1C | 0.2390 (4) | −0.0238 (5) | −0.06380 (16) | 0.0384 (13) | |
C2C | 0.2042 (5) | −0.1022 (6) | −0.09904 (17) | 0.0497 (15) | |
H2C1 | 0.2316 | −0.1841 | −0.1038 | 0.060* | |
C3C | 0.1262 (5) | −0.0529 (7) | −0.12699 (18) | 0.0594 (17) | |
H3C | 0.0999 | −0.1029 | −0.1511 | 0.071* | |
C4C | 0.0864 (5) | 0.0703 (7) | −0.11974 (19) | 0.0640 (18) | |
H4C | 0.0340 | 0.1003 | −0.1392 | 0.077* | |
C5C | 0.1218 (5) | 0.1488 (6) | −0.08492 (18) | 0.0579 (17) | |
H5C | 0.0947 | 0.2309 | −0.0801 | 0.069* | |
C6C | 0.1999 (4) | 0.0990 (5) | −0.05733 (16) | 0.0379 (13) | |
C7C | 0.3165 (4) | 0.0615 (5) | −0.00110 (15) | 0.0359 (12) | |
S1D | 0.12947 (13) | 0.19192 (16) | 0.08961 (6) | 0.0597 (4) | |
C7DA | 0.102 (3) | 0.308 (2) | 0.1295 (6) | 0.047 (2) | 0.510 (11) |
N1DA | 0.0514 (12) | 0.4204 (14) | 0.1195 (4) | 0.051 (2) | 0.510 (11) |
H1DA | 0.0251 | 0.4408 | 0.0932 | 0.062* | 0.510 (11) |
N2DA | 0.1402 (16) | 0.3218 (16) | 0.1726 (6) | 0.050 (2) | 0.510 (11) |
H2DA | 0.1817 | 0.2682 | 0.1861 | 0.060* | 0.510 (11) |
C1DA | 0.0483 (11) | 0.4972 (13) | 0.1579 (4) | 0.058 (2) | 0.510 (11) |
C2DA | 0.0083 (12) | 0.6206 (13) | 0.1639 (4) | 0.072 (3) | 0.510 (11) |
H2D1 | −0.0281 | 0.6643 | 0.1407 | 0.086* | 0.510 (11) |
C3DA | 0.0261 (13) | 0.6741 (13) | 0.2063 (4) | 0.077 (3) | 0.510 (11) |
H3DA | −0.0010 | 0.7557 | 0.2119 | 0.092* | 0.510 (11) |
C4DA | 0.0813 (12) | 0.6137 (14) | 0.2405 (4) | 0.073 (3) | 0.510 (11) |
H4DA | 0.0913 | 0.6549 | 0.2684 | 0.088* | 0.510 (11) |
C5DA | 0.1230 (12) | 0.4907 (13) | 0.2342 (4) | 0.066 (3) | 0.510 (11) |
H5DA | 0.1616 | 0.4493 | 0.2571 | 0.079* | 0.510 (11) |
C6DA | 0.1042 (16) | 0.4323 (16) | 0.1918 (5) | 0.058 (2) | 0.510 (11) |
C7DB | 0.100 (3) | 0.308 (2) | 0.1246 (6) | 0.047 (2) | 0.490 (11) |
N1DB | 0.0302 (13) | 0.4050 (16) | 0.1180 (5) | 0.052 (2) | 0.490 (11) |
H1DB | −0.0041 | 0.4196 | 0.0929 | 0.063* | 0.490 (11) |
N2DB | 0.1267 (17) | 0.3107 (17) | 0.1694 (6) | 0.050 (2) | 0.490 (11) |
H2DB | 0.1642 | 0.2532 | 0.1832 | 0.060* | 0.490 (11) |
C1DB | 0.0226 (13) | 0.4761 (14) | 0.1574 (4) | 0.057 (2) | 0.490 (11) |
C2DB | −0.0402 (12) | 0.5793 (14) | 0.1674 (4) | 0.068 (3) | 0.490 (11) |
H2D2 | −0.0856 | 0.6156 | 0.1458 | 0.081* | 0.490 (11) |
C3DB | −0.0308 (13) | 0.6243 (15) | 0.2113 (4) | 0.076 (3) | 0.490 (11) |
H3DB | −0.0674 | 0.6978 | 0.2187 | 0.092* | 0.490 (11) |
C4DB | 0.0294 (13) | 0.5667 (15) | 0.2445 (4) | 0.073 (3) | 0.490 (11) |
H4DB | 0.0308 | 0.5994 | 0.2738 | 0.088* | 0.490 (11) |
C5DB | 0.0890 (12) | 0.4592 (14) | 0.2348 (5) | 0.066 (3) | 0.490 (11) |
H5DB | 0.1290 | 0.4178 | 0.2573 | 0.079* | 0.490 (11) |
C6DB | 0.0861 (16) | 0.4164 (16) | 0.1898 (5) | 0.057 (2) | 0.490 (11) |
S1E | 0.56575 (11) | 0.32525 (13) | 0.00676 (4) | 0.0403 (3) | |
N2E | 0.5058 (4) | 0.2104 (4) | −0.07191 (15) | 0.0589 (15) | |
H2E | 0.5486 | 0.1479 | −0.0681 | 0.071* | |
N1E | 0.4215 (3) | 0.3827 (4) | −0.06072 (13) | 0.0421 (11) | |
H1E | 0.3998 | 0.4520 | −0.0481 | 0.051* | |
C1E | 0.4390 (5) | 0.2242 (5) | −0.10927 (17) | 0.0497 (15) | |
C2E | 0.4218 (6) | 0.1484 (7) | −0.1478 (2) | 0.083 (2) | |
H2E1 | 0.4580 | 0.0723 | −0.1522 | 0.100* | |
C3E | 0.3491 (6) | 0.1912 (7) | −0.1789 (2) | 0.075 (2) | |
H3E | 0.3366 | 0.1440 | −0.2055 | 0.090* | |
C4E | 0.2947 (5) | 0.3003 (7) | −0.17208 (19) | 0.0642 (19) | |
H4E | 0.2446 | 0.3244 | −0.1937 | 0.077* | |
C5E | 0.3113 (5) | 0.3769 (6) | −0.13401 (17) | 0.0547 (16) | |
H5E | 0.2747 | 0.4528 | −0.1298 | 0.066* | |
C6E | 0.3845 (4) | 0.3350 (5) | −0.10271 (16) | 0.0395 (13) | |
C7E | 0.4946 (4) | 0.3067 (5) | −0.04294 (15) | 0.0347 (12) | |
C3A | 0.1140 (5) | 0.8624 (5) | 0.0417 (2) | 0.0516 (15) | |
H3A | 0.0812 | 0.9424 | 0.0398 | 0.062* | |
C4A | 0.1721 (5) | 0.8318 (5) | 0.0802 (2) | 0.0520 (15) | |
H4A | 0.1788 | 0.8919 | 0.1037 | 0.062* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.0511 (5) | 0.0576 (5) | 0.0300 (4) | 0.0079 (4) | 0.0013 (3) | 0.0036 (3) |
Cu2 | 0.0444 (4) | 0.0630 (5) | 0.0349 (4) | 0.0075 (4) | −0.0048 (3) | −0.0015 (3) |
S2A | 0.0462 (9) | 0.0366 (7) | 0.0326 (7) | 0.0106 (7) | −0.0072 (6) | −0.0045 (6) |
S1A | 0.0516 (9) | 0.0402 (8) | 0.0292 (7) | 0.0107 (7) | −0.0076 (6) | −0.0043 (6) |
N1A | 0.042 (3) | 0.033 (2) | 0.032 (2) | 0.005 (2) | −0.0018 (19) | −0.0042 (18) |
O2A | 0.079 (3) | 0.057 (3) | 0.029 (2) | 0.012 (2) | 0.0069 (19) | 0.0065 (17) |
O1A | 0.054 (3) | 0.044 (2) | 0.052 (2) | 0.006 (2) | −0.0172 (19) | −0.0119 (18) |
C1A | 0.034 (3) | 0.033 (3) | 0.036 (3) | 0.004 (2) | 0.001 (2) | −0.004 (2) |
C2A | 0.046 (4) | 0.036 (3) | 0.046 (3) | 0.006 (3) | −0.001 (3) | 0.001 (2) |
C5A | 0.049 (4) | 0.043 (3) | 0.032 (3) | 0.006 (3) | −0.001 (2) | −0.009 (2) |
C6A | 0.034 (3) | 0.031 (3) | 0.032 (3) | 0.005 (2) | 0.003 (2) | 0.003 (2) |
C7A | 0.039 (3) | 0.030 (3) | 0.030 (3) | 0.002 (2) | 0.002 (2) | 0.000 (2) |
S2B | 0.0504 (9) | 0.0579 (10) | 0.0370 (8) | 0.0114 (8) | −0.0008 (7) | 0.0149 (7) |
O1B | 0.084 (4) | 0.056 (3) | 0.077 (3) | −0.006 (3) | −0.014 (3) | 0.013 (2) |
O2B | 0.061 (3) | 0.099 (3) | 0.041 (2) | 0.033 (3) | 0.010 (2) | 0.025 (2) |
S1B | 0.0454 (9) | 0.0625 (10) | 0.0317 (7) | 0.0035 (8) | −0.0042 (6) | 0.0049 (7) |
N1B | 0.047 (3) | 0.041 (3) | 0.025 (2) | 0.008 (2) | −0.0028 (19) | 0.0046 (18) |
C1B | 0.056 (4) | 0.047 (3) | 0.027 (3) | 0.019 (3) | −0.003 (3) | 0.005 (2) |
C2B | 0.089 (6) | 0.064 (4) | 0.045 (4) | 0.016 (4) | 0.000 (3) | 0.016 (3) |
C3B | 0.106 (7) | 0.086 (5) | 0.039 (4) | 0.013 (5) | −0.020 (4) | 0.012 (4) |
C4B | 0.089 (6) | 0.085 (5) | 0.059 (4) | 0.005 (5) | −0.041 (4) | 0.010 (4) |
C5B | 0.072 (5) | 0.070 (4) | 0.047 (4) | 0.001 (4) | −0.020 (3) | 0.009 (3) |
C6B | 0.055 (4) | 0.047 (3) | 0.024 (3) | 0.013 (3) | −0.009 (2) | −0.006 (2) |
C7B | 0.047 (3) | 0.038 (3) | 0.025 (3) | 0.010 (3) | −0.009 (2) | −0.003 (2) |
S1C | 0.0527 (9) | 0.0340 (7) | 0.0393 (8) | 0.0090 (7) | −0.0090 (6) | −0.0062 (6) |
N2C | 0.044 (3) | 0.035 (3) | 0.044 (3) | 0.010 (2) | −0.002 (2) | −0.008 (2) |
N1C | 0.052 (3) | 0.033 (2) | 0.037 (2) | 0.013 (2) | −0.007 (2) | −0.0055 (19) |
C1C | 0.042 (3) | 0.040 (3) | 0.033 (3) | 0.000 (3) | 0.004 (2) | −0.002 (2) |
C2C | 0.059 (4) | 0.045 (3) | 0.045 (3) | 0.005 (3) | −0.004 (3) | −0.010 (3) |
C3C | 0.065 (5) | 0.074 (5) | 0.039 (3) | −0.008 (4) | −0.005 (3) | −0.014 (3) |
C4C | 0.068 (5) | 0.076 (5) | 0.045 (4) | 0.008 (4) | −0.022 (3) | −0.002 (3) |
C5C | 0.064 (4) | 0.059 (4) | 0.049 (4) | 0.019 (4) | −0.011 (3) | 0.003 (3) |
C6C | 0.040 (3) | 0.040 (3) | 0.035 (3) | 0.005 (3) | 0.003 (2) | 0.000 (2) |
C7C | 0.045 (3) | 0.032 (3) | 0.032 (3) | 0.000 (3) | 0.004 (2) | −0.006 (2) |
S1D | 0.0449 (10) | 0.0576 (10) | 0.0747 (11) | 0.0057 (8) | −0.0136 (8) | −0.0153 (8) |
C7DA | 0.045 (4) | 0.051 (4) | 0.044 (4) | 0.007 (4) | −0.004 (4) | 0.000 (4) |
N1DA | 0.052 (5) | 0.056 (4) | 0.045 (4) | 0.014 (4) | −0.007 (4) | 0.002 (4) |
N2DA | 0.050 (5) | 0.058 (4) | 0.042 (4) | 0.014 (4) | −0.008 (4) | 0.003 (4) |
C1DA | 0.060 (5) | 0.064 (4) | 0.050 (4) | 0.022 (4) | −0.006 (4) | 0.000 (4) |
C2DA | 0.076 (6) | 0.073 (5) | 0.065 (4) | 0.025 (5) | −0.006 (5) | −0.005 (4) |
C3DA | 0.083 (6) | 0.077 (6) | 0.069 (5) | 0.021 (5) | 0.002 (5) | −0.012 (5) |
C4DA | 0.076 (6) | 0.081 (6) | 0.062 (4) | 0.016 (5) | −0.002 (5) | −0.008 (5) |
C5DA | 0.068 (6) | 0.079 (5) | 0.050 (4) | 0.015 (5) | −0.005 (5) | 0.002 (4) |
C6DA | 0.060 (5) | 0.066 (4) | 0.046 (4) | 0.016 (4) | −0.008 (4) | 0.000 (4) |
C7DB | 0.045 (4) | 0.052 (4) | 0.043 (4) | 0.006 (4) | −0.006 (4) | 0.001 (4) |
N1DB | 0.052 (5) | 0.057 (4) | 0.046 (4) | 0.015 (4) | −0.011 (4) | −0.001 (4) |
N2DB | 0.049 (5) | 0.056 (4) | 0.044 (4) | 0.016 (4) | −0.007 (4) | 0.004 (4) |
C1DB | 0.058 (5) | 0.063 (4) | 0.049 (4) | 0.020 (4) | −0.007 (4) | 0.001 (4) |
C2DB | 0.069 (6) | 0.071 (5) | 0.061 (4) | 0.023 (5) | −0.005 (5) | −0.005 (4) |
C3DB | 0.078 (6) | 0.081 (6) | 0.070 (5) | 0.028 (5) | −0.001 (5) | −0.012 (5) |
C4DB | 0.078 (6) | 0.083 (6) | 0.059 (4) | 0.018 (5) | −0.006 (5) | −0.011 (5) |
C5DB | 0.068 (6) | 0.078 (5) | 0.051 (4) | 0.012 (5) | −0.008 (5) | 0.002 (4) |
C6DB | 0.059 (5) | 0.066 (4) | 0.046 (4) | 0.014 (4) | −0.007 (4) | 0.001 (4) |
S1E | 0.0499 (9) | 0.0381 (8) | 0.0330 (7) | 0.0048 (7) | 0.0039 (6) | −0.0018 (6) |
N2E | 0.083 (4) | 0.044 (3) | 0.049 (3) | 0.028 (3) | −0.011 (3) | −0.014 (2) |
N1E | 0.056 (3) | 0.037 (3) | 0.034 (2) | 0.016 (2) | 0.006 (2) | −0.0056 (19) |
C1E | 0.072 (4) | 0.041 (3) | 0.036 (3) | 0.013 (3) | −0.005 (3) | −0.007 (3) |
C2E | 0.102 (6) | 0.064 (5) | 0.079 (5) | 0.030 (5) | −0.027 (4) | −0.037 (4) |
C3E | 0.101 (6) | 0.075 (5) | 0.047 (4) | 0.019 (5) | −0.016 (4) | −0.027 (3) |
C4E | 0.067 (5) | 0.087 (5) | 0.038 (3) | 0.013 (4) | −0.005 (3) | −0.011 (3) |
C5E | 0.064 (4) | 0.062 (4) | 0.039 (3) | 0.024 (4) | 0.004 (3) | −0.005 (3) |
C6E | 0.052 (4) | 0.039 (3) | 0.027 (3) | 0.002 (3) | 0.006 (2) | −0.003 (2) |
C7E | 0.045 (3) | 0.029 (3) | 0.031 (3) | 0.003 (3) | 0.008 (2) | −0.004 (2) |
C3A | 0.056 (4) | 0.029 (3) | 0.070 (4) | 0.008 (3) | 0.006 (3) | −0.009 (3) |
C4A | 0.057 (4) | 0.043 (3) | 0.057 (4) | 0.005 (3) | 0.003 (3) | −0.020 (3) |
Cu1—S1E | 2.2748 (16) | C5C—H5C | 0.9300 |
Cu1—S1B | 2.3057 (17) | S1D—C7DB | 1.643 (11) |
Cu1—S1A | 2.3261 (15) | S1D—C7DA | 1.728 (10) |
Cu1—S1C | 2.4795 (15) | C7DA—N2DA | 1.349 (8) |
Cu1—Cu2 | 2.6068 (11) | C7DA—N1DA | 1.362 (9) |
Cu2—N1B | 2.047 (4) | N1DA—C1DA | 1.384 (8) |
Cu2—S1D | 2.2532 (18) | N1DA—H1DA | 0.8600 |
Cu2—S1C | 2.3391 (16) | N2DA—C6DA | 1.367 (7) |
Cu2—S1A | 2.5470 (16) | N2DA—H2DA | 0.8600 |
S2A—O1A | 1.433 (4) | C1DA—C6DA | 1.382 (8) |
S2A—O2A | 1.440 (4) | C1DA—C2DA | 1.389 (10) |
S2A—N1A | 1.651 (4) | C2DA—C3DA | 1.376 (10) |
S2A—C1A | 1.754 (5) | C2DA—H2D1 | 0.9300 |
S1A—C7A | 1.690 (5) | C3DA—C4DA | 1.364 (10) |
N1A—C7A | 1.324 (6) | C3DA—H3DA | 0.9300 |
C1A—C2A | 1.374 (7) | C4DA—C5DA | 1.395 (10) |
C1A—C6A | 1.389 (6) | C4DA—H4DA | 0.9300 |
C2A—C3A | 1.384 (7) | C5DA—C6DA | 1.399 (9) |
C2A—H2A | 0.9300 | C5DA—H5DA | 0.9300 |
C5A—C6A | 1.376 (6) | C7DB—N2DB | 1.349 (8) |
C5A—C4A | 1.381 (7) | C7DB—N1DB | 1.363 (9) |
C5A—H5A | 0.9300 | N1DB—C1DB | 1.383 (8) |
C6A—C7A | 1.496 (6) | N1DB—H1DB | 0.8600 |
S2B—O1B | 1.436 (4) | N2DB—C6DB | 1.367 (7) |
S2B—O2B | 1.442 (4) | N2DB—H2DB | 0.8600 |
S2B—N1B | 1.659 (4) | C1DB—C6DB | 1.382 (8) |
S2B—C1B | 1.759 (6) | C1DB—C2DB | 1.389 (10) |
S1B—C7B | 1.674 (6) | C2DB—C3DB | 1.376 (10) |
N1B—C7B | 1.326 (7) | C2DB—H2D2 | 0.9300 |
C1B—C6B | 1.361 (8) | C3DB—C4DB | 1.364 (10) |
C1B—C2B | 1.379 (7) | C3DB—H3DB | 0.9300 |
C2B—C3B | 1.378 (10) | C4DB—C5DB | 1.395 (10) |
C2B—H2B | 0.9300 | C4DB—H4DB | 0.9300 |
C3B—C4B | 1.370 (10) | C5DB—C6DB | 1.399 (9) |
C3B—H3B | 0.9300 | C5DB—H5DB | 0.9300 |
C4B—C5B | 1.400 (8) | S1E—C7E | 1.711 (5) |
C4B—H4B | 0.9300 | N2E—C7E | 1.321 (6) |
C5B—C6B | 1.370 (8) | N2E—C1E | 1.383 (7) |
C5B—H5B | 0.9300 | N2E—H2E | 0.8600 |
C6B—C7B | 1.493 (6) | N1E—C7E | 1.330 (6) |
S1C—C7C | 1.698 (5) | N1E—C6E | 1.397 (6) |
N2C—C7C | 1.342 (6) | N1E—H1E | 0.8600 |
N2C—C1C | 1.391 (6) | C1E—C6E | 1.367 (7) |
N2C—H2C | 0.8600 | C1E—C2E | 1.388 (8) |
N1C—C7C | 1.336 (6) | C2E—C3E | 1.367 (9) |
N1C—C6C | 1.403 (6) | C2E—H2E1 | 0.9300 |
N1C—H1C | 0.8600 | C3E—C4E | 1.353 (8) |
C1C—C2C | 1.376 (7) | C3E—H3E | 0.9300 |
C1C—C6C | 1.381 (7) | C4E—C5E | 1.380 (8) |
C2C—C3C | 1.382 (8) | C4E—H4E | 0.9300 |
C2C—H2C1 | 0.9300 | C5E—C6E | 1.372 (7) |
C3C—C4C | 1.392 (8) | C5E—H5E | 0.9300 |
C3C—H3C | 0.9300 | C3A—C4A | 1.374 (7) |
C4C—C5C | 1.370 (8) | C3A—H3A | 0.9300 |
C4C—H4C | 0.9300 | C4A—H4A | 0.9300 |
C5C—C6C | 1.380 (7) | ||
S1E—Cu1—S1B | 107.65 (6) | C6C—C5C—H5C | 122.0 |
S1E—Cu1—S1A | 127.45 (6) | C5C—C6C—C1C | 122.1 (5) |
S1B—Cu1—S1A | 100.35 (6) | C5C—C6C—N1C | 131.2 (5) |
S1E—Cu1—S1C | 103.00 (5) | C1C—C6C—N1C | 106.5 (4) |
S1B—Cu1—S1C | 104.24 (6) | N1C—C7C—N2C | 107.5 (4) |
S1A—Cu1—S1C | 112.06 (6) | N1C—C7C—S1C | 127.8 (4) |
S1E—Cu1—Cu2 | 153.66 (5) | N2C—C7C—S1C | 124.7 (4) |
S1B—Cu1—Cu2 | 92.79 (5) | C7DB—S1D—C7DA | 4.1 (12) |
S1A—Cu1—Cu2 | 61.86 (4) | C7DB—S1D—Cu2 | 101.2 (14) |
S1C—Cu1—Cu2 | 54.69 (4) | C7DA—S1D—Cu2 | 99.4 (12) |
N1B—Cu2—S1D | 127.84 (14) | N2DA—C7DA—N1DA | 105.5 (7) |
N1B—Cu2—S1C | 98.41 (13) | N2DA—C7DA—S1D | 129.4 (10) |
S1D—Cu2—S1C | 118.17 (6) | N1DA—C7DA—S1D | 123.8 (9) |
N1B—Cu2—S1A | 100.65 (12) | C7DA—N1DA—C1DA | 110.1 (5) |
S1D—Cu2—S1A | 100.55 (6) | C7DA—N1DA—H1DA | 125.0 |
S1C—Cu2—S1A | 109.27 (5) | C1DA—N1DA—H1DA | 125.0 |
N1B—Cu2—Cu1 | 87.97 (13) | C7DA—N2DA—C6DA | 111.0 (5) |
S1D—Cu2—Cu1 | 141.59 (6) | C7DA—N2DA—H2DA | 124.5 |
S1C—Cu2—Cu1 | 59.89 (4) | C6DA—N2DA—H2DA | 124.5 |
S1A—Cu2—Cu1 | 53.64 (4) | C6DA—C1DA—N1DA | 106.2 (6) |
O1A—S2A—O2A | 115.1 (2) | C6DA—C1DA—C2DA | 122.8 (7) |
O1A—S2A—N1A | 110.7 (2) | N1DA—C1DA—C2DA | 130.8 (6) |
O2A—S2A—N1A | 109.6 (2) | C3DA—C2DA—C1DA | 115.6 (7) |
O1A—S2A—C1A | 113.0 (2) | C3DA—C2DA—H2D1 | 122.2 |
O2A—S2A—C1A | 109.8 (2) | C1DA—C2DA—H2D1 | 122.2 |
N1A—S2A—C1A | 97.1 (2) | C4DA—C3DA—C2DA | 123.4 (8) |
C7A—S1A—Cu1 | 114.24 (17) | C4DA—C3DA—H3DA | 118.3 |
C7A—S1A—Cu2 | 109.51 (17) | C2DA—C3DA—H3DA | 118.3 |
Cu1—S1A—Cu2 | 64.49 (4) | C3DA—C4DA—C5DA | 120.8 (8) |
C7A—N1A—S2A | 110.0 (3) | C3DA—C4DA—H4DA | 119.6 |
C2A—C1A—C6A | 122.6 (4) | C5DA—C4DA—H4DA | 119.6 |
C2A—C1A—S2A | 130.6 (4) | C4DA—C5DA—C6DA | 117.2 (7) |
C6A—C1A—S2A | 106.5 (4) | C4DA—C5DA—H5DA | 121.4 |
C1A—C2A—C3A | 117.3 (5) | C6DA—C5DA—H5DA | 121.4 |
C1A—C2A—H2A | 121.4 | N2DA—C6DA—C1DA | 106.6 (5) |
C3A—C2A—H2A | 121.4 | N2DA—C6DA—C5DA | 132.7 (6) |
C6A—C5A—C4A | 118.9 (5) | C1DA—C6DA—C5DA | 120.2 (7) |
C6A—C5A—H5A | 120.5 | N2DB—C7DB—N1DB | 105.5 (7) |
C4A—C5A—H5A | 120.5 | N2DB—C7DB—S1D | 124.8 (10) |
C5A—C6A—C1A | 119.2 (5) | N1DB—C7DB—S1D | 128.5 (12) |
C5A—C6A—C7A | 129.8 (4) | C7DB—N1DB—C1DB | 110.1 (5) |
C1A—C6A—C7A | 111.0 (4) | C7DB—N1DB—H1DB | 125.0 |
N1A—C7A—C6A | 114.9 (4) | C1DB—N1DB—H1DB | 125.0 |
N1A—C7A—S1A | 125.5 (4) | C7DB—N2DB—C6DB | 111.0 (5) |
C6A—C7A—S1A | 119.5 (3) | C7DB—N2DB—H2DB | 124.5 |
O1B—S2B—O2B | 116.8 (3) | C6DB—N2DB—H2DB | 124.5 |
O1B—S2B—N1B | 110.3 (2) | C6DB—C1DB—N1DB | 106.2 (6) |
O2B—S2B—N1B | 109.1 (2) | C6DB—C1DB—C2DB | 122.7 (7) |
O1B—S2B—C1B | 112.5 (3) | N1DB—C1DB—C2DB | 130.8 (6) |
O2B—S2B—C1B | 110.7 (2) | C3DB—C2DB—C1DB | 115.6 (7) |
N1B—S2B—C1B | 95.3 (3) | C3DB—C2DB—H2D2 | 122.2 |
C7B—S1B—Cu1 | 105.60 (19) | C1DB—C2DB—H2D2 | 122.2 |
C7B—N1B—S2B | 111.5 (3) | C4DB—C3DB—C2DB | 123.4 (8) |
C7B—N1B—Cu2 | 128.4 (3) | C4DB—C3DB—H3DB | 118.3 |
S2B—N1B—Cu2 | 120.0 (3) | C2DB—C3DB—H3DB | 118.3 |
C6B—C1B—C2B | 122.9 (6) | C3DB—C4DB—C5DB | 120.8 (8) |
C6B—C1B—S2B | 107.9 (4) | C3DB—C4DB—H4DB | 119.6 |
C2B—C1B—S2B | 129.3 (5) | C5DB—C4DB—H4DB | 119.6 |
C3B—C2B—C1B | 117.6 (7) | C4DB—C5DB—C6DB | 117.2 (7) |
C3B—C2B—H2B | 121.2 | C4DB—C5DB—H5DB | 121.4 |
C1B—C2B—H2B | 121.2 | C6DB—C5DB—H5DB | 121.4 |
C4B—C3B—C2B | 120.2 (6) | N2DB—C6DB—C1DB | 106.6 (5) |
C4B—C3B—H3B | 119.9 | N2DB—C6DB—C5DB | 132.8 (6) |
C2B—C3B—H3B | 119.9 | C1DB—C6DB—C5DB | 120.2 (7) |
C3B—C4B—C5B | 121.3 (7) | C7E—S1E—Cu1 | 106.33 (18) |
C3B—C4B—H4B | 119.3 | C7E—N2E—C1E | 110.5 (5) |
C5B—C4B—H4B | 119.3 | C7E—N2E—H2E | 124.7 |
C6B—C5B—C4B | 118.1 (7) | C1E—N2E—H2E | 124.7 |
C6B—C5B—H5B | 121.0 | C7E—N1E—C6E | 110.9 (4) |
C4B—C5B—H5B | 121.0 | C7E—N1E—H1E | 124.6 |
C1B—C6B—C5B | 119.9 (5) | C6E—N1E—H1E | 124.6 |
C1B—C6B—C7B | 111.9 (5) | C6E—C1E—N2E | 107.0 (4) |
C5B—C6B—C7B | 128.2 (6) | C6E—C1E—C2E | 121.3 (6) |
N1B—C7B—C6B | 113.3 (5) | N2E—C1E—C2E | 131.8 (6) |
N1B—C7B—S1B | 124.9 (4) | C3E—C2E—C1E | 116.7 (6) |
C6B—C7B—S1B | 121.8 (4) | C3E—C2E—H2E1 | 121.6 |
C7C—S1C—Cu2 | 106.24 (18) | C1E—C2E—H2E1 | 121.6 |
C7C—S1C—Cu1 | 114.12 (18) | C4E—C3E—C2E | 121.8 (6) |
Cu2—S1C—Cu1 | 65.43 (4) | C4E—C3E—H3E | 119.1 |
C7C—N2C—C1C | 110.5 (4) | C2E—C3E—H3E | 119.1 |
C7C—N2C—H2C | 124.7 | C3E—C4E—C5E | 122.2 (6) |
C1C—N2C—H2C | 124.7 | C3E—C4E—H4E | 118.9 |
C7C—N1C—C6C | 109.6 (4) | C5E—C4E—H4E | 118.9 |
C7C—N1C—H1C | 125.2 | C6E—C5E—C4E | 116.4 (6) |
C6C—N1C—H1C | 125.2 | C6E—C5E—H5E | 121.8 |
C2C—C1C—C6C | 121.8 (5) | C4E—C5E—H5E | 121.8 |
C2C—C1C—N2C | 132.4 (5) | C1E—C6E—C5E | 121.7 (5) |
C6C—C1C—N2C | 105.8 (4) | C1E—C6E—N1E | 104.8 (5) |
C1C—C2C—C3C | 116.5 (5) | C5E—C6E—N1E | 133.5 (5) |
C1C—C2C—H2C1 | 121.8 | N2E—C7E—N1E | 106.8 (4) |
C3C—C2C—H2C1 | 121.8 | N2E—C7E—S1E | 124.3 (4) |
C2C—C3C—C4C | 121.2 (5) | N1E—C7E—S1E | 128.9 (4) |
C2C—C3C—H3C | 119.4 | C4A—C3A—C2A | 120.9 (5) |
C4C—C3C—H3C | 119.4 | C4A—C3A—H3A | 119.5 |
C5C—C4C—C3C | 122.3 (6) | C2A—C3A—H3A | 119.5 |
C5C—C4C—H4C | 118.8 | C3A—C4A—C5A | 121.1 (5) |
C3C—C4C—H4C | 118.8 | C3A—C4A—H4A | 119.4 |
C4C—C5C—C6C | 116.1 (6) | C5A—C4A—H4A | 119.4 |
C4C—C5C—H5C | 122.0 |
D—H···A | D—H | H···A | D···A | D—H···A |
N1DA—H1DA···O1Ai | 0.86 | 2.13 | 2.957 (14) | 161 |
N1C—H1C···N1A | 0.86 | 2.17 | 3.014 (6) | 166 |
N2DA—H2DA···O2B | 0.86 | 1.90 | 2.756 (19) | 174 |
N2DB—H2DB···O2B | 0.86 | 1.97 | 2.827 (12) | 173 |
Symmetry code: (i) −x, −y+1, −z. |
Experimental details
(I) | (II) | |
Crystal data | ||
Chemical formula | [Cu2(C7H4NO2S2)2(C7H6N2S)2(C2H3N)] | [Cu2(C7H4NO2S2)2(C7H6N2S)3] |
Mr | 865.01 | 974.14 |
Crystal system, space group | Triclinic, P1 | Monoclinic, P21/c |
Temperature (K) | 293 | 293 |
a, b, c (Å) | 8.0466 (1), 13.8150 (2), 15.3621 (2) | 13.2395 (12), 10.2731 (10), 29.536 (15) |
α, β, γ (°) | 87.739 (1), 89.480 (1), 79.033 (1) | 90, 93.135 (16), 90 |
V (Å3) | 1675.21 (4) | 4011 (2) |
Z | 2 | 4 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 1.69 | 1.48 |
Crystal size (mm) | 0.30 × 0.20 × 0.10 | 0.25 × 0.15 × 0.10 |
Data collection | ||
Diffractometer | Oxford Xcalibur Eos Gemini diffractometer | Oxford Xcalibur Eos Gemini diffractometer |
Absorption correction | Multi-scan (CrysAlis PRO; Oxford Diffraction, 2009) | Multi-scan (CrysAlis PRO; Oxford Diffraction, 2009) |
Tmin, Tmax | 0.716, 0.801 | 0.814, 0.867 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 97442, 8285, 5570 | 18885, 8812, 4863 |
Rint | 0.046 | 0.066 |
(sin θ/λ)max (Å−1) | 0.684 | 0.650 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.036, 0.118, 1.10 | 0.067, 0.154, 1.01 |
No. of reflections | 8285 | 8812 |
No. of parameters | 443 | 587 |
No. of restraints | 0 | 317 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.50, −0.65 | 0.78, −0.39 |
Computer programs: CrysAlis PRO (Oxford Diffraction, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), Mercury [Version 1.4.2 (Build 2); Macrae et al., 2008], PLATON (Spek, 2009).
D—H···A | D—H | H···A | D···A | D—H···A |
N1D—H1DA···O1Ai | 0.86 | 2.00 | 2.841 (4) | 167 |
N1C—H1C···N1A | 0.86 | 2.10 | 2.918 (4) | 160 |
N2D—H2DA···O1B | 0.86 | 2.05 | 2.893 (4) | 166 |
Symmetry code: (i) −x+1, −y+1, −z. |
Plane | r.m.s. | tsac(A) | tsac(B) | Sbim(C) |
tsac(A) | 0.0159 | |||
tsac(B) | 0.0171 | 86.89 (5) | ||
Sbim(C) | 0.0414 | 14.68 (8) | 89.73 (7) | |
Sbim(D) | 0.0138 | 84.99 (8) | 23.30 (8) | 86.27 (9) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1DA—H1DA···O1Ai | 0.86 | 2.13 | 2.957 (14) | 161 |
N1C—H1C···N1A | 0.86 | 2.17 | 3.014 (6) | 166 |
N2DA—H2DA···O2B | 0.86 | 1.90 | 2.756 (19) | 174 |
N2DB—H2DB···O2B | 0.86 | 1.97 | 2.827 (12) | 173 |
Symmetry code: (i) −x, −y+1, −z. |
Plane | r.m.s. | tsac(A) | tsac(B) | Sbim(C) | Sbim(DA) |
tsac(A) | 0.0317 | ||||
tsac(B) | 0.0362 | 84.40 (8) | |||
Sbim(C) | 0.0448 | 11.33 (17) | 81.95 (11) | ||
Sbim(DA) | 0.0495 | 06.9 (5) | 88.6 (3) | 17.8 (5) | |
Sbim(E) | 0.0097 | 10.6 (2) | 88.89 (12) | 09.6 (2) | 13.9 (5) |
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Thionates, anions produced by the deprotonation of heterocyclic thioamides, can coordinate to metals, producing mononuclear or complex polynuclear species. Like other thioamides, thiosaccharin [or 1,1-dioxo-1λ6,2-benzothiazole-3(2H)-thione] is a versatile ligand, with the ability to coordinate metal centres in many ways (Dennehy et al., 2009). Particular attention has been devoted in recent decades to the synthesis of copper complexes, in both the mono- and divalent oxidation states, due to the great variety and flexibility of their coordination environments (Rapper, 1994). Most of the chemistry of CuI with thionates has been focused on the tetra- or hexanuclear binary complexes (García-Vázquez et al., 2005; Ruan & Shi, 2007; López-Torres et al., 2006). We have been working with binary and ternary copper thiosaccharinates, firstly synthesizing the Cu(tsac) complex (where tsac is the thiosaccharinate anion), which crystallized as the tetranuclear cluster [Cu4(tsac)4(CH3CN)2].2CH3CN from acetonitrile solutions (Dennehy et al., 2007), and then ternary phosphane complexes (Dennehy et al., 2009). To study the competition between two different thiones bound to copper, we have synthesized a ternary thiosaccharinate with thiosaccharin and 1H-benzimidazole-2(3H)-thione (Sbim), viz. [Cu2(tsac)2(Sbim)2(CH3CN)], (I), and [Cu2(tsac)2(Sbim)3], (II).
Compound (I) is a copper(I) thiosaccharinate and crystallizes in the space group P1. It is built of triply bridged dinuclear units. Two tsac anions and one Sbim molecule bind the metals. One anion bridges via the endocyclic N and exocyclic S atoms (µ-S:N), with Cu—N and Cu—S distances of 2.000 (2) and 2.2799 (9) Å, respectively. The other anion and one of the Sbim molecules bridge the metal centres through their exocyclic S atoms, with Cu—S distances of 2.3743 (9) and 2.6711 (10) Å for tsac, and 2.3785 (10) and 2.3901 (10) Å for Sbim. The second Sbim molecule coordinates in a monodentate fashion (κS), with a Cu—S distance of 2.2091 (10) Å, and the coordination of Cu2 is completed by an acetonitrile molecule, with a Cu—N distance of 1.964 (3) Å. Each CuI atom has a nearly distorted tetrahedral coordination environment. Given the proximity of the two CuI atoms, with a CuI—CuI distance of 2.6285 (6) Å, the two subunits form tetrahedra linked by edge-sharing. This short CuI—CuI distance indicates a strong cuprophilic interaction.
Each [Cu2(tsac)2(Sbim)2(CH3CN)] structural unit of (I) is stabilized by two intramolecular hydrogen bonds (N1D—H2DA···O1B and N1C—H1C···N1A) and one intermolecular hydrogen bond [N1D—H1DA···O1Ai; symmetry code: x, -y + 1, -z + 1], establishing an interaction with another inversion-symmetry related [Cu2(tsac)2(Sbim)2(CH3CN)] unit. The N2C—H2CA bond points towards a neighbouring Cu—Cu centre and away from acceptors. Therefore, it is blocked and unable to participate in any hydrogen bonds. Additionally, two Sbim and two tsac planar residues stack together through their six-membered planar rings in a four-layer group, with the negative tsac residues separated by the neutral Sbim molecules. There are also π–π interactions, with the rings arranged in the order tsaciii/Sbim/Sbimiv/tsacv [symmetry codes: (iii) x+1, y, z; (iv) -x+2, -y+1, -z; (v) -x+1, -y+1, -z]. Centroid–centroid distances are 3.588 (2) Å for tsaciii–Sbim (rings C1A–C6A and C1C–C6C, respectively) and equivalent Sbimiv–tsacv interactions; and 3.616 (2) Å between parallel Sbim–Sbimiv. The dihedral angle between tsac anions and nearby Sbim molecules is 12.53 (16)°.
Compound (II) crystallizes in the monoclinic space group P21/c. As mentioned before, this structure presents important similarities with the structure of (I). In the case of (II), the acetonitrile molecule is substituted by an additional disordered Sbim molecule, which binds to Cu from the exocyclic S atom (κS). In this case, the tsac anion bridges via the endocyclic N and exocyclic S atoms (µ-S:N), with Cu—N and Cu—S distances of 2.047 (4) and 2.3057 (17) Å, respectively. Each CuI atom presents a distorted tetrahedral coordination environment and both tetrahedra are linked by edge-sharing. The other anion and one of the Sbim molecules bridge the metal centres through their exocyclic S atoms, with Cu—S distances of 2.5470 (16) and 2.3261 (15) Å for tsac, and 2.4795 (15) and 2.3264 (15) Å for Sbim. The second Sbim molecule coordinates in a monodentate fashion (κS), with a Cu—S distance of 2.2748 (16) Å. An important difference between these two structures is the CuI—CuI distance; in the case of (II), the distance is 2.6068 (11) Å, which is slightly shorter than that in (I). Comparing the Cu—N distances, that in (I) is considerably shorter than that in (II), which leads to a weaker CuI—CuI interaction in (I). [Please check rephrasing - original text was not clear.]
The three-dimensional crystal structure of (II) is sustained by two intramolecular hydrogen bonds (N1C—H1C···N1A and N2DA—H2DA···O2B) and one intermolecular hydrogen bond (N1DA—H1DA···O1Av [symmetry code: (v) -x, -y + 1, -z] which correspond to a molecule related by inversion symmetry. The last two bonds involve the interaction between the disordered Sbim(D) molecule and two tsac molecules from two symmetry-related [Cu2(tsac)2(Sbim)3] units, as shown in Fig. 4. Finally, a possible intermolecular C—H···π interaction was identified as being responsible for the orientation of the Sbim(B) molecule, and responsible for the infinite packing along the plane defined by the [100] and [010] basis vectors. The C2E—H2E···Cg (Cg is the centroid of the S2B/N1B/C7B/C6B/C1B ring) angle is 162° and the H2E···Cg distance is 2.77 Å.
In order to compare the conformational geometries of (I) and (II), we performed a least-squares plane fitting of all the Sbim and tsac molecules in the two compounds, and the results are presented in Tables 1 and 2. The planes are constituted by atoms S1/S2/N1/C1/C2/C3/C4/C5 for Sbim and S1/N1/N2/C1/C2/C3/C4/C5/C6/C7 for tsac molecules. According to the calculations, the r.m.s. deviations of the fitted atoms are all below the limit of 0.0450 Å. A further comparison, assuming a common Cu1—Cu2 core, allows us to estimate the angles between the same kind of molecules in both conformations as 17.7, 14.2, 15.1 and 83.7° for tsac(A), tsac(B), Sbim(C) and Sbim(D), respectively (see Fig. 5). In the case of Sbim(D), we included the conformation with the higher site-occupation number, corresponding to Sbim(DA).