Sodium quercetin-8-sulfonate trihydrate

Zhang, X.; Li, Y.; Chen, P.; Han, T.; Zhao, W.

doi:10.1107/S1600536810029570

metal-organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 66| Part 8| August 2010| Pages m1036-m1037

https://doi.org/10.1107/S1600536810029570

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Sodium quercetin-8-sulfonate trihydrate

Xian Zhang,^a Yueqing Li,^a ^* Pingping Chen,^a Tianjiao Han ^a and Weijie Zhao ^a

^aSchool of Pharmaceutical Science and Technology, Dalian Unversity of Technology, PO Box 90, Zhongshan Road 158, Dalian 116012, People's Republic of China
^*Correspondence e-mail: yueqingli@dlut.edu.cn

(Received 30 June 2010; accepted 25 July 2010; online 31 July 2010)

The organic anion of the title compound, {[Na(C₁₅H₉O₁₀S)(H₂O)₂]·H₂O}_n {systematic name: poly[[diaqua[μ-2-(3,4-dihydroxyphenyl)-3,5,7-trihydroxy-4-oxo-4H-chromene-8-sulfonato]sodium] monohydrate]}, has a nearly planar structure. The Na atom is six-coordinated by O atoms, two from water molecules and four from the anion. The dihedral angle between the ring systems in the anion is 10.1 (1)°. Intramolecular O—H⋯S and O—H⋯O interactions occur. In the crystal structure, an extensive network of classical intermolecular O—H⋯S and O—H⋯O hydrogen bonds forms layers along the c axis.

Related literature

The title compound is of interest for its potential anti-inflammatory and antiviral properties. For the synthesis and structures of analogues of the title compound, see: Kopacz et al. (1978 , 1983 ); Cheng (2006 ); Wang (2007 ); Liu et al. (2009 ). For the anti-HIV properties of flavonoids and their derivatives, see: Kashiwada et al. (2005 ); Lameira et al. (2006 ); Reutrakul et al. (2007 ); Li et al. (2010 ).

Experimental

Crystal data

[Na(C₁₅H₉O₁₀S)(H₂O)₂]·H₂O
M_r = 458.33
Triclinic, $[P \overline 1]$
a = 7.595 (3) Å
b = 10.157 (3) Å
c = 12.183 (4) Å
α = 76.576 (4)°
β = 81.031 (4)°
γ = 77.385 (3)°
V = 886.6 (5) Å³
Z = 2
Mo Kα radiation
μ = 0.28 mm⁻¹
T = 295 K
0.60 × 0.31 × 0.24 mm

Data collection

Bruker SMART APEX CCD diffractometer
4109 measured reflections
2994 independent reflections
2691 reflections with I > 2σ(I)
R_int = 0.013

Refinement

R[F² > 2σ(F²)] = 0.034
wR(F²) = 0.101
S = 1.01
2994 reflections
289 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.24 e Å⁻³
Δρ_min = −0.41 e Å⁻³

Table 1
Selected bond lengths (Å)

Na1—O2ⁱ	2.3517 (16)
Na1—O6ⁱⁱ	2.3784 (16)
Na1—O1ⁱⁱ	2.3919 (17)
Na1—O13	2.4070 (18)
Na1—O12	2.555 (2)
Na1—O9	2.4074 (15)
Symmetry codes: (i) -x+1, -y, -z+1; (ii) x, y, z-1.

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1A⋯O13ⁱⁱⁱ	0.82	1.88	2.677 (2)	164
O4—H4A⋯O2ⁱ	0.82	1.97	2.786 (2)	170
O4—H4A⋯S1ⁱ	0.82	2.97	3.7139 (18)	152
O5—H5B⋯O9	0.82	1.89	2.619 (2)	148
O6—H6A⋯O12ⁱ	0.82	1.87	2.688 (2)	177
O8—H8B⋯O3	0.82	1.85	2.596 (2)	152
O8—H8B⋯S1	0.82	2.65	3.1344 (16)	120
O13—H13A⋯O11^iv	0.85 (3)	1.95 (3)	2.799 (3)	174 (3)
O13—H13B⋯O7^v	0.79 (3)	2.22 (3)	2.983 (2)	161 (3)
O13—H13B⋯O9	0.79 (3)	2.64 (3)	3.017 (2)	111 (2)
O13—H13B⋯S1^v	0.79 (3)	3.02 (3)	3.7333 (18)	152 (3)
O12—H12A⋯O11^vi	0.83 (3)	2.07 (3)	2.850 (3)	155 (3)
O12—H12B⋯O7ⁱ	0.90 (3)	1.87 (3)	2.767 (2)	172 (3)
O12—H12B⋯S1ⁱ	0.90 (3)	2.74 (3)	3.494 (2)	142 (2)
O11—H11A⋯O5^vii	0.86 (4)	2.10 (4)	2.914 (3)	158 (3)
O11—H11B⋯O3	0.87 (4)	1.99 (4)	2.832 (2)	163 (3)
Symmetry codes: (i) -x+1, -y, -z+1; (iii) -x+1, -y+1, -z+1; (iv) x, y+1, z-1; (v) -x+2, -y, -z+1; (vi) x-1, y+1, z-1; (vii) -x+2, -y-1, -z+1.

Data collection: APEX2 (Bruker, 2005 ); cell refinement: SAINT-Plus (Bruker, 2001 ); data reduction: SAINT-Plus; 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.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536810029570/rk2218sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810029570/rk2218Isup2.hkl

checkCIF report

Comment top

The flavonoids and their derivants have been investigated for a long time for their notable antiviral activity especially against HIV-1 (Kashiwada et al., 2005; Lameira et al., 2006; Reutrakul et al., 2007). A great many of substituents have been applied to modify the structures to develop their solubility in water such as sulfonic group (Cheng, 2006; Kopacz, et al., 1978; Kopacz et al., 1983; Liu et al., 2009; Wang, 2007). The title compound is an excellent antagonist of Vif which has been found to be a novel hit of HIV–1 (Li et al., 2010). The crystal structure of the title compound may be helpful to the understanding of quantitative structure–activity relationship.

Quercetin–8–sulfonate sodium is synthesized from quercetin via sulfonation (Fig.1). The asymmetric unit of the title compound contains a quercetin–8–sulfonic anion, a sodium cation and three molecules of water (Fig.2). The anion structure is nearly coplanar.

In the crystal structure, sodium cation form six contacts 2.392 (2)–2.555 (2)Å (Fig.3) with oxygen atoms: two water atoms and four with other atoms of anion.

The hydrogen bonds assist crystal packing in layers along the c axis, (Table 1, Fig. 4).

Related literature top

The title compound is of interest for its potential anti-inflammatory and antiviral properties. For the synthesis and structures of analogues of the title compound, see: Kopacz et al. (1978, 1983); Cheng (2006); Wang (2007); Liu et al. (2009). For the anti-HIV properties of flavonoids and their derivatives, see: Kashiwada et al. (2005); Lameira et al. (2006); Reutrakul et al. (2007); Li et al. (2010).

Structure description top

In the crystal structure, sodium cation form six contacts 2.392 (2)–2.555 (2)Å (Fig.3) with oxygen atoms: two water atoms and four with other atoms of anion.

The hydrogen bonds assist crystal packing in layers along the c axis, (Table 1, Fig. 4).

The title compound is of interest for its potential anti-inflammatory and antiviral properties. For the synthesis and structures of analogues of the title compound, see: Kopacz et al. (1978, 1983); Cheng (2006); Wang (2007); Liu et al. (2009). For the anti-HIV properties of flavonoids and their derivatives, see: Kashiwada et al. (2005); Lameira et al. (2006); Reutrakul et al. (2007); Li et al. (2010).

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus (Bruker, 2001); 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 synthetic route for title compound.
	Fig. 2. The part of molecular structure of title compound, showing the atom numbering scheme. Displacement ellipsoids are drawn at 30% probability level. H atoms are presented as a small spheres of arbitrary radius.
	Fig. 3. The oxygen environment of sodium cation. H atoms are omitted for clarity. Symmetry codes see in table of geometric parameters.
	Fig. 4. A view of the packing of title compound. Dashed lines indicate O—H···O hydrogen bonds.

poly[[diaqua[µ-2-(3,4-dihydroxyphenyl)-3,5,7-trihydroxy-4-oxo-4H- chromene-8-sulfonato]sodium] monoydrate]3,3',4',5,7-pentahydroxyflavone-8-sulfonate sodium trihydrate top

Crystal data top

[Na(C₁₅H₉O₁₀S)(H₂O)₂]·H₂O	Z = 2
M_r = 458.33	F(000) = 472
Triclinic, P1	D_x = 1.717 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.595 (3) Å	Cell parameters from 3467 reflections
b = 10.157 (3) Å	θ = 2.3–26.2°
c = 12.183 (4) Å	µ = 0.28 mm⁻¹
α = 76.576 (4)°	T = 295 K
β = 81.031 (4)°	Needle, pale yellow
γ = 77.385 (3)°	0.60 × 0.31 × 0.24 mm
V = 886.6 (5) Å³

Data collection top

Bruker SMART APEX CCD diffractometer	2691 reflections with I > 2σ(I)
Radiation source: fine–focus sealed tube	R_int = 0.013
Graphite monochromator	θ_max = 25.0°, θ_min = 2.4°
φ– and ω–scans	h = −9→8
4109 measured reflections	k = −12→10
2994 independent reflections	l = −14→9

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)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.101	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	w = 1/[σ²(F_o²) + (0.0667P)² + 0.3015P] where P = (F_o² + 2F_c²)/3
2994 reflections	(Δ/σ)_max < 0.001
289 parameters	Δρ_max = 0.24 e Å⁻³
0 restraints	Δρ_min = −0.41 e Å⁻³

Crystal data top

[Na(C₁₅H₉O₁₀S)(H₂O)₂]·H₂O	γ = 77.385 (3)°
M_r = 458.33	V = 886.6 (5) Å³
Triclinic, P1	Z = 2
a = 7.595 (3) Å	Mo Kα radiation
b = 10.157 (3) Å	µ = 0.28 mm⁻¹
c = 12.183 (4) Å	T = 295 K
α = 76.576 (4)°	0.60 × 0.31 × 0.24 mm
β = 81.031 (4)°

Data collection top

Bruker SMART APEX CCD diffractometer	2691 reflections with I > 2σ(I)
4109 measured reflections	R_int = 0.013
2994 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.034	0 restraints
wR(F²) = 0.101	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	Δρ_max = 0.24 e Å⁻³
2994 reflections	Δρ_min = −0.41 e Å⁻³
289 parameters

Special details top

Experimental. The synthesis of title compound is shown in Fig. 1. The crude product was recrystallized by CH₃OH/H₂O = 3/1 in the yield of 60%. However, the single crystals were obtained in 0.9% NaCl aqueous solution at a concentration of 0.3 mg ml^-1.

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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
S1	0.91509 (6)	−0.29304 (4)	0.71144 (4)	0.02554 (15)
O1	0.4645 (2)	0.37543 (14)	0.91755 (12)	0.0410 (4)
H1A	0.4085	0.4545	0.8995	0.062*
O2	0.72475 (18)	−0.29014 (14)	0.75277 (11)	0.0316 (3)
O3	1.0212 (2)	−0.43287 (15)	0.73041 (12)	0.0423 (4)
O4	0.5196 (2)	0.27317 (13)	0.40069 (11)	0.0347 (3)
H4A	0.4517	0.2682	0.3563	0.052*
O5	0.9040 (2)	−0.11772 (16)	0.21432 (11)	0.0427 (4)
H5B	0.8299	−0.0458	0.2001	0.064*
O6	0.6438 (2)	0.11901 (14)	0.94873 (11)	0.0409 (4)
H6A	0.6838	0.0365	0.9526	0.061*
O7	0.99190 (19)	−0.20151 (15)	0.75754 (12)	0.0373 (3)
O8	1.14625 (18)	−0.43644 (14)	0.52006 (12)	0.0357 (3)
H8B	1.1330	−0.4599	0.5895	0.054*
O9	0.66041 (18)	0.09603 (13)	0.25617 (11)	0.0308 (3)
O10	0.74224 (17)	−0.02632 (12)	0.58747 (10)	0.0260 (3)
C1	0.6350 (3)	0.11097 (19)	0.75271 (16)	0.0276 (4)
H1B	0.6968	0.0200	0.7645	0.033*
C2	0.9124 (3)	−0.1552 (2)	0.32742 (16)	0.0293 (4)
C3	0.4925 (3)	0.31432 (19)	0.62889 (16)	0.0297 (4)
H3B	0.4576	0.3606	0.5580	0.036*
C4	0.5007 (3)	0.31472 (19)	0.82552 (16)	0.0296 (4)
C5	0.4522 (3)	0.38082 (19)	0.71898 (17)	0.0317 (4)
H5A	0.3912	0.4720	0.7077	0.038*
C6	0.5936 (3)	0.17823 (19)	0.84191 (16)	0.0280 (4)
C7	1.0321 (2)	−0.31769 (18)	0.48751 (16)	0.0267 (4)
C8	1.0238 (3)	−0.2759 (2)	0.37051 (17)	0.0314 (4)
H8A	1.0939	−0.3301	0.3217	0.038*
C9	0.8119 (2)	−0.06762 (18)	0.39941 (15)	0.0244 (4)
C10	0.8272 (2)	−0.10881 (18)	0.51493 (15)	0.0239 (4)
C11	0.5857 (2)	0.17729 (18)	0.64382 (15)	0.0238 (4)
C12	0.6164 (2)	0.14599 (18)	0.43889 (15)	0.0250 (4)
C13	0.6439 (2)	0.10360 (18)	0.55063 (15)	0.0239 (4)
C14	0.6942 (2)	0.05993 (18)	0.35794 (15)	0.0241 (4)
C15	0.9291 (2)	−0.23665 (18)	0.56233 (15)	0.0245 (4)
Na1	0.49543 (10)	0.22781 (8)	0.10033 (6)	0.0340 (2)
O13	0.7175 (2)	0.36463 (15)	0.09986 (14)	0.0366 (3)
H13A	0.790 (4)	0.362 (3)	0.039 (2)	0.055*
H13B	0.776 (4)	0.325 (3)	0.150 (2)	0.055*
O12	0.2274 (2)	0.15022 (17)	0.04739 (15)	0.0459 (4)
H12A	0.182 (4)	0.209 (3)	−0.006 (3)	0.069*
H12B	0.151 (4)	0.161 (3)	0.110 (3)	0.069*
O11	0.9733 (3)	−0.6600 (2)	0.91012 (15)	0.0564 (5)
H11A	0.982 (5)	−0.731 (4)	0.882 (3)	0.085*
H11B	0.986 (5)	−0.582 (4)	0.866 (3)	0.085*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0235 (3)	0.0283 (3)	0.0212 (3)	−0.00011 (18)	−0.00574 (18)	−0.00029 (18)
O1	0.0618 (10)	0.0307 (7)	0.0262 (8)	0.0075 (7)	−0.0099 (7)	−0.0089 (6)
O2	0.0257 (7)	0.0430 (8)	0.0247 (7)	−0.0058 (6)	−0.0031 (5)	−0.0045 (6)
O3	0.0463 (9)	0.0363 (8)	0.0297 (8)	0.0110 (7)	−0.0030 (6)	0.0039 (6)
O4	0.0476 (9)	0.0261 (7)	0.0292 (7)	0.0043 (6)	−0.0207 (6)	−0.0031 (6)
O5	0.0553 (10)	0.0449 (8)	0.0197 (7)	0.0086 (7)	−0.0050 (6)	−0.0063 (6)
O6	0.0618 (10)	0.0324 (7)	0.0219 (7)	0.0103 (7)	−0.0124 (7)	−0.0051 (6)
O7	0.0377 (8)	0.0490 (9)	0.0286 (7)	−0.0148 (7)	−0.0095 (6)	−0.0045 (6)
O8	0.0338 (8)	0.0335 (7)	0.0316 (8)	0.0091 (6)	−0.0045 (6)	−0.0042 (6)
O9	0.0346 (7)	0.0344 (7)	0.0214 (7)	−0.0050 (6)	−0.0085 (6)	0.0002 (6)
O10	0.0303 (7)	0.0240 (6)	0.0201 (6)	0.0031 (5)	−0.0057 (5)	−0.0027 (5)
C1	0.0314 (10)	0.0235 (9)	0.0250 (10)	−0.0009 (7)	−0.0059 (8)	−0.0016 (7)
C2	0.0290 (10)	0.0354 (10)	0.0215 (9)	−0.0047 (8)	−0.0025 (7)	−0.0035 (8)
C3	0.0321 (10)	0.0292 (10)	0.0253 (10)	0.0012 (8)	−0.0099 (8)	−0.0028 (8)
C4	0.0311 (10)	0.0292 (10)	0.0280 (10)	−0.0023 (8)	−0.0045 (8)	−0.0073 (8)
C5	0.0347 (11)	0.0266 (9)	0.0299 (10)	0.0041 (8)	−0.0083 (8)	−0.0041 (8)
C6	0.0317 (10)	0.0293 (10)	0.0205 (9)	−0.0021 (8)	−0.0070 (7)	−0.0008 (8)
C7	0.0220 (9)	0.0277 (9)	0.0286 (10)	−0.0020 (7)	−0.0034 (7)	−0.0040 (8)
C8	0.0304 (10)	0.0341 (10)	0.0270 (10)	−0.0008 (8)	0.0010 (8)	−0.0088 (8)
C9	0.0232 (9)	0.0268 (9)	0.0225 (9)	−0.0058 (7)	−0.0040 (7)	−0.0015 (7)
C10	0.0211 (9)	0.0268 (9)	0.0230 (9)	−0.0041 (7)	−0.0021 (7)	−0.0046 (7)
C11	0.0226 (9)	0.0245 (9)	0.0244 (9)	−0.0048 (7)	−0.0051 (7)	−0.0031 (7)
C12	0.0241 (9)	0.0244 (9)	0.0258 (9)	−0.0048 (7)	−0.0074 (7)	−0.0005 (7)
C13	0.0213 (9)	0.0222 (8)	0.0266 (10)	−0.0025 (7)	−0.0064 (7)	−0.0007 (7)
C14	0.0219 (9)	0.0285 (9)	0.0219 (9)	−0.0092 (7)	−0.0044 (7)	0.0004 (7)
C15	0.0223 (9)	0.0269 (9)	0.0224 (9)	−0.0029 (7)	−0.0040 (7)	−0.0023 (7)
Na1	0.0363 (4)	0.0398 (4)	0.0239 (4)	−0.0026 (3)	−0.0038 (3)	−0.0064 (3)
O13	0.0419 (9)	0.0356 (8)	0.0295 (8)	−0.0001 (6)	−0.0124 (6)	−0.0025 (6)
O12	0.0565 (10)	0.0388 (8)	0.0330 (9)	0.0063 (7)	−0.0072 (8)	−0.0014 (7)
O11	0.0839 (14)	0.0463 (10)	0.0333 (9)	−0.0074 (9)	−0.0062 (9)	−0.0016 (8)

Geometric parameters (Å, º) top

S1—O7	1.4498 (15)	C3—C11	1.401 (3)
S1—O2	1.4510 (15)	C3—H3B	0.9300
S1—O3	1.4581 (15)	C4—C5	1.381 (3)
S1—C15	1.7671 (19)	C4—C6	1.396 (3)
O1—C4	1.365 (2)	C5—H5A	0.9300
O1—Na1ⁱ	2.3919 (17)	C7—C8	1.397 (3)
O1—H1A	0.8200	C7—C15	1.402 (3)
O2—Na1ⁱⁱ	2.3517 (16)	C8—H8A	0.9300
O4—C12	1.356 (2)	C9—C10	1.388 (3)
O4—H4A	0.8200	C9—C14	1.437 (3)
O5—C2	1.349 (2)	C10—C15	1.404 (2)
O5—H5B	0.8200	C11—C13	1.462 (3)
O6—C6	1.375 (2)	C12—C13	1.364 (3)
O6—Na1ⁱ	2.3784 (16)	C12—C14	1.442 (3)
O6—H6A	0.8200	Na1—O2ⁱⁱ	2.3517 (16)
O8—C7	1.339 (2)	Na1—O6ⁱⁱⁱ	2.3784 (16)
O8—H8B	0.8200	Na1—O1ⁱⁱⁱ	2.3919 (17)
O9—C14	1.259 (2)	Na1—O13	2.4070 (18)
O9—Na1	2.4074 (15)	Na1—O12	2.555 (2)
O10—C10	1.353 (2)	Na1—O9	2.4074 (15)
O10—C13	1.378 (2)	O13—H13A	0.85 (3)
C1—C6	1.375 (3)	O13—H13B	0.79 (3)
C1—C11	1.409 (3)	O12—H12A	0.83 (3)
C1—H1B	0.9300	O12—H12B	0.90 (3)
C2—C8	1.371 (3)	O11—H11A	0.86 (4)
C2—C9	1.414 (3)	O11—H11B	0.87 (4)
C3—C5	1.380 (3)

O7—S1—O2	112.09 (8)	C10—C9—C14	119.29 (16)
O7—S1—O3	111.69 (9)	C2—C9—C14	122.76 (17)
O2—S1—O3	111.94 (9)	O10—C10—C9	120.78 (16)
O7—S1—C15	108.31 (8)	O10—C10—C15	116.87 (16)
O2—S1—C15	107.22 (8)	C9—C10—C15	122.35 (17)
O3—S1—C15	105.18 (8)	C3—C11—C1	117.98 (16)
C4—O1—Na1ⁱ	117.41 (12)	C3—C11—C13	123.15 (16)
C4—O1—H1A	109.5	C1—C11—C13	118.75 (16)
Na1ⁱ—O1—H1A	130.6	O4—C12—C13	120.25 (16)
S1—O2—Na1ⁱⁱ	141.71 (9)	O4—C12—C14	118.36 (15)
C12—O4—H4A	109.5	C13—C12—C14	121.35 (16)
C2—O5—H5B	109.5	C12—C13—O10	119.16 (16)
C6—O6—Na1ⁱ	117.44 (11)	C12—C13—C11	129.68 (16)
C6—O6—H6A	109.5	O10—C13—C11	111.15 (15)
Na1ⁱ—O6—H6A	126.9	O9—C14—C9	122.20 (17)
C7—O8—H8B	109.5	O9—C14—C12	121.20 (16)
C14—O9—Na1	155.71 (12)	C9—C14—C12	116.61 (16)
C10—O10—C13	122.23 (14)	C7—C15—C10	117.60 (17)
C6—C1—C11	121.25 (16)	C7—C15—S1	122.63 (14)
C6—C1—H1B	119.4	C10—C15—S1	119.70 (14)
C11—C1—H1B	119.4	O2ⁱⁱ—Na1—O6ⁱⁱⁱ	160.25 (6)
O5—C2—C8	119.29 (17)	O2ⁱⁱ—Na1—O1ⁱⁱⁱ	115.40 (6)
O5—C2—C9	119.81 (17)	O6ⁱⁱⁱ—Na1—O1ⁱⁱⁱ	67.01 (5)
C8—C2—C9	120.86 (17)	O2ⁱⁱ—Na1—O13	102.00 (6)
C5—C3—C11	120.22 (17)	O6ⁱⁱⁱ—Na1—O13	97.74 (6)
C5—C3—H3B	119.9	O1ⁱⁱⁱ—Na1—O13	81.25 (6)
C11—C3—H3B	119.9	O2ⁱⁱ—Na1—O9	82.95 (6)
O1—C4—C5	123.83 (17)	O6ⁱⁱⁱ—Na1—O9	101.98 (6)
O1—C4—C6	116.98 (17)	O1ⁱⁱⁱ—Na1—O9	154.60 (6)
C5—C4—C6	119.19 (17)	O13—Na1—O9	77.62 (6)
C3—C5—C4	121.35 (17)	O2ⁱⁱ—Na1—O12	81.05 (6)
C3—C5—H5A	119.3	O6ⁱⁱⁱ—Na1—O12	80.12 (6)
C4—C5—H5A	119.3	O1ⁱⁱⁱ—Na1—O12	80.40 (6)
C1—C6—O6	123.26 (16)	O13—Na1—O12	160.82 (6)
C1—C6—C4	120.01 (17)	O9—Na1—O12	121.53 (6)
O6—C6—C4	116.70 (16)	Na1—O13—H13A	107.5 (19)
O8—C7—C8	115.11 (16)	Na1—O13—H13B	106 (2)
O8—C7—C15	124.11 (17)	H13A—O13—H13B	106 (3)
C8—C7—C15	120.77 (17)	Na1—O12—H12A	109 (2)
C2—C8—C7	120.17 (17)	Na1—O12—H12B	98.1 (19)
C2—C8—H8A	119.9	H12A—O12—H12B	106 (3)
C7—C8—H8A	119.9	H11A—O11—H11B	120 (3)
C10—C9—C2	117.94 (16)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···O13^iv	0.82	1.88	2.677 (2)	164
O4—H4A···O2ⁱⁱ	0.82	1.97	2.786 (2)	170
O4—H4A···S1ⁱⁱ	0.82	2.97	3.7139 (18)	152
O5—H5B···O9	0.82	1.89	2.619 (2)	148
O6—H6A···O12ⁱⁱ	0.82	1.87	2.688 (2)	177
O8—H8B···O3	0.82	1.85	2.596 (2)	152
O8—H8B···S1	0.82	2.65	3.1344 (16)	120
O13—H13A···O11^v	0.85 (3)	1.95 (3)	2.799 (3)	174 (3)
O13—H13B···O7^vi	0.79 (3)	2.22 (3)	2.983 (2)	161 (3)
O13—H13B···O9	0.79 (3)	2.64 (3)	3.017 (2)	111 (2)
O13—H13B···S1^vi	0.79 (3)	3.02 (3)	3.7333 (18)	152 (3)
O12—H12A···O11^vii	0.83 (3)	2.07 (3)	2.850 (3)	155 (3)
O12—H12B···O7ⁱⁱ	0.90 (3)	1.87 (3)	2.767 (2)	172 (3)
O12—H12B···S1ⁱⁱ	0.90 (3)	2.74 (3)	3.494 (2)	142 (2)
O11—H11A···O5^viii	0.86 (4)	2.10 (4)	2.914 (3)	158 (3)
O11—H11B···O3	0.87 (4)	1.99 (4)	2.832 (2)	163 (3)

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

Experimental details

Crystal data
Chemical formula	[Na(C₁₅H₉O₁₀S)(H₂O)₂]·H₂O
M_r	458.33
Crystal system, space group	Triclinic, P1
Temperature (K)	295
a, b, c (Å)	7.595 (3), 10.157 (3), 12.183 (4)
α, β, γ (°)	76.576 (4), 81.031 (4), 77.385 (3)
V (Å³)	886.6 (5)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.28
Crystal size (mm)	0.60 × 0.31 × 0.24

Data collection
Diffractometer	Bruker SMART APEX CCD
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	4109, 2994, 2691
R_int	0.013
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.034, 0.101, 1.01
No. of reflections	2994
No. of parameters	289
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.24, −0.41

Computer programs: APEX2 (Bruker, 2005), SAINT-Plus (Bruker, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Selected bond lengths (Å) top

Na1—O2ⁱ	2.3517 (16)	Na1—O13	2.4070 (18)
Na1—O6ⁱⁱ	2.3784 (16)	Na1—O12	2.555 (2)
Na1—O1ⁱⁱ	2.3919 (17)	Na1—O9	2.4074 (15)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···O13ⁱⁱⁱ	0.82	1.88	2.677 (2)	164.3
O4—H4A···O2ⁱ	0.82	1.97	2.786 (2)	170.3
O4—H4A···S1ⁱ	0.82	2.97	3.7139 (18)	152.1
O5—H5B···O9	0.82	1.89	2.619 (2)	147.7
O6—H6A···O12ⁱ	0.82	1.87	2.688 (2)	176.7
O8—H8B···O3	0.82	1.85	2.596 (2)	151.5
O8—H8B···S1	0.82	2.65	3.1344 (16)	119.8
O13—H13A···O11^iv	0.85 (3)	1.95 (3)	2.799 (3)	174 (3)
O13—H13B···O7^v	0.79 (3)	2.22 (3)	2.983 (2)	161 (3)
O13—H13B···O9	0.79 (3)	2.64 (3)	3.017 (2)	111 (2)
O13—H13B···S1^v	0.79 (3)	3.02 (3)	3.7333 (18)	152 (3)
O12—H12A···O11^vi	0.83 (3)	2.07 (3)	2.850 (3)	155 (3)
O12—H12B···O7ⁱ	0.90 (3)	1.87 (3)	2.767 (2)	172 (3)
O12—H12B···S1ⁱ	0.90 (3)	2.74 (3)	3.494 (2)	142 (2)
O11—H11A···O5^vii	0.86 (4)	2.10 (4)	2.914 (3)	158 (3)
O11—H11B···O3	0.87 (4)	1.99 (4)	2.832 (2)	163 (3)

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

Acknowledgements

We thank Dr Cheng He for his help during the refinement. This work was supported by the Fundamental Research Funds of the Central Universities of China.

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