A new Co^II complex of diniconazole: synthesis, crystal structure and anti­fungal activity

A new Co^II complex of diniconazole, namely di­aqua­[(E)-(RS)-1-(2,4-di­chloro­phen­yl)-4,4-dimethyl-2-(1H-1,2,4-triazol-1-yl-κN⁴)pent-1-en-3-ol]cobalt(II) di­nitrate dihydrate, [Co(C₁₅H₁₇Cl₂N₃O)₃(H₂O)₂](NO₃)₂·2H₂O, was synthesized and characterized by elemental analysis, IR spectroscopy and single-crystal X-ray diffraction. Crystal structural analysis shows that the centrosymmetric Co^II cation is coordinated by four diniconazole ligands and two water mol­ecules, forming a six-coordinated octa­hedral structure. There are also two free nitrate counter-anions and two additional solvent water mol­ecules in the structure. Inter­molecular O—H...O hydrogen bonds link the complex cations into a one-dimensional chain. In addition, the anti­fungal activity of the complex against Botryosphaeria ribis, Gibberella nicotiancola, Botryosphaeria berengriana and Alternariasolani was studied. The results indicate that the complex shows a higher anti­fungal activity for Botryosphaeria ribis and Botryosphaeria berengriana than diniconazole, but a lower anti­fungal activity for Gibberella nicotiancola and Alternariasolani.

S1. Introduction

\ 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.

S2. Experimental

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.

S2.1. Synthesis and crystallization

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.

S2.2. Refinement

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 U_iso(H) = 1.5U_eq(C) for methyl and hy­droxy H atoms, and 1.2U_eq(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 U_iso(H) = 1.5U_eq(O).

S2.3. Anti­fungal activity

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).

S3. Results and discussion

In the crystal structure of complex (1) (Fig. 1), each molecule consists of one Co^II cation, four coordinated diniconazole ligands, two coordinated water molecules, two free nitrate counter-anions and two additional lattice water molecules. Each Co^II 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 Co^II 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 Co^II 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.

Computing details

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).

Figures

	Fig. 1. The coordination environment of the Co^II cation in (1), showing a partial atom-numbering scheme. H atoms have been omitted for clarity. Displacement ellipsoids are drawn at the 50% probability level. [Symmetry code: (i) -x+1, -y+2, -z+1.]
	Fig. 2. A view of the hydrogen bonding of complex (1). Dashed lines indicate hydrogen bonds. Selected H atoms have been omitted for clarity. The symmetry codes are as in Table 3.
	Fig. 3. The crystal packing of complex (1).

Diaqua[1-(2,4-dichlorophenyl)-4,4-dimethyl-2-(1H-1,2,4-triazol-1-yl-κN⁴)pent-1-en-3-ol]cobalt(II) dinitrate dihydrate

Crystal data

[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) Å^3	0.25 × 0.25 × 0.20 mm

Data collection

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

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.034	H-atom parameters constrained
wR(F^2) = 0.134	w = 1/[σ^2(Fo^2) + (0.0934P)^2 + 0.6388P] where P = (Fo^2 + 2Fc^2)/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

Special details

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 U_iso(H)=1.5Ueq(O).

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	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*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

Geometric parameters (Å, º)

Co1—O3W^i	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—N4^i	2.1393 (19)	C18—C24	1.327 (3)
Co1—N1^i	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
O3W^i—Co1—O3W	180.0	N4—C17—H17	125.0
O3W^i—Co1—N4	88.38 (7)	N6—C17—H17	125.0
O3W—Co1—N4	91.62 (7)	C24—C18—N6	118.52 (19)
O3W^i—Co1—N4^i	91.62 (7)	C24—C18—C19	126.3 (2)
O3W—Co1—N4^i	88.38 (7)	N6—C18—C19	115.14 (18)
N4—Co1—N4^i	180.0	O2—C19—C18	110.95 (18)
O3W^i—Co1—N1^i	88.41 (7)	O2—C19—C20	109.13 (18)
O3W—Co1—N1^i	91.59 (7)	C18—C19—C20	114.18 (19)
N4—Co1—N1^i	90.77 (7)	O2—C19—H19	107.4
N4^i—Co1—N1^i	89.23 (7)	C18—C19—H19	107.4
O3W^i—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)
N4^i—Co1—N1	90.77 (7)	C21—C20—C23	108.9 (2)
N1^i—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.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O5^i	0.84	1.95	2.764 (3)	163
O1—H1···O6^i	0.84	2.56	3.129 (4)	126
O1—H1···N7^i	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···O7W^i	0.84	2.00	2.814 (3)	163
O3W—H2W···O6^ii	0.84	2.62	3.020 (3)	111
O3W—H1W···O7W^ii	0.83	1.95	2.759 (2)	168
O7W—H3W···O1^iii	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.