Preparation and X-ray analysis of potassium (2,3-dichlorophenyl) glucosinolate

Article abstract of DOI:10.1107/S2053229614009115

There has been much interest in obtaining crystals for crystallographic analysis of biologically active glucosinolates. Crystals of potassium (2,3-dichlorophenyl)glucosinolate were obtained as a dual solvate, containing one methanol and one ethanol molecule of crystallization, K⁺ C ₁₃H₁₄Cl₂NO₉S₂ ^- CH₃OH C₂H₅OH. The three-dimensional polymeric network consists of chains containing the potassium ions coordinated and bridged by sugar O atoms, which run parallel to the a axis and are further crosslinked through the sugar molecules. The channels of this network are occupied by the dichlorophenyl substituents and the ethanol and methanol solvent molecules. The structure of the S-(2,3,4,6-tetra-O-acetyl- β-d-glucopyranosyl)-2,3-dichlorophenylacetothiohydroxymate, C ₂₁H₂₃Cl₂NO₁₀S, precursor has also been determined and the β-configuration and Z isomer of the thiohydroximate substituent is confirmed.

Full text of DOI:10.1107/S2053229614009115

research papers
Acta Crystallographica Section C
characterized as crystalline acetates by 1959 (Kjaer et al., 1956;
Kjaer, 1961; Foo et al., 2000). The data showed that these
compounds were obtained as solids after crystallization;
however, there was a lack of diagnostic structural information
(X-ray analysis, NMR etc) to confirm the structures.
Structural Chemistry
ISSN 2053-2296
Preparation and X-ray analysis of
potassium (2,3-dichlorophenyl)-
glucosinolate
Quan V. Vo,a,b* Craige Trenerry,c Simone Rochfort,d,e
Jonathan Whitef and Andrew B. Hughesa
aDepartment of Chemistry, La Trobe University, Victoria 3086, Australia,
bDepartment of Natural Sciences, Quang Tri Teacher Training College, Quang Tri
Province, Vietnam, cDepartment of Primary Industries, Knoxfield Centre, 621
Burwood Highway, Knoxfield 3180, Australia, dDepartment of Primary Industries,
Victorian AgriBiosciences Centre, La Trobe University Research and Development
Park, 1 Park Drive, Bundoora 3083, Victoria, Australia, eLa Trobe University,
Later, studies by Marsh & Waser (1970) and Thies (1988)
reported the formation of crystalline sinigrin and gluco-
tropaeolin salts. The potassium salt of sinigrin and the tetra-
methylamine salt of glucotropaeolin were crystallized in a
suitable solvent and the HPLC (high-performance liquid
chromatography), melting point, UV–vis and X-ray crystal
structure analyses of sinigrin confirmed the high purity of the
crystallized compounds. Unfortunately, since these studies
there have not been any other published data on crystalline
GLs. Thus, up to now, crystallization has been one of the most
difficult issues in the study of GLs. This may be due to the very
high polarity of GLs and the instability of GLs in the crys-
tallizing solvent(s). The study of the crystallization of GLs in
order to investigate the structure as well as the relationships
between the structure and biological and medicinal properties
of GLs, however, is a crucial issue. We report here success in
the synthesis, crystallization and X-ray crystallographic analy-
sis of potassium (2,3-dichlorophenyl)glucosinolate–ethanol–
methanol (1/1/1), (11), and S-(2,3,4,6-tetra-O-acetyl-ꢀ-d-
glucopyranosyl)-2,3-dichlorophenylacetothiohydroxymate, (9).
f
Victoria 3086, Australia, and Bio21 Institute, School of Chemistry, University of
Melbourne, Parkville, Victoria 3010, Australia
Correspondence e-mail: quan_vv@qtttc.edu.vn
Received 13 January 2014
Accepted 22 April 2014
There has been much interest in obtaining crystals for
crystallographic analysis of biologically active glucosinolates.
Crystals of potassium (2,3-dichlorophenyl)glucosinolate were
obtained as a dual solvate, containing one methanol and one
ethanol molecule of crystallization, K+ꢀC13H14Cl2NO9S2ꢁꢀ-
CH3OHꢀC2H5OH. The three-dimensional polymeric network
consists of chains containing the potassium ions coordinated
and bridged by sugar O atoms, which run parallel to the a axis
and are further crosslinked through the sugar molecules. The
channels of this network are occupied by the dichlorophenyl
substituents and the ethanol and methanol solvent molecules.
The structure of the S-(2,3,4,6-tetra-O-acetyl-ꢀ-d-gluco-
pyranosyl)-2,3-dichlorophenylacetothiohydroxymate, C21H23-
Cl2NO10S, precursor has also been determined and the ꢀ-
configuration and Z isomer of the thiohydroximate substituent
is confirmed.
2. Experimental
2.1. Synthesis and crystallization
Keywords: crystal structure; 2,3-dichlorophenylglucosinolate; b-
thioglucoside N-hydroxysulfates; biologically active compounds;
natural products.
2.1.1. S-(2,3,4,6-Tetra-O-acetyl-b-D-glucopyranosyl)-2,3-
dichlorophenylacetothiohydroxymate, (9). To stirred a solu-
tion of hydroxymoyl chloride, (3) [2.02 g, 9 mmol; see
Scheme 1 and the Supporting information for the synthesis of
(3)], in dry Et2O–DCM (2:1 v/v, 45 ml; DCM is dichlor-
omethane) was added a solution of 2,3,4,6-tetra-O-acetyl-ꢀ-d-
glucopyranosyl thiol, (8) [2.2 g, 6 mmol; see Scheme 2 and the
Supporting information for the synthesis of (8)], in dry DCM
(6 ml). The resulting mixture was treated with Et3N (5 ml,
36 mmol) in Et2O (12 ml). The reaction mixture was stirred
for 2 h at room temperature under an N2 atmosphere and then
acidified with 1 M H2SO4 (42 ml). The mixture was left to
stand for 10 min and then separated. The aqueous phase was
extracted with DCM (3 ꢂ 30 ml). The combined organic layers
1. Introduction
Glucosinolates (GLs) are ꢀ-thioglucoside N-hydroxysulfates
with a side chain (R) and a sulfur-linked ꢀ-d-glucopyranose
moiety. These are natural compounds which are found in a
large number of Brassica species such as cabbage, broccoli and
canola (Clarke, 2010). The crystallization of GLs plays an
important role in identifying their structure and has been
studied previously (Fahey et al., 2001). Kjaer et al. reported a
list of GLs which had been crystallized as either potassium,
sodium or rubidium salts, and another seven that had been
588 # 2014 International Union of Crystallography
doi:10.1107/S2053229614009115
Acta Cryst. (2014). C70, 588–594

research papers
were dried over MgSO4, filtered and the filtrate was concen-
trated under reduced pressure. Thiohydroxymate (9) was
purified by flash chromatography, eluting with 0–3% MeOH–
DCM and then recrystallized from hexane–DCM. Thiohy-
droxymate (9) (50 mg) was completely dissolved in DCM.
Hexane was then added until the solution became cloudy. The
mixture was filtered and the filtrate was capped tightly and
stored in room temperature up to two months to grown
crystal.Pure (9) was obtained as white crystals (yield 3.55 g,
90%). RF =0.36 in hexane–EtOAc (2:3 v/v) (m.p. 445–446 K).
[ꢁ] = +22 (c 2.0, CHCl3). ꢂmax (NaCl)/cmꢁ1: 3319 (OH), 1749
(C O), 1602 (C N), 1597, 1411, 1367, 1222, 1053. ꢃH
(300 MHz, CDCl3, 300 K): ꢃ 7.59–7.56 (m, 1H, H40-Ph-H),
7.34–7.25 (m, 2H, H50 and H60-Ph-H), 5.02–4.97 (m, 3H, H2,
H3 and H4), 4.14–4.03 (m, 2H, H1 and H6b), 3.89–3.84 (m, 1H,
H6a), 2.86–2.84 (m, 1H, H5), 2.07, 2.03, 1.95, 1.93 (4 ꢂ s, 12H,
CH3COO). ꢃC (75 MHz, CDCl3, 300 K): 170.2, 169.9, 168.9,
168.8 (4 ꢂ CH3COO), 150.3 (C N), 133.4 (C-3 of Ph), 132.5
(C-2 of Ph), 132.4 (C-4 of Ph), 131.7 (C-6 of Ph), 129.6 (C-1 of
Ph), 126.7 (C-5 of Ph), 80.8 (C-1), 75.3 (C-5), 73.2 (C-3), 68.9
(C-2), 67.3 (C-4), 60.9 (C-6), 20.3, 20.2, 20.14, 20.08 (4 ꢂ
CH3COO). HRMS (ESI) m/z for C21H23O10Cl2NNaS [M +
Na]+: calculated 574.0312, found 574.0283.
(9) (800 mg, 1.45 mmol) in dry DCM (40 ml) was added pyri-
dine sulfur trioxide complex (610 mg, 3.36 mmol). After stir-
ring and refluxing under argon for 18 h, an additional portion
of the complex (72.5 mg, 0.435 mmol) was added and stirring
was continued for 2 h. After that, a solution of KHCO3 (2.00 g,
17 mmol) in water (40 ml) was added and the mixture was
stirred for 30 min and then concentrated under reduced pres-
sure. The residue was dissolved in water and extracted first with
chloroform (2 ꢂ 30 ml) and then with 80% CHCl3–MeOH (3 ꢂ
30 ml). The organic layers were dried (MgSO4), filtered and
concentrated under reduce pressure. To remove excess pyri-
dine, the mixture was co-distilled several times with toluene.
Compound (10) was obtained by flash chromatography, eluting
with 80–85% DCM–MeOH as a white solid (yield 780 mg,
81%). RF = 0.31 in 15% MeOH–DCM [m.p. 415–417 K
(decomposition)]. [ꢁ] = +15 (c 1.0, MeOH). ꢂmax (KBr drift)/
cmꢁ1: 2942, 2884, 1754 (C O), 1650, 1572, 1505, 1413, 1396,
1217, 1062. ꢃH (300 MHz, CD3OD, 300 K): 7.73–7.69 (m, 1H,
H40-Ph-H), 7.49–7.43 (m, 2H, H50 and H60-Ph-H), 5.12 (t, J2,3
=
J3,4 = 9.3 Hz, 1H, H3), 4.97–4.91 (m, 2H, H2 and H4), 4.37 (d,
J1,2 = 10.2 Hz, 1H, H1), 4.11 (dd, J5,6b = 4.2, J6a,6b = 12.6 Hz, 1H,
H6b), 3.90 (dd, J5,6a = 2.4, J6a,6b = 12.6 Hz, 1H, H6a), 3.06–3.01
(m, 1H, H5), 2.06, 2.02, 1.92, 1.92 (4 ꢂ s, 12H, CH3COO). ꢃC
(75 MHz, CD3OD, 300 K): 170.4, 169.7, 169.3, 169.1 (4 ꢂ
CH3COO), 154.7 (C N), 132.8 (C-3 of Ph), 131.8 (C-4 of Ph),
2.1.2. Potassium 2,3,4,6-tetra-O-acetyl-2,3-dichlorophenyl-
glucosinolate, (10). To a stirred solution of thiohydroxymate
C21H23Cl2NO10S and K+ꢀC13H14Cl2NO9S2ꢁꢀCH4OꢀC2H6O 589
ꢃ
Acta Cryst. (2014). C70, 588–594
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Table 1
Experimental details.
(9)
(11)
Crystal data
Chemical formula
Mr
C21H23Cl2NO10
552.36
Monoclinic, P21
130
7.1967 (2), 15.1383 (4), 11.9441 (3)
S
K+ꢀC13H14Cl2NO9S2ꢁꢀCH4OꢀC2H6O
580.48
Orthorhombic, P212121
Crystal system, space group
Temperature (K)
115
8.0043 (1), 15.5208 (4), 19.4586 (4)
90, 90, 90
2417.40 (9)
˚
a, b, c (A)
ꢁ, ꢀ, ꢄ (ꢄ)
90, 102.786 (3), 90
1268.99 (6)
3
˚
V (A )
Z
Radiation type
2
4
Mo Kꢁ
0.39
0.37 ꢂ 0.32 ꢂ 0.14
Cu Kꢁ
6.09
0.65 ꢂ 0.07 ꢂ 0.04
ꢅ (mmꢁ1
Crystal size (mm)
)
Data collection
Diffractometer
Oxford Diffraction SuperNova (Dual, Cu at
zero, Atlas) diffractometer
Gaussian (CrysAlis PRO; Oxford Diffraction,
2010)
Agilent SuperNova (Dual, Cu at zero, Atlas)
diffractometer
Multi-scan (CrysAlis PRO; Agilent, 2012)
Absorption correction
Tmin, Tmax
No. of measured, independent and observed
0.888, 0.949
6348, 3790, 3535
0.716, 1.000
17993, 5041, 4725
[I > 2ꢆ(I)] reflections
Rint
0.027
0.595
0.058
0.633
ꢁ1
˚
(sin ꢇ/ꢂ)max (A
)
Refinement
R[F2 > 2ꢆ(F2)], wR(F2), S
No. of reflections
0.031, 0.069, 1.05
3790
0.054, 0.146, 1.03
5041
No. of parameters
No. of restraints
H-atom treatment
324
1
327
0
H atoms treated by a mixture of independent
and constrained refinement
0.22, ꢁ0.19
H atoms treated by a mixture of independent
and constrained refinement
0.77, ꢁ0.84
ꢁ3
˚
Áꢈmax, Áꢈmin (e A
Absolute structure
)
Flack (1983), 1466 Friedel pairs
Flack x determined using 1921 quotients
(Parsons et al., 2013)
0.010 (12)
Absolute structure parameter
ꢁ0.10 (5)
Computer programs: CrysAlis PRO (Oxford Diffraction, 2010), CrysAlis PRO (Agilent, 2012), SHELXS2013 (Sheldrick, 2008), SHELXL2014 (Sheldrick, 2008), SHELXL97
(Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 2012) and WinGX (Farrugia, 2012).
131.8 (C-1 of Ph), 131.7 (C-2 of Ph), 129.8 (C-6 of Ph), 127.2 (C-
5 of Ph), 80.5 (C-1), 74.9 (C-5), 73.0 (C-3), 69.0 (C-2), 67.3 (C-
4), 60.8 (C-6), 18.9, 18.8, 18.7 (2) (4 ꢂ CH3COO). HRMS (ESI)
m/z for C21H22O13Cl2NS2 [M ꢁ K]ꢁ: calculated 629.9915; found
629.9971.
few holes were made in the film with a needle. After that the
large scintillation vial was capped tightly and stored at 273–
278 K for up to two years to grow the crystals.
Pure (11) was obtained as white crystals (yield 145 mg,
99%). RF = 0.14 in EtOAc–MeOH–H2O (16:4:1 v/v/v) [m.p.
2.1.3. Potassium (2,3-dichlorophenyl)glucosinolate–ethan-
ol–methanol (1/1/1), (11). To a solution of O-acetyl-
glucosinolate (10) (215 mg, 0.32 mmol) in anhydrous MeOH
(20 ml) under an N2 atmosphere was added dry MeOK (9 mg,
0.128 mmol) until a pH of 8–9 was reached. After stirring for
3 h at room temperature, the solution was made neutral by the
addition of glacial acetic acid and then concentrated under
reduced pressure. 2,3-Dichlorophenylglucosinolate (11) was
purified by flash chromatography, eluting with EtOAc–
MeOH–H2O (16:4:1 v/v/v).
The vial-in-a-vial vapour diffusion method was used to grow
the crystals of (11) as follows: 80 mg of the synthetic (11) was
dissolved in H2O (1–1.5 ml). MeOH was added until the
solution became cloudy and the resulting solution was then
filtered through Celite packed on tissue in a pipette to make
sure that the solution was homogeneous. The resulting solu-
tion was poured into a small vial. Ethanol (6–10 ml) was
placed in a scintillation vial and then the small vial with the
sample solution was placed carefully inside the larger scintil-
lation vial. The small vial was covered with plastic film and a
Figure 1
Displacement ellipsoid plot for (9), with ellipsoids drawn at the 20%
probability level. All H atoms have been omitted, except for the hydroxy
H atom.
590 Vo et al. C21H23Cl2NO10S and K+ꢀC13H14Cl2NO9S2ꢁꢀCH4OꢀC2H6O
Acta Cryst. (2014). C70, 588–594
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Table 2
Hydrogen-bond geometry (A, ) for (11).
390–392 K (decomposition)]. [ꢁ] = +60 (c 1.0, H2O). ꢂmax (KBr
drift)/cmꢁ1: 3354 (OH), 2882, 1566 (C N), 1412, 1276, 1265,
1064. ꢃH (300 MHz, D2O, 300 K): 7.62–7.57 (m, 1H, H40-Ph-H),
7.38–7.29 (m, 2H, H50 and H60-Ph-H), 4.01 (d, J1,2 = 9.9 Hz,
1H, H1), 3.47–3.41 (m, 2H, H6a and H6b), 3.31–3.18 (m, 2H,
H2 and H4), 3.10 (t, J2,3 = J3,4 = 9.0 Hz, 1H, H3), 2.43–2.38 (m,
1H, H5). ꢃC (75 MHz, D2O, 300 K): 160.5 (C N), 132.7 (C-3
of Ph), 132.4 (C-4 of Ph), 131.1 (C-1 of Ph), 130.3 (C-2 of Ph),
129.3 (C-6 of Ph), 127.7 (C-5 of Ph), 82.7 (C-1), 79.4 (C-5), 76.5
(C-3), 70.9 (C-2), 68.0 (C-4), 59.1 (C-6). HRMS (ESI) m/z
for C13H14O9Cl2NS2 [M ꢁ K]ꢁ: calculated 461.9493; found
461.9470.
ꢄ
˚
D—Hꢀ ꢀ ꢀA
D—H
Hꢀ ꢀ ꢀA
Dꢀ ꢀ ꢀA
D—Hꢀ ꢀ ꢀA
O11—H11Aꢀ ꢀ ꢀO8
O10—H10ꢀ ꢀ ꢀO8
O3—H3Aꢀ ꢀ ꢀN1v
O2—H2Aꢀ ꢀ ꢀO5vi
O5—H5Aꢀ ꢀ ꢀO11vii
O4—H4Aꢀ ꢀ ꢀO10viii
0.84
0.94
0.84 (6)
0.93 (8)
1.01 (10)
1.09 (10)
2.05
1.80
2.19 (7)
1.79 (8)
1.70 (10)
1.61 (10)
2.861 (8)
2.738 (7)
3.019 (6)
2.655 (5)
2.690 (7)
2.685 (8)
163
174
170 (5)
155 (7)
166 (9)
164 (9)
1
2
1
2
Symmetry codes: (v) ꢁx þ 2; y þ ; ꢁz þ ; (vi) x ꢁ 1; y; z; (vii) x þ 1; y; z; (viii)
3
2
1
2
ꢁx þ ; ꢁy; z ꢁ .
dry MeOH and pyridine. After work-up, oxime (2) was
obtained by recrystallization from hexane and ethyl acetate. In
the chlorination step, the yield was affected by the amount of
N-chlorosuccinimide (NCS) added (Liu et al., 1980). This is
because reaction of NCS with oximes in dimethylformamide
(DMF) exhibits an induction period and the reaction can
become strongly exothermic for most substrates if the reaction
initiates after a considerable portion of the NCS has been
added. It was found that it is desirable to initiate the reaction
prior to addition of no more than one-fifth of the NCS
required (Liu et al., 1980). Therefore, to improve the yield,
NCS (1.05 equivalents) was added one-fifth at a time (over a
period of 30 min) into a cold stirred solution of oxime (2) and
DMF. The reaction mixture was kept at 273 K for the duration
of the reaction and the temperature was then allowed to
increase to room temperature. After 4 h, the reaction was
worked up, and the product was purified by flash column
chromatography or recrystallization to provide chlorooxime
(3) in excellent yield (86% yield over two steps).
2.2. Refinement
Crystal data, data collection and structure refinement
details are summarized in Table 1. Crystals of (9) and (11)
were mounted in low-temperature oil and flash cooled to
130 K using a low-temperature device. All H atoms bonded to
C atoms and the methanol hydroxy H atom in (11) were
placed in geometrically optimized positions and constrained to
ride on their parent atoms, with Uiso(H) = 1.5Ueq(C,O) for
methyl and hydroxy groups and 1.2Ueq(C) otherwise. The
hydroxy H atoms of the nonsolvent molecules were refined
isotropically, while the ethanol hydroxy H atom in (11) was
constrained to ride on its parent atom in the position located
in a difference Fourier map, with Uiso(H) refining freely.
3. Results and discussion
3.1. Synthesis of 2,3-dichlorophenylglucosinolate (11)
2,3,4,6-Tetra-O-acetyl-ꢀ-d-glucopyranosyl thiol, (8), was
obtained in four steps from d-glucose (see Scheme 2 and the
Supporting information) (Yu et al., 2010; Floyd et al., 2009).
d-Glucose, (4), was peracetylated with acetic anhydride in
pyridine in the presence of N,N-dimethylaminopyridine
(DMAP) as catalyst to yield (5), which was able to undergo
selective displacement of the acetate group at the anomeric
position to yield, stereospecifically, 1ꢁ-bromo-2,3,4,6-tetra-O-
acetyl-d-glucopyranose, (6). The ꢁ-bromide was then treated
with thiourea to afford ꢀ-isothiouronium salt (7), followed by
mild hydrolysis with sodium metabisulfite to yield, stereo-
From our studies, the aldoxime pathway was the most
convenient method to synthesize aromatic hydroxymoyl
chlorides compared to the nitronate and nitrovinyl pathways
(Vo, Trenerry, Rochfort, Wadeson et al., 2013). Thus, 2,3-di-
chlorobenzohydroxymoyl chloride was synthesized by the
aldoxime method from 2,3-dichlorobenzaldehyde, (1) (see
Scheme 1 and the Supporting information) (Bialecki et al.,
2007).
To increase the yield, in the first step, hydroxylamine
hydrochloride was added in excess to the solution of reactants,
Figure 2
The hydrogen-bonded network of (9) extending along the c axis. [Symmetry code: (i) x, y, z ꢁ 1.] (Atom colors: yellow = sulfur, red = oxygen, black =
carbon, green = chlorine and white = nitrogen.)
C21H23Cl2NO10S and K+ꢀC13H14Cl2NO9S2ꢁꢀCH4OꢀC2H6O 591
ꢃ
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specifically, 2,3,4,6-tetra-O-acetyl-ꢀ-d-glucopyranosyl thiol,
(8), in an excellent yield (78%) from glucose over four steps.
The coupling of (8) with hydroxymoyl chloride (3) was
conducted by a general method (see Scheme 2) (Benn, 1963,
1964; Streicher et al., 1995). To guarantee that no thiol material
was wasted, the coupling was carried out with an excess of
hydroxymoyl chloride (3) to maximize the conversion of (8).
The thiohydroximates were purified by flash chromatography
eluting with DCM–MeOH in excellent yield (90%). The
coupling was stereospecific in that only the Z isomers were
formed (Viaud & Rollin, 1990). Single-crystal X-ray crystal-
lographic analysis of S-(2,3,4,6-tetra-O-acetyl-ꢀ-d-gluco-
pyranosyl)-2,3-dichlorophenylacetothiohydroximate, (9), con-
firmed that the thiohydroxymate was obtained as a (Z)-thio-
hydroximate (Fig. 1).
Figure 3
Displacement ellipsoid plot for glucosinolate (11)ꢀEtOHꢀMeOH, with
ellipsoids drawn at the 20% probability level. H atoms on C atoms have
been omitted.
The O-sulfation proved to be a tricky step, as evidenced by
previous work (Zhang et al., 1992; Morrison & Botting, 2007;
Rossiter et al., 2007; Vo, Trenerry, Rochfort & Hughes, 2013).
From our studies (Vo, Trenerry, Rochfort, Wadeson et al.,
2013), to improve the yield, the sulfation was carried out in
DCM at reflux temperature under an argon atmosphere rather
than in pyridine at room temperature (Scheme 2). The sulfa-
tion product (10) can be lost due to the high polarity of the
solvent which promotes hydrolysis. Therefore, in the work-up,
the solvent mixture of 20% MeOH–chloroform should be
used to extract organic phases instead of only chloroform in
order to avoid losing the product in the aqueous phase. As a
result, (10) was obtained in 81% yield. De-O-acetylation was
carried out by treatment of potassium methoxide in MeOH
¨
(see Scheme 2) (Rollin & Tatibouet, 2011). 2,3-Dichloro-
phenylglucosinolate (11) was obtained in 56% overall yield
(over seven steps from glucose) by flash column chromato-
graphy on silica gel eluting with EtOAc–MeOH–H2O and
then recrystallization following the vial-in-a-vial vapor diffu-
sion method with H2O–MeOH inside and EtOH outside at
273–278 K for a period of up to two years. The difficulties of
the dual solvation of (11) with one molecule of methanol and
one molecule of ethanol may be one of the main reasons for
the slow crystal growth of (11).
Figure 4
(Top) The sugar coordination mode to potassium ions and (bottom) the
simplified coordination sphere about the potassium ion. The symmetry
codes are as in Table 3. (Atom colors: purple = potassium, yellow = sulfur,
red = oxygen, black = carbon, green = chlorine and white = nitrogen.)
3.2. Description of the structures
In (9) (Fig. 1), the C5—O1—C1—S1 torsion angle of
177.25 (17)ꢄ establishes the ꢀ-configuration of the thio-
Figure 5
The chains of potassium ions linked by sulfonate and sugar O atoms extending along the a axis.
592 Vo et al. C21H23Cl2NO10S and K+ꢀC13H14Cl2NO9S2ꢁꢀCH4OꢀC2H6O
Acta Cryst. (2014). C70, 588–594
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Table 3
Selected geometric parameters (A, ) for (11).
ꢄ
˚
K1—O2i
K1—O9
K1—O7ii
K1—O3iii
2.645 (4)
2.648 (5)
2.713 (5)
2.751 (4)
K1—O4iv
K1—O3i
K1—O4iii
2.885 (4)
2.967 (4)
3.000 (4)
O2i—K1—O9
O2i—K1—O7ii
O9—K1—O7ii
O2i—K1—O3iii
O2i—K1—O4iv
O9—K1—O4iv
O7ii—K1—O4iv
O2i—K1—O3i
O9—K1—O3i
83.25 (14)
100.10 (16)
168.68 (19)
152.88 (12)
90.35 (11)
93.23 (17)
76.01 (15)
59.46 (10)
79.97 (14)
O7ii—K1—O3i
O3iii—K1—O3i
O4iv—K1—O3i
O2i—K1—O4iii
O9—K1—O4iii
O7ii—K1—O4iii
O4iv—K1—O4iii
O3i—K1—O4iii
111.09 (16)
127.98 (9)
149.51 (11)
130.97 (10)
82.14 (16)
103.20 (15)
136.94 (9)
71.98 (10)
3
2
1
1
2
1
2
1
2
1
2
Symmetry codes: (i) ꢁx þ ; ꢁy; z þ ; (ii) x þ ; ꢁy ꢁ ; ꢁz þ 1; (iii) ꢁx þ 2; y ꢁ ,
1
2
5
2
ꢁz þ ; (iv) ꢁx þ ; ꢁy; z þ .
2
further coordination contacts are shown in Fig. 4. Each
potassium ion bridges five sugar molecules and each sugar
molecule coordinates to five potassium ions, resulting in an
extensively crosslinked polymeric network (Table 3).
The resulting three-dimensional polymeric network of (11)
consists of chains containing the potassium ion and its coor-
dinated O atoms, which extends down the a axis (Fig. 5). These
chains are crosslinked in the bc direction by the sugar mol-
ecules to complete the three-dimensional polymeric network.
The channels of this network are occupied by the dichloro-
phenyl substituents and the ethanol and methanol solvent
molecules (Fig. 6).
Figure 6
The three-dimensional polymeric network of (11), including the methanol
and ethanol solvent molecules.
hydroximate substituent. The anomeric C—S bond length of
˚
˚
1.803 (3) A compares with the value of 1.809 A reported for
another ꢀ-thiohydroximate derivative (Tocher & Truter,
1990), but is significantly shorter than that observed for a
similar ꢁ-thiohydroximate, for which the C—S bond length
˚
was reported to be 1.838 A (Durier et al., 1992), which is
4. Conclusion
consistent with a strong structural anomeric effect expected
for this electronegative substituent (Kirby, 1983). The four
C—OAc bond lengths in (9) range from 1.436 (3) to
In conclusion, 2,3-dichlorophenylglucosinolate (11) was
successfully synthesized with a high overall yield (56%). The
study has demonstrated success in growing crystals of a
glucosinolate by the vial-in-a-vial vapour diffusion method.
The X-ray data analysis of (11) also confirmed the absolute
configuration of the glucosinolate structure.
˚
1.444 (3) A. The structure is stabilized by O—Hꢀ ꢀ ꢀO hydrogen
bonds between the oxime hydroxy donor and acetate atom O7
˚
as acceptor, with O10ꢀ ꢀ ꢀO7(x, y, z ꢁ 1) = 2.768 (3) A and
O10—H10ꢀ ꢀ ꢀO7(x, y, z ꢁ 1) = 159 (3)ꢄ, forming a chain
extending along the c axis (Fig. 2).
QVV thanks the Vietnamese Government for the grant of a
Postgraduate Scholarship and the Victorian Department of
Primary Industries for the award of an Aurora Scholarship.
Crystals of (11) were obtained as a dual solvate, containing
one methanol and one ethanol molecule of crystallization. The
methanol solvent molecule forms an intramolecular hydrogen-
bonded bridge between the O2 hydroxy group and sulfonate
atom O8 (Fig. 3), while the ethanol solvent molecule forms an
intermolecular hydrogen-bonded bridge between atom O8
and the O4 hydroxy group (see Table 2 for a list of hydrogen-
bonded contacts). The structure is stabilized by further
hydrogen-bonding interactions which are also summarized in
Table 2. The configuration at the anomeric centre is ꢀ, as
defined by the C5—O1—C1—S1 torsion angle of 169.9 (2)ꢄ,
Supporting information for this paper is available from the IUCr
electronic archives (Reference: SF3222).
References
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England.
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˚
while the anomeric C—S bond length is 1.805 (5) A, which is
comparable to the corresponding bond length in (9).
The potassium counter-ion is coordinated to seven O atoms
with a geometry which can be described as a distorted
pentagonal bipyramid, with atoms O3i, O3iii, O4iii, O4iv and
O2i (see Table 3 for symmetry codes) forming the pentagonal
base and atoms O9 and O7ii as the capping atoms. The
simplified coordination sphere about the potassium ion and
C21H23Cl2NO10S and K+ꢀC13H14Cl2NO9S2ꢁꢀCH4OꢀC2H6O 593
ꢃ
Acta Cryst. (2014). C70, 588–594
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594 Vo et al. C21H23Cl2NO10S and K+ꢀC13H14Cl2NO9S2ꢁꢀCH4OꢀC2H6O
Acta Cryst. (2014). C70, 588–594
ꢃ

supplementary materials
supplementary materials
Acta Cryst. (2014). C70, 588-594 [doi:10.1107/S2053229614009115]
Preparation and X-ray analysis of potassium (2,3-dichlorophenyl)glucosinolate
Quan V. Vo, Craige Trenerry, Simone Rochfort, Jonathan White and Andrew B. Hughes
Computing details
Data collection: CrysAlis PRO (Oxford Diffraction, 2010) for (9); CrysAlis PRO (Agilent, 2012) for (11). Cell
refinement: CrysAlis PRO (Oxford Diffraction, 2010) for (9); CrysAlis PRO (Agilent, 2012) for (11). Data reduction:
CrysAlis PRO (Oxford Diffraction, 2010) for (9); CrysAlis PRO (Agilent, 2012) for (11). Program(s) used to solve
structure: SHELXS97 (Sheldrick, 2008) for (9); SHELXL2014 (Sheldrick, 2008) for (11). Program(s) used to refine
structure: SHELXL97 (Sheldrick, 2008) for (9); SHELXL2014 (Sheldrick, 2008) for (11). For both compounds, molecular
graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: WinGX (Farrugia,
2012).
(9) S-(2,3,4,6-Tetra-O-acetyl-α-D-glucopyranosyl)-2,3-dichlorophenylacetothiohydroxymate
Crystal data
C21H23Cl2NO10S
Mr = 552.36
F(000) = 572
Dx = 1.446 Mg m−3
Mo Kα radiation, λ = 0.7107 Å
Cell parameters from 3604 reflections
θ = 2.9–29.2°
Monoclinic, P21
a = 7.1967 (2) Å
b = 15.1383 (4) Å
c = 11.9441 (3) Å
β = 102.786 (3)°
V = 1268.99 (6) Å3
Z = 2
µ = 0.39 mm−1
T = 130 K
Block, colourless
0.37 × 0.32 × 0.14 mm
Data collection
Oxford Diffraction SuperNova (Dual, Cu at
zero, Atlas)
diffractometer
Radiation source: SuperNova (Mo) X-ray
Source
Tmin = 0.888, Tmax = 0.949
6348 measured reflections
3790 independent reflections
3535 reflections with I > 2σ(I)
Rint = 0.027
Mirror monochromator
ω scans
θmax = 25.0°, θmin = 2.9°
h = −8→8
Absorption correction: gaussian
(CrysAlis PRO; Oxford Diffraction, 2010)
k = −18→18
l = −14→12
Refinement
Refinement on F2
Least-squares matrix: full
R[F2 > 2σ(F2)] = 0.031
wR(F2) = 0.069
1 restraint
Primary atom site location: structure-invariant
direct methods
Secondary atom site location: difference Fourier
map
S = 1.05
3790 reflections
324 parameters
Hydrogen site location: inferred from
neighbouring sites
Acta Cryst. (2014). C70, 588-594
sup-1

supplementary materials
H atoms treated by a mixture of independent
and constrained refinement
Δρmax = 0.22 e Å−3
Δρmin = −0.19 e Å−3
Absolute structure: Flack (1983), ???? Friedel
pairs
w = 1/[σ2(Fo2) + (0.0321P)2 + 0.0094P]
where P = (Fo2 + 2Fc2)/3
(Δ/σ)max = 0.002
Absolute structure parameter: −0.10 (5)
Special details
Experimental. Absorption correction: CrysAlis PRO, Oxford Diffraction Ltd., Version 1.171.34.40 (release 27–08-2010
CrysAlis171. NET) (compiled Aug 27 2010,11:50:40) Numerical absorption correction based on Gaussian integration
over a multifaceted crystal model
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full
covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and
torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry.
An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2,
conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used
only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2
are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
x
y
z
Uiso*/Ueq
Cl1
S1
0.44877 (9)
0.86715 (11)
0.42532 (10)
1.2021 (3)
0.6894 (2)
0.8321 (3)
1.1267 (3)
0.9346 (3)
1.7414 (3)
1.4752 (3)
0.9575 (4)
1.0686
0.68631 (4)
0.55216 (4)
0.86903 (5)
0.61837 (13)
0.50165 (12)
0.56559 (14)
0.61058 (12)
0.47062 (11)
0.73702 (13)
0.71646 (12)
0.79530 (17)
0.7812
0.52381 (6)
0.53502 (6)
0.64869 (7)
1.02012 (16)
0.74050 (16)
0.30744 (18)
0.70838 (15)
0.95260 (15)
0.86375 (17)
0.92931 (16)
0.5331 (2)
0.5094
0.02509 (16)
0.02610 (17)
0.03281 (19)
0.0279 (5)
0.0227 (4)
0.0310 (5)
0.0224 (4)
0.0209 (4)
0.0328 (5)
0.0268 (5)
0.0206 (6)
0.025*
Cl2
O4
O8
O10
O1
O6
O3
O2
C21
H21
C4
1.1623 (4)
1.2477
0.57708 (17)
0.5267
0.9091 (2)
0.9087
0.0203 (6)
0.024*
H4
C12
O7
0.8580 (4)
0.8170 (3)
1.1923 (4)
1.1214
0.4836 (2)
0.55539 (16)
0.64628 (18)
0.7002
1.0445 (2)
1.07422 (17)
0.8220 (2)
0.8307
0.0262 (7)
0.0392 (5)
0.0209 (6)
0.025*
C5
H5
C18
C17
N1
0.6291 (4)
0.6391 (3)
0.8075 (3)
0.7200 (3)
1.3731 (6)
0.8233 (4)
0.9447 (4)
1.0472
0.83854 (18)
0.75882 (17)
0.65176 (15)
0.36415 (16)
0.5010 (2)
0.65118 (17)
0.87462 (18)
0.9136
0.6046 (2)
0.5485 (2)
0.34747 (19)
0.6768 (2)
1.0986 (3)
0.4559 (2)
0.5890 (2)
0.6024
0.0206 (6)
0.0175 (6)
0.0234 (5)
0.0567 (7)
0.0947 (12)
0.0177 (6)
0.0247 (6)
0.030*
O9
O5
C15
C20
H20
C6
1.3981 (4)
1.4701
0.6682 (2)
0.6143
0.8261 (2)
0.8245
0.0282 (7)
0.034*
H6A
H6B
1.4073
0.7035
0.7597
0.034*
Acta Cryst. (2014). C70, 588-594
sup-2

supplementary materials
C13
H13A
H13B
H13C
C1
0.4108 (4)
0.3661
0.4173 (2)
0.3588
0.6887 (3)
0.6660
0.0378 (8)
0.057*
0.3499
0.4589
0.6316
0.057*
0.3810
0.4315
0.7610
0.057*
0.9291 (4)
0.8545
0.59086 (17)
0.6434
0.6813 (2)
0.6906
0.0198 (6)
0.024*
H1
C9
1.3331 (6)
1.4120
0.6248 (3)
0.5925
1.2173 (3)
1.2791
0.0652 (13)
0.098*
H9A
H9B
H9C
C19
H19
C3
1.2107
0.6350
1.2344
0.098*
1.3922
0.6804
1.2081
0.098*
0.7815 (4)
0.7739
0.89604 (18)
0.9492
0.6248 (3)
0.6626
0.0253 (6)
0.030*
0.9558 (4)
0.8739
0.54639 (18)
0.5944
0.8831 (2)
0.8987
0.0181 (5)
0.022*
H3
C16
C7
0.8047 (4)
1.7243 (5)
1.6750
0.73684 (17)
0.7944 (2)
0.8536
0.5125 (2)
1.0484 (3)
1.0427
0.0177 (6)
0.0496 (10)
0.074*
H7A
H7B
H7C
C2
1.8610
0.7962
1.0656
0.074*
1.6819
0.7636
1.1084
0.074*
0.8905 (4)
0.9567
0.51668 (17)
0.4625
0.7593 (2)
0.7456
0.0180 (6)
0.022*
H2
C8
1.6544 (4)
0.6218 (4)
0.8368 (5)
0.7584
0.74775 (18)
0.4212 (2)
0.3977 (2)
0.4060
0.9377 (3)
0.7001 (3)
1.1018 (3)
1.1564
0.0271 (7)
0.0318 (7)
0.0380 (8)
0.057*
C14
C11
H11A
H11B
H11C
C10
H10
0.9600
0.3767
1.1407
0.057*
0.7783
0.3553
1.0452
0.057*
1.3091 (5)
0.830 (5)
0.5728 (3)
0.576 (2)
1.1091 (3)
0.243 (3)
0.0476 (9)
0.037 (10)*
Atomic displacement parameters (Å2)
U11
U22
U33
U12
U13
U23
Cl1
S1
0.0204 (3)
0.0453 (4)
0.0266 (4)
0.0309 (12)
0.0230 (10)
0.0527 (14)
0.0288 (11)
0.0305 (10)
0.0266 (11)
0.0268 (11)
0.0172 (13)
0.0260 (14)
0.0331 (16)
0.0681 (15)
0.0277 (15)
0.0199 (13)
0.0181 (13)
0.0276 (4)
0.0192 (3)
0.0364 (4)
0.0367 (12)
0.0231 (10)
0.0281 (12)
0.0240 (10)
0.0179 (9)
0.0334 (11)
0.0287 (11)
0.0221 (15)
0.0219 (15)
0.0309 (17)
0.0317 (12)
0.0197 (14)
0.0230 (14)
0.0198 (14)
0.0278 (4)
−0.0048 (3)
0.0041 (3)
0.0064 (3)
0.0043 (3)
0.0114 (3)
0.0020 (9)
0.0028 (8)
0.0121 (10)
0.0076 (9)
0.0051 (8)
0.0125 (10)
0.0090 (9)
0.0049 (12)
0.0066 (12)
0.0048 (12)
0.0262 (11)
0.0079 (12)
0.0024 (11)
0.0011 (11)
−0.0040 (3)
−0.0009 (3)
−0.0086 (4)
−0.0029 (9)
−0.0028 (9)
−0.0014 (10)
−0.0006 (8)
0.0028 (8)
0.0128 (3)
Cl2
O4
0.0374 (4)
0.0075 (3)
0.0147 (10)
0.0209 (10)
0.0145 (10)
0.0155 (10)
0.0143 (10)
0.0408 (13)
0.0263 (11)
0.0229 (15)
0.0139 (13)
0.0145 (14)
0.0251 (11)
0.0167 (14)
0.0181 (14)
0.0135 (13)
−0.0086 (10)
0.0002 (8)
O8
O10
O1
0.0040 (10)
−0.0007 (8)
−0.0010 (8)
0.0014 (10)
−0.0068 (8)
0.0005 (11)
0.0033 (11)
−0.0093 (13)
−0.0016 (12)
−0.0003 (12)
0.0054 (11)
−0.0003 (11)
O6
O3
0.0032 (11)
−0.0062 (9)
0.0036 (13)
0.0019 (12)
−0.0008 (14)
−0.0014 (11)
−0.0019 (12)
0.0011 (12)
0.0006 (12)
O2
C21
C4
C12
O7
C5
C18
C17
Acta Cryst. (2014). C70, 588-594
sup-3

supplementary materials
N1
0.0348 (14)
0.0492 (15)
0.137 (3)
0.0202 (12)
0.0298 (13)
0.057 (2)
0.0168 (12)
0.093 (2)
0.0014 (10)
−0.0068 (12)
0.016 (2)
0.0088 (11)
0.0189 (15)
−0.049 (2)
−0.0021 (10)
−0.0278 (15)
0.0103 (17)
0.0013 (12)
−0.0023 (14)
−0.0063 (14)
−0.0075 (17)
−0.0020 (12)
−0.002 (2)
O9
O5
0.057 (2)
C15
C20
C6
0.0163 (13)
0.0210 (14)
0.0306 (16)
0.0377 (18)
0.0273 (15)
0.077 (3)
0.0210 (14)
0.0194 (14)
0.0299 (16)
0.0399 (19)
0.0186 (14)
0.091 (3)
0.0166 (14)
0.0314 (16)
0.0263 (16)
0.0351 (19)
0.0134 (13)
0.0199 (17)
0.0253 (15)
0.0114 (12)
0.0114 (12)
0.050 (2)
0.0018 (11)
−0.0062 (12)
−0.0046 (13)
−0.0107 (16)
0.0040 (11)
−0.044 (3)
0.0055 (11)
0.0010 (12)
0.0109 (14)
0.0065 (15)
0.0046 (12)
−0.0070 (18)
−0.0003 (13)
0.0052 (11)
0.0021 (11)
0.0121 (18)
0.0051 (11)
0.0085 (14)
0.0063 (15)
0.0119 (16)
−0.0109 (16)
C13
C1
C9
C19
C3
0.0289 (15)
0.0290 (14)
0.0228 (14)
0.044 (2)
0.0186 (14)
0.0142 (13)
0.0181 (14)
0.056 (2)
0.0028 (12)
0.0002 (12)
0.0041 (12)
−0.0164 (18)
0.0034 (11)
0.0006 (13)
−0.0045 (15)
−0.0120 (15)
−0.0164 (19)
−0.0014 (13)
0.0031 (12)
0.0056 (12)
−0.016 (2)
C16
C7
C2
0.0216 (13)
0.0260 (15)
0.0421 (18)
0.050 (2)
0.0183 (14)
0.0177 (15)
0.0273 (17)
0.0381 (19)
0.058 (3)
0.0146 (14)
0.0383 (17)
0.0255 (17)
0.0269 (17)
0.0242 (18)
0.0000 (12)
−0.0003 (14)
−0.0090 (14)
0.0056 (15)
0.0083 (18)
C8
C14
C11
C10
0.052 (2)
Geometric parameters (Å, º)
Cl1—C17
S1—C15
S1—C1
1.729 (3)
N1—C15
1.275 (3)
1.763 (3)
1.803 (3)
1.727 (2)
1.355 (4)
1.436 (3)
1.359 (3)
1.432 (3)
1.414 (3)
0.78 (3)
O9—C14
O5—C10
C15—C16
C20—C19
C20—H20
C6—H6A
C6—H6B
C13—C14
C13—H13A
C13—H13B
C13—H13C
C1—C2
1.188 (4)
1.199 (5)
1.482 (4)
1.375 (4)
0.9300
Cl2—C18
O4—C10
O4—C4
O8—C14
O8—C2
0.9700
0.9700
O10—N1
O10—H10
O1—C1
1.495 (4)
0.9600
1.419 (3)
1.439 (3)
1.347 (3)
1.444 (3)
1.201 (3)
1.357 (3)
1.434 (3)
1.387 (4)
1.390 (4)
0.9300
0.9600
O1—C5
0.9600
O6—C12
O6—C3
1.523 (4)
0.9800
C1—H1
O3—C8
C9—C10
C9—H9A
C9—H9B
C9—H9C
C19—H19
C3—C2
1.490 (5)
0.9600
O2—C8
O2—C6
0.9600
C21—C20
C21—C16
C21—H21
C4—C3
0.9600
0.9300
1.517 (3)
0.9800
1.522 (4)
1.526 (4)
0.9800
C3—H3
C4—C5
C7—C8
1.486 (4)
0.9600
C4—H4
C7—H7A
C7—H7B
C7—H7C
C2—H2
C12—O7
C12—C11
C5—C6
1.200 (4)
1.493 (4)
1.508 (4)
0.9800
0.9600
0.9600
0.9800
C5—H5
C11—H11A
C11—H11B
C11—H11C
0.9600
C18—C19
C18—C17
1.379 (4)
1.390 (4)
0.9600
0.9600
Acta Cryst. (2014). C70, 588-594
sup-4

supplementary materials
C17—C16
1.394 (3)
C15—S1—C1
C10—O4—C4
C14—O8—C2
N1—O10—H10
C1—O1—C5
102.69 (12)
117.7 (2)
117.9 (2)
99 (2)
O1—C1—S1
108.04 (16)
108.29 (18)
110.5
C2—C1—S1
O1—C1—H1
C2—C1—H1
110.5
113.37 (18)
117.8 (2)
114.9 (2)
120.1 (2)
119.9
S1—C1—H1
110.5
C12—O6—C3
C8—O2—C6
C10—C9—H9A
C10—C9—H9B
H9A—C9—H9B
C10—C9—H9C
H9A—C9—H9C
H9B—C9—H9C
C20—C19—C18
C20—C19—H19
C18—C19—H19
O6—C3—C2
109.5
109.5
C20—C21—C16
C20—C21—H21
C16—C21—H21
O4—C4—C3
109.5
109.5
119.9
109.5
107.93 (19)
107.6 (2)
110.5 (2)
110.3
109.5
O4—C4—C5
119.9 (3)
120.1
C3—C4—C5
O4—C4—H4
120.1
C3—C4—H4
110.3
106.0 (2)
110.4 (2)
111.58 (19)
109.6
C5—C4—H4
110.3
O6—C3—C4
O7—C12—O6
O7—C12—C11
O6—C12—C11
O1—C5—C6
123.1 (3)
126.6 (2)
110.4 (3)
103.19 (19)
108.6 (2)
114.5 (2)
110.1
C2—C3—C4
O6—C3—H3
C2—C3—H3
109.6
C4—C3—H3
109.6
O1—C5—C4
C21—C16—C17
C21—C16—C15
C17—C16—C15
C8—C7—H7A
C8—C7—H7B
H7A—C7—H7B
C8—C7—H7C
H7A—C7—H7C
H7B—C7—H7C
O8—C2—C3
119.3 (2)
119.4 (2)
121.3 (2)
109.5
C6—C5—C4
O1—C5—H5
C6—C5—H5
110.1
C4—C5—H5
110.1
109.5
C19—C18—C17
C19—C18—Cl2
C17—C18—Cl2
C18—C17—C16
C18—C17—Cl1
C16—C17—Cl1
C15—N1—O10
N1—C15—C16
N1—C15—S1
C16—C15—S1
C19—C20—C21
C19—C20—H20
C21—C20—H20
O2—C6—C5
120.5 (2)
118.3 (2)
121.1 (2)
119.7 (2)
120.66 (18)
119.7 (2)
110.3 (2)
117.4 (2)
121.0 (2)
121.57 (18)
120.4 (2)
119.8
109.5
109.5
109.5
109.5
106.53 (18)
109.6 (2)
108.6 (2)
110.7
O8—C2—C1
C3—C2—C1
O8—C2—H2
C3—C2—H2
110.7
C1—C2—H2
110.7
O3—C8—O2
122.7 (3)
126.2 (3)
111.1 (2)
123.4 (3)
126.4 (3)
110.2 (3)
109.5
O3—C8—C7
119.8
O2—C8—C7
109.3 (2)
109.8
O9—C14—O8
O9—C14—C13
O8—C14—C13
C12—C11—H11A
C12—C11—H11B
O2—C6—H6A
C5—C6—H6A
O2—C6—H6B
C5—C6—H6B
H6A—C6—H6B
C14—C13—H13A
C14—C13—H13B
H13A—C13—H13B
109.8
109.8
109.8
109.5
108.3
H11A—C11—H11B
C12—C11—H11C
H11A—C11—H11C
H11B—C11—H11C
109.5
109.5
109.5
109.5
109.5
109.5
109.5
Acta Cryst. (2014). C70, 588-594
sup-5

supplementary materials
C14—C13—H13C
H13A—C13—H13C
H13B—C13—H13C
O1—C1—C2
109.5
O5—C10—O4
O5—C10—C9
O4—C10—C9
123.0 (3)
126.6 (4)
110.4 (3)
109.5
109.5
109.0 (2)
C10—O4—C4—C3
C10—O4—C4—C5
C3—O6—C12—O7
C3—O6—C12—C11
C1—O1—C5—C6
C1—O1—C5—C4
O4—C4—C5—O1
C3—C4—C5—O1
O4—C4—C5—C6
C3—C4—C5—C6
C19—C18—C17—C16
Cl2—C18—C17—C16
C19—C18—C17—Cl1
Cl2—C18—C17—Cl1
O10—N1—C15—C16
O10—N1—C15—S1
C1—S1—C15—N1
C1—S1—C15—C16
C16—C21—C20—C19
C8—O2—C6—C5
O1—C5—C6—O2
C4—C5—C6—O2
C5—O1—C1—C2
C5—O1—C1—S1
105.2 (3)
−135.6 (3)
−4.2 (4)
O4—C4—C3—O6
C5—C4—C3—O6
O4—C4—C3—C2
C5—C4—C3—C2
−72.6 (2)
170.10 (19)
169.9 (2)
52.5 (3)
176.7 (3)
−175.6 (2)
62.5 (3)
C20—C21—C16—C17
C20—C21—C16—C15
C18—C17—C16—C21
Cl1—C17—C16—C21
C18—C17—C16—C15
Cl1—C17—C16—C15
N1—C15—C16—C21
S1—C15—C16—C21
N1—C15—C16—C17
S1—C15—C16—C17
C14—O8—C2—C3
C14—O8—C2—C1
O6—C3—C2—O8
C4—C3—C2—O8
0.0 (4)
−178.1 (2)
−0.1 (4)
−171.7 (2)
−54.1 (3)
73.6 (3)
−179.7 (2)
177.9 (2)
−1.7 (3)
−168.9 (2)
0.0 (4)
−78.0 (3)
101.6 (2)
104.0 (3)
−76.5 (3)
−125.1 (2)
117.6 (2)
67.9 (2)
179.0 (2)
179.6 (2)
−1.4 (3)
178.9 (2)
−0.7 (3)
167.6 (2)
−11.9 (2)
0.2 (4)
−171.9 (2)
−174.09 (19)
−53.9 (3)
174.60 (18)
−68.1 (2)
58.6 (3)
O6—C3—C2—C1
−173.7 (2)
171.7 (2)
−70.4 (3)
−65.3 (2)
177.25 (17)
−85.48 (18)
156.63 (17)
−0.3 (4)
C4—C3—C2—C1
O1—C1—C2—O8
S1—C1—C2—O8
O1—C1—C2—C3
S1—C1—C2—C3
175.90 (17)
0.9 (4)
C15—S1—C1—O1
C15—S1—C1—C2
C21—C20—C19—C18
C17—C18—C19—C20
Cl2—C18—C19—C20
C12—O6—C3—C2
C12—O6—C3—C4
C6—O2—C8—O3
C6—O2—C8—C7
−178.4 (3)
−2.2 (4)
C2—O8—C14—O9
C2—O8—C14—C13
C4—O4—C10—O5
C4—O4—C10—C9
0.2 (4)
178.7 (2)
1.1 (5)
−178.8 (2)
−136.3 (2)
102.8 (3)
−179.1 (2)
Hydrogen-bond geometry (Å, º)
D—H···A
O10—H10···O7i
D—H
H···A
D···A
D—H···A
159 (3)
0.78 (3)
2.03 (3)
2.768 (3)
Symmetry code: (i) x, y, z−1.
(11) Potassium 2,3-dichlorophenylglucosinolate–ethanol–methanol (1/1/1)
Crystal data
K+·C13H14Cl2NO9S2−·CH4O·C2H6O
Mr = 580.48
Orthorhombic, P212121
a = 8.0043 (1) Å
b = 15.5208 (4) Å
c = 19.4586 (4) Å
V = 2417.40 (9) Å3
Z = 4
Acta Cryst. (2014). C70, 588-594
sup-6

supplementary materials
F(000) = 1200
Dx = 1.595 Mg m−3
µ = 6.09 mm−1
T = 115 K
Cu Kα radiation, λ = 1.5418 Å
Cell parameters from 8197 reflections
θ = 2.9–77.4°
Needle, colourless
0.65 × 0.07 × 0.04 mm
Data collection
Agilent SuperNova (Dual, Cu at zero, Atlas)
diffractometer
Radiation source: SuperNova (Cu) X-ray
Source
17993 measured reflections
5041 independent reflections
4725 reflections with I > 2σ(I)
Rint = 0.058
Mirror monochromator
ω scans
θmax = 77.6°, θmin = 3.6°
h = −9→8
Absorption correction: multi-scan
(CrysAlis PRO; Agilent, 2012)
k = −19→13
l = −24→22
T
min = 0.716, Tmax = 1.000
Refinement
Refinement on F2
Least-squares matrix: full
R[F2 > 2σ(F2)] = 0.054
wR(F2) = 0.146
H atoms treated by a mixture of independent
and constrained refinement
w = 1/[σ2(Fo2) + (0.0865P)2 + 3.0655P]
where P = (Fo2 + 2Fc2)/3
S = 1.03
5041 reflections
327 parameters
(Δ/σ)max < 0.001
Δρmax = 0.77 e Å−3
Δρmin = −0.84 e Å−3
0 restraints
Hydrogen site location: mixed
Absolute structure: Flack x determined using
1921 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et
al., 2013)
Absolute structure parameter: 0.010 (12)
Special details
Experimental. Absorption correction: CrysAlis PRO, Agilent Technologies, Version 1.171.36.20 (release 27–06-2012
CrysAlis171. NET) (compiled Jul 11 2012,15:38:31) Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
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.
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
x
y
z
Uiso*/Ueq
Occ. (<1)
K1
S1
0.81320 (13)
0.89551 (15)
0.59342 (18)
0.7777 (3)
1.0311 (6)
1.0458 (4)
1.5311 (4)
0.8047 (4)
0.7190 (5)
1.1917 (4)
1.3631 (4)
−0.24630 (7)
0.07667 (8)
−0.06282 (10)
−0.10597 (15)
−0.2152 (2)
0.2622 (2)
0.54647 (5)
0.29475 (6)
0.43921 (8)
0.17322 (11)
0.08482 (12)
0.08230 (18)
0.2366 (2)
0.0245 (2)
0.0219 (3)
0.0350 (3)
0.0665 (6)
0.1080 (14)
0.0203 (7)
0.0267 (8)
0.0223 (7)
0.0291 (8)
0.0215 (7)
0.0264 (8)
S2
Cl1
Cl2
O3
O5
O2
O6
O1
O4
0.1603 (3)
0.1761 (2)
0.16045 (18)
0.3848 (2)
−0.0153 (3)
0.0953 (2)
0.23779 (18)
0.07274 (19)
0.1715 (3)
Acta Cryst. (2014). C70, 588-594
sup-7

supplementary materials
N1
0.8248 (6)
0.4930 (7)
0.5063 (6)
1.0208 (6)
1.0023
−0.0757 (3)
−0.1219 (4)
0.0133 (3)
0.0930 (3)
0.0438
0.3505 (2)
0.3995 (3)
0.4636 (3)
0.2187 (3)
0.1864
0.0275 (9)
0.0570 (15)
0.0414 (11)
0.0212 (10)
0.025*
O7
O8
C1
H1
C3
1.0813 (6)
1.0497
0.1843 (3)
0.1355
0.1183 (3)
0.0873
0.0184 (9)
0.022*
H3
O9
0.6961 (7)
0.9104 (6)
0.4829 (10)
0.5067
−0.1038 (4)
−0.0353 (4)
0.1584 (4)
0.1130
0.4892 (3)
0.3054 (3)
0.3734 (3)
0.3948
0.0527 (14)
0.0240 (10)
0.0644 (17)
0.097*
C7
O11
H11A
C16
H16A
H16B
H16C
C8
0.334 (2)
0.3314
0.1827 (10)
0.1995
0.3897 (8)
0.4382
0.112 (5)
0.168*
0.2555
0.1351
0.3820
0.168*
0.3015
0.2320
0.3611
0.168*
1.0288 (7)
0.9775 (10)
1.4737 (6)
1.4803
−0.0883 (4)
−0.1233 (4)
0.0837 (3)
0.0347
0.2635 (3)
0.2015 (3)
0.2030 (3)
0.2354
0.0294 (12)
0.0427 (16)
0.0267 (11)
0.032*
C9
C6
H6A
H6B
O10
H10
C4
1.5476
0.0709
0.1635
0.032*
0.1919 (8)
0.2991
−0.0183 (6)
−0.0035
0.5129 (5)
0.4973
0.099 (3)
0.08 (3)*
0.0208 (10)
0.025*
1.2672 (6)
1.3039
0.1744 (3)
0.2255
0.1345 (2)
0.1620
H4
C2
0.9727 (6)
0.9928
0.1770 (3)
0.2272
0.1828 (2)
0.2140
0.0176 (9)
0.021*
H2
C5
1.2961 (6)
1.2663
0.0930 (3)
0.0413
0.1778 (3)
0.1497
0.0222 (10)
0.027*
H5
C13
H13
C10
C12
H12
C11
H11
C14′
H14A
H14B
C15′
H15A
H15B
H15C
C14
H14C
H14D
C15
H15D
H15E
H15F
1.1917 (8)
1.2278
−0.1008 (4)
−0.0766
0.2867 (4)
0.3290
0.0406 (15)
0.049*
1.0905 (14)
1.3005 (9)
1.4118
−0.1718 (5)
−0.1497 (5)
−0.1584
0.1626 (4)
0.2465 (5)
0.2620
0.060 (2)
0.054 (2)
0.064*
1.2519 (12)
1.3280
−0.1850 (5)
−0.2186
0.1859 (4)
0.1597
0.061 (3)
0.073*
0.0611 (12)
−0.0084
0.1128
0.0318 (9)
−0.0075
0.4869 (5)
0.4588
0.075 (3)
0.090*
0.52 (5)
0.52 (5)
0.52 (5)
0.52 (5)
0.52 (5)
0.52 (5)
0.52 (5)
0.48 (5)
0.48 (5)
0.48 (5)
0.48 (5)
0.48 (5)
0.48 (5)
0.48 (5)
0.0731
0.4544
0.090*
−0.050 (5)
−0.1305
−0.1102
0.0121
0.080 (3)
0.1092
0.5272 (15)
0.4973
0.099 (11)
0.148*
0.0410
0.5584
0.148*
0.1224
0.5540
0.148*
0.0611 (12)
−0.0440
0.0878
0.0318 (9)
−0.0017
0.4869 (5)
0.4849
0.075 (3)
0.090*
0.0534
0.4403
0.090*
0.048 (5)
−0.0421
0.0228
0.1024 (18)
0.1414
0.5358 (12)
0.5215
0.077 (11)
0.115*
0.0794
0.5815
0.115*
0.1536
0.1341
0.5373
0.115*
Acta Cryst. (2014). C70, 588-594
sup-8

supplementary materials
H3A
H2A
H5A
H4A
1.083 (7)
0.304 (4)
0.178 (5)
0.150 (6)
0.107 (7)
0.106 (3)
0.197 (4)
0.287 (5)
0.055 (5)
0.012 (13)*
0.05 (2)*
0.07 (3)*
0.07 (3)*
0.729 (10)
1.515 (13)
1.326 (13)
Atomic displacement parameters (Å2)
U11
U22
U33
U12
U13
U23
K1
0.0226 (5)
0.0186 (5)
0.0316 (7)
0.0847 (15)
0.190 (4)
0.0199 (15)
0.0158 (16)
0.0103 (15)
0.0277 (19)
0.0117 (15)
0.0203 (17)
0.028 (2)
0.039 (3)
0.037 (2)
0.010 (2)
0.016 (2)
0.060 (3)
0.019 (2)
0.087 (5)
0.112 (11)
0.031 (3)
0.062 (4)
0.015 (2)
0.042 (3)
0.016 (2)
0.0104 (19)
0.013 (2)
0.032 (3)
0.101 (7)
0.041 (4)
0.082 (6)
0.057 (5)
0.062 (17)
0.057 (5)
0.09 (2)
0.0307 (5)
0.0239 (6)
0.0313 (7)
0.0602 (12)
0.0905 (19)
0.0196 (17)
0.033 (2)
0.0333 (19)
0.0267 (19)
0.0277 (18)
0.034 (2)
0.027 (2)
0.054 (3)
0.035 (2)
0.023 (2)
0.018 (2)
0.056 (3)
0.030 (3)
0.060 (4)
0.107 (11)
0.024 (3)
0.033 (3)
0.027 (3)
0.119 (6)
0.025 (2)
0.021 (2)
0.024 (2)
0.030 (3)
0.041 (4)
0.040 (4)
0.041 (4)
0.113 (9)
0.12 (2)
0.0202 (5)
0.0231 (5)
0.0422 (8)
0.0545 (10)
0.0438 (11)
0.0214 (16)
0.031 (2)
0.0233 (17)
0.0330 (19)
0.0252 (16)
0.0246 (18)
0.028 (2)
0.078 (4)
0.052 (3)
0.030 (2)
0.022 (2)
0.042 (2)
0.023 (2)
0.046 (3)
0.116 (11)
0.033 (3)
0.032 (3)
0.038 (3)
0.137 (7)
0.021 (2)
0.021 (2)
0.030 (2)
0.060 (4)
0.038 (4)
0.079 (6)
0.059 (5)
0.055 (5)
0.11 (2)
0.0033 (4)
0.0022 (4)
0.0055 (4)
0.0169 (6)
−0.0256 (10)
0.0056 (16)
0.0015 (13)
−0.0004 (14)
0.0010 (13)
0.0146 (16)
0.0019 (13)
0.0096 (14)
0.0098 (18)
0.017 (3)
−0.0027 (4)
0.0060 (5)
0.0100 (6)
−0.0196 (9)
−0.0192 (12)
0.0034 (14)
0.0055 (16)
0.0065 (14)
0.0071 (16)
0.0066 (14)
0.0028 (15)
0.0057 (18)
−0.012 (3)
0.008 (2)
S1
0.0026 (4)
0.0042 (6)
0.0270 (11)
0.066 (2)
S2
Cl1
Cl2
O3
−0.0008 (14)
0.0000 (15)
−0.0015 (14)
0.0064 (15)
0.0000 (13)
0.0009 (14)
0.0066 (19)
−0.017 (2)
0.0096 (19)
−0.0001 (18)
−0.0015 (17)
0.022 (3)
O5
O2
O6
O1
O4
N1
O7
O8
0.023 (2)
C1
0.0017 (17)
0.0024 (17)
0.015 (2)
0.0057 (19)
0.0045 (19)
0.024 (2)
C3
O9
C7
0.004 (2)
0.0032 (18)
0.015 (3)
0.003 (2)
O11
C16
C8
−0.003 (3)
0.022 (9)
0.019 (3)
0.023 (10)
0.013 (2)
0.024 (9)
0.007 (2)
0.012 (2)
C9
0.018 (3)
0.010 (3)
0.007 (3)
C6
0.001 (2)
0.005 (2)
0.006 (2)
O10
C4
0.020 (4)
0.028 (4)
0.094 (6)
0.0005 (18)
−0.0021 (17)
0.0026 (18)
0.007 (3)
0.0052 (17)
0.0000 (16)
0.0063 (18)
0.019 (3)
0.0029 (18)
0.0031 (17)
0.0041 (19)
0.018 (3)
C2
C5
C13
C10
C12
C11
C14′
C15′
C14
C15
0.028 (4)
0.028 (4)
0.006 (3)
0.017 (3)
0.034 (4)
0.022 (4)
0.027 (4)
0.045 (5)
0.017 (4)
0.025 (5)
−0.005 (4)
−0.023 (14)
−0.005 (4)
0.012 (12)
0.017 (6)
0.020 (15)
0.025 (5)
−0.054 (18)
0.017 (6)
0.113 (9)
0.091 (17)
0.055 (5)
0.051 (11)
0.002 (15)
−0.013 (11)
Geometric parameters (Å, º)
K1—O2i
K1—O9
K1—O7ii
K1—O3iii
2.645 (4)
C1—H1
1.0000
2.648 (5)
2.713 (5)
2.751 (4)
C3—C4
C3—C2
C3—K1vi
1.529 (6)
1.531 (6)
3.487 (5)
Acta Cryst. (2014). C70, 588-594
sup-9

supplementary materials
K1—O4iv
K1—O3i
K1—O4iii
K1—C3iii
K1—S2ii
K1—K1v
K1—K1ii
S1—C7
2.885 (4)
2.967 (4)
3.000 (4)
3.487 (5)
3.7264 (18)
4.3933 (8)
4.3933 (8)
1.754 (6)
1.805 (5)
1.423 (5)
1.443 (6)
1.452 (5)
1.636 (4)
3.7263 (18)
1.713 (8)
1.723 (10)
1.427 (6)
2.751 (4)
2.967 (4)
0.84 (6)
C3—H3
1.0000
C7—C8
1.496 (7)
1.291 (16)
0.8400
O11—C16
O11—H11A
C16—H16A
C16—H16B
C16—H16C
C8—C9
0.9800
0.9800
0.9800
1.385 (10)
1.393 (9)
1.400 (10)
1.511 (7)
0.9900
S1—C1
C8—C13
S2—O9
C9—C10
S2—O7
C6—C5
S2—O8
C6—H6A
C6—H6B
O10—C14′
O10—H10
C4—C5
S2—O6
0.9900
S2—K1v
Cl1—C9
Cl2—C10
O3—C3
O3—K1vi
O3—K1vii
O3—H3A
O5—C6
O5—H5A
O2—C2
O2—K1vii
O2—H2A
O6—N1
O1—C1
O1—C5
O4—C4
O4—K1viii
O4—K1vi
O4—H4A
N1—C7
O7—K1v
C1—C2
1.399 (11)
0.9383
1.536 (7)
1.0000
C4—H4
C2—H2
1.0000
C5—H5
1.0000
C13—C12
C13—H13
C10—C11
C12—C11
C12—H12
C11—H11
C14′—C15′
C14′—H14A
C14′—H14B
C15′—H15A
C15′—H15B
C15′—H15C
C15—H15D
C15—H15E
C15—H15F
1.394 (9)
0.9500
1.432 (7)
1.01 (10)
1.414 (5)
2.645 (4)
0.93 (8)
1.384 (14)
1.358 (13)
0.9500
0.9500
1.429 (6)
1.418 (6)
1.436 (6)
1.427 (6)
2.884 (4)
3.000 (4)
1.09 (10)
1.278 (7)
2.713 (5)
1.529 (7)
1.40 (3)
0.9900
0.9900
0.9800
0.9800
0.9800
0.9800
0.9800
0.9800
O2i—K1—O9
O2i—K1—O7ii
O9—K1—O7ii
O2i—K1—O3iii
O9—K1—O3iii
O7ii—K1—O3iii
O2i—K1—O4iv
O9—K1—O4iv
O7ii—K1—O4iv
O3iii—K1—O4iv
O2i—K1—O3i
O9—K1—O3i
O7ii—K1—O3i
83.25 (14)
100.10 (16)
168.68 (19)
152.88 (12)
73.85 (13)
99.86 (16)
90.35 (11)
93.23 (17)
76.01 (15)
76.91 (11)
59.46 (10)
79.97 (14)
111.09 (16)
O1—C1—C2
O1—C1—S1
C2—C1—S1
O1—C1—H1
C2—C1—H1
S1—C1—H1
O3—C3—C4
O3—C3—C2
C4—C3—C2
O3—C3—K1vi
C4—C3—K1vi
C2—C3—K1vi
O3—C3—H3
109.9 (4)
108.9 (3)
110.7 (3)
109.1
109.1
109.1
112.4 (4)
110.6 (4)
112.1 (4)
48.3 (2)
89.2 (3)
156.1 (3)
107.2
Acta Cryst. (2014). C70, 588-594
sup-10

supplementary materials
O3iii—K1—O3i
O4iv—K1—O3i
O2i—K1—O4iii
O9—K1—O4iii
O7ii—K1—O4iii
O3iii—K1—O4iii
O4iv—K1—O4iii
O3i—K1—O4iii
O2i—K1—C3iii
O9—K1—C3iii
O7ii—K1—C3iii
O3iii—K1—C3iii
O4iv—K1—C3iii
O3i—K1—C3iii
O4iii—K1—C3iii
O2i—K1—S2ii
O9—K1—S2ii
O7ii—K1—S2ii
O3iii—K1—S2ii
O4iv—K1—S2ii
O3i—K1—S2ii
O4iii—K1—S2ii
C3iii—K1—S2ii
O2i—K1—K1v
O9—K1—K1v
O7ii—K1—K1v
O3iii—K1—K1v
O4iv—K1—K1v
O3i—K1—K1v
O4iii—K1—K1v
C3iii—K1—K1v
S2ii—K1—K1v
O2i—K1—K1ii
O9—K1—K1ii
O7ii—K1—K1ii
O3iii—K1—K1ii
O4iv—K1—K1ii
O3i—K1—K1ii
O4iii—K1—K1ii
C3iii—K1—K1ii
S2ii—K1—K1ii
K1v—K1—K1ii
C7—S1—C1
127.98 (9)
149.51 (11)
130.97 (10)
82.14 (16)
103.20 (15)
60.61 (10)
136.94 (9)
71.98 (10)
170.01 (12)
87.52 (14)
89.69 (16)
22.77 (11)
94.00 (11)
115.14 (10)
43.23 (10)
118.66 (9)
155.30 (12)
18.59 (13)
81.92 (8)
76.46 (8)
119.94 (8)
90.17 (8)
71.17 (8)
91.78 (8)
61.72 (14)
128.52 (13)
90.01 (8)
154.39 (10)
38.03 (7)
40.71 (7)
80.44 (8)
123.94 (5)
132.91 (8)
99.84 (12)
69.91 (14)
41.64 (8)
42.71 (8)
167.62 (8)
95.69 (7)
52.61 (8)
57.43 (3)
131.28 (5)
101.4 (2)
113.8 (4)
C4—C3—H3
107.2
C2—C3—H3
K1vi—C3—H3
107.2
75.0
S2—O9—K1
149.9 (4)
116.3 (5)
122.0 (4)
121.6 (4)
109.5
N1—C7—C8
N1—C7—S1
C8—C7—S1
C16—O11—H11A
O11—C16—H16A
O11—C16—H16B
109.5
109.5
H16A—C16—H16B
O11—C16—H16C
H16A—C16—H16C
H16B—C16—H16C
C9—C8—C13
C9—C8—C7
109.5
109.5
109.5
109.5
120.3 (6)
120.1 (5)
119.5 (6)
119.4 (8)
119.7 (5)
120.9 (7)
111.8 (4)
109.3
C13—C8—C7
C8—C9—C10
C8—C9—Cl1
C10—C9—Cl1
O5—C6—C5
O5—C6—H6A
C5—C6—H6A
O5—C6—H6B
C5—C6—H6B
H6A—C6—H6B
C14′—O10—H10
O4—C4—C3
109.3
109.3
109.3
107.9
115.5
110.6 (4)
110.8 (4)
110.0 (4)
108.4
O4—C4—C5
C3—C4—C5
O4—C4—H4
C3—C4—H4
108.4
C5—C4—H4
108.4
O2—C2—C1
111.8 (4)
106.8 (4)
107.1 (4)
110.4
O2—C2—C3
C1—C2—C3
O2—C2—H2
C1—C2—H2
110.4
C3—C2—H2
110.4
O1—C5—C6
106.7 (4)
109.7 (4)
113.4 (4)
109.0
O1—C5—C4
C6—C5—C4
O1—C5—H5
C6—C5—H5
O9—S2—O7
109.0
O9—S2—O8
114.7 (3)
C4—C5—H5
109.0
O7—S2—O8
115.1 (3)
C8—C13—C12
C8—C13—H13
C12—C13—H13
C11—C10—C9
118.6 (8)
120.7
O9—S2—O6
106.8 (3)
106.4 (3)
98.0 (2)
O7—S2—O6
120.7
O8—S2—O6
120.3 (8)
Acta Cryst. (2014). C70, 588-594
sup-11

supplementary materials
O9—S2—K1v
O7—S2—K1v
O8—S2—K1v
O6—S2—K1v
C3—O3—K1vi
C3—O3—K1vii
K1vi—O3—K1vii
C3—O3—H3A
K1vi—O3—H3A
K1vii—O3—H3A
C6—O5—H5A
C2—O2—K1vii
C2—O2—H2A
K1vii—O2—H2A
N1—O6—S2
86.6 (3)
36.8 (2)
109.5 (2)
140.95 (17)
109.0 (3)
103.8 (3)
100.33 (11)
108 (4)
C11—C10—Cl2
C9—C10—Cl2
119.2 (6)
120.5 (8)
121.8 (8)
119.1
C11—C12—C13
C11—C12—H12
C13—C12—H12
C12—C11—C10
C12—C11—H11
C10—C11—H11
O10—C14′—C15′
O10—C14′—H14A
119.1
119.5 (7)
120.2
120.2
113 (4)
124.6 (14)
106.2
122 (4)
106 (6)
C15′—C14′—H14A
O10—C14′—H14B
C15′—C14′—H14B
H14A—C14′—H14B
C14′—C15′—H15A
C14′—C15′—H15B
H15A—C15′—H15B
C14′—C15′—H15C
H15A—C15′—H15C
H15B—C15′—H15C
H15D—C15—H15E
H15D—C15—H15F
H15E—C15—H15F
106.2
106.2
106.2
106.4
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
126.4 (3)
113 (5)
113 (5)
111.8 (3)
110.4 (4)
128.3 (3)
112.7 (3)
96.58 (11)
98 (5)
C1—O1—C5
C4—O4—K1viii
C4—O4—K1vi
K1viii—O4—K1vi
C4—O4—H4A
K1viii—O4—H4A
K1vi—O4—H4A
C7—N1—O6
124 (6)
91 (5)
108.5 (4)
124.6 (4)
S2—O7—K1v
O9—S2—O6—N1
O7—S2—O6—N1
O8—S2—O6—N1
K1v—S2—O6—N1
S2—O6—N1—C7
O9—S2—O7—K1v
O8—S2—O7—K1v
O6—S2—O7—K1v
C5—O1—C1—C2
C5—O1—C1—S1
C7—S1—C1—O1
C7—S1—C1—C2
K1vi—O3—C3—C4
K1vii—O3—C3—C4
K1vi—O3—C3—C2
K1vii—O3—C3—C2
K1vii—O3—C3—K1vi
O7—S2—O9—K1
O8—S2—O9—K1
O6—S2—O9—K1
K1v—S2—O9—K1
O6—N1—C7—C8
O6—N1—C7—S1
C1—S1—C7—N1
61.6 (4)
O3—C3—C4—O4
C2—C3—C4—O4
K1vi—C3—C4—O4
O3—C3—C4—C5
C2—C3—C4—C5
K1vi—C3—C4—C5
K1vii—O2—C2—C1
K1vii—O2—C2—C3
O1—C1—C2—O2
S1—C1—C2—O2
O1—C1—C2—C3
S1—C1—C2—C3
O3—C3—C2—O2
C4—C3—C2—O2
K1vi—C3—C2—O2
O3—C3—C2—C1
C4—C3—C2—C1
K1vi—C3—C2—C1
C1—O1—C5—C6
C1—O1—C5—C4
O5—C6—C5—O1
O5—C6—C5—C4
O4—C4—C5—O1
C3—C4—C5—O1
−61.4 (6)
173.3 (4)
−17.9 (4)
175.9 (4)
50.6 (6)
−60.3 (4)
−179.5 (4)
−44.4 (5)
175.3 (4)
45.9 (4)
−140.7 (3)
−143.9 (3)
−27.1 (5)
177.7 (4)
−61.9 (5)
61.1 (5)
−89.4 (4)
163.2 (3)
−68.6 (5)
169.9 (3)
−81.6 (4)
157.4 (4)
67.1 (4)
−178.5 (3)
61.1 (5)
173.4 (3)
−166.8 (3)
−60.5 (4)
106.2 (2)
4.9 (7)
−172.7 (4)
36.1 (9)
−179.1 (4)
−52.8 (5)
156.0 (6)
−172.6 (4)
64.1 (5)
140.4 (5)
−112.2 (6)
30.4 (6)
−69.5 (5)
51.4 (6)
−179.6 (5)
2.4 (6)
−176.9 (4)
−54.3 (5)
−173.0 (5)
Acta Cryst. (2014). C70, 588-594
sup-12

supplementary materials
C1—S1—C7—C8
N1—C7—C8—C9
S1—C7—C8—C9
N1—C7—C8—C13
S1—C7—C8—C13
C13—C8—C9—C10
C7—C8—C9—C10
C13—C8—C9—Cl1
C7—C8—C9—Cl1
K1viii—O4—C4—C3
K1vi—O4—C4—C3
K1viii—O4—C4—C5
K1vi—O4—C4—C5
9.1 (5)
O4—C4—C5—C6
C3—C4—C5—C6
63.9 (6)
91.8 (7)
−90.2 (6)
−89.4 (7)
88.6 (6)
0.4 (9)
−173.4 (4)
C9—C8—C13—C12
C7—C8—C13—C12
C8—C9—C10—C11
Cl1—C9—C10—C11
C8—C9—C10—Cl2
Cl1—C9—C10—Cl2
C8—C13—C12—C11
C13—C12—C11—C10
C9—C10—C11—C12
Cl2—C10—C11—C12
−0.5 (9)
−179.3 (5)
0.3 (11)
179.7 (6)
−179.3 (5)
0.1 (9)
179.2 (6)
−179.1 (5)
−0.3 (8)
142.0 (3)
22.8 (5)
−95.7 (4)
145.1 (3)
0.0 (10)
0.7 (11)
−0.8 (12)
178.8 (6)
Symmetry codes: (i) −x+3/2, −y, z+1/2; (ii) x+1/2, −y−1/2, −z+1; (iii) −x+2, y−1/2, −z+1/2; (iv) −x+5/2, −y, z+1/2; (v) x−1/2, −y−1/2, −z+1; (vi) −x+2,
y+1/2, −z+1/2; (vii) −x+3/2, −y, z−1/2; (viii) −x+5/2, −y, z−1/2.
Hydrogen-bond geometry (Å, º)
D—H···A
D—H
H···A
D···A
D—H···A
O11—H11A···S2
O11—H11A···O6
O11—H11A···O8
C16—H16C···Cl1ix
C6—H6B···O2x
0.84
2.95
3.770 (6)
3.300 (8)
2.861 (8)
3.613 (15)
3.124 (6)
3.586 (7)
2.738 (7)
3.428 (10)
3.461 (11)
3.40 (3)
167
0.84
2.63
138
0.84
2.05
163
0.98
2.68
160
0.99
2.63
111
O10—H10···S2
0.94
2.77
146
O10—H10···O8
C11—H11···O11iii
C14′—H14A···O6xi
C15′—H15B···Cl1xii
C14—H14C···O9xi
C15—H15F···Cl2i
O3—H3A···N1vi
O2—H2A···O5xi
O5—H5A···O11x
O4—H4A···O10vii
0.94
1.80
174
0.95
2.52
160
0.99
2.62
143
0.98
2.79
121
0.99
2.62
3.601 (14)
3.92 (4)
173
0.98
2.97
163
0.84 (6)
0.93 (8)
1.01 (10)
1.09 (10)
2.19 (7)
1.79 (8)
1.70 (10)
1.61 (10)
3.019 (6)
2.655 (5)
2.690 (7)
2.685 (8)
170 (5)
155 (7)
166 (9)
164 (9)
Symmetry codes: (i) −x+3/2, −y, z+1/2; (iii) −x+2, y−1/2, −z+1/2; (vi) −x+2, y+1/2, −z+1/2; (vii) −x+3/2, −y, z−1/2; (ix) −x+1, y+1/2, −z+1/2; (x) x+1, y, z;
(xi) x−1, y, z; (xii) −x+1/2, −y, z+1/2.
Acta Cryst. (2014). C70, 588-594
sup-13

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