Hexaqua­cobalt(II) bis­(5-hydr­oxy-7-meth­oxy-4-oxo-2-phenyl-4H-chromene-6-sulfonate) tetra­hydrate

The title compound, [Co(H₂O)₆](C₁₆H₁₁O₇S)₂·4H₂O, with cobalt(II) at the centre of symmetry, exhibits alternating hydro­philic and hydro­phobic regions. Hydro­philic regions are generated by O-H...O hydrogen bonds among sulfonate groups, involving solvent water mol­ecules and coordinated water mol­ecules; [pi]-[pi] stacking inter­actions assemble the flavone skeletons into columns which form the hydro­phobic regions. A three-dimensional network is built up from an extensive array of hydrogen bonds, [pi]-[pi] stacking inter­actions and electrostatic inter­actions between the cation and anion. As a salt of the sulfonated derivative of naturally occurring tectochrysin (5-hydr­oxy-7-methoxy­flavone), this compound offers enhanced solubility and potential biological activity over the natural product.

S1. Comment

Tectochrysin (5-hydroxyl-7-methoxyflavone), a naturally occurring flavonoid and one of the effective components of propolis (Fujimoto et al., 2001), has many different biological properties such as anti-cancer (Ahmed-Belkacem et al., 2005), anti-oxidant (Lee et al., 2003) and trypanocidal activity (Takeara et al., 2003). The aqueous solubility of flavonoids in general is poor and their biological utilization rate is low. It is therefore necessary to synthesize water-soluble flavonoid derivatives in order to improve their possible biological activities, and this may be achieved by the introduction of a sulfonate group (Hiroyuki et al., 1996; Jiang et al., 2001). We have synthesized some flavonoidsulfonates (Zhang & Wang, 2005; Wang & Zhang, 2005) and studied the biological activities of sodium 4',7-dihydroxyisoflavone-3'-sulfonate (Liu et al., 2003) and sodium 4'-hydroxyl-7-methoxyisoflavone-3'-sulfonate (Zhang et al., 2002). The results show that the biological activities of flavonoidsulfonates are better in comparison with the corresponding parent flavonoids. Given the biological activity of tectochrysin, it is important to prepare and study sulfonated derivatives that may offer improved properties. In this paper, we report the crystal structure of the cobalt(II) salt of 5-hydroxyl-7-methoxyflavone-6-sulfonate, (I).

As shown in Fig. 1, (I) consists of a metal cation [Co(H₂O)₆]²⁺, two 5-hydroxyl-7-methoxyflavone-6-sulfonate anions and four water molecules. The Co^II ion, lying on an inversion centre, has a nearly ideal octahedral environment of six O atoms from coordinated water molecules. The equatorial plane of the octahedron is defined by O1, O2, O1ⁱ and O2ⁱ [symmetry code: (i) -x, -y + 2, -z + 2] with the average Co—O bond length 2.072 (2) Å. The axes of the octahedron are defined by O3 and O3ⁱ with the Co—O3(O3ⁱ) bond length 2.1107 (19) Å. The dihedral angle between ring A (C1–C6) and ring C (C3–C4/O4/C8–C10) is 1.85 (11)°, and that of the benzopyrane ring A/C (C1–C6/O4/C8–C10) and ring B (C11–C16) is 1.95 (11)°. The flavone skeleton is essentially planar, with the mean deviation from the least-squares plane being 0.0248 Å; this is similar to what has been found in tectochrysin itself (Chantrapromma et al., 1989).

Sulfonate groups, coordinated water molecules and solvate water molecules in (I) are linked by numerous O—H···O hydrogen bonds (Fig. 1, Table 1). For example, a hydrogen-bond chain O1—H1B···O12—H12B···O9 exists between the sulfonate group and a coordinated water molecule, bridged by the solvate water molecule O12. O3—H3B···O9 and O12—H12B···O9 are involved in a three-centred hydrogen bond. Additionally, cyclic hydrogen-bond motifs R₂²(8) and R₂²(14) (Fig. 2) are formed by paired `soft' hydrogen bonds C9—H9···O5^v and C12—H12···O5^v [symmetry code: (v) -x, -y + 2, -z + 1], respectively. An independent hydrogen bond O6—H6···O5 forms an intramolecular motif S(6) (Fig. 2). The three sulfonate O atoms are involved in seven O—H···O hydrogen bonds. According to Haynes et al. (2004), this indicates that the sulfonate moiety behaves as a steric tightener, i.e. brings several hydrogen-bond acceptors into close contact. The extensive array of hydrogen bonds makes this region hydrophilic (Fig. 3).

Additionally, π···π stacking interactions between the flavone skeletons are observed (Fig. 3). The ring B of the flavone at (x, y, z) has stacking interactions with the ring C of the flavone at (-x + 1, -y + 2, -z + 1), with a centroid–centroid (CgB–CgC*) [* indicates the symmetry operation (-x, -y + 2, -z + 1)] distance of 3.5553 (16) Å and a perpendicular distance (CgB on ring C*) of 3.429 (2) Å. The ring B of the flavone at (x, y, z) has stacking interactions with the ring A of the flavone at (-x + 1, -y + 1, -z + 1), with a centroid–centroid (CgB–CgA#) [# indicates the symmetry operation (-x + 1, -y + 1, -z + 1)] distance of 3.6396 (16) Å and a perpendicular distance (CgB on ring A#) of 3.458 (2) Å. These values are close to those reported for typical aromatic π···π stacking interactions (Hunter, 1994). The arrangement of the flavone skeletons of (I) in antiparallel fashion and stacked into columns along the (101) direction is driven by these interactions. The columns are linked by hydrogen-bond motifs R₂²(8) and R₂²(14) forming the hydrophobic regions of (I) (Fig. 3). The structure of (I) is quite different from the zinc complex of the related 5,7-dihydroxyflavone-6-sulfonate, [Zn(C₁₅H₈O₇S)(DMSO)]₂·H₂O [DMSO = dimethyl sulfoxide?] (Zhang et al., 2006). The Zn compound is a coordination polymer in which the cation and anion are linked together by Zn—O coordination bonds. By contrast, (I) is a metal salt of 5-hydroxyl-7-methoxyflavone-6-sulfonate in which the cation and anion are linked together by hydrogen bonds and electrostatic interactions.

Related literature

For related literature, see: Ahmed-Belkacem, Pozza, Munoz-Martinez, Bates, Castanys, Gamarro, Di Pietro & Perez-Victoria (2005); Chantrapromma et al. (1989); Fujimoto et al. (2001); Haynes et al. (2004); Hiroyuki et al. (1996); Hunter (1994); Jiang et al. (2001); Lee et al. (2003); Liu et al. (2003); Takeara et al. (2003); Wang & Zhang (2005); Zhang & Wang (2005); Zhang et al. (2002).

S2. Experimental

Tectochrysin (2.0 g) was slowly added to concentrated sulfuric acid (10 ml) while stirring. The reaction was maintained at room temperature for 15 h, then poured into a saturated aqueous NaCl solution (50 ml) and a yellow precipitate appeared. After 5 h, the precipitate was filtered and washed with saturated aqueous NaCl solution until the pH value of the filtrate was 7. The precipitate was recrystallized from an ethanol–water (v/v = 1:1) solution to afford sodium tectochrysin-6-sulfonate. The product was dried at 378 K for 10 h under vacuum. Yield = 75%. IR (cm^-1, KBr) ν: 3465, 1646, 1607, 1487, 1447, 1205, 1144, 1099, 1045, 899, 807, 771, 687. ¹H NMR (DMSO-d₆, 300 MHz) δ: 13.15 (s, 1H, H–C5–OH), 7.58–7.88 (m, 5H, H–C2', C3', C4', C5', C6'), 6.77 (s, 1H, H–C8), 6.53 (s, 1H, H–C3), 3.88 (s, 3H, C7–OCH₃). ¹³C NMR (DMSO-d₆, 75 MHz) δ: 177.5 (C4), 162.1 (C7), 160.4 (C2), 158.8 (C8A), 156.2 (C5), 131.6 (C1'), 130.5 (C4'), 129.0 (C3', C5'), 126.0 (C2', C6'), 115.6 (C6), 107.6 (C4A), 106.6 (C3), 91.4 (C8), 56.4 (C7–OCH₃). Analysis calculated for C₁₆H₁₁NaO₇S (%): C 51.89, H 2.99; found C 51.15, H 3.21. An aqueous solution of CoCl₂·6H₂O (10%, 5 ml) was mixed with a hot aqueous solution of sodium tectochrysin-6-sulfonate (5%, 10 ml) and (I) was obtained after 24 h. It was recrystallized from an ethanol–water (v/v = 3:1) solution. Pink block-shaped crystals suitable for X-ray analysis were obtained by slow evaporation of the solvent for about 5 d at room temperature. Yield = 81%. IR (cm^-1, KBr) ν: 3460, 1646, 1611, 1488, 1445, 1208, 1179, 1099, 1042, 887, 804, 769, 687.

S3. Refinement

H atoms bonded to C atoms were positioned geometrically (C—H = 0.93–0.96 Å) and refined using a riding model with U_iso(H) = 1.2U_eq(C). H atoms of the water molecules were found in difference maps and positionally refined with constraints of O—H = 0.82 (4) Å and U_iso(H) = 1.5U_eq(O). The phenol hydroxyl H atom was positioned geometrically with O—H = 0.82 Å and included as a riding atom with U_iso(H) = 1.5U_eq(O).

Computing details

Data collection: SMART (Bruker, 1999); cell refinement: SMART (Bruker, 1999); data reduction: SAINT or SAINT-Plus (Bruker, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures

	Fig. 1. Molecular structure of (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. Hydrogen bonds are shown as dashed lines.
	Fig. 2. Hydrogen-bond motifs R2^2(8), R2^2(14) and S(6) in (I). Displacement ellipsoids are drawn at the 30% probability level. The dashed lines indicate hydrogen bonds. Symmetry codes: (v) -x, -y + 2, -z + 1.
	Fig. 3. A view of the packing of (I), illustrating the alternating hydrophilic and hydrophobic regions and non-bonded contacts. CgA, CgB and CgC are the centroids of rings A, B and C, respectively. Atoms labelled # and * are generated by the symmetry operations (-x + 1, -y + 1, -z + 1) and (-x + 1, -y + 2, -z + 1), respectively.

Hexaquacobalt(II) bis(5-hydroxy-7-methoxy-4-oxo-2-phenyl-4H-chromene-6-sulfonate) tetrahydrate

Crystal data

[Co(H2O)6](C16H11O7S)2·4H2O	Z = 1
Mr = 933.71	F(000) = 485
Triclinic, P1	Dx = 1.549 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.978 (2) Å	Cell parameters from 2496 reflections
b = 7.2034 (2) Å	θ = 2.9–27.0°
c = 20.145 (1) Å	µ = 0.62 mm^−1
α = 83.970 (2)°	T = 296 K
β = 89.286 (3)°	Block, pink
γ = 83.597 (2)°	0.34 × 0.25 × 0.14 mm
V = 1000.7 (3) Å^3

Data collection

CCD area detector diffractometer	3500 independent reflections
Radiation source: fine-focus sealed tube	2949 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.013
ϕ and ω scans	θmax = 25.1°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Bruker, 1999)	h = −8→6
Tmin = 0.814, Tmax = 0.915	k = −8→8
5062 measured reflections	l = −24→23

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.037	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.131	w = 1/[σ^2(Fo^2) + (0.0967P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.04	(Δ/σ)max < 0.001
3500 reflections	Δρmax = 0.30 e Å^−3
311 parameters	Δρmin = −0.41 e Å^−3
10 restraints	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: none

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. 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 (Ų)

	x	y	z	Uiso*/Ueq
Co1	0.0000	1.0000	1.0000	0.03652 (19)
S1	0.29042 (8)	0.58372 (8)	0.84070 (3)	0.0332 (2)
O2	0.2360 (3)	0.7967 (3)	0.99917 (10)	0.0523 (5)
O3	−0.0478 (3)	0.9960 (3)	0.89693 (9)	0.0459 (5)
O4	0.5501 (2)	0.6859 (3)	0.55930 (8)	0.0389 (4)
O5	−0.0121 (3)	0.8628 (3)	0.59487 (10)	0.0607 (6)
O6	0.0480 (2)	0.7771 (3)	0.71944 (9)	0.0495 (5)
H6	−0.0088	0.8165	0.6845	0.074*
O7	0.6606 (2)	0.4719 (3)	0.78698 (8)	0.0432 (5)
O9	0.0915 (2)	0.6584 (3)	0.84767 (8)	0.0421 (4)
O8	0.3191 (3)	0.3820 (3)	0.85733 (9)	0.0494 (5)
O10	0.4180 (3)	0.6845 (3)	0.87757 (8)	0.0447 (5)
C16	0.7270 (5)	0.7106 (4)	0.43960 (14)	0.0513 (7)
H16	0.7939	0.6577	0.4779	0.062*
C15	0.8212 (5)	0.7232 (5)	0.37834 (16)	0.0616 (8)
H15	0.9511	0.6785	0.3757	0.074*
C14	0.7231 (5)	0.8017 (5)	0.32147 (15)	0.0605 (9)
H14	0.7862	0.8089	0.2805	0.073*
C13	0.5319 (5)	0.8693 (4)	0.32543 (14)	0.0544 (8)
H13	0.4662	0.9228	0.2870	0.065*
C12	0.4365 (4)	0.8587 (4)	0.38562 (13)	0.0489 (7)
H12	0.3073	0.9061	0.3878	0.059*
C11	0.5340 (4)	0.7765 (4)	0.44366 (12)	0.0393 (6)
C10	0.4303 (4)	0.7657 (4)	0.50846 (12)	0.0371 (6)
C9	0.2458 (4)	0.8245 (4)	0.51869 (13)	0.0449 (6)
H9	0.1692	0.8760	0.4824	0.054*
C8	0.1611 (4)	0.8103 (4)	0.58466 (13)	0.0426 (6)
C3	0.2921 (3)	0.7306 (3)	0.63808 (11)	0.0329 (5)
C2	0.2289 (3)	0.7121 (3)	0.70590 (12)	0.0339 (5)
C1	0.3564 (3)	0.6245 (3)	0.75516 (11)	0.0305 (5)
C6	0.5477 (3)	0.5604 (3)	0.73677 (11)	0.0329 (5)
C5	0.6115 (3)	0.5848 (4)	0.67143 (11)	0.0360 (6)
H5	0.7382	0.5460	0.6601	0.043*
C4	0.4802 (3)	0.6690 (3)	0.62351 (11)	0.0332 (5)
C7	0.8427 (3)	0.3752 (4)	0.77083 (13)	0.0414 (6)
H7A	0.8236	0.2861	0.7399	0.062*
H7B	0.9018	0.3103	0.8108	0.062*
H7C	0.9249	0.4640	0.7510	0.062*
H2B	0.240 (5)	0.695 (3)	1.0209 (16)	0.075 (12)*
H3B	0.001 (6)	0.906 (4)	0.878 (2)	0.100 (15)*
H2C	0.302 (4)	0.780 (5)	0.9660 (11)	0.065 (10)*
H3C	−0.153 (3)	1.025 (5)	0.8785 (15)	0.068 (11)*
O12	−0.2187 (3)	0.5481 (3)	0.92937 (9)	0.0455 (5)
H12B	−0.122 (4)	0.568 (7)	0.9073 (19)	0.112 (17)*
H12C	−0.309 (3)	0.587 (5)	0.9046 (14)	0.069 (11)*
O1	−0.1787 (4)	0.7928 (3)	1.02398 (10)	0.0583 (6)
H1B	−0.212 (5)	0.721 (4)	0.9987 (15)	0.078 (12)*
H1C	−0.209 (5)	0.743 (5)	1.0600 (9)	0.068 (10)*
O11	−0.4146 (4)	1.0457 (4)	0.84568 (13)	0.0628 (6)
H11C	−0.476 (6)	1.147 (4)	0.852 (2)	0.108 (17)*
H11B	−0.485 (5)	0.964 (5)	0.857 (2)	0.095 (15)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Co1	0.0457 (3)	0.0317 (3)	0.0311 (3)	−0.0020 (2)	0.0080 (2)	−0.0020 (2)
S1	0.0343 (3)	0.0357 (4)	0.0289 (3)	−0.0013 (3)	0.0078 (2)	−0.0038 (2)
O2	0.0641 (13)	0.0431 (12)	0.0450 (12)	0.0117 (10)	0.0163 (10)	−0.0035 (10)
O3	0.0546 (13)	0.0457 (12)	0.0360 (10)	0.0011 (10)	0.0021 (9)	−0.0055 (9)
O4	0.0414 (9)	0.0466 (11)	0.0270 (8)	−0.0001 (8)	0.0062 (7)	−0.0019 (7)
O5	0.0367 (11)	0.0880 (17)	0.0492 (11)	0.0063 (10)	0.0033 (9)	0.0173 (11)
O6	0.0323 (10)	0.0659 (14)	0.0434 (10)	0.0092 (9)	0.0090 (8)	0.0101 (10)
O7	0.0351 (9)	0.0575 (12)	0.0324 (9)	0.0093 (8)	0.0031 (7)	0.0012 (8)
O9	0.0346 (9)	0.0533 (12)	0.0379 (9)	−0.0010 (8)	0.0098 (7)	−0.0073 (8)
O8	0.0624 (12)	0.0384 (11)	0.0436 (10)	0.0010 (9)	0.0220 (9)	0.0044 (8)
O10	0.0415 (10)	0.0576 (12)	0.0363 (9)	−0.0044 (9)	0.0031 (7)	−0.0133 (8)
C16	0.0625 (18)	0.0495 (18)	0.0397 (15)	−0.0002 (14)	0.0089 (13)	−0.0015 (13)
C15	0.069 (2)	0.060 (2)	0.0527 (18)	0.0004 (16)	0.0263 (15)	−0.0064 (15)
C14	0.090 (3)	0.0549 (19)	0.0384 (16)	−0.0136 (18)	0.0230 (16)	−0.0083 (14)
C13	0.081 (2)	0.0518 (18)	0.0321 (14)	−0.0173 (16)	0.0055 (14)	−0.0034 (13)
C12	0.0583 (18)	0.0512 (17)	0.0381 (14)	−0.0112 (14)	0.0010 (12)	−0.0036 (12)
C11	0.0537 (16)	0.0319 (13)	0.0337 (13)	−0.0085 (12)	0.0075 (11)	−0.0073 (10)
C10	0.0431 (14)	0.0348 (13)	0.0340 (13)	−0.0079 (11)	0.0016 (11)	−0.0026 (10)
C9	0.0470 (15)	0.0523 (17)	0.0329 (13)	−0.0047 (13)	−0.0033 (11)	0.0063 (12)
C8	0.0370 (14)	0.0465 (16)	0.0415 (14)	−0.0025 (11)	0.0020 (11)	0.0061 (12)
C3	0.0325 (12)	0.0347 (13)	0.0311 (12)	−0.0047 (10)	0.0016 (9)	−0.0001 (10)
C2	0.0313 (12)	0.0311 (13)	0.0384 (13)	−0.0029 (10)	0.0050 (10)	−0.0007 (10)
C1	0.0320 (12)	0.0298 (12)	0.0295 (12)	−0.0023 (10)	0.0059 (9)	−0.0032 (9)
C6	0.0314 (12)	0.0351 (13)	0.0317 (12)	−0.0018 (10)	0.0024 (9)	−0.0028 (10)
C5	0.0304 (12)	0.0427 (14)	0.0335 (13)	0.0022 (10)	0.0043 (10)	−0.0050 (11)
C4	0.0381 (13)	0.0315 (12)	0.0303 (12)	−0.0052 (10)	0.0050 (10)	−0.0039 (10)
C7	0.0303 (12)	0.0471 (16)	0.0436 (14)	0.0043 (11)	0.0014 (10)	0.0008 (12)
O12	0.0433 (11)	0.0509 (12)	0.0408 (10)	−0.0026 (9)	−0.0024 (9)	−0.0012 (9)
O1	0.0880 (16)	0.0528 (13)	0.0392 (11)	−0.0316 (12)	0.0168 (11)	−0.0061 (10)
O11	0.0556 (14)	0.0555 (15)	0.0752 (15)	−0.0004 (12)	0.0009 (11)	−0.0028 (13)

Geometric parameters (Å, º)

Co1—O1^i	2.065 (2)	C14—H14	0.9300
Co1—O1	2.065 (2)	C13—C12	1.375 (4)
Co1—O2	2.079 (2)	C13—H13	0.9300
Co1—O2^i	2.079 (2)	C12—C11	1.402 (4)
Co1—O3	2.1107 (19)	C12—H12	0.9300
Co1—O3^i	2.1107 (19)	C11—C10	1.484 (3)
S1—O9	1.4424 (18)	C10—C9	1.331 (4)
S1—O8	1.449 (2)	C9—C8	1.446 (4)
S1—O10	1.4650 (19)	C9—H9	0.9300
S1—C1	1.781 (2)	C8—C3	1.449 (3)
O2—H2B	0.81 (3)	C3—C4	1.376 (3)
O2—H2C	0.816 (10)	C3—C2	1.428 (3)
O3—H3B	0.82 (3)	C2—C1	1.393 (3)
O3—H3C	0.821 (10)	C1—C6	1.421 (3)
O4—C10	1.367 (3)	C6—C5	1.384 (3)
O4—C4	1.375 (3)	C5—C4	1.384 (3)
O5—C8	1.247 (3)	C5—H5	0.9300
O6—C2	1.332 (3)	C7—H7A	0.9600
O6—H6	0.8200	C7—H7B	0.9600
O7—C6	1.350 (3)	C7—H7C	0.9600
O7—C7	1.431 (3)	O12—H12B	0.82 (3)
C16—C11	1.381 (4)	O12—H12C	0.82 (3)
C16—C15	1.391 (4)	O1—H1B	0.82 (3)
C16—H16	0.9300	O1—H1C	0.811 (10)
C15—C14	1.378 (5)	O11—H11C	0.82 (3)
C15—H15	0.9300	O11—H11B	0.82 (4)
C14—C13	1.372 (5)
O1^i—Co1—O1	180.0	C13—C12—H12	120.0
O1^i—Co1—O2	89.89 (10)	C11—C12—H12	120.0
O1—Co1—O2	90.11 (10)	C16—C11—C12	119.1 (2)
O1^i—Co1—O2^i	90.11 (10)	C16—C11—C10	121.1 (2)
O1—Co1—O2^i	89.89 (10)	C12—C11—C10	119.7 (2)
O2—Co1—O2^i	180.000 (1)	C9—C10—O4	122.1 (2)
O1^i—Co1—O3	88.29 (8)	C9—C10—C11	126.7 (2)
O1—Co1—O3	91.71 (8)	O4—C10—C11	111.2 (2)
O2—Co1—O3	91.90 (8)	C10—C9—C8	121.7 (2)
O2^i—Co1—O3	88.10 (8)	C10—C9—H9	119.1
O1^i—Co1—O3^i	91.71 (8)	C8—C9—H9	119.1
O1—Co1—O3^i	88.29 (8)	O5—C8—C9	122.4 (2)
O2—Co1—O3^i	88.10 (8)	O5—C8—C3	122.4 (2)
O2^i—Co1—O3^i	91.90 (8)	C9—C8—C3	115.2 (2)
O3—Co1—O3^i	180.000 (1)	C4—C3—C2	119.0 (2)
O9—S1—O8	112.03 (11)	C4—C3—C8	119.8 (2)
O9—S1—O10	111.03 (11)	C2—C3—C8	121.2 (2)
O8—S1—O10	113.28 (12)	O6—C2—C1	122.4 (2)
O9—S1—C1	108.22 (11)	O6—C2—C3	118.3 (2)
O8—S1—C1	105.95 (10)	C1—C2—C3	119.2 (2)
O10—S1—C1	105.88 (11)	C2—C1—C6	119.0 (2)
Co1—O2—H2B	123 (3)	C2—C1—S1	123.19 (18)
Co1—O2—H2C	123 (3)	C6—C1—S1	117.76 (17)
H2B—O2—H2C	106 (4)	O7—C6—C5	122.7 (2)
Co1—O3—H3B	119 (3)	O7—C6—C1	115.47 (19)
Co1—O3—H3C	124 (2)	C5—C6—C1	121.8 (2)
H3B—O3—H3C	104 (4)	C4—C5—C6	117.7 (2)
C10—O4—C4	119.4 (2)	C4—C5—H5	121.2
C2—O6—H6	109.5	C6—C5—H5	121.2
C6—O7—C7	118.63 (18)	O4—C4—C3	121.7 (2)
C11—C16—C15	120.0 (3)	O4—C4—C5	115.2 (2)
C11—C16—H16	120.0	C3—C4—C5	123.1 (2)
C15—C16—H16	120.0	O7—C7—H7A	109.5
C14—C15—C16	120.3 (3)	O7—C7—H7B	109.5
C14—C15—H15	119.9	H7A—C7—H7B	109.5
C16—C15—H15	119.9	O7—C7—H7C	109.5
C13—C14—C15	119.9 (3)	H7A—C7—H7C	109.5
C13—C14—H14	120.1	H7B—C7—H7C	109.5
C15—C14—H14	120.1	H12B—O12—H12C	105 (4)
C14—C13—C12	120.7 (3)	Co1—O1—H1B	126 (3)
C14—C13—H13	119.7	Co1—O1—H1C	130 (3)
C12—C13—H13	119.7	H1B—O1—H1C	102 (4)
C13—C12—C11	120.0 (3)	H11C—O11—H11B	107 (5)
C11—C16—C15—C14	0.1 (5)	O6—C2—C1—C6	−179.4 (2)
C16—C15—C14—C13	0.6 (5)	C3—C2—C1—C6	1.7 (3)
C15—C14—C13—C12	−0.3 (5)	O6—C2—C1—S1	1.9 (3)
C14—C13—C12—C11	−0.6 (4)	C3—C2—C1—S1	−176.98 (18)
C15—C16—C11—C12	−1.1 (4)	O9—S1—C1—C2	−0.8 (2)
C15—C16—C11—C10	−179.6 (3)	O8—S1—C1—C2	119.5 (2)
C13—C12—C11—C16	1.3 (4)	O10—S1—C1—C2	−120.0 (2)
C13—C12—C11—C10	179.9 (2)	O9—S1—C1—C6	−179.56 (18)
C4—O4—C10—C9	−1.5 (4)	O8—S1—C1—C6	−59.2 (2)
C4—O4—C10—C11	178.2 (2)	O10—S1—C1—C6	61.3 (2)
C16—C11—C10—C9	179.9 (3)	C7—O7—C6—C5	−9.6 (4)
C12—C11—C10—C9	1.3 (4)	C7—O7—C6—C1	169.3 (2)
C16—C11—C10—O4	0.2 (3)	C2—C1—C6—O7	−178.1 (2)
C12—C11—C10—O4	−178.4 (2)	S1—C1—C6—O7	0.7 (3)
O4—C10—C9—C8	1.1 (4)	C2—C1—C6—C5	0.8 (4)
C11—C10—C9—C8	−178.6 (3)	S1—C1—C6—C5	179.6 (2)
C10—C9—C8—O5	−179.2 (3)	O7—C6—C5—C4	176.7 (2)
C10—C9—C8—C3	0.8 (4)	C1—C6—C5—C4	−2.1 (4)
O5—C8—C3—C4	177.7 (3)	C10—O4—C4—C3	0.0 (3)
C9—C8—C3—C4	−2.2 (4)	C10—O4—C4—C5	179.4 (2)
O5—C8—C3—C2	−1.4 (4)	C2—C3—C4—O4	−178.9 (2)
C9—C8—C3—C2	178.6 (2)	C8—C3—C4—O4	1.9 (4)
C4—C3—C2—O6	178.1 (2)	C2—C3—C4—C5	1.7 (4)
C8—C3—C2—O6	−2.7 (4)	C8—C3—C4—C5	−177.4 (2)
C4—C3—C2—C1	−3.0 (4)	C6—C5—C4—O4	−178.6 (2)
C8—C3—C2—C1	176.2 (2)	C6—C5—C4—C3	0.8 (4)

Symmetry code: (i) −x, −y+2, −z+2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1B···O12	0.82 (3)	1.97 (3)	2.765 (3)	164 (3)
O1—H1C···O8^ii	0.81 (2)	2.00 (3)	2.801 (3)	172 (3)
O2—H2B···O12^ii	0.81 (3)	1.94 (3)	2.751 (3)	173 (4)
O2—H2C···O10	0.82 (2)	2.10 (3)	2.894 (3)	164 (3)
O3—H3B···O9	0.83 (3)	1.98 (3)	2.793 (3)	165 (4)
O3—H3C···O11	0.82 (2)	1.93 (2)	2.744 (3)	168 (3)
O6—H6···O5	0.82	1.80	2.549 (3)	151
O11—H11B···O10^iii	0.82 (4)	2.19 (4)	2.976 (3)	160 (4)
O11—H11C···O8^iv	0.83 (3)	2.10 (3)	2.912 (3)	166 (4)
O12—H12B···O9	0.82 (3)	2.02 (3)	2.837 (3)	169 (4)
O12—H12C···O10^iii	0.82 (3)	2.02 (2)	2.789 (3)	158 (3)
C7—H7C···O6^v	0.96	2.52	3.430 (3)	159
C9—H9···O5^vi	0.93	2.48	3.340 (3)	154
C12—H12···O5^vi	0.93	2.54	3.429 (4)	159

Symmetry codes: (ii) −x, −y+1, −z+2; (iii) x−1, y, z; (iv) x−1, y+1, z; (v) x+1, y, z; (vi) −x, −y+2, −z+1.