Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270107052602/sq3102sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270107052602/sq3102Isup2.hkl |
CCDC reference: 677074
For related literature, see: Che & Wang (2006b); Che et al. (2006a); Gabe et al. (1969); Kovala-Demertzi, Miller, Kourkoumelis, Hadjikakou & Demertzis (1999); Mathew & Palenik (1971); Matthews et al. (2001); Reiter et al. (1985); Restivo & Palenik (1970); Singh et al. (1978).
All reagents were purchased from Aldrich and used without further purification. The ligand L was synthesized according to a reported method (Che et al., 2006). Ligand L (0.760 g, 0.002 mol) was dissolved in DMF (20 ml) and then Zn(OAc)2·6H2O (0.237 g, 0.001 mol) was added. After heating at 373 K for 20 min, the mixture was allowed to cool and evaporate naturally. After a few days, red crystalline lumps formed (yield 0.51 g, ca 56.6% based on Zn). Analysis found: C 47.30, H 4.71, N 24.12, S 6.71%; C39H47N17O6S2Zn requires: C 47.83, H 4.84, N 24.31, S 6.55%.
H atoms were generated geometrically and refined as riding atoms with C—H = 0.93 Å (CH), 0.96 Å (CH3) and 0.97 Å (CH2), N—H = 0.86 Å (NH2), Uiso(H)= 1.2*Ueq(C) or Ueq(N) for CH and NH2, Uiso(H)= 1.5*Ueq(C) for CH3 and CH2. One of three DMF solvent molecules is disordered over a major and minor orientation with refined occupancies 0.79 and 0.21. The O2 and C30 atoms in the hydroxyethyl group on one ligand are disordered with refined occupancies of 0.51 and 0.49. Standard DFIX and SIMU restraints were used for the dimensions of the disordered DMF and the hydroxyethyl group. The H atoms attached to the ligand hydroxyl groups and the water molecule were not located. All non-H atoms were refined anisotropically. The highest peak 0.652 e·A-3 in the final difference map is located 0.98 Å from N3.
Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXTL (Sheldrick, 2001); program(s) used to refine structure: SHELXTL (Sheldrick, 2001); molecular graphics: SHELXTL (Sheldrick, 2001); software used to prepare material for publication: SHELXTL (Sheldrick, 2001) and local programs.
[Zn(C15H12N7OS)2]·3C3H7NO·H2O | F(000) = 2032 |
Mr = 979.43 | Dx = 1.378 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71069 Å |
a = 16.530 (5) Å | Cell parameters from 1864 reflections |
b = 12.104 (5) Å | θ = 3.7–22.8° |
c = 23.601 (5) Å | µ = 0.67 mm−1 |
β = 95.191 (5)° | T = 293 K |
V = 4703 (3) Å3 | Block, red |
Z = 4 | 0.28 × 0.25 × 0.20 mm |
Bruker SMART APEXII CCD diffractometer | 11219 independent reflections |
Radiation source: fine-focus sealed tube | 5488 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.064 |
phi and ω scans | θmax = 28.3°, θmin = 1.7° |
Absorption correction: multi-scan (SADABS; Bruker, 2004) | h = −20→22 |
Tmin = 0.834, Tmax = 0.877 | k = −14→15 |
28631 measured reflections | l = −27→31 |
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)] = 0.059 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.166 | H-atom parameters constrained |
S = 1.02 | w = 1/[σ2(Fo2) + (0.0681P)2 + 0.5414P] where P = (Fo2 + 2Fc2)/3 |
11219 reflections | (Δ/σ)max = 0.003 |
659 parameters | Δρmax = 0.65 e Å−3 |
221 restraints | Δρmin = −0.46 e Å−3 |
[Zn(C15H12N7OS)2]·3C3H7NO·H2O | V = 4703 (3) Å3 |
Mr = 979.43 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 16.530 (5) Å | µ = 0.67 mm−1 |
b = 12.104 (5) Å | T = 293 K |
c = 23.601 (5) Å | 0.28 × 0.25 × 0.20 mm |
β = 95.191 (5)° |
Bruker SMART APEXII CCD diffractometer | 11219 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2004) | 5488 reflections with I > 2σ(I) |
Tmin = 0.834, Tmax = 0.877 | Rint = 0.064 |
28631 measured reflections |
R[F2 > 2σ(F2)] = 0.059 | 221 restraints |
wR(F2) = 0.166 | H-atom parameters constrained |
S = 1.02 | Δρmax = 0.65 e Å−3 |
11219 reflections | Δρmin = −0.46 e Å−3 |
659 parameters |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Zn1 | 0.28853 (2) | 0.29336 (3) | 0.566007 (18) | 0.05546 (15) | |
S1 | 0.43175 (6) | 0.40097 (8) | 0.55393 (5) | 0.0666 (3) | |
S2 | 0.26569 (7) | 0.36666 (10) | 0.66953 (4) | 0.0799 (3) | |
O1 | 0.2400 (2) | −0.1279 (3) | 0.32034 (14) | 0.1113 (11) | |
O2 | −0.0955 (5) | 0.0229 (7) | 0.4924 (4) | 0.113 (3) | 0.515 (11) |
O2' | −0.0603 (6) | −0.0882 (8) | 0.5548 (4) | 0.125 (4) | 0.485 (11) |
N1 | 0.3310 (2) | 0.2085 (3) | 0.73387 (19) | 0.0922 (12) | |
H1A | 0.3556 | 0.1460 | 0.7380 | 0.111* | |
H1B | 0.3198 | 0.2454 | 0.7633 | 0.111* | |
N2 | 0.32707 (19) | 0.1911 (3) | 0.62803 (16) | 0.0839 (11) | |
N3 | 0.3628 (2) | 0.1043 (3) | 0.64264 (18) | 0.0923 (13) | |
N4 | 0.32163 (17) | 0.1572 (2) | 0.50524 (14) | 0.0596 (8) | |
N5 | 0.38312 (17) | −0.0289 (2) | 0.44344 (13) | 0.0548 (7) | |
N6 | 0.2904 (2) | 0.1763 (3) | 0.35280 (16) | 0.0817 (10) | |
N7 | 0.3281 (2) | 0.0760 (3) | 0.36269 (14) | 0.0690 (9) | |
N8 | 0.37734 (18) | 0.5373 (3) | 0.47002 (14) | 0.0752 (9) | |
H8B | 0.3383 | 0.5638 | 0.4475 | 0.090* | |
H8A | 0.4260 | 0.5616 | 0.4686 | 0.090* | |
N9 | 0.28585 (17) | 0.4190 (2) | 0.51005 (13) | 0.0574 (7) | |
N10 | 0.23015 (18) | 0.4653 (2) | 0.47206 (13) | 0.0590 (8) | |
N11 | 0.15973 (16) | 0.2753 (2) | 0.54575 (12) | 0.0524 (7) | |
N12 | −0.01435 (18) | 0.2659 (3) | 0.51332 (14) | 0.0671 (9) | |
N13 | −0.00747 (19) | 0.1312 (3) | 0.58857 (15) | 0.0716 (9) | |
N14 | 0.0505 (2) | 0.0836 (3) | 0.62609 (15) | 0.0820 (10) | |
C1 | 0.3106 (3) | 0.2480 (4) | 0.68229 (19) | 0.0806 (14) | |
C2 | 0.3781 (2) | 0.0495 (3) | 0.59043 (16) | 0.0665 (11) | |
C3 | 0.4203 (2) | −0.0558 (3) | 0.59608 (17) | 0.0618 (10) | |
C4 | 0.4518 (3) | −0.1155 (4) | 0.64344 (18) | 0.0816 (13) | |
H4 | 0.4477 | −0.0886 | 0.6800 | 0.098* | |
C5 | 0.4890 (3) | −0.2149 (4) | 0.6352 (2) | 0.0904 (14) | |
H5 | 0.5097 | −0.2561 | 0.6664 | 0.108* | |
C6 | 0.4959 (3) | −0.2538 (4) | 0.5814 (2) | 0.0807 (12) | |
H6 | 0.5217 | −0.3212 | 0.5769 | 0.097* | |
C7 | 0.4660 (2) | −0.1964 (3) | 0.53383 (18) | 0.0650 (10) | |
H7 | 0.4713 | −0.2239 | 0.4976 | 0.078* | |
C8 | 0.4278 (2) | −0.0967 (3) | 0.54132 (15) | 0.0533 (9) | |
C9 | 0.3902 (2) | −0.0192 (3) | 0.49981 (16) | 0.0534 (9) | |
C10 | 0.3595 (2) | 0.0715 (3) | 0.53061 (17) | 0.0576 (9) | |
C11 | 0.3449 (2) | 0.0590 (3) | 0.41903 (16) | 0.0572 (9) | |
C12 | 0.3149 (2) | 0.1508 (3) | 0.44815 (19) | 0.0607 (10) | |
C13 | 0.2821 (3) | 0.2197 (3) | 0.4029 (2) | 0.0797 (12) | |
H13 | 0.2577 | 0.2877 | 0.4082 | 0.096* | |
C14 | 0.3460 (3) | 0.0062 (3) | 0.31593 (17) | 0.0779 (12) | |
H14A | 0.3842 | −0.0505 | 0.3300 | 0.094* | |
H14B | 0.3718 | 0.0502 | 0.2883 | 0.094* | |
C15 | 0.2711 (3) | −0.0486 (4) | 0.28677 (19) | 0.0957 (15) | |
H15A | 0.2299 | 0.0072 | 0.2773 | 0.115* | |
H15B | 0.2847 | −0.0823 | 0.2516 | 0.115* | |
C16 | 0.3625 (2) | 0.4583 (3) | 0.50724 (17) | 0.0595 (9) | |
C17 | 0.1557 (2) | 0.4250 (3) | 0.47190 (15) | 0.0544 (9) | |
C18 | 0.0877 (2) | 0.4686 (3) | 0.43320 (16) | 0.0584 (9) | |
C19 | 0.0871 (3) | 0.5500 (3) | 0.39254 (17) | 0.0722 (11) | |
H19 | 0.1343 | 0.5873 | 0.3854 | 0.087* | |
C20 | 0.0134 (3) | 0.5739 (4) | 0.36274 (19) | 0.0855 (13) | |
H20 | 0.0113 | 0.6280 | 0.3346 | 0.103* | |
C21 | −0.0569 (3) | 0.5204 (4) | 0.3733 (2) | 0.0895 (14) | |
H21 | −0.1055 | 0.5397 | 0.3528 | 0.107* | |
C22 | −0.0564 (2) | 0.4386 (4) | 0.41381 (19) | 0.0792 (12) | |
H22 | −0.1041 | 0.4022 | 0.4207 | 0.095* | |
C23 | 0.0163 (2) | 0.4115 (3) | 0.44403 (16) | 0.0623 (10) | |
C24 | 0.0358 (2) | 0.3332 (3) | 0.48975 (16) | 0.0586 (9) | |
C25 | 0.1225 (2) | 0.3394 (3) | 0.50576 (15) | 0.0530 (8) | |
C26 | 0.0250 (2) | 0.2053 (3) | 0.55472 (17) | 0.0615 (9) | |
C27 | 0.1092 (2) | 0.2077 (3) | 0.57149 (16) | 0.0582 (9) | |
C28 | 0.1202 (2) | 0.1308 (3) | 0.61558 (18) | 0.0714 (11) | |
H28 | 0.1701 | 0.1146 | 0.6352 | 0.086* | |
C29 | −0.0922 (2) | 0.0924 (4) | 0.5863 (2) | 0.0893 (14) | |
H29A | −0.1280 | 0.1528 | 0.5738 | 0.107* | |
H29B | −0.1043 | 0.0720 | 0.6244 | 0.107* | |
C30 | −0.1098 (17) | −0.0045 (16) | 0.5475 (8) | 0.142 (10) | 0.515 (11) |
H30A | −0.0755 | −0.0662 | 0.5604 | 0.170* | 0.515 (11) |
H30B | −0.1660 | −0.0267 | 0.5485 | 0.170* | 0.515 (11) |
C30' | −0.1041 (10) | 0.0017 (13) | 0.5431 (7) | 0.079 (6) | 0.485 (11) |
H30C | −0.1611 | −0.0188 | 0.5394 | 0.095* | 0.485 (11) |
H30D | −0.0911 | 0.0303 | 0.5067 | 0.095* | 0.485 (11) |
O6W | 0.2810 (2) | 0.7268 (3) | 0.41141 (16) | 0.1246 (13) | |
O3 | 0.2369 (11) | 0.821 (2) | 0.5176 (7) | 0.186 (6) | 0.789 (17) |
O3' | 0.2336 (19) | 0.826 (2) | 0.5140 (10) | 0.067 (8) | 0.211 (17) |
N15 | 0.2491 (11) | 0.7490 (12) | 0.6025 (7) | 0.097 (4) | 0.789 (17) |
N15' | 0.241 (4) | 0.752 (4) | 0.604 (2) | 0.082 (10) | 0.211 (17) |
C31 | 0.2586 (5) | 0.7465 (8) | 0.5494 (4) | 0.096 (3) | 0.789 (17) |
H31 | 0.2833 | 0.6850 | 0.5347 | 0.115* | 0.789 (17) |
C31' | 0.219 (2) | 0.872 (5) | 0.564 (3) | 0.166 (16) | 0.211 (17) |
H31' | 0.2024 | 0.9428 | 0.5739 | 0.200* | 0.211 (17) |
C32 | 0.2079 (8) | 0.8406 (11) | 0.6274 (6) | 0.155 (4) | 0.789 (17) |
H32A | 0.1620 | 0.8133 | 0.6452 | 0.232* | 0.789 (17) |
H32B | 0.1899 | 0.8924 | 0.5981 | 0.232* | 0.789 (17) |
H32C | 0.2447 | 0.8766 | 0.6553 | 0.232* | 0.789 (17) |
C32' | 0.285 (2) | 0.653 (3) | 0.603 (2) | 0.119 (12) | 0.211 (17) |
H32D | 0.2546 | 0.5947 | 0.6192 | 0.178* | 0.211 (17) |
H32E | 0.3364 | 0.6610 | 0.6248 | 0.178* | 0.211 (17) |
H32F | 0.2932 | 0.6344 | 0.5644 | 0.178* | 0.211 (17) |
C33 | 0.2773 (9) | 0.6582 (12) | 0.6390 (5) | 0.145 (5) | 0.789 (17) |
H33A | 0.3016 | 0.6029 | 0.6168 | 0.218* | 0.789 (17) |
H33B | 0.2322 | 0.6267 | 0.6562 | 0.218* | 0.789 (17) |
H33C | 0.3168 | 0.6848 | 0.6681 | 0.218* | 0.789 (17) |
C33' | 0.231 (4) | 0.785 (5) | 0.659 (2) | 0.179 (16) | 0.211 (17) |
H33D | 0.2033 | 0.7279 | 0.6778 | 0.269* | 0.211 (17) |
H33E | 0.1998 | 0.8516 | 0.6580 | 0.269* | 0.211 (17) |
H33F | 0.2833 | 0.7977 | 0.6791 | 0.269* | 0.211 (17) |
O4 | 0.5316 (3) | 0.5614 (4) | 0.71619 (19) | 0.1447 (16) | |
N16 | 0.5668 (2) | 0.3888 (3) | 0.69505 (16) | 0.0867 (11) | |
C34 | 0.5405 (3) | 0.2784 (4) | 0.6781 (2) | 0.1134 (18) | |
H34A | 0.4825 | 0.2776 | 0.6701 | 0.170* | |
H34B | 0.5559 | 0.2275 | 0.7084 | 0.170* | |
H34C | 0.5656 | 0.2570 | 0.6447 | 0.170* | |
C35 | 0.6527 (4) | 0.4112 (6) | 0.7073 (3) | 0.159 (3) | |
H35A | 0.6677 | 0.4009 | 0.7472 | 0.238* | |
H35B | 0.6638 | 0.4860 | 0.6970 | 0.238* | |
H35C | 0.6834 | 0.3616 | 0.6859 | 0.238* | |
C36 | 0.5142 (3) | 0.4681 (5) | 0.6997 (2) | 0.0985 (16) | |
H36 | 0.4597 | 0.4524 | 0.6898 | 0.118* | |
O5 | −0.1045 (4) | 0.2077 (6) | 0.7441 (3) | 0.183 (3) | |
N17 | 0.0247 (4) | 0.2275 (6) | 0.7772 (2) | 0.142 (2) | |
C37 | 0.1040 (6) | 0.1765 (9) | 0.7771 (4) | 0.218 (5) | |
H37A | 0.0982 | 0.1037 | 0.7611 | 0.328* | |
H37B | 0.1288 | 0.1716 | 0.8154 | 0.328* | |
H37C | 0.1376 | 0.2203 | 0.7547 | 0.328* | |
C38 | 0.0197 (8) | 0.3267 (9) | 0.8067 (4) | 0.274 (7) | |
H38A | −0.0324 | 0.3599 | 0.7968 | 0.412* | |
H38B | 0.0617 | 0.3758 | 0.7966 | 0.412* | |
H38C | 0.0263 | 0.3125 | 0.8468 | 0.412* | |
C39 | −0.0349 (6) | 0.1761 (8) | 0.7495 (3) | 0.157 (3) | |
H39 | −0.0234 | 0.1094 | 0.7324 | 0.188* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Zn1 | 0.0482 (2) | 0.0487 (2) | 0.0677 (3) | 0.00276 (18) | −0.00461 (19) | 0.0070 (2) |
S1 | 0.0513 (5) | 0.0683 (6) | 0.0803 (7) | −0.0056 (5) | 0.0065 (5) | 0.0068 (5) |
S2 | 0.0839 (7) | 0.0961 (9) | 0.0587 (6) | 0.0006 (6) | 0.0016 (6) | −0.0176 (6) |
O1 | 0.143 (3) | 0.101 (2) | 0.089 (2) | −0.016 (2) | 0.007 (2) | 0.0266 (19) |
O2 | 0.127 (6) | 0.121 (6) | 0.089 (6) | −0.023 (4) | 0.007 (4) | −0.027 (5) |
O2' | 0.132 (8) | 0.114 (8) | 0.130 (7) | −0.023 (6) | 0.011 (5) | −0.015 (5) |
N1 | 0.107 (3) | 0.057 (2) | 0.112 (3) | 0.019 (2) | 0.011 (3) | −0.011 (2) |
N2 | 0.0547 (19) | 0.100 (3) | 0.093 (3) | −0.0179 (19) | −0.0151 (18) | 0.047 (2) |
N3 | 0.062 (2) | 0.072 (2) | 0.137 (4) | −0.0155 (18) | −0.025 (2) | 0.051 (2) |
N4 | 0.0589 (18) | 0.0546 (19) | 0.068 (2) | −0.0095 (15) | 0.0191 (16) | −0.0158 (16) |
N5 | 0.0584 (18) | 0.0449 (17) | 0.063 (2) | −0.0006 (14) | 0.0132 (15) | −0.0074 (14) |
N6 | 0.096 (3) | 0.065 (2) | 0.082 (3) | 0.0124 (19) | 0.002 (2) | 0.0014 (19) |
N7 | 0.083 (2) | 0.0533 (19) | 0.072 (2) | 0.0054 (17) | 0.0118 (19) | −0.0053 (16) |
N8 | 0.0486 (17) | 0.084 (2) | 0.092 (3) | −0.0047 (17) | 0.0004 (17) | 0.019 (2) |
N9 | 0.0489 (17) | 0.0507 (17) | 0.072 (2) | 0.0024 (14) | 0.0021 (15) | 0.0028 (15) |
N10 | 0.0582 (19) | 0.0532 (18) | 0.065 (2) | 0.0076 (15) | 0.0028 (16) | −0.0031 (14) |
N11 | 0.0469 (16) | 0.0503 (17) | 0.0596 (18) | −0.0031 (13) | 0.0031 (14) | −0.0076 (14) |
N12 | 0.0489 (18) | 0.072 (2) | 0.079 (2) | −0.0041 (16) | −0.0030 (17) | −0.0069 (18) |
N13 | 0.0538 (19) | 0.081 (2) | 0.079 (2) | −0.0088 (17) | −0.0022 (17) | 0.0008 (19) |
N14 | 0.076 (2) | 0.091 (3) | 0.078 (2) | −0.016 (2) | 0.005 (2) | 0.012 (2) |
C1 | 0.073 (3) | 0.114 (4) | 0.058 (3) | −0.033 (3) | 0.019 (2) | −0.044 (3) |
C2 | 0.067 (2) | 0.082 (3) | 0.054 (2) | −0.027 (2) | 0.024 (2) | −0.036 (2) |
C3 | 0.060 (2) | 0.061 (2) | 0.068 (3) | −0.0095 (19) | 0.019 (2) | −0.013 (2) |
C4 | 0.084 (3) | 0.109 (4) | 0.051 (2) | −0.020 (3) | 0.000 (2) | −0.002 (2) |
C5 | 0.090 (3) | 0.097 (4) | 0.082 (4) | 0.008 (3) | 0.000 (3) | 0.011 (3) |
C6 | 0.075 (3) | 0.081 (3) | 0.086 (3) | 0.006 (2) | 0.004 (3) | 0.008 (3) |
C7 | 0.068 (2) | 0.057 (2) | 0.071 (3) | −0.0008 (19) | 0.011 (2) | −0.003 (2) |
C8 | 0.053 (2) | 0.051 (2) | 0.057 (2) | −0.0100 (17) | 0.0117 (17) | −0.0060 (17) |
C9 | 0.050 (2) | 0.046 (2) | 0.066 (3) | −0.0098 (16) | 0.0167 (18) | −0.0123 (18) |
C10 | 0.049 (2) | 0.042 (2) | 0.083 (3) | −0.0053 (16) | 0.0149 (19) | −0.0127 (19) |
C11 | 0.058 (2) | 0.058 (2) | 0.056 (2) | −0.0013 (18) | 0.0090 (18) | −0.0050 (18) |
C12 | 0.054 (2) | 0.043 (2) | 0.085 (3) | −0.0006 (16) | 0.010 (2) | −0.004 (2) |
C13 | 0.086 (3) | 0.058 (3) | 0.095 (3) | 0.011 (2) | 0.012 (3) | −0.014 (2) |
C14 | 0.108 (3) | 0.064 (3) | 0.064 (3) | 0.007 (2) | 0.022 (2) | 0.001 (2) |
C15 | 0.145 (5) | 0.077 (3) | 0.064 (3) | −0.022 (3) | 0.005 (3) | 0.005 (2) |
C16 | 0.052 (2) | 0.054 (2) | 0.075 (3) | −0.0130 (17) | 0.0182 (19) | −0.0096 (19) |
C17 | 0.046 (2) | 0.053 (2) | 0.064 (2) | 0.0022 (17) | 0.0039 (17) | −0.0054 (18) |
C18 | 0.051 (2) | 0.059 (2) | 0.064 (2) | 0.0072 (18) | −0.0008 (18) | −0.0040 (19) |
C19 | 0.070 (3) | 0.072 (3) | 0.074 (3) | 0.006 (2) | 0.003 (2) | 0.006 (2) |
C20 | 0.085 (3) | 0.095 (3) | 0.075 (3) | 0.016 (3) | −0.003 (3) | 0.011 (3) |
C21 | 0.069 (3) | 0.101 (4) | 0.094 (4) | 0.019 (3) | −0.022 (3) | 0.004 (3) |
C22 | 0.053 (2) | 0.090 (3) | 0.091 (3) | 0.009 (2) | −0.012 (2) | 0.000 (3) |
C23 | 0.049 (2) | 0.067 (2) | 0.069 (3) | 0.0064 (18) | −0.0037 (18) | −0.004 (2) |
C24 | 0.0419 (19) | 0.062 (2) | 0.071 (3) | −0.0026 (17) | 0.0000 (18) | −0.0069 (19) |
C25 | 0.0461 (19) | 0.055 (2) | 0.057 (2) | 0.0054 (17) | −0.0011 (17) | −0.0091 (18) |
C26 | 0.050 (2) | 0.064 (2) | 0.071 (3) | −0.0088 (19) | 0.0049 (19) | 0.001 (2) |
C27 | 0.056 (2) | 0.055 (2) | 0.063 (2) | 0.0016 (18) | 0.0022 (18) | −0.0063 (19) |
C28 | 0.060 (2) | 0.076 (3) | 0.076 (3) | −0.009 (2) | −0.001 (2) | 0.007 (2) |
C29 | 0.060 (3) | 0.110 (4) | 0.100 (4) | −0.021 (3) | 0.019 (2) | −0.003 (3) |
C30 | 0.129 (18) | 0.090 (16) | 0.20 (2) | −0.002 (13) | −0.002 (15) | 0.022 (15) |
C30' | 0.040 (7) | 0.075 (12) | 0.121 (14) | −0.025 (7) | 0.000 (7) | 0.010 (10) |
O6W | 0.149 (3) | 0.107 (3) | 0.118 (3) | 0.025 (2) | 0.014 (2) | 0.030 (2) |
O3 | 0.112 (10) | 0.267 (16) | 0.172 (12) | −0.044 (10) | −0.017 (9) | 0.044 (13) |
O3' | 0.065 (16) | 0.097 (16) | 0.039 (12) | −0.001 (12) | 0.013 (11) | 0.042 (11) |
N15 | 0.099 (7) | 0.098 (7) | 0.097 (7) | −0.019 (6) | 0.019 (5) | −0.018 (6) |
N15' | 0.083 (17) | 0.088 (17) | 0.073 (17) | 0.005 (14) | −0.006 (14) | 0.063 (14) |
C31 | 0.075 (4) | 0.114 (6) | 0.097 (7) | −0.007 (4) | 0.002 (4) | 0.017 (5) |
C31' | 0.10 (2) | 0.22 (3) | 0.18 (4) | −0.05 (2) | −0.01 (3) | −0.03 (3) |
C32 | 0.167 (9) | 0.139 (9) | 0.164 (12) | 0.019 (7) | 0.051 (9) | −0.015 (8) |
C32' | 0.087 (17) | 0.076 (18) | 0.20 (3) | 0.023 (14) | 0.03 (2) | 0.03 (2) |
C33 | 0.165 (10) | 0.139 (9) | 0.126 (8) | −0.032 (7) | −0.024 (8) | 0.072 (8) |
C33' | 0.18 (3) | 0.19 (3) | 0.17 (3) | 0.00 (3) | 0.05 (3) | 0.02 (3) |
O4 | 0.184 (4) | 0.101 (3) | 0.140 (3) | 0.006 (3) | −0.035 (3) | −0.012 (3) |
N16 | 0.085 (3) | 0.088 (3) | 0.084 (3) | 0.003 (2) | −0.005 (2) | −0.011 (2) |
C34 | 0.125 (5) | 0.082 (4) | 0.131 (5) | −0.005 (3) | −0.003 (4) | −0.005 (3) |
C35 | 0.090 (4) | 0.219 (8) | 0.164 (6) | 0.011 (5) | −0.001 (4) | −0.063 (6) |
C36 | 0.112 (4) | 0.087 (4) | 0.091 (4) | 0.001 (3) | −0.025 (3) | −0.014 (3) |
O5 | 0.159 (5) | 0.235 (7) | 0.155 (5) | −0.062 (5) | 0.006 (4) | −0.016 (4) |
N17 | 0.140 (5) | 0.181 (6) | 0.103 (4) | −0.072 (5) | −0.004 (4) | 0.011 (4) |
C37 | 0.170 (9) | 0.332 (14) | 0.152 (8) | −0.048 (9) | 0.007 (7) | 0.037 (8) |
C38 | 0.365 (17) | 0.237 (11) | 0.221 (11) | −0.119 (11) | 0.024 (10) | −0.119 (9) |
C39 | 0.155 (7) | 0.208 (9) | 0.107 (5) | −0.064 (8) | 0.018 (6) | 0.010 (5) |
Zn1—N2 | 1.978 (3) | C19—C20 | 1.381 (5) |
Zn1—N9 | 2.012 (3) | C19—H19 | 0.9300 |
Zn1—N11 | 2.151 (3) | C20—C21 | 1.373 (6) |
Zn1—N4 | 2.284 (3) | C20—H20 | 0.9300 |
Zn1—S2 | 2.6581 (12) | C21—C22 | 1.375 (6) |
Zn1—S1 | 2.7394 (12) | C21—H21 | 0.9300 |
S1—C16 | 1.667 (4) | C22—C23 | 1.380 (5) |
S2—C1 | 1.632 (6) | C22—H22 | 0.9300 |
O1—C15 | 1.373 (5) | C23—C24 | 1.450 (5) |
O2—C30 | 1.382 (17) | C24—C25 | 1.451 (5) |
O2'—C30' | 1.323 (16) | C26—C27 | 1.413 (5) |
N1—C1 | 1.323 (6) | C27—C28 | 1.396 (5) |
N1—H1A | 0.8600 | C28—H28 | 0.9300 |
N1—H1B | 0.8600 | C29—C30' | 1.498 (13) |
N2—N3 | 1.239 (4) | C29—C30 | 1.501 (16) |
N2—C1 | 1.500 (5) | C29—H29A | 0.9700 |
N3—C2 | 1.442 (5) | C29—H29B | 0.9700 |
N4—C10 | 1.326 (4) | C30—H30A | 0.9700 |
N4—C12 | 1.344 (5) | C30—H30B | 0.9700 |
N5—C9 | 1.330 (4) | C30'—H30C | 0.9700 |
N5—C11 | 1.340 (4) | C30'—H30D | 0.9700 |
N6—C13 | 1.312 (5) | O3—C31 | 1.202 (17) |
N6—N7 | 1.375 (4) | O3'—C31' | 1.35 (8) |
N7—C11 | 1.349 (5) | N15—C31 | 1.277 (18) |
N7—C14 | 1.442 (5) | N15—C33 | 1.447 (17) |
N8—C16 | 1.336 (5) | N15—C32 | 1.45 (2) |
N8—H8NB | 0.8600 | N15'—C33' | 1.38 (8) |
N8—H8NA | 0.8600 | N15'—C32' | 1.40 (7) |
N9—N10 | 1.348 (4) | N15'—C31' | 1.76 (7) |
N9—C16 | 1.360 (4) | C31—H31 | 0.9300 |
N10—C17 | 1.324 (4) | C31'—H31' | 0.9300 |
N11—C25 | 1.329 (4) | C32—H32A | 0.9600 |
N11—C27 | 1.352 (4) | C32—H32B | 0.9600 |
N12—C24 | 1.320 (5) | C32—H32C | 0.9600 |
N12—C26 | 1.342 (5) | C32'—H32D | 0.9600 |
N13—C26 | 1.345 (5) | C32'—H32E | 0.9600 |
N13—N14 | 1.372 (4) | C32'—H32F | 0.9600 |
N13—C29 | 1.474 (5) | C33—H33A | 0.9600 |
N14—C28 | 1.329 (5) | C33—H33B | 0.9600 |
C2—C10 | 1.442 (5) | C33—H33C | 0.9600 |
C2—C3 | 1.453 (5) | C33'—H33D | 0.9600 |
C3—C4 | 1.391 (6) | C33'—H33E | 0.9600 |
C3—C8 | 1.400 (5) | C33'—H33F | 0.9600 |
C4—C5 | 1.373 (6) | O4—C36 | 1.220 (5) |
C4—H4 | 0.9300 | N16—C36 | 1.307 (6) |
C5—C6 | 1.369 (6) | N16—C35 | 1.447 (6) |
C5—H5 | 0.9300 | N16—C34 | 1.450 (6) |
C6—C7 | 1.374 (6) | C34—H34A | 0.9600 |
C6—H6 | 0.9300 | C34—H34B | 0.9600 |
C7—C8 | 1.380 (5) | C34—H34C | 0.9600 |
C7—H7 | 0.9300 | C35—H35A | 0.9600 |
C8—C9 | 1.455 (5) | C35—H35B | 0.9600 |
C9—C10 | 1.434 (5) | C35—H35C | 0.9600 |
C11—C12 | 1.420 (5) | C36—H36 | 0.9300 |
C12—C13 | 1.423 (6) | O5—C39 | 1.208 (10) |
C13—H13 | 0.9300 | N17—C39 | 1.292 (9) |
C14—C15 | 1.515 (6) | N17—C38 | 1.394 (11) |
C14—H14A | 0.9700 | N17—C37 | 1.448 (10) |
C14—H14B | 0.9700 | C37—H37A | 0.9600 |
C15—H15A | 0.9700 | C37—H37B | 0.9600 |
C15—H15B | 0.9700 | C37—H37C | 0.9600 |
C17—C25 | 1.447 (5) | C38—H38A | 0.9600 |
C17—C18 | 1.480 (5) | C38—H38B | 0.9600 |
C18—C19 | 1.374 (5) | C38—H38C | 0.9600 |
C18—C23 | 1.411 (5) | C39—H39 | 0.9300 |
N2—Zn1—N9 | 160.95 (12) | C21—C20—C19 | 122.0 (4) |
N2—Zn1—N11 | 110.31 (12) | C21—C20—H20 | 119.0 |
N9—Zn1—N11 | 88.19 (11) | C19—C20—H20 | 119.0 |
N2—Zn1—N4 | 86.21 (16) | C20—C21—C22 | 121.0 (4) |
N9—Zn1—N4 | 97.22 (12) | C20—C21—H21 | 119.5 |
N11—Zn1—N4 | 94.34 (10) | C22—C21—H21 | 119.5 |
N2—Zn1—S2 | 65.89 (13) | C21—C22—C23 | 118.7 (4) |
N9—Zn1—S2 | 110.76 (9) | C21—C22—H22 | 120.7 |
N11—Zn1—S2 | 91.04 (8) | C23—C22—H22 | 120.7 |
N4—Zn1—S2 | 151.67 (9) | C22—C23—C18 | 119.6 (4) |
N2—Zn1—S1 | 98.68 (9) | C22—C23—C24 | 131.6 (4) |
N9—Zn1—S1 | 62.63 (8) | C18—C23—C24 | 108.8 (3) |
N11—Zn1—S1 | 150.77 (8) | N12—C24—C23 | 127.7 (3) |
N4—Zn1—S1 | 91.11 (8) | N12—C24—C25 | 124.4 (3) |
S2—Zn1—S1 | 97.64 (4) | C23—C24—C25 | 107.9 (3) |
C16—S1—Zn1 | 73.63 (13) | N11—C25—C17 | 129.5 (3) |
C1—S2—Zn1 | 77.05 (16) | N11—C25—C24 | 122.6 (3) |
C1—N1—H1A | 120.0 | C17—C25—C24 | 107.9 (3) |
C1—N1—H1B | 120.0 | N12—C26—N13 | 127.2 (3) |
H1A—N1—H1B | 120.0 | N12—C26—C27 | 126.4 (4) |
N3—N2—C1 | 105.7 (4) | N13—C26—C27 | 106.4 (3) |
N3—N2—Zn1 | 148.2 (4) | N11—C27—C28 | 134.0 (3) |
C1—N2—Zn1 | 105.9 (3) | N11—C27—C26 | 121.3 (3) |
N2—N3—C2 | 105.6 (4) | C28—C27—C26 | 104.7 (3) |
C10—N4—C12 | 113.6 (3) | N14—C28—C27 | 111.7 (4) |
C10—N4—Zn1 | 114.3 (2) | N14—C28—H28 | 124.1 |
C12—N4—Zn1 | 131.9 (3) | C27—C28—H28 | 124.1 |
C9—N5—C11 | 110.8 (3) | N13—C29—C30' | 108.9 (7) |
C13—N6—N7 | 106.5 (3) | N13—C29—C30 | 113.7 (11) |
C11—N7—N6 | 110.6 (3) | C30'—C29—C30 | 6.2 (14) |
C11—N7—C14 | 128.8 (3) | N13—C29—H29A | 108.8 |
N6—N7—C14 | 120.6 (3) | C30'—C29—H29A | 107.7 |
C16—N8—H8NB | 120.0 | C30—C29—H29A | 108.8 |
C16—N8—H8NA | 120.0 | N13—C29—H29B | 108.8 |
H8NB—N8—H8NA | 120.0 | C30'—C29—H29B | 114.7 |
N10—N9—C16 | 113.9 (3) | C30—C29—H29B | 108.8 |
N10—N9—Zn1 | 136.4 (2) | H29A—C29—H29B | 107.7 |
C16—N9—Zn1 | 109.3 (2) | O2—C30—C29 | 110.3 (14) |
C17—N10—N9 | 115.3 (3) | O2—C30—H30A | 109.6 |
C25—N11—C27 | 114.0 (3) | C29—C30—H30A | 109.6 |
C25—N11—Zn1 | 119.0 (2) | O2—C30—H30B | 109.6 |
C27—N11—Zn1 | 126.9 (2) | C29—C30—H30B | 109.6 |
C24—N12—C26 | 111.3 (3) | H30A—C30—H30B | 108.1 |
C26—N13—N14 | 111.8 (3) | O2'—C30'—C29 | 115.2 (11) |
C26—N13—C29 | 128.3 (4) | O2'—C30'—H30C | 108.5 |
N14—N13—C29 | 119.7 (4) | C29—C30'—H30C | 108.5 |
C28—N14—N13 | 105.4 (3) | O2'—C30'—H30D | 108.5 |
N1—C1—N2 | 124.6 (5) | C29—C30'—H30D | 108.5 |
N1—C1—S2 | 124.2 (3) | H30C—C30'—H30D | 107.5 |
N2—C1—S2 | 111.2 (4) | C31—N15—C33 | 120.3 (15) |
N3—C2—C10 | 135.5 (4) | C31—N15—C32 | 121.3 (14) |
N3—C2—C3 | 116.4 (4) | C33—N15—C32 | 118.4 (15) |
C10—C2—C3 | 108.1 (3) | C33'—N15'—C32' | 112 (3) |
C4—C3—C8 | 120.0 (4) | C33'—N15'—C31' | 103 (5) |
C4—C3—C2 | 132.1 (4) | C32'—N15'—C31' | 142 (5) |
C8—C3—C2 | 107.9 (3) | O3—C31—N15 | 122.5 (15) |
C5—C4—C3 | 118.7 (4) | O3—C31—H31 | 118.8 |
C5—C4—H4 | 120.6 | N15—C31—H31 | 118.8 |
C3—C4—H4 | 120.6 | O3'—C31'—N15' | 95 (4) |
C6—C5—C4 | 120.7 (4) | O3'—C31'—H31' | 132.7 |
C6—C5—H5 | 119.7 | N15'—C31'—H31' | 132.7 |
C4—C5—H5 | 119.7 | N15'—C32'—H32D | 109.5 |
C5—C6—C7 | 121.9 (4) | N15'—C32'—H32E | 109.5 |
C5—C6—H6 | 119.0 | H32D—C32'—H32E | 109.5 |
C7—C6—H6 | 119.0 | N15'—C32'—H32F | 109.5 |
C6—C7—C8 | 118.2 (4) | H32D—C32'—H32F | 109.5 |
C6—C7—H7 | 120.9 | H32E—C32'—H32F | 109.5 |
C8—C7—H7 | 120.9 | N15'—C33'—H33D | 109.5 |
C7—C8—C3 | 120.5 (4) | N15'—C33'—H33E | 109.5 |
C7—C8—C9 | 130.6 (3) | H33D—C33'—H33E | 109.5 |
C3—C8—C9 | 109.0 (3) | N15'—C33'—H33F | 109.5 |
N5—C9—C10 | 124.9 (3) | H33D—C33'—H33F | 109.5 |
N5—C9—C8 | 127.6 (3) | H33E—C33'—H33F | 109.5 |
C10—C9—C8 | 107.6 (3) | C36—N16—C35 | 119.5 (5) |
N4—C10—C9 | 122.9 (4) | C36—N16—C34 | 121.0 (4) |
N4—C10—C2 | 129.5 (3) | C35—N16—C34 | 119.5 (5) |
C9—C10—C2 | 107.5 (3) | N16—C34—H34A | 109.5 |
N5—C11—N7 | 126.3 (3) | N16—C34—H34B | 109.5 |
N5—C11—C12 | 125.8 (3) | H34A—C34—H34B | 109.5 |
N7—C11—C12 | 107.9 (3) | N16—C34—H34C | 109.5 |
N4—C12—C11 | 121.9 (3) | H34A—C34—H34C | 109.5 |
N4—C12—C13 | 135.2 (4) | H34B—C34—H34C | 109.5 |
C11—C12—C13 | 102.8 (4) | N16—C35—H35A | 109.5 |
N6—C13—C12 | 112.2 (4) | N16—C35—H35B | 109.5 |
N6—C13—H13 | 123.9 | H35A—C35—H35B | 109.5 |
C12—C13—H13 | 123.9 | N16—C35—H35C | 109.5 |
N7—C14—C15 | 112.8 (4) | H35A—C35—H35C | 109.5 |
N7—C14—H14A | 109.0 | H35B—C35—H35C | 109.5 |
C15—C14—H14A | 109.0 | O4—C36—N16 | 124.6 (5) |
N7—C14—H14B | 109.0 | O4—C36—H36 | 117.7 |
C15—C14—H14B | 109.0 | N16—C36—H36 | 117.7 |
H14A—C14—H14B | 107.8 | C39—N17—C38 | 126.1 (10) |
O1—C15—C14 | 112.1 (4) | C39—N17—C37 | 116.3 (9) |
O1—C15—H15A | 109.2 | C38—N17—C37 | 117.6 (8) |
C14—C15—H15A | 109.2 | N17—C37—H37A | 109.5 |
O1—C15—H15B | 109.2 | N17—C37—H37B | 109.5 |
C14—C15—H15B | 109.2 | H37A—C37—H37B | 109.5 |
H15A—C15—H15B | 107.9 | N17—C37—H37C | 109.5 |
N8—C16—N9 | 120.7 (3) | H37A—C37—H37C | 109.5 |
N8—C16—S1 | 125.2 (3) | H37B—C37—H37C | 109.5 |
N9—C16—S1 | 114.2 (3) | N17—C38—H38A | 109.5 |
N10—C17—C25 | 131.4 (3) | N17—C38—H38B | 109.5 |
N10—C17—C18 | 121.6 (3) | H38A—C38—H38B | 109.5 |
C25—C17—C18 | 107.0 (3) | N17—C38—H38C | 109.5 |
C19—C18—C23 | 121.6 (3) | H38A—C38—H38C | 109.5 |
C19—C18—C17 | 130.1 (3) | H38B—C38—H38C | 109.5 |
C23—C18—C17 | 108.3 (3) | O5—C39—N17 | 125.3 (11) |
C18—C19—C20 | 117.2 (4) | O5—C39—H39 | 117.4 |
C18—C19—H19 | 121.4 | N17—C39—H39 | 117.4 |
C20—C19—H19 | 121.4 | ||
N2—Zn1—S1—C16 | −178.87 (18) | N3—C2—C10—C9 | −178.1 (4) |
N9—Zn1—S1—C16 | −2.76 (16) | C3—C2—C10—C9 | −0.2 (4) |
N11—Zn1—S1—C16 | −6.1 (2) | C9—N5—C11—N7 | 179.7 (3) |
N4—Zn1—S1—C16 | 94.79 (16) | C9—N5—C11—C12 | −0.4 (5) |
S2—Zn1—S1—C16 | −112.23 (14) | N6—N7—C11—N5 | −178.3 (3) |
N2—Zn1—S2—C1 | 1.10 (17) | C14—N7—C11—N5 | 0.3 (6) |
N9—Zn1—S2—C1 | −158.59 (17) | N6—N7—C11—C12 | 1.8 (4) |
N11—Zn1—S2—C1 | 112.95 (16) | C14—N7—C11—C12 | −179.7 (4) |
N4—Zn1—S2—C1 | 11.8 (2) | C10—N4—C12—C11 | 1.0 (5) |
S1—Zn1—S2—C1 | −95.03 (15) | Zn1—N4—C12—C11 | 175.7 (2) |
N9—Zn1—N2—N3 | −90.6 (7) | C10—N4—C12—C13 | −178.5 (4) |
N11—Zn1—N2—N3 | 103.8 (5) | Zn1—N4—C12—C13 | −3.8 (6) |
N4—Zn1—N2—N3 | 10.6 (5) | N5—C11—C12—N4 | −0.8 (6) |
S2—Zn1—N2—N3 | −174.5 (5) | N7—C11—C12—N4 | 179.1 (3) |
S1—Zn1—N2—N3 | −79.9 (5) | N5—C11—C12—C13 | 178.8 (4) |
N9—Zn1—N2—C1 | 82.7 (5) | N7—C11—C12—C13 | −1.2 (4) |
N11—Zn1—N2—C1 | −82.9 (2) | N7—N6—C13—C12 | 0.7 (5) |
N4—Zn1—N2—C1 | −176.1 (2) | N4—C12—C13—N6 | 179.9 (4) |
S2—Zn1—N2—C1 | −1.21 (19) | C11—C12—C13—N6 | 0.3 (5) |
S1—Zn1—N2—C1 | 93.3 (2) | C11—N7—C14—C15 | 108.3 (5) |
C1—N2—N3—C2 | 179.6 (3) | N6—N7—C14—C15 | −73.3 (5) |
Zn1—N2—N3—C2 | −7.1 (6) | N7—C14—C15—O1 | −70.0 (5) |
N2—Zn1—N4—C10 | −6.5 (2) | N10—N9—C16—N8 | 1.2 (5) |
N9—Zn1—N4—C10 | 154.7 (2) | Zn1—N9—C16—N8 | 175.4 (3) |
N11—Zn1—N4—C10 | −116.6 (2) | N10—N9—C16—S1 | −179.7 (2) |
S2—Zn1—N4—C10 | −16.3 (3) | Zn1—N9—C16—S1 | −5.5 (3) |
S1—Zn1—N4—C10 | 92.1 (2) | Zn1—S1—C16—N8 | −177.0 (4) |
N2—Zn1—N4—C12 | 178.8 (3) | Zn1—S1—C16—N9 | 4.0 (2) |
N9—Zn1—N4—C12 | −20.1 (3) | N9—N10—C17—C25 | 0.4 (5) |
N11—Zn1—N4—C12 | 68.6 (3) | N9—N10—C17—C18 | 179.0 (3) |
S2—Zn1—N4—C12 | 169.0 (2) | N10—C17—C18—C19 | 1.4 (6) |
S1—Zn1—N4—C12 | −82.6 (3) | C25—C17—C18—C19 | −179.7 (4) |
C13—N6—N7—C11 | −1.6 (5) | N10—C17—C18—C23 | −178.4 (3) |
C13—N6—N7—C14 | 179.8 (4) | C25—C17—C18—C23 | 0.5 (4) |
N2—Zn1—N9—N10 | −172.4 (4) | C23—C18—C19—C20 | 0.2 (6) |
N11—Zn1—N9—N10 | −5.9 (3) | C17—C18—C19—C20 | −179.6 (4) |
N4—Zn1—N9—N10 | 88.3 (3) | C18—C19—C20—C21 | 0.8 (7) |
S2—Zn1—N9—N10 | −96.3 (3) | C19—C20—C21—C22 | −1.1 (8) |
S1—Zn1—N9—N10 | 175.8 (4) | C20—C21—C22—C23 | 0.4 (7) |
N2—Zn1—N9—C16 | 15.3 (6) | C21—C22—C23—C18 | 0.6 (6) |
N11—Zn1—N9—C16 | −178.2 (2) | C21—C22—C23—C24 | 177.7 (4) |
N4—Zn1—N9—C16 | −84.1 (2) | C19—C18—C23—C22 | −0.9 (6) |
S2—Zn1—N9—C16 | 91.4 (2) | C17—C18—C23—C22 | 178.9 (3) |
S1—Zn1—N9—C16 | 3.4 (2) | C19—C18—C23—C24 | −178.7 (3) |
C16—N9—N10—C17 | 176.9 (3) | C17—C18—C23—C24 | 1.2 (4) |
Zn1—N9—N10—C17 | 4.8 (5) | C26—N12—C24—C23 | −179.8 (4) |
N2—Zn1—N11—C25 | 178.5 (3) | C26—N12—C24—C25 | 1.1 (5) |
N9—Zn1—N11—C25 | 3.1 (3) | C22—C23—C24—N12 | 1.0 (7) |
N4—Zn1—N11—C25 | −94.0 (3) | C18—C23—C24—N12 | 178.4 (4) |
S2—Zn1—N11—C25 | 113.9 (2) | C22—C23—C24—C25 | −179.8 (4) |
S1—Zn1—N11—C25 | 6.1 (3) | C18—C23—C24—C25 | −2.4 (4) |
N2—Zn1—N11—C27 | 1.9 (3) | C27—N11—C25—C17 | 176.3 (3) |
N9—Zn1—N11—C27 | −173.4 (3) | Zn1—N11—C25—C17 | −0.7 (5) |
N4—Zn1—N11—C27 | 89.5 (3) | C27—N11—C25—C24 | −2.6 (5) |
S2—Zn1—N11—C27 | −62.7 (3) | Zn1—N11—C25—C24 | −179.5 (2) |
S1—Zn1—N11—C27 | −170.4 (2) | N10—C17—C25—N11 | −2.2 (6) |
C26—N13—N14—C28 | 0.9 (5) | C18—C17—C25—N11 | 179.0 (3) |
C29—N13—N14—C28 | 176.3 (4) | N10—C17—C25—C24 | 176.8 (4) |
N3—N2—C1—N1 | −0.5 (5) | C18—C17—C25—C24 | −2.0 (4) |
Zn1—N2—C1—N1 | −176.8 (3) | N12—C24—C25—N11 | 1.1 (6) |
N3—N2—C1—S2 | 178.3 (3) | C23—C24—C25—N11 | −178.2 (3) |
Zn1—N2—C1—S2 | 1.9 (3) | N12—C24—C25—C17 | −178.0 (3) |
Zn1—S2—C1—N1 | 177.3 (4) | C23—C24—C25—C17 | 2.7 (4) |
Zn1—S2—C1—N2 | −1.4 (2) | C24—N12—C26—N13 | 177.8 (4) |
N2—N3—C2—C10 | −2.3 (6) | C24—N12—C26—C27 | −1.7 (5) |
N2—N3—C2—C3 | 179.8 (3) | N14—N13—C26—N12 | 179.5 (4) |
N3—C2—C3—C4 | −1.8 (6) | C29—N13—C26—N12 | 4.7 (7) |
C10—C2—C3—C4 | 179.8 (4) | N14—N13—C26—C27 | −0.8 (4) |
N3—C2—C3—C8 | 178.8 (3) | C29—N13—C26—C27 | −175.7 (4) |
C10—C2—C3—C8 | 0.4 (4) | C25—N11—C27—C28 | −177.8 (4) |
C8—C3—C4—C5 | −0.8 (6) | Zn1—N11—C27—C28 | −1.1 (6) |
C2—C3—C4—C5 | 179.8 (4) | C25—N11—C27—C26 | 2.0 (5) |
C3—C4—C5—C6 | 0.9 (7) | Zn1—N11—C27—C26 | 178.7 (3) |
C4—C5—C6—C7 | −0.4 (7) | N12—C26—C27—N11 | 0.2 (6) |
C5—C6—C7—C8 | −0.1 (6) | N13—C26—C27—N11 | −179.5 (3) |
C6—C7—C8—C3 | 0.2 (5) | N12—C26—C27—C28 | −179.9 (4) |
C6—C7—C8—C9 | −179.5 (4) | N13—C26—C27—C28 | 0.4 (4) |
C4—C3—C8—C7 | 0.3 (5) | N13—N14—C28—C27 | −0.6 (5) |
C2—C3—C8—C7 | 179.8 (3) | N11—C27—C28—N14 | 180.0 (4) |
C4—C3—C8—C9 | −180.0 (3) | C26—C27—C28—N14 | 0.1 (5) |
C2—C3—C8—C9 | −0.4 (4) | C26—N13—C29—C30' | 83.7 (9) |
C11—N5—C9—C10 | 1.4 (5) | N14—N13—C29—C30' | −90.8 (8) |
C11—N5—C9—C8 | −180.0 (3) | C26—N13—C29—C30 | 87.9 (11) |
C7—C8—C9—N5 | 1.2 (6) | N14—N13—C29—C30 | −86.6 (11) |
C3—C8—C9—N5 | −178.5 (3) | N13—C29—C30—O2 | −60 (2) |
C7—C8—C9—C10 | −180.0 (3) | C30'—C29—C30—O2 | −20 (14) |
C3—C8—C9—C10 | 0.3 (4) | N13—C29—C30'—O2' | 63.4 (14) |
C12—N4—C10—C9 | 0.0 (5) | C30—C29—C30'—O2' | −78 (15) |
Zn1—N4—C10—C9 | −175.8 (2) | C33—N15—C31—O3 | −179.3 (15) |
C12—N4—C10—C2 | 179.9 (3) | C32—N15—C31—O3 | 3 (2) |
Zn1—N4—C10—C2 | 4.2 (5) | C33'—N15'—C31'—O3' | 178 (4) |
N5—C9—C10—N4 | −1.3 (5) | C32'—N15'—C31'—O3' | 23 (7) |
C8—C9—C10—N4 | 179.8 (3) | C35—N16—C36—O4 | −3.1 (9) |
N5—C9—C10—C2 | 178.8 (3) | C34—N16—C36—O4 | 176.5 (5) |
C8—C9—C10—C2 | −0.1 (4) | C38—N17—C39—O5 | 1.6 (14) |
N3—C2—C10—N4 | 1.9 (7) | C37—N17—C39—O5 | −178.3 (8) |
C3—C2—C10—N4 | 179.9 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
N8—H8A···S1i | 0.86 | 2.50 | 3.340 (3) | 166 |
N8—H8B···O6W | 0.86 | 2.32 | 3.051 (5) | 144 |
N1—H1B···N6ii | 0.86 | 2.40 | 3.258 (6) | 172 |
N1—H1A···O4iii | 0.86 | 2.31 | 3.039 (6) | 143 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x, −y+1/2, z+1/2; (iii) −x+1, y−1/2, −z+3/2. |
Experimental details
Crystal data | |
Chemical formula | [Zn(C15H12N7OS)2]·3C3H7NO·H2O |
Mr | 979.43 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 293 |
a, b, c (Å) | 16.530 (5), 12.104 (5), 23.601 (5) |
β (°) | 95.191 (5) |
V (Å3) | 4703 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.67 |
Crystal size (mm) | 0.28 × 0.25 × 0.20 |
Data collection | |
Diffractometer | Bruker SMART APEXII CCD diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2004) |
Tmin, Tmax | 0.834, 0.877 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 28631, 11219, 5488 |
Rint | 0.064 |
(sin θ/λ)max (Å−1) | 0.668 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.059, 0.166, 1.02 |
No. of reflections | 11219 |
No. of parameters | 659 |
No. of restraints | 221 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.65, −0.46 |
Computer programs: APEX2 (Bruker, 2004), SAINT (Bruker, 2004), SHELXTL (Sheldrick, 2001) and local programs.
Zn1—N2 | 1.978 (3) | Zn1—N4 | 2.284 (3) |
Zn1—N9 | 2.012 (3) | Zn1—S2 | 2.6581 (12) |
Zn1—N11 | 2.151 (3) | Zn1—S1 | 2.7394 (12) |
N2—Zn1—N11 | 110.31 (12) | N9—Zn1—S2 | 110.76 (9) |
N9—Zn1—N11 | 88.19 (11) | N11—Zn1—S2 | 91.04 (8) |
N2—Zn1—N4 | 86.21 (16) | N2—Zn1—S1 | 98.68 (9) |
N9—Zn1—N4 | 97.22 (12) | N9—Zn1—S1 | 62.63 (8) |
N11—Zn1—N4 | 94.34 (10) | N4—Zn1—S1 | 91.11 (8) |
N2—Zn1—S2 | 65.89 (13) | S2—Zn1—S1 | 97.64 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
N8—H8A···S1i | 0.86 | 2.50 | 3.340 (3) | 166.4 |
N8—H8B···O6W | 0.86 | 2.32 | 3.051 (5) | 143.5 |
N1—H1B···N6ii | 0.86 | 2.40 | 3.258 (6) | 171.8 |
N1—H1A···O4iii | 0.86 | 2.31 | 3.039 (6) | 142.8 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x, −y+1/2, z+1/2; (iii) −x+1, y−1/2, −z+3/2. |
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Owing to their photoelectromagnetic characteristics and physiologically important bactericidal and cancer-fighting activities, the hydrazone class of Schiff bases and their complexes have attracted much attention (Reiter et al., 1985; Kovala-Demertzi et al., 1999; Matthews et al., 2001). Among these, the thiosemicarbazide Schiff base and its complexes have been particularly widely studied, because they are not only organic colorants with excellent performance, showing antibacterial and antiviral activities, but also templates for studying biological activity (Singh et al., 1978). The title compound, [ZnL2]·3DMF·H2O, (I) {L is 3-(2-hydroxyethyl)-4,10-diazapyrazolo[3,4-b]fluoren-9(3H)-one thiosemicarbazone and DMF is dimethylformamide}, has been synthesized because the ligand L is not only a novel thiosemicarbazone Schiff base but also a member of an important class of pyrazole-containing ring structures. This type of ligand displays unusual characteristics, including cis–trans isomerism in complexes (Che & Wang, 2006; Che et al., 2006). Therefore, we aim to determine the single-crystal structures of examples of this class of compound, in order to understand their coordination mode and structural characteristics, as a guide for further studies. To our knowledge, this is the first report of the synthesis and crystal structure of a complex of this ligand.
The title complex, (I), in which the molecular structure unit is identical to the asymmetric unit, is composed of one ZnL2 unit, one water molecule and three DMF molecules, with the solvent molecules not participating in coordination. Within the complex, each ZnII ion is six-coordinated (Fig. 1) by four N and two S atoms from two ligands. The bond angles formed between atom Zn1 and coordination atoms N2, N4, S1, N9, N11 and S2 are in the range of 62.63 (8)–110.76 (9)°, while the bond lengths involving atom Zn1 and these coordination atoms are in the range 1.978 (3)–2.739 (1) Å. Thus, the central Zn coordination geometry is best described as a distorted octahedron (Table 1). Each ligand L, as a tridentate chelate, provides two N atoms and one S atom to coordinate to ZnII, forming a six-membered ring and a four-membered ring. As demonstrated by the relevant literature (Mathew & Palenik, 1971; Restivo & Palenik, 1970; Gabe et al., 1969), this type of thiosemicarbazide Schiff base has a large conformational diversity, so that cis–trans isomerism is observed. The coordination mode of the present ligand L is very different from that of these reported examples. Using one of the independent L ligands as an example, atom N2 is in the cis (not trans) position with respect to N4 on the diazafluorenone ring, and it is N2 (not N3) that coordinates to the ZnII atom. The cause may that the present Schiff base ligand L is synthesized directly from the carbonyl group in the aromatic ring, while most Schiff base ligands are synthesized from aldehyde groups and those carbonyl groups that are not in the aromatic ring (Mathew & Palenik, 1971; Restivo & Palenik, 1970; Gabe et al., 1969). There may exist cis–trans isomerism for this ligand as well, because this coordination mode is similar to that observed in bis(µ-11-thiosemicarbazonoindeno[1,2-b]quinoxaline-8-carboxyl- ato)bis[(dimethyl sulfoxide)zinc(II)] dimethyl sulfoxide trisolvate, (IIa) (Che et al., 2006), but different from that found in the indene[1,2-b]quinoxalin-11-alkone thiosemicarbazone–cobalt(II) Schiff base complex (Che & Wang, 2006), (IIb), in which N3 (not N2) coordinates to the metal atom. Although many examples of cis–trans isomerism in Schiff base ligands have been observed, the existence of complexes with both isomers of a given ligand are rarely reported. The reason for the cis–trans conversion is still unknown.
The C17—N10 bond length in (I) [1.324 (4) Å] indicates a double bond and the compound exists in the imide form. The C16—S1 bond length [1.667 (4) Å] is intermediate between 1.82 Å for a C—S single bond and 1.56 Å for a C═ S double bond. The C16—N8, C16—N9 and N9—N10 bonds [1.336 (5), 1.360 (4) and 1.348 (4) Å] are indicative of some double-bond character. Except for the hydroxyethyl group, all other non-H atoms (C1–C13, N1–N7 and S1) within L are in the same plane (the mean deviation of the atoms from the least-squares plane is 0.0180 Å), with the ZnII ion located in the center, 0.181 (1) Å from the plane. The dihedral angle between the least-squares planes of the two ligands is 87.4 (2)°. Atom N5 at another potential coordinating position of the diazafluorenone ring does not participate in coordination, and so only a simple coordination compound forms rather than a coordination polymer. This is presumably due to steric hindrance. Thus, the complex is a simple structure rather than a dimeric structure and the metal center is six-coordinate rather than five-coordinate, which is diffrent from what was previously observed in bis(µ-11-thiosemicarbazonoindeno[1,2-b]quinoxaline-8-carboxyl- ato)bis[(dimethyl sulfoxide)zinc(II)] dimethyl sulfoxide trisolvate (Che et al., 2006).
The packing diagram of (I) (Fig. 2) shows that the intermolecular interactions are mainly mediated by hydrogen bonds between NH donors and N, O and S acceptors (Table 2), which lead to the formation of a three-dimensional supermolecular structure. There are also some hydrogen-bonding interactions between the disordered DMF molecules and the hydroxyethyl group, but these are difficult to evaluate with precision because of the disorder.