Crystal structure of the sodium salt of mesotrione: a triketone herbicide

The crystal structure of the sodium salt of mesotrione [2-(4-methyl­sulfonyl-2-nitro­benzo­yl)cyclo­hexane-1,3-dione] is described. A one-dimensional polymer is formed by the coordination of all functional groups except the NO₂ group. The coordination number of the sodium atom in the compound is 5.

Abstract

The crystal structure of the sodium salt of mesotrione, namely, catena-poly[[sodium-μ₃-2-[(4-methane­sulfonyl-2-nitro­phen­yl)carbon­yl]-3-oxo­cyclo­hex-1-en-1-olato] ethanol monosolvate], {[Na(C₁₄H₁₂NO₇S)]C₂H₅OH} _n , is described. The X-ray structural analysis results reveal that the coordination sphere is established by two chelating O atoms, the O atom of the coordinated ethanol mol­ecule, and an O atom from the methyl­sulfonyl group of a neighboring mol­ecule. Simultaneously, an O atom of the cyclo­hexane fragment serves as a bridge to a neighboring sodium ion, forming a flat Na–O–Na–O quadrangle, thereby forming a mono-periodic polymer. The structure displays O—H⋯O hydrogen bonds and C—H⋯O short contacts. Thermogravimetric analysis (TGA) data indicate that the sodium salt of mesotrione decomposes in four stages.

1. Chemical context

Mesotrione, 2-(4-methyl­sulfonyl-2-nitro­benzo­yl) cyclo­hexane-1,3-dione, is an organic compound classified as a triketone herbicide that is widely used in modern agriculture to control weeds and increase crop yields of corn (Mitchell et al., 2001 ▸). The coordination properties of triketone herbicides are dictated by the presence of three ketone functional groups, which act as ligands, forming stable coordination complexes with metal ions such as Cu²⁺, Co²⁺ and Fe³⁺ (Le Person et al., 2016 ▸). The stability of the chelates depends largely on the pH, as mesotrione is a weak acid that dissociates from the mol­ecular to the anionic form at higher pH, which is more resistant to hydrolysis and photolysis processes (Reynolds et al., 2007 ▸). For a comparative study, the crystal structure of the sodium salt of mesotrione, NaL, as well as analogues structures were retrieved from the Cambridge Structural Database (CSD, vesion 5.44, update of September 2023; Groom et al., 2016 ▸) and their geometries and confirmations are discussed (Kang et al., 2015 ▸); Hou et al., 2010 ▸; Wu et al., 2002 ▸).

2. Structural commentary

Selected geometrical parameters of the sodium salt of mesotrione are summarized in Table 1 ▸. The ligand shows a polydentate function. Coordination to the sodium ion occurs through the formation of a 6-membered chelate involving two oxygen atoms from the two keto groups (Fig. 1 ▸). This leads to the occurrence of π-conjugation within the chelate ring, leading to a shortening of the C—C bonds by 0.06 (3) Å and lengthening of C=O bonds by 0.062 (3) Å in comparison to the free ligand HL (Table 2 ▸). In turn, in the mesotrione sodium salt, the occurrence of conjugation in the triketonate ligand results in a decrease in the conjugation between the benzene ring and the chelate ring, as evidenced by a 0.014 (3) Å increase in the C4—C8 bond length (Table 2 ▸).

Table 1. Selected geometric parameters (Å, °).

Na1—O6	2.2815 (17)	O3—N1	1.218 (3)
Na1—O5	2.3191 (18)	O4—N1	1.218 (2)
Na1—O5i	2.3215 (17)	O5—C14	1.251 (3)
Na1—O8	2.347 (2)	O6—C8	1.237 (3)
Na1—O1ii	2.3700 (19)	O7—C10	1.245 (3)
Na1—Na1i	3.3927 (18)	O8—C15	1.443 (3)
S1—O2	1.4386 (18)	N1—C3	1.466 (3)
S1—O1	1.4445 (18)	C4—C8	1.528 (3)
S1—C7	1.754 (3)	C8—C9	1.440 (3)
S1—C1	1.773 (2)	C9—C14	1.442 (3)
O6—Na1—O5	73.86 (6)	O1ii—Na1—Na1i	120.78 (6)
O6—Na1—O5i	159.89 (7)	O2—S1—O1	118.31 (11)
O5—Na1—O5i	86.04 (6)	O2—S1—C7	108.75 (13)
O6—Na1—O8	93.06 (7)	O1—S1—C7	108.40 (12)
O5—Na1—O8	122.94 (7)	S1—O1—Na1ii	144.85 (11)
O5i—Na1—O8	98.52 (7)	C14—O5—Na1	136.71 (15)
O6—Na1—O1ii	90.74 (7)	C14—O5—Na1i	129.29 (15)
O5—Na1—O1ii	124.59 (7)	Na1—O5—Na1i	93.96 (6)
O5i—Na1—O1ii	100.42 (7)	C8—O6—Na1	136.56 (15)
O8—Na1—O1ii	110.49 (7)	C15—O8—Na1	109.47 (15)
O6—Na1—Na1i	116.90 (6)	O3—N1—O4	123.5 (2)
O5—Na1—Na1i	43.05 (4)	O3—N1—C3	118.18 (19)
O5i—Na1—Na1i	42.99 (4)	O4—N1—C3	118.3 (2)
O8—Na1—Na1i	118.24 (6)

Symmetry codes: (i) ; (ii) .

Figure 1.

The fragment of the structure of the sodium salt of mesotrione, showing the atom-numbering scheme for non-hydrogen atoms and displacement ellipsoids at 50% probability level.

Table 2. Comparison between some geometrical parameters (Å) in the chelate ring for HL and NaL .

Note that the numbering of atoms in the HL structure has brought into accordance with the numbering in the published structure.

Bond	NaL	HL	Δ
C14—O5	1.252 (3)	1.314 (2)	0.062
C9—C14	1.442 (3)	1.382 (2)	0.06
C8—C9	1.439 (3)	1.448 (2)	0.009
C8—O6	1.237 (3)	1.239 (2)	0.02
C4—C8	1.528 (3)	1.514 (2)	0.014

The chelate fragment tends towards a planar structure. Simultaneously, the oxygen atom O5 of the cyclo­hexane fragment serves as a bridge to a neighboring sodium ion, forming a flat quadrangle Na1–O5–Na1ⁱ–O5ⁱ constituting the linker that forms the polymer chain (Fig. 2 ▸).

Figure 2.

Coordination polyhedron of the sodium salt of mesotrione.

The benzene and cyclo­hexane ring conformations in the structure of sodium salt and free ligand are similar. The benzene ring has a planar conformation, while the cyclo­hexane ring represents a semi chair with a bend in the line linking atoms C11–C13. The main geometrical characteristics of hydrogen bonds of the compound [NaL(EtOH)]·EtOH are given in Table 3 ▸.

Table 3. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O9A—H9⋯O8	0.90 (4)	1.98 (4)	2.875 (5)	170 (4)
O9B—H9⋯O8	0.91 (4)	1.98 (4)	2.81 (2)	152 (4)
O8—H8⋯O7iii	0.76 (3)	1.92 (3)	2.681 (2)	171 (3)
C2—H2⋯O6ii	0.95	2.59	3.229 (3)	125
C7—H7B⋯O4ii	0.98	2.43	3.200 (3)	135
C7—H7C⋯O9A iv	0.98	2.37	3.349 (5)	176

Symmetry codes: (ii) ; (iii) ; (iv) .

The environment sphere of the sodium ion comprises the oxygen atoms O5 and O6 of the chelate, the bridging oxygen atom O5ⁱ, the oxygen atom O8 from the coordinated ethanol mol­ecule, and the oxygen atom O1ⁱⁱ from the methyl sulfonyl group of a neighboring mol­ecule (Fig. 2 ▸). Using the SHAPE program (Version 2.1; Llunell et al., 2013 ▸), it was determined that the environment of the sodium atom is close to D _3h symmetry (trigonal bipyramid) with a convergence factor of 1.6.

3. Supra­molecular features

In the crystal structure of the sodium salt of mesotrione, the mol­ecules are assembled in a polymer chain (Fig. 3 ▸). Two types of hydrogen bonds are observed: the first between the oxygen atom of the uncoordinated ethanol mol­ecule (O9A) and the oxygen atom (O8) of the coordinated ethanol mol­ecule [2.870 (4) Å] and the second between the oxygen atom (O8) of a coordinated ethanol mol­ecule and the free oxygen atom (O7) of the keto group of a neighboring mol­ecule not involved in coordination [2.681 (2) Å]. In the structure of the coordination compound, three types of short contacts are observed, viz. C2—H2⋯O6ⁱⁱ [3.229 (3) Å], C7—H7B⋯O4ⁱⁱ [3.200 (3) Å], and C7—H7C⋯O9A ^iv [3.356 (4) Å] (symmetry codes are as per Table 3 ▸).

Figure 3.

Crystal packing in a cell with projection onto the ac plane. Hydrogen bonds are highlighted in blue.

Table 4. Experimental details.

Crystal data
Chemical formula	[Na(C14H12NO7S)]·C2H6O
M r	453.43
Crystal system, space group	Triclinic, P
Temperature (K)	173
a, b, c (Å)	9.9014 (5), 10.7214 (6), 11.9401 (6)
α, β, γ (°)	69.789 (3), 71.074 (3), 66.439 (3)
V (Å3)	1064.45 (10)
Z	2
Radiation type	Mo Kα
μ (mm−1)	0.22
Crystal size (mm)	0.36 × 0.23 × 0.18
Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Krause et al., 2015 ▸)
T min, T max	0.679, 0.745
No. of measured, independent and observed [I > 2σ(I)] reflections	15328, 4340, 3259
R int	0.039
(sin θ/λ)max (Å−1)	0.625
Refinement
R[F 2 > 2σ(F 2)], wR(F 2), S	0.050, 0.133, 1.05
No. of reflections	4340
No. of parameters	308
No. of restraints	22
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å−3)	0.47, −0.41

Computer programs: APEX2 and SAINT (Bruker, 2012 ▸), SHELXS and SHELXTL (Sheldrick, 2008 ▸) and SHELXL (Sheldrick, 2015 ▸).

4. Experimental

The FT–IR spectra of the solids were recorded in a KBr matrix in the range 4000–400cm⁻¹ using a Perkin-Elmer Spectrum BX2 spectrometer. ¹H NMR spectra were recorded using a WR-400 Bruker NMR spectrometer at room temperature in DMSO-d⁶ , with TMS used as the inter­nal standard. Studies on the thermal properties of the sodium salt of mesotrione were conducted using a synchronous TG/DTA analyzer, the Shimadzu DTG-60H. The sample was heated in an air atmosphere to 600°C in aluminum crucibles at a heating rate of 10°C min⁻¹.

5. Synthesis and crystallization

Mesotrione was obtained commercially. Other chemicals and solvents used in this study were purchased from Aldrich and used without further purification.

The sodium salt was prepared as shown in Fig. 4 ▸, where 2-(4-methyl­sulfonyl-2-nitro­benzo­yl)cyclo­hexane-1,3-dione was added to a freshly prepared sodium methyl­ate solution. For the monovalent metal sodium, the molar ratio of mesotrione to metal ions is 2:1. The resulting mixture was filtered, and the solvent was removed under vacuum. The yellowish crystalline powder (80% yield) was dissolved in a mixture of ethanol and methanol under heating (∼333 K) and then cooled to room temperature. After a while (∼72 h), monocrystals of the sodium salt of mesotrione, which were suitable for X-ray analysis, were formed.

Figure 4.

Synthesis of the sodium salt of mesotrione.

[NaL(EtOH)]·EtOH: IR (KBr, cm⁻¹): 1642 [ν_as(C=O)_keto], 1582 [ν_s(C=O)_enol], 1524 [ν_as(NO₂)], 1328 [ν_s(NO₂)], 1312 [ν_as(SO₂)], 1148 [ν_s(SO₂)].

[NaL(EtOH)]·EtOH: NMR ¹H (400 MHz, DMSO-d ⁶, 298 K, TMS): Δ = 1.75 ppm (m, 2H), 2.17 ppm (m, 4H), 7.29–7.31 ppm (d, 1H), 8.11–8.12 ppm (d, 1H), 8.45 ppm (s, 1H), 3.39 ppm (m, 3H, CH₃), 4.39 ppm (m, 2H, OH), 1.05 ppm (m, 6H, CH₃), 3.43 ppm (m, 4H, CH₂).

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 4 ▸. Non-coordinated ethanol mol­ecules forming hydrogen bonds with the coordination fragment are disordered at two positions H9–O9A–C17A–C18A with an occupancy ratio of 0.8 and 0.2 for H9–O9B–C17B–C18B. Both disordered mol­ecules were refined anisotropically, with certain constraints applied to bond lengths and the same U ^ij components in the minor constituent. C-bound H atoms were positioned geometrically (C—H = 0.95–0.99 Å) and refined as riding with U _iso(H) = 1.2U _eq(C).

7. Thermogravimetric analysis

Four different stages of decomposition of the mesotrione-based sodium complex were observed in the investigated temperature range (Fig. 5 ▸). The first stage of thermal decomposition is characterized by a distinct exothermic effect and a mass loss of ∼12% in the temperature range of 25–182°C. The exothermic effect is observed at a temperature of 147°C (m.p. = 149–151°C), corresponding to the loss of the first ethanol mol­ecule.

Figure 5.

The DTA (red line), DrTGA (pink line) and TGA (blue line) weight loss trace for the sodium salt of mesotrione.

At the second stage of the decomposition of the coordination compound in the temperature range 182–281°C, the loss (∼11%) of the second ethanol mol­ecule occurs, which is accompanied by an endothermic effect. The third stage of thermal decomposition is characterized by exothermic effect and a mass loss of ∼8.5% in the temperature range 280–340°C. The exothermic effect is observed at a temperature of 318.8°C, corresponding to the combustion of the entire organic components.

The fourth stage begins at 500°C and ends at 600°C and cannot be detected by the Shimadzu DTG-60H.

The TGV analysis and calculations based on its results show that the third and fourth stages consist of the combustion of the entire organic component of the mol­ecule and the formation of sodium pyro­sulfate.

According to the thermal studies, the fourth stage is accompanied by a strong exothermic effect and includes the further transformation of Na₂S₂O₇ into Na₂SO₄, which is confirmed by the results of IR spectroscopy (Fig. 6 ▸).

Figure 6.

The IR spectrum for the final product after TGA (Na₂SO₄).

Supplementary Material

CCDC reference: 2072869

Additional supporting information: crystallographic information; 3D view; checkCIF report

supplementary crystallographic information

Crystal data

[Na(C14H12NO7S)]·C2H6O	Z = 2
Mr = 453.43	F(000) = 476
Triclinic, P1	Dx = 1.415 Mg m−3
a = 9.9014 (5) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.7214 (6) Å	Cell parameters from 4340 reflections
c = 11.9401 (6) Å	θ = 1.9–26.4°
α = 69.789 (3)°	µ = 0.22 mm−1
β = 71.074 (3)°	T = 173 K
γ = 66.439 (3)°	Prizm, yellow
V = 1064.45 (10) Å3	0.36 × 0.23 × 0.18 mm

Data collection

Bruker APEXII CCD diffractometer	3259 reflections with I > 2σ(I)
Radiation source: sealed tube	Rint = 0.039
φ and ω scans	θmax = 26.4°, θmin = 1.9°
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	h = −12→12
Tmin = 0.679, Tmax = 0.745	k = −13→10
15328 measured reflections	l = −14→14
4340 independent reflections

Refinement

Refinement on F2	22 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F2 > 2σ(F2)] = 0.050	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.133	w = 1/[σ2(Fo2) + (0.0686P)2 + 0.3718P] where P = (Fo2 + 2Fc2)/3
S = 1.05	(Δ/σ)max < 0.001
4340 reflections	Δρmax = 0.47 e Å−3
308 parameters	Δρmin = −0.41 e Å−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
Na1	0.46287 (10)	0.49578 (10)	0.15007 (8)	0.0271 (2)
S1	−0.20329 (6)	0.18062 (6)	0.76443 (5)	0.02386 (17)
O1	−0.34311 (18)	0.29415 (18)	0.78282 (15)	0.0337 (4)
O2	−0.2105 (2)	0.04798 (18)	0.76771 (16)	0.0361 (5)
O3	−0.2679 (2)	0.6168 (2)	0.3932 (2)	0.0674 (8)
O4	−0.0518 (2)	0.60798 (18)	0.27209 (15)	0.0346 (4)
O5	0.37328 (18)	0.43201 (18)	0.02826 (14)	0.0295 (4)
O6	0.27562 (18)	0.4081 (2)	0.27717 (15)	0.0317 (4)
O7	−0.07874 (17)	0.3379 (2)	0.23648 (15)	0.0315 (4)
O8	0.6424 (2)	0.3351 (2)	0.26488 (16)	0.0312 (4)
H8	0.723 (4)	0.338 (3)	0.249 (3)	0.046 (10)*
N1	−0.1331 (2)	0.5579 (2)	0.36258 (18)	0.0288 (5)
C1	−0.0937 (2)	0.2401 (2)	0.6198 (2)	0.0201 (5)
C2	−0.1495 (2)	0.3751 (2)	0.5520 (2)	0.0204 (5)
H2	−0.243164	0.437557	0.583606	0.025*
C3	−0.0661 (2)	0.4176 (2)	0.4367 (2)	0.0198 (5)
C4	0.0718 (2)	0.3301 (2)	0.38681 (19)	0.0212 (5)
C5	0.1247 (3)	0.1941 (3)	0.4576 (2)	0.0331 (6)
H5	0.218752	0.131642	0.426409	0.040*
C6	0.0421 (3)	0.1481 (3)	0.5734 (2)	0.0310 (6)
H6	0.078492	0.054489	0.620104	0.037*
C7	−0.1024 (3)	0.1529 (3)	0.8723 (2)	0.0360 (6)
H7A	−0.155609	0.115410	0.954261	0.054*
H7B	−0.093852	0.242129	0.868964	0.054*
H7C	−0.001251	0.085614	0.853847	0.054*
C8	0.1760 (2)	0.3745 (2)	0.2656 (2)	0.0228 (5)
C9	0.1652 (2)	0.3566 (2)	0.1551 (2)	0.0214 (5)
C10	0.0378 (3)	0.3228 (2)	0.1541 (2)	0.0226 (5)
C11	0.0423 (3)	0.2744 (3)	0.0483 (2)	0.0257 (5)
H11A	−0.016765	0.354371	−0.007590	0.031*
H11B	−0.006094	0.200559	0.079509	0.031*
C12	0.2020 (3)	0.2168 (3)	−0.0229 (2)	0.0276 (5)
H12A	0.198851	0.194847	−0.095847	0.033*
H12B	0.258493	0.129274	0.028904	0.033*
C13	0.2798 (3)	0.3266 (3)	−0.0617 (2)	0.0277 (5)
H13A	0.385898	0.286890	−0.103136	0.033*
H13B	0.229579	0.408757	−0.121612	0.033*
C14	0.2778 (2)	0.3753 (2)	0.0438 (2)	0.0222 (5)
C15	0.5810 (3)	0.3345 (3)	0.3924 (2)	0.0428 (7)
H15A	0.471176	0.351126	0.410164	0.051*
H15B	0.594531	0.413466	0.407564	0.051*
C16	0.6491 (4)	0.2045 (4)	0.4767 (3)	0.0584 (9)
H16A	0.601652	0.212192	0.560994	0.088*
H16B	0.633868	0.125845	0.464123	0.088*
H16C	0.757414	0.188282	0.461518	0.088*
O9A	0.7557 (4)	0.0676 (4)	0.2067 (4)	0.0470 (10)	0.815 (5)
C17A	0.6460 (4)	−0.0028 (4)	0.2653 (3)	0.0462 (11)	0.815 (5)
H17B	0.603839	0.007405	0.350234	0.055*	0.815 (5)
H17A	0.695169	−0.104216	0.268723	0.055*	0.815 (5)
C18A	0.5179 (5)	0.0571 (5)	0.1970 (5)	0.0668 (14)	0.815 (5)
H18C	0.444488	0.006821	0.239201	0.100*	0.815 (5)
H18B	0.467983	0.157119	0.194744	0.100*	0.815 (5)
H18A	0.559228	0.045602	0.113309	0.100*	0.815 (5)
O9B	0.7192 (18)	0.101 (2)	0.174 (2)	0.051 (4)	0.185 (5)
C17B	0.5847 (18)	0.0752 (18)	0.1820 (15)	0.045 (2)	0.185 (5)
H17C	0.601398	0.030955	0.116176	0.054*	0.185 (5)
H17D	0.501848	0.165750	0.169959	0.054*	0.185 (5)
C18B	0.538 (2)	−0.021 (2)	0.3067 (16)	0.080 (4)	0.185 (5)
H18D	0.445848	−0.036455	0.309274	0.120*	0.185 (5)
H18E	0.619223	−0.111630	0.318195	0.120*	0.185 (5)
H18F	0.519738	0.023078	0.371944	0.120*	0.185 (5)
H9	0.709 (4)	0.153 (4)	0.223 (4)	0.078 (13)*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
Na1	0.0234 (5)	0.0371 (6)	0.0197 (5)	−0.0147 (4)	−0.0002 (4)	−0.0042 (4)
S1	0.0249 (3)	0.0274 (3)	0.0163 (3)	−0.0136 (3)	−0.0001 (2)	0.0001 (2)
O1	0.0266 (9)	0.0376 (11)	0.0238 (9)	−0.0107 (8)	0.0063 (7)	−0.0027 (8)
O2	0.0493 (11)	0.0315 (10)	0.0288 (10)	−0.0248 (9)	−0.0026 (8)	−0.0005 (8)
O3	0.0473 (14)	0.0426 (13)	0.0484 (14)	0.0102 (10)	0.0132 (11)	0.0123 (10)
O4	0.0408 (11)	0.0342 (10)	0.0242 (9)	−0.0214 (9)	−0.0043 (8)	0.0066 (8)
O5	0.0272 (9)	0.0438 (11)	0.0191 (9)	−0.0216 (8)	0.0012 (7)	−0.0036 (8)
O6	0.0289 (9)	0.0544 (12)	0.0191 (9)	−0.0259 (9)	−0.0009 (7)	−0.0072 (8)
O7	0.0196 (9)	0.0551 (12)	0.0245 (9)	−0.0200 (8)	0.0034 (7)	−0.0137 (8)
O8	0.0224 (10)	0.0427 (11)	0.0277 (10)	−0.0150 (8)	−0.0043 (8)	−0.0035 (8)
N1	0.0326 (12)	0.0253 (11)	0.0214 (11)	−0.0096 (10)	−0.0015 (9)	−0.0015 (9)
C1	0.0213 (12)	0.0264 (13)	0.0138 (11)	−0.0117 (10)	−0.0014 (9)	−0.0038 (9)
C2	0.0181 (11)	0.0241 (13)	0.0179 (11)	−0.0072 (10)	−0.0001 (9)	−0.0070 (10)
C3	0.0226 (12)	0.0209 (12)	0.0173 (11)	−0.0099 (10)	−0.0054 (9)	−0.0019 (9)
C4	0.0199 (12)	0.0302 (13)	0.0138 (11)	−0.0119 (10)	−0.0029 (9)	−0.0020 (10)
C5	0.0224 (13)	0.0358 (15)	0.0222 (13)	−0.0007 (11)	0.0027 (10)	−0.0026 (11)
C6	0.0276 (13)	0.0248 (13)	0.0237 (13)	−0.0031 (11)	−0.0025 (10)	0.0044 (11)
C7	0.0393 (16)	0.0509 (18)	0.0184 (13)	−0.0244 (14)	−0.0039 (11)	0.0001 (12)
C8	0.0180 (11)	0.0279 (13)	0.0176 (12)	−0.0083 (10)	−0.0021 (9)	−0.0006 (10)
C9	0.0182 (11)	0.0284 (13)	0.0156 (11)	−0.0101 (10)	−0.0011 (9)	−0.0022 (10)
C10	0.0213 (12)	0.0235 (12)	0.0195 (12)	−0.0078 (10)	−0.0054 (10)	0.0004 (10)
C11	0.0251 (13)	0.0313 (14)	0.0237 (13)	−0.0139 (11)	−0.0043 (10)	−0.0057 (11)
C12	0.0297 (13)	0.0288 (14)	0.0231 (13)	−0.0094 (11)	−0.0042 (10)	−0.0064 (11)
C13	0.0276 (13)	0.0368 (15)	0.0164 (12)	−0.0149 (11)	0.0007 (10)	−0.0039 (10)
C14	0.0188 (11)	0.0264 (13)	0.0165 (11)	−0.0069 (10)	−0.0048 (9)	0.0009 (10)
C15	0.0311 (15)	0.060 (2)	0.0326 (16)	−0.0143 (14)	−0.0024 (12)	−0.0106 (14)
C16	0.067 (2)	0.065 (2)	0.046 (2)	−0.0285 (19)	−0.0158 (17)	−0.0064 (17)
O9A	0.034 (2)	0.042 (2)	0.059 (3)	−0.0073 (17)	−0.0052 (15)	−0.0159 (18)
C17A	0.056 (3)	0.037 (2)	0.044 (2)	−0.0167 (18)	−0.0024 (18)	−0.0139 (17)
C18A	0.047 (3)	0.063 (3)	0.090 (4)	−0.023 (2)	−0.009 (3)	−0.017 (3)
O9B	0.034 (6)	0.048 (6)	0.057 (7)	−0.005 (5)	0.001 (5)	−0.017 (5)
C17B	0.056 (4)	0.037 (4)	0.045 (4)	−0.013 (3)	−0.006 (3)	−0.020 (3)
C18B	0.052 (6)	0.075 (6)	0.097 (7)	−0.015 (6)	−0.010 (6)	−0.015 (6)

Geometric parameters (Å, º)

Na1—O6	2.2815 (17)	C9—C10	1.449 (3)
Na1—O5	2.3191 (18)	C10—C11	1.504 (3)
Na1—O5i	2.3215 (17)	C11—C12	1.521 (3)
Na1—O8	2.347 (2)	C11—H11A	0.9900
Na1—O1ii	2.3699 (19)	C11—H11B	0.9900
Na1—Na1i	3.3928 (18)	C12—C13	1.520 (3)
S1—O2	1.4386 (18)	C12—H12A	0.9900
S1—O1	1.4445 (18)	C12—H12B	0.9900
S1—C7	1.754 (3)	C13—C14	1.514 (3)
S1—C1	1.773 (2)	C13—H13A	0.9900
O3—N1	1.218 (3)	C13—H13B	0.9900
O4—N1	1.218 (2)	C15—C16	1.459 (4)
O5—C14	1.251 (3)	C15—H15A	0.9900
O6—C8	1.237 (3)	C15—H15B	0.9900
O7—C10	1.245 (3)	C16—H16A	0.9800
O8—C15	1.443 (3)	C16—H16B	0.9800
O8—H8	0.76 (3)	C16—H16C	0.9800
N1—C3	1.466 (3)	O9A—C17A	1.4270 (19)
C1—C2	1.377 (3)	O9A—H9	0.90 (4)
C1—C6	1.386 (3)	C17A—C18A	1.531 (2)
C2—C3	1.384 (3)	C17A—H17B	0.9900
C2—H2	0.9500	C17A—H17A	0.9900
C3—C4	1.390 (3)	C18A—H18C	0.9800
C4—C5	1.393 (3)	C18A—H18B	0.9800
C4—C8	1.528 (3)	C18A—H18A	0.9800
C5—C6	1.393 (3)	O9B—C17B	1.429 (2)
C5—H5	0.9500	O9B—H9	0.91 (4)
C6—H6	0.9500	C17B—C18B	1.539 (2)
C7—H7A	0.9800	C17B—H17C	0.9900
C7—H7B	0.9800	C17B—H17D	0.9900
C7—H7C	0.9800	C18B—H18D	0.9800
C8—C9	1.440 (3)	C18B—H18E	0.9800
C9—C14	1.442 (3)	C18B—H18F	0.9800
O6—Na1—O5	73.86 (6)	O7—C10—C9	121.8 (2)
O6—Na1—O5i	159.89 (7)	O7—C10—C11	118.6 (2)
O5—Na1—O5i	86.04 (6)	C9—C10—C11	119.58 (19)
O6—Na1—O8	93.06 (7)	C10—C11—C12	112.88 (19)
O5—Na1—O8	122.94 (7)	C10—C11—H11A	109.0
O5i—Na1—O8	98.52 (7)	C12—C11—H11A	109.0
O6—Na1—O1ii	90.74 (7)	C10—C11—H11B	109.0
O5—Na1—O1ii	124.59 (7)	C12—C11—H11B	109.0
O5i—Na1—O1ii	100.41 (7)	H11A—C11—H11B	107.8
O8—Na1—O1ii	110.49 (7)	C13—C12—C11	108.7 (2)
O6—Na1—Na1i	116.90 (6)	C13—C12—H12A	109.9
O5—Na1—Na1i	43.05 (4)	C11—C12—H12A	109.9
O5i—Na1—Na1i	42.99 (4)	C13—C12—H12B	109.9
O8—Na1—Na1i	118.24 (6)	C11—C12—H12B	109.9
O1ii—Na1—Na1i	120.78 (6)	H12A—C12—H12B	108.3
O2—S1—O1	118.31 (11)	C14—C13—C12	113.39 (19)
O2—S1—C7	108.75 (13)	C14—C13—H13A	108.9
O1—S1—C7	108.40 (12)	C12—C13—H13A	108.9
O2—S1—C1	107.70 (10)	C14—C13—H13B	108.9
O1—S1—C1	107.16 (11)	C12—C13—H13B	108.9
C7—S1—C1	105.83 (11)	H13A—C13—H13B	107.7
S1—O1—Na1ii	144.85 (11)	O5—C14—C9	123.8 (2)
C14—O5—Na1	136.71 (15)	O5—C14—C13	117.54 (19)
C14—O5—Na1i	129.29 (15)	C9—C14—C13	118.67 (19)
Na1—O5—Na1i	93.96 (6)	O8—C15—C16	114.3 (3)
C8—O6—Na1	136.56 (15)	O8—C15—H15A	108.7
C15—O8—Na1	109.47 (15)	C16—C15—H15A	108.7
C15—O8—H8	108 (2)	O8—C15—H15B	108.7
Na1—O8—H8	122 (2)	C16—C15—H15B	108.7
O3—N1—O4	123.5 (2)	H15A—C15—H15B	107.6
O3—N1—C3	118.18 (19)	C15—C16—H16A	109.5
O4—N1—C3	118.3 (2)	C15—C16—H16B	109.5
C2—C1—C6	120.9 (2)	H16A—C16—H16B	109.5
C2—C1—S1	119.19 (17)	C15—C16—H16C	109.5
C6—C1—S1	119.77 (18)	H16A—C16—H16C	109.5
C1—C2—C3	118.5 (2)	H16B—C16—H16C	109.5
C1—C2—H2	120.8	C17A—O9A—H9	104 (2)
C3—C2—H2	120.8	O9A—C17A—C18A	111.3 (4)
C2—C3—C4	122.8 (2)	O9A—C17A—H17B	109.4
C2—C3—N1	117.48 (19)	C18A—C17A—H17B	109.4
C4—C3—N1	119.59 (19)	O9A—C17A—H17A	109.4
C3—C4—C5	117.3 (2)	C18A—C17A—H17A	109.4
C3—C4—C8	125.3 (2)	H17B—C17A—H17A	108.0
C5—C4—C8	117.2 (2)	C17A—C18A—H18C	109.5
C4—C5—C6	121.1 (2)	C17A—C18A—H18B	109.5
C4—C5—H5	119.5	H18C—C18A—H18B	109.5
C6—C5—H5	119.5	C17A—C18A—H18A	109.5
C1—C6—C5	119.4 (2)	H18C—C18A—H18A	109.5
C1—C6—H6	120.3	H18B—C18A—H18A	109.5
C5—C6—H6	120.3	C17B—O9B—H9	115 (3)
S1—C7—H7A	109.5	O9B—C17B—C18B	111.6 (17)
S1—C7—H7B	109.5	O9B—C17B—H17C	109.3
H7A—C7—H7B	109.5	C18B—C17B—H17C	109.3
S1—C7—H7C	109.5	O9B—C17B—H17D	109.3
H7A—C7—H7C	109.5	C18B—C17B—H17D	109.3
H7B—C7—H7C	109.5	H17C—C17B—H17D	108.0
O6—C8—C9	126.1 (2)	C17B—C18B—H18D	109.5
O6—C8—C4	113.4 (2)	C17B—C18B—H18E	109.5
C9—C8—C4	119.87 (19)	H18D—C18B—H18E	109.5
C8—C9—C14	120.88 (19)	C17B—C18B—H18F	109.5
C8—C9—C10	119.83 (19)	H18D—C18B—H18F	109.5
C14—C9—C10	119.3 (2)	H18E—C18B—H18F	109.5

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O9A—H9···O8	0.90 (4)	1.98 (4)	2.875 (5)	170 (4)
O9B—H9···O8	0.91 (4)	1.98 (4)	2.81 (2)	152 (4)
O8—H8···O7iii	0.76 (3)	1.92 (3)	2.681 (2)	171 (3)
C2—H2···O6ii	0.95	2.59	3.229 (3)	125
C7—H7B···O4ii	0.98	2.43	3.200 (3)	135
C7—H7C···O9Aiv	0.98	2.37	3.349 (5)	176

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