Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229615016241/lf3016sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S2053229615016241/lf3016Isup2.hkl |
CCDC reference: 1421618
\ Heterocyclic ligands have attracted much interest as versatile ligands with a variety of coordination modes with transition metal centres (Galani et al., 2014; Vimal Kumar & Radhakrishnan, 2011; Coropceanu et al., 2014; Wang, Chen et al., 2012; Wang, Zhang et al., 2012). In particular, 1,2,4-triazole derivatives and their metal complexes have been studied extensively in recent years (Naik et al., 2011; Wang, Chen et al., 2012; Wang, Zhang et al., 2012; Wang et al., 2014; Liu, He et al., 2009; Liu, Lu & Yan, 2009), mainly because of their unique structures and their potential applications in optical (Manjunatha et al., 2013 ), electrical (Luo et al., 2013; Matesanz et al., 2004), and biological and antimicrobial areas (Tabatabaee et al., 2013; Xiong et al., 2014; Singh et al., 2012).
Diniconazole [systematic name: (E)-(RS)-1-(2,4-dichlorophenyl)-4,4-dimethyl-2-(1H-1,2,\ 4-triazol-1-yl)pent-1-en-3-ol, denoted L], as a broad-spectrum systemic triazole fungicide, was successfully developed by the Japanese Sumitomo Chemical Company in 1984, and has also been used as an effective plant growth regulator (Sumitomo, 1984). It inhibits demethylation of fungal ergosterol biosynthesis, resulting in the death of fungi, especially for ascomycetes and basidiomycetes, such as Powdery mildew, Rust, Smut fungus, Venturia, and so on (Zhao et al., 2008; Zhang et al., 2005). However, the extensive use and single-acting mechanism of diniconazole have led to a rapid selection of resistance strains. In addition, basic studies of the metal complexes of diniconazole are still rare (Nie et al., 2012; Gao et al., 2001). Given the limitations of the current diniconazole and the aim to possibly improve its properties and potential applications, in this present work, the title complex, [Co(L)4(H2O)2](NO3)2.2H2O, (1), has been synthesized from cobalt nitrate and diniconazole. We have determined the crystal structure of (1) and have compared the antifungal activities of coordination complex (1) with that of diniconazole. The microbial results show that the antifungal activities of the metal coordination compound were improved for Botryosphaeria ribis and Botryosphaeria berengriana compared to those of the conventional triazole fungicide diniconazole.
Diniconazole was acquired from commercial sources and was used after repeated recrystallizations. All other reagents were of reagent grade and were used as received. Elemental analysis was performed on a Vario EL III elemental analyzer. The IR spectrum was measured using a EQUINX 55 with a KBr presser bit.
Co(NO3)2.6H2O (0.2910 g, 1 mmol) in ethanol (5 ml) was added dropwise to a solution of diniconazole (0.6524 g, 2 mmol) in ethanol (10 ml) under stirring for 4 h at room temperature. The resulting solution was filtered and the filtrate was left undisturbed at room temperature. Red block-shaped crystals suitable for X-ray analysis were obtained by slow evaporation afetr 12 d.
Crystal data, data collection and structure refinement details are summarized in Table 1. H atoms bonded to C atoms and hydroxy O atoms were placed at calculated positions and refined using a riding-model approximation, with C—H = 0.95–1.00 Å and O—H = 0.84 Å, and with Uiso(H) = 1.5Ueq(C) for methyl and hydroxy H atoms, and 1.2Ueq(C) for all other H atoms. H atoms bonded to water O atoms were located in difference Fourier maps and treated as riding atoms, with O—H = 0.8252–0.8597 Å and Uiso(H) = 1.5Ueq(O).
The antifungal activities of complex (1) and the ligand diniconazole were evaluated by the mycelial growth rate method (Saetae & Suntornsuk, 2010; Devappa et al., 2012) against the selected phytopathogens Botryosphaeria ribis, (I), Gibberella nicotiancola, (II), Botryosphaeria berengriana, (III), and Alternariasolani, (IV), which were provided by Shaanxi Microbiology Institute, China. Sterilized potato dextrose agar (PDA) was cooled to 323 K and mixed with these target compounds to obtain four concentrations (0.5, 1, 2 and 4 µg l-1) immediately before pouring into the petri plates (7.5 cm in diameter). The prepared phytopathogens were inoculated in each well of 8 mm diameter (made with a borer), and then the fungi strains were cultured at 301 K for 72 h in the incubator. Petri plates inoculated with the fungal strains without compounds were also incubated as control. Each experiment was performed in triplicate. The diameter of the fungal colonies on PDA plates was measured after 72 h. The percentage inhibition of mycelial growth was calculated using the following formula:
% inhibition of mycelia growth = (dc - dt)/dc × 100,
where dc is average diameter of fungal colony in control set and dt is the average diameter fungal colony in experimental sets. The EC50 values were calculated through the EXCEL program (Liu, He et al., 2009; Liu, Lu & Yan, 2009).
In the crystal structure of complex (1) (Fig. 1), each molecule consists of one CoII cation, four coordinated diniconazole ligands, two coordinated water molecules, two free nitrate counter-anions and two additional lattice water molecules. Each CoII centre exhibits a six-coordinated octahedral geometry. The axial positions are occupied by atoms O3W and O3Wi from two coordinated water (see Table 2 for symmetry code). The equatorial positions are occupied by atoms N1, N1i, N4 and N4i atoms of four triazole rings . The Co—O/N bond lengths (Table 2) are all consistent with corresponding bond lengths found in the literature (Gökçe et al., 2015; Adach et al., 2015).
As shown in Table 3 and Fig. 2, there are two kinds of hydrogen bonds in the crystal structure. The hydroxy O2 atom acts as a hydrogen-bond donor to nitrate atoms O4, O6 and N7 and as a hydrogen-bond acceptor to water atom O7W of the same asymmetric unit. Hydroxy O1 atom also acts as a hydrogen-bond donor to nitrate atoms O5i, O6i and N7i (Table 3). The O3W atom takes part in three intermolecular hydrogen bonds, viz. O3W—H2W···O7Wi, O3W—H1W···O7Wiii and O3W—H2W···O6iii (Table 3). Meanwhile, the O7W atom of lattice water takes part in one intermolecular hydrogen bond, viz. O7W—H3W···O1ii (Table 3). The intermolecular hydrogen bonds contribute to the formation of a one-dimensional chain in the crystal structure. Furthermore, the one-dimensional chains are connected by van der Waals forces and electrostatic interactions, giving rise to the three-dimensional framework (Fig. 3).
According to the antifungal screening data (Table 4), metal complex (1) shows enhanced inhibitory effects on the selected plant pathogenic fungi than diniconazole against the two fungi Botryosphaeria ribis, (I), and Botryosphaeria berengriana, (III). Especially, the title complex has the best inhibitory activity for (III) with an EC50 value of 0.0031 mg l-1. And for the fungi (I), the EC50 value of complex (1) is 1.397 mg l-1. However, the inhibitory activities of complex (1) are lower than those of diniconazole for selected plant pathogenic fungi Gibberella nicotiancola, (II), and Alternariasolani, (IV), with EC50 values of 0.4438 and 0.4655 mg l-1, respectively. In general, the title complex has the higher selectivity of antifungal activities for the fungi (I) and (III) but lower selectivity for the fungi (II) and (IV).
In summary, we have synthesized a new CoII complex using diniconazole as a ligand and characterized it by elemental analysis, IR spectroscopy and single-crystal analysis techniques. The crystal structure analysis shows that CoII adopts an octahedral geometry, coordinated by two water O atoms and by four N atoms from diniconazole ligands. There are also two free nitrate anions and two lattice water molecules in the crystal molecule. The antifungal activities of complex (1) were enhanced for Botryosphaeria ribis and Botryosphaeria berengriana, but reduced for Gibberella nicotiancola and Alternariasolani compared to the activities of the parent diniconazole.
Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
[Co(C15H17Cl2N3O)3(H2O)2](NO3)2·2H2O | Z = 1 |
Mr = 1559.87 | F(000) = 809 |
Triclinic, P1 | Dx = 1.410 Mg m−3 |
a = 7.7531 (10) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 15.2639 (19) Å | Cell parameters from 7521 reflections |
c = 16.290 (2) Å | θ = 2.6–25.2° |
α = 100.775 (1)° | µ = 0.59 mm−1 |
β = 98.323 (1)° | T = 153 K |
γ = 99.464 (1)° | Block, red |
V = 1837.2 (4) Å3 | 0.25 × 0.25 × 0.20 mm |
Bruker APEXII CCD diffractometer | 5614 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.019 |
φ and ω scans | θmax = 25.0°, θmin = 1.3° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2000) | h = −9→9 |
Tmin = 0.841, Tmax = 0.922 | k = −18→15 |
11518 measured reflections | l = −19→19 |
6247 independent reflections |
Refinement on F2 | 0 restraints |
Least-squares matrix: full | Hydrogen site location: mixed |
R[F2 > 2σ(F2)] = 0.034 | H-atom parameters constrained |
wR(F2) = 0.134 | w = 1/[σ2(Fo2) + (0.0934P)2 + 0.6388P] where P = (Fo2 + 2Fc2)/3 |
S = 1.11 | (Δ/σ)max = 0.001 |
6247 reflections | Δρmax = 0.52 e Å−3 |
447 parameters | Δρmin = −0.42 e Å−3 |
[Co(C15H17Cl2N3O)3(H2O)2](NO3)2·2H2O | γ = 99.464 (1)° |
Mr = 1559.87 | V = 1837.2 (4) Å3 |
Triclinic, P1 | Z = 1 |
a = 7.7531 (10) Å | Mo Kα radiation |
b = 15.2639 (19) Å | µ = 0.59 mm−1 |
c = 16.290 (2) Å | T = 153 K |
α = 100.775 (1)° | 0.25 × 0.25 × 0.20 mm |
β = 98.323 (1)° |
Bruker APEXII CCD diffractometer | 6247 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2000) | 5614 reflections with I > 2σ(I) |
Tmin = 0.841, Tmax = 0.922 | Rint = 0.019 |
11518 measured reflections |
R[F2 > 2σ(F2)] = 0.034 | 0 restraints |
wR(F2) = 0.134 | H-atom parameters constrained |
S = 1.11 | Δρmax = 0.52 e Å−3 |
6247 reflections | Δρmin = −0.42 e Å−3 |
447 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. H atoms bonded to C and hydroxy O atoms were placed at calculated positions and refined using a riding model approximation. H atoms bonded to water O atoms were located in a difference Fourier maps and treated as riding atoms,with Uiso(H)=1.5Ueq(O). |
x | y | z | Uiso*/Ueq | ||
Co1 | 0.5000 | 1.0000 | 0.5000 | 0.00909 (14) | |
C1 | 0.6264 (4) | 0.9043 (2) | 0.65000 (17) | 0.0303 (7) | |
H1A | 0.7317 | 0.8962 | 0.6286 | 0.036* | |
C2 | 0.3811 (3) | 0.94304 (15) | 0.66178 (13) | 0.0118 (4) | |
H2 | 0.2759 | 0.9671 | 0.6537 | 0.014* | |
C3 | 0.3372 (3) | 0.88126 (16) | 0.79238 (14) | 0.0145 (5) | |
C4 | 0.1461 (3) | 0.83060 (16) | 0.76534 (14) | 0.0157 (5) | |
H4 | 0.0894 | 0.8366 | 0.8170 | 0.019* | |
C5 | 0.1242 (4) | 0.72775 (18) | 0.72694 (16) | 0.0270 (6) | |
C6 | 0.2166 (5) | 0.6835 (2) | 0.79392 (19) | 0.0434 (9) | |
H6A | 0.1887 | 0.6172 | 0.7740 | 0.065* | |
H6B | 0.1744 | 0.6999 | 0.8475 | 0.065* | |
H6C | 0.3455 | 0.7051 | 0.8029 | 0.065* | |
C7 | 0.2035 (4) | 0.7090 (2) | 0.64591 (17) | 0.0336 (7) | |
H7A | 0.1647 | 0.6446 | 0.6179 | 0.050* | |
H7B | 0.3336 | 0.7237 | 0.6607 | 0.050* | |
H7C | 0.1630 | 0.7466 | 0.6074 | 0.050* | |
C8 | −0.0745 (5) | 0.6873 (2) | 0.70692 (19) | 0.0421 (8) | |
H8A | −0.1334 | 0.7150 | 0.6639 | 0.063* | |
H8B | −0.1249 | 0.6994 | 0.7587 | 0.063* | |
H8C | −0.0929 | 0.6215 | 0.6853 | 0.063* | |
C9 | 0.4379 (3) | 0.90384 (16) | 0.86923 (14) | 0.0155 (5) | |
H9 | 0.5568 | 0.9338 | 0.8719 | 0.019* | |
C10 | 0.3917 (3) | 0.88912 (16) | 0.95151 (14) | 0.0147 (5) | |
C11 | 0.5142 (3) | 0.86083 (16) | 1.00818 (14) | 0.0148 (5) | |
C12 | 0.4865 (3) | 0.85147 (16) | 1.08831 (14) | 0.0172 (5) | |
H12 | 0.5719 | 0.8326 | 1.1256 | 0.021* | |
C13 | 0.3304 (3) | 0.87047 (16) | 1.11251 (14) | 0.0170 (5) | |
C14 | 0.2043 (3) | 0.89892 (17) | 1.05952 (15) | 0.0189 (5) | |
H14 | 0.0977 | 0.9112 | 1.0773 | 0.023* | |
C15 | 0.2372 (3) | 0.90899 (17) | 0.98010 (14) | 0.0163 (5) | |
H15 | 0.1529 | 0.9299 | 0.9440 | 0.020* | |
C16 | 0.3034 (3) | 0.79554 (17) | 0.40723 (15) | 0.0179 (5) | |
H16 | 0.1975 | 0.8016 | 0.4288 | 0.021* | |
C17 | 0.5638 (3) | 0.82775 (15) | 0.38400 (13) | 0.0110 (4) | |
H17 | 0.6806 | 0.8580 | 0.3830 | 0.013* | |
C18 | 0.5719 (3) | 0.67761 (15) | 0.29394 (14) | 0.0115 (4) | |
C19 | 0.7407 (3) | 0.65722 (16) | 0.34029 (14) | 0.0142 (5) | |
H19 | 0.7964 | 0.6221 | 0.2968 | 0.017* | |
C20 | 0.7090 (3) | 0.59912 (17) | 0.40727 (15) | 0.0206 (5) | |
C21 | 0.5761 (4) | 0.5113 (2) | 0.36356 (19) | 0.0341 (7) | |
H21A | 0.6119 | 0.4842 | 0.3108 | 0.051* | |
H21B | 0.4573 | 0.5250 | 0.3505 | 0.051* | |
H21C | 0.5739 | 0.4683 | 0.4014 | 0.051* | |
C22 | 0.6411 (4) | 0.6482 (2) | 0.48326 (16) | 0.0294 (6) | |
H22A | 0.5175 | 0.6532 | 0.4654 | 0.044* | |
H22B | 0.7148 | 0.7092 | 0.5048 | 0.044* | |
H22C | 0.6475 | 0.6136 | 0.5282 | 0.044* | |
C23 | 0.8880 (4) | 0.5751 (2) | 0.43833 (19) | 0.0328 (7) | |
H23A | 0.8741 | 0.5381 | 0.4809 | 0.049* | |
H23B | 0.9758 | 0.6311 | 0.4637 | 0.049* | |
H23C | 0.9285 | 0.5407 | 0.3902 | 0.049* | |
C24 | 0.4904 (3) | 0.63855 (16) | 0.21504 (14) | 0.0130 (5) | |
H24 | 0.3813 | 0.6545 | 0.1946 | 0.016* | |
C25 | 0.5596 (3) | 0.57148 (16) | 0.15680 (13) | 0.0130 (5) | |
C26 | 0.7277 (3) | 0.59408 (16) | 0.13553 (14) | 0.0153 (5) | |
H26 | 0.7959 | 0.6538 | 0.1571 | 0.018* | |
C27 | 0.7968 (3) | 0.53066 (17) | 0.08340 (14) | 0.0165 (5) | |
H27 | 0.9113 | 0.5466 | 0.0697 | 0.020* | |
C28 | 0.6960 (3) | 0.44438 (16) | 0.05196 (13) | 0.0138 (5) | |
C29 | 0.5258 (3) | 0.41947 (16) | 0.06892 (13) | 0.0141 (5) | |
H29 | 0.4565 | 0.3603 | 0.0457 | 0.017* | |
C30 | 0.4617 (3) | 0.48469 (16) | 0.12111 (13) | 0.0138 (5) | |
Cl1 | 0.70903 (7) | 0.83417 (4) | 0.97719 (4) | 0.02122 (17) | |
Cl2 | 0.29313 (9) | 0.85886 (5) | 1.21322 (4) | 0.03050 (19) | |
Cl3 | 0.24889 (7) | 0.45335 (4) | 0.14305 (4) | 0.02130 (16) | |
Cl4 | 0.78125 (8) | 0.36329 (4) | −0.01189 (3) | 0.01948 (16) | |
N1 | 0.5035 (3) | 0.94583 (14) | 0.61250 (11) | 0.0145 (4) | |
N2 | 0.5881 (3) | 0.87659 (19) | 0.71783 (15) | 0.0310 (6) | |
N3 | 0.4279 (3) | 0.90141 (14) | 0.72450 (12) | 0.0156 (4) | |
N4 | 0.4493 (2) | 0.86427 (13) | 0.42538 (11) | 0.0130 (4) | |
N5 | 0.3213 (3) | 0.72005 (14) | 0.35739 (13) | 0.0184 (4) | |
N6 | 0.4913 (2) | 0.74239 (13) | 0.34401 (11) | 0.0117 (4) | |
N7 | 0.9032 (3) | 0.90243 (14) | 0.26049 (12) | 0.0171 (4) | |
O1 | 0.0492 (2) | 0.87034 (11) | 0.70514 (10) | 0.0156 (3) | |
H1 | 0.0394 | 0.9226 | 0.7289 | 0.023* | |
O2 | 0.8654 (2) | 0.73935 (11) | 0.38016 (10) | 0.0148 (3) | |
H2A | 0.8859 | 0.7702 | 0.3437 | 0.022* | |
O3W | 0.22767 (19) | 0.99713 (11) | 0.49560 (10) | 0.0137 (3) | |
O4 | 0.8594 (3) | 0.81795 (12) | 0.23708 (11) | 0.0257 (4) | |
O5 | 0.9065 (2) | 0.95174 (12) | 0.20692 (11) | 0.0231 (4) | |
O6 | 0.9416 (2) | 0.93801 (12) | 0.33846 (10) | 0.0199 (4) | |
O7W | 0.9712 (2) | 0.86915 (11) | 0.53178 (10) | 0.0166 (4) | |
H1W | 0.1507 | 0.9546 | 0.4995 | 0.025* | |
H2W | 0.1575 | 1.0289 | 0.4784 | 0.025* | |
H3W | 0.9931 | 0.8539 | 0.5788 | 0.025* | |
H4W | 0.9314 | 0.8207 | 0.4927 | 0.025* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Co1 | 0.0110 (2) | 0.0103 (2) | 0.0069 (2) | 0.00484 (17) | 0.00184 (16) | 0.00155 (17) |
C1 | 0.0257 (14) | 0.052 (2) | 0.0273 (14) | 0.0248 (13) | 0.0130 (11) | 0.0241 (14) |
C2 | 0.0153 (11) | 0.0119 (11) | 0.0085 (10) | 0.0037 (9) | 0.0009 (8) | 0.0028 (8) |
C3 | 0.0208 (12) | 0.0116 (12) | 0.0134 (11) | 0.0048 (9) | 0.0051 (9) | 0.0059 (9) |
C4 | 0.0219 (12) | 0.0173 (13) | 0.0073 (10) | 0.0011 (10) | 0.0005 (9) | 0.0053 (9) |
C5 | 0.0481 (17) | 0.0155 (14) | 0.0136 (12) | 0.0021 (12) | −0.0056 (11) | 0.0058 (10) |
C6 | 0.080 (2) | 0.0177 (15) | 0.0255 (15) | 0.0061 (15) | −0.0149 (15) | 0.0095 (12) |
C7 | 0.060 (2) | 0.0175 (15) | 0.0210 (13) | 0.0156 (14) | −0.0017 (13) | −0.0011 (11) |
C8 | 0.060 (2) | 0.0228 (16) | 0.0291 (15) | −0.0194 (14) | −0.0093 (14) | 0.0071 (13) |
C9 | 0.0175 (11) | 0.0141 (12) | 0.0155 (11) | 0.0023 (9) | 0.0020 (9) | 0.0060 (9) |
C10 | 0.0186 (11) | 0.0107 (12) | 0.0112 (11) | −0.0009 (9) | −0.0024 (9) | 0.0004 (9) |
C11 | 0.0157 (11) | 0.0116 (12) | 0.0142 (11) | −0.0002 (9) | −0.0010 (9) | 0.0008 (9) |
C12 | 0.0234 (12) | 0.0129 (12) | 0.0118 (11) | 0.0027 (10) | −0.0046 (9) | 0.0010 (9) |
C13 | 0.0263 (12) | 0.0145 (12) | 0.0083 (10) | 0.0020 (10) | 0.0004 (9) | 0.0015 (9) |
C14 | 0.0218 (12) | 0.0184 (13) | 0.0138 (11) | 0.0030 (10) | 0.0011 (9) | −0.0006 (10) |
C15 | 0.0193 (11) | 0.0154 (12) | 0.0112 (11) | 0.0019 (9) | −0.0039 (9) | 0.0018 (9) |
C16 | 0.0133 (11) | 0.0185 (13) | 0.0199 (12) | 0.0028 (9) | 0.0044 (9) | −0.0015 (10) |
C17 | 0.0135 (10) | 0.0112 (11) | 0.0091 (10) | 0.0039 (9) | 0.0026 (8) | 0.0028 (9) |
C18 | 0.0139 (10) | 0.0096 (11) | 0.0123 (10) | 0.0044 (9) | 0.0030 (9) | 0.0031 (9) |
C19 | 0.0154 (11) | 0.0116 (12) | 0.0130 (11) | 0.0045 (9) | −0.0024 (9) | −0.0017 (9) |
C20 | 0.0253 (13) | 0.0164 (13) | 0.0191 (12) | 0.0037 (10) | −0.0041 (10) | 0.0073 (10) |
C21 | 0.0457 (17) | 0.0191 (15) | 0.0331 (15) | −0.0037 (13) | −0.0060 (13) | 0.0135 (12) |
C22 | 0.0388 (15) | 0.0316 (16) | 0.0194 (13) | 0.0028 (13) | 0.0046 (11) | 0.0137 (12) |
C23 | 0.0386 (16) | 0.0256 (16) | 0.0326 (15) | 0.0110 (13) | −0.0101 (12) | 0.0112 (12) |
C24 | 0.0141 (10) | 0.0107 (11) | 0.0140 (11) | 0.0028 (9) | 0.0013 (9) | 0.0025 (9) |
C25 | 0.0167 (11) | 0.0139 (12) | 0.0080 (10) | 0.0050 (9) | −0.0004 (8) | 0.0019 (9) |
C26 | 0.0195 (12) | 0.0118 (12) | 0.0113 (11) | 0.0003 (9) | 0.0005 (9) | −0.0015 (9) |
C27 | 0.0157 (11) | 0.0201 (13) | 0.0139 (11) | 0.0036 (10) | 0.0035 (9) | 0.0036 (10) |
C28 | 0.0209 (11) | 0.0138 (12) | 0.0084 (10) | 0.0081 (9) | 0.0029 (9) | 0.0023 (9) |
C29 | 0.0198 (11) | 0.0095 (12) | 0.0112 (11) | 0.0011 (9) | −0.0009 (9) | 0.0022 (9) |
C30 | 0.0170 (11) | 0.0155 (12) | 0.0090 (10) | 0.0028 (9) | 0.0007 (8) | 0.0042 (9) |
Cl1 | 0.0187 (3) | 0.0262 (4) | 0.0202 (3) | 0.0073 (2) | 0.0021 (2) | 0.0072 (2) |
Cl2 | 0.0397 (4) | 0.0466 (5) | 0.0126 (3) | 0.0198 (3) | 0.0076 (3) | 0.0126 (3) |
Cl3 | 0.0182 (3) | 0.0210 (3) | 0.0227 (3) | −0.0009 (2) | 0.0063 (2) | 0.0021 (2) |
Cl4 | 0.0265 (3) | 0.0157 (3) | 0.0162 (3) | 0.0079 (2) | 0.0054 (2) | −0.0012 (2) |
N1 | 0.0174 (9) | 0.0175 (11) | 0.0115 (9) | 0.0078 (8) | 0.0039 (7) | 0.0059 (8) |
N2 | 0.0264 (12) | 0.0546 (17) | 0.0294 (12) | 0.0266 (11) | 0.0147 (10) | 0.0285 (12) |
N3 | 0.0173 (9) | 0.0195 (11) | 0.0133 (9) | 0.0087 (8) | 0.0039 (8) | 0.0065 (8) |
N4 | 0.0145 (9) | 0.0136 (10) | 0.0109 (9) | 0.0051 (8) | 0.0015 (7) | 0.0010 (8) |
N5 | 0.0146 (10) | 0.0180 (11) | 0.0206 (10) | 0.0021 (8) | 0.0050 (8) | −0.0012 (8) |
N6 | 0.0121 (9) | 0.0116 (10) | 0.0109 (9) | 0.0028 (7) | 0.0015 (7) | 0.0010 (7) |
N7 | 0.0170 (10) | 0.0159 (11) | 0.0183 (10) | 0.0040 (8) | 0.0038 (8) | 0.0020 (8) |
O1 | 0.0188 (8) | 0.0142 (9) | 0.0131 (8) | 0.0037 (7) | 0.0001 (6) | 0.0031 (7) |
O2 | 0.0152 (8) | 0.0132 (9) | 0.0134 (8) | 0.0006 (6) | −0.0006 (6) | 0.0009 (6) |
O3W | 0.0122 (7) | 0.0157 (9) | 0.0154 (8) | 0.0055 (6) | 0.0026 (6) | 0.0062 (7) |
O4 | 0.0397 (11) | 0.0114 (10) | 0.0229 (9) | −0.0001 (8) | 0.0071 (8) | −0.0004 (7) |
O5 | 0.0354 (10) | 0.0186 (10) | 0.0165 (8) | 0.0057 (8) | 0.0043 (7) | 0.0064 (7) |
O6 | 0.0256 (9) | 0.0210 (10) | 0.0107 (8) | 0.0034 (7) | 0.0007 (7) | 0.0006 (7) |
O7W | 0.0211 (8) | 0.0137 (9) | 0.0134 (8) | 0.0032 (7) | −0.0007 (6) | 0.0018 (7) |
Co1—O3Wi | 2.0951 (15) | C17—N4 | 1.323 (3) |
Co1—O3W | 2.0952 (15) | C17—N6 | 1.332 (3) |
Co1—N4 | 2.1392 (19) | C17—H17 | 0.9500 |
Co1—N4i | 2.1393 (19) | C18—C24 | 1.327 (3) |
Co1—N1i | 2.1454 (18) | C18—N6 | 1.443 (3) |
Co1—N1 | 2.1454 (18) | C18—C19 | 1.521 (3) |
C1—N2 | 1.310 (3) | C19—O2 | 1.430 (3) |
C1—N1 | 1.363 (3) | C19—C20 | 1.551 (3) |
C1—H1A | 0.9500 | C19—H19 | 1.0000 |
C2—N1 | 1.329 (3) | C20—C22 | 1.531 (4) |
C2—N3 | 1.338 (3) | C20—C21 | 1.531 (4) |
C2—H2 | 0.9500 | C20—C23 | 1.533 (4) |
C3—C9 | 1.328 (3) | C21—H21A | 0.9800 |
C3—N3 | 1.447 (3) | C21—H21B | 0.9800 |
C3—C4 | 1.515 (3) | C21—H21C | 0.9800 |
C4—O1 | 1.433 (3) | C22—H22A | 0.9800 |
C4—C5 | 1.549 (4) | C22—H22B | 0.9800 |
C4—H4 | 1.0000 | C22—H22C | 0.9800 |
C5—C8 | 1.526 (4) | C23—H23A | 0.9800 |
C5—C7 | 1.534 (4) | C23—H23B | 0.9800 |
C5—C6 | 1.539 (3) | C23—H23C | 0.9800 |
C6—H6A | 0.9800 | C24—C25 | 1.483 (3) |
C6—H6B | 0.9800 | C24—H24 | 0.9500 |
C6—H6C | 0.9800 | C25—C30 | 1.387 (3) |
C7—H7A | 0.9800 | C25—C26 | 1.402 (3) |
C7—H7B | 0.9800 | C26—C27 | 1.393 (3) |
C7—H7C | 0.9800 | C26—H26 | 0.9500 |
C8—H8A | 0.9800 | C27—C28 | 1.379 (4) |
C8—H8B | 0.9800 | C27—H27 | 0.9500 |
C8—H8C | 0.9800 | C28—C29 | 1.393 (3) |
C9—C10 | 1.483 (3) | C28—Cl4 | 1.743 (2) |
C9—H9 | 0.9500 | C29—C30 | 1.389 (3) |
C10—C15 | 1.404 (3) | C29—H29 | 0.9500 |
C10—C11 | 1.404 (3) | C30—Cl3 | 1.748 (2) |
C11—C12 | 1.383 (3) | N2—N3 | 1.370 (3) |
C11—Cl1 | 1.746 (2) | N5—N6 | 1.365 (3) |
C12—C13 | 1.384 (4) | N7—O4 | 1.248 (3) |
C12—H12 | 0.9500 | N7—O5 | 1.255 (3) |
C13—C14 | 1.387 (3) | N7—O6 | 1.255 (3) |
C13—Cl2 | 1.742 (2) | O1—H1 | 0.8400 |
C14—C15 | 1.385 (3) | O2—H2A | 0.8400 |
C14—H14 | 0.9500 | O3W—H1W | 0.8252 |
C15—H15 | 0.9500 | O3W—H2W | 0.8390 |
C16—N5 | 1.320 (3) | O7W—H3W | 0.8438 |
C16—N4 | 1.365 (3) | O7W—H4W | 0.8597 |
C16—H16 | 0.9500 | ||
O3Wi—Co1—O3W | 180.0 | N4—C17—H17 | 125.0 |
O3Wi—Co1—N4 | 88.38 (7) | N6—C17—H17 | 125.0 |
O3W—Co1—N4 | 91.62 (7) | C24—C18—N6 | 118.52 (19) |
O3Wi—Co1—N4i | 91.62 (7) | C24—C18—C19 | 126.3 (2) |
O3W—Co1—N4i | 88.38 (7) | N6—C18—C19 | 115.14 (18) |
N4—Co1—N4i | 180.0 | O2—C19—C18 | 110.95 (18) |
O3Wi—Co1—N1i | 88.41 (7) | O2—C19—C20 | 109.13 (18) |
O3W—Co1—N1i | 91.59 (7) | C18—C19—C20 | 114.18 (19) |
N4—Co1—N1i | 90.77 (7) | O2—C19—H19 | 107.4 |
N4i—Co1—N1i | 89.23 (7) | C18—C19—H19 | 107.4 |
O3Wi—Co1—N1 | 91.59 (7) | C20—C19—H19 | 107.4 |
O3W—Co1—N1 | 88.41 (7) | C22—C20—C21 | 109.7 (2) |
N4—Co1—N1 | 89.23 (7) | C22—C20—C23 | 109.4 (2) |
N4i—Co1—N1 | 90.77 (7) | C21—C20—C23 | 108.9 (2) |
N1i—Co1—N1 | 180.0 | C22—C20—C19 | 113.5 (2) |
N2—C1—N1 | 114.8 (2) | C21—C20—C19 | 108.5 (2) |
N2—C1—H1A | 122.6 | C23—C20—C19 | 106.7 (2) |
N1—C1—H1A | 122.6 | C20—C21—H21A | 109.5 |
N1—C2—N3 | 110.00 (19) | C20—C21—H21B | 109.5 |
N1—C2—H2 | 125.0 | H21A—C21—H21B | 109.5 |
N3—C2—H2 | 125.0 | C20—C21—H21C | 109.5 |
C9—C3—N3 | 115.0 (2) | H21A—C21—H21C | 109.5 |
C9—C3—C4 | 128.9 (2) | H21B—C21—H21C | 109.5 |
N3—C3—C4 | 115.84 (19) | C20—C22—H22A | 109.5 |
O1—C4—C3 | 111.01 (18) | C20—C22—H22B | 109.5 |
O1—C4—C5 | 108.31 (18) | H22A—C22—H22B | 109.5 |
C3—C4—C5 | 114.5 (2) | C20—C22—H22C | 109.5 |
O1—C4—H4 | 107.6 | H22A—C22—H22C | 109.5 |
C3—C4—H4 | 107.6 | H22B—C22—H22C | 109.5 |
C5—C4—H4 | 107.6 | C20—C23—H23A | 109.5 |
C8—C5—C7 | 109.6 (2) | C20—C23—H23B | 109.5 |
C8—C5—C6 | 109.4 (2) | H23A—C23—H23B | 109.5 |
C7—C5—C6 | 109.1 (3) | C20—C23—H23C | 109.5 |
C8—C5—C4 | 107.3 (2) | H23A—C23—H23C | 109.5 |
C7—C5—C4 | 112.9 (2) | H23B—C23—H23C | 109.5 |
C6—C5—C4 | 108.5 (2) | C18—C24—C25 | 123.9 (2) |
C5—C6—H6A | 109.5 | C18—C24—H24 | 118.0 |
C5—C6—H6B | 109.5 | C25—C24—H24 | 118.0 |
H6A—C6—H6B | 109.5 | C30—C25—C26 | 117.4 (2) |
C5—C6—H6C | 109.5 | C30—C25—C24 | 121.8 (2) |
H6A—C6—H6C | 109.5 | C26—C25—C24 | 120.8 (2) |
H6B—C6—H6C | 109.5 | C27—C26—C25 | 121.3 (2) |
C5—C7—H7A | 109.5 | C27—C26—H26 | 119.3 |
C5—C7—H7B | 109.5 | C25—C26—H26 | 119.3 |
H7A—C7—H7B | 109.5 | C28—C27—C26 | 118.8 (2) |
C5—C7—H7C | 109.5 | C28—C27—H27 | 120.6 |
H7A—C7—H7C | 109.5 | C26—C27—H27 | 120.6 |
H7B—C7—H7C | 109.5 | C27—C28—C29 | 122.1 (2) |
C5—C8—H8A | 109.5 | C27—C28—Cl4 | 119.58 (18) |
C5—C8—H8B | 109.5 | C29—C28—Cl4 | 118.30 (18) |
H8A—C8—H8B | 109.5 | C30—C29—C28 | 117.3 (2) |
C5—C8—H8C | 109.5 | C30—C29—H29 | 121.3 |
H8A—C8—H8C | 109.5 | C28—C29—H29 | 121.3 |
H8B—C8—H8C | 109.5 | C25—C30—C29 | 123.0 (2) |
C3—C9—C10 | 129.4 (2) | C25—C30—Cl3 | 119.58 (18) |
C3—C9—H9 | 115.3 | C29—C30—Cl3 | 117.40 (18) |
C10—C9—H9 | 115.3 | C2—N1—C1 | 102.96 (18) |
C15—C10—C11 | 116.8 (2) | C2—N1—Co1 | 127.58 (15) |
C15—C10—C9 | 123.8 (2) | C1—N1—Co1 | 129.45 (16) |
C11—C10—C9 | 119.1 (2) | C1—N2—N3 | 102.70 (19) |
C12—C11—C10 | 122.7 (2) | C2—N3—N2 | 109.57 (18) |
C12—C11—Cl1 | 117.65 (17) | C2—N3—C3 | 130.27 (19) |
C10—C11—Cl1 | 119.65 (18) | N2—N3—C3 | 120.17 (18) |
C11—C12—C13 | 117.9 (2) | C17—N4—C16 | 102.98 (19) |
C11—C12—H12 | 121.0 | C17—N4—Co1 | 124.96 (16) |
C13—C12—H12 | 121.0 | C16—N4—Co1 | 132.05 (15) |
C12—C13—C14 | 122.1 (2) | C16—N5—N6 | 101.95 (19) |
C12—C13—Cl2 | 118.53 (18) | C17—N6—N5 | 110.42 (18) |
C14—C13—Cl2 | 119.36 (19) | C17—N6—C18 | 128.02 (18) |
C15—C14—C13 | 118.6 (2) | N5—N6—C18 | 121.55 (18) |
C15—C14—H14 | 120.7 | O4—N7—O5 | 120.6 (2) |
C13—C14—H14 | 120.7 | O4—N7—O6 | 119.4 (2) |
C14—C15—C10 | 121.8 (2) | O5—N7—O6 | 120.0 (2) |
C14—C15—H15 | 119.1 | C4—O1—H1 | 109.5 |
C10—C15—H15 | 119.1 | C19—O2—H2A | 109.5 |
N5—C16—N4 | 114.7 (2) | Co1—O3W—H1W | 127.8 |
N5—C16—H16 | 122.7 | Co1—O3W—H2W | 134.2 |
N4—C16—H16 | 122.7 | H1W—O3W—H2W | 96.5 |
N4—C17—N6 | 110.0 (2) | H3W—O7W—H4W | 108.6 |
C9—C3—C4—O1 | 139.1 (2) | C18—C24—C25—C26 | −58.3 (3) |
N3—C3—C4—O1 | −46.6 (3) | C30—C25—C26—C27 | −2.6 (3) |
C9—C3—C4—C5 | −97.9 (3) | C24—C25—C26—C27 | 177.6 (2) |
N3—C3—C4—C5 | 76.4 (2) | C25—C26—C27—C28 | 0.5 (3) |
O1—C4—C5—C8 | −57.9 (2) | C26—C27—C28—C29 | 1.7 (3) |
C3—C4—C5—C8 | 177.7 (2) | C26—C27—C28—Cl4 | −178.88 (16) |
O1—C4—C5—C7 | 63.1 (3) | C27—C28—C29—C30 | −1.6 (3) |
C3—C4—C5—C7 | −61.4 (3) | Cl4—C28—C29—C30 | 178.95 (16) |
O1—C4—C5—C6 | −175.9 (2) | C26—C25—C30—C29 | 2.7 (3) |
C3—C4—C5—C6 | 59.6 (3) | C24—C25—C30—C29 | −177.5 (2) |
N3—C3—C9—C10 | −176.7 (2) | C26—C25—C30—Cl3 | −178.41 (17) |
C4—C3—C9—C10 | −2.4 (4) | C24—C25—C30—Cl3 | 1.4 (3) |
C3—C9—C10—C15 | −47.2 (4) | C28—C29—C30—C25 | −0.6 (3) |
C3—C9—C10—C11 | 138.3 (3) | C28—C29—C30—Cl3 | −179.58 (16) |
C15—C10—C11—C12 | 0.7 (3) | N3—C2—N1—C1 | −0.6 (3) |
C9—C10—C11—C12 | 175.6 (2) | N3—C2—N1—Co1 | 178.01 (16) |
C15—C10—C11—Cl1 | 179.61 (18) | N2—C1—N1—C2 | 0.1 (3) |
C9—C10—C11—Cl1 | −5.5 (3) | N2—C1—N1—Co1 | −178.5 (2) |
C10—C11—C12—C13 | 0.4 (4) | N1—C1—N2—N3 | 0.4 (4) |
Cl1—C11—C12—C13 | −178.53 (19) | N1—C2—N3—N2 | 0.9 (3) |
C11—C12—C13—C14 | −0.6 (4) | N1—C2—N3—C3 | −179.0 (2) |
C11—C12—C13—Cl2 | 179.91 (18) | C1—N2—N3—C2 | −0.8 (3) |
C12—C13—C14—C15 | −0.4 (4) | C1—N2—N3—C3 | 179.2 (2) |
Cl2—C13—C14—C15 | 179.13 (19) | C9—C3—N3—C2 | −131.9 (3) |
C13—C14—C15—C10 | 1.6 (4) | C4—C3—N3—C2 | 53.0 (3) |
C11—C10—C15—C14 | −1.7 (4) | C9—C3—N3—N2 | 48.2 (3) |
C9—C10—C15—C14 | −176.3 (2) | C4—C3—N3—N2 | −127.0 (2) |
C24—C18—C19—O2 | 131.9 (2) | N6—C17—N4—C16 | −0.3 (2) |
N6—C18—C19—O2 | −51.6 (2) | N6—C17—N4—Co1 | 179.87 (13) |
C24—C18—C19—C20 | −104.3 (3) | N5—C16—N4—C17 | −0.3 (3) |
N6—C18—C19—C20 | 72.2 (3) | N5—C16—N4—Co1 | 179.47 (15) |
O2—C19—C20—C22 | 58.0 (3) | N4—C16—N5—N6 | 0.8 (3) |
C18—C19—C20—C22 | −66.8 (3) | N4—C17—N6—N5 | 0.8 (2) |
O2—C19—C20—C21 | −179.7 (2) | N4—C17—N6—C18 | −177.99 (19) |
C18—C19—C20—C21 | 55.5 (3) | C16—N5—N6—C17 | −0.9 (2) |
O2—C19—C20—C23 | −62.6 (2) | C16—N5—N6—C18 | 177.96 (19) |
C18—C19—C20—C23 | 172.7 (2) | C24—C18—N6—C17 | −125.4 (2) |
N6—C18—C24—C25 | 179.6 (2) | C19—C18—N6—C17 | 57.8 (3) |
C19—C18—C24—C25 | −4.1 (4) | C24—C18—N6—N5 | 55.9 (3) |
C18—C24—C25—C30 | 121.9 (3) | C19—C18—N6—N5 | −120.9 (2) |
Symmetry code: (i) −x+1, −y+2, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···O5i | 0.84 | 1.95 | 2.764 (3) | 163 |
O1—H1···O6i | 0.84 | 2.56 | 3.129 (4) | 126 |
O1—H1···N7i | 0.84 | 2.60 | 3.357 (4) | 150 |
O2—H2A···O4 | 0.84 | 2.00 | 2.812 (3) | 161 |
O2—H2A···O6 | 0.84 | 2.55 | 3.210 (4) | 137 |
O2—H2A···N7 | 0.84 | 2.63 | 3.438 (3) | 162 |
O3W—H2W···O7Wi | 0.84 | 2.00 | 2.814 (3) | 163 |
O3W—H2W···O6ii | 0.84 | 2.62 | 3.020 (3) | 111 |
O3W—H1W···O7Wii | 0.83 | 1.95 | 2.759 (2) | 168 |
O7W—H3W···O1iii | 0.84 | 2.00 | 2.797 (4) | 157 |
O7W—H4W···O2 | 0.86 | 1.96 | 2.783 (3) | 161 |
Symmetry codes: (i) −x+1, −y+2, −z+1; (ii) x−1, y, z; (iii) x+1, y, z. |
Experimental details
Crystal data | |
Chemical formula | [Co(C15H17Cl2N3O)3(H2O)2](NO3)2·2H2O |
Mr | 1559.87 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 153 |
a, b, c (Å) | 7.7531 (10), 15.2639 (19), 16.290 (2) |
α, β, γ (°) | 100.775 (1), 98.323 (1), 99.464 (1) |
V (Å3) | 1837.2 (4) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 0.59 |
Crystal size (mm) | 0.25 × 0.25 × 0.20 |
Data collection | |
Diffractometer | Bruker APEXII CCD diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2000) |
Tmin, Tmax | 0.841, 0.922 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 11518, 6247, 5614 |
Rint | 0.019 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.034, 0.134, 1.11 |
No. of reflections | 6247 |
No. of parameters | 447 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.52, −0.42 |
Computer programs: APEX2 (Bruker, 2008), SAINT (Bruker, 2008), SHELXS97 (Sheldrick, 2008), SHELXL2014 (Sheldrick, 2015), SHELXTL (Sheldrick, 2008).
Co1—O3W | 2.0952 (15) | Co1—N1i | 2.1454 (18) |
Co1—N4 | 2.1392 (19) | ||
O3Wi—Co1—O3W | 180.0 | O3W—Co1—N1i | 91.59 (7) |
O3Wi—Co1—N4 | 88.38 (7) | N4—Co1—N1i | 90.77 (7) |
O3W—Co1—N4 | 91.62 (7) | N4—Co1—N1 | 89.23 (7) |
N4—Co1—N4i | 180.0 | N1i—Co1—N1 | 180.0 |
O3Wi—Co1—N1i | 88.41 (7) |
Symmetry code: (i) −x+1, −y+2, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···O5i | 0.840 | 1.951 | 2.764 (3) | 162.86 |
O1—H1···O6i | 0.840 | 2.563 | 3.129 (4) | 125.78 |
O1—H1···N7i | 0.840 | 2.602 | 3.357 (4) | 150.23 |
O2—H2A···O4 | 0.840 | 2.003 | 2.812 (3) | 161.33 |
O2—H2A···O6 | 0.840 | 2.547 | 3.210 (4) | 136.61 |
O2—H2A···N7 | 0.840 | 2.632 | 3.438 (3) | 161.70 |
O3W—H2W···O7Wi | 0.839 | 2.000 | 2.814 (3) | 163.17 |
O3W—H2W···O6ii | 0.839 | 2.622 | 3.020 (3) | 110.54 |
O3W—H1W···O7Wii | 0.825 | 1.946 | 2.759 (2) | 168.18 |
O7W—H3W···O1iii | 0.844 | 2.000 | 2.797 (4) | 157.33 |
O7W—H4W···O2 | 0.860 | 1.958 | 2.783 (3) | 160.61 |
Symmetry codes: (i) −x+1, −y+2, −z+1; (ii) x−1, y, z; (iii) x+1, y, z. |
Compound | Fungus | Drug concentration–effect curves | R2 | EC50 (mg l-1) |
Complex (1) | (I) | Y = 0.3927x + 5.0179 | 0.9415 | 1.397 |
(II) | Y = 0.3231x + 5.1758 | 0.9610 | 0.4438 | |
(III) | Y = 0.3121x + 5.8412 | 0.8811 | 0.0031 | |
(IV) | Y = 0.7125x + 5.374 | 0.9677 | 0.4655 | |
L | (I) | Y = 0.4786x + 4.5595 | 0.9966 | 2.717 |
(II) | Y = 0.2614x + 5.0863 | 0.9211 | 0.153 | |
(III) | Y = 0.4828x + 5.4304 | 0.9658 | 0.420 | |
(IV) | Y = 0.7125x + 5.374 | 0.9519 | 0.362 |
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