Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229614009115/sf3222sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S2053229614009115/sf32229sup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S2053229614009115/sf322211sup3.hkl | |
Portable Document Format (PDF) file https://doi.org/10.1107/S2053229614009115/sf3222sup4.pdf |
CCDC references: 998883; 999489
Glucosinolates (GLs) are β-thioglucoside N-hydroxysulfates with a side chain (R) and a sulfur-linked β-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 the structure of GLs 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 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.
Later, studies by Marsh & Waser (1970) and Thies (1988) reported the formation of crystalline sinigrin and glucotropaeolin salts. The potassium salt of sinigrin and the tetramethylamine 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 crystallizing 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 analysis of potassium (2,3-dichlorophenyl)glucosinolate–ethanol–methanol (1/1/1), (11).
Crystals of (9) and (11) were mounted in low-temperature oil and flash cooled to 130 K using a low-temperature device. Intensity data were collected at 130 K with an X-ray diffractometer equipped with a CCD detector using Mo Kα radiation (λ = 0.71073 Å). Data were reduced and corrected for absorption (CrysAlis CCD). The structures were solved by direct methods and difference Fourier synthesis using the SHELX suite of programs (Sheldrick, 2008) as implemented within the WinGX (Farrugia, 2012) software.
To stirred a solution of hydroxymoyl chloride, (3) (2.02 g, 9 mmol) in dry Et2O–DCM (2:1 v/v, 45 ml) was added a solution of 2,3,4,6-tetra-O-acetyl-α-D-glucopyranosylthiol, (8) (2.2 g, 6 mmol) 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 × 30 ml). The combined organic layers were dried over MgSO4, filtered and the filtrate was concentrated under reduced pressure. Thiohydroxymate (9) was purified by flash chromatography eluting with 0–3% MeOH/DCM and then recrystallized from hexane/DCM. 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). [α]+22 (c 2.0, CHCl3). λmax (NaCl)/cm-1: 3319 (OH), 1749 (C═O), 1602 (C═N), 1597, 1411, 1367, 1222, 1053. δH (300 MHz, CDCl3, 300 K): δ 7.59–7.56 (m, 1H, H4'-Ph—H), 7.34–7.25 (m, 2H, H5' and H6'-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 × s, 12H, CH3COO). δC (75 MHz, CDCl3, 300 K): δ 170.2, 169.9, 168.9, 168.8 (4 × 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 × CH3COO). HRMS (ESI) m/z for C21H23O10Cl2NNaS [M + Na]+: calculated 574.0312, found 574.0283.
To a stirred solution of thiohydroxymate (9) (800 mg, 1.45 mmol) in dry DCM (40 ml) was added pyridine sulfur trioxide complex (610 mg, 3.36 mmol). After stirring 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 pressure. The residue was dissolved in water and extracted with chloroform (2 × 30 ml) and then with 80% CHCl3/MeOH (3 × 30 ml). The organic layers were dried (MgSO4), filtered and concentrated under reduce pressure. To remove excess pyridine, 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)]. [α]+15 (c 1.0, MeOH). λmax (KBr drift)/cm-1: 2942, 2884, 1754 (C═O), 1650, 1572, 1505, 1413, 1396, 1217, 1062. δH (300 MHz, CD3OD, 300 K): 7.73–7.69 (m, 1H, H4'-Ph—H), 7.49–7.43 (m, 2H, H5' and H6'-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 × s, 12H, CH3COO). δC (75 MHz, CD3OD, 300 K): 170.4, 169.7, 169.3, 169.1 (4 × CH3COO), 154.7 (C═N), 132.8 (C-3 of Ph), 131.8 (C-4 of Ph), 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 ? CH3COO). HRMS (ESI) m/z for C21H22O13Cl2NS2 [M - K]-: calculated 629.9915 found 629.9971.
To a solution of O-acetylglucosinolate (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 pH = 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 vapor 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). To the solution was added MeOH until it became cloudy and then it was filtered through Celite packed on tissue in a pipette to make sure that the solution was homogeneous. The resulting solution 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 scintillation vial. The small vial was covered with plastic film and a few holes were made in the film by 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. 390–392 K (decomposition)]. [α] +60 (c 1.0, H2O); λmax (KBr drift)/cm-1: 3354 (OH), 2882, 1566 (C═N), 1412, 1276, 1265, 1064. δH (300 MHz, D2O, 300 K): 7.62–7.57 (m, 1H, H4'-Ph—H), 7.38–7.29 (m, 2H, H5' and H6'-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). δC (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.
Crystal data, data collection and structure refinement details are summarized in Table 1.
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-dichlorobenzohydroxymoyl chloride was synthesized by the aldoxime method from 2,3-dichlorobenzaldehyde, (1) (see Scheme 1) (Bialecki et al., 2007).
To increase the yield, in the first step, hydroxylamine hydrochloride was added in excess to the solution of reactants, 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).
2,3,4,6-Tetra-O-acetyl-β-D-glucopyranosyl thiol, (8), was obtained in four steps from D-glucose (see Scheme 2) (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, 1α-bromo-2,3,4,6-tetra-O-acetyl-D-glucopyranose, (6). The α-bromide was then treated with thiourea to afford β-isothiouronium salt (7), followed by mild hydrolysis with sodium metabisulfite to yield, stereospecifically, 2,3,4,6-tetra-O-acetyl-β-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 crystallographic analysis of S-(2,3,4,6-tetra-O-acetyl-β-D-glucopyranosyl)-2,3-dichlorophenylacetothiohydroximate, (9), confirmed that the thiohydroxymate was obtained as a (Z)-thiohydroximate (Fig. 1).
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 dichloromethane (DCM) at reflux temperature under an argon atmosphere rather than in pyridine at room temperature (Scheme 2). The sulfation product (10) can be lost due to the high polarity of the solvent which promotes hydrolysis. Therefore, in the work-up, the solvent mixture 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 & Tatibouët, 2011). 2,3-Dichlorophenylglucosinolate (11) was obtained in 56% overall yield (over seven steps from glucose) by flash column chromatography on silica gel eluting with EtOAc/MeOH/H2O and then recrystallization following the vial-in-a-vial vapor diffusion method with H2O/MeOH inside and EtOH outside at 273–278 K for a period up to two years. The difficulties of the dual solvation of (11) with one methanol and one ethanol solvent molecule of crystallization may be one of the main reasons for the slow crystal growth of (11).
In (9) (Fig. 1), the C5—O1—C1—S1 torsion angle of 177.2 (2)° establishes the β-configuration of the thiohydroximate substituent. The anomeric C—S bond length of 1.806 (3) Å compares with the value of 1.809 Å reported for another β-thiohydroximate derivative (Tocher & Truter, 1990), but is significantly shorter than that observed for a similar α-thiohydroximate, for which the C—S bond length was reported to be 1.838 Å (Durier et al., 1992), which is 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 (4) to 1.442 (4) Å. The structure is stabilized by O—H···O hydrogen bonds between the oxime hydroxy donor and acetate atom O7 as acceptor, with O10···O7(x, y, z-1) = 2.768 (4) Å and O10—H10···O7 = 158 (4)°, forming a chain extending along the c axis (Fig. 2).
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 β, as defined by the C5—O1—C1—S1 torsion angle of 169.9 (2)°, while the anomeric C—S bond length is 1.805 (5) Å, 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 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 coordinated O atoms, which extends down the a axis (Fig. 5). These chains are crosslinked in the bc direction by the sugar molecules to complete the three-dimensional polymeric network. The channels of this network are occupied by the dichlorophenyl substituents (Fig. 6) and the ethanol and methanol solvent molecules (Fig. 7).
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 2,3-dichlorophenylglucosinolate also confirmed the configuration of the glucosinolate structure.
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).
Displacement ellipsoid plot for (9), with ellipsoids drawn at the 20%
probability level. [The ellipsoid for C20 is missing] The hydrogen-bonded network of (9) extending along the c axis. (Atom colors: yellow = sulfur, red = oxygen, black = carbon, green = chlorine and white = nitrogen.) Displacement ellipsoid plot for glucosinolate (11)·EtOH·MeOH, with ellipsoids drawn at the 20% probability level. (Top) The sugar coordination mode to the potassium ion and (bottom) the simplified coordination sphere about the potassium ion. The symmetry codes are as in Table 2. (Atom colors: purple = potassium, yellow = sulfur, red = oxygen, black = carbon, green = chlorine and white = nitrogen.) The chains of potassium ions linked by sulfonate and sugar O atoms extending down the a axis. The three-dimensional polymeric network of (11), including the dichlorophenyl substituent. The three-dimensional polymeric network of (11), including the methanol and ethanol solvent molecules. |
C21H23Cl2NO10S | F(000) = 572 |
Mr = 552.36 | Dx = 1.446 Mg m−3 |
Monoclinic, P21 | Mo Kα radiation, λ = 0.7107 Å |
a = 7.1967 (2) Å | Cell parameters from 3604 reflections |
b = 15.1383 (4) Å | θ = 2.9–29.2° |
c = 11.9441 (3) Å | µ = 0.39 mm−1 |
β = 102.786 (3)° | T = 130 K |
V = 1268.99 (6) Å3 | Block, colourless |
Z = 2 | 0.37 × 0.32 × 0.14 mm |
Oxford Diffraction SuperNova (Dual, Cu at zero, Atlas) diffractometer | 3790 independent reflections |
Radiation source: SuperNova (Mo) X-ray Source | 3535 reflections with I > 2σ(I) |
Mirror monochromator | Rint = 0.027 |
ω scans | θmax = 25.0°, θmin = 2.9° |
Absorption correction: gaussian (CrysAlis PRO; Oxford Diffraction, 2010) | h = −8→8 |
Tmin = 0.888, Tmax = 0.949 | k = −18→18 |
6348 measured reflections | l = −14→12 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.031 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.069 | w = 1/[σ2(Fo2) + (0.0321P)2 + 0.0094P] where P = (Fo2 + 2Fc2)/3 |
S = 1.05 | (Δ/σ)max = 0.002 |
3790 reflections | Δρmax = 0.22 e Å−3 |
324 parameters | Δρmin = −0.19 e Å−3 |
1 restraint | Absolute structure: Flack (1983), ???? Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: −0.10 (5) |
C21H23Cl2NO10S | V = 1268.99 (6) Å3 |
Mr = 552.36 | Z = 2 |
Monoclinic, P21 | Mo Kα radiation |
a = 7.1967 (2) Å | µ = 0.39 mm−1 |
b = 15.1383 (4) Å | T = 130 K |
c = 11.9441 (3) Å | 0.37 × 0.32 × 0.14 mm |
β = 102.786 (3)° |
Oxford Diffraction SuperNova (Dual, Cu at zero, Atlas) diffractometer | 3790 independent reflections |
Absorption correction: gaussian (CrysAlis PRO; Oxford Diffraction, 2010) | 3535 reflections with I > 2σ(I) |
Tmin = 0.888, Tmax = 0.949 | Rint = 0.027 |
6348 measured reflections |
R[F2 > 2σ(F2)] = 0.031 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.069 | Δρmax = 0.22 e Å−3 |
S = 1.05 | Δρmin = −0.19 e Å−3 |
3790 reflections | Absolute structure: Flack (1983), ???? Friedel pairs |
324 parameters | Absolute structure parameter: −0.10 (5) |
1 restraint |
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. |
x | y | z | Uiso*/Ueq | ||
Cl1 | 0.44877 (9) | 0.68631 (4) | 0.52381 (6) | 0.02509 (16) | |
S1 | 0.86715 (11) | 0.55216 (4) | 0.53502 (6) | 0.02610 (17) | |
Cl2 | 0.42532 (10) | 0.86903 (5) | 0.64869 (7) | 0.03281 (19) | |
O4 | 1.2021 (3) | 0.61837 (13) | 1.02012 (16) | 0.0279 (5) | |
O8 | 0.6894 (2) | 0.50165 (12) | 0.74050 (16) | 0.0227 (4) | |
O10 | 0.8321 (3) | 0.56559 (14) | 0.30744 (18) | 0.0310 (5) | |
O1 | 1.1267 (3) | 0.61058 (12) | 0.70838 (15) | 0.0224 (4) | |
O6 | 0.9346 (3) | 0.47062 (11) | 0.95260 (15) | 0.0209 (4) | |
O3 | 1.7414 (3) | 0.73702 (13) | 0.86375 (17) | 0.0328 (5) | |
O2 | 1.4752 (3) | 0.71646 (12) | 0.92931 (16) | 0.0268 (5) | |
C21 | 0.9575 (4) | 0.79530 (17) | 0.5331 (2) | 0.0206 (6) | |
H21 | 1.0686 | 0.7812 | 0.5094 | 0.025* | |
C4 | 1.1623 (4) | 0.57708 (17) | 0.9091 (2) | 0.0203 (6) | |
H4 | 1.2477 | 0.5267 | 0.9087 | 0.024* | |
C12 | 0.8580 (4) | 0.4836 (2) | 1.0445 (2) | 0.0262 (7) | |
O7 | 0.8170 (3) | 0.55539 (16) | 1.07422 (17) | 0.0392 (5) | |
C5 | 1.1923 (4) | 0.64628 (18) | 0.8220 (2) | 0.0209 (6) | |
H5 | 1.1214 | 0.7002 | 0.8307 | 0.025* | |
C18 | 0.6291 (4) | 0.83854 (18) | 0.6046 (2) | 0.0206 (6) | |
C17 | 0.6391 (3) | 0.75882 (17) | 0.5485 (2) | 0.0175 (6) | |
N1 | 0.8075 (3) | 0.65176 (15) | 0.34747 (19) | 0.0234 (5) | |
O9 | 0.7200 (3) | 0.36415 (16) | 0.6768 (2) | 0.0567 (7) | |
O5 | 1.3731 (6) | 0.5010 (2) | 1.0986 (3) | 0.0947 (12) | |
C15 | 0.8233 (4) | 0.65118 (17) | 0.4559 (2) | 0.0177 (6) | |
C20 | 0.9447 (4) | 0.87462 (18) | 0.5890 (2) | 0.0247 (6) | |
H20 | 1.0472 | 0.9136 | 0.6024 | 0.030* | |
C6 | 1.3981 (4) | 0.6682 (2) | 0.8261 (2) | 0.0282 (7) | |
H6A | 1.4701 | 0.6143 | 0.8245 | 0.034* | |
H6B | 1.4073 | 0.7035 | 0.7597 | 0.034* | |
C13 | 0.4108 (4) | 0.4173 (2) | 0.6887 (3) | 0.0378 (8) | |
H13A | 0.3661 | 0.3588 | 0.6660 | 0.057* | |
H13B | 0.3499 | 0.4589 | 0.6316 | 0.057* | |
H13C | 0.3810 | 0.4315 | 0.7610 | 0.057* | |
C1 | 0.9291 (4) | 0.59086 (17) | 0.6813 (2) | 0.0198 (6) | |
H1 | 0.8545 | 0.6434 | 0.6906 | 0.024* | |
C9 | 1.3331 (6) | 0.6248 (3) | 1.2173 (3) | 0.0652 (13) | |
H9A | 1.4120 | 0.5925 | 1.2791 | 0.098* | |
H9B | 1.2107 | 0.6350 | 1.2344 | 0.098* | |
H9C | 1.3922 | 0.6804 | 1.2081 | 0.098* | |
C19 | 0.7815 (4) | 0.89604 (18) | 0.6248 (3) | 0.0253 (6) | |
H19 | 0.7739 | 0.9492 | 0.6626 | 0.030* | |
C3 | 0.9558 (4) | 0.54639 (18) | 0.8831 (2) | 0.0181 (5) | |
H3 | 0.8739 | 0.5944 | 0.8987 | 0.022* | |
C16 | 0.8047 (4) | 0.73684 (17) | 0.5125 (2) | 0.0177 (6) | |
C7 | 1.7243 (5) | 0.7944 (2) | 1.0484 (3) | 0.0496 (10) | |
H7A | 1.6750 | 0.8536 | 1.0427 | 0.074* | |
H7B | 1.8610 | 0.7962 | 1.0656 | 0.074* | |
H7C | 1.6819 | 0.7636 | 1.1084 | 0.074* | |
C2 | 0.8905 (4) | 0.51668 (17) | 0.7593 (2) | 0.0180 (6) | |
H2 | 0.9567 | 0.4625 | 0.7456 | 0.022* | |
C8 | 1.6544 (4) | 0.74775 (18) | 0.9377 (3) | 0.0271 (7) | |
C14 | 0.6218 (4) | 0.4212 (2) | 0.7001 (3) | 0.0318 (7) | |
C11 | 0.8368 (5) | 0.3977 (2) | 1.1018 (3) | 0.0380 (8) | |
H11A | 0.7584 | 0.4060 | 1.1564 | 0.057* | |
H11B | 0.9600 | 0.3767 | 1.1407 | 0.057* | |
H11C | 0.7783 | 0.3553 | 1.0452 | 0.057* | |
C10 | 1.3091 (5) | 0.5728 (3) | 1.1091 (3) | 0.0476 (9) | |
H10 | 0.830 (5) | 0.576 (2) | 0.243 (3) | 0.037 (10)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl1 | 0.0204 (3) | 0.0276 (4) | 0.0278 (4) | −0.0048 (3) | 0.0064 (3) | −0.0040 (3) |
S1 | 0.0453 (4) | 0.0192 (3) | 0.0128 (3) | 0.0041 (3) | 0.0043 (3) | −0.0009 (3) |
Cl2 | 0.0266 (4) | 0.0364 (4) | 0.0374 (4) | 0.0075 (3) | 0.0114 (3) | −0.0086 (4) |
O4 | 0.0309 (12) | 0.0367 (12) | 0.0147 (10) | −0.0086 (10) | 0.0020 (9) | −0.0029 (9) |
O8 | 0.0230 (10) | 0.0231 (10) | 0.0209 (10) | 0.0002 (8) | 0.0028 (8) | −0.0028 (9) |
O10 | 0.0527 (14) | 0.0281 (12) | 0.0145 (10) | 0.0040 (10) | 0.0121 (10) | −0.0014 (10) |
O1 | 0.0288 (11) | 0.0240 (10) | 0.0155 (10) | −0.0007 (8) | 0.0076 (9) | −0.0006 (8) |
O6 | 0.0305 (10) | 0.0179 (9) | 0.0143 (10) | −0.0010 (8) | 0.0051 (8) | 0.0028 (8) |
O3 | 0.0266 (11) | 0.0334 (11) | 0.0408 (13) | 0.0014 (10) | 0.0125 (10) | 0.0032 (11) |
O2 | 0.0268 (11) | 0.0287 (11) | 0.0263 (11) | −0.0068 (8) | 0.0090 (9) | −0.0062 (9) |
C21 | 0.0172 (13) | 0.0221 (15) | 0.0229 (15) | 0.0005 (11) | 0.0049 (12) | 0.0036 (13) |
C4 | 0.0260 (14) | 0.0219 (15) | 0.0139 (13) | 0.0033 (11) | 0.0066 (12) | 0.0019 (12) |
C12 | 0.0331 (16) | 0.0309 (17) | 0.0145 (14) | −0.0093 (13) | 0.0048 (12) | −0.0008 (14) |
O7 | 0.0681 (15) | 0.0317 (12) | 0.0251 (11) | −0.0016 (12) | 0.0262 (11) | −0.0014 (11) |
C5 | 0.0277 (15) | 0.0197 (14) | 0.0167 (14) | −0.0003 (12) | 0.0079 (12) | −0.0019 (12) |
C18 | 0.0199 (13) | 0.0230 (14) | 0.0181 (14) | 0.0054 (11) | 0.0024 (11) | 0.0011 (12) |
C17 | 0.0181 (13) | 0.0198 (14) | 0.0135 (13) | −0.0003 (11) | 0.0011 (11) | 0.0006 (12) |
N1 | 0.0348 (14) | 0.0202 (12) | 0.0168 (12) | 0.0014 (10) | 0.0088 (11) | −0.0021 (10) |
O9 | 0.0492 (15) | 0.0298 (13) | 0.093 (2) | −0.0068 (12) | 0.0189 (15) | −0.0278 (15) |
O5 | 0.137 (3) | 0.057 (2) | 0.057 (2) | 0.016 (2) | −0.049 (2) | 0.0103 (17) |
C15 | 0.0163 (13) | 0.0210 (14) | 0.0166 (14) | 0.0018 (11) | 0.0055 (11) | 0.0013 (12) |
C20 | 0.0210 (14) | 0.0194 (14) | 0.0314 (16) | −0.0062 (12) | 0.0010 (12) | −0.0023 (14) |
C6 | 0.0306 (16) | 0.0299 (16) | 0.0263 (16) | −0.0046 (13) | 0.0109 (14) | −0.0063 (14) |
C13 | 0.0377 (18) | 0.0399 (19) | 0.0351 (19) | −0.0107 (16) | 0.0065 (15) | −0.0075 (17) |
C1 | 0.0273 (15) | 0.0186 (14) | 0.0134 (13) | 0.0040 (11) | 0.0046 (12) | −0.0020 (12) |
C9 | 0.077 (3) | 0.091 (3) | 0.0199 (17) | −0.044 (3) | −0.0070 (18) | −0.002 (2) |
C19 | 0.0289 (15) | 0.0186 (14) | 0.0253 (15) | 0.0028 (12) | −0.0003 (13) | −0.0014 (13) |
C3 | 0.0290 (14) | 0.0142 (13) | 0.0114 (12) | 0.0002 (12) | 0.0052 (11) | 0.0031 (12) |
C16 | 0.0228 (14) | 0.0181 (14) | 0.0114 (12) | 0.0041 (12) | 0.0021 (11) | 0.0056 (12) |
C7 | 0.044 (2) | 0.056 (2) | 0.050 (2) | −0.0164 (18) | 0.0121 (18) | −0.016 (2) |
C2 | 0.0216 (13) | 0.0183 (14) | 0.0146 (14) | 0.0034 (11) | 0.0051 (11) | 0.0000 (12) |
C8 | 0.0260 (15) | 0.0177 (15) | 0.0383 (17) | 0.0006 (13) | 0.0085 (14) | −0.0003 (14) |
C14 | 0.0421 (18) | 0.0273 (17) | 0.0255 (17) | −0.0045 (15) | 0.0063 (15) | −0.0090 (14) |
C11 | 0.050 (2) | 0.0381 (19) | 0.0269 (17) | −0.0120 (15) | 0.0119 (16) | 0.0056 (15) |
C10 | 0.052 (2) | 0.058 (3) | 0.0242 (18) | −0.0164 (19) | −0.0109 (16) | 0.0083 (18) |
Cl1—C17 | 1.729 (3) | N1—C15 | 1.275 (3) |
S1—C15 | 1.763 (3) | O9—C14 | 1.188 (4) |
S1—C1 | 1.803 (3) | O5—C10 | 1.199 (5) |
Cl2—C18 | 1.727 (2) | C15—C16 | 1.482 (4) |
O4—C10 | 1.355 (4) | C20—C19 | 1.375 (4) |
O4—C4 | 1.436 (3) | C20—H20 | 0.9300 |
O8—C14 | 1.359 (3) | C6—H6A | 0.9700 |
O8—C2 | 1.432 (3) | C6—H6B | 0.9700 |
O10—N1 | 1.414 (3) | C13—C14 | 1.495 (4) |
O10—H10 | 0.78 (3) | C13—H13A | 0.9600 |
O1—C1 | 1.419 (3) | C13—H13B | 0.9600 |
O1—C5 | 1.439 (3) | C13—H13C | 0.9600 |
O6—C12 | 1.347 (3) | C1—C2 | 1.523 (4) |
O6—C3 | 1.444 (3) | C1—H1 | 0.9800 |
O3—C8 | 1.201 (3) | C9—C10 | 1.490 (5) |
O2—C8 | 1.357 (3) | C9—H9A | 0.9600 |
O2—C6 | 1.434 (3) | C9—H9B | 0.9600 |
C21—C20 | 1.387 (4) | C9—H9C | 0.9600 |
C21—C16 | 1.390 (4) | C19—H19 | 0.9300 |
C21—H21 | 0.9300 | C3—C2 | 1.517 (3) |
C4—C3 | 1.522 (4) | C3—H3 | 0.9800 |
C4—C5 | 1.526 (4) | C7—C8 | 1.486 (4) |
C4—H4 | 0.9800 | C7—H7A | 0.9600 |
C12—O7 | 1.200 (4) | C7—H7B | 0.9600 |
C12—C11 | 1.493 (4) | C7—H7C | 0.9600 |
C5—C6 | 1.508 (4) | C2—H2 | 0.9800 |
C5—H5 | 0.9800 | C11—H11A | 0.9600 |
C18—C19 | 1.379 (4) | C11—H11B | 0.9600 |
C18—C17 | 1.390 (4) | C11—H11C | 0.9600 |
C17—C16 | 1.394 (3) | ||
C15—S1—C1 | 102.69 (12) | O1—C1—S1 | 108.04 (16) |
C10—O4—C4 | 117.7 (2) | C2—C1—S1 | 108.29 (18) |
C14—O8—C2 | 117.9 (2) | O1—C1—H1 | 110.5 |
N1—O10—H10 | 99 (2) | C2—C1—H1 | 110.5 |
C1—O1—C5 | 113.37 (18) | S1—C1—H1 | 110.5 |
C12—O6—C3 | 117.8 (2) | C10—C9—H9A | 109.5 |
C8—O2—C6 | 114.9 (2) | C10—C9—H9B | 109.5 |
C20—C21—C16 | 120.1 (2) | H9A—C9—H9B | 109.5 |
C20—C21—H21 | 119.9 | C10—C9—H9C | 109.5 |
C16—C21—H21 | 119.9 | H9A—C9—H9C | 109.5 |
O4—C4—C3 | 107.93 (19) | H9B—C9—H9C | 109.5 |
O4—C4—C5 | 107.6 (2) | C20—C19—C18 | 119.9 (3) |
C3—C4—C5 | 110.5 (2) | C20—C19—H19 | 120.1 |
O4—C4—H4 | 110.3 | C18—C19—H19 | 120.1 |
C3—C4—H4 | 110.3 | O6—C3—C2 | 106.0 (2) |
C5—C4—H4 | 110.3 | O6—C3—C4 | 110.4 (2) |
O7—C12—O6 | 123.1 (3) | C2—C3—C4 | 111.58 (19) |
O7—C12—C11 | 126.6 (2) | O6—C3—H3 | 109.6 |
O6—C12—C11 | 110.4 (3) | C2—C3—H3 | 109.6 |
O1—C5—C6 | 103.19 (19) | C4—C3—H3 | 109.6 |
O1—C5—C4 | 108.6 (2) | C21—C16—C17 | 119.3 (2) |
C6—C5—C4 | 114.5 (2) | C21—C16—C15 | 119.4 (2) |
O1—C5—H5 | 110.1 | C17—C16—C15 | 121.3 (2) |
C6—C5—H5 | 110.1 | C8—C7—H7A | 109.5 |
C4—C5—H5 | 110.1 | C8—C7—H7B | 109.5 |
C19—C18—C17 | 120.5 (2) | H7A—C7—H7B | 109.5 |
C19—C18—Cl2 | 118.3 (2) | C8—C7—H7C | 109.5 |
C17—C18—Cl2 | 121.1 (2) | H7A—C7—H7C | 109.5 |
C18—C17—C16 | 119.7 (2) | H7B—C7—H7C | 109.5 |
C18—C17—Cl1 | 120.66 (18) | O8—C2—C3 | 106.53 (18) |
C16—C17—Cl1 | 119.7 (2) | O8—C2—C1 | 109.6 (2) |
C15—N1—O10 | 110.3 (2) | C3—C2—C1 | 108.6 (2) |
N1—C15—C16 | 117.4 (2) | O8—C2—H2 | 110.7 |
N1—C15—S1 | 121.0 (2) | C3—C2—H2 | 110.7 |
C16—C15—S1 | 121.57 (18) | C1—C2—H2 | 110.7 |
C19—C20—C21 | 120.4 (2) | O3—C8—O2 | 122.7 (3) |
C19—C20—H20 | 119.8 | O3—C8—C7 | 126.2 (3) |
C21—C20—H20 | 119.8 | O2—C8—C7 | 111.1 (2) |
O2—C6—C5 | 109.3 (2) | O9—C14—O8 | 123.4 (3) |
O2—C6—H6A | 109.8 | O9—C14—C13 | 126.4 (3) |
C5—C6—H6A | 109.8 | O8—C14—C13 | 110.2 (3) |
O2—C6—H6B | 109.8 | C12—C11—H11A | 109.5 |
C5—C6—H6B | 109.8 | C12—C11—H11B | 109.5 |
H6A—C6—H6B | 108.3 | H11A—C11—H11B | 109.5 |
C14—C13—H13A | 109.5 | C12—C11—H11C | 109.5 |
C14—C13—H13B | 109.5 | H11A—C11—H11C | 109.5 |
H13A—C13—H13B | 109.5 | H11B—C11—H11C | 109.5 |
C14—C13—H13C | 109.5 | O5—C10—O4 | 123.0 (3) |
H13A—C13—H13C | 109.5 | O5—C10—C9 | 126.6 (4) |
H13B—C13—H13C | 109.5 | O4—C10—C9 | 110.4 (3) |
O1—C1—C2 | 109.0 (2) | ||
C10—O4—C4—C3 | 105.2 (3) | O4—C4—C3—O6 | −72.6 (2) |
C10—O4—C4—C5 | −135.6 (3) | C5—C4—C3—O6 | 170.10 (19) |
C3—O6—C12—O7 | −4.2 (4) | O4—C4—C3—C2 | 169.9 (2) |
C3—O6—C12—C11 | 176.7 (3) | C5—C4—C3—C2 | 52.5 (3) |
C1—O1—C5—C6 | −175.6 (2) | C20—C21—C16—C17 | 0.0 (4) |
C1—O1—C5—C4 | 62.5 (3) | C20—C21—C16—C15 | −178.1 (2) |
O4—C4—C5—O1 | −171.7 (2) | C18—C17—C16—C21 | −0.1 (4) |
C3—C4—C5—O1 | −54.1 (3) | Cl1—C17—C16—C21 | −179.7 (2) |
O4—C4—C5—C6 | 73.6 (3) | C18—C17—C16—C15 | 177.9 (2) |
C3—C4—C5—C6 | −168.9 (2) | Cl1—C17—C16—C15 | −1.7 (3) |
C19—C18—C17—C16 | 0.0 (4) | N1—C15—C16—C21 | −78.0 (3) |
Cl2—C18—C17—C16 | 179.0 (2) | S1—C15—C16—C21 | 101.6 (2) |
C19—C18—C17—Cl1 | 179.6 (2) | N1—C15—C16—C17 | 104.0 (3) |
Cl2—C18—C17—Cl1 | −1.4 (3) | S1—C15—C16—C17 | −76.5 (3) |
O10—N1—C15—C16 | 178.9 (2) | C14—O8—C2—C3 | −125.1 (2) |
O10—N1—C15—S1 | −0.7 (3) | C14—O8—C2—C1 | 117.6 (2) |
C1—S1—C15—N1 | 167.6 (2) | O6—C3—C2—O8 | 67.9 (2) |
C1—S1—C15—C16 | −11.9 (2) | C4—C3—C2—O8 | −171.9 (2) |
C16—C21—C20—C19 | 0.2 (4) | O6—C3—C2—C1 | −174.09 (19) |
C8—O2—C6—C5 | −173.7 (2) | C4—C3—C2—C1 | −53.9 (3) |
O1—C5—C6—O2 | 171.7 (2) | O1—C1—C2—O8 | 174.60 (18) |
C4—C5—C6—O2 | −70.4 (3) | S1—C1—C2—O8 | −68.1 (2) |
C5—O1—C1—C2 | −65.3 (2) | O1—C1—C2—C3 | 58.6 (3) |
C5—O1—C1—S1 | 177.25 (17) | S1—C1—C2—C3 | 175.90 (17) |
C15—S1—C1—O1 | −85.48 (18) | C6—O2—C8—O3 | 0.9 (4) |
C15—S1—C1—C2 | 156.63 (17) | C6—O2—C8—C7 | −178.4 (3) |
C21—C20—C19—C18 | −0.3 (4) | C2—O8—C14—O9 | −2.2 (4) |
C17—C18—C19—C20 | 0.2 (4) | C2—O8—C14—C13 | 178.7 (2) |
Cl2—C18—C19—C20 | −178.8 (2) | C4—O4—C10—O5 | 1.1 (5) |
C12—O6—C3—C2 | −136.3 (2) | C4—O4—C10—C9 | −179.1 (2) |
C12—O6—C3—C4 | 102.8 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
O10—H10···O7i | 0.78 (3) | 2.03 (3) | 2.768 (3) | 159 (3) |
Symmetry code: (i) x, y, z−1. |
K+·C13H14Cl2NO9S2−·CH4O·C2H6O | Dx = 1.595 Mg m−3 |
Mr = 580.48 | Cu Kα radiation, λ = 1.5418 Å |
Orthorhombic, P212121 | Cell parameters from 8197 reflections |
a = 8.0043 (1) Å | θ = 2.9–77.4° |
b = 15.5208 (4) Å | µ = 6.09 mm−1 |
c = 19.4586 (4) Å | T = 115 K |
V = 2417.40 (9) Å3 | Needle, colourless |
Z = 4 | 0.65 × 0.07 × 0.04 mm |
F(000) = 1200 |
Agilent SuperNova (Dual, Cu at zero, Atlas) diffractometer | 5041 independent reflections |
Radiation source: SuperNova (Cu) X-ray Source | 4725 reflections with I > 2σ(I) |
Mirror monochromator | Rint = 0.058 |
ω scans | θmax = 77.6°, θmin = 3.6° |
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012) | h = −9→8 |
Tmin = 0.716, Tmax = 1.000 | k = −19→13 |
17993 measured reflections | l = −24→22 |
Refinement on F2 | Hydrogen site location: mixed |
Least-squares matrix: full | H atoms treated by a mixture of independent and constrained refinement |
R[F2 > 2σ(F2)] = 0.054 | w = 1/[σ2(Fo2) + (0.0865P)2 + 3.0655P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.146 | (Δ/σ)max < 0.001 |
S = 1.03 | Δρmax = 0.77 e Å−3 |
5041 reflections | Δρmin = −0.84 e Å−3 |
327 parameters | Absolute structure: Flack x determined using 1921 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013) |
0 restraints | Absolute structure parameter: 0.010 (12) |
K+·C13H14Cl2NO9S2−·CH4O·C2H6O | V = 2417.40 (9) Å3 |
Mr = 580.48 | Z = 4 |
Orthorhombic, P212121 | Cu Kα radiation |
a = 8.0043 (1) Å | µ = 6.09 mm−1 |
b = 15.5208 (4) Å | T = 115 K |
c = 19.4586 (4) Å | 0.65 × 0.07 × 0.04 mm |
Agilent SuperNova (Dual, Cu at zero, Atlas) diffractometer | 5041 independent reflections |
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012) | 4725 reflections with I > 2σ(I) |
Tmin = 0.716, Tmax = 1.000 | Rint = 0.058 |
17993 measured reflections |
R[F2 > 2σ(F2)] = 0.054 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.146 | Δρmax = 0.77 e Å−3 |
S = 1.03 | Δρmin = −0.84 e Å−3 |
5041 reflections | Absolute structure: Flack x determined using 1921 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013) |
327 parameters | Absolute structure parameter: 0.010 (12) |
0 restraints |
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. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
K1 | 0.81320 (13) | −0.24630 (7) | 0.54647 (5) | 0.0245 (2) | |
S1 | 0.89551 (15) | 0.07667 (8) | 0.29475 (6) | 0.0219 (3) | |
S2 | 0.59342 (18) | −0.06282 (10) | 0.43921 (8) | 0.0350 (3) | |
Cl1 | 0.7777 (3) | −0.10597 (15) | 0.17322 (11) | 0.0665 (6) | |
Cl2 | 1.0311 (6) | −0.2152 (2) | 0.08482 (12) | 0.1080 (14) | |
O3 | 1.0458 (4) | 0.2622 (2) | 0.08230 (18) | 0.0203 (7) | |
O5 | 1.5311 (4) | 0.1603 (3) | 0.2366 (2) | 0.0267 (8) | |
O2 | 0.8047 (4) | 0.1761 (2) | 0.16045 (18) | 0.0223 (7) | |
O6 | 0.7190 (5) | −0.0153 (3) | 0.3848 (2) | 0.0291 (8) | |
O1 | 1.1917 (4) | 0.0953 (2) | 0.23779 (18) | 0.0215 (7) | |
O4 | 1.3631 (4) | 0.1715 (3) | 0.07274 (19) | 0.0264 (8) | |
N1 | 0.8248 (6) | −0.0757 (3) | 0.3505 (2) | 0.0275 (9) | |
O7 | 0.4930 (7) | −0.1219 (4) | 0.3995 (3) | 0.0570 (15) | |
O8 | 0.5063 (6) | 0.0133 (3) | 0.4636 (3) | 0.0414 (11) | |
C1 | 1.0208 (6) | 0.0930 (3) | 0.2187 (3) | 0.0212 (10) | |
H1 | 1.0023 | 0.0438 | 0.1864 | 0.025* | |
C3 | 1.0813 (6) | 0.1843 (3) | 0.1183 (3) | 0.0184 (9) | |
H3 | 1.0497 | 0.1355 | 0.0873 | 0.022* | |
O9 | 0.6961 (7) | −0.1038 (4) | 0.4892 (3) | 0.0527 (14) | |
C7 | 0.9104 (6) | −0.0353 (4) | 0.3054 (3) | 0.0240 (10) | |
O11 | 0.4829 (10) | 0.1584 (4) | 0.3734 (3) | 0.0644 (17) | |
H11A | 0.5067 | 0.1130 | 0.3948 | 0.097* | |
C16 | 0.334 (2) | 0.1827 (10) | 0.3897 (8) | 0.112 (5) | |
H16A | 0.3314 | 0.1995 | 0.4382 | 0.168* | |
H16B | 0.2555 | 0.1351 | 0.3820 | 0.168* | |
H16C | 0.3015 | 0.2320 | 0.3611 | 0.168* | |
C8 | 1.0288 (7) | −0.0883 (4) | 0.2635 (3) | 0.0294 (12) | |
C9 | 0.9775 (10) | −0.1233 (4) | 0.2015 (3) | 0.0427 (16) | |
C6 | 1.4737 (6) | 0.0837 (3) | 0.2030 (3) | 0.0267 (11) | |
H6A | 1.4803 | 0.0347 | 0.2354 | 0.032* | |
H6B | 1.5476 | 0.0709 | 0.1635 | 0.032* | |
O10 | 0.1919 (8) | −0.0183 (6) | 0.5129 (5) | 0.099 (3) | |
H10 | 0.2991 | −0.0035 | 0.4973 | 0.08 (3)* | |
C4 | 1.2672 (6) | 0.1744 (3) | 0.1345 (2) | 0.0208 (10) | |
H4 | 1.3039 | 0.2255 | 0.1620 | 0.025* | |
C2 | 0.9727 (6) | 0.1770 (3) | 0.1828 (2) | 0.0176 (9) | |
H2 | 0.9928 | 0.2272 | 0.2140 | 0.021* | |
C5 | 1.2961 (6) | 0.0930 (3) | 0.1778 (3) | 0.0222 (10) | |
H5 | 1.2663 | 0.0413 | 0.1497 | 0.027* | |
C13 | 1.1917 (8) | −0.1008 (4) | 0.2867 (4) | 0.0406 (15) | |
H13 | 1.2278 | −0.0766 | 0.3290 | 0.049* | |
C10 | 1.0905 (14) | −0.1718 (5) | 0.1626 (4) | 0.060 (2) | |
C12 | 1.3005 (9) | −0.1497 (5) | 0.2465 (5) | 0.054 (2) | |
H12 | 1.4118 | −0.1584 | 0.2620 | 0.064* | |
C11 | 1.2519 (12) | −0.1850 (5) | 0.1859 (4) | 0.061 (3) | |
H11 | 1.3280 | −0.2186 | 0.1597 | 0.073* | |
C14' | 0.0611 (12) | 0.0318 (9) | 0.4869 (5) | 0.075 (3) | 0.52 (5) |
H14A | −0.0084 | −0.0075 | 0.4588 | 0.090* | 0.52 (5) |
H14B | 0.1128 | 0.0731 | 0.4544 | 0.090* | 0.52 (5) |
C15' | −0.050 (5) | 0.080 (3) | 0.5272 (15) | 0.099 (11) | 0.52 (5) |
H15A | −0.1305 | 0.1092 | 0.4973 | 0.148* | 0.52 (5) |
H15B | −0.1102 | 0.0410 | 0.5584 | 0.148* | 0.52 (5) |
H15C | 0.0121 | 0.1224 | 0.5540 | 0.148* | 0.52 (5) |
C14 | 0.0611 (12) | 0.0318 (9) | 0.4869 (5) | 0.075 (3) | 0.48 (5) |
H14C | −0.0440 | −0.0017 | 0.4849 | 0.090* | 0.48 (5) |
H14D | 0.0878 | 0.0534 | 0.4403 | 0.090* | 0.48 (5) |
C15 | 0.048 (5) | 0.1024 (18) | 0.5358 (12) | 0.077 (11) | 0.48 (5) |
H15D | −0.0421 | 0.1414 | 0.5215 | 0.115* | 0.48 (5) |
H15E | 0.0228 | 0.0794 | 0.5815 | 0.115* | 0.48 (5) |
H15F | 0.1536 | 0.1341 | 0.5373 | 0.115* | 0.48 (5) |
H3A | 1.083 (7) | 0.304 (4) | 0.106 (3) | 0.012 (13)* | |
H2A | 0.729 (10) | 0.178 (5) | 0.197 (4) | 0.05 (2)* | |
H5A | 1.515 (13) | 0.150 (6) | 0.287 (5) | 0.07 (3)* | |
H4A | 1.326 (13) | 0.107 (7) | 0.055 (5) | 0.07 (3)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
K1 | 0.0226 (5) | 0.0307 (5) | 0.0202 (5) | 0.0033 (4) | 0.0022 (4) | −0.0027 (4) |
S1 | 0.0186 (5) | 0.0239 (6) | 0.0231 (5) | 0.0026 (4) | 0.0055 (4) | 0.0060 (5) |
S2 | 0.0316 (7) | 0.0313 (7) | 0.0422 (8) | 0.0042 (6) | 0.0169 (6) | 0.0100 (6) |
Cl1 | 0.0847 (15) | 0.0602 (12) | 0.0545 (10) | 0.0270 (11) | −0.0256 (10) | −0.0196 (9) |
Cl2 | 0.190 (4) | 0.0905 (19) | 0.0438 (11) | 0.066 (2) | 0.0056 (16) | −0.0192 (12) |
O3 | 0.0199 (15) | 0.0196 (17) | 0.0214 (16) | −0.0008 (14) | 0.0015 (13) | 0.0034 (14) |
O5 | 0.0158 (16) | 0.033 (2) | 0.031 (2) | 0.0000 (15) | −0.0004 (14) | 0.0055 (16) |
O2 | 0.0103 (15) | 0.0333 (19) | 0.0233 (17) | −0.0015 (14) | 0.0010 (13) | 0.0065 (14) |
O6 | 0.0277 (19) | 0.0267 (19) | 0.0330 (19) | 0.0064 (15) | 0.0146 (16) | 0.0071 (16) |
O1 | 0.0117 (15) | 0.0277 (18) | 0.0252 (16) | 0.0000 (13) | 0.0019 (13) | 0.0066 (14) |
O4 | 0.0203 (17) | 0.034 (2) | 0.0246 (18) | 0.0009 (14) | 0.0096 (14) | 0.0028 (15) |
N1 | 0.028 (2) | 0.027 (2) | 0.028 (2) | 0.0066 (19) | 0.0098 (18) | 0.0057 (18) |
O7 | 0.039 (3) | 0.054 (3) | 0.078 (4) | −0.017 (2) | 0.017 (3) | −0.012 (3) |
O8 | 0.037 (2) | 0.035 (2) | 0.052 (3) | 0.0096 (19) | 0.023 (2) | 0.008 (2) |
C1 | 0.010 (2) | 0.023 (2) | 0.030 (2) | −0.0001 (18) | 0.0017 (17) | 0.0057 (19) |
C3 | 0.016 (2) | 0.018 (2) | 0.022 (2) | −0.0015 (17) | 0.0024 (17) | 0.0045 (19) |
O9 | 0.060 (3) | 0.056 (3) | 0.042 (2) | 0.022 (3) | 0.015 (2) | 0.024 (2) |
C7 | 0.019 (2) | 0.030 (3) | 0.023 (2) | 0.004 (2) | 0.0032 (18) | 0.003 (2) |
O11 | 0.087 (5) | 0.060 (4) | 0.046 (3) | −0.003 (3) | 0.015 (3) | 0.019 (3) |
C16 | 0.112 (11) | 0.107 (11) | 0.116 (11) | 0.022 (9) | 0.023 (10) | 0.024 (9) |
C8 | 0.031 (3) | 0.024 (3) | 0.033 (3) | 0.007 (2) | 0.013 (2) | 0.012 (2) |
C9 | 0.062 (4) | 0.033 (3) | 0.032 (3) | 0.018 (3) | 0.010 (3) | 0.007 (3) |
C6 | 0.015 (2) | 0.027 (3) | 0.038 (3) | 0.001 (2) | 0.005 (2) | 0.006 (2) |
O10 | 0.042 (3) | 0.119 (6) | 0.137 (7) | 0.020 (4) | 0.028 (4) | 0.094 (6) |
C4 | 0.016 (2) | 0.025 (2) | 0.021 (2) | 0.0005 (18) | 0.0052 (17) | 0.0029 (18) |
C2 | 0.0104 (19) | 0.021 (2) | 0.021 (2) | −0.0021 (17) | 0.0000 (16) | 0.0031 (17) |
C5 | 0.013 (2) | 0.024 (2) | 0.030 (2) | 0.0026 (18) | 0.0063 (18) | 0.0041 (19) |
C13 | 0.032 (3) | 0.030 (3) | 0.060 (4) | 0.007 (3) | 0.019 (3) | 0.018 (3) |
C10 | 0.101 (7) | 0.041 (4) | 0.038 (4) | 0.028 (4) | 0.028 (4) | 0.006 (3) |
C12 | 0.041 (4) | 0.040 (4) | 0.079 (6) | 0.017 (3) | 0.034 (4) | 0.022 (4) |
C11 | 0.082 (6) | 0.041 (4) | 0.059 (5) | 0.027 (4) | 0.045 (5) | 0.017 (4) |
C14' | 0.057 (5) | 0.113 (9) | 0.055 (5) | 0.025 (5) | −0.005 (4) | 0.017 (6) |
C15' | 0.062 (17) | 0.12 (2) | 0.11 (2) | 0.020 (15) | −0.023 (14) | −0.054 (18) |
C14 | 0.057 (5) | 0.113 (9) | 0.055 (5) | 0.025 (5) | −0.005 (4) | 0.017 (6) |
C15 | 0.09 (2) | 0.091 (17) | 0.051 (11) | 0.002 (15) | 0.012 (12) | −0.013 (11) |
K1—O2i | 2.645 (4) | C1—H1 | 1.0000 |
K1—O9 | 2.648 (5) | C3—C4 | 1.529 (6) |
K1—O7ii | 2.713 (5) | C3—C2 | 1.531 (6) |
K1—O3iii | 2.751 (4) | C3—K1vi | 3.487 (5) |
K1—O4iv | 2.885 (4) | C3—H3 | 1.0000 |
K1—O3i | 2.967 (4) | C7—C8 | 1.496 (7) |
K1—O4iii | 3.000 (4) | O11—C16 | 1.291 (16) |
K1—C3iii | 3.487 (5) | O11—H11A | 0.8400 |
K1—S2ii | 3.7264 (18) | C16—H16A | 0.9800 |
K1—K1v | 4.3933 (8) | C16—H16B | 0.9800 |
K1—K1ii | 4.3933 (8) | C16—H16C | 0.9800 |
S1—C7 | 1.754 (6) | C8—C9 | 1.385 (10) |
S1—C1 | 1.805 (5) | C8—C13 | 1.393 (9) |
S2—O9 | 1.423 (5) | C9—C10 | 1.400 (10) |
S2—O7 | 1.443 (6) | C6—C5 | 1.511 (7) |
S2—O8 | 1.452 (5) | C6—H6A | 0.9900 |
S2—O6 | 1.636 (4) | C6—H6B | 0.9900 |
S2—K1v | 3.7263 (18) | O10—C14' | 1.399 (11) |
Cl1—C9 | 1.713 (8) | O10—H10 | 0.9383 |
Cl2—C10 | 1.723 (10) | C4—C5 | 1.536 (7) |
O3—C3 | 1.427 (6) | C4—H4 | 1.0000 |
O3—K1vi | 2.751 (4) | C2—H2 | 1.0000 |
O3—K1vii | 2.967 (4) | C5—H5 | 1.0000 |
O3—H3A | 0.84 (6) | C13—C12 | 1.394 (9) |
O5—C6 | 1.432 (7) | C13—H13 | 0.9500 |
O5—H5A | 1.01 (10) | C10—C11 | 1.384 (14) |
O2—C2 | 1.414 (5) | C12—C11 | 1.358 (13) |
O2—K1vii | 2.645 (4) | C12—H12 | 0.9500 |
O2—H2A | 0.93 (8) | C11—H11 | 0.9500 |
O6—N1 | 1.429 (6) | C14'—C15' | 1.40 (3) |
O1—C1 | 1.418 (6) | C14'—H14A | 0.9900 |
O1—C5 | 1.436 (6) | C14'—H14B | 0.9900 |
O4—C4 | 1.427 (6) | C15'—H15A | 0.9800 |
O4—K1viii | 2.884 (4) | C15'—H15B | 0.9800 |
O4—K1vi | 3.000 (4) | C15'—H15C | 0.9800 |
O4—H4A | 1.09 (10) | C15—H15D | 0.9800 |
N1—C7 | 1.278 (7) | C15—H15E | 0.9800 |
O7—K1v | 2.713 (5) | C15—H15F | 0.9800 |
C1—C2 | 1.529 (7) | ||
O2i—K1—O9 | 83.25 (14) | O1—C1—C2 | 109.9 (4) |
O2i—K1—O7ii | 100.10 (16) | O1—C1—S1 | 108.9 (3) |
O9—K1—O7ii | 168.68 (19) | C2—C1—S1 | 110.7 (3) |
O2i—K1—O3iii | 152.88 (12) | O1—C1—H1 | 109.1 |
O9—K1—O3iii | 73.85 (13) | C2—C1—H1 | 109.1 |
O7ii—K1—O3iii | 99.86 (16) | S1—C1—H1 | 109.1 |
O2i—K1—O4iv | 90.35 (11) | O3—C3—C4 | 112.4 (4) |
O9—K1—O4iv | 93.23 (17) | O3—C3—C2 | 110.6 (4) |
O7ii—K1—O4iv | 76.01 (15) | C4—C3—C2 | 112.1 (4) |
O3iii—K1—O4iv | 76.91 (11) | O3—C3—K1vi | 48.3 (2) |
O2i—K1—O3i | 59.46 (10) | C4—C3—K1vi | 89.2 (3) |
O9—K1—O3i | 79.97 (14) | C2—C3—K1vi | 156.1 (3) |
O7ii—K1—O3i | 111.09 (16) | O3—C3—H3 | 107.2 |
O3iii—K1—O3i | 127.98 (9) | C4—C3—H3 | 107.2 |
O4iv—K1—O3i | 149.51 (11) | C2—C3—H3 | 107.2 |
O2i—K1—O4iii | 130.97 (10) | K1vi—C3—H3 | 75.0 |
O9—K1—O4iii | 82.14 (16) | S2—O9—K1 | 149.9 (4) |
O7ii—K1—O4iii | 103.20 (15) | N1—C7—C8 | 116.3 (5) |
O3iii—K1—O4iii | 60.61 (10) | N1—C7—S1 | 122.0 (4) |
O4iv—K1—O4iii | 136.94 (9) | C8—C7—S1 | 121.6 (4) |
O3i—K1—O4iii | 71.98 (10) | C16—O11—H11A | 109.5 |
O2i—K1—C3iii | 170.01 (12) | O11—C16—H16A | 109.5 |
O9—K1—C3iii | 87.52 (14) | O11—C16—H16B | 109.5 |
O7ii—K1—C3iii | 89.69 (16) | H16A—C16—H16B | 109.5 |
O3iii—K1—C3iii | 22.77 (11) | O11—C16—H16C | 109.5 |
O4iv—K1—C3iii | 94.00 (11) | H16A—C16—H16C | 109.5 |
O3i—K1—C3iii | 115.14 (10) | H16B—C16—H16C | 109.5 |
O4iii—K1—C3iii | 43.23 (10) | C9—C8—C13 | 120.3 (6) |
O2i—K1—S2ii | 118.66 (9) | C9—C8—C7 | 120.1 (5) |
O9—K1—S2ii | 155.30 (12) | C13—C8—C7 | 119.5 (6) |
O7ii—K1—S2ii | 18.59 (13) | C8—C9—C10 | 119.4 (8) |
O3iii—K1—S2ii | 81.92 (8) | C8—C9—Cl1 | 119.7 (5) |
O4iv—K1—S2ii | 76.46 (8) | C10—C9—Cl1 | 120.9 (7) |
O3i—K1—S2ii | 119.94 (8) | O5—C6—C5 | 111.8 (4) |
O4iii—K1—S2ii | 90.17 (8) | O5—C6—H6A | 109.3 |
C3iii—K1—S2ii | 71.17 (8) | C5—C6—H6A | 109.3 |
O2i—K1—K1v | 91.78 (8) | O5—C6—H6B | 109.3 |
O9—K1—K1v | 61.72 (14) | C5—C6—H6B | 109.3 |
O7ii—K1—K1v | 128.52 (13) | H6A—C6—H6B | 107.9 |
O3iii—K1—K1v | 90.01 (8) | C14'—O10—H10 | 115.5 |
O4iv—K1—K1v | 154.39 (10) | O4—C4—C3 | 110.6 (4) |
O3i—K1—K1v | 38.03 (7) | O4—C4—C5 | 110.8 (4) |
O4iii—K1—K1v | 40.71 (7) | C3—C4—C5 | 110.0 (4) |
C3iii—K1—K1v | 80.44 (8) | O4—C4—H4 | 108.4 |
S2ii—K1—K1v | 123.94 (5) | C3—C4—H4 | 108.4 |
O2i—K1—K1ii | 132.91 (8) | C5—C4—H4 | 108.4 |
O9—K1—K1ii | 99.84 (12) | O2—C2—C1 | 111.8 (4) |
O7ii—K1—K1ii | 69.91 (14) | O2—C2—C3 | 106.8 (4) |
O3iii—K1—K1ii | 41.64 (8) | C1—C2—C3 | 107.1 (4) |
O4iv—K1—K1ii | 42.71 (8) | O2—C2—H2 | 110.4 |
O3i—K1—K1ii | 167.62 (8) | C1—C2—H2 | 110.4 |
O4iii—K1—K1ii | 95.69 (7) | C3—C2—H2 | 110.4 |
C3iii—K1—K1ii | 52.61 (8) | O1—C5—C6 | 106.7 (4) |
S2ii—K1—K1ii | 57.43 (3) | O1—C5—C4 | 109.7 (4) |
K1v—K1—K1ii | 131.28 (5) | C6—C5—C4 | 113.4 (4) |
C7—S1—C1 | 101.4 (2) | O1—C5—H5 | 109.0 |
O9—S2—O7 | 113.8 (4) | C6—C5—H5 | 109.0 |
O9—S2—O8 | 114.7 (3) | C4—C5—H5 | 109.0 |
O7—S2—O8 | 115.1 (3) | C8—C13—C12 | 118.6 (8) |
O9—S2—O6 | 106.8 (3) | C8—C13—H13 | 120.7 |
O7—S2—O6 | 106.4 (3) | C12—C13—H13 | 120.7 |
O8—S2—O6 | 98.0 (2) | C11—C10—C9 | 120.3 (8) |
O9—S2—K1v | 86.6 (3) | C11—C10—Cl2 | 119.2 (6) |
O7—S2—K1v | 36.8 (2) | C9—C10—Cl2 | 120.5 (8) |
O8—S2—K1v | 109.5 (2) | C11—C12—C13 | 121.8 (8) |
O6—S2—K1v | 140.95 (17) | C11—C12—H12 | 119.1 |
C3—O3—K1vi | 109.0 (3) | C13—C12—H12 | 119.1 |
C3—O3—K1vii | 103.8 (3) | C12—C11—C10 | 119.5 (7) |
K1vi—O3—K1vii | 100.33 (11) | C12—C11—H11 | 120.2 |
C3—O3—H3A | 108 (4) | C10—C11—H11 | 120.2 |
K1vi—O3—H3A | 113 (4) | O10—C14'—C15' | 124.6 (14) |
K1vii—O3—H3A | 122 (4) | O10—C14'—H14A | 106.2 |
C6—O5—H5A | 106 (6) | C15'—C14'—H14A | 106.2 |
C2—O2—K1vii | 126.4 (3) | O10—C14'—H14B | 106.2 |
C2—O2—H2A | 113 (5) | C15'—C14'—H14B | 106.2 |
K1vii—O2—H2A | 113 (5) | H14A—C14'—H14B | 106.4 |
N1—O6—S2 | 111.8 (3) | C14'—C15'—H15A | 109.5 |
C1—O1—C5 | 110.4 (4) | C14'—C15'—H15B | 109.5 |
C4—O4—K1viii | 128.3 (3) | H15A—C15'—H15B | 109.5 |
C4—O4—K1vi | 112.7 (3) | C14'—C15'—H15C | 109.5 |
K1viii—O4—K1vi | 96.58 (11) | H15A—C15'—H15C | 109.5 |
C4—O4—H4A | 98 (5) | H15B—C15'—H15C | 109.5 |
K1viii—O4—H4A | 124 (6) | H15D—C15—H15E | 109.5 |
K1vi—O4—H4A | 91 (5) | H15D—C15—H15F | 109.5 |
C7—N1—O6 | 108.5 (4) | H15E—C15—H15F | 109.5 |
S2—O7—K1v | 124.6 (4) | ||
O9—S2—O6—N1 | 61.6 (4) | O3—C3—C4—O4 | −61.4 (6) |
O7—S2—O6—N1 | −60.3 (4) | C2—C3—C4—O4 | 173.3 (4) |
O8—S2—O6—N1 | −179.5 (4) | K1vi—C3—C4—O4 | −17.9 (4) |
K1v—S2—O6—N1 | −44.4 (5) | O3—C3—C4—C5 | 175.9 (4) |
S2—O6—N1—C7 | 175.3 (4) | C2—C3—C4—C5 | 50.6 (6) |
O9—S2—O7—K1v | 45.9 (4) | K1vi—C3—C4—C5 | −140.7 (3) |
O8—S2—O7—K1v | −89.4 (4) | K1vii—O2—C2—C1 | −143.9 (3) |
O6—S2—O7—K1v | 163.2 (3) | K1vii—O2—C2—C3 | −27.1 (5) |
C5—O1—C1—C2 | −68.6 (5) | O1—C1—C2—O2 | 177.7 (4) |
C5—O1—C1—S1 | 169.9 (3) | S1—C1—C2—O2 | −61.9 (5) |
C7—S1—C1—O1 | −81.6 (4) | O1—C1—C2—C3 | 61.1 (5) |
C7—S1—C1—C2 | 157.4 (4) | S1—C1—C2—C3 | −178.5 (3) |
K1vi—O3—C3—C4 | 67.1 (4) | O3—C3—C2—O2 | 61.1 (5) |
K1vii—O3—C3—C4 | 173.4 (3) | C4—C3—C2—O2 | −172.7 (4) |
K1vi—O3—C3—C2 | −166.8 (3) | K1vi—C3—C2—O2 | 36.1 (9) |
K1vii—O3—C3—C2 | −60.5 (4) | O3—C3—C2—C1 | −179.1 (4) |
K1vii—O3—C3—K1vi | 106.2 (2) | C4—C3—C2—C1 | −52.8 (5) |
O7—S2—O9—K1 | 4.9 (7) | K1vi—C3—C2—C1 | 156.0 (6) |
O8—S2—O9—K1 | 140.4 (5) | C1—O1—C5—C6 | −172.6 (4) |
O6—S2—O9—K1 | −112.2 (6) | C1—O1—C5—C4 | 64.1 (5) |
K1v—S2—O9—K1 | 30.4 (6) | O5—C6—C5—O1 | −69.5 (5) |
O6—N1—C7—C8 | −179.6 (5) | O5—C6—C5—C4 | 51.4 (6) |
O6—N1—C7—S1 | 2.4 (6) | O4—C4—C5—O1 | −176.9 (4) |
C1—S1—C7—N1 | −173.0 (5) | C3—C4—C5—O1 | −54.3 (5) |
C1—S1—C7—C8 | 9.1 (5) | O4—C4—C5—C6 | 63.9 (6) |
N1—C7—C8—C9 | 91.8 (7) | C3—C4—C5—C6 | −173.4 (4) |
S1—C7—C8—C9 | −90.2 (6) | C9—C8—C13—C12 | −0.5 (9) |
N1—C7—C8—C13 | −89.4 (7) | C7—C8—C13—C12 | −179.3 (5) |
S1—C7—C8—C13 | 88.6 (6) | C8—C9—C10—C11 | 0.3 (11) |
C13—C8—C9—C10 | 0.4 (9) | Cl1—C9—C10—C11 | 179.7 (6) |
C7—C8—C9—C10 | 179.2 (6) | C8—C9—C10—Cl2 | −179.3 (5) |
C13—C8—C9—Cl1 | −179.1 (5) | Cl1—C9—C10—Cl2 | 0.1 (9) |
C7—C8—C9—Cl1 | −0.3 (8) | C8—C13—C12—C11 | 0.0 (10) |
K1viii—O4—C4—C3 | 142.0 (3) | C13—C12—C11—C10 | 0.7 (11) |
K1vi—O4—C4—C3 | 22.8 (5) | C9—C10—C11—C12 | −0.8 (12) |
K1viii—O4—C4—C5 | −95.7 (4) | Cl2—C10—C11—C12 | 178.8 (6) |
K1vi—O4—C4—C5 | 145.1 (3) |
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. |
D—H···A | D—H | H···A | D···A | D—H···A |
O11—H11A···S2 | 0.84 | 2.95 | 3.770 (6) | 167 |
O11—H11A···O6 | 0.84 | 2.63 | 3.300 (8) | 138 |
O11—H11A···O8 | 0.84 | 2.05 | 2.861 (8) | 163 |
C16—H16C···Cl1ix | 0.98 | 2.68 | 3.613 (15) | 160 |
C6—H6B···O2x | 0.99 | 2.63 | 3.124 (6) | 111 |
O10—H10···S2 | 0.94 | 2.77 | 3.586 (7) | 146 |
O10—H10···O8 | 0.94 | 1.80 | 2.738 (7) | 174 |
C11—H11···O11iii | 0.95 | 2.52 | 3.428 (10) | 160 |
C14′—H14A···O6xi | 0.99 | 2.62 | 3.461 (11) | 143 |
C15′—H15B···Cl1xii | 0.98 | 2.79 | 3.40 (3) | 121 |
C14—H14C···O9xi | 0.99 | 2.62 | 3.601 (14) | 173 |
C15—H15F···Cl2i | 0.98 | 2.97 | 3.92 (4) | 163 |
O3—H3A···N1vi | 0.84 (6) | 2.19 (7) | 3.019 (6) | 170 (5) |
O2—H2A···O5xi | 0.93 (8) | 1.79 (8) | 2.655 (5) | 155 (7) |
O5—H5A···O11x | 1.01 (10) | 1.70 (10) | 2.690 (7) | 166 (9) |
O4—H4A···O10vii | 1.09 (10) | 1.61 (10) | 2.685 (8) | 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. |
Experimental details
(9) | (11) | |
Crystal data | ||
Chemical formula | C21H23Cl2NO10S | K+·C13H14Cl2NO9S2−·CH4O·C2H6O |
Mr | 552.36 | 580.48 |
Crystal system, space group | Monoclinic, P21 | Orthorhombic, P212121 |
Temperature (K) | 130 | 115 |
a, b, c (Å) | 7.1967 (2), 15.1383 (4), 11.9441 (3) | 8.0043 (1), 15.5208 (4), 19.4586 (4) |
α, β, γ (°) | 90, 102.786 (3), 90 | 90, 90, 90 |
V (Å3) | 1268.99 (6) | 2417.40 (9) |
Z | 2 | 4 |
Radiation type | Mo Kα | Cu Kα |
µ (mm−1) | 0.39 | 6.09 |
Crystal size (mm) | 0.37 × 0.32 × 0.14 | 0.65 × 0.07 × 0.04 |
Data collection | ||
Diffractometer | Oxford Diffraction SuperNova (Dual, Cu at zero, Atlas) diffractometer | Agilent SuperNova (Dual, Cu at zero, Atlas) diffractometer |
Absorption correction | Gaussian (CrysAlis PRO; Oxford Diffraction, 2010) | Multi-scan (CrysAlis PRO; Agilent, 2012) |
Tmin, Tmax | 0.888, 0.949 | 0.716, 1.000 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 6348, 3790, 3535 | 17993, 5041, 4725 |
Rint | 0.027 | 0.058 |
(sin θ/λ)max (Å−1) | 0.595 | 0.633 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.031, 0.069, 1.05 | 0.054, 0.146, 1.03 |
No. of reflections | 3790 | 5041 |
No. of parameters | 324 | 327 |
No. of restraints | 1 | 0 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.22, −0.19 | 0.77, −0.84 |
Absolute structure | Flack (1983), ???? Friedel pairs | Flack x determined using 1921 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013) |
Absolute structure parameter | −0.10 (5) | 0.010 (12) |
Computer programs: CrysAlis PRO (Oxford Diffraction, 2010), CrysAlis PRO (Agilent, 2012), SHELXS97 (Sheldrick, 2008), SHELXL2014 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 2012), WinGX (Farrugia, 2012).
D—H···A | D—H | H···A | D···A | D—H···A |
O11—H11A···O8 | 0.84 | 2.05 | 2.861 (8) | 163.3 |
O10—H10···O8 | 0.94 | 1.80 | 2.738 (7) | 173.9 |
O3—H3A···N1v | 0.84 (6) | 2.19 (7) | 3.019 (6) | 170 (5) |
O2—H2A···O5vi | 0.93 (8) | 1.79 (8) | 2.655 (5) | 155 (7) |
O5—H5A···O11vii | 1.01 (10) | 1.70 (10) | 2.690 (7) | 166 (9) |
O4—H4A···O10viii | 1.09 (10) | 1.61 (10) | 2.685 (8) | 164 (9) |
Symmetry codes: (v) −x+2, y+1/2, −z+1/2; (vi) x−1, y, z; (vii) x+1, y, z; (viii) −x+3/2, −y, z−1/2. |
K1—O2i | 2.645 (4) | K1—O4iv | 2.885 (4) |
K1—O9 | 2.648 (5) | K1—O3i | 2.967 (4) |
K1—O7ii | 2.713 (5) | K1—O4iii | 3.000 (4) |
K1—O3iii | 2.751 (4) | ||
O2i—K1—O9 | 83.25 (14) | O7ii—K1—O3i | 111.09 (16) |
O2i—K1—O7ii | 100.10 (16) | O3iii—K1—O3i | 127.98 (9) |
O9—K1—O7ii | 168.68 (19) | O4iv—K1—O3i | 149.51 (11) |
O2i—K1—O3iii | 152.88 (12) | O2i—K1—O4iii | 130.97 (10) |
O2i—K1—O4iv | 90.35 (11) | O9—K1—O4iii | 82.14 (16) |
O9—K1—O4iv | 93.23 (17) | O7ii—K1—O4iii | 103.20 (15) |
O7ii—K1—O4iv | 76.01 (15) | O4iv—K1—O4iii | 136.94 (9) |
O2i—K1—O3i | 59.46 (10) | O3i—K1—O4iii | 71.98 (10) |
O9—K1—O3i | 79.97 (14) |
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. |