Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270110041843/gz3184sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270110041843/gz31841sup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270110041843/gz31842sup3.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270110041843/gz31843sup4.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270110041843/gz31844sup5.hkl |
CCDC references: 810020; 810021; 810022; 810023
For related literature, see: Chen et al. (1996); Etter et al. (1990); Gavezzotti (2008, 2010); Spek (2009); Steiner (2003).
Details of the preparation of the compounds can be found elsewhere (Wilke et al., 2010).
In each refinement several low-angle reflections were excluded from the final cycles of refinement because of beam-stop shadowing effects. H atoms were fully refined with isotropic displacement parameters in all structures. The bond distance ranges for C—H were: (1) 0.86 (2) - 1.06 (2) Å, (2) 0.92 (3) - 1.09 (3) Å, (3) 0.93 (2) - 1.06 (2) Å, (4) 0.91 (2) - 1.03 (3) Å. There are two O—H bonds – one in (3) [0.85 (3) Å] and one in (4) [0.87 (3) Å]. For (1) 1265 Friedel pairs were measured, for (2) 1394 Friedel pairs were measured, for (3) 1281 Friedel pairs were measured and for (4) 1440 Friedel pairs were measured.
For all compounds, data collection: COLLECT (Nonius, 2000); cell refinement: SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO (Otwinowski & Minor, 1997) and SCALEPACK; program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: publCIF (Westrip, 2010).
C12H17NO4S | F(000) = 288 |
Mr = 271.33 | Dx = 1.468 Mg m−3 |
Monoclinic, P21 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2yb | Cell parameters from 2811 reflections |
a = 7.7873 (9) Å | θ = 1.0–27.9° |
b = 7.1895 (8) Å | µ = 0.27 mm−1 |
c = 11.1111 (12) Å | T = 210 K |
β = 99.274 (5)° | Plate, colorless |
V = 613.94 (12) Å3 | 0.32 × 0.29 × 0.03 mm |
Z = 2 |
Nonius KappaCCD diffractometer | 2845 independent reflections |
Radiation source: fine-focus sealed tube | 2565 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.022 |
Detector resolution: 9 pixels mm-1 | θmax = 27.9°, θmin = 3.4° |
CCD ϕ and ω scans | h = −10→10 |
Absorption correction: multi-scan (SCALEPACK; Otwinowski & Minor, 1997) | k = −9→9 |
Tmin = 0.918, Tmax = 0.992 | l = −14→14 |
15611 measured reflections |
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 | All H-atom parameters refined |
wR(F2) = 0.072 | w = 1/[σ2(Fo2) + (0.0326P)2 + 0.0875P] where P = (Fo2 + 2Fc2)/3 |
S = 1.06 | (Δ/σ)max < 0.001 |
2845 reflections | Δρmax = 0.18 e Å−3 |
232 parameters | Δρmin = −0.26 e Å−3 |
1 restraint | Absolute structure: Flack (1983) |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: −0.01 (6) |
C12H17NO4S | V = 613.94 (12) Å3 |
Mr = 271.33 | Z = 2 |
Monoclinic, P21 | Mo Kα radiation |
a = 7.7873 (9) Å | µ = 0.27 mm−1 |
b = 7.1895 (8) Å | T = 210 K |
c = 11.1111 (12) Å | 0.32 × 0.29 × 0.03 mm |
β = 99.274 (5)° |
Nonius KappaCCD diffractometer | 2845 independent reflections |
Absorption correction: multi-scan (SCALEPACK; Otwinowski & Minor, 1997) | 2565 reflections with I > 2σ(I) |
Tmin = 0.918, Tmax = 0.992 | Rint = 0.022 |
15611 measured reflections |
R[F2 > 2σ(F2)] = 0.031 | All H-atom parameters refined |
wR(F2) = 0.072 | Δρmax = 0.18 e Å−3 |
S = 1.06 | Δρmin = −0.26 e Å−3 |
2845 reflections | Absolute structure: Flack (1983) |
232 parameters | Absolute structure parameter: −0.01 (6) |
1 restraint |
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. Several low angle reflections were omitted due to beam-stop shadowing effects. |
x | y | z | Uiso*/Ueq | ||
O1 | 0.42646 (17) | 0.77619 (17) | 0.28852 (12) | 0.0329 (3) | |
C2 | 0.5652 (3) | 0.8218 (3) | 0.2224 (2) | 0.0415 (5) | |
H2A | 0.545 (4) | 0.958 (4) | 0.187 (2) | 0.065 (8)* | |
H2B | 0.671 (3) | 0.818 (4) | 0.279 (2) | 0.054 (7)* | |
C3 | 0.5589 (3) | 0.6767 (3) | 0.1217 (2) | 0.0360 (5) | |
H3A | 0.555 (3) | 0.727 (3) | 0.043 (2) | 0.044 (6)* | |
H3B | 0.658 (3) | 0.600 (4) | 0.135 (2) | 0.054 (7)* | |
N4 | 0.40246 (19) | 0.5655 (2) | 0.13153 (13) | 0.0265 (3) | |
S5 | 0.22102 (5) | 0.62616 (6) | 0.03479 (4) | 0.02774 (11) | |
O2 | 0.18527 (18) | 0.4842 (2) | −0.05669 (12) | 0.0392 (4) | |
O3 | 0.23538 (19) | 0.8131 (2) | −0.00872 (13) | 0.0407 (3) | |
C6 | 0.0720 (2) | 0.6150 (3) | 0.14194 (15) | 0.0280 (3) | |
H6A | 0.033 (3) | 0.732 (4) | 0.1457 (19) | 0.041 (6)* | |
H6B | −0.021 (3) | 0.527 (3) | 0.109 (2) | 0.037 (6)* | |
C6A | 0.1779 (2) | 0.5519 (2) | 0.26180 (15) | 0.0255 (3) | |
C7 | 0.1391 (3) | 0.6410 (3) | 0.38013 (16) | 0.0326 (4) | |
H7A | 0.019 (3) | 0.640 (3) | 0.3804 (18) | 0.037 (5)* | |
H7B | 0.178 (3) | 0.780 (4) | 0.3869 (19) | 0.046 (6)* | |
C8 | 0.2454 (3) | 0.5184 (3) | 0.48031 (17) | 0.0384 (5) | |
H8A | 0.165 (3) | 0.463 (4) | 0.538 (2) | 0.062 (8)* | |
H8B | 0.336 (3) | 0.589 (3) | 0.5291 (17) | 0.027 (5)* | |
C9 | 0.3221 (3) | 0.3635 (3) | 0.40763 (18) | 0.0350 (4) | |
H9 | 0.352 (4) | 0.264 (4) | 0.449 (2) | 0.060 (7)* | |
C10 | 0.4649 (2) | 0.4539 (3) | 0.35165 (18) | 0.0336 (4) | |
O4 | 0.62152 (19) | 0.4387 (3) | 0.37788 (15) | 0.0530 (4) | |
C10A | 0.3710 (2) | 0.5919 (2) | 0.25629 (15) | 0.0259 (4) | |
C11 | 0.1810 (2) | 0.3385 (3) | 0.29320 (17) | 0.0292 (4) | |
C12 | 0.0072 (3) | 0.2675 (3) | 0.3223 (2) | 0.0392 (5) | |
H12A | 0.022 (3) | 0.131 (5) | 0.348 (2) | 0.059 (7)* | |
H12B | −0.087 (3) | 0.263 (4) | 0.252 (2) | 0.054 (7)* | |
H12C | −0.034 (3) | 0.342 (4) | 0.388 (2) | 0.057 (7)* | |
C13 | 0.2384 (3) | 0.2068 (3) | 0.1991 (2) | 0.0372 (5) | |
H13A | 0.237 (3) | 0.072 (4) | 0.236 (2) | 0.050 (7)* | |
H13B | 0.353 (3) | 0.236 (3) | 0.1803 (18) | 0.041 (6)* | |
H13C | 0.160 (3) | 0.216 (3) | 0.122 (2) | 0.041 (6)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0367 (7) | 0.0299 (7) | 0.0342 (7) | −0.0047 (6) | 0.0119 (6) | −0.0052 (6) |
C2 | 0.0348 (11) | 0.0431 (13) | 0.0492 (12) | −0.0105 (9) | 0.0150 (10) | −0.0092 (10) |
C3 | 0.0298 (10) | 0.0409 (12) | 0.0401 (11) | −0.0062 (8) | 0.0141 (8) | −0.0055 (8) |
N4 | 0.0238 (7) | 0.0292 (7) | 0.0276 (7) | 0.0004 (6) | 0.0073 (6) | −0.0004 (6) |
S5 | 0.0289 (2) | 0.0290 (2) | 0.02624 (18) | 0.00087 (19) | 0.00726 (15) | 0.00173 (19) |
O2 | 0.0384 (8) | 0.0487 (9) | 0.0306 (7) | −0.0011 (7) | 0.0061 (6) | −0.0111 (6) |
O3 | 0.0441 (8) | 0.0364 (8) | 0.0426 (8) | 0.0010 (6) | 0.0096 (7) | 0.0153 (7) |
C6 | 0.0249 (8) | 0.0309 (9) | 0.0294 (8) | 0.0057 (9) | 0.0080 (6) | 0.0035 (9) |
C6A | 0.0258 (8) | 0.0247 (8) | 0.0275 (8) | 0.0037 (7) | 0.0086 (7) | 0.0028 (7) |
C7 | 0.0350 (9) | 0.0346 (10) | 0.0309 (8) | 0.0055 (9) | 0.0133 (7) | −0.0010 (9) |
C8 | 0.0420 (11) | 0.0478 (13) | 0.0262 (9) | 0.0009 (9) | 0.0079 (9) | 0.0008 (9) |
C9 | 0.0384 (11) | 0.0350 (11) | 0.0321 (10) | 0.0084 (8) | 0.0073 (8) | 0.0101 (8) |
C10 | 0.0326 (10) | 0.0356 (11) | 0.0333 (10) | 0.0069 (8) | 0.0068 (8) | 0.0033 (8) |
O4 | 0.0328 (8) | 0.0681 (12) | 0.0570 (10) | 0.0122 (8) | 0.0039 (7) | 0.0204 (9) |
C10A | 0.0259 (8) | 0.0261 (11) | 0.0265 (8) | 0.0027 (7) | 0.0068 (7) | −0.0011 (7) |
C11 | 0.0327 (10) | 0.0258 (9) | 0.0309 (9) | 0.0027 (7) | 0.0106 (8) | 0.0042 (7) |
C12 | 0.0398 (11) | 0.0390 (12) | 0.0419 (12) | −0.0065 (9) | 0.0157 (10) | 0.0011 (10) |
C13 | 0.0461 (12) | 0.0244 (9) | 0.0440 (13) | 0.0028 (9) | 0.0158 (10) | 0.0001 (9) |
O1—C10A | 1.421 (2) | C7—C8 | 1.551 (3) |
O1—C2 | 1.439 (2) | C7—H7A | 0.94 (2) |
C2—C3 | 1.525 (3) | C7—H7B | 1.05 (3) |
C2—H2A | 1.06 (3) | C8—C9 | 1.551 (3) |
C2—H2B | 0.95 (2) | C8—H8A | 1.04 (3) |
C3—N4 | 1.476 (2) | C8—H8B | 0.96 (2) |
C3—H3A | 0.94 (2) | C9—C10 | 1.506 (3) |
C3—H3B | 0.94 (3) | C9—C11 | 1.551 (3) |
N4—C10A | 1.459 (2) | C9—H9 | 0.86 (3) |
N4—S5 | 1.6890 (15) | C10—O4 | 1.213 (2) |
S5—O2 | 1.4357 (14) | C10—C10A | 1.547 (2) |
S5—O3 | 1.4384 (15) | C11—C12 | 1.529 (3) |
S5—C6 | 1.7934 (16) | C11—C13 | 1.530 (3) |
C6—C6A | 1.518 (2) | C12—H12A | 1.02 (3) |
C6—H6A | 0.90 (3) | C12—H12B | 0.98 (3) |
C6—H6B | 0.99 (2) | C12—H12C | 1.00 (3) |
C6A—C7 | 1.536 (2) | C13—H13A | 1.05 (3) |
C6A—C10A | 1.542 (2) | C13—H13B | 0.97 (2) |
C6A—C11 | 1.573 (3) | C13—H13C | 0.97 (2) |
C10A—O1—C2 | 107.86 (14) | C9—C8—C7 | 103.91 (15) |
O1—C2—C3 | 106.29 (16) | C9—C8—H8A | 111.4 (15) |
O1—C2—H2A | 108.6 (15) | C7—C8—H8A | 110.8 (15) |
C3—C2—H2A | 112.1 (14) | C9—C8—H8B | 111.3 (11) |
O1—C2—H2B | 107.3 (15) | C7—C8—H8B | 111.3 (12) |
C3—C2—H2B | 112.6 (15) | H8A—C8—H8B | 108.2 (17) |
H2A—C2—H2B | 110 (2) | C10—C9—C8 | 106.09 (18) |
N4—C3—C2 | 104.21 (15) | C10—C9—C11 | 100.60 (15) |
N4—C3—H3A | 111.8 (14) | C8—C9—C11 | 103.23 (16) |
C2—C3—H3A | 114.0 (14) | C10—C9—H9 | 115.2 (18) |
N4—C3—H3B | 109.7 (15) | C8—C9—H9 | 114.4 (17) |
C2—C3—H3B | 111.0 (15) | C11—C9—H9 | 115.7 (18) |
H3A—C3—H3B | 106.1 (19) | O4—C10—C9 | 130.02 (18) |
C10A—N4—C3 | 105.50 (14) | O4—C10—C10A | 124.64 (17) |
C10A—N4—S5 | 108.64 (11) | C9—C10—C10A | 105.12 (15) |
C3—N4—S5 | 115.38 (13) | O1—C10A—N4 | 105.68 (13) |
O2—S5—O3 | 116.28 (9) | O1—C10A—C6A | 115.01 (13) |
O2—S5—N4 | 108.29 (8) | N4—C10A—C6A | 109.13 (14) |
O3—S5—N4 | 110.66 (8) | O1—C10A—C10 | 109.55 (14) |
O2—S5—C6 | 111.46 (10) | N4—C10A—C10 | 115.72 (14) |
O3—S5—C6 | 111.01 (10) | C6A—C10A—C10 | 102.09 (13) |
N4—S5—C6 | 97.50 (7) | C12—C11—C13 | 107.70 (17) |
C6A—C6—S5 | 106.11 (11) | C12—C11—C9 | 113.55 (16) |
C6A—C6—H6A | 112.3 (14) | C13—C11—C9 | 112.67 (16) |
S5—C6—H6A | 104.3 (15) | C12—C11—C6A | 112.95 (15) |
C6A—C6—H6B | 113.5 (13) | C13—C11—C6A | 116.64 (15) |
S5—C6—H6B | 107.0 (13) | C9—C11—C6A | 93.00 (14) |
H6A—C6—H6B | 112.8 (19) | C11—C12—H12A | 108.6 (14) |
C6—C6A—C7 | 118.19 (15) | C11—C12—H12B | 114.6 (14) |
C6—C6A—C10A | 107.74 (13) | H12A—C12—H12B | 103.1 (19) |
C7—C6A—C10A | 106.48 (14) | C11—C12—H12C | 112.0 (15) |
C6—C6A—C11 | 118.23 (16) | H12A—C12—H12C | 110 (2) |
C7—C6A—C11 | 102.43 (15) | H12B—C12—H12C | 108 (2) |
C10A—C6A—C11 | 102.14 (13) | C11—C13—H13A | 106.4 (14) |
C6A—C7—C8 | 102.80 (15) | C11—C13—H13B | 113.2 (13) |
C6A—C7—H7A | 109.4 (13) | H13A—C13—H13B | 110 (2) |
C8—C7—H7A | 114.2 (13) | C11—C13—H13C | 110.6 (13) |
C6A—C7—H7B | 111.4 (12) | H13A—C13—H13C | 112 (2) |
C8—C7—H7B | 112.1 (12) | H13B—C13—H13C | 104.9 (18) |
H7A—C7—H7B | 106.9 (19) | ||
C10A—O1—C2—C3 | 15.3 (2) | C3—N4—C10A—C10 | −88.54 (18) |
O1—C2—C3—N4 | 5.0 (2) | S5—N4—C10A—C10 | 147.20 (13) |
C2—C3—N4—C10A | −22.7 (2) | C6—C6A—C10A—O1 | 84.26 (18) |
C2—C3—N4—S5 | 97.20 (18) | C7—C6A—C10A—O1 | −43.46 (19) |
C10A—N4—S5—O2 | −133.76 (12) | C11—C6A—C10A—O1 | −150.52 (14) |
C3—N4—S5—O2 | 108.07 (14) | C6—C6A—C10A—N4 | −34.26 (19) |
C10A—N4—S5—O3 | 97.71 (12) | C7—C6A—C10A—N4 | −161.98 (15) |
C3—N4—S5—O3 | −20.46 (15) | C11—C6A—C10A—N4 | 90.96 (15) |
C10A—N4—S5—C6 | −18.15 (13) | C6—C6A—C10A—C10 | −157.21 (15) |
C3—N4—S5—C6 | −136.32 (14) | C7—C6A—C10A—C10 | 75.06 (17) |
O2—S5—C6—C6A | 111.18 (14) | C11—C6A—C10A—C10 | −31.99 (16) |
O3—S5—C6—C6A | −117.48 (14) | O4—C10—C10A—O1 | −57.2 (2) |
N4—S5—C6—C6A | −1.90 (15) | C9—C10—C10A—O1 | 117.88 (16) |
S5—C6—C6A—C7 | 140.80 (15) | O4—C10—C10A—N4 | 62.1 (3) |
S5—C6—C6A—C10A | 20.18 (18) | C9—C10—C10A—N4 | −122.82 (17) |
S5—C6—C6A—C11 | −94.80 (17) | O4—C10—C10A—C6A | −179.5 (2) |
C6—C6A—C7—C8 | 170.03 (17) | C9—C10—C10A—C6A | −4.45 (18) |
C10A—C6A—C7—C8 | −68.70 (19) | C10—C9—C11—C12 | −173.57 (16) |
C11—C6A—C7—C8 | 38.15 (19) | C8—C9—C11—C12 | −64.1 (2) |
C6A—C7—C8—C9 | −4.1 (2) | C10—C9—C11—C13 | 63.6 (2) |
C7—C8—C9—C10 | 73.6 (2) | C8—C9—C11—C13 | 173.14 (17) |
C7—C8—C9—C11 | −31.8 (2) | C10—C9—C11—C6A | −56.91 (16) |
C8—C9—C10—O4 | 107.2 (3) | C8—C9—C11—C6A | 52.58 (16) |
C11—C9—C10—O4 | −145.5 (2) | C6—C6A—C11—C12 | −70.3 (2) |
C8—C9—C10—C10A | −67.45 (19) | C7—C6A—C11—C12 | 61.5 (2) |
C11—C9—C10—C10A | 39.78 (18) | C10A—C6A—C11—C12 | 171.69 (16) |
C2—O1—C10A—N4 | −30.03 (18) | C6—C6A—C11—C13 | 55.2 (2) |
C2—O1—C10A—C6A | −150.46 (16) | C7—C6A—C11—C13 | −172.90 (16) |
C2—O1—C10A—C10 | 95.28 (17) | C10A—C6A—C11—C13 | −62.74 (19) |
C3—N4—C10A—O1 | 32.85 (17) | C6—C6A—C11—C9 | 172.50 (14) |
S5—N4—C10A—O1 | −91.40 (13) | C7—C6A—C11—C9 | −55.64 (15) |
C3—N4—C10A—C6A | 157.06 (14) | C10A—C6A—C11—C9 | 54.52 (14) |
S5—N4—C10A—C6A | 32.80 (16) |
D—H···A | D—H | H···A | D···A | D—H···A |
C6—H6A···O2i | 0.90 (3) | 2.57 (3) | 3.368 (2) | 148 (2) |
C6—H6B···O3ii | 0.99 (2) | 2.41 (2) | 3.390 (3) | 174 (2) |
C13—H13A···O1iii | 1.05 (3) | 2.60 (3) | 3.499 (3) | 143 (2) |
C3—H3B···O3iv | 0.94 (3) | 2.70 (3) | 3.409 (3) | 133 (2) |
C8—H8B···O4v | 0.96 (2) | 2.72 (2) | 3.487 (3) | 137 (2) |
C2—H2A···O2vi | 1.06 (3) | 2.75 (3) | 3.111 (3) | 100 (2) |
C3—H3A···O2vi | 0.94 (2) | 2.73 (2) | 3.137 (2) | 107 (2) |
Symmetry codes: (i) −x, y+1/2, −z; (ii) −x, y−1/2, −z; (iii) x, y−1, z; (iv) −x+1, y−1/2, −z; (v) −x+1, y+1/2, −z+1; (vi) −x+1, y+1/2, −z. |
C13H19NO4S | F(000) = 304 |
Mr = 285.35 | Dx = 1.447 Mg m−3 |
Monoclinic, P21 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2yb | Cell parameters from 3030 reflections |
a = 7.6970 (9) Å | θ = 1.0–27.9° |
b = 6.9954 (8) Å | µ = 0.26 mm−1 |
c = 12.2852 (13) Å | T = 210 K |
β = 98.145 (5)° | Plate, colorless |
V = 654.81 (13) Å3 | 0.22 × 0.14 × 0.07 mm |
Z = 2 |
Nonius KappaCCD diffractometer | 3084 independent reflections |
Radiation source: fine-focus sealed tube | 2783 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.028 |
Detector resolution: 9 pixels mm-1 | θmax = 27.9°, θmin = 2.7° |
CCD ϕ and ω scans | h = −10→10 |
Absorption correction: multi-scan (SCALEPACK; Otwinowski & Minor, 1997) | k = −9→8 |
Tmin = 0.946, Tmax = 0.982 | l = −16→16 |
15564 measured reflections |
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 | All H-atom parameters refined |
wR(F2) = 0.076 | w = 1/[σ2(Fo2) + (0.0406P)2 + 0.037P] where P = (Fo2 + 2Fc2)/3 |
S = 1.04 | (Δ/σ)max = 0.006 |
3084 reflections | Δρmax = 0.19 e Å−3 |
249 parameters | Δρmin = −0.26 e Å−3 |
1 restraint | Absolute structure: Flack (1983) |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: −0.01 (6) |
C13H19NO4S | V = 654.81 (13) Å3 |
Mr = 285.35 | Z = 2 |
Monoclinic, P21 | Mo Kα radiation |
a = 7.6970 (9) Å | µ = 0.26 mm−1 |
b = 6.9954 (8) Å | T = 210 K |
c = 12.2852 (13) Å | 0.22 × 0.14 × 0.07 mm |
β = 98.145 (5)° |
Nonius KappaCCD diffractometer | 3084 independent reflections |
Absorption correction: multi-scan (SCALEPACK; Otwinowski & Minor, 1997) | 2783 reflections with I > 2σ(I) |
Tmin = 0.946, Tmax = 0.982 | Rint = 0.028 |
15564 measured reflections |
R[F2 > 2σ(F2)] = 0.031 | All H-atom parameters refined |
wR(F2) = 0.076 | Δρmax = 0.19 e Å−3 |
S = 1.04 | Δρmin = −0.26 e Å−3 |
3084 reflections | Absolute structure: Flack (1983) |
249 parameters | Absolute structure parameter: −0.01 (6) |
1 restraint |
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 | ||
O1 | 0.34596 (16) | 0.81283 (17) | 0.31615 (10) | 0.0275 (3) | |
C2 | 0.5257 (2) | 0.8774 (3) | 0.32130 (16) | 0.0343 (4) | |
H2A | 0.605 (3) | 0.795 (4) | 0.376 (2) | 0.054 (7)* | |
H2B | 0.537 (3) | 1.003 (4) | 0.3576 (19) | 0.041 (6)* | |
C3 | 0.5817 (3) | 0.8787 (3) | 0.20777 (17) | 0.0355 (4) | |
H3A | 0.511 (3) | 0.978 (3) | 0.1662 (18) | 0.043 (6)* | |
H3B | 0.703 (3) | 0.910 (3) | 0.2151 (16) | 0.032 (5)* | |
C4 | 0.5537 (2) | 0.6861 (3) | 0.15377 (15) | 0.0312 (4) | |
H4A | 0.567 (2) | 0.682 (3) | 0.0802 (18) | 0.034 (5)* | |
H4B | 0.627 (3) | 0.584 (3) | 0.1878 (18) | 0.034 (6)* | |
N5 | 0.37493 (19) | 0.6134 (2) | 0.16208 (11) | 0.0254 (3) | |
S6 | 0.21759 (5) | 0.66565 (6) | 0.05877 (3) | 0.02599 (11) | |
O2 | 0.20787 (18) | 0.5152 (2) | −0.02146 (11) | 0.0392 (4) | |
O3 | 0.23942 (19) | 0.8555 (2) | 0.01740 (11) | 0.0373 (3) | |
C7 | 0.0386 (2) | 0.6551 (3) | 0.13706 (13) | 0.0254 (3) | |
H7A | −0.002 (3) | 0.778 (4) | 0.1410 (18) | 0.045 (7)* | |
H7B | −0.052 (3) | 0.566 (3) | 0.1044 (18) | 0.033 (6)* | |
C7A | 0.1152 (2) | 0.5826 (2) | 0.25063 (13) | 0.0230 (3) | |
C8 | 0.0402 (2) | 0.6627 (4) | 0.35040 (13) | 0.0292 (3) | |
H8A | −0.081 (3) | 0.650 (3) | 0.3388 (15) | 0.029 (5)* | |
H8B | 0.070 (3) | 0.793 (4) | 0.3553 (19) | 0.044 (6)* | |
C9 | 0.1304 (3) | 0.5367 (3) | 0.44586 (15) | 0.0372 (5) | |
H9A | 0.216 (3) | 0.611 (3) | 0.5005 (18) | 0.042 (6)* | |
H9B | 0.043 (3) | 0.478 (3) | 0.4880 (19) | 0.044 (6)* | |
C10 | 0.2276 (2) | 0.3814 (3) | 0.38750 (15) | 0.0316 (4) | |
H10 | 0.257 (3) | 0.264 (4) | 0.4290 (19) | 0.044 (6)* | |
C11 | 0.3879 (2) | 0.4734 (3) | 0.35319 (14) | 0.0295 (4) | |
O4 | 0.54103 (19) | 0.4392 (2) | 0.38397 (12) | 0.0441 (4) | |
C11A | 0.3155 (2) | 0.6296 (2) | 0.26794 (13) | 0.0232 (4) | |
C12 | 0.1124 (2) | 0.3622 (2) | 0.27305 (14) | 0.0274 (4) | |
C13 | −0.0722 (3) | 0.2839 (3) | 0.27983 (19) | 0.0382 (5) | |
H13A | −0.069 (3) | 0.155 (5) | 0.296 (2) | 0.069 (8)* | |
H13B | −0.139 (3) | 0.298 (3) | 0.2087 (18) | 0.029 (5)* | |
H13C | −0.142 (3) | 0.360 (4) | 0.327 (2) | 0.061 (8)* | |
C14 | 0.1956 (3) | 0.2329 (3) | 0.19402 (19) | 0.0352 (4) | |
H14A | 0.189 (4) | 0.086 (4) | 0.223 (2) | 0.068 (9)* | |
H14B | 0.328 (3) | 0.272 (3) | 0.1864 (17) | 0.037 (6)* | |
H14C | 0.131 (3) | 0.246 (3) | 0.1187 (19) | 0.038 (6)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0282 (6) | 0.0272 (7) | 0.0269 (6) | −0.0032 (5) | 0.0027 (5) | −0.0051 (5) |
C2 | 0.0300 (10) | 0.0380 (11) | 0.0329 (10) | −0.0073 (8) | −0.0017 (8) | −0.0048 (9) |
C3 | 0.0264 (10) | 0.0412 (11) | 0.0387 (10) | −0.0072 (9) | 0.0033 (8) | 0.0020 (9) |
C4 | 0.0235 (8) | 0.0415 (11) | 0.0290 (9) | 0.0000 (8) | 0.0046 (6) | 0.0027 (9) |
N5 | 0.0214 (7) | 0.0326 (8) | 0.0217 (6) | 0.0025 (5) | 0.0017 (5) | 0.0005 (5) |
S6 | 0.0263 (2) | 0.0322 (2) | 0.01902 (18) | 0.00068 (19) | 0.00185 (14) | 0.00044 (19) |
O2 | 0.0391 (8) | 0.0504 (9) | 0.0276 (7) | −0.0005 (7) | 0.0029 (6) | −0.0137 (6) |
O3 | 0.0376 (7) | 0.0406 (8) | 0.0328 (7) | −0.0015 (6) | 0.0017 (6) | 0.0145 (6) |
C7 | 0.0233 (8) | 0.0295 (9) | 0.0228 (7) | 0.0027 (9) | 0.0012 (6) | 0.0030 (8) |
C7A | 0.0230 (8) | 0.0240 (8) | 0.0212 (8) | 0.0016 (6) | 0.0008 (6) | 0.0003 (7) |
C8 | 0.0284 (9) | 0.0343 (9) | 0.0260 (8) | 0.0021 (9) | 0.0073 (6) | −0.0021 (9) |
C9 | 0.0427 (12) | 0.0469 (12) | 0.0231 (9) | 0.0024 (10) | 0.0082 (8) | 0.0033 (9) |
C10 | 0.0358 (10) | 0.0313 (10) | 0.0268 (9) | 0.0021 (8) | 0.0007 (7) | 0.0080 (8) |
C11 | 0.0323 (10) | 0.0307 (9) | 0.0239 (9) | 0.0042 (7) | −0.0012 (7) | 0.0005 (7) |
O4 | 0.0320 (8) | 0.0567 (10) | 0.0410 (8) | 0.0115 (7) | −0.0040 (6) | 0.0139 (7) |
C11A | 0.0219 (8) | 0.0256 (10) | 0.0216 (7) | 0.0020 (6) | 0.0017 (6) | −0.0016 (6) |
C12 | 0.0328 (10) | 0.0232 (9) | 0.0257 (9) | 0.0010 (7) | 0.0022 (7) | 0.0032 (7) |
C13 | 0.0393 (11) | 0.0355 (12) | 0.0395 (12) | −0.0074 (9) | 0.0043 (9) | 0.0047 (9) |
C14 | 0.0435 (12) | 0.0223 (9) | 0.0386 (12) | 0.0032 (8) | 0.0023 (9) | −0.0017 (8) |
O1—C11A | 1.417 (2) | C7A—C12 | 1.567 (2) |
O1—C2 | 1.449 (2) | C8—C9 | 1.550 (3) |
C2—C3 | 1.517 (3) | C8—H8A | 0.93 (2) |
C2—H2A | 1.02 (3) | C8—H8B | 0.94 (3) |
C2—H2B | 0.98 (3) | C9—C10 | 1.551 (3) |
C3—C4 | 1.504 (3) | C9—H9A | 1.02 (2) |
C3—H3A | 0.98 (2) | C9—H9B | 1.00 (2) |
C3—H3B | 0.95 (2) | C10—C11 | 1.504 (3) |
C4—N5 | 1.484 (2) | C10—C12 | 1.558 (2) |
C4—H4A | 0.92 (2) | C10—H10 | 0.97 (2) |
C4—H4B | 0.97 (2) | C11—O4 | 1.209 (2) |
N5—C11A | 1.443 (2) | C11—C11A | 1.561 (2) |
N5—S6 | 1.6659 (14) | C12—C14 | 1.532 (3) |
S6—O2 | 1.4369 (14) | C12—C13 | 1.536 (3) |
S6—O3 | 1.4405 (15) | C13—H13A | 0.93 (3) |
S6—C7 | 1.7898 (16) | C13—H13B | 0.95 (2) |
C7—C7A | 1.523 (2) | C13—H13C | 1.00 (3) |
C7—H7A | 0.92 (3) | C14—H14A | 1.09 (3) |
C7—H7B | 0.97 (2) | C14—H14B | 1.07 (2) |
C7A—C8 | 1.533 (2) | C14—H14C | 0.99 (2) |
C7A—C11A | 1.561 (2) | ||
C11A—O1—C2 | 113.64 (13) | C7A—C8—H8B | 106.9 (14) |
O1—C2—C3 | 110.84 (15) | C9—C8—H8B | 115.1 (14) |
O1—C2—H2A | 109.2 (14) | H8A—C8—H8B | 109 (2) |
C3—C2—H2A | 112.8 (14) | C8—C9—C10 | 104.01 (14) |
O1—C2—H2B | 108.6 (13) | C8—C9—H9A | 112.7 (13) |
C3—C2—H2B | 113.3 (13) | C10—C9—H9A | 110.8 (12) |
H2A—C2—H2B | 102 (2) | C8—C9—H9B | 111.4 (14) |
C4—C3—C2 | 111.02 (17) | C10—C9—H9B | 110.8 (14) |
C4—C3—H3A | 111.9 (14) | H9A—C9—H9B | 107.2 (17) |
C2—C3—H3A | 105.9 (13) | C11—C10—C9 | 107.36 (16) |
C4—C3—H3B | 108.9 (13) | C11—C10—C12 | 99.70 (14) |
C2—C3—H3B | 108.5 (12) | C9—C10—C12 | 103.16 (15) |
H3A—C3—H3B | 110.6 (17) | C11—C10—H10 | 111.5 (14) |
N5—C4—C3 | 110.67 (15) | C9—C10—H10 | 116.0 (13) |
N5—C4—H4A | 106.6 (12) | C12—C10—H10 | 117.5 (14) |
C3—C4—H4A | 115.4 (15) | O4—C11—C10 | 129.01 (17) |
N5—C4—H4B | 101.7 (12) | O4—C11—C11A | 126.03 (18) |
C3—C4—H4B | 115.8 (13) | C10—C11—C11A | 104.95 (14) |
H4A—C4—H4B | 105.4 (19) | O1—C11A—N5 | 113.12 (13) |
C11A—N5—C4 | 116.79 (14) | O1—C11A—C11 | 109.29 (13) |
C11A—N5—S6 | 112.34 (11) | N5—C11A—C11 | 114.89 (14) |
C4—N5—S6 | 116.96 (12) | O1—C11A—C7A | 110.46 (13) |
O2—S6—O3 | 115.52 (9) | N5—C11A—C7A | 107.08 (13) |
O2—S6—N5 | 108.87 (8) | C11—C11A—C7A | 101.30 (13) |
O3—S6—N5 | 111.26 (8) | C14—C12—C13 | 107.26 (17) |
O2—S6—C7 | 111.66 (9) | C14—C12—C10 | 112.78 (15) |
O3—S6—C7 | 111.40 (9) | C13—C12—C10 | 113.21 (15) |
N5—S6—C7 | 96.51 (7) | C14—C12—C7A | 116.88 (15) |
C7A—C7—S6 | 106.17 (11) | C13—C12—C7A | 113.35 (15) |
C7A—C7—H7A | 110.8 (14) | C10—C12—C7A | 93.07 (13) |
S6—C7—H7A | 106.6 (14) | C12—C13—H13A | 111.1 (17) |
C7A—C7—H7B | 109.0 (13) | C12—C13—H13B | 107.1 (12) |
S6—C7—H7B | 111.3 (12) | H13A—C13—H13B | 107 (2) |
H7A—C7—H7B | 112.8 (19) | C12—C13—H13C | 114.8 (15) |
C7—C7A—C8 | 118.03 (14) | H13A—C13—H13C | 113 (2) |
C7—C7A—C11A | 107.54 (13) | H13B—C13—H13C | 102.6 (19) |
C8—C7A—C11A | 106.88 (14) | C12—C14—H14A | 108.1 (15) |
C7—C7A—C12 | 118.40 (15) | C12—C14—H14B | 113.0 (12) |
C8—C7A—C12 | 101.71 (15) | H14A—C14—H14B | 111.1 (19) |
C11A—C7A—C12 | 102.81 (13) | C12—C14—H14C | 109.5 (12) |
C7A—C8—C9 | 102.59 (15) | H14A—C14—H14C | 110.5 (19) |
C7A—C8—H8A | 109.0 (12) | H14B—C14—H14C | 104.7 (17) |
C9—C8—H8A | 113.2 (13) | ||
C11A—O1—C2—C3 | 56.7 (2) | S6—N5—C11A—C11 | 141.53 (13) |
O1—C2—C3—C4 | −54.8 (2) | C4—N5—C11A—C7A | 169.07 (14) |
C2—C3—C4—N5 | 48.5 (2) | S6—N5—C11A—C7A | 29.89 (16) |
C3—C4—N5—C11A | −45.7 (2) | O4—C11—C11A—O1 | −71.5 (2) |
C3—C4—N5—S6 | 91.56 (17) | C10—C11—C11A—O1 | 107.79 (15) |
C11A—N5—S6—O2 | −129.82 (12) | O4—C11—C11A—N5 | 56.9 (3) |
C4—N5—S6—O2 | 91.08 (15) | C10—C11—C11A—N5 | −123.83 (15) |
C11A—N5—S6—O3 | 101.75 (13) | O4—C11—C11A—C7A | 171.91 (19) |
C4—N5—S6—O3 | −37.34 (15) | C10—C11—C11A—C7A | −8.80 (16) |
C11A—N5—S6—C7 | −14.25 (13) | C7—C7A—C11A—O1 | 89.74 (16) |
C4—N5—S6—C7 | −153.35 (15) | C8—C7A—C11A—O1 | −37.92 (18) |
O2—S6—C7—C7A | 106.76 (14) | C12—C7A—C11A—O1 | −144.56 (13) |
O3—S6—C7—C7A | −122.43 (13) | C7—C7A—C11A—N5 | −33.84 (18) |
N5—S6—C7—C7A | −6.54 (14) | C8—C7A—C11A—N5 | −161.50 (15) |
S6—C7—C7A—C8 | 144.40 (15) | C12—C7A—C11A—N5 | 91.86 (15) |
S6—C7—C7A—C11A | 23.51 (17) | C7—C7A—C11A—C11 | −154.53 (14) |
S6—C7—C7A—C12 | −92.28 (17) | C8—C7A—C11A—C11 | 77.80 (16) |
C7—C7A—C8—C9 | 172.40 (17) | C12—C7A—C11A—C11 | −28.84 (15) |
C11A—C7A—C8—C9 | −66.38 (19) | C11—C10—C12—C14 | 62.24 (19) |
C12—C7A—C8—C9 | 41.05 (18) | C9—C10—C12—C14 | 172.77 (16) |
C7A—C8—C9—C10 | −7.3 (2) | C11—C10—C12—C13 | −175.73 (16) |
C8—C9—C10—C11 | 75.61 (19) | C9—C10—C12—C13 | −65.2 (2) |
C8—C9—C10—C12 | −29.1 (2) | C11—C10—C12—C7A | −58.67 (15) |
C9—C10—C11—O4 | 115.4 (2) | C9—C10—C12—C7A | 51.87 (16) |
C12—C10—C11—O4 | −137.4 (2) | C7—C7A—C12—C14 | 54.4 (2) |
C9—C10—C11—C11A | −63.81 (17) | C8—C7A—C12—C14 | −174.46 (15) |
C12—C10—C11—C11A | 43.37 (16) | C11A—C7A—C12—C14 | −63.90 (18) |
C2—O1—C11A—N5 | −52.18 (18) | C7—C7A—C12—C13 | −71.1 (2) |
C2—O1—C11A—C11 | 77.18 (17) | C8—C7A—C12—C13 | 59.99 (19) |
C2—O1—C11A—C7A | −172.20 (14) | C11A—C7A—C12—C13 | 170.56 (14) |
C4—N5—C11A—O1 | 47.1 (2) | C7—C7A—C12—C10 | 171.93 (14) |
S6—N5—C11A—O1 | −92.03 (14) | C8—C7A—C12—C10 | −56.95 (15) |
C4—N5—C11A—C11 | −79.30 (19) | C11A—C7A—C12—C10 | 53.62 (14) |
D—H···A | D—H | H···A | D···A | D—H···A |
C7—H7A···O2i | 0.92 (3) | 2.60 (2) | 3.346 (2) | 139 (2) |
C7—H7B···O3ii | 0.97 (2) | 2.43 (2) | 3.380 (2) | 166 (2) |
C14—H14A···O1iii | 1.09 (3) | 2.46 (3) | 3.425 (2) | 147 (2) |
C13—H13C···O4iv | 1.00 (3) | 2.69 (3) | 3.572 (3) | 147 (2) |
C3—H3B···O2v | 0.95 (2) | 2.67 (2) | 3.134 (2) | 111 (1) |
Symmetry codes: (i) −x, y+1/2, −z; (ii) −x, y−1/2, −z; (iii) x, y−1, z; (iv) x−1, y, z; (v) −x+1, y+1/2, −z. |
C12H19NO4S | F(000) = 584 |
Mr = 273.34 | Dx = 1.498 Mg m−3 |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 5567 reflections |
a = 7.3091 (8) Å | θ = 1.0–27.9° |
b = 10.9033 (12) Å | µ = 0.27 mm−1 |
c = 15.2110 (16) Å | T = 190 K |
V = 1212.2 (2) Å3 | Plate, colorless |
Z = 4 | 0.26 × 0.24 × 0.11 mm |
Nonius KappaCCD diffractometer | 2898 independent reflections |
Radiation source: fine-focus sealed tube | 2662 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.041 |
Detector resolution: 9 pixels mm-1 | θmax = 27.9°, θmin = 3.1° |
CCD ϕ and ω scans | h = −9→9 |
Absorption correction: multi-scan (SCALEPACK; Otwinowski & Minor, 1997) | k = −14→14 |
Tmin = 0.932, Tmax = 0.970 | l = −20→19 |
30886 measured reflections |
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 | All H-atom parameters refined |
wR(F2) = 0.077 | w = 1/[σ2(Fo2) + (0.0428P)2 + 0.2065P] where P = (Fo2 + 2Fc2)/3 |
S = 1.06 | (Δ/σ)max < 0.001 |
2898 reflections | Δρmax = 0.20 e Å−3 |
240 parameters | Δρmin = −0.32 e Å−3 |
0 restraints | Absolute structure: Flack (1983) |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: −0.01 (6) |
C12H19NO4S | V = 1212.2 (2) Å3 |
Mr = 273.34 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 7.3091 (8) Å | µ = 0.27 mm−1 |
b = 10.9033 (12) Å | T = 190 K |
c = 15.2110 (16) Å | 0.26 × 0.24 × 0.11 mm |
Nonius KappaCCD diffractometer | 2898 independent reflections |
Absorption correction: multi-scan (SCALEPACK; Otwinowski & Minor, 1997) | 2662 reflections with I > 2σ(I) |
Tmin = 0.932, Tmax = 0.970 | Rint = 0.041 |
30886 measured reflections |
R[F2 > 2σ(F2)] = 0.031 | All H-atom parameters refined |
wR(F2) = 0.077 | Δρmax = 0.20 e Å−3 |
S = 1.06 | Δρmin = −0.32 e Å−3 |
2898 reflections | Absolute structure: Flack (1983) |
240 parameters | Absolute structure parameter: −0.01 (6) |
0 restraints |
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. Several low angle reflections were omitted due to beam-stop shadowing effects. |
x | y | z | Uiso*/Ueq | ||
O1 | 0.05367 (16) | −0.01982 (11) | 0.20184 (8) | 0.0239 (3) | |
C2 | 0.0018 (3) | 0.04165 (18) | 0.28189 (13) | 0.0292 (4) | |
H2A | 0.046 (3) | −0.009 (2) | 0.3305 (15) | 0.041 (6)* | |
H2B | −0.134 (4) | 0.049 (2) | 0.2828 (16) | 0.048 (7)* | |
C3 | 0.1064 (3) | 0.16394 (16) | 0.28040 (12) | 0.0272 (4) | |
H3A | 0.025 (4) | 0.238 (2) | 0.2729 (15) | 0.045 (7)* | |
H3B | 0.172 (3) | 0.1743 (19) | 0.3364 (14) | 0.029 (5)* | |
N4 | 0.2392 (2) | 0.14833 (12) | 0.20731 (9) | 0.0198 (3) | |
S5 | 0.19278 (5) | 0.22720 (3) | 0.11503 (3) | 0.02080 (10) | |
O2 | 0.33036 (17) | 0.32056 (11) | 0.10442 (8) | 0.0298 (3) | |
O3 | 0.00667 (16) | 0.26972 (11) | 0.11457 (9) | 0.0303 (3) | |
C6 | 0.2259 (3) | 0.10489 (15) | 0.03780 (11) | 0.0221 (3) | |
H6A | 0.103 (3) | 0.0837 (19) | 0.0140 (13) | 0.028 (5)* | |
H6B | 0.306 (3) | 0.137 (2) | −0.0085 (13) | 0.030 (5)* | |
C6A | 0.2996 (2) | −0.00233 (14) | 0.09106 (10) | 0.0188 (3) | |
C7 | 0.2371 (3) | −0.13191 (16) | 0.06543 (12) | 0.0258 (4) | |
H7B | 0.260 (3) | −0.149 (2) | 0.0037 (13) | 0.029 (5)* | |
H7A | 0.103 (3) | −0.1458 (18) | 0.0763 (12) | 0.025 (5)* | |
C8 | 0.3651 (3) | −0.21502 (16) | 0.12152 (14) | 0.0296 (4) | |
H8A | 0.301 (3) | −0.265 (2) | 0.1647 (16) | 0.039 (6)* | |
H8B | 0.433 (3) | −0.271 (2) | 0.0884 (14) | 0.037 (6)* | |
C9 | 0.4906 (3) | −0.12175 (15) | 0.16942 (11) | 0.0256 (4) | |
H9 | 0.610 (3) | −0.1563 (19) | 0.1901 (14) | 0.036 (6)* | |
C10 | 0.3735 (3) | −0.06328 (16) | 0.24234 (11) | 0.0238 (4) | |
H10 | 0.306 (3) | −0.1296 (17) | 0.2729 (12) | 0.017 (4)* | |
O4 | 0.4704 (2) | 0.00792 (13) | 0.30538 (8) | 0.0323 (3) | |
H4 | 0.527 (4) | −0.046 (3) | 0.3356 (18) | 0.060 (8)* | |
C10A | 0.2387 (2) | 0.01669 (14) | 0.18747 (10) | 0.0184 (3) | |
C11 | 0.5124 (2) | −0.01861 (15) | 0.10017 (10) | 0.0219 (3) | |
C12 | 0.6050 (3) | −0.0630 (2) | 0.01531 (13) | 0.0319 (4) | |
H12A | 0.546 (4) | −0.135 (3) | −0.0138 (16) | 0.051 (7)* | |
H12B | 0.732 (4) | −0.082 (3) | 0.0263 (19) | 0.061 (8)* | |
H12C | 0.604 (3) | 0.005 (2) | −0.0270 (15) | 0.036 (6)* | |
C13 | 0.6195 (3) | 0.09444 (17) | 0.12991 (13) | 0.0272 (4) | |
H13A | 0.746 (4) | 0.067 (2) | 0.1335 (16) | 0.049 (7)* | |
H13B | 0.580 (3) | 0.1276 (19) | 0.1844 (14) | 0.032 (5)* | |
H13C | 0.612 (3) | 0.155 (2) | 0.0838 (15) | 0.041 (6)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0212 (6) | 0.0236 (6) | 0.0268 (6) | −0.0025 (5) | 0.0034 (5) | −0.0005 (5) |
C2 | 0.0285 (10) | 0.0302 (10) | 0.0291 (9) | −0.0002 (8) | 0.0071 (8) | −0.0008 (7) |
C3 | 0.0338 (10) | 0.0240 (9) | 0.0238 (8) | 0.0040 (7) | 0.0069 (8) | −0.0022 (7) |
N4 | 0.0247 (7) | 0.0164 (6) | 0.0182 (6) | 0.0023 (5) | 0.0002 (5) | 0.0010 (5) |
S5 | 0.0243 (2) | 0.01588 (17) | 0.02222 (18) | 0.00072 (15) | −0.00416 (17) | 0.00117 (14) |
O2 | 0.0387 (7) | 0.0217 (6) | 0.0288 (6) | −0.0103 (5) | −0.0044 (6) | 0.0048 (5) |
O3 | 0.0273 (6) | 0.0288 (6) | 0.0347 (6) | 0.0099 (5) | −0.0066 (6) | 0.0006 (6) |
C6 | 0.0265 (9) | 0.0200 (7) | 0.0197 (7) | −0.0003 (7) | −0.0032 (7) | 0.0001 (6) |
C6A | 0.0208 (7) | 0.0165 (7) | 0.0193 (7) | 0.0008 (7) | 0.0001 (6) | 0.0008 (5) |
C7 | 0.0303 (9) | 0.0201 (8) | 0.0270 (8) | −0.0023 (7) | −0.0008 (7) | −0.0038 (7) |
C8 | 0.0368 (9) | 0.0173 (8) | 0.0346 (9) | 0.0011 (7) | 0.0006 (8) | −0.0001 (8) |
C9 | 0.0259 (9) | 0.0217 (8) | 0.0292 (8) | 0.0062 (7) | 0.0000 (7) | 0.0034 (7) |
C10 | 0.0277 (8) | 0.0232 (8) | 0.0204 (8) | 0.0026 (7) | −0.0007 (7) | 0.0036 (6) |
O4 | 0.0389 (8) | 0.0326 (7) | 0.0253 (6) | 0.0064 (6) | −0.0109 (6) | 0.0009 (5) |
C10A | 0.0190 (7) | 0.0165 (7) | 0.0196 (7) | 0.0003 (6) | 0.0004 (6) | 0.0006 (6) |
C11 | 0.0195 (7) | 0.0228 (7) | 0.0234 (8) | 0.0013 (6) | 0.0009 (6) | 0.0030 (6) |
C12 | 0.0299 (10) | 0.0331 (10) | 0.0327 (10) | 0.0049 (8) | 0.0069 (8) | 0.0004 (8) |
C13 | 0.0219 (9) | 0.0272 (9) | 0.0326 (10) | −0.0033 (7) | −0.0027 (7) | 0.0020 (7) |
O1—C10A | 1.427 (2) | C7—H7B | 0.97 (2) |
O1—C2 | 1.441 (2) | C7—H7A | 1.01 (2) |
C2—C3 | 1.537 (3) | C8—C9 | 1.551 (3) |
C2—H2A | 0.98 (2) | C8—H8A | 0.97 (2) |
C2—H2B | 1.00 (3) | C8—H8B | 0.93 (2) |
C3—N4 | 1.485 (2) | C9—C10 | 1.539 (2) |
C3—H3A | 1.01 (2) | C9—C11 | 1.549 (2) |
C3—H3B | 0.99 (2) | C9—H9 | 1.00 (2) |
N4—C10A | 1.467 (2) | C10—O4 | 1.423 (2) |
N4—S5 | 1.6807 (14) | C10—C10A | 1.558 (2) |
S5—O3 | 1.4371 (12) | C10—H10 | 0.991 (19) |
S5—O2 | 1.4399 (13) | O4—H4 | 0.85 (3) |
S5—C6 | 1.7937 (17) | C11—C13 | 1.529 (2) |
C6—C6A | 1.521 (2) | C11—C12 | 1.536 (2) |
C6—H6A | 0.99 (2) | C12—H12A | 1.00 (3) |
C6—H6B | 0.98 (2) | C12—H12B | 0.97 (3) |
C6A—C7 | 1.535 (2) | C12—H12C | 0.98 (2) |
C6A—C10A | 1.546 (2) | C13—H13A | 0.97 (3) |
C6A—C11 | 1.572 (2) | C13—H13B | 0.95 (2) |
C7—C8 | 1.557 (3) | C13—H13C | 0.97 (2) |
C10A—O1—C2 | 104.44 (13) | C7—C8—H8A | 113.9 (14) |
O1—C2—C3 | 105.08 (14) | C9—C8—H8B | 111.8 (14) |
O1—C2—H2A | 106.9 (13) | C7—C8—H8B | 113.8 (14) |
C3—C2—H2A | 109.5 (14) | H8A—C8—H8B | 104.8 (18) |
O1—C2—H2B | 108.1 (15) | C10—C9—C11 | 104.28 (13) |
C3—C2—H2B | 115.5 (15) | C10—C9—C8 | 106.32 (15) |
H2A—C2—H2B | 111 (2) | C11—C9—C8 | 102.56 (14) |
N4—C3—C2 | 103.69 (13) | C10—C9—H9 | 114.4 (13) |
N4—C3—H3A | 113.0 (14) | C11—C9—H9 | 113.4 (13) |
C2—C3—H3A | 113.8 (14) | C8—C9—H9 | 114.6 (12) |
N4—C3—H3B | 109.9 (12) | O4—C10—C9 | 115.77 (15) |
C2—C3—H3B | 109.3 (12) | O4—C10—C10A | 111.74 (14) |
H3A—C3—H3B | 107.1 (17) | C9—C10—C10A | 101.38 (13) |
C10A—N4—C3 | 105.36 (13) | O4—C10—H10 | 109.3 (10) |
C10A—N4—S5 | 109.17 (10) | C9—C10—H10 | 108.2 (11) |
C3—N4—S5 | 115.77 (11) | C10A—C10—H10 | 110.2 (11) |
O3—S5—O2 | 115.62 (8) | C10—O4—H4 | 103.1 (18) |
O3—S5—N4 | 111.10 (8) | O1—C10A—N4 | 104.09 (13) |
O2—S5—N4 | 108.33 (7) | O1—C10A—C6A | 112.36 (13) |
O3—S5—C6 | 111.37 (8) | N4—C10A—C6A | 109.02 (12) |
O2—S5—C6 | 110.97 (8) | O1—C10A—C10 | 111.16 (13) |
N4—S5—C6 | 98.01 (7) | N4—C10A—C10 | 115.86 (13) |
C6A—C6—S5 | 105.69 (11) | C6A—C10A—C10 | 104.56 (13) |
C6A—C6—H6A | 109.5 (12) | C13—C11—C12 | 106.11 (15) |
S5—C6—H6A | 106.9 (12) | C13—C11—C9 | 115.90 (14) |
C6A—C6—H6B | 116.5 (13) | C12—C11—C9 | 112.83 (14) |
S5—C6—H6B | 106.6 (12) | C13—C11—C6A | 116.22 (14) |
H6A—C6—H6B | 111.0 (17) | C12—C11—C6A | 113.43 (14) |
C6—C6A—C7 | 117.84 (13) | C9—C11—C6A | 92.29 (12) |
C6—C6A—C10A | 107.48 (12) | C11—C12—H12A | 115.5 (15) |
C7—C6A—C10A | 106.19 (13) | C11—C12—H12B | 110.3 (17) |
C6—C6A—C11 | 118.95 (14) | H12A—C12—H12B | 109 (2) |
C7—C6A—C11 | 102.30 (13) | C11—C12—H12C | 108.2 (13) |
C10A—C6A—C11 | 102.48 (12) | H12A—C12—H12C | 108 (2) |
C6A—C7—C8 | 102.57 (14) | H12B—C12—H12C | 106 (2) |
C6A—C7—H7B | 112.0 (13) | C11—C13—H13A | 105.0 (15) |
C8—C7—H7B | 108.1 (13) | C11—C13—H13B | 114.1 (14) |
C6A—C7—H7A | 112.8 (11) | H13A—C13—H13B | 111 (2) |
C8—C7—H7A | 114.1 (11) | C11—C13—H13C | 108.0 (14) |
H7B—C7—H7A | 107.2 (17) | H13A—C13—H13C | 108 (2) |
C9—C8—C7 | 103.37 (14) | H13B—C13—H13C | 110.7 (18) |
C9—C8—H8A | 109.4 (14) | ||
C10A—O1—C2—C3 | 33.40 (17) | C3—N4—C10A—C10 | −87.40 (17) |
O1—C2—C3—N4 | −11.49 (19) | S5—N4—C10A—C10 | 147.66 (12) |
C2—C3—N4—C10A | −13.91 (18) | C6—C6A—C10A—O1 | 79.97 (16) |
C2—C3—N4—S5 | 106.80 (14) | C7—C6A—C10A—O1 | −46.98 (16) |
C10A—N4—S5—O3 | 102.75 (12) | C11—C6A—C10A—O1 | −153.92 (13) |
C3—N4—S5—O3 | −15.88 (15) | C6—C6A—C10A—N4 | −34.88 (17) |
C10A—N4—S5—O2 | −129.22 (11) | C7—C6A—C10A—N4 | −161.83 (13) |
C3—N4—S5—O2 | 112.16 (13) | C11—C6A—C10A—N4 | 91.23 (14) |
C10A—N4—S5—C6 | −13.92 (13) | C6—C6A—C10A—C10 | −159.36 (13) |
C3—N4—S5—C6 | −132.55 (13) | C7—C6A—C10A—C10 | 73.69 (16) |
O3—S5—C6—C6A | −122.90 (12) | C11—C6A—C10A—C10 | −33.25 (15) |
O2—S5—C6—C6A | 106.76 (12) | O4—C10—C10A—O1 | −116.56 (15) |
N4—S5—C6—C6A | −6.45 (13) | C9—C10—C10A—O1 | 119.54 (15) |
S5—C6—C6A—C7 | 143.47 (13) | O4—C10—C10A—N4 | 2.0 (2) |
S5—C6—C6A—C10A | 23.69 (15) | C9—C10—C10A—N4 | −121.92 (15) |
S5—C6—C6A—C11 | −91.97 (15) | O4—C10—C10A—C6A | 121.98 (14) |
C6—C6A—C7—C8 | 170.13 (15) | C9—C10—C10A—C6A | −1.92 (16) |
C10A—C6A—C7—C8 | −69.42 (16) | C10—C9—C11—C13 | 64.87 (18) |
C11—C6A—C7—C8 | 37.65 (17) | C8—C9—C11—C13 | 175.58 (15) |
C6A—C7—C8—C9 | −2.28 (19) | C10—C9—C11—C12 | −172.51 (15) |
C7—C8—C9—C10 | 74.77 (17) | C8—C9—C11—C12 | −61.79 (18) |
C7—C8—C9—C11 | −34.41 (18) | C10—C9—C11—C6A | −55.86 (15) |
C11—C9—C10—O4 | −83.66 (17) | C8—C9—C11—C6A | 54.86 (15) |
C8—C9—C10—O4 | 168.38 (14) | C6—C6A—C11—C13 | 50.92 (19) |
C11—C9—C10—C10A | 37.45 (16) | C7—C6A—C11—C13 | −177.27 (14) |
C8—C9—C10—C10A | −70.50 (16) | C10A—C6A—C11—C13 | −67.36 (16) |
C2—O1—C10A—N4 | −42.78 (15) | C6—C6A—C11—C12 | −72.48 (19) |
C2—O1—C10A—C6A | −160.59 (13) | C7—C6A—C11—C12 | 59.34 (17) |
C2—O1—C10A—C10 | 82.62 (15) | C10A—C6A—C11—C12 | 169.24 (14) |
C3—N4—C10A—O1 | 34.97 (16) | C6—C6A—C11—C9 | 171.39 (13) |
S5—N4—C10A—O1 | −89.98 (12) | C7—C6A—C11—C9 | −56.80 (14) |
C3—N4—C10A—C6A | 155.05 (14) | C10A—C6A—C11—C9 | 53.10 (13) |
S5—N4—C10A—C6A | 30.11 (15) |
D—H···A | D—H | H···A | D···A | D—H···A |
O4—H4···O2i | 0.85 (3) | 2.01 (3) | 2.860 (2) | 174 (3) |
C6—H6B···O3ii | 0.98 (2) | 2.41 (2) | 3.384 (2) | 175 (2) |
C2—H2A···O3iii | 0.98 (2) | 2.59 (2) | 3.358 (2) | 136 (2) |
C13—H13A···O1iv | 0.97 (3) | 2.65 (3) | 3.581 (2) | 160 (2) |
Symmetry codes: (i) −x+1, y−1/2, −z+1/2; (ii) x+1/2, −y+1/2, −z; (iii) −x, y−1/2, −z+1/2; (iv) x+1, y, z. |
C13H21NO4S | F(000) = 616 |
Mr = 287.37 | Dx = 1.455 Mg m−3 |
Monoclinic, C2 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: C 2y | Cell parameters from 3089 reflections |
a = 16.5474 (18) Å | θ = 1.0–27.9° |
b = 7.5668 (9) Å | µ = 0.26 mm−1 |
c = 11.5945 (13) Å | T = 210 K |
β = 115.376 (5)° | Rod, colorless |
V = 1311.7 (3) Å3 | 0.24 × 0.07 × 0.07 mm |
Z = 4 |
Nonius KappaCCD diffractometer | 3118 independent reflections |
Radiation source: fine-focus sealed tube | 2852 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.027 |
Detector resolution: 9 pixels mm-1 | θmax = 27.9°, θmin = 3.0° |
CCD ϕ and ω scans | h = −21→21 |
Absorption correction: multi-scan (SCALEPACK; Otwinowski & Minor, 1997) | k = −9→9 |
Tmin = 0.941, Tmax = 0.982 | l = −15→15 |
13727 measured reflections |
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)] = 0.032 | All H-atom parameters refined |
wR(F2) = 0.073 | w = 1/[σ2(Fo2) + (0.0378P)2 + 0.0333P] where P = (Fo2 + 2Fc2)/3 |
S = 1.05 | (Δ/σ)max = 0.004 |
3118 reflections | Δρmax = 0.16 e Å−3 |
257 parameters | Δρmin = −0.27 e Å−3 |
1 restraint | Absolute structure: Flack (1983) |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: −0.07 (5) |
C13H21NO4S | V = 1311.7 (3) Å3 |
Mr = 287.37 | Z = 4 |
Monoclinic, C2 | Mo Kα radiation |
a = 16.5474 (18) Å | µ = 0.26 mm−1 |
b = 7.5668 (9) Å | T = 210 K |
c = 11.5945 (13) Å | 0.24 × 0.07 × 0.07 mm |
β = 115.376 (5)° |
Nonius KappaCCD diffractometer | 3118 independent reflections |
Absorption correction: multi-scan (SCALEPACK; Otwinowski & Minor, 1997) | 2852 reflections with I > 2σ(I) |
Tmin = 0.941, Tmax = 0.982 | Rint = 0.027 |
13727 measured reflections |
R[F2 > 2σ(F2)] = 0.032 | All H-atom parameters refined |
wR(F2) = 0.073 | Δρmax = 0.16 e Å−3 |
S = 1.05 | Δρmin = −0.27 e Å−3 |
3118 reflections | Absolute structure: Flack (1983) |
257 parameters | Absolute structure parameter: −0.07 (5) |
1 restraint |
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. Several low angle reflections were omitted due to beam-stop shadowing effects. |
x | y | z | Uiso*/Ueq | ||
O1 | 0.66086 (8) | 0.55136 (17) | 0.38706 (12) | 0.0254 (3) | |
C2 | 0.57270 (13) | 0.6132 (3) | 0.3627 (2) | 0.0313 (4) | |
H2A | 0.5639 (12) | 0.733 (3) | 0.3183 (19) | 0.027 (5)* | |
H2B | 0.5743 (14) | 0.627 (3) | 0.451 (2) | 0.043 (6)* | |
C3 | 0.50214 (13) | 0.4847 (3) | 0.2780 (2) | 0.0313 (4) | |
H3A | 0.4432 (14) | 0.533 (3) | 0.2643 (19) | 0.024 (5)* | |
H3B | 0.5087 (13) | 0.363 (3) | 0.3236 (18) | 0.025 (5)* | |
C4 | 0.51113 (12) | 0.4590 (2) | 0.15427 (19) | 0.0262 (4) | |
H4A | 0.4737 (14) | 0.359 (3) | 0.0970 (19) | 0.036 (6)* | |
H4B | 0.4933 (14) | 0.565 (3) | 0.1011 (19) | 0.034 (6)* | |
N5 | 0.60549 (9) | 0.42143 (18) | 0.18081 (13) | 0.0200 (3) | |
S6 | 0.63508 (3) | 0.21104 (4) | 0.20406 (4) | 0.02160 (11) | |
O2 | 0.62043 (9) | 0.13265 (16) | 0.08356 (12) | 0.0310 (3) | |
O3 | 0.59476 (8) | 0.11904 (17) | 0.27415 (13) | 0.0303 (3) | |
C7 | 0.75140 (12) | 0.2471 (2) | 0.30155 (19) | 0.0271 (4) | |
H7A | 0.7628 (13) | 0.208 (3) | 0.385 (2) | 0.034 (5)* | |
H7B | 0.7852 (14) | 0.192 (3) | 0.267 (2) | 0.035 (6)* | |
C7A | 0.76530 (11) | 0.4471 (2) | 0.30387 (16) | 0.0220 (4) | |
C8 | 0.83347 (13) | 0.5280 (3) | 0.42856 (19) | 0.0283 (4) | |
H8A | 0.8927 (14) | 0.469 (3) | 0.4607 (19) | 0.024 (5)* | |
H8B | 0.8127 (13) | 0.525 (3) | 0.497 (2) | 0.024 (5)* | |
C9 | 0.83965 (13) | 0.7216 (3) | 0.38768 (18) | 0.0314 (4) | |
H9A | 0.8183 (16) | 0.803 (3) | 0.428 (2) | 0.043 (6)* | |
H9B | 0.9032 (15) | 0.755 (3) | 0.411 (2) | 0.039 (6)* | |
C10 | 0.78082 (11) | 0.7205 (3) | 0.24131 (16) | 0.0257 (4) | |
H10 | 0.7931 (13) | 0.817 (3) | 0.1967 (19) | 0.030 (5)* | |
C11 | 0.68303 (11) | 0.7233 (2) | 0.22219 (15) | 0.0231 (3) | |
H11 | 0.6745 (13) | 0.817 (3) | 0.2776 (19) | 0.023 (5)* | |
O4 | 0.61874 (9) | 0.74975 (16) | 0.09433 (13) | 0.0315 (3) | |
H4 | 0.6111 (16) | 0.864 (4) | 0.086 (2) | 0.048 (7)* | |
C11A | 0.67357 (11) | 0.5361 (2) | 0.27309 (16) | 0.0199 (3) | |
C12 | 0.79396 (12) | 0.5296 (2) | 0.20293 (19) | 0.0244 (4) | |
C13 | 0.89088 (14) | 0.4865 (3) | 0.2293 (3) | 0.0369 (5) | |
H13A | 0.9045 (16) | 0.559 (4) | 0.170 (2) | 0.054 (7)* | |
H13B | 0.8975 (15) | 0.358 (3) | 0.213 (2) | 0.043 (6)* | |
H13C | 0.9346 (16) | 0.509 (3) | 0.312 (2) | 0.041 (7)* | |
C14 | 0.73723 (14) | 0.4814 (3) | 0.06287 (19) | 0.0293 (4) | |
H14A | 0.7576 (18) | 0.558 (4) | 0.007 (3) | 0.054 (7)* | |
H14B | 0.6715 (14) | 0.510 (3) | 0.0308 (19) | 0.027 (5)* | |
H14C | 0.7473 (15) | 0.356 (3) | 0.057 (2) | 0.042 (6)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0253 (6) | 0.0300 (6) | 0.0216 (7) | 0.0004 (5) | 0.0107 (5) | −0.0028 (5) |
C2 | 0.0299 (10) | 0.0330 (11) | 0.0347 (12) | 0.0000 (8) | 0.0173 (9) | −0.0079 (8) |
C3 | 0.0265 (10) | 0.0308 (10) | 0.0406 (12) | 0.0017 (8) | 0.0182 (9) | −0.0018 (8) |
C4 | 0.0208 (9) | 0.0238 (9) | 0.0292 (10) | 0.0015 (7) | 0.0062 (8) | 0.0011 (8) |
N5 | 0.0197 (7) | 0.0147 (6) | 0.0226 (8) | −0.0003 (5) | 0.0063 (6) | −0.0004 (5) |
S6 | 0.0257 (2) | 0.01410 (17) | 0.0239 (2) | 0.00056 (17) | 0.00954 (16) | 0.00112 (17) |
O2 | 0.0442 (8) | 0.0188 (5) | 0.0279 (7) | 0.0026 (6) | 0.0135 (6) | −0.0031 (5) |
O3 | 0.0343 (7) | 0.0238 (6) | 0.0347 (8) | −0.0025 (5) | 0.0165 (6) | 0.0071 (6) |
C7 | 0.0253 (9) | 0.0244 (10) | 0.0293 (10) | 0.0039 (7) | 0.0095 (8) | 0.0054 (7) |
C7A | 0.0211 (8) | 0.0194 (8) | 0.0245 (9) | 0.0006 (7) | 0.0087 (7) | 0.0008 (7) |
C8 | 0.0237 (9) | 0.0329 (10) | 0.0229 (10) | −0.0025 (8) | 0.0047 (8) | 0.0011 (7) |
C9 | 0.0297 (9) | 0.0313 (9) | 0.0285 (9) | −0.0080 (9) | 0.0080 (7) | −0.0056 (9) |
C10 | 0.0299 (9) | 0.0204 (8) | 0.0268 (9) | −0.0053 (8) | 0.0120 (7) | 0.0001 (8) |
C11 | 0.0290 (8) | 0.0156 (7) | 0.0225 (8) | 0.0008 (8) | 0.0089 (7) | −0.0005 (8) |
O4 | 0.0371 (8) | 0.0179 (7) | 0.0284 (7) | −0.0003 (5) | 0.0035 (6) | 0.0042 (5) |
C11A | 0.0240 (9) | 0.0170 (7) | 0.0167 (8) | −0.0008 (6) | 0.0069 (7) | −0.0015 (6) |
C12 | 0.0272 (9) | 0.0229 (8) | 0.0255 (9) | −0.0027 (7) | 0.0136 (8) | −0.0007 (7) |
C13 | 0.0304 (11) | 0.0412 (12) | 0.0452 (14) | −0.0013 (9) | 0.0220 (11) | −0.0006 (10) |
C14 | 0.0417 (12) | 0.0230 (9) | 0.0283 (10) | −0.0051 (8) | 0.0199 (9) | −0.0028 (8) |
O1—C11A | 1.429 (2) | C8—C9 | 1.557 (3) |
O1—C2 | 1.440 (2) | C8—H8A | 0.99 (2) |
C2—C3 | 1.514 (3) | C8—H8B | 0.99 (2) |
C2—H2A | 1.02 (2) | C9—C10 | 1.553 (2) |
C2—H2B | 1.01 (2) | C9—H9A | 0.93 (3) |
C3—C4 | 1.517 (3) | C9—H9B | 1.00 (2) |
C3—H3A | 0.99 (2) | C10—C11 | 1.537 (2) |
C3—H3B | 1.04 (2) | C10—C12 | 1.554 (3) |
C4—N5 | 1.484 (2) | C10—H10 | 0.97 (2) |
C4—H4A | 1.02 (2) | C11—O4 | 1.421 (2) |
C4—H4B | 0.97 (2) | C11—C11A | 1.568 (3) |
N5—C11A | 1.461 (2) | C11—H11 | 1.01 (2) |
N5—S6 | 1.6534 (14) | O4—H4 | 0.87 (3) |
S6—O3 | 1.4334 (12) | C12—C14 | 1.531 (3) |
S6—O2 | 1.4396 (13) | C12—C13 | 1.533 (3) |
S6—C7 | 1.7867 (19) | C13—H13A | 0.98 (3) |
C7—C7A | 1.529 (2) | C13—H13B | 1.01 (2) |
C7—H7A | 0.96 (2) | C13—H13C | 0.93 (3) |
C7—H7B | 0.91 (2) | C14—H14A | 1.03 (3) |
C7A—C8 | 1.529 (3) | C14—H14B | 1.01 (2) |
C7A—C11A | 1.556 (2) | C14—H14C | 0.97 (3) |
C7A—C12 | 1.568 (2) | ||
C11A—O1—C2 | 112.55 (14) | H8A—C8—H8B | 108.3 (16) |
O1—C2—C3 | 110.68 (15) | C10—C9—C8 | 103.62 (16) |
O1—C2—H2A | 107.5 (11) | C10—C9—H9A | 111.0 (14) |
C3—C2—H2A | 109.8 (11) | C8—C9—H9A | 112.5 (15) |
O1—C2—H2B | 104.5 (12) | C10—C9—H9B | 113.1 (12) |
C3—C2—H2B | 113.7 (13) | C8—C9—H9B | 110.6 (13) |
H2A—C2—H2B | 110.5 (17) | H9A—C9—H9B | 106.2 (19) |
C2—C3—C4 | 109.59 (15) | C11—C10—C12 | 103.86 (15) |
C2—C3—H3A | 107.5 (12) | C11—C10—C9 | 106.60 (14) |
C4—C3—H3A | 112.7 (11) | C12—C10—C9 | 102.65 (16) |
C2—C3—H3B | 110.7 (11) | C11—C10—H10 | 111.2 (12) |
C4—C3—H3B | 109.5 (10) | C12—C10—H10 | 117.6 (12) |
H3A—C3—H3B | 106.8 (15) | C9—C10—H10 | 113.8 (12) |
N5—C4—C3 | 110.45 (15) | O4—C11—C10 | 115.08 (14) |
N5—C4—H4A | 106.5 (12) | O4—C11—C11A | 111.68 (14) |
C3—C4—H4A | 115.6 (11) | C10—C11—C11A | 101.66 (14) |
N5—C4—H4B | 107.1 (12) | O4—C11—H11 | 108.6 (11) |
C3—C4—H4B | 111.6 (12) | C10—C11—H11 | 110.2 (11) |
H4A—C4—H4B | 105.1 (17) | C11A—C11—H11 | 109.4 (11) |
C11A—N5—C4 | 116.80 (14) | C11—O4—H4 | 105.4 (16) |
C11A—N5—S6 | 111.77 (10) | O1—C11A—N5 | 110.63 (13) |
C4—N5—S6 | 115.47 (11) | O1—C11A—C7A | 109.79 (13) |
O3—S6—O2 | 115.11 (8) | N5—C11A—C7A | 106.34 (13) |
O3—S6—N5 | 112.51 (7) | O1—C11A—C11 | 110.68 (13) |
O2—S6—N5 | 108.88 (7) | N5—C11A—C11 | 115.53 (14) |
O3—S6—C7 | 110.63 (9) | C7A—C11A—C11 | 103.44 (13) |
O2—S6—C7 | 111.38 (9) | C14—C12—C13 | 105.91 (17) |
N5—S6—C7 | 96.87 (7) | C14—C12—C10 | 115.33 (15) |
C7A—C7—S6 | 105.99 (12) | C13—C12—C10 | 113.78 (15) |
C7A—C7—H7A | 109.0 (15) | C14—C12—C7A | 116.90 (14) |
S6—C7—H7A | 106.6 (12) | C13—C12—C7A | 113.06 (16) |
C7A—C7—H7B | 110.1 (15) | C10—C12—C7A | 91.83 (13) |
S6—C7—H7B | 110.4 (13) | C12—C13—H13A | 106.0 (15) |
H7A—C7—H7B | 114.4 (19) | C12—C13—H13B | 110.9 (13) |
C7—C7A—C8 | 117.19 (15) | H13A—C13—H13B | 110 (2) |
C7—C7A—C11A | 107.43 (14) | C12—C13—H13C | 116.8 (14) |
C8—C7A—C11A | 107.19 (14) | H13A—C13—H13C | 107 (2) |
C7—C7A—C12 | 118.17 (15) | H13B—C13—H13C | 106 (2) |
C8—C7A—C12 | 102.11 (14) | C12—C14—H14A | 108.2 (15) |
C11A—C7A—C12 | 103.53 (13) | C12—C14—H14B | 114.4 (11) |
C7A—C8—C9 | 101.93 (15) | H14A—C14—H14B | 103.8 (18) |
C7A—C8—H8A | 112.6 (12) | C12—C14—H14C | 105.2 (13) |
C9—C8—H8A | 110.7 (11) | H14A—C14—H14C | 113 (2) |
C7A—C8—H8B | 112.4 (12) | H14B—C14—H14C | 111.9 (17) |
C9—C8—H8B | 110.7 (12) | ||
C11A—O1—C2—C3 | 61.7 (2) | S6—N5—C11A—C7A | 32.67 (16) |
O1—C2—C3—C4 | −57.3 (2) | C4—N5—C11A—C11 | −77.12 (18) |
C2—C3—C4—N5 | 49.0 (2) | S6—N5—C11A—C11 | 146.77 (12) |
C3—C4—N5—C11A | −47.1 (2) | C7—C7A—C11A—O1 | 84.51 (17) |
C3—C4—N5—S6 | 87.37 (16) | C8—C7A—C11A—O1 | −42.25 (17) |
C11A—N5—S6—O3 | 98.82 (12) | C12—C7A—C11A—O1 | −149.73 (13) |
C4—N5—S6—O3 | −37.91 (15) | C7—C7A—C11A—N5 | −35.21 (18) |
C11A—N5—S6—O2 | −132.34 (11) | C8—C7A—C11A—N5 | −161.97 (13) |
C4—N5—S6—O2 | 90.94 (13) | C12—C7A—C11A—N5 | 90.55 (15) |
C11A—N5—S6—C7 | −16.91 (13) | C7—C7A—C11A—C11 | −157.34 (14) |
C4—N5—S6—C7 | −153.64 (13) | C8—C7A—C11A—C11 | 75.90 (16) |
O3—S6—C7—C7A | −122.00 (13) | C12—C7A—C11A—C11 | −31.57 (16) |
O2—S6—C7—C7A | 108.62 (13) | O4—C11—C11A—O1 | −123.68 (14) |
N5—S6—C7—C7A | −4.78 (14) | C10—C11—C11A—O1 | 113.11 (14) |
S6—C7—C7A—C8 | 143.96 (14) | O4—C11—C11A—N5 | 3.0 (2) |
S6—C7—C7A—C11A | 23.33 (17) | C10—C11—C11A—N5 | −120.19 (15) |
S6—C7—C7A—C12 | −93.18 (16) | O4—C11—C11A—C7A | 118.79 (15) |
C7—C7A—C8—C9 | 171.45 (16) | C10—C11—C11A—C7A | −4.43 (16) |
C11A—C7A—C8—C9 | −67.79 (18) | C11—C10—C12—C14 | 64.25 (18) |
C12—C7A—C8—C9 | 40.68 (17) | C9—C10—C12—C14 | 175.16 (15) |
C7A—C8—C9—C10 | −5.31 (19) | C11—C10—C12—C13 | −173.07 (17) |
C8—C9—C10—C11 | 76.78 (19) | C9—C10—C12—C13 | −62.2 (2) |
C8—C9—C10—C12 | −32.06 (18) | C11—C10—C12—C7A | −56.82 (14) |
C12—C10—C11—O4 | −81.16 (18) | C9—C10—C12—C7A | 54.10 (14) |
C9—C10—C11—O4 | 170.85 (16) | C7—C7A—C12—C14 | 51.7 (2) |
C12—C10—C11—C11A | 39.71 (16) | C8—C7A—C12—C14 | −178.14 (16) |
C9—C10—C11—C11A | −68.29 (18) | C11A—C7A—C12—C14 | −66.89 (18) |
C2—O1—C11A—N5 | −55.93 (17) | C7—C7A—C12—C13 | −71.7 (2) |
C2—O1—C11A—C7A | −173.00 (14) | C8—C7A—C12—C13 | 58.50 (19) |
C2—O1—C11A—C11 | 73.43 (17) | C11A—C7A—C12—C13 | 169.75 (16) |
C4—N5—C11A—O1 | 49.60 (18) | C7—C7A—C12—C10 | 171.45 (15) |
S6—N5—C11A—O1 | −86.50 (14) | C8—C7A—C12—C10 | −58.39 (15) |
C4—N5—C11A—C7A | 168.77 (14) | C11A—C7A—C12—C10 | 52.86 (14) |
D—H···A | D—H | H···A | D···A | D—H···A |
O4—H4···O2i | 0.87 (3) | 2.04 (3) | 2.901 (2) | 169 (2) |
C4—H4A···O2ii | 1.02 (2) | 2.64 (2) | 3.646 (2) | 170 (2) |
C11—H11···O3i | 1.01 (2) | 2.63 (2) | 3.496 (2) | 144 (1) |
C8—H8B···O3iii | 0.99 (2) | 2.53 (2) | 3.203 (2) | 125 (1) |
C7—H7A···O1iv | 0.96 (2) | 2.67 (2) | 3.584 (2) | 162 (2) |
C4—H4B···O4ii | 0.97 (2) | 2.63 (2) | 3.530 (2) | 153 (2) |
Symmetry codes: (i) x, y+1, z; (ii) −x+1, y, −z; (iii) −x+3/2, y+1/2, −z+1; (iv) −x+3/2, y−1/2, −z+1. |
Experimental details
(1) | (2) | (3) | (4) | |
Crystal data | ||||
Chemical formula | C12H17NO4S | C13H19NO4S | C12H19NO4S | C13H21NO4S |
Mr | 271.33 | 285.35 | 273.34 | 287.37 |
Crystal system, space group | Monoclinic, P21 | Monoclinic, P21 | Orthorhombic, P212121 | Monoclinic, C2 |
Temperature (K) | 210 | 210 | 190 | 210 |
a, b, c (Å) | 7.7873 (9), 7.1895 (8), 11.1111 (12) | 7.6970 (9), 6.9954 (8), 12.2852 (13) | 7.3091 (8), 10.9033 (12), 15.2110 (16) | 16.5474 (18), 7.5668 (9), 11.5945 (13) |
α, β, γ (°) | 90, 99.274 (5), 90 | 90, 98.145 (5), 90 | 90, 90, 90 | 90, 115.376 (5), 90 |
V (Å3) | 613.94 (12) | 654.81 (13) | 1212.2 (2) | 1311.7 (3) |
Z | 2 | 2 | 4 | 4 |
Radiation type | Mo Kα | Mo Kα | Mo Kα | Mo Kα |
µ (mm−1) | 0.27 | 0.26 | 0.27 | 0.26 |
Crystal size (mm) | 0.32 × 0.29 × 0.03 | 0.22 × 0.14 × 0.07 | 0.26 × 0.24 × 0.11 | 0.24 × 0.07 × 0.07 |
Data collection | ||||
Diffractometer | Nonius KappaCCD diffractometer | Nonius KappaCCD diffractometer | Nonius KappaCCD diffractometer | Nonius KappaCCD diffractometer |
Absorption correction | Multi-scan (SCALEPACK; Otwinowski & Minor, 1997) | Multi-scan (SCALEPACK; Otwinowski & Minor, 1997) | Multi-scan (SCALEPACK; Otwinowski & Minor, 1997) | Multi-scan (SCALEPACK; Otwinowski & Minor, 1997) |
Tmin, Tmax | 0.918, 0.992 | 0.946, 0.982 | 0.932, 0.970 | 0.941, 0.982 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 15611, 2845, 2565 | 15564, 3084, 2783 | 30886, 2898, 2662 | 13727, 3118, 2852 |
Rint | 0.022 | 0.028 | 0.041 | 0.027 |
(sin θ/λ)max (Å−1) | 0.658 | 0.658 | 0.658 | 0.658 |
Refinement | ||||
R[F2 > 2σ(F2)], wR(F2), S | 0.031, 0.072, 1.06 | 0.031, 0.076, 1.04 | 0.031, 0.077, 1.06 | 0.032, 0.073, 1.05 |
No. of reflections | 2845 | 3084 | 2898 | 3118 |
No. of parameters | 232 | 249 | 240 | 257 |
No. of restraints | 1 | 1 | 0 | 1 |
H-atom treatment | All H-atom parameters refined | All H-atom parameters refined | All H-atom parameters refined | All H-atom parameters refined |
Δρmax, Δρmin (e Å−3) | 0.18, −0.26 | 0.19, −0.26 | 0.20, −0.32 | 0.16, −0.27 |
Absolute structure | Flack (1983) | Flack (1983) | Flack (1983) | Flack (1983) |
Absolute structure parameter | −0.01 (6) | −0.01 (6) | −0.01 (6) | −0.07 (5) |
Computer programs: COLLECT (Nonius, 2000), SCALEPACK (Otwinowski & Minor, 1997), DENZO (Otwinowski & Minor, 1997) and SCALEPACK, SHELXTL (Sheldrick, 2008), publCIF (Westrip, 2010).
(1) | (2) | (3) | (4) | |
S(5/6)—O2 | 1.4357 (14) | 1.4369 (14) | 1.4399 (13) | 1.4396 (13) |
S(5/6)—O3 | 1.4384 (15) | 1.4405 (15) | 1.4371 (12) | 1.4334 (12) |
S(5/6)—N(4/5) | 1.6890 (15) | 1.6659 (14) | 1.6807 (14) | 1.6534 (14) |
S(5/6)—C(6/7) | 1.7934 (16) | 1.7898 (16) | 1.7937 (17) | 1.7867 (19) |
O1—C2 | 1.439 (2) | 1.449 (2) | 1.441 (2) | 1.440 (2) |
O1—C(10A/11A) | 1.421 (2) | 1.417 (2) | 1.427 (2) | 1.429 (2) |
N(4/5)—C(3/4) | 1.476 (2) | 1.484 (2) | 1.485 (2) | 1.484 (2) |
N(4/5)—C(10A/11A) | 1.459 (2) | 1.443 (2) | 1.467 (2) | 1.461 (2) |
C(10/11)—O4 | 1.213 (2) | 1.209 (2) | 1.423 (2) | 1.421 (2) |
O2—S(5/6)—O3 | 116.28 (9) | 115.52 (9) | 115.62 (8) | 115.11 (8) |
O2—S(5/6)—N(4/5) | 108.29 (8) | 108.87 (8) | 108.33 (7) | 108.88 (7) |
O2—S(5/6)—C(6/7) | 111.46 (10) | 111.66 (9) | 110.97 (8) | 111.38 (9) |
O3—S(5/6)—N(4/5) | 110.66 (8) | 111.26 (8) | 111.10 (8) | 112.51 (7) |
O3—S(5/6)—C(6/7) | 111.01 (10) | 111.40 (9) | 111.37 (8) | 110.63 (9) |
N(4/5)—S(5/6)—C(6/7) | 97.50 (7) | 96.51 (7) | 98.01 (7) | 96.87 (7) |
C2—O1—C(10A/11A) | 107.86 (14) | 113.64 (13) | 104.44 (13) | 112.55 (14) |
S(5/6)—N(4/5)—C(3/4) | 115.38 (13) | 116.96 (12) | 115.77 (11) | 115.47 (11) |
S(5/6)—N(4/5)—C(10A/11A) | 108.64 (11) | 112.34 (11) | 109.17 (10) | 111.77 (10) |
C(3/4)—N(4/5)—C(10A/11A) | 105.50 (15) | 116.79 (14) | 105.36 (13) | 116.80 (14) |
Note: numbers in parenthesis complete the atom label with the first used with compounds (1) and (2) and the second used with compounds (3) and (4). |
Motif | D—H (Å) | H···A (Å) | D···A (Å) | D—H···A (°) | Site symmetry A | Priority | Graph set | Direction |
Compound (1) | ||||||||
C6—H6B···O3 | 0.99 (2) | 2.41 (2) | 3.390 (3) | 174 (2) | -x, y-1/2, -z | 2 | C(4)[R22(8)] | b axis |
C6—H6A···O2 | 0.90 (3) | 2.57 (3) | 3.368 (2) | 148 (2) | -x, y+1/2, -z | 2 | C(4)[R22(8)] | b axis |
C13—H13A···O1 | 1.05 (3) | 2.60 (3) | 3.499 (3) | 143 (2) | x, y-1, z | 6 | C(6) | b axis |
C3—H3B···O3 | 0.94 (3) | 2.70 (3) | 3.409 (3) | 133 (2) | -x+1, y-1/2, -z | 4 | C(5) | b axis |
C8—H8B···O4 | 0.96 (2) | 2.72 (2) | 3.487 (3) | 137 (2) | -x+1, y+1/2, -z+1 | 5 | C(5) | b axis |
C3—H3A···O2 | 0.94 (2) | 2.73 (2) | 3.137 (2) | 107 (2) | -x+1, y+1/2, -z | 4 | C(5) | a axis |
C2—H2A···O2 | 1.06 (3) | 2.75 (3) | 3.111 (3) | 100 (2) | -x+1, y+1/2, -z | 3 | C(5) | a axis |
Compound (2) | ||||||||
C7—H7B···O3 | 0.97 (2) | 2.43 (2) | 3.380 (2) | 166 (2) | -x, y-1/2, -z | 2 | C(4)[R22(8)] | b axis |
C7—H7A···O2 | 0.92 (3) | 2.60 (2) | 3.346 (2) | 139 (2) | -x, y+1/2, -z | 2 | C(4)[R22(8)] | b axis |
C14—H14A···O1 | 1.09 (3) | 2.46 (3) | 3.425 (2) | 147 (2) | x, y-1, z | 6 | C(6) | b axis |
C3—H3B···O2 | 0.95 (2) | 2.67 (2) | 3.134 (2) | 111 (1) | -x+1, y+1/2, -z | 4 | C(6) | b axis |
C13—H13C···O4 | 1.00 (3) | 2.69 (3) | 3.572 (3) | 147 (2) | x-1, y, z | 6 | C(6) | a axis |
Compound (3) | ||||||||
O4—H4···O2 | 0.85 (3) | 2.01 (3) | 2.860 (2) | 174 (3) | -x+1, y-1/2, -z+1/2 | 1 | C(7) | b axis |
C6—H6B···O3 | 0.98 (2) | 2.41 (2) | 3.384 (2) | 175 (2) | x+1/2, -y+1/2, -z | 2 | C(4) | a axis |
C2—H2A···O3 | 0.98 (2) | 2.59 (2) | 3.358 (2) | 136 (2) | -x, y-1/2, -z+1/2 | 3 | C(6) | b axis |
C13—H13A···O1 | 0.97 (3) | 2.65 (3) | 3.581 (2) | 160 (2) | x+1, y, z | 6 | C(6) | a axis |
Compound (4) | ||||||||
O4—H4···O2 | 0.87 (3) | 2.04 (3) | 2.901 (2) | 169 (2) | x, y+1, z | 1 | C(7) | b axis |
C8—H8B···O3 | 0.99 (2) | 2.53 (2) | 3.203 (2) | 125 (1) | -x+3/2, y+1/2, -z+1 | 5 | C(6) | |
C11—H11···O3 | 1.01 (2) | 2.63 (2) | 3.496 (2) | 144 (1) | x, y+1, z | 3 | C(6) | b axis |
C4—H4B···O4 | 0.97 (2) | 2.63 (2) | 3.530 (2) | 153 (2) | -x+1, y, -z | 4 | R22(12) | |
C4—H4A···O2 | 1.02 (2) | 2.64 (2) | 3.646 (2) | 170 (2) | -x+1, y, -z | 4 | R22(10) | |
C7—H7A···O1 | 0.96 (2) | 2.67 (2) | 3.584 (2) | 162 (2) | -x+3/2, y-1/2, -z+1 | 2 | C(5) | a axis |
Graph-set designations of Etter (1990) used. Motif priories based on the priority of the H-donor atom: (1) O—H···; (2) S—C—H···; (3) O—C—H···; (4) N—C—H···; (5) Cmethylene—H···; (6) Cmethyl—H··· |
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During the course of our studies toward the synthesis of camphor-based acetals (Wilke et al., 2010), an unexpected crystalline product was discovered. X-ray diffraction confirmed that the anticipated acetalization reaction (Magnus et al., 1992) of the ketone (Chen et al., 1996) instead resulted in reaction of the imine to produce spirooxazolidines, (1) and (2), that were further reduced to the exo alcohols, (3) and (4), shown in the Scheme. The alcohol functionality may provide a logical attachment point for use of these compounds as chiral auxiliaries.
The structures of the four compounds are shown in Fig. 1 and Table 1 gives the geometries of the functional groups in the four molecules. The only significant deviations in these geometries can be ascribed to chemical differences (C═O versus C—OH and the five- versus six-member oxaza ring). The six-member oxaza ring (the only ring with conformational possibilities) adopts the chair conformation in (2) and (4). Perhaps the most surprising feature revealed in comparing structures is the ordering in the variation of melting points [457–458, 459–461, 474–478 and 507–508 K for (2) (4), (3) and (1), respectively]. As these are quite similar molecules, one might expect the hydroxy compounds [(3) and (4)] to have higher melting points relative to the keto compounds [(1) and (2)] based on the expected formation of O—H···O═S hydrogen bonds. However, the 5-keto structure, (1), has the highest melting point of the four compounds (by approximately 3 K) and the 6-keto structure, (2), the lowest. As the packing coefficients for the structures are about the same with index slightly higher for the hydroxy compounds [0.708, 0.708, 0.732 and 0.720 for (1), (2), (3) and (4), respectively, as calculated with PLATON (Spek, 2009)], we decided to analyze the intermolecular interactions (including C—H···O contacts) for clues to explain the melting-point anomalies. Using the method of Etter et al. (1990) a graph-set analysis was done for the four structures. The analysis (first level only) included traditional hydrogen-bond networks as well as those generated by all possible C—H···O motifs (any with H···O or C···O less than the sum of van der Waals radii: 2.72 Å, 3.22 Å, respectively). There are no intermolecular C—H···N motifs that meet the close contact criteria. Table 2 summarizes the analysis.
In each structure there is at least one contact involving each O atom. The strongest interactions (based on the shortest H···O distance) in all structures involve the sulfonyl O atoms with the donor of highest priority (see footnote of Table 2): a traditional hydrogen bond (priority 1) in the hydroxy structures and two S—C—H···O═S hydrogen bonds (priority 2) in the keto structures. The two S—C—H···O═ S interactions (in the keto structures) form a ring motif subset (R22) analogous to what would be considered cooperative hydrogen bonding (for traditional hydrogen bonds). These strongest interactions form columns of molecules in the b-axis direction. A search for C—H···O═S interactions in the Cambridge Structural Database (CSD version 5.31, November 2009; Allen, 2002) finds 207 camphor sultams (see Scheme) with 173 having C—H···O═S intermolecular interactions less than the sum of van der Waals radii (2.72 Å), indicating this is a common feature of camphor sultams. Of these, 65 have an intermolecular interaction between the methylene α (priority 2 donor) to the sulfonyl group and a sulfonyl O atom. Seven of these have two interactions forming R22(8) rings as found in (1) and (2).
For (1), the molecules are situated with the >SO2 group near the 21 axis at (0,y,0) allowing formation of the two (cooperative) S—C—H···O═S hydrogen bonds. This orientation also allows the C—H···O interaction between H13A and O1 to occur. These interactions form doubled molecular columns parallel to the b axis. The proximity of the doubled molecular columns at x = 0 and x = 1 yields the H3B···O3 interaction and the H2A···O2 and H3A···O2 close contacts connecting adjacent columns in the a-axis direction. The 21 axis at (1/2,y,1/2) produces the H8B···O4 interactions that connect adjacent columns in the c-axis direction giving connectivity of the molecular columns in three dimensions. The geometry of the H2A···O2 and H3A···O2 contacts suggests they may be repulsive interactions although C—H···O interactions with similar geometries have been reported as attractive interactions (Steiner, 2003).
As in (1), in (2) a doubled molecular column parallel to the b axis is generated by a 21 axis at (0,y,0) which allows the two (cooperative) S—C—H···O═S hydrogen bonds and the H14A···O1 contact. The columns are linked in the a-axis direction via the H3B···O2 and H13C···O4 interactions to form molecular sheets. There are no close contacts (less than van der Waals radius sums) between the molecular sheets. The lack of three-dimensional interconnectedness correlates with (2) having the lowest melting point.
The O—H···O hydrogen bond in (3) forms molecular columns in the b-axis direction. The H6B···O3 interaction interconnects the columns in the c-axis direction and the H2A···O3 and H13A···O1 interactions interconnect the columns in the a-axis direction to give the three-dimensional network.
In (4) the O—H···O hydrogen bond forms molecular columns also in the b-axis direction with an assist from the H11···O3 interaction. The H4A···O2 and H4B···O4 interactions interconnect molecular columns forming the doubled molecular columns. The H7A···O1 and H8B···O3 interactions connect the doubled columns into sheets. There are no close contacts (less than van der Waals radius sums) between the molecular sheets.
Although there is a correlation between the number and direction of intermolecular contacts and the melting point order (more contacts forming three-dimensional connectivity occur with higher melting solids; fewer contacts and two-dimensional connectivity occur with lower melting solids), attributing the differences in melting to differences in very weak intermolecular interactions suggests there are other more important factors in play.
The packing of the keto structures [(1) and (2)] is quite similar, as also confrimed by their very similar unit-cell parameters, but their melting points differ by 50 K. There are two differences in intermolecular interactions between the two structures: (a) the presence of the C2—H2A···O2 and C3—H3A···O2 interactions in (1) but only the C3—H3B···O2 in (2); (b) the weak interaction with O4 in (1) (H8B···O4) is involved in connecting adjacent columns the c-axis direction and in (2) the weak interaction with O4 (H13C···O4) is involved in connecting adjacent columns in the a-axis direction. Changing from a five-member envelope conformation oxaza-ring [in (1)] to the six-member chair conformation oxaza-ring of (2) precludes the doubled close contact of this ring with the O2 sulfonyl oxygen atom resulting in a slight twist (about the column axis, i. e. parallel to the b-cell axis) of each half of the doubled molecular columns (in opposite directions) in (2) versus (1). This twist also changes the closest contact of O4 from a H atom in an adjacent column in the a-axis direction to one in the c-cell direction. These slight differences in molecular packing seem unlikely to explain the large difference in melting points on the basis of weak C—H···O interactions. Considering that the sulfonyl group is highly polar, it seems more likely that the smaller five-member oxaza ring of (1) allows for a more favorable arrangement of polar groups resulting in a greater degree of electrostatic interaction and a higher melting point. The C2—H2A···O2 and C3—H3A···O2 close contacts in (1) may in fact be repulsive contacts that are `tolerated' to allow the more favorable arrangement of polar groups. A recent paper by Gavezzotti (2010) presents a quantitative analysis of relative stabilities in organic crystal structure by calculating interaction energies between pairs of molecules for 1108 non-ionic and 98 ionic molecules using the PIXEL method (Gavezzotti, 2008). He concludes that repulsive destabilizing contacts regularly appear in crystals of very strongly polar compounds. We are contemplating calculating the interaction energies for this series of compounds to provide further insight to explain the differences in melting points of this series of compounds.