A compressed octa­hedral cobalt(II) complex in the crystal structure of di­aqua­[6,6′-sulfanediylbis(2,2′-bi­pyridine)]cobalt(II) dinitrate

Li, G.-L.; Sato, O.

doi:10.1107/S2056989017008428

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Volume 73| Part 7| July 2017| Pages 993-995

https://doi.org/10.1107/S2056989017008428

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A compressed octahedral cobalt(II) complex in the crystal structure of diaqua[6,6′-sulfanediylbis(2,2′-bipyridine)]cobalt(II) dinitrate

Guo-Ling Li ^a and Osamu Sato ^a ^*

^aInstitute for Materials Chemistry and Engineering, Kyushu University, 744 Motoka, Nishi-ku, Fukuoka 819-0395, Japan
^*Correspondence e-mail: sato@cm.kyushu-u.ac.jp

Edited by M. Weil, Vienna University of Technology, Austria (Received 24 May 2017; accepted 7 June 2017; online 13 June 2017)

The asymmetric unit of the title salt, [Co(C₂₀H₁₄N₄S)(H₂O)₂](NO₃)₂, comprises a [Co(C₂₀H₁₄N₄S)(H₂O)₂]²⁺ cation and two NO₃⁻ anions. In the complex, [Co(C₂₀H₁₄N₄S)(H₂O)₂]²⁺ cation, the tetradentate 6,6′-sulfanediylbis(2,2′-bipyridine) ligand coordinates to the Co^II cation in the equatorial positions, while two water molecules occupy the axial positions, forming a compressed octahedral CoN₄O₂ coordination sphere. The NO₃⁻ anions are linked to the [Co(C₂₀H₁₄N₄S)(H₂O)₂]²⁺ cations via O—H⋯O hydrogen bonds, yielding a layered arrangement parallel to (001).

Keywords: crystal structure; cobalt complex; 2,2′-bipyridine derivative; compressed octahedral geometry; hydrogen bond.

CCDC reference: 1554624

1. Chemical context

The control of the molecular structure of coordination compounds is an important task in crystal engineering. It is well known that organic ligands play a significant role in determining the crystal structure of coordination complexes. For example, bidentate 2,2′-bipyridine or its derivatives are common ligands that can be employed to assemble functional compounds (Zhang et al., 2014 ; Kamdar et al., 2016 ; Pal et al., 2014 ). Linking two 2,2′-bipyridine units through a suitable atom leads to a tetradentate ligand (Knight et al., 2010 ) and, more importantly, the distance of the two 2,2′-bipyridine moieties can then be controlled by the type and size of the bridging atom. As a consequence, the coordination geometry of the metal cation can be affected.

Recently, we obtained the title salt, [Co(C₂₀H₁₄N₄S)(H₂O)₂](NO₃)₂, using a tetradentate ligand in which two 2,2′-bipyridine moieties are linked by a sulfur atom. Herein, we report the crystal structure of this cobalt complex.

2. Structural commentary

The asymmetric unit of the title salt (Fig. 1) is composed of a [Co(C₂₀H₁₄N₄S)(H₂O)₂]²⁺ cation and two NO₃⁻ anions. The cobalt(II) atom of the complex [Co(C₂₀H₁₄N₄S)(H₂O)₂]²⁺ cation features a compressed octahedral CoN₄O₂ coordination sphere with the N atoms of the tetradentate ligand in equatorial positions and two water molecules located at the trans axial sites. The corresponding Co—O bond lengths are 2.0444 (18) Å and 2.0821 (17) Å, which are obviously shorter than the equatorial Co—N bond lengths [2.1213 (18) −2.1574 (18) Å]. These coordination bond lengths indicate that the Co^II cation is in a high-spin state at 123 K, comparable with other high-spin Co^II complexes (Li et al., 2016 ; Knight et al., 2010; Suckert et al., 2017 ; Zhong et al., 2008 ; Hathwar et al., 2017 ). The O—Co—O angle is almost linear at 178.59 (7)°. The four equatorial N atoms and the Co^II cation are approximately coplanar, with the largest deviation from the least-squares plane being 0.039 Å for N3.

Figure 1
The structures of the molecular entities in the structure of the title salt. Displacement ellipsoids are drawn at the 50% probability level.

In a similar Co^II complex with the 6,6′-sulfanediylbis(2,2′-bipyridine) ligand replaced by the tetradentate ligand bis(2,2′-bipyrid-6′-yl)ketone (Knight et al., 2010), the Co^II cation is slightly convex (0.098 Å) from the plane formed through four coordination N atoms. The Co—O bond lengths of the two axial sites are significantly different at 2.075 (4) Å for that in the convex site and 2.118 (4) Å for that in the concave site. The corresponding O—Co—O bond angle deviates more distinctly from linearity with a value of 172.46 (17)°. The structural differences between the title complex and the similar reported compound are ascribed to the bridging atom between the two 2,2′-bipyridine moieties, i.e. an S atom in the title complex versus a C atom of a keto group in the related compound. The bridging bonds [C—S: 1.761 (2) and 1.764 (2) Å] of the title complex are longer than those [C—C: 1.496 (10) and 1.500 (10) Å] in the related complex.

3. Supramolecular features

The coordinating water molecules act as proton donors, forming O—H⋯O hydrogen bonds with the NO₃⁻ anions and leading to an extended layer structure parallel to (001) for the title complex (Fig. 2). For these hydrogen bonds, the O⋯O distances are in the range of 2.688 (2)–2.789 (2) Å, indicating they are of medium strength (Table 1), and are comparable with other hydrogen bonds formed between coordinating water molecules and NO₃⁻ anions (Kurdziel et al., 2000 ; Kunz et al., 2007 ; Wang et al., 2012 ). There are no intermolecular π–π interactions in the molecular packing of the title complex.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2WB⋯O7ⁱ	0.80 (2)	2.02 (2)	2.766 (3)	155 (2)
O2—H2WA⋯O6	0.84 (2)	1.88 (2)	2.698 (2)	168 (3)
O1—H1WB⋯O5ⁱⁱ	0.83 (2)	1.96 (2)	2.789 (2)	179 (3)
O1—H1WA⋯O3	0.80 (2)	1.89 (2)	2.688 (2)	174 (3)
Symmetry codes: (i) $[-x, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Figure 2
The layer structure in the title salt formed through hydrogen bonds (green dotted lines) between complex cations and nitrate anions.

4. Synthesis and crystallization

The ligand 6,6′-sulfanediylbis(2,2′-bipyridine) was synthesized by a method analogous to that for the preparation of 2,2′-sulfanediylbis(1,10-phenanthroline) (Krapcho et al., 2007 ). The title complex was obtained as follows: An ethanolic solution (10 ml) of Co^II(NO₃)₂·6H₂O (29.1 mg, 0.1 mmol) was added to a ethanolic solution (10 ml) of 6,6′-sulfanediylbis(2,2′-bipyridine) (34.4 mg, 0.1 mmol), which afforded a light-yellow solution, which was stored at ambient conditions. Yellow crystals of the title compound were obtained by slow evaporation of the solvent, yield: ca. 50%.

5. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. All hydrogen atoms bound to carbon atoms were placed geometrically, with C—H = 0.93 Å and with U_iso(H) = 1.2U_eq(C). The hydrogen atoms of water molecules were found from difference-Fourier maps and their O—H bond lengths were normalized to 0.82 Å and refined with a common U_iso(H) parameter.

Table 2
Experimental details

Crystal data
Chemical formula	[Co(C₂₀H₁₄N₄S)(H₂O)₂](NO₃)₂
M_r	561.39
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	123
a, b, c (Å)	13.412 (3), 11.421 (2), 15.441 (3)
β (°)	110.50 (3)
V (Å³)	2215.4 (9)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.93
Crystal size (mm)	0.15 × 0.14 × 0.11

Data collection
Diffractometer	Rigaku Saturn724
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2008 )
T_min, T_max	0.893, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	17851, 5045, 3984
R_int	0.044
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.042, 0.090, 1.06
No. of reflections	5045
No. of parameters	337
No. of restraints	4
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.46, −0.42
Computer programs: CrystalClear (Rigaku, 2008), SHELXS97 and SHELXTL (Sheldrick, 2008 ), SHELXL2014 (Sheldrick, 2015 ) and publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 1554624

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989017008428/wm5395sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989017008428/wm5395Isup2.hkl

checkCIF report

Computing details top

Data collection: CrystalClear (Rigaku, 2008); cell refinement: CrystalClear (Rigaku, 2008); data reduction: CrystalClear (Rigaku, 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: publCIF (Westrip, 2010).

Diaqua[6,6'-sulfanediylbis(2,2'-bipyridine)]cobalt(II) dinitrate top

Crystal data top

[Co(C₂₀H₁₄N₄S)(H₂O)₂](NO₃)₂	F(000) = 1148
M_r = 561.39	D_x = 1.683 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 13.412 (3) Å	Cell parameters from 5682 reflections
b = 11.421 (2) Å	θ = 3.1–27.5°
c = 15.441 (3) Å	µ = 0.93 mm⁻¹
β = 110.50 (3)°	T = 123 K
V = 2215.4 (9) Å³	Block, yellow
Z = 4	0.15 × 0.14 × 0.11 mm

Data collection top

Rigaku Saturn724 diffractometer	5045 independent reflections
Radiation source: Rotating Anode	3984 reflections with I > 2σ(I)
Detector resolution: 28.5714 pixels mm^-1	R_int = 0.044
dtprofit.ref scans	θ_max = 27.5°, θ_min = 3.1°
Absorption correction: multi-scan (CrystalClear; Rigaku, 2008)	h = −17→17
T_min = 0.893, T_max = 1.000	k = −14→10
17851 measured reflections	l = −20→19

Refinement top

Refinement on F²	4 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.042	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.090	w = 1/[σ²(F_o²) + (0.040P)² + 0.524P] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max = 0.001
5045 reflections	Δρ_max = 0.46 e Å⁻³
337 parameters	Δρ_min = −0.42 e Å⁻³

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
S2	0.34784 (7)	0.53580 (6)	0.48067 (4)	0.0421 (2)
Co1	0.24302 (2)	0.43855 (2)	0.24018 (2)	0.01606 (9)
O1	0.39231 (13)	0.40239 (14)	0.23348 (10)	0.0187 (3)
O2	0.09507 (14)	0.47032 (15)	0.24506 (13)	0.0285 (4)
O3	0.50179 (13)	0.23807 (13)	0.35394 (10)	0.0236 (4)
O4	0.54960 (14)	0.06402 (14)	0.40822 (11)	0.0300 (4)
O6	0.05056 (14)	0.33139 (14)	0.36815 (11)	0.0292 (4)
O5	0.47102 (14)	0.08860 (15)	0.26072 (10)	0.0297 (4)
O7	0.02144 (15)	0.14605 (15)	0.36918 (13)	0.0393 (5)
O8	−0.06083 (17)	0.2472 (2)	0.24938 (13)	0.0593 (7)
N5	0.50719 (15)	0.12943 (16)	0.34121 (13)	0.0198 (4)
N6	0.00328 (15)	0.24137 (17)	0.32853 (13)	0.0212 (4)
N2	0.19761 (15)	0.26188 (16)	0.19352 (12)	0.0186 (4)
N4	0.20317 (14)	0.55097 (15)	0.12099 (12)	0.0166 (4)
N3	0.29863 (14)	0.60458 (15)	0.29886 (12)	0.0172 (4)
N1	0.28384 (14)	0.34360 (15)	0.36610 (12)	0.0175 (4)
C7	0.18108 (19)	0.0673 (2)	0.24432 (16)	0.0238 (5)
H7A	0.1923	0.0149	0.2929	0.029*
C8	0.1315 (2)	0.0304 (2)	0.15461 (17)	0.0276 (6)
H8A	0.1085	−0.0466	0.1419	0.033*
C6	0.21437 (17)	0.18271 (19)	0.26220 (14)	0.0176 (5)
C4	0.30035 (18)	0.1515 (2)	0.43295 (15)	0.0229 (5)
H4A	0.2909	0.0711	0.4245	0.027*
C10	0.15035 (19)	0.2232 (2)	0.10636 (16)	0.0250 (5)
H10A	0.1398	0.2763	0.0583	0.030*
C9	0.1167 (2)	0.1098 (2)	0.08414 (16)	0.0280 (6)
H9A	0.0846	0.0871	0.0227	0.034*
C5	0.26838 (17)	0.22627 (19)	0.35760 (15)	0.0179 (5)
C2	0.36036 (19)	0.3163 (2)	0.53060 (16)	0.0242 (5)
H2A	0.3905	0.3495	0.5890	0.029*
C1	0.32874 (18)	0.3862 (2)	0.45197 (15)	0.0214 (5)
C3	0.34627 (19)	0.1974 (2)	0.52047 (16)	0.0262 (5)
H3A	0.3674	0.1486	0.5719	0.031*
C14	0.33856 (18)	0.8009 (2)	0.26565 (16)	0.0220 (5)
H14A	0.3370	0.8578	0.2221	0.026*
C16	0.23741 (17)	0.66245 (19)	0.13919 (14)	0.0175 (5)
C19	0.11790 (19)	0.6048 (2)	−0.03804 (15)	0.0236 (5)
H19A	0.0759	0.5828	−0.0977	0.028*
C17	0.21498 (19)	0.7466 (2)	0.07011 (15)	0.0232 (5)
H17A	0.2403	0.8226	0.0844	0.028*
C20	0.14367 (18)	0.5253 (2)	0.03312 (15)	0.0224 (5)
H20A	0.1184	0.4492	0.0197	0.027*
C11	0.34248 (18)	0.63032 (19)	0.38876 (15)	0.0202 (5)
C15	0.29568 (17)	0.69114 (18)	0.23791 (14)	0.0166 (5)
C18	0.15527 (19)	0.7174 (2)	−0.01954 (15)	0.0242 (5)
H18A	0.1405	0.7726	−0.0666	0.029*
C13	0.38377 (18)	0.8247 (2)	0.35920 (16)	0.0249 (5)
H13A	0.4132	0.8979	0.3793	0.030*
C12	0.38477 (19)	0.7396 (2)	0.42191 (16)	0.0240 (5)
H12B	0.4130	0.7544	0.4851	0.029*
H1WA	0.4237 (19)	0.3504 (18)	0.2663 (15)	0.029*
H1WB	0.4339 (18)	0.4572 (18)	0.2351 (17)	0.029*
H2WA	0.072 (2)	0.430 (2)	0.2791 (15)	0.029*
H2WB	0.0665 (19)	0.5317 (17)	0.2273 (17)	0.029*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S2	0.0871 (6)	0.0210 (3)	0.0148 (3)	0.0028 (4)	0.0135 (3)	−0.0002 (3)
Co1	0.02039 (16)	0.01296 (16)	0.01403 (17)	0.00085 (12)	0.00502 (12)	0.00167 (12)
O1	0.0214 (9)	0.0152 (8)	0.0188 (8)	0.0018 (7)	0.0061 (7)	0.0044 (6)
O2	0.0270 (10)	0.0227 (10)	0.0398 (11)	0.0072 (8)	0.0165 (8)	0.0158 (8)
O3	0.0325 (10)	0.0146 (8)	0.0223 (9)	0.0043 (7)	0.0077 (7)	0.0010 (7)
O4	0.0419 (11)	0.0178 (9)	0.0241 (9)	0.0056 (8)	0.0038 (8)	0.0073 (7)
O6	0.0407 (11)	0.0191 (9)	0.0325 (9)	−0.0100 (8)	0.0186 (8)	−0.0077 (7)
O5	0.0388 (11)	0.0276 (10)	0.0172 (9)	0.0020 (8)	0.0030 (8)	−0.0066 (7)
O7	0.0359 (11)	0.0206 (9)	0.0598 (12)	0.0024 (8)	0.0148 (9)	0.0163 (9)
O8	0.0515 (14)	0.0879 (18)	0.0237 (11)	−0.0330 (13)	−0.0057 (10)	0.0093 (11)
N5	0.0200 (10)	0.0177 (10)	0.0228 (10)	−0.0004 (8)	0.0087 (8)	−0.0011 (8)
N6	0.0193 (10)	0.0231 (11)	0.0231 (11)	0.0000 (8)	0.0097 (9)	0.0003 (9)
N2	0.0214 (10)	0.0158 (9)	0.0173 (10)	−0.0014 (8)	0.0052 (8)	0.0008 (8)
N4	0.0178 (9)	0.0159 (9)	0.0149 (9)	−0.0006 (8)	0.0041 (7)	0.0011 (7)
N3	0.0192 (9)	0.0161 (9)	0.0150 (9)	0.0023 (8)	0.0045 (8)	−0.0006 (8)
N1	0.0206 (10)	0.0162 (10)	0.0164 (9)	0.0025 (8)	0.0075 (8)	0.0027 (8)
C7	0.0293 (13)	0.0169 (12)	0.0281 (13)	−0.0005 (10)	0.0139 (11)	0.0028 (10)
C8	0.0337 (14)	0.0179 (12)	0.0329 (14)	−0.0062 (11)	0.0138 (11)	−0.0031 (10)
C6	0.0184 (11)	0.0155 (11)	0.0213 (12)	0.0029 (9)	0.0102 (9)	0.0037 (9)
C4	0.0254 (12)	0.0184 (12)	0.0254 (13)	0.0023 (10)	0.0095 (10)	0.0076 (10)
C10	0.0328 (14)	0.0204 (12)	0.0197 (12)	−0.0018 (11)	0.0064 (10)	0.0029 (10)
C9	0.0340 (14)	0.0250 (13)	0.0227 (13)	−0.0054 (11)	0.0071 (11)	−0.0035 (10)
C5	0.0188 (11)	0.0164 (11)	0.0219 (12)	0.0012 (9)	0.0113 (9)	0.0032 (9)
C2	0.0275 (13)	0.0272 (13)	0.0172 (12)	0.0040 (11)	0.0069 (10)	0.0031 (10)
C1	0.0252 (12)	0.0202 (12)	0.0198 (12)	0.0029 (10)	0.0091 (10)	0.0011 (10)
C3	0.0288 (13)	0.0283 (14)	0.0207 (12)	0.0032 (11)	0.0079 (10)	0.0112 (10)
C14	0.0214 (12)	0.0185 (12)	0.0251 (13)	−0.0028 (10)	0.0070 (10)	0.0014 (10)
C16	0.0165 (11)	0.0173 (12)	0.0182 (11)	0.0013 (9)	0.0055 (9)	0.0021 (9)
C19	0.0265 (13)	0.0253 (13)	0.0149 (11)	0.0013 (10)	0.0019 (10)	0.0008 (10)
C17	0.0315 (13)	0.0155 (11)	0.0222 (12)	−0.0021 (10)	0.0089 (10)	0.0022 (9)
C20	0.0271 (13)	0.0169 (12)	0.0187 (12)	−0.0019 (10)	0.0023 (10)	−0.0008 (9)
C11	0.0227 (12)	0.0185 (12)	0.0183 (12)	0.0050 (10)	0.0057 (9)	0.0006 (9)
C15	0.0176 (11)	0.0145 (11)	0.0174 (11)	0.0024 (9)	0.0059 (9)	0.0017 (9)
C18	0.0296 (13)	0.0239 (13)	0.0172 (12)	0.0022 (10)	0.0059 (10)	0.0091 (10)
C13	0.0235 (12)	0.0196 (12)	0.0284 (13)	−0.0027 (10)	0.0051 (10)	−0.0065 (10)
C12	0.0264 (13)	0.0244 (13)	0.0172 (12)	0.0011 (10)	0.0027 (10)	−0.0068 (10)

Geometric parameters (Å, º) top

S2—C1	1.761 (2)	N1—C1	1.341 (3)
S2—C11	1.764 (2)	N1—C5	1.355 (3)
Co1—O2	2.0444 (18)	C7—C8	1.376 (3)
Co1—O1	2.0821 (17)	C7—C6	1.388 (3)
Co1—N3	2.1213 (18)	C8—C9	1.376 (3)
Co1—N1	2.1238 (17)	C6—C5	1.481 (3)
Co1—N4	2.1523 (18)	C4—C3	1.377 (3)
Co1—N2	2.1574 (18)	C4—C5	1.384 (3)
O3—N5	1.262 (2)	C10—C9	1.375 (3)
O4—N5	1.241 (2)	C2—C3	1.373 (3)
O6—N6	1.250 (2)	C2—C1	1.390 (3)
O5—N5	1.255 (2)	C14—C15	1.383 (3)
O7—N6	1.238 (2)	C14—C13	1.384 (3)
O8—N6	1.225 (2)	C16—C17	1.388 (3)
N2—C10	1.346 (3)	C16—C15	1.486 (3)
N2—C6	1.351 (3)	C19—C20	1.373 (3)
N4—C20	1.344 (3)	C19—C18	1.373 (3)
N4—C16	1.349 (3)	C17—C18	1.376 (3)
N3—C11	1.337 (3)	C11—C12	1.392 (3)
N3—C15	1.356 (3)	C13—C12	1.369 (3)

C1—S2—C11	115.45 (11)	C5—N1—Co1	115.76 (14)
O2—Co1—O1	178.59 (7)	C8—C7—C6	120.0 (2)
O2—Co1—N3	91.50 (7)	C7—C8—C9	118.6 (2)
O1—Co1—N3	89.90 (7)	N2—C6—C7	121.7 (2)
O2—Co1—N1	89.95 (7)	N2—C6—C5	116.40 (19)
O1—Co1—N1	90.02 (7)	C7—C6—C5	121.9 (2)
N3—Co1—N1	97.24 (7)	C3—C4—C5	119.4 (2)
O2—Co1—N4	88.40 (7)	N2—C10—C9	123.9 (2)
O1—Co1—N4	91.77 (7)	C10—C9—C8	118.7 (2)
N3—Co1—N4	77.10 (7)	N1—C5—C4	122.4 (2)
N1—Co1—N4	174.06 (7)	N1—C5—C6	115.68 (18)
O2—Co1—N2	90.81 (7)	C4—C5—C6	121.9 (2)
O1—Co1—N2	87.81 (7)	C3—C2—C1	118.8 (2)
N3—Co1—N2	174.08 (7)	N1—C1—C2	123.3 (2)
N1—Co1—N2	77.31 (7)	N1—C1—S2	125.20 (17)
N4—Co1—N2	108.41 (7)	C2—C1—S2	111.39 (17)
O4—N5—O5	120.48 (18)	C2—C3—C4	119.0 (2)
O4—N5—O3	119.77 (18)	C15—C14—C13	119.0 (2)
O5—N5—O3	119.74 (18)	N4—C16—C17	121.8 (2)
O8—N6—O7	119.9 (2)	N4—C16—C15	116.12 (18)
O8—N6—O6	120.1 (2)	C17—C16—C15	122.0 (2)
O7—N6—O6	119.96 (19)	C20—C19—C18	118.8 (2)
C10—N2—C6	117.12 (19)	C18—C17—C16	119.9 (2)
C10—N2—Co1	128.32 (15)	N4—C20—C19	123.9 (2)
C6—N2—Co1	114.45 (14)	N3—C11—C12	123.6 (2)
C20—N4—C16	117.03 (18)	N3—C11—S2	125.44 (17)
C20—N4—Co1	127.97 (15)	C12—C11—S2	110.88 (16)
C16—N4—Co1	114.86 (13)	N3—C15—C14	122.5 (2)
C11—N3—C15	117.11 (19)	N3—C15—C16	115.36 (19)
C11—N3—Co1	126.95 (15)	C14—C15—C16	122.0 (2)
C15—N3—Co1	115.77 (14)	C19—C18—C17	118.6 (2)
C1—N1—C5	117.09 (18)	C12—C13—C14	119.4 (2)
C1—N1—Co1	127.03 (15)	C13—C12—C11	118.4 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2WB···O7ⁱ	0.80 (2)	2.02 (2)	2.766 (3)	155 (2)
O2—H2WA···O6	0.84 (2)	1.88 (2)	2.698 (2)	168 (3)
O1—H1WB···O5ⁱⁱ	0.83 (2)	1.96 (2)	2.789 (2)	179 (3)
O1—H1WA···O3	0.80 (2)	1.89 (2)	2.688 (2)	174 (3)

Symmetry codes: (i) −x, y+1/2, −z+1/2; (ii) −x+1, y+1/2, −z+1/2.

Acknowledgements

GLL thanks the China Scholarship Council for support.

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