Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270110035754/gd3359sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270110035754/gd3359Isup2.hkl |
CCDC reference: 798586
An aqueous solution of copper(II) acetate (20 ml, 5 mM) was stirred for 2 h with an ethanolic solution of salicylaldehyde 4-N-allylthiosemicarbazone (20 ml, 10 mM). The resulting solution was then set aside for 3 d in the dark, giving violet needle-like crystals of (I) suitable for single-crystal X-ray diffraction.
The structure refinement indicated disorder of one allyl group, atoms C10 and C11, over two sets of positions with occupancies of 0.669 (8) and 0.331 (8). C10 and C11 from both positions were refined with equal isotropic and anisotropic parameters. Due to disorder, the C9—C10 and C10—C11 distances were refined with restraints of 1.52 (2) and 1.33 (2) Å, respectively. The coordinates of H atoms bonded to N or O atoms were found from Fourier difference map and refined, with Uiso(H) = 1.2Ueq(N) or 1.5Ueq(O), using distance restraints 0.82 (4) Å for O5—H51O, O6—H61O, O6—H62O and O4—H4O, and 0.87 (4) Å for N6—H6N, N3—H3N, N4—H4N, N9—H9N and N10—H10N. All other H atoms were treated as riding, with C—H = 0.95 or 0.99 Å, and with Uiso(H) = 1.2Ueq(C). The structure was handled as an inversion twin, with twin fractions 0.535 (13) and 0.465 (13).
Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); 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); software used to prepare material for publication: publCIF (Westrip, 2010).
[Cu(C11H11N3OS)(C11H13N3OS)]·H2O | F(000) = 2280 |
Mr = 550.15 | Dx = 1.513 Mg m−3 |
Monoclinic, Cc | Melting point: 231 K |
Hall symbol: C -2yc | Mo Kα radiation, λ = 0.71073 Å |
a = 25.763 (3) Å | Cell parameters from 5321 reflections |
b = 8.5526 (9) Å | θ = 2.5–25.2° |
c = 24.496 (3) Å | µ = 1.11 mm−1 |
β = 116.458 (3)° | T = 173 K |
V = 4832.1 (10) Å3 | Needle, violet |
Z = 8 | 0.50 × 0.05 × 0.05 mm |
Bruker APEXII CCD diffractometer | 8043 independent reflections |
Radiation source: fine-focus sealed tube | 6716 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.048 |
ϕ and ω scans | θmax = 26.6°, θmin = 1.9° |
Absorption correction: multi-scan (SADABS; Bruker, 2005) | h = −29→32 |
Tmin = 0.606, Tmax = 0.946 | k = −10→10 |
25072 measured reflections | l = −30→28 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.036 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.074 | w = 1/[σ2(Fo2) + (0.0294P)2 + 1.6385P] where P = (Fo2 + 2Fc2)/3 |
S = 1.03 | (Δ/σ)max = 0.002 |
8043 reflections | Δρmax = 0.48 e Å−3 |
656 parameters | Δρmin = −0.36 e Å−3 |
16 restraints | Absolute structure: Flack (1983), 3047 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.464 (13) |
[Cu(C11H11N3OS)(C11H13N3OS)]·H2O | V = 4832.1 (10) Å3 |
Mr = 550.15 | Z = 8 |
Monoclinic, Cc | Mo Kα radiation |
a = 25.763 (3) Å | µ = 1.11 mm−1 |
b = 8.5526 (9) Å | T = 173 K |
c = 24.496 (3) Å | 0.50 × 0.05 × 0.05 mm |
β = 116.458 (3)° |
Bruker APEXII CCD diffractometer | 8043 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2005) | 6716 reflections with I > 2σ(I) |
Tmin = 0.606, Tmax = 0.946 | Rint = 0.048 |
25072 measured reflections |
R[F2 > 2σ(F2)] = 0.036 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.074 | Δρmax = 0.48 e Å−3 |
S = 1.03 | Δρmin = −0.36 e Å−3 |
8043 reflections | Absolute structure: Flack (1983), 3047 Friedel pairs |
656 parameters | Absolute structure parameter: 0.464 (13) |
16 restraints |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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 | 0.40946 (2) | 0.23917 (5) | 0.11016 (2) | 0.01915 (11) | |
S1 | 0.47493 (6) | 0.36162 (13) | 0.19397 (5) | 0.0226 (3) | |
S2 | 0.34069 (5) | 0.35102 (12) | 0.13596 (5) | 0.0242 (2) | |
O1 | 0.35948 (12) | 0.1031 (3) | 0.04694 (14) | 0.0253 (7) | |
O2 | 0.09263 (13) | 0.0620 (4) | −0.02904 (15) | 0.0274 (8) | |
H2O | 0.121 (2) | 0.099 (6) | −0.009 (2) | 0.041* | |
N1 | 0.52671 (19) | 0.2851 (5) | 0.1227 (2) | 0.0223 (10) | |
N2 | 0.47390 (15) | 0.2075 (4) | 0.09008 (15) | 0.0203 (8) | |
N3 | 0.5797 (2) | 0.4281 (6) | 0.2074 (2) | 0.0355 (12) | |
H3N | 0.581 (2) | 0.475 (6) | 0.2354 (19) | 0.043* | |
N4 | 0.25815 (19) | 0.2184 (5) | 0.0390 (2) | 0.0197 (10) | |
H4N | 0.2821 (17) | 0.170 (5) | 0.032 (2) | 0.024* | |
N5 | 0.20338 (15) | 0.1575 (4) | 0.00493 (15) | 0.0196 (8) | |
N6 | 0.22710 (17) | 0.3505 (4) | 0.10128 (17) | 0.0225 (9) | |
H6N | 0.1949 (16) | 0.325 (6) | 0.079 (2) | 0.027* | |
C1 | 0.52978 (19) | 0.3554 (5) | 0.17135 (18) | 0.0224 (10) | |
C2 | 0.47400 (19) | 0.1148 (4) | 0.04825 (19) | 0.0199 (9) | |
H2A | 0.5089 | 0.1077 | 0.0442 | 0.024* | |
C3 | 0.42584 (19) | 0.0218 (4) | 0.00742 (18) | 0.0207 (9) | |
C4 | 0.3718 (3) | 0.0167 (5) | 0.0087 (3) | 0.0196 (12) | |
C5 | 0.3299 (2) | −0.0849 (5) | −0.0319 (2) | 0.0248 (10) | |
H5A | 0.2935 | −0.0931 | −0.0310 | 0.030* | |
C6 | 0.3399 (2) | −0.1725 (5) | −0.07291 (19) | 0.0258 (10) | |
H6A | 0.3103 | −0.2400 | −0.0999 | 0.031* | |
C7 | 0.3919 (2) | −0.1649 (5) | −0.0758 (2) | 0.0283 (12) | |
H7A | 0.3981 | −0.2244 | −0.1051 | 0.034* | |
C8 | 0.4347 (2) | −0.0693 (5) | −0.0353 (2) | 0.0258 (10) | |
H8A | 0.4711 | −0.0649 | −0.0363 | 0.031* | |
C9 | 0.6313 (2) | 0.4200 (8) | 0.1973 (2) | 0.0569 (17) | |
H9A | 0.6398 | 0.3087 | 0.1935 | 0.068* | 0.67 |
H9B | 0.6228 | 0.4718 | 0.1581 | 0.068* | 0.67 |
H9C | 0.6228 | 0.3516 | 0.1617 | 0.068* | 0.33 |
H9D | 0.6395 | 0.5259 | 0.1869 | 0.068* | 0.33 |
C10A | 0.6819 (3) | 0.4904 (10) | 0.2442 (3) | 0.0441 (17) | 0.67 |
H10A | 0.6791 | 0.5986 | 0.2512 | 0.053* | 0.67 |
C11A | 0.7319 (8) | 0.423 (3) | 0.2788 (19) | 0.064 (2) | 0.67 |
H11A | 0.7374 | 0.3153 | 0.2739 | 0.077* | 0.67 |
H11B | 0.7626 | 0.4829 | 0.3086 | 0.077* | 0.67 |
C10B | 0.6810 (6) | 0.364 (2) | 0.2467 (6) | 0.0441 (17) | 0.33 |
H10B | 0.6789 | 0.2607 | 0.2598 | 0.053* | 0.33 |
C11B | 0.7307 (15) | 0.439 (6) | 0.277 (4) | 0.064 (2) | 0.33 |
H11C | 0.7351 | 0.5428 | 0.2661 | 0.077* | 0.33 |
H11D | 0.7618 | 0.3891 | 0.3103 | 0.077* | 0.33 |
Cu2 | 0.71165 (2) | 0.00134 (5) | 0.43649 (2) | 0.01832 (11) | |
S3 | 0.64769 (5) | 0.12090 (13) | 0.35181 (5) | 0.0222 (3) | |
S4 | 0.78095 (5) | 0.11502 (13) | 0.41212 (5) | 0.0239 (2) | |
O3 | 0.76156 (12) | −0.1299 (3) | 0.50184 (13) | 0.0226 (7) | |
O4 | 1.02785 (14) | −0.1829 (4) | 0.57227 (14) | 0.0286 (7) | |
H4O | 0.9978 (17) | −0.142 (6) | 0.553 (2) | 0.043* | |
N7 | 0.59260 (18) | 0.0427 (5) | 0.4206 (2) | 0.0215 (10) | |
N8 | 0.64498 (15) | −0.0347 (4) | 0.45353 (16) | 0.0180 (8) | |
N9 | 0.54375 (18) | 0.1984 (5) | 0.3380 (2) | 0.0230 (9) | |
H9N | 0.5393 (19) | 0.240 (5) | 0.3066 (16) | 0.028* | |
N10 | 0.8642 (2) | −0.0147 (4) | 0.5090 (2) | 0.0191 (10) | |
H10N | 0.8382 (16) | −0.053 (5) | 0.516 (2) | 0.023* | |
N11 | 0.91835 (15) | −0.0831 (4) | 0.54169 (15) | 0.0196 (8) | |
N12 | 0.89361 (18) | 0.1033 (4) | 0.44378 (18) | 0.0209 (9) | |
H12N | 0.929 (2) | 0.085 (5) | 0.467 (2) | 0.025* | |
C12 | 0.26968 (19) | 0.3038 (5) | 0.08882 (19) | 0.0197 (10) | |
C13 | 0.19869 (18) | 0.0857 (4) | −0.04314 (18) | 0.0199 (9) | |
H13A | 0.2303 | 0.0918 | −0.0531 | 0.024* | |
C14 | 0.14868 (18) | −0.0034 (4) | −0.08293 (19) | 0.0185 (9) | |
C15 | 0.0981 (3) | −0.0129 (5) | −0.0749 (3) | 0.0230 (13) | |
C16 | 0.0518 (2) | −0.1037 (5) | −0.1141 (2) | 0.0295 (11) | |
H16A | 0.0178 | −0.1114 | −0.1082 | 0.035* | |
C17 | 0.0552 (2) | −0.1827 (6) | −0.1614 (3) | 0.0327 (13) | |
H17A | 0.0229 | −0.2420 | −0.1888 | 0.039* | |
C18 | 0.1052 (2) | −0.1768 (5) | −0.1697 (2) | 0.0323 (11) | |
H18A | 0.1076 | −0.2338 | −0.2018 | 0.039* | |
C19 | 0.1508 (2) | −0.0881 (5) | −0.1310 (2) | 0.0263 (12) | |
H19A | 0.1849 | −0.0834 | −0.1368 | 0.032* | |
C20 | 0.23493 (19) | 0.4489 (5) | 0.15240 (19) | 0.0244 (10) | |
H20A | 0.1996 | 0.5128 | 0.1411 | 0.029* | |
H20B | 0.2676 | 0.5213 | 0.1609 | 0.029* | |
C21 | 0.2467 (2) | 0.3597 (6) | 0.2091 (2) | 0.0343 (11) | |
H21A | 0.2707 | 0.2697 | 0.2179 | 0.041* | |
C22 | 0.2264 (2) | 0.3972 (7) | 0.2471 (2) | 0.0495 (15) | |
H22A | 0.2022 | 0.4865 | 0.2396 | 0.059* | |
H22B | 0.2355 | 0.3353 | 0.2824 | 0.059* | |
C23 | 0.59128 (19) | 0.1173 (5) | 0.37296 (19) | 0.0207 (9) | |
C24 | 0.64412 (18) | −0.1295 (5) | 0.49362 (19) | 0.0207 (9) | |
H24A | 0.6083 | −0.1413 | 0.4955 | 0.025* | |
C25 | 0.69211 (18) | −0.2196 (4) | 0.53584 (19) | 0.0187 (9) | |
C26 | 0.7479 (2) | −0.2177 (6) | 0.5380 (2) | 0.0194 (12) | |
C27 | 0.7900 (2) | −0.3162 (5) | 0.5804 (2) | 0.0233 (10) | |
H27A | 0.8273 | −0.3206 | 0.5815 | 0.028* | |
C28 | 0.7791 (2) | −0.4067 (5) | 0.6205 (2) | 0.0268 (10) | |
H28A | 0.8090 | −0.4704 | 0.6492 | 0.032* | |
C29 | 0.7249 (2) | −0.4060 (5) | 0.6194 (2) | 0.0258 (11) | |
H29A | 0.7173 | −0.4679 | 0.6473 | 0.031* | |
C30 | 0.6825 (2) | −0.3140 (5) | 0.5773 (2) | 0.0245 (10) | |
H30A | 0.6451 | −0.3142 | 0.5760 | 0.029* | |
C31 | 0.49110 (18) | 0.2020 (5) | 0.34599 (19) | 0.0272 (10) | |
H31A | 0.4669 | 0.2912 | 0.3226 | 0.033* | |
H31B | 0.5017 | 0.2198 | 0.3896 | 0.033* | |
C32 | 0.45642 (18) | 0.0564 (5) | 0.32585 (19) | 0.0284 (10) | |
H32A | 0.4732 | −0.0380 | 0.3467 | 0.034* | |
C33 | 0.4036 (2) | 0.0507 (7) | 0.2808 (2) | 0.0497 (14) | |
H33A | 0.3858 | 0.1433 | 0.2592 | 0.060* | |
H33B | 0.3834 | −0.0460 | 0.2698 | 0.060* | |
C34 | 0.85155 (18) | 0.0637 (5) | 0.45776 (19) | 0.0168 (9) | |
C35 | 0.92363 (18) | −0.1547 (4) | 0.59007 (18) | 0.0197 (9) | |
H35A | 0.8934 | −0.1441 | 0.6020 | 0.024* | |
C36 | 0.97292 (19) | −0.2500 (5) | 0.6271 (2) | 0.0193 (9) | |
C37 | 1.0220 (3) | −0.2640 (5) | 0.6178 (3) | 0.0199 (12) | |
C38 | 1.0670 (2) | −0.3603 (5) | 0.65349 (19) | 0.0275 (10) | |
H38A | 1.1004 | −0.3682 | 0.6465 | 0.033* | |
C39 | 1.0635 (2) | −0.4452 (6) | 0.6995 (2) | 0.0280 (12) | |
H39A | 1.0945 | −0.5125 | 0.7241 | 0.034* | |
C40 | 1.0158 (2) | −0.4336 (5) | 0.71008 (19) | 0.0273 (10) | |
H40A | 1.0137 | −0.4929 | 0.7418 | 0.033* | |
C41 | 0.9711 (2) | −0.3366 (5) | 0.6750 (2) | 0.0235 (11) | |
H41A | 0.9384 | −0.3277 | 0.6831 | 0.028* | |
C42 | 0.88606 (19) | 0.1936 (5) | 0.39004 (19) | 0.0237 (10) | |
H42A | 0.9231 | 0.2453 | 0.3981 | 0.028* | |
H42B | 0.8568 | 0.2763 | 0.3826 | 0.028* | |
C43 | 0.8672 (2) | 0.0940 (6) | 0.3343 (2) | 0.0339 (11) | |
H43A | 0.8360 | 0.0238 | 0.3259 | 0.041* | |
C44 | 0.8898 (2) | 0.0953 (6) | 0.2964 (2) | 0.0431 (13) | |
H44A | 0.9211 | 0.1637 | 0.3031 | 0.052* | |
H44B | 0.8751 | 0.0278 | 0.2620 | 0.052* | |
O5 | 1.01768 (14) | 0.1061 (4) | 0.50618 (15) | 0.0272 (7) | |
H51O | 1.0408 (19) | 0.052 (5) | 0.506 (2) | 0.041* | |
H52O | 1.031 (2) | 0.132 (5) | 0.540 (2) | 0.041* | |
O6 | 0.10257 (14) | 0.3495 (4) | 0.03666 (14) | 0.0284 (7) | |
H61O | 0.089 (2) | 0.362 (5) | −0.0033 (14) | 0.043* | |
H62O | 0.0763 (18) | 0.293 (5) | 0.041 (2) | 0.043* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.0159 (3) | 0.0212 (2) | 0.0198 (2) | −0.0028 (2) | 0.0075 (2) | −0.0014 (2) |
S1 | 0.0187 (7) | 0.0281 (6) | 0.0194 (7) | −0.0037 (5) | 0.0072 (5) | −0.0011 (5) |
S2 | 0.0171 (6) | 0.0299 (6) | 0.0243 (6) | −0.0032 (5) | 0.0080 (5) | −0.0077 (5) |
O1 | 0.0177 (17) | 0.0280 (17) | 0.0321 (18) | −0.0031 (13) | 0.0129 (15) | −0.0078 (14) |
O2 | 0.0191 (18) | 0.0341 (18) | 0.0299 (19) | −0.0121 (14) | 0.0117 (15) | −0.0102 (14) |
N1 | 0.016 (3) | 0.028 (2) | 0.022 (3) | −0.0051 (19) | 0.008 (2) | 0.0017 (19) |
N2 | 0.017 (2) | 0.0248 (18) | 0.0174 (19) | −0.0039 (16) | 0.0059 (17) | 0.0006 (15) |
N3 | 0.023 (3) | 0.060 (3) | 0.023 (3) | −0.016 (2) | 0.010 (2) | −0.009 (2) |
N4 | 0.013 (2) | 0.0208 (19) | 0.025 (3) | −0.0004 (17) | 0.008 (2) | −0.0037 (17) |
N5 | 0.0156 (19) | 0.0229 (18) | 0.0179 (18) | −0.0030 (15) | 0.0052 (16) | −0.0011 (14) |
N6 | 0.014 (2) | 0.030 (2) | 0.023 (2) | −0.0038 (17) | 0.0077 (19) | −0.0020 (17) |
C1 | 0.020 (3) | 0.028 (2) | 0.016 (2) | −0.0040 (19) | 0.004 (2) | 0.0031 (18) |
C2 | 0.023 (2) | 0.018 (2) | 0.022 (2) | 0.0028 (18) | 0.013 (2) | 0.0042 (17) |
C3 | 0.025 (3) | 0.018 (2) | 0.015 (2) | −0.0022 (18) | 0.006 (2) | 0.0007 (16) |
C4 | 0.023 (3) | 0.020 (2) | 0.018 (3) | 0.004 (2) | 0.011 (2) | 0.0010 (19) |
C5 | 0.019 (3) | 0.025 (2) | 0.025 (3) | 0.001 (2) | 0.005 (2) | 0.0006 (19) |
C6 | 0.026 (3) | 0.023 (2) | 0.021 (2) | −0.001 (2) | 0.005 (2) | 0.0003 (18) |
C7 | 0.042 (3) | 0.022 (2) | 0.023 (3) | −0.002 (2) | 0.016 (3) | −0.005 (2) |
C8 | 0.031 (3) | 0.024 (2) | 0.030 (3) | 0.001 (2) | 0.020 (2) | −0.0001 (19) |
C9 | 0.025 (3) | 0.109 (5) | 0.040 (3) | −0.032 (3) | 0.018 (3) | −0.021 (3) |
C10A | 0.036 (4) | 0.052 (4) | 0.053 (4) | −0.012 (4) | 0.029 (3) | −0.008 (4) |
C11A | 0.032 (3) | 0.105 (6) | 0.051 (4) | 0.007 (4) | 0.014 (3) | 0.004 (6) |
C10B | 0.036 (4) | 0.052 (4) | 0.053 (4) | −0.012 (4) | 0.029 (3) | −0.008 (4) |
C11B | 0.032 (3) | 0.105 (6) | 0.051 (4) | 0.007 (4) | 0.014 (3) | 0.004 (6) |
Cu2 | 0.0151 (2) | 0.0204 (2) | 0.0190 (2) | 0.0023 (2) | 0.0072 (2) | 0.0017 (2) |
S3 | 0.0172 (7) | 0.0296 (6) | 0.0195 (7) | 0.0016 (5) | 0.0079 (5) | 0.0025 (5) |
S4 | 0.0154 (6) | 0.0302 (6) | 0.0255 (6) | 0.0036 (5) | 0.0086 (5) | 0.0088 (5) |
O3 | 0.0162 (16) | 0.0249 (15) | 0.0280 (17) | 0.0040 (13) | 0.0110 (14) | 0.0089 (13) |
O4 | 0.0229 (18) | 0.0383 (19) | 0.0286 (18) | 0.0076 (15) | 0.0151 (16) | 0.0112 (14) |
N7 | 0.014 (2) | 0.026 (2) | 0.024 (2) | 0.0082 (19) | 0.007 (2) | 0.0065 (19) |
N8 | 0.020 (2) | 0.0167 (17) | 0.0195 (19) | 0.0029 (15) | 0.0104 (17) | −0.0003 (15) |
N9 | 0.018 (2) | 0.030 (2) | 0.021 (2) | 0.0081 (18) | 0.0080 (19) | 0.0063 (18) |
N10 | 0.013 (2) | 0.026 (2) | 0.023 (2) | 0.0018 (16) | 0.012 (2) | 0.0023 (17) |
N11 | 0.0151 (19) | 0.0182 (17) | 0.0223 (19) | 0.0020 (15) | 0.0054 (16) | −0.0026 (15) |
N12 | 0.014 (2) | 0.025 (2) | 0.021 (2) | −0.0017 (17) | 0.0052 (18) | 0.0037 (16) |
C12 | 0.017 (3) | 0.021 (2) | 0.019 (2) | 0.0015 (19) | 0.007 (2) | 0.0025 (18) |
C13 | 0.020 (2) | 0.022 (2) | 0.019 (2) | 0.0005 (18) | 0.010 (2) | 0.0007 (17) |
C14 | 0.016 (2) | 0.019 (2) | 0.018 (2) | −0.0014 (17) | 0.0051 (19) | 0.0037 (16) |
C15 | 0.028 (3) | 0.020 (3) | 0.022 (3) | −0.002 (2) | 0.012 (3) | −0.002 (2) |
C16 | 0.021 (3) | 0.034 (3) | 0.029 (3) | −0.005 (2) | 0.008 (2) | −0.004 (2) |
C17 | 0.027 (3) | 0.037 (3) | 0.025 (3) | −0.014 (2) | 0.004 (2) | −0.008 (2) |
C18 | 0.041 (3) | 0.031 (2) | 0.022 (2) | −0.007 (2) | 0.012 (2) | −0.0069 (19) |
C19 | 0.019 (3) | 0.032 (3) | 0.027 (3) | −0.002 (2) | 0.010 (2) | 0.000 (2) |
C20 | 0.023 (3) | 0.027 (2) | 0.028 (3) | −0.0015 (19) | 0.016 (2) | −0.008 (2) |
C21 | 0.027 (3) | 0.047 (3) | 0.028 (3) | −0.005 (2) | 0.012 (2) | −0.002 (2) |
C22 | 0.044 (3) | 0.068 (4) | 0.038 (3) | −0.012 (3) | 0.020 (3) | −0.007 (3) |
C23 | 0.019 (2) | 0.020 (2) | 0.020 (2) | 0.0000 (18) | 0.006 (2) | −0.0060 (18) |
C24 | 0.018 (2) | 0.024 (2) | 0.021 (2) | 0.0023 (18) | 0.0091 (19) | −0.0018 (18) |
C25 | 0.014 (2) | 0.019 (2) | 0.023 (2) | −0.0003 (17) | 0.0081 (19) | −0.0007 (17) |
C26 | 0.021 (3) | 0.016 (2) | 0.019 (3) | −0.001 (2) | 0.007 (2) | −0.0004 (19) |
C27 | 0.018 (3) | 0.024 (2) | 0.025 (3) | −0.001 (2) | 0.007 (2) | 0.0016 (19) |
C28 | 0.028 (3) | 0.025 (2) | 0.021 (2) | 0.004 (2) | 0.006 (2) | 0.0027 (19) |
C29 | 0.026 (3) | 0.026 (2) | 0.026 (3) | −0.001 (2) | 0.012 (2) | 0.000 (2) |
C30 | 0.026 (3) | 0.024 (2) | 0.027 (2) | 0.0007 (19) | 0.015 (2) | 0.0012 (19) |
C31 | 0.017 (2) | 0.040 (3) | 0.021 (2) | 0.008 (2) | 0.005 (2) | 0.0021 (19) |
C32 | 0.023 (2) | 0.039 (3) | 0.026 (2) | 0.004 (2) | 0.013 (2) | 0.0028 (19) |
C33 | 0.036 (3) | 0.057 (3) | 0.047 (3) | −0.003 (3) | 0.010 (3) | 0.005 (3) |
C34 | 0.016 (2) | 0.016 (2) | 0.017 (2) | 0.0012 (18) | 0.006 (2) | −0.0020 (17) |
C35 | 0.017 (2) | 0.021 (2) | 0.022 (2) | −0.0040 (18) | 0.0086 (19) | −0.0041 (17) |
C36 | 0.018 (2) | 0.020 (2) | 0.016 (2) | 0.0010 (17) | 0.0044 (19) | −0.0031 (16) |
C37 | 0.019 (3) | 0.021 (2) | 0.018 (3) | 0.0021 (19) | 0.006 (2) | −0.0021 (18) |
C38 | 0.025 (3) | 0.035 (3) | 0.020 (2) | 0.007 (2) | 0.007 (2) | 0.0028 (19) |
C39 | 0.032 (3) | 0.022 (2) | 0.021 (3) | 0.005 (2) | 0.004 (2) | −0.0005 (19) |
C40 | 0.038 (3) | 0.025 (2) | 0.016 (2) | 0.001 (2) | 0.009 (2) | 0.0001 (18) |
C41 | 0.028 (3) | 0.023 (2) | 0.018 (3) | −0.005 (2) | 0.010 (2) | −0.0029 (19) |
C42 | 0.018 (2) | 0.028 (2) | 0.025 (2) | −0.0015 (18) | 0.009 (2) | 0.0040 (19) |
C43 | 0.035 (3) | 0.038 (3) | 0.023 (2) | −0.007 (2) | 0.008 (2) | 0.003 (2) |
C44 | 0.042 (3) | 0.058 (3) | 0.028 (3) | 0.002 (3) | 0.015 (3) | 0.000 (2) |
O5 | 0.0170 (18) | 0.0378 (19) | 0.0267 (17) | 0.0071 (14) | 0.0097 (15) | −0.0018 (15) |
O6 | 0.0219 (18) | 0.0416 (19) | 0.0244 (17) | −0.0075 (14) | 0.0126 (15) | −0.0011 (14) |
Cu1—O1 | 1.906 (3) | N11—C35 | 1.286 (5) |
Cu1—N2 | 1.949 (4) | N12—C34 | 1.318 (6) |
Cu1—S1 | 2.2519 (13) | N12—C42 | 1.463 (5) |
Cu1—S2 | 2.3347 (12) | N12—H12N | 0.84 (5) |
S1—C1 | 1.733 (5) | C13—C14 | 1.439 (5) |
S2—C12 | 1.721 (4) | C13—H13A | 0.9500 |
O1—C4 | 1.337 (6) | C14—C19 | 1.404 (6) |
O2—C15 | 1.354 (6) | C14—C15 | 1.405 (7) |
O2—H2O | 0.75 (5) | C15—C16 | 1.387 (7) |
N1—C1 | 1.305 (6) | C16—C17 | 1.378 (7) |
N1—N2 | 1.401 (5) | C16—H16A | 0.9500 |
N2—C2 | 1.296 (5) | C17—C18 | 1.394 (7) |
N3—C1 | 1.345 (6) | C17—H17A | 0.9500 |
N3—C9 | 1.457 (6) | C18—C19 | 1.364 (6) |
N3—H3N | 0.78 (3) | C18—H18A | 0.9500 |
N4—C12 | 1.338 (6) | C19—H19A | 0.9500 |
N4—N5 | 1.382 (5) | C20—C21 | 1.493 (6) |
N4—H4N | 0.83 (3) | C20—H20A | 0.9900 |
N5—C13 | 1.285 (5) | C20—H20B | 0.9900 |
N6—C12 | 1.324 (6) | C21—C22 | 1.296 (7) |
N6—C20 | 1.447 (5) | C21—H21A | 0.9500 |
N6—H6N | 0.79 (3) | C22—H22A | 0.9500 |
C2—C3 | 1.437 (6) | C22—H22B | 0.9500 |
C2—H2A | 0.9500 | C24—C25 | 1.432 (6) |
C3—C8 | 1.403 (6) | C24—H24A | 0.9500 |
C3—C4 | 1.407 (7) | C25—C30 | 1.404 (6) |
C4—C5 | 1.398 (7) | C25—C26 | 1.414 (6) |
C5—C6 | 1.366 (6) | C26—C27 | 1.401 (7) |
C5—H5A | 0.9500 | C27—C28 | 1.374 (6) |
C6—C7 | 1.375 (7) | C27—H27A | 0.9500 |
C6—H6A | 0.9500 | C28—C29 | 1.386 (7) |
C7—C8 | 1.376 (6) | C28—H28A | 0.9500 |
C7—H7A | 0.9500 | C29—C30 | 1.368 (7) |
C8—H8A | 0.9500 | C29—H29A | 0.9500 |
C9—C10B | 1.396 (14) | C30—H30A | 0.9500 |
C9—C10A | 1.431 (8) | C31—C32 | 1.483 (6) |
C9—H9A | 0.9900 | C31—H31A | 0.9900 |
C9—H9B | 0.9900 | C31—H31B | 0.9900 |
C9—H9C | 0.9900 | C32—C33 | 1.316 (6) |
C9—H9D | 0.9900 | C32—H32A | 0.9500 |
C10A—C11A | 1.317 (18) | C33—H33A | 0.9500 |
C10A—H10A | 0.9500 | C33—H33B | 0.9500 |
C11A—H11A | 0.9500 | C35—C36 | 1.440 (6) |
C11A—H11B | 0.9500 | C35—H35A | 0.9500 |
C10B—C11B | 1.33 (2) | C36—C37 | 1.386 (7) |
C10B—H10B | 0.9500 | C36—C41 | 1.405 (6) |
C11B—H11C | 0.9500 | C37—C38 | 1.373 (6) |
C11B—H11D | 0.9500 | C38—C39 | 1.378 (7) |
Cu2—O3 | 1.908 (3) | C38—H38A | 0.9500 |
Cu2—N8 | 1.964 (4) | C39—C40 | 1.368 (7) |
Cu2—S3 | 2.2401 (13) | C39—H39A | 0.9500 |
Cu2—S4 | 2.3320 (12) | C40—C41 | 1.367 (6) |
S3—C23 | 1.747 (4) | C40—H40A | 0.9500 |
S4—C34 | 1.714 (4) | C41—H41A | 0.9500 |
O3—C26 | 1.323 (6) | C42—C43 | 1.495 (6) |
O4—C37 | 1.377 (6) | C42—H42A | 0.9900 |
O4—H4O | 0.79 (3) | C42—H42B | 0.9900 |
N7—C23 | 1.317 (6) | C43—C44 | 1.297 (7) |
N7—N8 | 1.393 (5) | C43—H43A | 0.9500 |
N8—C24 | 1.282 (5) | C44—H44A | 0.9500 |
N9—C23 | 1.334 (6) | C44—H44B | 0.9500 |
N9—C31 | 1.454 (6) | O5—H51O | 0.75 (3) |
N9—H9N | 0.81 (3) | O5—H52O | 0.78 (4) |
N10—C34 | 1.330 (6) | O6—H61O | 0.89 (3) |
N10—N11 | 1.391 (5) | O6—H62O | 0.87 (3) |
N10—H10N | 0.82 (3) | ||
O1—Cu1—N2 | 93.03 (13) | N5—C13—C14 | 124.3 (4) |
O1—Cu1—S1 | 170.07 (10) | N5—C13—H13A | 117.8 |
N2—Cu1—S1 | 85.32 (11) | C14—C13—H13A | 117.8 |
O1—Cu1—S2 | 98.68 (9) | C19—C14—C15 | 118.1 (4) |
N2—Cu1—S2 | 163.67 (10) | C19—C14—C13 | 118.9 (4) |
S1—Cu1—S2 | 85.02 (5) | C15—C14—C13 | 122.9 (4) |
C1—S1—Cu1 | 94.62 (15) | O2—C15—C16 | 117.6 (5) |
C12—S2—Cu1 | 115.49 (15) | O2—C15—C14 | 122.3 (5) |
C4—O1—Cu1 | 128.4 (3) | C16—C15—C14 | 120.1 (5) |
C15—O2—H2O | 109 (4) | C17—C16—C15 | 119.9 (5) |
C1—N1—N2 | 112.8 (4) | C17—C16—H16A | 120.0 |
C2—N2—N1 | 113.4 (4) | C15—C16—H16A | 120.0 |
C2—N2—Cu1 | 125.9 (3) | C16—C17—C18 | 121.0 (5) |
N1—N2—Cu1 | 120.7 (3) | C16—C17—H17A | 119.5 |
C1—N3—C9 | 122.9 (4) | C18—C17—H17A | 119.5 |
C1—N3—H3N | 118 (4) | C19—C18—C17 | 118.9 (5) |
C9—N3—H3N | 119 (4) | C19—C18—H18A | 120.5 |
C12—N4—N5 | 120.6 (4) | C17—C18—H18A | 120.5 |
C12—N4—H4N | 126 (3) | C18—C19—C14 | 121.9 (5) |
N5—N4—H4N | 110 (3) | C18—C19—H19A | 119.1 |
C13—N5—N4 | 112.8 (4) | C14—C19—H19A | 119.1 |
C12—N6—C20 | 124.4 (4) | N6—C20—C21 | 113.6 (4) |
C12—N6—H6N | 118 (4) | N6—C20—H20A | 108.8 |
C20—N6—H6N | 117 (4) | C21—C20—H20A | 108.8 |
N1—C1—N3 | 117.7 (4) | N6—C20—H20B | 108.8 |
N1—C1—S1 | 125.4 (4) | C21—C20—H20B | 108.8 |
N3—C1—S1 | 116.9 (3) | H20A—C20—H20B | 107.7 |
N2—C2—C3 | 125.7 (4) | C22—C21—C20 | 124.2 (5) |
N2—C2—H2A | 117.2 | C22—C21—H21A | 117.9 |
C3—C2—H2A | 117.2 | C20—C21—H21A | 117.9 |
C8—C3—C4 | 119.4 (4) | C21—C22—H22A | 120.0 |
C8—C3—C2 | 116.7 (4) | C21—C22—H22B | 120.0 |
C4—C3—C2 | 123.8 (4) | H22A—C22—H22B | 120.0 |
O1—C4—C5 | 119.5 (5) | N7—C23—N9 | 118.3 (4) |
O1—C4—C3 | 123.1 (5) | N7—C23—S3 | 125.1 (3) |
C5—C4—C3 | 117.5 (4) | N9—C23—S3 | 116.6 (3) |
C6—C5—C4 | 121.7 (5) | N8—C24—C25 | 126.1 (4) |
C6—C5—H5A | 119.1 | N8—C24—H24A | 116.9 |
C4—C5—H5A | 119.1 | C25—C24—H24A | 116.9 |
C5—C6—C7 | 121.2 (4) | C30—C25—C26 | 118.9 (4) |
C5—C6—H6A | 119.4 | C30—C25—C24 | 117.2 (4) |
C7—C6—H6A | 119.4 | C26—C25—C24 | 123.8 (4) |
C8—C7—C6 | 118.5 (5) | O3—C26—C27 | 119.2 (5) |
C8—C7—H7A | 120.7 | O3—C26—C25 | 123.4 (4) |
C6—C7—H7A | 120.7 | C27—C26—C25 | 117.4 (4) |
C7—C8—C3 | 121.6 (5) | C28—C27—C26 | 122.1 (5) |
C7—C8—H8A | 119.2 | C28—C27—H27A | 119.0 |
C3—C8—H8A | 119.2 | C26—C27—H27A | 119.0 |
C10B—C9—C10A | 45.0 (7) | C27—C28—C29 | 120.6 (4) |
C10B—C9—N3 | 115.1 (7) | C27—C28—H28A | 119.7 |
C10A—C9—N3 | 114.7 (5) | C29—C28—H28A | 119.7 |
C10B—C9—H9A | 66.2 | C30—C29—C28 | 118.4 (5) |
C10A—C9—H9A | 108.6 | C30—C29—H29A | 120.8 |
N3—C9—H9A | 108.6 | C28—C29—H29A | 120.8 |
C10B—C9—H9B | 135.6 | C29—C30—C25 | 122.5 (4) |
C10A—C9—H9B | 108.6 | C29—C30—H30A | 118.7 |
N3—C9—H9B | 108.6 | C25—C30—H30A | 118.7 |
H9A—C9—H9B | 107.6 | N9—C31—C32 | 113.4 (4) |
C10B—C9—H9C | 108.5 | N9—C31—H31A | 108.9 |
C10A—C9—H9C | 136.0 | C32—C31—H31A | 108.9 |
N3—C9—H9C | 108.5 | N9—C31—H31B | 108.9 |
H9A—C9—H9C | 47.2 | C32—C31—H31B | 108.9 |
H9B—C9—H9C | 62.8 | H31A—C31—H31B | 107.7 |
C10B—C9—H9D | 108.5 | C33—C32—C31 | 123.7 (5) |
C10A—C9—H9D | 66.3 | C33—C32—H32A | 118.2 |
N3—C9—H9D | 108.5 | C31—C32—H32A | 118.2 |
H9A—C9—H9D | 140.6 | C32—C33—H33A | 120.0 |
H9B—C9—H9D | 47.1 | C32—C33—H33B | 120.0 |
H9C—C9—H9D | 107.5 | H33A—C33—H33B | 120.0 |
C11A—C10A—C9 | 127.9 (14) | N12—C34—N10 | 119.4 (4) |
C11A—C10A—H10A | 116.1 | N12—C34—S4 | 121.4 (3) |
C9—C10A—H10A | 116.1 | N10—C34—S4 | 119.2 (3) |
C10A—C11A—H11A | 120.0 | N11—C35—C36 | 123.5 (4) |
C10A—C11A—H11B | 120.0 | N11—C35—H35A | 118.3 |
H11A—C11A—H11B | 120.0 | C36—C35—H35A | 118.3 |
C11B—C10B—C9 | 127 (3) | C37—C36—C41 | 117.6 (4) |
C11B—C10B—H10B | 116.4 | C37—C36—C35 | 123.9 (4) |
C9—C10B—H10B | 116.4 | C41—C36—C35 | 118.5 (4) |
C10B—C11B—H11C | 120.0 | C38—C37—O4 | 116.8 (5) |
C10B—C11B—H11D | 120.0 | C38—C37—C36 | 121.3 (5) |
H11C—C11B—H11D | 120.0 | O4—C37—C36 | 121.8 (4) |
O3—Cu2—N8 | 93.19 (13) | C37—C38—C39 | 119.5 (5) |
O3—Cu2—S3 | 171.12 (9) | C37—C38—H38A | 120.2 |
N8—Cu2—S3 | 85.19 (11) | C39—C38—H38A | 120.2 |
O3—Cu2—S4 | 98.83 (9) | C40—C39—C38 | 120.6 (5) |
N8—Cu2—S4 | 164.03 (10) | C40—C39—H39A | 119.7 |
S3—Cu2—S4 | 84.48 (4) | C38—C39—H39A | 119.7 |
C23—S3—Cu2 | 94.78 (15) | C39—C40—C41 | 120.1 (4) |
C34—S4—Cu2 | 115.93 (15) | C39—C40—H40A | 120.0 |
C26—O3—Cu2 | 127.9 (3) | C41—C40—H40A | 120.0 |
C37—O4—H4O | 105 (4) | C40—C41—C36 | 120.9 (5) |
C23—N7—N8 | 112.3 (4) | C40—C41—H41A | 119.6 |
C24—N8—N7 | 113.7 (4) | C36—C41—H41A | 119.6 |
C24—N8—Cu2 | 125.3 (3) | N12—C42—C43 | 112.3 (4) |
N7—N8—Cu2 | 121.0 (3) | N12—C42—H42A | 109.1 |
C23—N9—C31 | 124.7 (4) | C43—C42—H42A | 109.1 |
C23—N9—H9N | 123 (3) | N12—C42—H42B | 109.1 |
C31—N9—H9N | 112 (3) | C43—C42—H42B | 109.1 |
C34—N10—N11 | 121.1 (4) | H42A—C42—H42B | 107.9 |
C34—N10—H10N | 121 (3) | C44—C43—C42 | 125.6 (5) |
N11—N10—H10N | 115 (3) | C44—C43—H43A | 117.2 |
C35—N11—N10 | 113.4 (4) | C42—C43—H43A | 117.2 |
C34—N12—C42 | 125.0 (4) | C43—C44—H44A | 120.0 |
C34—N12—H12N | 122 (4) | C43—C44—H44B | 120.0 |
C42—N12—H12N | 113 (4) | H44A—C44—H44B | 120.0 |
N6—C12—N4 | 120.3 (4) | H51O—O5—H52O | 102 (5) |
N6—C12—S2 | 121.1 (3) | H61O—O6—H62O | 105 (4) |
N4—C12—S2 | 118.5 (3) | ||
O1—Cu1—S1—C1 | 88.0 (6) | N5—N4—C12—N6 | −10.0 (7) |
N2—Cu1—S1—C1 | 7.14 (17) | N5—N4—C12—S2 | 170.0 (3) |
S2—Cu1—S1—C1 | −159.67 (14) | Cu1—S2—C12—N6 | 174.9 (3) |
O1—Cu1—S2—C12 | −7.56 (19) | Cu1—S2—C12—N4 | −5.0 (4) |
N2—Cu1—S2—C12 | 127.8 (4) | N4—N5—C13—C14 | 172.7 (4) |
S1—Cu1—S2—C12 | −178.27 (17) | N5—C13—C14—C19 | −174.4 (4) |
N2—Cu1—O1—C4 | 3.7 (4) | N5—C13—C14—C15 | 3.9 (6) |
S1—Cu1—O1—C4 | −76.5 (7) | C19—C14—C15—O2 | 178.6 (4) |
S2—Cu1—O1—C4 | 172.3 (3) | C13—C14—C15—O2 | 0.3 (7) |
C1—N1—N2—C2 | −168.4 (4) | C19—C14—C15—C16 | −0.2 (7) |
C1—N1—N2—Cu1 | 10.2 (5) | C13—C14—C15—C16 | −178.5 (4) |
O1—Cu1—N2—C2 | −2.7 (3) | O2—C15—C16—C17 | −179.8 (4) |
S1—Cu1—N2—C2 | 167.5 (3) | C14—C15—C16—C17 | −1.0 (7) |
S2—Cu1—N2—C2 | −138.6 (3) | C15—C16—C17—C18 | 1.9 (8) |
O1—Cu1—N2—N1 | 178.9 (3) | C16—C17—C18—C19 | −1.6 (8) |
S1—Cu1—N2—N1 | −10.9 (3) | C17—C18—C19—C14 | 0.4 (7) |
S2—Cu1—N2—N1 | 43.1 (6) | C15—C14—C19—C18 | 0.5 (7) |
C12—N4—N5—C13 | 176.5 (4) | C13—C14—C19—C18 | 178.9 (4) |
N2—N1—C1—N3 | 177.3 (4) | C12—N6—C20—C21 | −89.1 (5) |
N2—N1—C1—S1 | −2.1 (6) | N6—C20—C21—C22 | −141.8 (5) |
C9—N3—C1—N1 | −5.4 (8) | N8—N7—C23—N9 | −178.9 (4) |
C9—N3—C1—S1 | 174.0 (4) | N8—N7—C23—S3 | 0.3 (6) |
Cu1—S1—C1—N1 | −5.0 (4) | C31—N9—C23—N7 | −4.6 (7) |
Cu1—S1—C1—N3 | 175.7 (4) | C31—N9—C23—S3 | 176.1 (3) |
N1—N2—C2—C3 | −179.3 (4) | Cu2—S3—C23—N7 | −8.1 (4) |
Cu1—N2—C2—C3 | 2.2 (6) | Cu2—S3—C23—N9 | 171.2 (3) |
N2—C2—C3—C8 | 179.1 (4) | N7—N8—C24—C25 | −177.1 (4) |
N2—C2—C3—C4 | −1.7 (7) | Cu2—N8—C24—C25 | 4.1 (6) |
Cu1—O1—C4—C5 | 175.4 (3) | N8—C24—C25—C30 | 178.4 (4) |
Cu1—O1—C4—C3 | −4.2 (6) | N8—C24—C25—C26 | −1.3 (7) |
C8—C3—C4—O1 | −178.2 (4) | Cu2—O3—C26—C27 | 174.8 (3) |
C2—C3—C4—O1 | 2.6 (7) | Cu2—O3—C26—C25 | −4.3 (6) |
C8—C3—C4—C5 | 2.3 (6) | C30—C25—C26—O3 | −178.4 (4) |
C2—C3—C4—C5 | −177.0 (4) | C24—C25—C26—O3 | 1.3 (7) |
O1—C4—C5—C6 | 178.3 (4) | C30—C25—C26—C27 | 2.5 (6) |
C3—C4—C5—C6 | −2.1 (7) | C24—C25—C26—C27 | −177.8 (4) |
C4—C5—C6—C7 | 0.2 (7) | O3—C26—C27—C28 | 178.0 (4) |
C5—C6—C7—C8 | 1.5 (7) | C25—C26—C27—C28 | −2.8 (7) |
C6—C7—C8—C3 | −1.4 (7) | C26—C27—C28—C29 | 1.4 (7) |
C4—C3—C8—C7 | −0.6 (7) | C27—C28—C29—C30 | 0.5 (7) |
C2—C3—C8—C7 | 178.8 (4) | C28—C29—C30—C25 | −0.8 (7) |
C1—N3—C9—C10B | −123.5 (9) | C26—C25—C30—C29 | −0.7 (7) |
C1—N3—C9—C10A | −173.4 (6) | C24—C25—C30—C29 | 179.5 (4) |
C10B—C9—C10A—C11A | 19 (3) | C23—N9—C31—C32 | −74.2 (6) |
N3—C9—C10A—C11A | 120 (3) | N9—C31—C32—C33 | −116.7 (5) |
C10A—C9—C10B—C11B | −18 (5) | C42—N12—C34—N10 | −177.9 (4) |
N3—C9—C10B—C11B | −119 (5) | C42—N12—C34—S4 | 0.6 (6) |
O3—Cu2—S3—C23 | 89.0 (6) | N11—N10—C34—N12 | −13.1 (6) |
N8—Cu2—S3—C23 | 9.12 (16) | N11—N10—C34—S4 | 168.3 (3) |
S4—Cu2—S3—C23 | −158.68 (14) | Cu2—S4—C34—N12 | 170.7 (3) |
O3—Cu2—S4—C34 | −3.31 (18) | Cu2—S4—C34—N10 | −10.7 (4) |
N8—Cu2—S4—C34 | 135.1 (4) | N10—N11—C35—C36 | 172.2 (4) |
S3—Cu2—S4—C34 | −175.00 (17) | N11—C35—C36—C37 | 5.8 (7) |
N8—Cu2—O3—C26 | 5.2 (4) | N11—C35—C36—C41 | −173.0 (4) |
S3—Cu2—O3—C26 | −74.0 (8) | C41—C36—C37—C38 | 0.7 (7) |
S4—Cu2—O3—C26 | 174.7 (3) | C35—C36—C37—C38 | −178.1 (4) |
C23—N7—N8—C24 | −168.7 (4) | C41—C36—C37—O4 | −179.6 (4) |
C23—N7—N8—Cu2 | 10.2 (5) | C35—C36—C37—O4 | 1.7 (7) |
O3—Cu2—N8—C24 | −5.0 (3) | O4—C37—C38—C39 | −179.6 (4) |
S3—Cu2—N8—C24 | 166.2 (3) | C36—C37—C38—C39 | 0.2 (7) |
S4—Cu2—N8—C24 | −143.9 (3) | C37—C38—C39—C40 | −0.5 (7) |
O3—Cu2—N8—N7 | 176.2 (3) | C38—C39—C40—C41 | −0.2 (7) |
S3—Cu2—N8—N7 | −12.6 (3) | C39—C40—C41—C36 | 1.1 (7) |
S4—Cu2—N8—N7 | 37.3 (6) | C37—C36—C41—C40 | −1.4 (6) |
C34—N10—N11—C35 | −179.9 (4) | C35—C36—C41—C40 | 177.5 (4) |
C20—N6—C12—N4 | −177.0 (4) | C34—N12—C42—C43 | −82.6 (5) |
C20—N6—C12—S2 | 3.0 (6) | N12—C42—C43—C44 | −132.2 (5) |
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2O···N5 | 0.75 (5) | 2.05 (5) | 2.718 (5) | 148 (6) |
N4—H4N···O1 | 0.83 (3) | 1.94 (3) | 2.715 (5) | 155 (4) |
N6—H6N···O6 | 0.79 (3) | 2.14 (4) | 2.876 (5) | 154 (5) |
O4—H4O···N11 | 0.79 (3) | 2.00 (4) | 2.714 (5) | 151 (6) |
N9—H9N···S1 | 0.81 (3) | 2.71 (3) | 3.460 (4) | 154 (4) |
N10—H10N···O3 | 0.82 (3) | 1.96 (3) | 2.753 (5) | 160 (4) |
N12—H12N···O5 | 0.84 (5) | 2.06 (5) | 2.864 (5) | 159 (5) |
O5—H51O···O2i | 0.75 (3) | 2.13 (4) | 2.833 (4) | 157 (5) |
O5—H52O···N1ii | 0.78 (4) | 2.19 (5) | 2.912 (6) | 155 (5) |
O6—H61O···N7iii | 0.89 (3) | 2.07 (3) | 2.890 (5) | 153 (4) |
O6—H62O···O4iv | 0.87 (3) | 1.97 (3) | 2.827 (4) | 165 (4) |
Symmetry codes: (i) x+1, −y, z+1/2; (ii) x+1/2, −y+1/2, z+1/2; (iii) x−1/2, −y+1/2, z−1/2; (iv) x−1, −y, z−1/2. |
Experimental details
Crystal data | |
Chemical formula | [Cu(C11H11N3OS)(C11H13N3OS)]·H2O |
Mr | 550.15 |
Crystal system, space group | Monoclinic, Cc |
Temperature (K) | 173 |
a, b, c (Å) | 25.763 (3), 8.5526 (9), 24.496 (3) |
β (°) | 116.458 (3) |
V (Å3) | 4832.1 (10) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 1.11 |
Crystal size (mm) | 0.50 × 0.05 × 0.05 |
Data collection | |
Diffractometer | Bruker APEXII CCD diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2005) |
Tmin, Tmax | 0.606, 0.946 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 25072, 8043, 6716 |
Rint | 0.048 |
(sin θ/λ)max (Å−1) | 0.629 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.036, 0.074, 1.03 |
No. of reflections | 8043 |
No. of parameters | 656 |
No. of restraints | 16 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.48, −0.36 |
Absolute structure | Flack (1983), 3047 Friedel pairs |
Absolute structure parameter | 0.464 (13) |
Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), publCIF (Westrip, 2010).
Cu1—O1 | 1.906 (3) | Cu2—O3 | 1.908 (3) |
Cu1—N2 | 1.949 (4) | Cu2—N8 | 1.964 (4) |
Cu1—S1 | 2.2519 (13) | Cu2—S3 | 2.2401 (13) |
Cu1—S2 | 2.3347 (12) | Cu2—S4 | 2.3320 (12) |
S1—C1 | 1.733 (5) | S3—C23 | 1.747 (4) |
S2—C12 | 1.721 (4) | S4—C34 | 1.714 (4) |
O1—Cu1—N2 | 93.03 (13) | O3—Cu2—N8 | 93.19 (13) |
N2—Cu1—S1 | 85.32 (11) | N8—Cu2—S3 | 85.19 (11) |
O1—Cu1—S2 | 98.68 (9) | O3—Cu2—S4 | 98.83 (9) |
S1—Cu1—S2 | 85.02 (5) | S3—Cu2—S4 | 84.48 (4) |
N2—N1—C1—N3 | 177.3 (4) | N8—N7—C23—N9 | −178.9 (4) |
N5—N4—C12—N6 | −10.0 (7) | N11—N10—C34—N12 | −13.1 (6) |
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2O···N5 | 0.75 (5) | 2.05 (5) | 2.718 (5) | 148 (6) |
N4—H4N···O1 | 0.83 (3) | 1.94 (3) | 2.715 (5) | 155 (4) |
N6—H6N···O6 | 0.79 (3) | 2.14 (4) | 2.876 (5) | 154 (5) |
O4—H4O···N11 | 0.79 (3) | 2.00 (4) | 2.714 (5) | 151 (6) |
N9—H9N···S1 | 0.81 (3) | 2.71 (3) | 3.460 (4) | 154 (4) |
N10—H10N···O3 | 0.82 (3) | 1.96 (3) | 2.753 (5) | 160 (4) |
N12—H12N···O5 | 0.84 (5) | 2.06 (5) | 2.864 (5) | 159 (5) |
O5—H51O···O2i | 0.75 (3) | 2.13 (4) | 2.833 (4) | 157 (5) |
O5—H52O···N1ii | 0.78 (4) | 2.19 (5) | 2.912 (6) | 155 (5) |
O6—H61O···N7iii | 0.89 (3) | 2.07 (3) | 2.890 (5) | 153 (4) |
O6—H62O···O4iv | 0.87 (3) | 1.97 (3) | 2.827 (4) | 165 (4) |
Symmetry codes: (i) x+1, −y, z+1/2; (ii) x+1/2, −y+1/2, z+1/2; (iii) x−1/2, −y+1/2, z−1/2; (iv) x−1, −y, z−1/2. |
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Thiosemicarbazones and their metal complexes attract constant scientific interest due to their antimicrobial, antifungal and antitumour activities (Garoufilis et al., 2009; Stanojkovic et al., 2010). Some thiosemicarbazones are also used as reagents for the determination of CoII, NiII, CuII and PdII by solid-phase microextraction in high-performance liquid chromatography (Kaur et al., 2007).
The potentially tridentate salicylaldehyde thiosemicarbazone derivatives can give mono-, bi- or polynuclear complexes with transition metals, in each of which the multiple ligands usually all coordinate to the metal centre in the same manner (Soriano-García et al., 1985; Labisbal et al., 2003). However, the Cambridge Structural Database (Version?; Allen, 2002) records two structures of 1:2 square-planar PdII and PtII complexes, each containing two differently coordinated thiosemicarbazone ligands (Papathanasis et al., 2004). The present paper reports the structure of the title square-planar copper(II) complex, (I), containing two salicylaldehyde 4-N-allylthiosemicarbazone ligands which exhibit different coordination behaviours.
Compound (I) crystallizes in the noncentrosymmetric space group Cc as a inversion twin, with two molecules of the metal complex and two solvent water molecules in the asymmetric unit. The geometric parameters of the two independent complexes are very similar (Fig. 1); the only difference between them is the presence of a disordered allyl fragment (atoms C9 and C10) in one of them. The CuII centres exhibit a distorted square-planar coordination geometry, with mean deviations from the planes Cu1/O1/N2/S1/S2 and Cu2/O3/N8/S3/S4 of 0.1635 and 0.1498 Å, respectively.
The main interest in the structure lies in the different coordination modes of the two ligands around each CuII ion: one ligand is bonded in a tridentate manner via phenyl O, azomethine N and thioamide S atoms, while the other is coordinated in monodentate fashion via the thioamide S atom only (Fig. 1). The resulting six-membered Cu1/N2/C2/C3/C4/O1 (A) and Cu2/N8/C24/C25/C26/O3 (B) rings and five-membered Cu1/S1/C1/N1/N2 (C) and Cu2/S3/C23/N7/N8 (D) rings are nearly planar, with mean deviations from the planes of 0.0111, 0.0538, 0.0191 and 0.0658 Å, respectively. The dihedral angles between planes A/C and B/D are 9.78 (14) and 9.87 (14)°, respectively, which confirms the slight tetrahedral distortion of the coordination geometry at the CuII ion. The values of Cu—O and Cu—N bond lengths (Table 1) are in good agreement with those in related structures (Bon et al., 2010). The Cu1—S1 and Cu2—S3 bonds are shorter than Cu1—S2 and Cu2—S4 (Table 1), which can be explained by the strong influence of the chelate effect in the former case.
The C—S bond lengths (Table 1) do not permit a clear assignment of the dominant tautomeric form of the coordinated ligands, although the C—S bond lengths in the tridentate ligands are closer to the value expected for the thiolic tautomeric form, while the monodentate ligands have slightly shorter C—S bonds (Table 1). The values of adjacent angles around the CuII ions are in the range 84.48 (4)–98.83 (9)° (Table 1), which confirms the distorted square-planar geometry. The valence angles O1—Cu1—S2 and O3—Cu2—S4 deviate significantly from the ideal square-planar values (Table 1), which can be explained in terms of the six-membered pseudo-chelate metalla-rings Cu1/S2/C12/N4/H4N/O1 and Cu2/S4/C34/N10/H10N/O3, formed via intramolecular hydrogen bonds (Fig. 1, Table 2). The torsion angles N2—N1—C1—N3, N5—N4—C12—N6, N8—N7—C23—N9 and N11—N10—C34—N12 (Table 1) confirm the presence of the E isomer in the tridentate ligands and the Z isomer in the monodentate ligands. The intramolecular O2—H2O···N5 and O4—H4O···N11 hydrogen bonds (Table 2) are characteristic for structures containing noncoordinated azomethine fragments (Rubčić et al., 2008). The crystal structure of (I) contains an extended three-dimensional network of intermolecular O—H···O, N—H···O, O—H···N and N—H···S hydrogen bonds (Fig. 2, Table 2).