Hexaaqua­(5,7-dihydr­oxy-4-oxo-2-phenyl-4H-chromene-8-sulfonato)calcium(II) 5,7-dihydr­oxy-4-oxo-2-phenyl-4H-chromene-8-sulfonate trihydrate

Liu, B.; Yang, B.-L.

doi:10.1107/S1600536808037586

Hexaaqua(5,7-dihydroxy-4-oxo-2-phenyl-4H-chromene-8-sulfonato)calcium(II) 5,7-dihydroxy-4-oxo-2-phenyl-4H-chromene-8-sulfonate trihydrate

In the title compound, [Ca(C₁₅H₉O₇S)(H₂O)₆](C₁₅H₉O₇S)·3H₂O, the Ca centre has a distorted decahedral geometry, coordinated by six O atoms from water molecules and one sulfonate O atom. The crystal structure is stabilized by aromatic π–π interactions, with centroid–centroid distances of 3.765 (5) and 3.896 (5) Å between the phenyl ring and the benzene ring of the chromene unit of neighbouring molecules. In addition, the stacked molecules exhibit inter- and intramolecular O—H

O hydrogen bonds, including the uncoordinated water molecules.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536808037586/lx2072sup1.cif Contains datablocks I, global
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536808037586/lx2072Isup2.hkl Contains datablock I

CCDC reference: 712317

checkCIF report

Key indicators

Single-crystal X-ray study
T = 296 K
Mean (C-C) = 0.005 Å
H-atom completeness 95%
R factor = 0.055
wR factor = 0.167
Data-to-parameter ratio = 11.3

checkCIF/PLATON results

No syntax errors found



Alert level A
PLAT306_ALERT_2_A Isolated Oxygen Atom (H-atoms Missing ?) .......        O22

Author Response: : Explained in _publ_section_exptl_refinement.


Alert level B
PLAT430_ALERT_2_B Short Inter D...A Contact  O19    ..  O22     ..       2.82 Ang.

Author Response: : Because of strong HY bond.


Alert level C
            Value of measurement temperature given =   296.000
            Value of melting point given =     0.000
SHFSU01_ALERT_2_C  Test not performed. _refine_ls_shift/su_max and
            _refine_ls_shift/esd_max not present.
            Absolute value of the parameter shift to su ratio given   0.001
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        Ca1
PLAT041_ALERT_1_C Calc. and Rep. SumFormula Strings    Differ ....          ?

Author Response: : Because excepted H atoms in O22.

PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT068_ALERT_1_C Reported F000 Differs from Calcd (or Missing)...          ?

Author Response: : Because excepted H atoms in O22.

PLAT234_ALERT_4_C Large Hirshfeld Difference C20    --  C21     ..       0.10  Ang.
PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd.  #          2
              C15 H9 O7 S

Alert level G
FORMU01_ALERT_2_G  There is a discrepancy between the atom counts in the
            _chemical_formula_sum and the formula from the _atom_site* data.
            Atom count from _chemical_formula_sum:C30 H36 Ca1 O23 S2
            Atom count from the _atom_site data:  C30 H34 Ca1 O23 S2
CELLZ01_ALERT_1_G Difference between formula and atom_site contents detected.
CELLZ01_ALERT_1_G WARNING: H atoms missing from atom site list. Is this intentional?
           From the CIF: _cell_formula_units_Z    2
           From the CIF: _chemical_formula_sum  C30 H36 Ca O23 S2
           TEST: Compare cell contents of formula and atom_site data

           atom    Z*formula  cif sites diff
           C         60.00     60.00    0.00
           H         72.00     68.00    4.00
           Ca         2.00      2.00    0.00
           O         46.00     46.00    0.00
           S          4.00      4.00    0.00
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......         16

   1 ALERT level A = In general: serious problem
   1 ALERT level B = Potentially serious problem
   7 ALERT level C = Check and explain
   4 ALERT level G = General alerts; check

   5 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   5 ALERT type 2 Indicator that the structure model may be wrong or deficient
   1 ALERT type 3 Indicator that the structure quality may be low
   2 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

Comment top

Chrysin (5,7-dihydroxyflavone), a naturally wide distributed flavonoid, has many different biological activities such as anti-oxidant (Chan et al., 2000), anti-virus (Lee et al., 1999), anti-diabetogenic activity (Shin et al., 1999), anti-anxiolytic effect (Zanoli et al., 2000). Sulfonates belong to an important class of organic compounds, particularly flavonoidsulfonates have many different biological activities (Hiroyuki et al., 1996; Jiang et al., 2001). Previously, two chrysinsulfonate derivatives have been prepared. Zhang et al. (2004, 2006a, 2006b) have synthesized chrysin-6-sulfonate and its derivates, such as [Ba(C₁₅H₉O₇S)₂]_n, [Zn(C₁₅H₈O₇S)(DMSO)]₂.H₂O and [{Ca(C₁₅H₈O₇S)(H₂O)(DMSO)}₃ {Ca(C₁₅H₈O₇S)(DMSO)₂}].4DMSO. Pusz et al. (2001) have reported chrysin-4'-sulfonate and its Ti⁴⁺, Mn²⁺ and Fe³⁺ complexes. On the other hand, the weak coordination nature of SO3^- makes its coordination mode very flexible and sensitive to the chemical environment (Cote & Shimizu, 2003). Here we report the crystal structure of the title compound (Fig. 1).

As shown in Fig. 1, the Ca atom is seven-coordinated by the six O atoms from water molecules and the one sulfonate O atom. The Ca—O bond lengths are in agreement with the corresponding values in [Ca(C₁₆H₁₂O₄)(H₂O)₆]. H₂O (Morin et al., 2000). The flavone skeleton is essentially planar, the bond lengths and angles are similar to those reported for other flavonesulfonates, [Co(H₂O)₆](C₁₆H₁₁O₇S)₂.4H₂O (Li & Zhang, 2008). The molecular packing (Fig. 2) is stabilized by two different aromatic π–π interactions within each stack of molecule; one between the phenyl ring (Cg1) and the benzene ring (Cg4ⁱⁱ) of the adjacent molecules {distance; 3.765 (5) Å}, and the other between the benzene ring (Cg2) and the phenyl ring (Cg3ⁱⁱ) of the neighbouring molecules {distance; 3.896 (5) Å} (Fig. 2; Cg1, Cg2, Cg3 and Cg4 are the centroids of the C1–C6 phenyl, the C10–C15 benzene, the C16–C21 phenyl and the C25–C30 benzene rings, respectively, symmetry code as in Fig. 2). Additionally, the crystal structure exhibits numerous inter- and intramolecular O—H···O hydrogen bonds (Fig. 1 & Hydrogen-bond geometry).

Related literature top

For biological activity, see: Chan et al. (2000); Hiroyuki et al. (1996); Jiang et al. (2001); Lee et al. (1999); Shin et al. (1999); Zanoli et al. (2000). For related structures, see: Cote & Shimizu (2003); Li & Zhang (2008); Morin et al. (2000); Pusz et al. (2001); Zhang et al. (2004, 2006a,b).

Experimental top

5,7-Dihydroxyflavone (chrysin, 1.0 g, 3.9 mmol) was added slowly to concentrated sulfuric acid (6 ml) with stirring. The reaction was maintained at room temperature for 12 h. Then, it was poured into NaCl saturated aqueous solution (50 ml) and a yellow precipitate appeared. After 5 h, the precipitate was filtered and washed with NaCl saturated aqueous solution until the pH value of the filtrate was 7. It was dissolved in water (50 ml), and mixed with saturated CaCl₂ solution (10 ml). (I) was obtained after 24 h. It was recrystallized from an ethanol-water (1:1 v/v) solution. Colorless sheet-shaped crystals suitable for X-ray analysis were obtained by slow evaporation of the solvent for about 3 d at room temperature (yield 78%).

Computing details top

Data collection: SMART (Bruker, 1999); cell refinement: SAINT-Plus (Bruker, 1999); data reduction: 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 top

	Fig. 1. The molecular structure of the title compound, showing displacement ellipsoids drawn at the 30% probability level. Hydrogen bonds are illustrated as dashed lines.
	Fig. 2. π–π interactions (dotted lines) in the title compound. Cg denotes the ring centroid. [Symmetry codes: (i) x - 1, y - 1, z; (ii) x + 1, y + 1, z.]

Hexaaqua(5,7-dihydroxy-4-oxo-2-phenyl-4H-chromene-8-sulfonato)calcium(II) 5,7-dihydroxy-4-oxo-2-phenyl-4H-chromene-8-sulfonate trihydrate top

Crystal data top

[Ca(C₁₅H₉O₇S)(H₂O)₆](C₁₅H₉O₇S)·3H₂O	Z = 2
M_r = 868.79	F(000) = 904
Triclinic, P1	D_x = 1.594 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 11.360 (2) Å	Cell parameters from 2128 reflections
b = 12.390 (1) Å	θ = 2.5–23.9°
c = 13.975 (2) Å	µ = 0.38 mm⁻¹
α = 95.136 (2)°	T = 296 K
β = 102.167 (3)°	Sheet, colourless
γ = 107.423 (2)°	0.36 × 0.23 × 0.14 mm
V = 1809.9 (4) Å³

Data collection top

Bruker SMART CCD area-detector diffractometer	6299 independent reflections
Radiation source: fine-focus sealed tube	4416 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.026
Detector resolution: 10.0 pixels mm^-1	θ_max = 25.1°, θ_min = 1.5°
ϕ and ω scans	h = −9→13
Absorption correction: multi-scan (SADABS; Bruker, 1999)	k = −14→14
T_min = 0.874, T_max = 0.947	l = −16→16
9179 measured reflections

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)] = 0.055	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.167	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ²(F_o²) + (0.0956P)²] where P = (F_o² + 2F_c²)/3
6299 reflections	(Δ/σ)_max < 0.001
558 parameters	Δρ_max = 0.40 e Å⁻³
16 restraints	Δρ_min = −0.40 e Å⁻³

Crystal data top

[Ca(C₁₅H₉O₇S)(H₂O)₆](C₁₅H₉O₇S)·3H₂O	γ = 107.423 (2)°
M_r = 868.79	V = 1809.9 (4) Å³
Triclinic, P1	Z = 2
a = 11.360 (2) Å	Mo Kα radiation
b = 12.390 (1) Å	µ = 0.38 mm⁻¹
c = 13.975 (2) Å	T = 296 K
α = 95.136 (2)°	0.36 × 0.23 × 0.14 mm
β = 102.167 (3)°

Data collection top

Bruker SMART CCD area-detector diffractometer	6299 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 1999)	4416 reflections with I > 2σ(I)
T_min = 0.874, T_max = 0.947	R_int = 0.026
9179 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.055	16 restraints
wR(F²) = 0.167	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	Δρ_max = 0.40 e Å⁻³
6299 reflections	Δρ_min = −0.40 e Å⁻³
558 parameters

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.

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 > 2sigma(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
Ca1	0.10081 (6)	0.62071 (6)	0.23114 (5)	0.0393 (2)
S2	0.33030 (8)	0.65555 (7)	0.07174 (7)	0.0427 (3)
O1	0.46932 (19)	0.90038 (18)	0.11438 (16)	0.0358 (5)
O2	0.8501 (2)	1.0701 (2)	0.17925 (19)	0.0492 (6)
O3	0.8907 (2)	0.8768 (2)	0.1856 (2)	0.0551 (7)
H3	0.9073	0.9455	0.1833	0.083*
O4	0.5425 (3)	0.5415 (2)	0.1183 (3)	0.0636 (8)
H4	0.4644	0.5167	0.1030	0.095*
O5	0.3082 (3)	0.5319 (2)	0.0591 (2)	0.0645 (8)
O6	0.2916 (2)	0.6914 (2)	−0.02215 (19)	0.0582 (7)
O7	0.2732 (2)	0.6922 (2)	0.14628 (19)	0.0489 (6)
O8	0.3056 (3)	0.6613 (3)	0.3527 (2)	0.0547 (7)
H8A	0.289 (4)	0.653 (4)	0.4063 (18)	0.080*
H8B	0.332 (4)	0.612 (3)	0.331 (3)	0.080*
O9	0.1102 (3)	0.4520 (2)	0.1496 (3)	0.0698 (9)
H9A	0.053 (3)	0.390 (2)	0.128 (3)	0.080*
H9B	0.170 (3)	0.462 (4)	0.124 (3)	0.080*
O10	0.0505 (3)	0.5170 (3)	0.3609 (2)	0.0716 (9)
H10A	0.011 (4)	0.4479 (12)	0.345 (3)	0.080*
H10B	0.088 (4)	0.534 (4)	0.4197 (12)	0.080*
O11	−0.1277 (3)	0.5121 (2)	0.1799 (2)	0.0533 (7)
H11B	−0.169 (4)	0.487 (4)	0.1221 (13)	0.080*
H11A	−0.171 (4)	0.473 (3)	0.212 (3)	0.080*
O12	0.0807 (3)	0.7627 (2)	0.3400 (2)	0.0597 (8)
H12A	0.039 (4)	0.746 (4)	0.381 (2)	0.065 (15)*
H12B	0.096 (4)	0.8316 (11)	0.343 (3)	0.080*
O13	0.0262 (3)	0.7350 (3)	0.1202 (2)	0.0633 (8)
H13B	−0.009 (4)	0.780 (3)	0.137 (3)	0.080*
H13A	0.036 (5)	0.742 (4)	0.0644 (16)	0.080*
C1	0.4349 (3)	1.1836 (3)	0.1122 (3)	0.0416 (8)
H1	0.5183	1.2318	0.1219	0.050*
C2	0.3361 (4)	1.2284 (3)	0.0989 (3)	0.0489 (9)
H2	0.3534	1.3068	0.0996	0.059*
C3	0.2126 (4)	1.1585 (3)	0.0846 (3)	0.0528 (10)
H3A	0.1466	1.1894	0.0751	0.063*
C4	0.1863 (4)	1.0421 (3)	0.0843 (3)	0.0533 (10)
H4A	0.1026	0.9949	0.0752	0.064*
C5	0.2837 (3)	0.9957 (3)	0.0974 (3)	0.0438 (9)
H5	0.2654	0.9173	0.0973	0.053*
C6	0.4093 (3)	1.0654 (3)	0.1110 (2)	0.0341 (7)
C7	0.5135 (3)	1.0167 (3)	0.1252 (2)	0.0329 (7)
C8	0.6398 (3)	1.0755 (3)	0.1468 (3)	0.0383 (8)
H8	0.6672	1.1550	0.1527	0.046*
C9	0.7315 (3)	1.0169 (3)	0.1605 (2)	0.0373 (8)
C10	0.6825 (3)	0.8946 (3)	0.1508 (2)	0.0364 (8)
C11	0.7630 (3)	0.8262 (3)	0.1641 (3)	0.0408 (8)
C12	0.7130 (3)	0.7104 (3)	0.1546 (3)	0.0485 (9)
H12	0.7671	0.6669	0.1655	0.058*
C13	0.5817 (3)	0.6561 (3)	0.1287 (3)	0.0435 (8)
C14	0.4975 (3)	0.7200 (3)	0.1131 (3)	0.0373 (8)
C15	0.5518 (3)	0.8389 (3)	0.1270 (2)	0.0334 (7)
S1	−0.31929 (8)	0.40326 (7)	0.37480 (7)	0.0416 (2)
O14	−0.4556 (2)	0.16187 (18)	0.37202 (17)	0.0391 (6)
O15	−0.8338 (2)	−0.0055 (2)	0.3292 (2)	0.0579 (7)
O16	−0.8755 (2)	0.1864 (2)	0.3212 (3)	0.0693 (9)
H16	−0.8920	0.1170	0.3196	0.104*
O17	−0.5301 (3)	0.5183 (2)	0.3526 (3)	0.0708 (9)
H17	−0.4520	0.5427	0.3656	0.106*
O18	−0.2978 (3)	0.5258 (2)	0.3808 (3)	0.0689 (9)
O19	−0.2916 (2)	0.3558 (2)	0.28751 (19)	0.0521 (7)
O20	−0.2531 (2)	0.3747 (2)	0.46429 (19)	0.0556 (7)
C16	−0.2675 (3)	0.0700 (3)	0.4116 (3)	0.0474 (9)
H16A	−0.2490	0.1491	0.4187	0.057*
C17	−0.1700 (4)	0.0242 (4)	0.4252 (3)	0.0601 (11)
H17A	−0.0859	0.0725	0.4406	0.072*
C18	−0.1959 (4)	−0.0926 (4)	0.4162 (3)	0.0614 (11)
H18	−0.1297	−0.1232	0.4251	0.074*
C19	−0.3201 (4)	−0.1637 (3)	0.3939 (3)	0.0613 (11)
H19	−0.3379	−0.2425	0.3893	0.074*
C20	−0.4183 (4)	−0.1186 (3)	0.3784 (3)	0.0543 (10)
H20	−0.5022	−0.1675	0.3619	0.065*
C21	−0.3936 (3)	−0.0018 (3)	0.3871 (2)	0.0396 (8)
C22	−0.4987 (3)	0.0466 (3)	0.3714 (2)	0.0392 (8)
C23	−0.6230 (4)	−0.0108 (3)	0.3576 (3)	0.0460 (9)
H23	−0.6490	−0.0896	0.3570	0.055*
C24	−0.7170 (3)	0.0460 (3)	0.3437 (3)	0.0440 (9)
C25	−0.6679 (3)	0.1687 (3)	0.3477 (3)	0.0398 (8)
C26	−0.7489 (3)	0.2363 (3)	0.3370 (3)	0.0486 (9)
C27	−0.6996 (3)	0.3518 (3)	0.3409 (3)	0.0537 (10)
H27	−0.7534	0.3958	0.3355	0.064*
C28	−0.5694 (4)	0.4046 (3)	0.3529 (3)	0.0491 (9)
C29	−0.4845 (3)	0.3408 (3)	0.3635 (3)	0.0378 (8)
C30	−0.5383 (3)	0.2232 (3)	0.3608 (2)	0.0371 (8)
O21	−0.0582 (3)	0.7003 (3)	0.4724 (3)	0.0810 (10)
H21B	−0.126 (3)	0.648 (3)	0.448 (3)	0.080*
H21A	−0.022 (4)	0.698 (4)	0.5295 (16)	0.080*
O22	−0.0730 (3)	0.2875 (2)	0.3291 (2)	0.0699 (8)
O23	0.0758 (3)	0.7542 (2)	−0.0680 (2)	0.0539 (7)
H23B	0.139 (3)	0.734 (4)	−0.063 (4)	0.080*
H23A	0.091 (4)	0.809 (3)	−0.098 (3)	0.080*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ca1	0.0356 (4)	0.0336 (4)	0.0470 (4)	0.0079 (3)	0.0112 (3)	0.0073 (3)
S2	0.0317 (5)	0.0357 (5)	0.0573 (6)	0.0038 (4)	0.0169 (4)	0.0026 (4)
O1	0.0277 (12)	0.0306 (12)	0.0481 (14)	0.0090 (10)	0.0077 (10)	0.0067 (10)
O2	0.0272 (13)	0.0438 (14)	0.0663 (17)	0.0011 (11)	0.0060 (12)	0.0070 (12)
O3	0.0255 (13)	0.0534 (16)	0.083 (2)	0.0134 (12)	0.0080 (13)	0.0070 (15)
O4	0.0544 (17)	0.0368 (15)	0.104 (2)	0.0180 (13)	0.0249 (18)	0.0126 (15)
O5	0.0462 (16)	0.0341 (14)	0.112 (2)	0.0042 (12)	0.0365 (16)	−0.0017 (15)
O6	0.0365 (15)	0.0751 (19)	0.0498 (16)	0.0051 (14)	0.0038 (12)	0.0060 (14)
O7	0.0452 (15)	0.0417 (14)	0.0638 (17)	0.0107 (12)	0.0272 (13)	0.0079 (12)
O8	0.0415 (15)	0.0599 (18)	0.0611 (18)	0.0136 (13)	0.0134 (14)	0.0121 (15)
O9	0.056 (2)	0.0396 (16)	0.110 (3)	0.0005 (14)	0.0415 (18)	−0.0045 (16)
O10	0.075 (2)	0.0539 (18)	0.0548 (18)	−0.0136 (16)	−0.0018 (16)	0.0158 (16)
O11	0.0375 (15)	0.0555 (17)	0.0581 (18)	0.0041 (13)	0.0096 (13)	0.0097 (14)
O12	0.077 (2)	0.0357 (15)	0.071 (2)	0.0152 (15)	0.0338 (17)	0.0048 (15)
O13	0.069 (2)	0.079 (2)	0.071 (2)	0.0456 (17)	0.0370 (17)	0.0371 (18)
C1	0.043 (2)	0.038 (2)	0.045 (2)	0.0132 (16)	0.0130 (16)	0.0061 (16)
C2	0.058 (3)	0.039 (2)	0.058 (2)	0.0242 (19)	0.0158 (19)	0.0144 (17)
C3	0.051 (2)	0.058 (3)	0.059 (2)	0.031 (2)	0.0124 (19)	0.012 (2)
C4	0.032 (2)	0.058 (3)	0.067 (3)	0.0143 (18)	0.0086 (18)	0.007 (2)
C5	0.034 (2)	0.0360 (19)	0.057 (2)	0.0088 (16)	0.0074 (17)	0.0053 (16)
C6	0.0340 (18)	0.0350 (18)	0.0333 (17)	0.0119 (15)	0.0086 (14)	0.0039 (14)
C7	0.0328 (18)	0.0322 (17)	0.0322 (17)	0.0095 (14)	0.0073 (14)	0.0038 (13)
C8	0.0359 (19)	0.0288 (17)	0.048 (2)	0.0078 (15)	0.0110 (16)	0.0069 (15)
C9	0.0287 (18)	0.0381 (19)	0.0389 (19)	0.0031 (15)	0.0067 (14)	0.0057 (15)
C10	0.0298 (18)	0.0387 (19)	0.0399 (19)	0.0103 (15)	0.0076 (14)	0.0084 (15)
C11	0.0295 (18)	0.047 (2)	0.046 (2)	0.0126 (16)	0.0089 (15)	0.0082 (16)
C12	0.040 (2)	0.047 (2)	0.065 (3)	0.0236 (18)	0.0120 (18)	0.0141 (19)
C13	0.043 (2)	0.036 (2)	0.056 (2)	0.0152 (16)	0.0180 (17)	0.0113 (16)
C14	0.0336 (18)	0.0337 (18)	0.0451 (19)	0.0093 (15)	0.0133 (15)	0.0074 (15)
C15	0.0246 (16)	0.0385 (18)	0.0394 (18)	0.0108 (14)	0.0113 (14)	0.0084 (14)
S1	0.0318 (5)	0.0354 (5)	0.0513 (6)	0.0048 (4)	0.0067 (4)	0.0057 (4)
O14	0.0316 (13)	0.0314 (12)	0.0528 (14)	0.0078 (10)	0.0110 (11)	0.0072 (10)
O15	0.0353 (15)	0.0471 (15)	0.084 (2)	−0.0010 (12)	0.0207 (14)	0.0092 (14)
O16	0.0327 (15)	0.0594 (18)	0.115 (3)	0.0123 (13)	0.0231 (16)	0.0089 (19)
O17	0.0482 (17)	0.0341 (15)	0.133 (3)	0.0165 (13)	0.0234 (19)	0.0167 (16)
O18	0.0450 (16)	0.0344 (15)	0.117 (3)	0.0049 (13)	0.0109 (16)	0.0090 (15)
O19	0.0381 (14)	0.0573 (16)	0.0547 (16)	0.0056 (12)	0.0149 (12)	0.0051 (13)
O20	0.0424 (15)	0.0631 (17)	0.0486 (15)	0.0074 (13)	−0.0013 (12)	0.0090 (13)
C16	0.046 (2)	0.0358 (19)	0.056 (2)	0.0113 (17)	0.0063 (18)	0.0089 (17)
C17	0.045 (2)	0.053 (2)	0.075 (3)	0.018 (2)	0.000 (2)	0.007 (2)
C18	0.061 (3)	0.060 (3)	0.066 (3)	0.034 (2)	0.002 (2)	0.007 (2)
C19	0.075 (3)	0.039 (2)	0.072 (3)	0.023 (2)	0.014 (2)	0.014 (2)
C20	0.051 (2)	0.045 (2)	0.064 (3)	0.0120 (19)	0.015 (2)	0.0100 (19)
C21	0.043 (2)	0.0350 (19)	0.0396 (19)	0.0107 (16)	0.0095 (16)	0.0111 (15)
C22	0.042 (2)	0.0309 (18)	0.0414 (19)	0.0065 (16)	0.0105 (16)	0.0062 (15)
C23	0.045 (2)	0.0340 (19)	0.055 (2)	0.0047 (17)	0.0159 (18)	0.0086 (16)
C24	0.038 (2)	0.040 (2)	0.050 (2)	0.0037 (17)	0.0170 (17)	0.0067 (16)
C25	0.0315 (19)	0.0391 (19)	0.046 (2)	0.0062 (15)	0.0127 (15)	0.0041 (15)
C26	0.033 (2)	0.049 (2)	0.061 (2)	0.0096 (17)	0.0142 (17)	0.0027 (18)
C27	0.036 (2)	0.047 (2)	0.082 (3)	0.0186 (18)	0.0180 (19)	0.007 (2)
C28	0.042 (2)	0.040 (2)	0.066 (3)	0.0147 (17)	0.0131 (18)	0.0093 (18)
C29	0.0322 (18)	0.0332 (18)	0.046 (2)	0.0076 (15)	0.0108 (15)	0.0045 (15)
C30	0.0335 (18)	0.0367 (19)	0.0392 (19)	0.0092 (15)	0.0087 (15)	0.0054 (15)
O21	0.065 (2)	0.079 (2)	0.077 (2)	−0.0047 (18)	0.0171 (19)	0.003 (2)
O22	0.072 (2)	0.0505 (17)	0.087 (2)	0.0173 (15)	0.0254 (17)	0.0091 (15)
O23	0.0456 (16)	0.0439 (16)	0.0679 (18)	0.0051 (13)	0.0177 (14)	0.0126 (13)

Geometric parameters (Å, º) top

Ca1—O12	2.317 (3)	C9—C10	1.432 (5)
Ca1—O9	2.331 (3)	C10—C15	1.389 (4)
Ca1—O10	2.383 (3)	C10—C11	1.417 (5)
Ca1—O13	2.383 (3)	C11—C12	1.359 (5)
Ca1—O11	2.453 (3)	C12—C13	1.391 (5)
Ca1—O8	2.456 (3)	C12—H12	0.9300
Ca1—O7	2.481 (3)	C13—C14	1.409 (5)
Ca1—H8B	2.74 (4)	C14—C15	1.393 (4)
Ca1—H9B	2.77 (4)	S1—O19	1.441 (3)
S2—O7	1.445 (3)	S1—O20	1.448 (3)
S2—O6	1.446 (3)	S1—O18	1.456 (3)
S2—O5	1.464 (3)	S1—C29	1.769 (3)
S2—C14	1.768 (3)	O14—C22	1.363 (4)
O1—C7	1.359 (4)	O14—C30	1.368 (4)
O1—C15	1.368 (4)	O15—C24	1.251 (4)
O2—C9	1.267 (4)	O16—C26	1.344 (4)
O3—C11	1.351 (4)	O16—H16	0.8200
O3—H3	0.8200	O17—C28	1.345 (4)
O4—C13	1.340 (4)	O17—H17	0.8200
O4—H4	0.8200	C16—C17	1.375 (5)
O8—H8A	0.82 (3)	C16—C21	1.392 (5)
O8—H8B	0.82 (4)	C16—H16A	0.9300
O9—H9A	0.83 (3)	C17—C18	1.376 (6)
O9—H9B	0.82 (3)	C17—H17A	0.9300
O10—H10A	0.82 (3)	C18—C19	1.372 (6)
O10—H10B	0.82 (3)	C18—H18	0.9300
O11—H11B	0.82 (3)	C19—C20	1.378 (6)
O11—H11A	0.82 (4)	C19—H19	0.9300
O12—H12A	0.82 (4)	C20—C21	1.377 (5)
O12—H12B	0.81 (3)	C20—H20	0.9300
O13—H13B	0.82 (3)	C21—C22	1.474 (5)
O13—H13A	0.82 (3)	C22—C23	1.340 (5)
C1—C2	1.381 (5)	C23—C24	1.435 (5)
C1—C6	1.403 (4)	C23—H23	0.9300
C1—H1	0.9300	C24—C25	1.446 (5)
C2—C3	1.372 (5)	C25—C30	1.387 (5)
C2—H2	0.9300	C25—C26	1.413 (5)
C3—C4	1.381 (5)	C26—C27	1.363 (5)
C3—H3A	0.9300	C27—C28	1.393 (5)
C4—C5	1.380 (5)	C27—H27	0.9300
C4—H4A	0.9300	C28—C29	1.412 (5)
C5—C6	1.391 (5)	C29—C30	1.395 (4)
C5—H5	0.9300	O21—H21B	0.82 (3)
C6—C7	1.468 (4)	O21—H21A	0.83 (4)
C7—C8	1.354 (4)	O23—H23B	0.82 (4)
C8—C9	1.429 (5)	O23—H23A	0.82 (4)
C8—H8	0.9300

O12—Ca1—O9	166.74 (12)	C8—C7—C6	126.7 (3)
O12—Ca1—O10	79.54 (12)	O1—C7—C6	111.8 (3)
O9—Ca1—O10	87.19 (13)	C7—C8—C9	120.9 (3)
O12—Ca1—O13	78.35 (12)	C7—C8—H8	119.6
O9—Ca1—O13	113.01 (13)	C9—C8—H8	119.6
O10—Ca1—O13	142.40 (12)	O2—C9—C8	121.9 (3)
O12—Ca1—O11	95.00 (11)	O2—C9—C10	121.5 (3)
O9—Ca1—O11	81.03 (11)	C8—C9—C10	116.5 (3)
O10—Ca1—O11	72.82 (10)	C15—C10—C11	117.6 (3)
O13—Ca1—O11	79.24 (11)	C15—C10—C9	120.0 (3)
O12—Ca1—O8	82.43 (11)	C11—C10—C9	122.4 (3)
O9—Ca1—O8	94.11 (11)	O3—C11—C12	119.7 (3)
O10—Ca1—O8	74.99 (11)	O3—C11—C10	119.6 (3)
O13—Ca1—O8	130.90 (11)	C12—C11—C10	120.7 (3)
O11—Ca1—O8	147.62 (10)	C11—C12—C13	120.7 (3)
O12—Ca1—O7	113.40 (10)	C11—C12—H12	119.6
O9—Ca1—O7	77.30 (9)	C13—C12—H12	119.6
O10—Ca1—O7	142.23 (12)	O4—C13—C12	115.9 (3)
O13—Ca1—O7	75.02 (10)	O4—C13—C14	123.2 (3)
O11—Ca1—O7	136.16 (10)	C12—C13—C14	120.8 (3)
O8—Ca1—O7	72.10 (10)	C15—C14—C13	117.0 (3)
O12—Ca1—H8B	99.3 (5)	C15—C14—S2	120.0 (2)
O9—Ca1—H8B	77.3 (5)	C13—C14—S2	122.9 (3)
O10—Ca1—H8B	76.7 (10)	O1—C15—C10	120.3 (3)
O13—Ca1—H8B	136.9 (10)	O1—C15—C14	116.6 (3)
O11—Ca1—H8B	143.1 (10)	C10—C15—C14	123.1 (3)
O8—Ca1—H8B	17.0 (5)	O19—S1—O20	111.90 (16)
O7—Ca1—H8B	66.5 (10)	O19—S1—O18	112.13 (18)
O12—Ca1—H9B	169.3 (9)	O20—S1—O18	112.59 (17)
O9—Ca1—H9B	15.9 (7)	O19—S1—C29	107.48 (15)
O10—Ca1—H9B	98.9 (8)	O20—S1—C29	107.24 (16)
O13—Ca1—H9B	108.1 (10)	O18—S1—C29	105.01 (16)
O11—Ca1—H9B	94.7 (8)	C22—O14—C30	120.7 (3)
O8—Ca1—H9B	86.9 (9)	C26—O16—H16	109.5
O7—Ca1—H9B	61.6 (7)	C28—O17—H17	109.5
H8B—Ca1—H9B	70.1 (11)	C17—C16—C21	120.1 (3)
O7—S2—O6	112.63 (17)	C17—C16—H16A	120.0
O7—S2—O5	112.18 (16)	C21—C16—H16A	120.0
O6—S2—O5	111.20 (18)	C16—C17—C18	120.5 (4)
O7—S2—C14	108.38 (16)	C16—C17—H17A	119.7
O6—S2—C14	106.78 (16)	C18—C17—H17A	119.7
O5—S2—C14	105.20 (16)	C19—C18—C17	119.6 (4)
C7—O1—C15	120.8 (2)	C19—C18—H18	120.2
C11—O3—H3	109.5	C17—C18—H18	120.2
C13—O4—H4	109.5	C18—C19—C20	120.3 (4)
S2—O7—Ca1	141.98 (14)	C18—C19—H19	119.9
Ca1—O8—H8A	106 (3)	C20—C19—H19	119.9
Ca1—O8—H8B	102 (3)	C21—C20—C19	120.6 (4)
H8A—O8—H8B	114 (5)	C21—C20—H20	119.7
Ca1—O9—H9A	129 (3)	C19—C20—H20	119.7
Ca1—O9—H9B	114 (3)	C20—C21—C16	118.9 (3)
H9A—O9—H9B	114 (5)	C20—C21—C22	120.7 (3)
Ca1—O10—H10A	117 (3)	C16—C21—C22	120.4 (3)
Ca1—O10—H10B	127 (3)	C23—C22—O14	121.4 (3)
H10A—O10—H10B	112 (5)	C23—C22—C21	126.8 (3)
Ca1—O11—H11B	125 (3)	O14—C22—C21	111.8 (3)
Ca1—O11—H11A	128 (3)	C22—C23—C24	121.8 (3)
H11B—O11—H11A	104 (5)	C22—C23—H23	119.1
Ca1—O12—H12A	121 (3)	C24—C23—H23	119.1
Ca1—O12—H12B	134 (4)	O15—C24—C23	123.3 (3)
H12A—O12—H12B	105 (5)	O15—C24—C25	121.3 (3)
Ca1—O13—H13B	122 (3)	C23—C24—C25	115.4 (3)
Ca1—O13—H13A	129 (4)	C30—C25—C26	118.1 (3)
H13B—O13—H13A	109 (5)	C30—C25—C24	120.1 (3)
C2—C1—C6	119.9 (3)	C26—C25—C24	121.8 (3)
C2—C1—H1	120.1	O16—C26—C27	119.8 (3)
C6—C1—H1	120.1	O16—C26—C25	120.0 (3)
C3—C2—C1	120.7 (3)	C27—C26—C25	120.3 (3)
C3—C2—H2	119.6	C26—C27—C28	120.7 (3)
C1—C2—H2	119.6	C26—C27—H27	119.6
C2—C3—C4	119.9 (4)	C28—C27—H27	119.6
C2—C3—H3A	120.0	O17—C28—C27	116.5 (3)
C4—C3—H3A	120.0	O17—C28—C29	122.3 (3)
C5—C4—C3	120.3 (4)	C27—C28—C29	121.2 (3)
C5—C4—H4A	119.9	C30—C29—C28	116.4 (3)
C3—C4—H4A	119.9	C30—C29—S1	120.7 (3)
C4—C5—C6	120.4 (3)	C28—C29—S1	122.8 (3)
C4—C5—H5	119.8	O14—C30—C25	120.5 (3)
C6—C5—H5	119.8	O14—C30—C29	116.2 (3)
C5—C6—C1	118.8 (3)	C25—C30—C29	123.3 (3)
C5—C6—C7	120.7 (3)	H21B—O21—H21A	115 (5)
C1—C6—C7	120.4 (3)	H23B—O23—H23A	103 (5)
C8—C7—O1	121.4 (3)

O6—S2—O7—Ca1	102.4 (3)	C13—C14—C15—O1	−178.3 (3)
O5—S2—O7—Ca1	−23.9 (3)	S2—C14—C15—O1	4.8 (4)
C14—S2—O7—Ca1	−139.7 (2)	C13—C14—C15—C10	2.8 (5)
O12—Ca1—O7—S2	−176.2 (2)	S2—C14—C15—C10	−174.1 (3)
O9—Ca1—O7—S2	12.1 (3)	C21—C16—C17—C18	−0.9 (6)
O10—Ca1—O7—S2	80.2 (3)	C16—C17—C18—C19	−0.3 (7)
O13—Ca1—O7—S2	−106.3 (3)	C17—C18—C19—C20	1.5 (7)
O11—Ca1—O7—S2	−50.2 (3)	C18—C19—C20—C21	−1.4 (7)
O8—Ca1—O7—S2	110.7 (3)	C19—C20—C21—C16	0.2 (6)
C6—C1—C2—C3	0.1 (5)	C19—C20—C21—C22	−179.4 (4)
C1—C2—C3—C4	0.6 (6)	C17—C16—C21—C20	1.0 (6)
C2—C3—C4—C5	−0.6 (6)	C17—C16—C21—C22	−179.4 (4)
C3—C4—C5—C6	−0.1 (6)	C30—O14—C22—C23	1.6 (5)
C4—C5—C6—C1	0.7 (5)	C30—O14—C22—C21	−178.6 (3)
C4—C5—C6—C7	179.9 (3)	C20—C21—C22—C23	6.8 (6)
C2—C1—C6—C5	−0.8 (5)	C16—C21—C22—C23	−172.7 (4)
C2—C1—C6—C7	−179.9 (3)	C20—C21—C22—O14	−173.0 (3)
C15—O1—C7—C8	1.3 (5)	C16—C21—C22—O14	7.4 (5)
C15—O1—C7—C6	−178.5 (3)	O14—C22—C23—C24	−0.6 (5)
C5—C6—C7—C8	−174.4 (3)	C21—C22—C23—C24	179.6 (3)
C1—C6—C7—C8	4.7 (5)	C22—C23—C24—O15	179.0 (3)
C5—C6—C7—O1	5.4 (4)	C22—C23—C24—C25	−1.2 (5)
C1—C6—C7—O1	−175.5 (3)	O15—C24—C25—C30	−178.0 (3)
O1—C7—C8—C9	−1.0 (5)	C23—C24—C25—C30	2.1 (5)
C6—C7—C8—C9	178.8 (3)	O15—C24—C25—C26	1.0 (6)
C7—C8—C9—O2	178.9 (3)	C23—C24—C25—C26	−178.9 (3)
C7—C8—C9—C10	−0.4 (5)	C30—C25—C26—O16	178.1 (3)
O2—C9—C10—C15	−177.9 (3)	C24—C25—C26—O16	−1.0 (6)
C8—C9—C10—C15	1.3 (5)	C30—C25—C26—C27	−0.8 (6)
O2—C9—C10—C11	1.8 (5)	C24—C25—C26—C27	−179.9 (4)
C8—C9—C10—C11	−178.9 (3)	O16—C26—C27—C28	−177.2 (4)
C15—C10—C11—O3	178.8 (3)	C25—C26—C27—C28	1.6 (6)
C9—C10—C11—O3	−0.9 (5)	C26—C27—C28—O17	177.9 (4)
C15—C10—C11—C12	−0.5 (5)	C26—C27—C28—C29	−1.4 (6)
C9—C10—C11—C12	179.8 (3)	O17—C28—C29—C30	−178.9 (4)
O3—C11—C12—C13	−177.4 (3)	C27—C28—C29—C30	0.3 (6)
C10—C11—C12—C13	1.9 (6)	O17—C28—C29—S1	−1.4 (6)
C11—C12—C13—O4	178.1 (4)	C27—C28—C29—S1	177.9 (3)
C11—C12—C13—C14	−1.0 (6)	O19—S1—C29—C30	63.6 (3)
O4—C13—C14—C15	179.7 (3)	O20—S1—C29—C30	−56.9 (3)
C12—C13—C14—C15	−1.3 (5)	O18—S1—C29—C30	−176.8 (3)
O4—C13—C14—S2	−3.5 (5)	O19—S1—C29—C28	−113.8 (3)
C12—C13—C14—S2	175.5 (3)	O20—S1—C29—C28	125.7 (3)
O7—S2—C14—C15	−63.6 (3)	O18—S1—C29—C28	5.7 (4)
O6—S2—C14—C15	58.0 (3)	C22—O14—C30—C25	−0.6 (5)
O5—S2—C14—C15	176.3 (3)	C22—O14—C30—C29	179.4 (3)
O7—S2—C14—C13	119.7 (3)	C26—C25—C30—O14	179.6 (3)
O6—S2—C14—C13	−118.7 (3)	C24—C25—C30—O14	−1.2 (5)
O5—S2—C14—C13	−0.5 (4)	C26—C25—C30—C29	−0.3 (5)
C7—O1—C15—C10	−0.3 (4)	C24—C25—C30—C29	178.8 (3)
C7—O1—C15—C14	−179.2 (3)	C28—C29—C30—O14	−179.4 (3)
C11—C10—C15—O1	179.2 (3)	S1—C29—C30—O14	3.0 (4)
C9—C10—C15—O1	−1.0 (5)	C28—C29—C30—C25	0.5 (5)
C11—C10—C15—C14	−2.0 (5)	S1—C29—C30—C25	−177.1 (3)
C9—C10—C15—C14	177.8 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···O2	0.82	1.85	2.576 (4)	148
O4—H4···O5	0.82	1.82	2.579 (4)	153
O8—H8B···O17ⁱ	0.82 (4)	2.20 (3)	2.934 (4)	149 (4)
O8—H8A···O20ⁱⁱ	0.82 (3)	1.97 (3)	2.790 (4)	176 (5)
O9—H9B···O5	0.82 (4)	1.99 (4)	2.780 (4)	163 (5)
O9—H9A···O23ⁱⁱⁱ	0.83 (3)	1.92 (3)	2.743 (4)	175 (5)
O10—H10B···O20ⁱⁱ	0.82 (3)	2.13 (2)	2.874 (4)	151 (5)
O10—H10A···O22	0.82 (3)	1.90 (3)	2.715 (4)	171 (5)
O11—H11B···O6ⁱⁱⁱ	0.82 (3)	2.36 (3)	3.024 (4)	139 (4)
O11—H11A···O19	0.82 (4)	2.19 (4)	3.003 (4)	175 (5)
O12—H12B···O15^iv	0.81 (3)	1.98 (3)	2.771 (4)	165 (5)
O12—H12A···O21	0.82 (4)	1.88 (4)	2.695 (5)	177 (4)
O13—H13B···O3^v	0.82 (4)	2.05 (4)	2.867 (4)	174 (5)
O13—H13A···O23	0.82 (3)	2.00 (3)	2.819 (4)	173 (5)
O16—H16···O15	0.82	1.83	2.567 (4)	148
O17—H17···O18	0.82	1.80	2.556 (4)	153
O21—H21B···O18	0.82 (3)	2.05 (4)	2.870 (4)	176 (5)
O21—H21A···O22ⁱⁱ	0.82 (3)	2.01 (3)	2.826 (5)	173 (5)
O23—H23A···O2^vi	0.82 (4)	2.00 (4)	2.816 (4)	171 (5)
O23—H23B···O6	0.82 (4)	1.95 (4)	2.755 (4)	168 (5)
C12—H12···O11ⁱ	0.93	2.55	3.462 (5)	168
C20—H20···O8^vii	0.93	2.52	3.410 (5)	161

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

Experimental details

Crystal data
Chemical formula	[Ca(C₁₅H₉O₇S)(H₂O)₆](C₁₅H₉O₇S)·3H₂O
M_r	868.79
Crystal system, space group	Triclinic, P1
Temperature (K)	296
a, b, c (Å)	11.360 (2), 12.390 (1), 13.975 (2)
α, β, γ (°)	95.136 (2), 102.167 (3), 107.423 (2)
V (Å³)	1809.9 (4)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.38
Crystal size (mm)	0.36 × 0.23 × 0.14

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 1999)
T_min, T_max	0.874, 0.947
No. of measured, independent and observed [I > 2σ(I)] reflections	9179, 6299, 4416
R_int	0.026
(sin θ/λ)_max (Å⁻¹)	0.596

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.055, 0.167, 1.04
No. of reflections	6299
No. of parameters	558
No. of restraints	16
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.40, −0.40

Computer programs: SMART (Bruker, 1999), SAINT-Plus (Bruker, 1999), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).