The sotagliflozin molecule exhibits two fundamentally different molecular conformations in form 1 {systematic name: (2S,3R,4R,5S,6R)-2-[4-chloro-3-(4-ethoxybenzyl)phenyl]-6-(methylsulfanyl)tetrahydro-2H-pyran-3,4,5-triol, C21H25ClO5S, (I)} and the monohydrate [C21H25ClO5S·H2O, (II)]. Both crystals display hydrogen-bonded layers formed by intermolecular interactions which involve the three –OH groups of the xyloside fragment of the molecule. The layer architectures of (I) and (II) contain a non-hydrogen-bonded molecule–molecule interaction along the short crystallographic axis (a axis) whose total PIXEL energy exceeds that of each hydrogen-bonded molecule–molecule pair. The hydrogen-bonded layer of (I) has the topology of the 4-connected sql net and that formed by the water and sotagliflozin molecules of (II) has the topology of a 3,7-connected net.
Supporting information
CCDC references: 1567263; 1567262
For both structures, data collection: CrysAlis PRO (Rigaku Oxford Diffraction, 2015); cell refinement: CrysAlis PRO (Rigaku Oxford Diffraction, 2015); data reduction: CrysAlis PRO (Rigaku Oxford Diffraction, 2015); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: XP (Bruker, 1998), Mercury (Macrae et al., 2006) and TOPOS (Blatov, 2006); software used to prepare material for publication: PLATON (Spek, 2009) and publCIF (Westrip, 2010).
(2
S,3
R,4
R,5
S,6
R)-2-[4-Chloro-3-(4-ethoxybenzyl)phenyl]-6-(methylsulfanyl)tetrahydro-2
H-pyran-3,4,5-triol (I)
top
Crystal data top
C21H25ClO5S | Dx = 1.314 Mg m−3 |
Mr = 424.92 | Cu Kα radiation, λ = 1.54184 Å |
Orthorhombic, P212121 | Cell parameters from 2082 reflections |
a = 5.3945 (4) Å | θ = 4.0–67.4° |
b = 9.1577 (5) Å | µ = 2.73 mm−1 |
c = 43.475 (4) Å | T = 253 K |
V = 2147.7 (3) Å3 | Prism, colourless |
Z = 4 | 0.15 × 0.08 × 0.04 mm |
F(000) = 896 | |
Data collection top
Rigaku Xcalibur Ruby (Gemini ultra) diffractometer | 3849 independent reflections |
Radiation source: fine-focus sealed X-ray tube, Enhance Ultra (Cu) X-ray Source | 3081 reflections with I > 2σ(I) |
Mirror monochromator | Rint = 0.065 |
Detector resolution: 10.3575 pixels mm-1 | θmax = 68.1°, θmin = 4.1° |
ω scans | h = −6→6 |
Absorption correction: multi-scan (CrysAlis PRO, Rigaku Oxford Diffraction, 2015) | k = −10→10 |
Tmin = 0.678, Tmax = 1.000 | l = −49→51 |
12259 measured reflections | |
Refinement top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: mixed |
R[F2 > 2σ(F2)] = 0.044 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.108 | w = 1/[σ2(Fo2) + (0.0315P)2 + 0.2004P] where P = (Fo2 + 2Fc2)/3 |
S = 1.07 | (Δ/σ)max = 0.001 |
3849 reflections | Δρmax = 0.17 e Å−3 |
269 parameters | Δρmin = −0.21 e Å−3 |
3 restraints | Absolute structure: Flack x determined using 1021 quotients [(I+)-(I-)]/[(I+)+(I-)]
(Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259). |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.031 (18) |
Special details top
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell esds are taken
into account individually in the estimation of esds in distances, angles
and torsion angles; correlations between esds in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell esds is used for estimating esds involving l.s. planes. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
O1 | 0.5532 (6) | 0.7137 (3) | 0.67757 (6) | 0.0416 (7) | |
C2 | 0.5324 (8) | 0.8155 (4) | 0.70215 (9) | 0.0388 (9) | |
H2 | 0.3816 | 0.7912 | 0.7136 | 0.047* | |
C3 | 0.7474 (8) | 0.7994 (4) | 0.72382 (9) | 0.0353 (8) | |
H3 | 0.9001 | 0.8289 | 0.7133 | 0.042* | |
C4 | 0.7747 (8) | 0.6434 (4) | 0.73522 (8) | 0.0338 (8) | |
H4 | 0.6379 | 0.6224 | 0.7494 | 0.041* | |
C5 | 0.7656 (8) | 0.5334 (4) | 0.70900 (8) | 0.0346 (8) | |
H5 | 0.9159 | 0.5446 | 0.6966 | 0.041* | |
C6 | 0.5402 (8) | 0.5661 (4) | 0.68863 (8) | 0.0369 (8) | |
H6 | 0.3901 | 0.5559 | 0.7011 | 0.044* | |
S7 | 0.4926 (2) | 0.99677 (11) | 0.68675 (3) | 0.0521 (3) | |
C8 | 0.7782 (13) | 1.0243 (7) | 0.66669 (16) | 0.0871 (19) | |
H8A | 0.9136 | 1.0195 | 0.6810 | 0.131* | |
H8B | 0.7765 | 1.1185 | 0.6570 | 0.131* | |
H8C | 0.7978 | 0.9498 | 0.6513 | 0.131* | |
O9 | 0.7144 (5) | 0.8871 (3) | 0.75063 (6) | 0.0411 (6) | |
H9 | 0.807 (8) | 0.960 (4) | 0.7491 (12) | 0.058 (15)* | |
O10 | 1.0025 (7) | 0.6281 (3) | 0.75158 (6) | 0.0462 (6) | |
H10 | 1.015 (11) | 0.699 (3) | 0.7635 (9) | 0.056 (13)* | |
O11 | 0.7565 (6) | 0.3873 (3) | 0.72033 (7) | 0.0431 (7) | |
H11 | 0.618 (5) | 0.376 (6) | 0.7287 (12) | 0.064 (17)* | |
C12 | 0.5191 (8) | 0.4648 (4) | 0.66126 (8) | 0.0391 (9) | |
C13 | 0.6882 (9) | 0.4738 (5) | 0.63690 (9) | 0.0468 (10) | |
H13 | 0.8096 | 0.5459 | 0.6373 | 0.056* | |
C14 | 0.6789 (9) | 0.3773 (5) | 0.61211 (9) | 0.0493 (11) | |
C15 | 0.4919 (10) | 0.2720 (4) | 0.61243 (9) | 0.0491 (10) | |
C16 | 0.3231 (10) | 0.2630 (5) | 0.63612 (10) | 0.0491 (11) | |
H16 | 0.1994 | 0.1923 | 0.6356 | 0.059* | |
C17 | 0.3373 (9) | 0.3583 (5) | 0.66051 (9) | 0.0434 (10) | |
H17 | 0.2241 | 0.3512 | 0.6766 | 0.052* | |
C18 | 0.8757 (10) | 0.3829 (7) | 0.58731 (10) | 0.0629 (14) | |
H18A | 0.9515 | 0.2870 | 0.5860 | 0.075* | |
H18B | 1.0034 | 0.4504 | 0.5940 | 0.075* | |
C19 | 0.7951 (10) | 0.4271 (6) | 0.55509 (10) | 0.0566 (12) | |
C20 | 0.5988 (11) | 0.5178 (8) | 0.54861 (11) | 0.0737 (16) | |
H20 | 0.5002 | 0.5516 | 0.5646 | 0.088* | |
C21 | 0.5444 (12) | 0.5601 (7) | 0.51875 (12) | 0.0758 (16) | |
H21 | 0.4097 | 0.6207 | 0.5149 | 0.091* | |
C22 | 0.6903 (12) | 0.5121 (6) | 0.49492 (11) | 0.0654 (14) | |
C23 | 0.8842 (12) | 0.4198 (7) | 0.50102 (12) | 0.0754 (17) | |
H23 | 0.9831 | 0.3861 | 0.4850 | 0.090* | |
C24 | 0.9329 (11) | 0.3770 (7) | 0.53060 (11) | 0.0668 (14) | |
H24 | 1.0625 | 0.3124 | 0.5342 | 0.069 (17)* | |
Cl25 | 0.4717 (4) | 0.14452 (15) | 0.58310 (3) | 0.0790 (5) | |
O26 | 0.6608 (10) | 0.5511 (5) | 0.46459 (8) | 0.0909 (14) | |
C27 | 0.4644 (17) | 0.6439 (8) | 0.45612 (14) | 0.094 (2) | |
H27A | 0.4767 | 0.7358 | 0.4671 | 0.113* | |
H27B | 0.3069 | 0.5989 | 0.4612 | 0.113* | |
C28 | 0.481 (2) | 0.6698 (9) | 0.42195 (14) | 0.115 (3) | |
H28A | 0.3348 | 0.7201 | 0.4151 | 0.173* | |
H28B | 0.4938 | 0.5779 | 0.4115 | 0.173* | |
H28C | 0.6244 | 0.7281 | 0.4175 | 0.173* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O1 | 0.0534 (19) | 0.0379 (13) | 0.0336 (13) | 0.0018 (13) | −0.0008 (13) | 0.0029 (11) |
C2 | 0.042 (2) | 0.0351 (18) | 0.0397 (19) | 0.0028 (18) | −0.0013 (19) | 0.0017 (15) |
C3 | 0.035 (2) | 0.0323 (18) | 0.038 (2) | 0.0004 (17) | 0.0036 (17) | 0.0003 (15) |
C4 | 0.035 (2) | 0.0309 (18) | 0.0355 (19) | 0.0024 (16) | −0.0036 (17) | −0.0010 (15) |
C5 | 0.036 (2) | 0.0311 (19) | 0.0366 (19) | −0.0005 (16) | 0.0008 (16) | −0.0009 (15) |
C6 | 0.040 (2) | 0.0355 (17) | 0.0348 (18) | 0.0016 (17) | 0.0005 (18) | −0.0003 (15) |
S7 | 0.0537 (6) | 0.0399 (5) | 0.0626 (6) | 0.0086 (5) | −0.0028 (6) | 0.0117 (5) |
C8 | 0.077 (4) | 0.089 (4) | 0.096 (4) | 0.008 (3) | 0.011 (4) | 0.048 (4) |
O9 | 0.0440 (16) | 0.0346 (14) | 0.0446 (15) | −0.0014 (13) | −0.0011 (13) | −0.0072 (12) |
O10 | 0.0509 (16) | 0.0379 (13) | 0.0497 (14) | 0.0080 (15) | −0.0195 (15) | −0.0073 (12) |
O11 | 0.048 (2) | 0.0300 (13) | 0.0515 (17) | 0.0027 (14) | −0.0070 (15) | 0.0022 (12) |
C12 | 0.044 (2) | 0.0401 (19) | 0.0336 (18) | 0.002 (2) | −0.0064 (19) | 0.0009 (14) |
C13 | 0.048 (2) | 0.057 (3) | 0.036 (2) | −0.005 (2) | −0.0033 (19) | −0.0002 (19) |
C14 | 0.051 (3) | 0.065 (3) | 0.032 (2) | 0.011 (2) | −0.0040 (19) | −0.001 (2) |
C15 | 0.062 (3) | 0.049 (2) | 0.036 (2) | 0.010 (2) | −0.010 (2) | −0.0060 (17) |
C16 | 0.061 (3) | 0.040 (2) | 0.046 (2) | −0.005 (2) | −0.017 (2) | 0.0011 (19) |
C17 | 0.051 (3) | 0.044 (2) | 0.035 (2) | 0.001 (2) | −0.0025 (18) | 0.0004 (17) |
C18 | 0.051 (3) | 0.102 (4) | 0.036 (2) | 0.014 (3) | 0.000 (2) | −0.007 (3) |
C19 | 0.058 (3) | 0.073 (3) | 0.039 (2) | 0.002 (3) | 0.004 (2) | −0.008 (2) |
C20 | 0.070 (4) | 0.106 (4) | 0.045 (3) | 0.026 (3) | 0.007 (2) | −0.004 (3) |
C21 | 0.075 (4) | 0.096 (4) | 0.056 (3) | 0.023 (3) | 0.002 (3) | 0.003 (3) |
C22 | 0.085 (4) | 0.073 (3) | 0.039 (2) | −0.003 (3) | 0.001 (2) | 0.000 (2) |
C23 | 0.091 (4) | 0.095 (4) | 0.039 (2) | 0.021 (3) | 0.012 (3) | −0.005 (3) |
C24 | 0.069 (4) | 0.087 (4) | 0.045 (2) | 0.016 (3) | 0.002 (2) | −0.006 (3) |
Cl25 | 0.1166 (13) | 0.0693 (7) | 0.0513 (6) | 0.0050 (9) | −0.0106 (8) | −0.0229 (5) |
O26 | 0.122 (4) | 0.107 (3) | 0.0438 (19) | 0.027 (3) | −0.002 (2) | 0.006 (2) |
C27 | 0.118 (6) | 0.096 (4) | 0.068 (3) | 0.016 (5) | −0.017 (4) | 0.008 (3) |
C28 | 0.170 (8) | 0.110 (5) | 0.064 (3) | 0.019 (6) | −0.020 (5) | 0.021 (3) |
Geometric parameters (Å, º) top
O1—C2 | 1.423 (5) | C14—C18 | 1.514 (7) |
O1—C6 | 1.436 (5) | C15—C16 | 1.377 (7) |
C2—C3 | 1.501 (6) | C15—Cl25 | 1.732 (4) |
C2—S7 | 1.803 (4) | C16—C17 | 1.376 (6) |
C2—H2 | 0.9800 | C16—H16 | 0.9300 |
C3—O9 | 1.427 (5) | C17—H17 | 0.9300 |
C3—C4 | 1.519 (5) | C18—C19 | 1.522 (7) |
C3—H3 | 0.9800 | C18—H18A | 0.9700 |
C4—O10 | 1.427 (5) | C18—H18B | 0.9700 |
C4—C5 | 1.522 (5) | C19—C20 | 1.375 (8) |
C4—H4 | 0.9800 | C19—C24 | 1.377 (7) |
C5—O11 | 1.426 (5) | C20—C21 | 1.386 (8) |
C5—C6 | 1.534 (6) | C20—H20 | 0.9300 |
C5—H5 | 0.9800 | C21—C22 | 1.373 (8) |
C6—C12 | 1.513 (5) | C21—H21 | 0.9300 |
C6—H6 | 0.9800 | C22—C23 | 1.371 (9) |
S7—C8 | 1.788 (7) | C22—O26 | 1.375 (6) |
C8—H8A | 0.9600 | C23—C24 | 1.370 (8) |
C8—H8B | 0.9600 | C23—H23 | 0.9300 |
C8—H8C | 0.9600 | C24—H24 | 0.9300 |
O9—H9 | 0.836 (14) | O26—C27 | 1.407 (9) |
O10—H10 | 0.838 (14) | C27—C28 | 1.507 (9) |
O11—H11 | 0.839 (14) | C27—H27A | 0.9700 |
C12—C17 | 1.383 (6) | C27—H27B | 0.9700 |
C12—C13 | 1.400 (6) | C28—H28A | 0.9600 |
C13—C14 | 1.395 (6) | C28—H28B | 0.9600 |
C13—H13 | 0.9300 | C28—H28C | 0.9600 |
C14—C15 | 1.396 (7) | | |
| | | |
C2—O1—C6 | 111.2 (3) | C13—C14—C18 | 120.2 (5) |
O1—C2—C3 | 110.3 (3) | C15—C14—C18 | 122.5 (4) |
O1—C2—S7 | 109.5 (2) | C16—C15—C14 | 121.8 (4) |
C3—C2—S7 | 114.5 (3) | C16—C15—Cl25 | 117.9 (4) |
O1—C2—H2 | 107.4 | C14—C15—Cl25 | 120.3 (4) |
C3—C2—H2 | 107.4 | C17—C16—C15 | 120.1 (4) |
S7—C2—H2 | 107.4 | C17—C16—H16 | 120.0 |
O9—C3—C2 | 111.2 (3) | C15—C16—H16 | 120.0 |
O9—C3—C4 | 106.0 (3) | C16—C17—C12 | 120.3 (4) |
C2—C3—C4 | 111.8 (3) | C16—C17—H17 | 119.8 |
O9—C3—H3 | 109.3 | C12—C17—H17 | 119.8 |
C2—C3—H3 | 109.3 | C14—C18—C19 | 117.7 (4) |
C4—C3—H3 | 109.3 | C14—C18—H18A | 107.9 |
O10—C4—C3 | 109.8 (3) | C19—C18—H18A | 107.9 |
O10—C4—C5 | 109.7 (3) | C14—C18—H18B | 107.9 |
C3—C4—C5 | 112.0 (3) | C19—C18—H18B | 107.9 |
O10—C4—H4 | 108.4 | H18A—C18—H18B | 107.2 |
C3—C4—H4 | 108.4 | C20—C19—C24 | 117.3 (5) |
C5—C4—H4 | 108.4 | C20—C19—C18 | 124.7 (4) |
O11—C5—C4 | 111.3 (3) | C24—C19—C18 | 117.9 (5) |
O11—C5—C6 | 110.8 (3) | C19—C20—C21 | 121.6 (5) |
C4—C5—C6 | 109.2 (3) | C19—C20—H20 | 119.2 |
O11—C5—H5 | 108.5 | C21—C20—H20 | 119.2 |
C4—C5—H5 | 108.5 | C22—C21—C20 | 119.7 (5) |
C6—C5—H5 | 108.5 | C22—C21—H21 | 120.1 |
O1—C6—C12 | 108.5 (3) | C20—C21—H21 | 120.1 |
O1—C6—C5 | 109.8 (3) | C23—C22—C21 | 119.3 (5) |
C12—C6—C5 | 113.2 (3) | C23—C22—O26 | 115.7 (5) |
O1—C6—H6 | 108.4 | C21—C22—O26 | 125.0 (5) |
C12—C6—H6 | 108.4 | C24—C23—C22 | 120.3 (5) |
C5—C6—H6 | 108.4 | C24—C23—H23 | 119.9 |
C8—S7—C2 | 102.0 (3) | C22—C23—H23 | 119.9 |
S7—C8—H8A | 109.5 | C23—C24—C19 | 121.8 (5) |
S7—C8—H8B | 109.5 | C23—C24—H24 | 119.1 |
H8A—C8—H8B | 109.5 | C19—C24—H24 | 119.1 |
S7—C8—H8C | 109.5 | C22—O26—C27 | 119.7 (5) |
H8A—C8—H8C | 109.5 | O26—C27—C28 | 108.0 (7) |
H8B—C8—H8C | 109.5 | O26—C27—H27A | 110.1 |
C3—O9—H9 | 108 (4) | C28—C27—H27A | 110.1 |
C4—O10—H10 | 108 (4) | O26—C27—H27B | 110.1 |
C5—O11—H11 | 107 (4) | C28—C27—H27B | 110.1 |
C17—C12—C13 | 119.1 (4) | H27A—C27—H27B | 108.4 |
C17—C12—C6 | 120.3 (4) | C27—C28—H28A | 109.5 |
C13—C12—C6 | 120.6 (4) | C27—C28—H28B | 109.5 |
C14—C13—C12 | 121.6 (4) | H28A—C28—H28B | 109.5 |
C14—C13—H13 | 119.2 | C27—C28—H28C | 109.5 |
C12—C13—H13 | 119.2 | H28A—C28—H28C | 109.5 |
C13—C14—C15 | 117.2 (4) | H28B—C28—H28C | 109.5 |
| | | |
C6—O1—C2—C3 | 63.6 (4) | C12—C13—C14—C15 | 0.6 (6) |
C6—O1—C2—S7 | −169.6 (3) | C12—C13—C14—C18 | −175.5 (4) |
O1—C2—C3—O9 | −172.6 (3) | C13—C14—C15—C16 | 0.0 (6) |
S7—C2—C3—O9 | 63.4 (4) | C18—C14—C15—C16 | 176.0 (4) |
O1—C2—C3—C4 | −54.4 (4) | C13—C14—C15—Cl25 | −178.2 (4) |
S7—C2—C3—C4 | −178.4 (3) | C18—C14—C15—Cl25 | −2.2 (6) |
O9—C3—C4—O10 | −68.1 (4) | C14—C15—C16—C17 | −0.7 (7) |
C2—C3—C4—O10 | 170.6 (3) | Cl25—C15—C16—C17 | 177.6 (4) |
O9—C3—C4—C5 | 169.8 (3) | C15—C16—C17—C12 | 0.7 (6) |
C2—C3—C4—C5 | 48.6 (4) | C13—C12—C17—C16 | −0.1 (6) |
O10—C4—C5—O11 | 66.0 (4) | C6—C12—C17—C16 | −177.8 (4) |
C3—C4—C5—O11 | −171.9 (3) | C13—C14—C18—C19 | −114.6 (6) |
O10—C4—C5—C6 | −171.3 (3) | C15—C14—C18—C19 | 69.4 (7) |
C3—C4—C5—C6 | −49.2 (4) | C14—C18—C19—C20 | 28.8 (9) |
C2—O1—C6—C12 | 170.4 (3) | C14—C18—C19—C24 | −153.5 (5) |
C2—O1—C6—C5 | −65.4 (4) | C24—C19—C20—C21 | −1.4 (10) |
O11—C5—C6—O1 | 179.9 (3) | C18—C19—C20—C21 | 176.3 (6) |
C4—C5—C6—O1 | 56.9 (4) | C19—C20—C21—C22 | −0.7 (10) |
O11—C5—C6—C12 | −58.7 (4) | C20—C21—C22—C23 | 1.7 (10) |
C4—C5—C6—C12 | 178.3 (3) | C20—C21—C22—O26 | −177.3 (6) |
O1—C2—S7—C8 | −63.5 (4) | C21—C22—C23—C24 | −0.6 (10) |
C3—C2—S7—C8 | 60.9 (4) | O26—C22—C23—C24 | 178.5 (6) |
O1—C6—C12—C17 | −130.3 (4) | C22—C23—C24—C19 | −1.6 (10) |
C5—C6—C12—C17 | 107.6 (4) | C20—C19—C24—C23 | 2.6 (10) |
O1—C6—C12—C13 | 52.0 (5) | C18—C19—C24—C23 | −175.3 (6) |
C5—C6—C12—C13 | −70.1 (5) | C23—C22—O26—C27 | 179.1 (6) |
C17—C12—C13—C14 | −0.6 (6) | C21—C22—O26—C27 | −1.9 (10) |
C6—C12—C13—C14 | 177.1 (4) | C22—O26—C27—C28 | 178.9 (7) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O9—H9···O10i | 0.84 (1) | 1.85 (2) | 2.686 (4) | 175 (5) |
O10—H10···O11i | 0.84 (1) | 2.23 (3) | 2.970 (4) | 147 (5) |
O11—H11···O9ii | 0.84 (1) | 2.01 (2) | 2.837 (5) | 170 (6) |
Symmetry codes: (i) −x+2, y+1/2, −z+3/2; (ii) −x+1, y−1/2, −z+3/2. |
(2
S,3
R,4
R,5
S,6
R)-2-[4-Chloro-3-(4-ethoxybenzyl)phenyl]-6-(methylsulfanyl)tetrahydro-2
H-pyran-3,4,5-triol
monohydrate (II)
top
Crystal data top
C21H25ClO5S·H2O | Dx = 1.384 Mg m−3 |
Mr = 442.93 | Cu Kα radiation, λ = 1.54184 Å |
Orthorhombic, P212121 | Cell parameters from 2038 reflections |
a = 4.4659 (3) Å | θ = 4.6–67.2° |
b = 9.8994 (8) Å | µ = 2.81 mm−1 |
c = 48.073 (5) Å | T = 173 K |
V = 2125.3 (3) Å3 | Prism, colourless |
Z = 4 | 0.08 × 0.08 × 0.05 mm |
F(000) = 936 | |
Data collection top
Rigaku Xcalibur Ruby (Gemini ultra) diffractometer | 3737 independent reflections |
Radiation source: fine-focus sealed X-ray tube, Enhance Ultra (Cu) X-ray Source | 3253 reflections with I > 2σ(I) |
Mirror monochromator | Rint = 0.083 |
Detector resolution: 10.3575 pixels mm-1 | θmax = 67.6°, θmin = 3.7° |
ω scans | h = −5→5 |
Absorption correction: multi-scan (CrysAlis PRO; Rigaku Oxford Diffraction, 2015) | k = −7→11 |
Tmin = 0.560, Tmax = 1.000 | l = −57→53 |
11848 measured reflections | |
Refinement top
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)] = 0.073 | w = 1/[σ2(Fo2) + (0.0183P)2 + 2.0927P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.149 | (Δ/σ)max < 0.001 |
S = 1.35 | Δρmax = 0.71 e Å−3 |
3737 reflections | Δρmin = −0.39 e Å−3 |
279 parameters | Absolute structure: Flack x determined using 1099 quotients [(I+)-(I-)]/[(I+)+(I-)]
(Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259). |
8 restraints | Absolute structure parameter: 0.02 (3) |
Special details top
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell esds are taken
into account individually in the estimation of esds in distances, angles
and torsion angles; correlations between esds in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell esds is used for estimating esds involving l.s. planes. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
O1 | 0.4138 (10) | 0.2338 (4) | 0.32594 (9) | 0.0300 (10) | |
C2 | 0.2965 (17) | 0.1227 (6) | 0.31066 (14) | 0.0292 (15) | |
H2 | 0.0739 | 0.1203 | 0.3129 | 0.035* | |
C3 | 0.3725 (15) | 0.1378 (6) | 0.27997 (13) | 0.0273 (15) | |
H3 | 0.5946 | 0.1319 | 0.2776 | 0.033* | |
C4 | 0.2648 (16) | 0.2740 (6) | 0.26914 (12) | 0.0282 (14) | |
H4 | 0.0427 | 0.2693 | 0.2666 | 0.034* | |
C5 | 0.3344 (17) | 0.3897 (6) | 0.28882 (14) | 0.0296 (15) | |
H5 | 0.5530 | 0.4104 | 0.2874 | 0.036* | |
C6 | 0.2645 (17) | 0.3581 (6) | 0.31885 (13) | 0.0277 (14) | |
H6 | 0.0435 | 0.3452 | 0.3209 | 0.033* | |
S7 | 0.4542 (4) | −0.02891 (17) | 0.32496 (4) | 0.0358 (4) | |
C8 | 0.282 (2) | −0.0248 (8) | 0.35884 (14) | 0.0448 (19) | |
H8A | 0.3580 | 0.0531 | 0.3693 | 0.067* | |
H8B | 0.3308 | −0.1081 | 0.3689 | 0.067* | |
H8C | 0.0646 | −0.0172 | 0.3568 | 0.067* | |
O9 | 0.2341 (12) | 0.0346 (4) | 0.26364 (9) | 0.0328 (11) | |
H9 | 0.361 (14) | −0.028 (6) | 0.2639 (15) | 0.039* | |
O10 | 0.3951 (12) | 0.3081 (5) | 0.24320 (10) | 0.0342 (12) | |
H10 | 0.269 (8) | 0.291 (8) | 0.2308 (3) | 0.041* | |
O11 | 0.1713 (13) | 0.5085 (5) | 0.28115 (10) | 0.0392 (13) | |
H11 | 0.134 (17) | 0.500 (4) | 0.2640 (5) | 0.047* | |
C12 | 0.3698 (15) | 0.4589 (6) | 0.34025 (13) | 0.0260 (14) | |
C13 | 0.2978 (16) | 0.4369 (7) | 0.36771 (14) | 0.0307 (15) | |
H13 | 0.1606 | 0.3664 | 0.3719 | 0.037* | |
C14 | 0.4143 (16) | 0.5120 (7) | 0.38983 (14) | 0.0336 (16) | |
C15 | 0.6019 (17) | 0.6201 (7) | 0.38196 (15) | 0.0330 (16) | |
C16 | 0.6726 (17) | 0.6477 (7) | 0.35477 (14) | 0.0331 (16) | |
H16 | 0.7987 | 0.7219 | 0.3503 | 0.040* | |
C17 | 0.5577 (18) | 0.5659 (6) | 0.33381 (14) | 0.0326 (16) | |
H17 | 0.6082 | 0.5835 | 0.3150 | 0.039* | |
C18 | 0.3475 (17) | 0.4741 (7) | 0.41914 (14) | 0.0361 (16) | |
H18A | 0.1416 | 0.4374 | 0.4201 | 0.043* | |
H18B | 0.3543 | 0.5564 | 0.4308 | 0.043* | |
C19 | 0.5647 (18) | 0.3699 (7) | 0.43105 (15) | 0.0354 (17) | |
C20 | 0.6680 (18) | 0.2602 (7) | 0.41556 (15) | 0.0394 (18) | |
H20 | 0.6121 | 0.2528 | 0.3966 | 0.047* | |
C21 | 0.8488 (19) | 0.1624 (8) | 0.42711 (16) | 0.0401 (19) | |
H21 | 0.9159 | 0.0886 | 0.4161 | 0.048* | |
C22 | 0.932 (2) | 0.1719 (7) | 0.45475 (15) | 0.0407 (19) | |
C23 | 0.8321 (18) | 0.2803 (8) | 0.47028 (16) | 0.0406 (18) | |
H23 | 0.8905 | 0.2885 | 0.4892 | 0.049* | |
C24 | 0.6489 (18) | 0.3762 (7) | 0.45862 (15) | 0.0372 (18) | |
H24 | 0.5784 | 0.4486 | 0.4698 | 0.045* | |
Cl25 | 0.7588 (5) | 0.72261 (18) | 0.40774 (4) | 0.0463 (5) | |
O26 | 1.1092 (13) | 0.0793 (5) | 0.46841 (11) | 0.0449 (14) | |
C27 | 1.212 (2) | −0.0365 (8) | 0.45391 (16) | 0.049 (2) | |
H27A | 1.3441 | −0.0095 | 0.4384 | 0.059* | |
H27B | 1.0398 | −0.0874 | 0.4462 | 0.059* | |
C28 | 1.381 (3) | −0.1227 (9) | 0.47430 (19) | 0.066 (3) | |
H28A | 1.5540 | −0.0725 | 0.4813 | 0.099* | |
H28B | 1.4491 | −0.2053 | 0.4650 | 0.099* | |
H28C | 1.2491 | −0.1466 | 0.4899 | 0.099* | |
O1W | 0.0159 (12) | 0.2555 (5) | 0.20304 (11) | 0.0376 (12) | |
H1W | −0.104 (13) | 0.314 (5) | 0.1982 (17) | 0.056* | |
H2W | −0.073 (15) | 0.184 (4) | 0.2055 (17) | 0.056* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O1 | 0.029 (3) | 0.024 (2) | 0.036 (2) | −0.001 (2) | −0.004 (2) | −0.0004 (19) |
C2 | 0.023 (4) | 0.019 (3) | 0.046 (4) | −0.001 (3) | −0.007 (3) | 0.000 (3) |
C3 | 0.014 (3) | 0.026 (3) | 0.041 (4) | −0.001 (3) | −0.001 (3) | −0.005 (3) |
C4 | 0.027 (4) | 0.025 (3) | 0.033 (3) | 0.007 (3) | −0.001 (3) | 0.000 (3) |
C5 | 0.027 (4) | 0.019 (3) | 0.043 (4) | 0.000 (3) | −0.003 (3) | −0.002 (3) |
C6 | 0.024 (4) | 0.022 (3) | 0.038 (4) | 0.001 (3) | 0.000 (3) | −0.001 (2) |
S7 | 0.0382 (11) | 0.0249 (8) | 0.0443 (10) | 0.0028 (8) | −0.0045 (8) | 0.0024 (7) |
C8 | 0.058 (6) | 0.038 (4) | 0.038 (4) | 0.001 (5) | −0.003 (4) | 0.009 (3) |
O9 | 0.032 (3) | 0.025 (2) | 0.041 (3) | 0.001 (2) | −0.005 (2) | −0.005 (2) |
O10 | 0.038 (3) | 0.031 (3) | 0.033 (3) | −0.005 (2) | −0.001 (2) | 0.0011 (19) |
O11 | 0.049 (3) | 0.028 (3) | 0.041 (3) | 0.008 (2) | −0.006 (2) | −0.0025 (19) |
C12 | 0.020 (3) | 0.019 (3) | 0.040 (4) | 0.005 (3) | −0.004 (3) | −0.002 (3) |
C13 | 0.020 (4) | 0.028 (3) | 0.045 (4) | 0.008 (3) | −0.004 (3) | −0.005 (3) |
C14 | 0.026 (4) | 0.033 (4) | 0.042 (4) | 0.011 (3) | −0.002 (3) | −0.006 (3) |
C15 | 0.026 (4) | 0.028 (4) | 0.045 (4) | 0.000 (3) | −0.008 (3) | −0.013 (3) |
C16 | 0.027 (4) | 0.028 (4) | 0.044 (4) | 0.004 (3) | 0.001 (3) | 0.000 (3) |
C17 | 0.032 (4) | 0.027 (4) | 0.039 (4) | 0.009 (3) | −0.003 (3) | 0.001 (3) |
C18 | 0.030 (4) | 0.038 (4) | 0.040 (4) | 0.002 (4) | 0.001 (3) | −0.006 (3) |
C19 | 0.033 (4) | 0.031 (4) | 0.043 (4) | −0.006 (3) | 0.006 (3) | 0.001 (3) |
C20 | 0.039 (5) | 0.043 (4) | 0.036 (4) | −0.009 (4) | −0.001 (3) | −0.002 (3) |
C21 | 0.038 (5) | 0.037 (4) | 0.046 (5) | −0.003 (4) | 0.005 (3) | −0.003 (3) |
C22 | 0.047 (5) | 0.034 (4) | 0.042 (4) | −0.002 (4) | 0.000 (4) | 0.001 (3) |
C23 | 0.037 (5) | 0.047 (4) | 0.038 (4) | −0.003 (4) | 0.003 (3) | 0.000 (3) |
C24 | 0.041 (5) | 0.033 (4) | 0.038 (4) | −0.004 (4) | 0.004 (3) | −0.006 (3) |
Cl25 | 0.0522 (12) | 0.0413 (10) | 0.0453 (10) | −0.0086 (10) | −0.0066 (9) | −0.0098 (8) |
O26 | 0.049 (4) | 0.038 (3) | 0.048 (3) | 0.007 (3) | −0.004 (2) | −0.003 (2) |
C27 | 0.051 (6) | 0.041 (4) | 0.056 (5) | 0.002 (5) | 0.001 (4) | −0.001 (4) |
C28 | 0.077 (8) | 0.056 (5) | 0.064 (6) | 0.011 (6) | 0.012 (5) | 0.006 (4) |
O1W | 0.037 (3) | 0.025 (2) | 0.050 (3) | −0.002 (2) | −0.003 (2) | 0.002 (2) |
Geometric parameters (Å, º) top
O1—C2 | 1.423 (8) | C15—C16 | 1.372 (10) |
O1—C6 | 1.440 (8) | C15—Cl25 | 1.748 (6) |
C2—C3 | 1.521 (10) | C16—C17 | 1.391 (10) |
C2—S7 | 1.795 (6) | C16—H16 | 0.9500 |
C2—H2 | 1.0000 | C17—H17 | 0.9500 |
C3—O9 | 1.428 (8) | C18—C19 | 1.528 (11) |
C3—C4 | 1.524 (9) | C18—H18A | 0.9900 |
C3—H3 | 1.0000 | C18—H18B | 0.9900 |
C4—O10 | 1.417 (8) | C19—C24 | 1.379 (10) |
C4—C5 | 1.518 (9) | C19—C20 | 1.395 (10) |
C4—H4 | 1.0000 | C20—C21 | 1.377 (11) |
C5—O11 | 1.431 (8) | C20—H20 | 0.9500 |
C5—C6 | 1.510 (9) | C21—C22 | 1.383 (11) |
C5—H5 | 1.0000 | C21—H21 | 0.9500 |
C6—C12 | 1.508 (9) | C22—O26 | 1.377 (9) |
C6—H6 | 1.0000 | C22—C23 | 1.382 (11) |
S7—C8 | 1.801 (8) | C23—C24 | 1.373 (11) |
C8—H8A | 0.9800 | C23—H23 | 0.9500 |
C8—H8B | 0.9800 | C24—H24 | 0.9500 |
C8—H8C | 0.9800 | O26—C27 | 1.417 (9) |
O9—H9 | 0.837 (13) | C27—C28 | 1.503 (12) |
O10—H10 | 0.836 (14) | C27—H27A | 0.9900 |
O11—H11 | 0.843 (13) | C27—H27B | 0.9900 |
C12—C13 | 1.376 (10) | C28—H28A | 0.9800 |
C12—C17 | 1.387 (10) | C28—H28B | 0.9800 |
C13—C14 | 1.398 (10) | C28—H28C | 0.9800 |
C13—H13 | 0.9500 | O1W—H1W | 0.821 (13) |
C14—C15 | 1.411 (10) | O1W—H2W | 0.820 (14) |
C14—C18 | 1.488 (10) | | |
| | | |
C2—O1—C6 | 111.6 (5) | C15—C14—C18 | 124.3 (6) |
O1—C2—C3 | 110.0 (5) | C16—C15—C14 | 122.9 (6) |
O1—C2—S7 | 107.7 (4) | C16—C15—Cl25 | 117.9 (6) |
C3—C2—S7 | 111.5 (5) | C14—C15—Cl25 | 119.2 (5) |
O1—C2—H2 | 109.2 | C15—C16—C17 | 119.3 (7) |
C3—C2—H2 | 109.2 | C15—C16—H16 | 120.3 |
S7—C2—H2 | 109.2 | C17—C16—H16 | 120.3 |
O9—C3—C2 | 111.5 (5) | C12—C17—C16 | 120.4 (7) |
O9—C3—C4 | 107.9 (5) | C12—C17—H17 | 119.8 |
C2—C3—C4 | 110.3 (5) | C16—C17—H17 | 119.8 |
O9—C3—H3 | 109.0 | C14—C18—C19 | 113.4 (6) |
C2—C3—H3 | 109.0 | C14—C18—H18A | 108.9 |
C4—C3—H3 | 109.0 | C19—C18—H18A | 108.9 |
O10—C4—C5 | 106.5 (5) | C14—C18—H18B | 108.9 |
O10—C4—C3 | 112.4 (5) | C19—C18—H18B | 108.9 |
C5—C4—C3 | 113.0 (5) | H18A—C18—H18B | 107.7 |
O10—C4—H4 | 108.2 | C24—C19—C20 | 117.3 (7) |
C5—C4—H4 | 108.2 | C24—C19—C18 | 120.2 (6) |
C3—C4—H4 | 108.2 | C20—C19—C18 | 122.4 (7) |
O11—C5—C6 | 108.1 (5) | C21—C20—C19 | 121.7 (7) |
O11—C5—C4 | 110.8 (5) | C21—C20—H20 | 119.1 |
C6—C5—C4 | 113.4 (5) | C19—C20—H20 | 119.1 |
O11—C5—H5 | 108.1 | C20—C21—C22 | 119.8 (7) |
C6—C5—H5 | 108.1 | C20—C21—H21 | 120.1 |
C4—C5—H5 | 108.1 | C22—C21—H21 | 120.1 |
O1—C6—C12 | 105.0 (5) | O26—C22—C23 | 116.4 (7) |
O1—C6—C5 | 107.9 (5) | O26—C22—C21 | 124.6 (7) |
C12—C6—C5 | 116.8 (5) | C23—C22—C21 | 119.0 (7) |
O1—C6—H6 | 109.0 | C24—C23—C22 | 120.6 (7) |
C12—C6—H6 | 109.0 | C24—C23—H23 | 119.7 |
C5—C6—H6 | 109.0 | C22—C23—H23 | 119.7 |
C2—S7—C8 | 99.2 (3) | C23—C24—C19 | 121.6 (7) |
S7—C8—H8A | 109.5 | C23—C24—H24 | 119.2 |
S7—C8—H8B | 109.5 | C19—C24—H24 | 119.2 |
H8A—C8—H8B | 109.5 | C22—O26—C27 | 119.3 (6) |
S7—C8—H8C | 109.5 | O26—C27—C28 | 107.5 (7) |
H8A—C8—H8C | 109.5 | O26—C27—H27A | 110.2 |
H8B—C8—H8C | 109.5 | C28—C27—H27A | 110.2 |
C3—O9—H9 | 103 (5) | O26—C27—H27B | 110.2 |
C4—O10—H10 | 107.6 (17) | C28—C27—H27B | 110.2 |
C5—O11—H11 | 105.9 (16) | H27A—C27—H27B | 108.5 |
C13—C12—C17 | 118.5 (6) | C27—C28—H28A | 109.5 |
C13—C12—C6 | 118.5 (6) | C27—C28—H28B | 109.5 |
C17—C12—C6 | 122.8 (6) | H28A—C28—H28B | 109.5 |
C12—C13—C14 | 124.0 (7) | C27—C28—H28C | 109.5 |
C12—C13—H13 | 118.0 | H28A—C28—H28C | 109.5 |
C14—C13—H13 | 118.0 | H28B—C28—H28C | 109.5 |
C13—C14—C15 | 114.9 (6) | H1W—O1W—H2W | 109 (2) |
C13—C14—C18 | 120.8 (7) | | |
| | | |
C6—O1—C2—C3 | 67.4 (7) | C12—C13—C14—C15 | 3.7 (10) |
C6—O1—C2—S7 | −170.9 (4) | C12—C13—C14—C18 | −174.4 (6) |
O1—C2—C3—O9 | −174.5 (5) | C13—C14—C15—C16 | −1.8 (10) |
S7—C2—C3—O9 | 66.1 (6) | C18—C14—C15—C16 | 176.2 (7) |
O1—C2—C3—C4 | −54.6 (7) | C13—C14—C15—Cl25 | 179.4 (5) |
S7—C2—C3—C4 | −174.0 (5) | C18—C14—C15—Cl25 | −2.6 (10) |
O9—C3—C4—O10 | −73.3 (7) | C14—C15—C16—C17 | −0.4 (11) |
C2—C3—C4—O10 | 164.7 (6) | Cl25—C15—C16—C17 | 178.4 (6) |
O9—C3—C4—C5 | 166.1 (6) | C13—C12—C17—C16 | 0.8 (10) |
C2—C3—C4—C5 | 44.1 (8) | C6—C12—C17—C16 | −173.4 (6) |
O10—C4—C5—O11 | 69.5 (7) | C15—C16—C17—C12 | 1.0 (10) |
C3—C4—C5—O11 | −166.6 (6) | C13—C14—C18—C19 | 87.0 (8) |
O10—C4—C5—C6 | −168.7 (6) | C15—C14—C18—C19 | −90.9 (9) |
C3—C4—C5—C6 | −44.8 (8) | C14—C18—C19—C24 | 144.3 (7) |
C2—O1—C6—C12 | 169.5 (5) | C14—C18—C19—C20 | −40.6 (10) |
C2—O1—C6—C5 | −65.3 (7) | C24—C19—C20—C21 | −0.6 (11) |
O11—C5—C6—O1 | 176.4 (5) | C18—C19—C20—C21 | −175.8 (7) |
C4—C5—C6—O1 | 53.1 (8) | C19—C20—C21—C22 | −0.1 (12) |
O11—C5—C6—C12 | −65.7 (8) | C20—C21—C22—O26 | 179.2 (8) |
C4—C5—C6—C12 | 171.0 (6) | C20—C21—C22—C23 | −0.1 (12) |
O1—C2—S7—C8 | 66.4 (5) | O26—C22—C23—C24 | −178.5 (7) |
C3—C2—S7—C8 | −172.8 (5) | C21—C22—C23—C24 | 0.9 (12) |
O1—C6—C12—C13 | −63.6 (8) | C22—C23—C24—C19 | −1.6 (12) |
C5—C6—C12—C13 | 176.9 (6) | C20—C19—C24—C23 | 1.4 (11) |
O1—C6—C12—C17 | 110.6 (7) | C18—C19—C24—C23 | 176.8 (7) |
C5—C6—C12—C17 | −8.9 (10) | C23—C22—O26—C27 | 178.0 (7) |
C17—C12—C13—C14 | −3.3 (10) | C21—C22—O26—C27 | −1.3 (12) |
C6—C12—C13—C14 | 171.1 (7) | C22—O26—C27—C28 | −176.5 (8) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O9—H9···O10i | 0.84 (1) | 1.99 (2) | 2.807 (7) | 166 (7) |
O10—H10···O1W | 0.84 (1) | 1.79 (2) | 2.621 (7) | 177 (3) |
O11—H11···O9ii | 0.84 (1) | 2.14 (4) | 2.825 (7) | 138 (5) |
O1W—H1W···S7ii | 0.82 (1) | 2.47 (2) | 3.282 (5) | 170 (8) |
O1W—H2W···O11iii | 0.82 (1) | 1.90 (3) | 2.694 (6) | 162 (7) |
Symmetry codes: (i) −x+1, y−1/2, −z+1/2; (ii) −x, y+1/2, −z+1/2; (iii) −x, y−1/2, −z+1/2. |