Crystal structure of tetraaquabis(8-chloro-9,10-dioxo-9,10-dihydroanthracene-1-carboxyl­ato-κO1)cobalt(II) dihydrate

Cai, W.-J.; Liu, B.; Liu, F.-Y.; Kou, J.-F.

doi:10.1107/S1600536814020972

metal-organic compounds

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ISSN: 2056-9890

Volume 70| Part 10| October 2014| Pages m357-m358

doi:10.1107/S1600536814020972

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Crystal structure of tetraaquabis(8-chloro-9,10-dioxo-9,10-dihydroanthracene-1-carboxylato-κO¹)cobalt(II) dihydrate

Wen-Juan Cai,^a Bo Liu,^a Feng-Yi Liu ^a and Jun-Feng Kou ^a ^*

^aCollege of Chemistry and Chemical Engineering, Yunnan Normal University, Kunming 650500, People's Republic of China
^*Correspondence e-mail: kjf416@163.com

Edited by T. J. Prior, University of Hull, England (Received 16 September 2014; accepted 20 September 2014; online 27 September 2014)

In the title complex, [Co(C₁₅H₆ClO₄)₂(H₂O)₄]·2H₂O, the Co^II ion is bound by two carboxylate O atoms of two 5-chloro-9,10-anthraquinone-1-carboxylate anions and four water O atoms in a trans conformation, forming an irregular octahedral coordination geometry. This arrangement is stabilized by intramolecular O—H⋯O hydrogen bonds between water and carboxylate. Further O—H⋯O hydrogen bonds between coordinating and non-coordinating water and carboxylate produce layers of molecules that extend parallel to (001). The organic ligands project above and below the plane. Those ligands of adjacent planes are interdigitated and there are π–π interactions between them with centroid–centroid distances of 3.552 (2) and 3.767 (2) Å that generate a three-dimensional supramolecular structure.

Keywords: crystal structure; cobalt; antitumor; hydrogen bond.

CCDC reference: 1025297

1. Related literature

For the synthesis of the title complex, see: George et al. (2006 ). The major advantage of metal-based over organic-based drugs is the ability to vary coordination number, geometry and redox states, and metals can also change the pharmacological properties of organic-based drugs by forming coordination complexes with them, see: Hambley (2007 ). Anthraquinones are highly effective chemotherapeutic agents with a wide spectrum of antitumor activity, see: Unverferth et al. (1983 ); Kantrowitz & Bristow (1984 ); Stuart et al. (1984 ); Arcamone (1987 ). For related compounds, see: Bruijnincx & Sadler (2008 ); Gruber et al. (2010 ); Neufeind et al. (2011 ).

2. Experimental

2.1. Crystal data

[Co(C₁₅H₆ClO₄)₂(H₂O)₄]·2H₂O
M_r = 738.32
Triclinic, $[P \overline 1]$
a = 6.8655 (14) Å
b = 8.1623 (16) Å
c = 14.285 (3) Å
α = 73.97 (3)°
β = 88.86 (3)°
γ = 73.35 (3)°
V = 735.6 (3) Å³
Z = 1
Mo Kα radiation
μ = 0.84 mm⁻¹
T = 293 K
0.22 × 0.19 × 0.17 mm

2.2. Data collection

Rigaku MM007-HF CCD (Saturn 724+) diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.837, T_max = 0.870
7246 measured reflections
3329 independent reflections
2171 reflections with I > 2σ(I)
R_int = 0.041
2 standard reflections every 150 reflections intensity decay: none

2.3. Refinement

R[F² > 2σ(F²)] = 0.052
wR(F²) = 0.179
S = 1.12
3329 reflections
235 parameters
9 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.59 e Å⁻³
Δρ_min = −0.64 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O7—H7B⋯O3	0.80 (4)	2.37 (5)	3.121 (5)	157 (8)
O7—H7A⋯O4ⁱ	0.82 (3)	2.24 (4)	3.049 (4)	169 (8)
O6—H6B⋯O4	0.82 (3)	1.92 (3)	2.717 (4)	164 (5)
O6—H6A⋯O4ⁱⁱ	0.82 (3)	2.17 (4)	2.916 (4)	152 (6)
O5—H5B⋯O7ⁱⁱⁱ	0.78 (3)	2.08 (4)	2.821 (4)	159 (5)
O5—H5A⋯O2	0.81 (3)	2.22 (4)	2.932 (4)	147 (5)
Symmetry codes: (i) x+1, y, z; (ii) -x, -y, -z+1; (iii) x, y-1, z.

Data collection: CrystalStructure (Rigaku/MSC, 2006 ); cell refinement: CrystalStructure; data reduction: CrystalStructure; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 1999 ); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Supporting information

CCDC reference: 1025297

Crystal structure: contains datablocks I, new_global_publ_block. DOI: 10.1107/S1600536814020972/pj2015sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536814020972/pj2015Isup2.hkl

checkCIF report

Comment top

The major advantage of metal-based over organic-based drugs is the ability to vary coordination number, geometry, and redox states and metals can also change the pharmacological properties of organic-based drugs by forming coordination complexes with them. (Hambley et al. 2007) Medicinal inorganic chemistry, covering applications of metals in therapeutics and diagnostics, is a field of increasing prominence (Bruijnincx et al. 2008) after the discovery and successful clinical applications of the Pt-based anticancer drug cisplatin. Anthraquinones are highly effective chemotherapeutic agents with a wide spectrum of antitumor activity. (Unverferth et al. 1983; Kantrowitz et al. 1984; Stuart et al. 1984; Arcamone et al. 1987;). Herein we report the synthesis and structure of the title cobalt(II) anthraquione complex.

The structure of the title complex is shown in Fig. 1, Fig. 2 and hydrogen-bond geometry is given in Table 1. The complex crystallizes in the triclinic space group P1 and the asymmetric unit consists of one crystallographically independent co(II) cation, one 5-cyclo-9,10-anthraquinone-1-carboxylate anion, two coordination water molecules and one free water molecule. As shown in Fig.1, the Co(II) ion is bound by two carboxylate O atom (O3,O3A), four water molecules forming an irregular coordination geometry. Strong hydrogen bonds involving an aqua ligand (as a donor) and carboxy O atoms (as an acceptor) may further stabilize the three-dimensional structure (O5···O2=2.932 (4) Å, O5···O7#1=2.821 (4) Å, O6···O4#2=2.916 (4) Å, O6···O4=2.717 (4) Å, symmetry codes:#1 x, y–1, z #2 –x, –y, –z+1). The interstitial water molecules are attached via hydrogen bonding to carboxylate O atoms (O7···O4#3=3.049 (4) Å, O7···O3=3.121 (5) Å, symmetry code:#3 x+1, y, z) (Table 1 & Fig.2).

Related literature top

For the synthesis of the title complex, see: George et al. (2006). The major advantage of metal-based over organic-based drugs is the ability to vary coordination number, geometry and redox states, and metals can also change the pharmacological properties of organic-based drugs by forming coordination complexes with them, see: Hambley (2007). Anthraquinones are highly effective chemotherapeutic agents with a wide spectrum of antitumor activity, see: Unverferth et al. (1983); Kantrowitz & Bristow (1984); Stuart et al. (1984); Arcamone et al. (1987). For related compounds, see: Bruijnincx & Sadler (2008); Gruber et al. (2010); Neufeind et al. (2011).

Experimental top

An aqueous solution (2 ml) of cobalt(II) chloride hexahydrate (0.1 mmol, 23.7 mg) was mixed with a methanolic solution (2 mL) of 5-cyclo-9,10-anthraquinone-1-carboxylate (0.1 mmol, 28.6 mg) in presence of two drops of aqueous sodium hydroxide (0.1 M). The resulting mixture was allowed to evaporate for one week to yield red crystals, suitable for X-ray work. Yield: 75% (based on the 5-cyclo-9,10-anthraquinone-1-carboxylate)

Computing details top

Data collection: CrystalStructure (Rigaku/MSC, 2006); cell refinement: CrystalStructure (Rigaku/MSC, 2006); data reduction: CrystalStructure (Rigaku/MSC, 2006); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 1999); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound, with atom labels and 30 % probability displacement ellipsoids. Symmetry equivalent atoms labelled with an A (eg O1A) are generated by the symmetry operator 1–x, –y, 1–z.
	Fig. 2. A view of the crystal packing. Hydrogen bonds are shown as brown dashed lines.

Tetraaquabis(8-chloro-9,10-dioxo-9,10-dihydroanthracene-1-carboxylato-κO¹)cobalt(II) dihydrate top

Crystal data top

[Co(C₁₅H₆ClO₄)₂(H₂O)₄]·2H₂O	Z = 1
M_r = 738.32	F(000) = 377
Triclinic, P1	D_x = 1.667 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.8655 (14) Å	Cell parameters from 25 reflections
b = 8.1623 (16) Å	θ = 3.1–25.0°
c = 14.285 (3) Å	µ = 0.84 mm⁻¹
α = 73.97 (3)°	T = 293 K
β = 88.86 (3)°	Block, red
γ = 73.35 (3)°	0.22 × 0.19 × 0.17 mm
V = 735.6 (3) Å³

Data collection top

Rigaku MM007-HF CCD (Saturn 724+) diffractometer	3329 independent reflections
Radiation source: rotating anode	2171 reflections with I > 2σ(I)
Confocal monochromator	R_int = 0.041
ω scans at fixed χ = 45°	θ_max = 27.5°, θ_min = 3.1°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −7→8
T_min = 0.837, T_max = 0.870	k = −10→10
7246 measured reflections	l = −18→18

Refinement top

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)] = 0.052	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.179	H atoms treated by a mixture of independent and constrained refinement
S = 1.12	w = 1/[σ²(F_o²) + (0.0859P)² + 0.2785P] where P = (F_o² + 2F_c²)/3
3329 reflections	(Δ/σ)_max < 0.001
235 parameters	Δρ_max = 0.59 e Å⁻³
9 restraints	Δρ_min = −0.64 e Å⁻³

Crystal data top

[Co(C₁₅H₆ClO₄)₂(H₂O)₄]·2H₂O	γ = 73.35 (3)°
M_r = 738.32	V = 735.6 (3) Å³
Triclinic, P1	Z = 1
a = 6.8655 (14) Å	Mo Kα radiation
b = 8.1623 (16) Å	µ = 0.84 mm⁻¹
c = 14.285 (3) Å	T = 293 K
α = 73.97 (3)°	0.22 × 0.19 × 0.17 mm
β = 88.86 (3)°

Data collection top

Rigaku MM007-HF CCD (Saturn 724+) diffractometer	3329 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	2171 reflections with I > 2σ(I)
T_min = 0.837, T_max = 0.870	R_int = 0.041
7246 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.052	9 restraints
wR(F²) = 0.179	H atoms treated by a mixture of independent and constrained refinement
S = 1.12	Δρ_max = 0.59 e Å⁻³
3329 reflections	Δρ_min = −0.64 e Å⁻³
235 parameters

Special details top

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.

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

	x	y	z	U_iso*/U_eq
Co1	0.5000	0.0000	0.5000	0.0521 (3)
O1	0.2123 (5)	0.3055 (4)	1.0202 (2)	0.0734 (8)
O2	0.2651 (4)	−0.0771 (3)	0.76542 (19)	0.0618 (7)
O3	0.3637 (4)	0.1703 (3)	0.58318 (18)	0.0565 (6)
O4	0.0299 (4)	0.1985 (4)	0.5694 (2)	0.0631 (7)
O5	0.4564 (6)	−0.2191 (4)	0.6077 (2)	0.0798 (10)
H5A	0.431 (8)	−0.222 (7)	0.663 (3)	0.101 (9)*
H5B	0.469 (8)	−0.317 (5)	0.607 (4)	0.101 (9)*
O6	0.2118 (5)	0.0420 (4)	0.4326 (2)	0.0664 (8)
H6A	0.181 (8)	−0.050 (6)	0.442 (4)	0.101 (9)*
H6B	0.141 (7)	0.079 (7)	0.474 (3)	0.101 (9)*
O7	0.6143 (6)	0.4206 (5)	0.6095 (3)	0.0832 (9)
H7A	0.724 (7)	0.371 (10)	0.591 (6)	0.16 (2)*
H7B	0.527 (8)	0.385 (10)	0.594 (6)	0.16 (2)*
C1	0.1499 (5)	0.3019 (5)	0.6896 (3)	0.0497 (8)
C2	0.0846 (6)	0.4864 (5)	0.6614 (3)	0.0624 (10)
H2	0.0601	0.5482	0.5955	0.075*
C3	0.0552 (7)	0.5804 (5)	0.7312 (3)	0.0666 (11)
H3	0.0103	0.7043	0.7116	0.080*
C4	0.0924 (6)	0.4908 (5)	0.8284 (3)	0.0590 (10)
H4	0.0715	0.5541	0.8746	0.071*
C5	0.2727 (5)	−0.0750 (5)	1.0984 (3)	0.0506 (8)
C6	0.3092 (5)	−0.2598 (5)	1.1281 (3)	0.0583 (9)
H6	0.3266	−0.3212	1.1942	0.070*
C7	0.3193 (6)	−0.3514 (5)	1.0589 (3)	0.0619 (10)
H7	0.3390	−0.4738	1.0783	0.074*
C8	0.3001 (6)	−0.2605 (5)	0.9614 (3)	0.0562 (9)
H8	0.3107	−0.3230	0.9152	0.067*
C9	0.2065 (5)	0.2169 (5)	0.9648 (3)	0.0508 (8)
C10	0.2436 (5)	0.0117 (5)	0.8235 (3)	0.0466 (8)
C11	0.1858 (5)	0.2093 (5)	0.7891 (3)	0.0476 (8)
C12	0.1613 (5)	0.3057 (5)	0.8584 (3)	0.0482 (8)
C13	0.2495 (5)	0.0193 (5)	1.0001 (2)	0.0459 (8)
C14	0.2651 (5)	−0.0773 (5)	0.9307 (3)	0.0477 (8)
C15	0.1838 (6)	0.2122 (5)	0.6087 (3)	0.0525 (8)
Cl1	0.25829 (17)	0.02230 (15)	1.19317 (7)	0.0696 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co1	0.0629 (5)	0.0479 (4)	0.0531 (4)	−0.0121 (3)	0.0195 (3)	−0.0316 (3)
O1	0.106 (2)	0.0652 (17)	0.0646 (17)	−0.0219 (16)	0.0088 (16)	−0.0472 (14)
O2	0.0817 (18)	0.0561 (14)	0.0632 (16)	−0.0195 (13)	0.0199 (13)	−0.0434 (12)
O3	0.0627 (15)	0.0581 (15)	0.0598 (15)	−0.0146 (12)	0.0214 (12)	−0.0389 (12)
O4	0.0655 (16)	0.0728 (18)	0.0649 (16)	−0.0171 (14)	0.0081 (13)	−0.0453 (14)
O5	0.121 (3)	0.0548 (16)	0.0705 (19)	−0.0255 (17)	0.0424 (19)	−0.0311 (15)
O6	0.0744 (19)	0.0636 (17)	0.0722 (19)	−0.0160 (14)	0.0169 (14)	−0.0419 (15)
O7	0.083 (2)	0.065 (2)	0.104 (3)	−0.0127 (17)	0.012 (2)	−0.0370 (18)
C1	0.0487 (18)	0.0543 (19)	0.055 (2)	−0.0088 (15)	0.0092 (15)	−0.0359 (16)
C2	0.076 (3)	0.054 (2)	0.058 (2)	−0.0064 (19)	0.0075 (19)	−0.0311 (18)
C3	0.082 (3)	0.050 (2)	0.073 (3)	−0.0062 (19)	0.009 (2)	−0.0377 (19)
C4	0.067 (2)	0.056 (2)	0.066 (2)	−0.0103 (18)	0.0129 (19)	−0.0445 (19)
C5	0.0410 (17)	0.065 (2)	0.056 (2)	−0.0157 (16)	0.0121 (15)	−0.0355 (17)
C6	0.054 (2)	0.063 (2)	0.062 (2)	−0.0151 (18)	0.0108 (17)	−0.0269 (18)
C7	0.061 (2)	0.055 (2)	0.075 (3)	−0.0146 (18)	0.0123 (19)	−0.0302 (19)
C8	0.055 (2)	0.058 (2)	0.070 (2)	−0.0168 (17)	0.0136 (18)	−0.0410 (19)
C9	0.0468 (18)	0.058 (2)	0.061 (2)	−0.0128 (15)	0.0140 (16)	−0.0421 (17)
C10	0.0423 (17)	0.0548 (19)	0.057 (2)	−0.0143 (15)	0.0128 (15)	−0.0385 (16)
C11	0.0428 (17)	0.0524 (18)	0.060 (2)	−0.0111 (15)	0.0124 (15)	−0.0387 (16)
C12	0.0446 (17)	0.0546 (19)	0.058 (2)	−0.0133 (15)	0.0136 (15)	−0.0384 (16)
C13	0.0394 (16)	0.0551 (19)	0.0528 (19)	−0.0117 (14)	0.0112 (14)	−0.0332 (16)
C14	0.0404 (16)	0.0548 (19)	0.059 (2)	−0.0126 (15)	0.0102 (15)	−0.0346 (16)
C15	0.065 (2)	0.0494 (19)	0.0489 (19)	−0.0108 (17)	0.0078 (17)	−0.0300 (15)
Cl1	0.0773 (7)	0.0832 (7)	0.0594 (6)	−0.0203 (6)	0.0136 (5)	−0.0419 (5)

Geometric parameters (Å, º) top

Co1—O3ⁱ	2.083 (2)	C2—H2	0.9300
Co1—O3	2.083 (2)	C3—C4	1.369 (6)
Co1—O5ⁱ	2.104 (3)	C3—H3	0.9300
Co1—O5	2.104 (3)	C4—C12	1.390 (5)
Co1—O6ⁱ	2.113 (3)	C4—H4	0.9300
Co1—O6	2.113 (3)	C5—C13	1.390 (5)
O1—C9	1.219 (4)	C5—C6	1.397 (5)
O2—C10	1.225 (4)	C5—Cl1	1.737 (3)
O3—C15	1.259 (4)	C6—C7	1.385 (5)
O4—C15	1.253 (4)	C6—H6	0.9300
O5—H5A	0.81 (3)	C7—C8	1.373 (6)
O5—H5B	0.78 (3)	C7—H7	0.9300
O6—H6A	0.82 (3)	C8—C14	1.387 (5)
O6—H6B	0.82 (3)	C8—H8	0.9300
O7—H7A	0.82 (3)	C9—C12	1.487 (5)
O7—H7B	0.80 (4)	C9—C13	1.492 (5)
C1—C2	1.385 (5)	C10—C11	1.485 (5)
C1—C11	1.402 (5)	C10—C14	1.493 (5)
C1—C15	1.511 (4)	C11—C12	1.405 (4)
C2—C3	1.395 (5)	C13—C14	1.412 (4)

O3ⁱ—Co1—O3	180.00 (10)	C12—C4—H4	119.8
O3ⁱ—Co1—O5ⁱ	90.64 (11)	C13—C5—C6	121.2 (3)
O3—Co1—O5ⁱ	89.36 (11)	C13—C5—Cl1	124.1 (3)
O3ⁱ—Co1—O5	89.36 (11)	C6—C5—Cl1	114.7 (3)
O3—Co1—O5	90.64 (11)	C7—C6—C5	119.8 (4)
O5ⁱ—Co1—O5	180.0	C7—C6—H6	120.1
O3ⁱ—Co1—O6ⁱ	89.78 (11)	C5—C6—H6	120.1
O3—Co1—O6ⁱ	90.22 (11)	C8—C7—C6	119.7 (4)
O5ⁱ—Co1—O6ⁱ	89.38 (15)	C8—C7—H7	120.1
O5—Co1—O6ⁱ	90.62 (15)	C6—C7—H7	120.1
O3ⁱ—Co1—O6	90.22 (11)	C7—C8—C14	121.2 (3)
O3—Co1—O6	89.78 (11)	C7—C8—H8	119.4
O5ⁱ—Co1—O6	90.62 (15)	C14—C8—H8	119.4
O5—Co1—O6	89.38 (15)	O1—C9—C12	119.7 (3)
O6ⁱ—Co1—O6	180.0	O1—C9—C13	121.8 (3)
C15—O3—Co1	130.3 (2)	C12—C9—C13	118.4 (3)
Co1—O5—H5A	126 (4)	O2—C10—C11	120.9 (3)
Co1—O5—H5B	131 (4)	O2—C10—C14	120.3 (3)
H5A—O5—H5B	103 (4)	C11—C10—C14	118.7 (3)
Co1—O6—H6A	112 (4)	C1—C11—C12	119.4 (3)
Co1—O6—H6B	98 (4)	C1—C11—C10	121.7 (3)
H6A—O6—H6B	96 (4)	C12—C11—C10	118.9 (3)
H7A—O7—H7B	110 (5)	C4—C12—C11	120.0 (3)
C2—C1—C11	119.5 (3)	C4—C12—C9	117.6 (3)
C2—C1—C15	116.7 (3)	C11—C12—C9	122.4 (3)
C11—C1—C15	123.8 (3)	C5—C13—C14	118.0 (3)
C1—C2—C3	120.6 (4)	C5—C13—C9	123.2 (3)
C1—C2—H2	119.7	C14—C13—C9	118.8 (3)
C3—C2—H2	119.7	C8—C14—C13	120.1 (3)
C4—C3—C2	120.2 (4)	C8—C14—C10	117.9 (3)
C4—C3—H3	119.9	C13—C14—C10	122.1 (3)
C2—C3—H3	119.9	O4—C15—O3	126.6 (3)
C3—C4—C12	120.3 (3)	O4—C15—C1	117.3 (3)
C3—C4—H4	119.8	O3—C15—C1	115.9 (3)

O3ⁱ—Co1—O3—C15	−8 (100)	C13—C9—C12—C4	170.7 (3)
O5ⁱ—Co1—O3—C15	115.4 (3)	O1—C9—C12—C11	169.1 (3)
O5—Co1—O3—C15	−64.6 (3)	C13—C9—C12—C11	−9.3 (5)
O6ⁱ—Co1—O3—C15	−155.2 (3)	C6—C5—C13—C14	−0.3 (5)
O6—Co1—O3—C15	24.8 (3)	Cl1—C5—C13—C14	180.0 (2)
C11—C1—C2—C3	0.3 (6)	C6—C5—C13—C9	178.8 (3)
C15—C1—C2—C3	−178.1 (4)	Cl1—C5—C13—C9	−0.9 (5)
C1—C2—C3—C4	0.5 (7)	O1—C9—C13—C5	8.6 (5)
C2—C3—C4—C12	0.5 (6)	C12—C9—C13—C5	−173.1 (3)
C13—C5—C6—C7	−1.1 (6)	O1—C9—C13—C14	−172.2 (3)
Cl1—C5—C6—C7	178.6 (3)	C12—C9—C13—C14	6.1 (5)
C5—C6—C7—C8	2.1 (6)	C7—C8—C14—C13	0.3 (6)
C6—C7—C8—C14	−1.7 (6)	C7—C8—C14—C10	−179.3 (3)
C2—C1—C11—C12	−2.1 (5)	C5—C13—C14—C8	0.8 (5)
C15—C1—C11—C12	176.1 (3)	C9—C13—C14—C8	−178.5 (3)
C2—C1—C11—C10	176.2 (3)	C5—C13—C14—C10	−179.7 (3)
C15—C1—C11—C10	−5.6 (5)	C9—C13—C14—C10	1.1 (5)
O2—C10—C11—C1	1.2 (5)	O2—C10—C14—C8	−3.0 (5)
C14—C10—C11—C1	−175.8 (3)	C11—C10—C14—C8	174.0 (3)
O2—C10—C11—C12	179.5 (3)	O2—C10—C14—C13	177.4 (3)
C14—C10—C11—C12	2.5 (5)	C11—C10—C14—C13	−5.6 (5)
C3—C4—C12—C11	−2.4 (6)	Co1—O3—C15—O4	−20.4 (6)
C3—C4—C12—C9	177.6 (4)	Co1—O3—C15—C1	165.0 (2)
C1—C11—C12—C4	3.2 (5)	C2—C1—C15—O4	−80.0 (5)
C10—C11—C12—C4	−175.2 (3)	C11—C1—C15—O4	101.7 (4)
C1—C11—C12—C9	−176.8 (3)	C2—C1—C15—O3	95.1 (4)
C10—C11—C12—C9	4.8 (5)	C11—C1—C15—O3	−83.2 (4)
O1—C9—C12—C4	−11.0 (5)

Symmetry code: (i) −x+1, −y, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O7—H7B···O3	0.80 (4)	2.37 (5)	3.121 (5)	157 (8)
O7—H7A···O4ⁱⁱ	0.82 (3)	2.24 (4)	3.049 (4)	169 (8)
O6—H6B···O4	0.82 (3)	1.92 (3)	2.717 (4)	164 (5)
O6—H6A···O4ⁱⁱⁱ	0.82 (3)	2.17 (4)	2.916 (4)	152 (6)
O5—H5B···O7^iv	0.78 (3)	2.08 (4)	2.821 (4)	159 (5)
O5—H5A···O2	0.81 (3)	2.22 (4)	2.932 (4)	147 (5)

Symmetry codes: (ii) x+1, y, z; (iii) −x, −y, −z+1; (iv) x, y−1, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O7—H7B···O3	0.80 (4)	2.37 (5)	3.121 (5)	157 (8)
O7—H7A···O4ⁱ	0.82 (3)	2.24 (4)	3.049 (4)	169 (8)
O6—H6B···O4	0.82 (3)	1.92 (3)	2.717 (4)	164 (5)
O6—H6A···O4ⁱⁱ	0.82 (3)	2.17 (4)	2.916 (4)	152 (6)
O5—H5B···O7ⁱⁱⁱ	0.78 (3)	2.08 (4)	2.821 (4)	159 (5)
O5—H5A···O2	0.81 (3)	2.22 (4)	2.932 (4)	147 (5)

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

Acknowledgements

This work was supported by Natural Science Foundation of Yunnan Provice (grant No. 2009CD048), the Applied Basic Research Projects of Yunnan Provine (grant No. 2014fz042) and the Scientific Research Fund of Yunnan Education (grant No. 2013Y431)

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