Information on the geometrical structures of α-(p-phenylsulfinyl)-p-substituted acetophenones X—PhC(O)CH2S(O)Ph—Y [X = OMe, Y = H (1); X = NO2, Y = OMe (2); X = OMe, Y = NO2 (3); IUPAC names: (1) 4-methoxyphenyl phenylsulfinylmethyl ketone; (2) 4-nitrophenyl 4-methoxyphenylsulfinylmethyl ketone; (3) 4-methoxyphenyl 4-nitrophenylsulfinylmethyl ketone] have been obtained from X-ray diffraction analyses. A comparison of these results with those previously obtained from X-ray diffraction and ab initio computations of α-methylsulfinylacetophenone, PhC(O)CH2S(O)Me, indicated that (1) and (2) adopt in the crystal a cis1 conformation and (3) assumes a quasi-gauche geometry. The stabilization of these conformations in the crystal is discussed in terms of the dipole moment coupling, Coulombic and intramolecular charge transfer interactions between the oppositely charged atoms of the C=O and S=O dipoles. The p-substituted benzene ring is quasi-coplanar with the sulfinyl group for (1) and (3), but is quasi-perpendicular for (2). Conjugation and repulsion between the sulfinyl sulfur lone pair and the π-benzene ring seem to be responsible for the observed geometries.
Supporting information
CCDC references: 141658; 141659; 141660
For all compounds, data collection: CAD-4 Software (Enraf-Nonius,1989); cell refinement: CAD-4 Software (Enraf-Nonius,1989); data reduction: MolEN (Fair, 1990); program(s) used to solve structure: SHELXS86 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ZORTEP (Zsolnai, 1995); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997) and PARST95 (Nardelli, 1995).
Crystal data top
C15H14O3S | F(000) = 1152 |
Mr = 274.32 | Dx = 1.345 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 10.4698 (9) Å | Cell parameters from 20 reflections |
b = 10.2770 (9) Å | θ = 8.1–12.0° |
c = 25.449 (2) Å | µ = 0.24 mm−1 |
β = 98.429 (1)° | T = 293 K |
V = 2708.7 (4) Å3 | Irregular, colorless |
Z = 8 | 0.25 × 0.22 × 0.10 mm |
Data collection top
Enraf-Nonius CAD-4 diffractometer | Rint = 0.133 |
Radiation source: fine-focus sealed tube | θmax = 21.6° |
Graphite monochromator | h = −10→10 |
ω/2θ scans | k = 0→10 |
3670 measured reflections | l = −26→0 |
3162 independent reflections | 3 standard reflections every 60 min |
1198 reflections with F2 > 2σF2 | intensity decay: −1.0% |
Refinement top
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.057 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.104 | H-atom parameters constrained |
S = 0.93 | Calculated w = 1/[σ2(Fo2) + (0.0495)2] where P = (Fo2 + 2Fc2)/3 |
3162 reflections | (Δ/σ)max < 0.001 |
355 parameters | Δρmax = 0.35 e Å−3 |
0 restraints | Δρmin = −0.22 e Å−3 |
Special details top
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 on F2 for ALL reflections except for 0 with very negative
F2 or flagged by the user for potential systematic errors. Weighted
R-factors wR and all goodnesses of fit S are based on
F2, conventional R-factors R are based on F,
with F set to zero for negative F2. The observed criterion of
F2 > σ(F2) is used only for calculating _R_factor_obs
etc. and is not relevant to the choice of reflections for refinement.
R-factors based on F2 are statistically about twice as large
as those based on F, and R- factors based on ALL data will be
even larger. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | Occ. (<1) |
S1 | 0.4424 (2) | 0.5124 (2) | 0.08843 (11) | 0.0670 (7) | |
O11A | 0.4005 (9) | 0.5241 (9) | 0.0278 (4) | 0.110 (4) | 0.624 (9) |
O11B | 0.3817 (12) | 0.5572 (12) | 0.1394 (5) | 0.070 (6) | 0.376 (9) |
O12 | 0.5423 (5) | 0.7658 (5) | 0.0813 (2) | 0.079 (2) | |
O13 | 1.1150 (6) | 0.8703 (5) | 0.0486 (2) | 0.0714 (17) | |
C11 | 0.6109 (6) | 0.5493 (7) | 0.0981 (3) | 0.066 (2) | |
H11A | 0.6474 | 0.5309 | 0.1346 | 0.079* | |
H11B | 0.6542 | 0.4946 | 0.0752 | 0.079* | |
C12 | 0.6331 (8) | 0.6910 (8) | 0.0859 (3) | 0.056 (2) | |
C13 | 0.7627 (7) | 0.7312 (8) | 0.0775 (3) | 0.049 (2) | |
C14 | 0.7783 (7) | 0.8537 (8) | 0.0555 (3) | 0.052 (2) | |
H14 | 0.7069 | 0.9077 | 0.0471 | 0.062* | |
C15 | 0.8949 (8) | 0.8946 (7) | 0.0463 (3) | 0.055 (2) | |
H15 | 0.9026 | 0.9754 | 0.0305 | 0.066* | |
C16 | 1.0035 (8) | 0.8186 (9) | 0.0598 (3) | 0.056 (2) | |
C17 | 0.9900 (8) | 0.6989 (8) | 0.0830 (3) | 0.061 (2) | |
H17 | 1.0624 | 0.6475 | 0.0933 | 0.073* | |
C18 | 0.8707 (8) | 0.6556 (7) | 0.0909 (3) | 0.059 (2) | |
H18 | 0.8627 | 0.5736 | 0.1055 | 0.071* | |
C19 | 0.4596 (6) | 0.3407 (8) | 0.1012 (4) | 0.054 (2) | |
C110 | 0.4676 (8) | 0.2540 (11) | 0.0612 (4) | 0.074 (3) | |
H110 | 0.4743 | 0.2825 | 0.0270 | 0.089* | |
C111 | 0.4655 (9) | 0.1240 (12) | 0.0728 (5) | 0.102 (4) | |
H111 | 0.4717 | 0.0631 | 0.0463 | 0.123* | |
C112 | 0.4546 (9) | 0.0835 (12) | 0.1221 (7) | 0.109 (5) | |
H112 | 0.4522 | −0.0053 | 0.1290 | 0.130* | |
C113 | 0.4469 (9) | 0.1692 (16) | 0.1626 (5) | 0.110 (5) | |
H113 | 0.4411 | 0.1404 | 0.1968 | 0.132* | |
C114 | 0.4482 (8) | 0.3003 (11) | 0.1507 (4) | 0.077 (3) | |
H114 | 0.4412 | 0.3613 | 0.1772 | 0.093* | |
C115 | 1.2303 (7) | 0.7942 (8) | 0.0586 (3) | 0.094 (3) | |
H11C | 1.2212 | 0.7178 | 0.0366 | 0.141* | |
H11D | 1.2451 | 0.7689 | 0.0953 | 0.141* | |
H11E | 1.3022 | 0.8448 | 0.0506 | 0.141* | |
S2 | 0.7232 (2) | 0.8156 (3) | 0.24842 (10) | 0.0794 (8) | |
O21 | 0.7222 (6) | 0.6853 (6) | 0.2174 (3) | 0.117 (2) | |
O22 | 0.9668 (5) | 0.8952 (6) | 0.2201 (2) | 0.100 (2) | |
O23 | 0.9938 (5) | 1.3565 (5) | 0.0560 (2) | 0.0660 (16) | |
C21 | 0.7418 (6) | 0.9409 (7) | 0.2009 (3) | 0.049 (2) | |
H21A | 0.6946 | 0.9166 | 0.1666 | 0.059* | |
H21B | 0.7052 | 1.0214 | 0.2119 | 0.059* | |
C22 | 0.8825 (8) | 0.9626 (8) | 0.1955 (3) | 0.060 (2) | |
C23 | 0.9125 (8) | 1.0675 (8) | 0.1597 (3) | 0.052 (2) | |
C24 | 0.8173 (7) | 1.1452 (8) | 0.1308 (3) | 0.051 (2) | |
H24 | 0.7313 | 1.1323 | 0.1347 | 0.062* | |
C25 | 0.8480 (7) | 1.2393 (8) | 0.0971 (3) | 0.058 (2) | |
H25 | 0.7827 | 1.2898 | 0.0786 | 0.070* | |
C26 | 0.9746 (8) | 1.2611 (8) | 0.0899 (3) | 0.048 (2) | |
C27 | 1.0704 (7) | 1.1840 (9) | 0.1177 (3) | 0.059 (2) | |
H27 | 1.1560 | 1.1959 | 0.1129 | 0.071* | |
C28 | 1.0397 (8) | 1.0901 (9) | 0.1524 (3) | 0.063 (2) | |
H28 | 1.1054 | 1.0407 | 0.1713 | 0.075* | |
C29 | 0.5597 (7) | 0.8503 (9) | 0.2517 (3) | 0.055 (2) | |
C210 | 0.4619 (12) | 0.7759 (9) | 0.2247 (4) | 0.088 (3) | |
H210 | 0.4812 | 0.7066 | 0.2037 | 0.106* | |
C211 | 0.3321 (12) | 0.8058 (14) | 0.2290 (5) | 0.111 (4) | |
H211 | 0.2645 | 0.7560 | 0.2117 | 0.133* | |
C212 | 0.3091 (11) | 0.9105 (15) | 0.2596 (5) | 0.102 (4) | |
H212 | 0.2242 | 0.9337 | 0.2616 | 0.122* | |
C213 | 0.4053 (14) | 0.9809 (11) | 0.2867 (4) | 0.099 (3) | |
H213 | 0.3877 | 1.0491 | 0.3086 | 0.119* | |
C214 | 0.5283 (9) | 0.9501 (10) | 0.2814 (3) | 0.075 (3) | |
H214 | 0.5947 | 1.0007 | 0.2991 | 0.089* | |
C215 | 1.1239 (7) | 1.3873 (7) | 0.0503 (3) | 0.076 (3) | |
H21C | 1.1626 | 1.3143 | 0.0352 | 0.114* | |
H21D | 1.1716 | 1.4069 | 0.0845 | 0.114* | |
H21E | 1.1249 | 1.4614 | 0.0274 | 0.114* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
S1 | 0.0554 (14) | 0.0521 (16) | 0.092 (2) | 0.0002 (12) | 0.0075 (14) | 0.0074 (15) |
O11A | 0.136 (9) | 0.091 (8) | 0.087 (9) | −0.038 (7) | −0.034 (6) | 0.036 (6) |
O11B | 0.066 (10) | 0.055 (10) | 0.097 (13) | −0.004 (8) | 0.038 (9) | −0.019 (9) |
O12 | 0.066 (4) | 0.047 (4) | 0.131 (6) | 0.011 (3) | 0.035 (4) | 0.007 (4) |
O13 | 0.054 (4) | 0.054 (4) | 0.106 (5) | 0.001 (3) | 0.008 (3) | 0.007 (3) |
C11 | 0.062 (6) | 0.049 (6) | 0.088 (6) | −0.001 (5) | 0.011 (5) | 0.003 (5) |
C12 | 0.071 (7) | 0.039 (6) | 0.059 (6) | 0.001 (5) | 0.013 (5) | −0.003 (5) |
C13 | 0.048 (6) | 0.047 (6) | 0.051 (6) | 0.000 (5) | 0.003 (5) | 0.002 (5) |
C14 | 0.044 (5) | 0.045 (6) | 0.065 (6) | 0.010 (4) | 0.007 (4) | −0.002 (5) |
C15 | 0.061 (6) | 0.029 (5) | 0.077 (7) | 0.006 (5) | 0.016 (5) | 0.003 (4) |
C16 | 0.041 (5) | 0.048 (6) | 0.078 (7) | −0.010 (5) | 0.008 (5) | −0.002 (5) |
C17 | 0.062 (6) | 0.044 (6) | 0.074 (7) | −0.009 (5) | 0.004 (5) | 0.004 (5) |
C18 | 0.060 (6) | 0.047 (6) | 0.069 (6) | 0.007 (5) | 0.004 (5) | 0.018 (5) |
C19 | 0.047 (5) | 0.063 (7) | 0.054 (6) | −0.001 (4) | 0.012 (4) | 0.031 (6) |
C110 | 0.102 (8) | 0.066 (8) | 0.050 (7) | 0.019 (6) | 0.000 (6) | −0.006 (6) |
C111 | 0.097 (8) | 0.054 (9) | 0.136 (12) | 0.019 (7) | −0.047 (8) | −0.022 (7) |
C112 | 0.047 (6) | 0.079 (10) | 0.189 (16) | −0.012 (6) | −0.017 (9) | 0.063 (11) |
C113 | 0.078 (7) | 0.157 (15) | 0.097 (11) | 0.019 (9) | 0.024 (7) | 0.065 (10) |
C114 | 0.080 (7) | 0.068 (8) | 0.087 (9) | 0.011 (6) | 0.023 (6) | 0.010 (7) |
C115 | 0.055 (6) | 0.093 (7) | 0.136 (9) | −0.001 (6) | 0.019 (6) | 0.014 (7) |
S2 | 0.0642 (16) | 0.095 (2) | 0.0813 (18) | 0.0186 (15) | 0.0173 (13) | 0.0354 (17) |
O21 | 0.164 (6) | 0.054 (4) | 0.143 (6) | 0.032 (4) | 0.058 (5) | 0.015 (4) |
O22 | 0.068 (4) | 0.137 (6) | 0.097 (5) | 0.028 (4) | 0.013 (4) | 0.055 (5) |
O23 | 0.049 (4) | 0.057 (4) | 0.093 (5) | −0.005 (3) | 0.013 (3) | 0.016 (4) |
C21 | 0.046 (5) | 0.053 (5) | 0.050 (5) | 0.005 (4) | 0.015 (4) | 0.005 (4) |
C22 | 0.061 (6) | 0.065 (7) | 0.051 (6) | 0.010 (5) | −0.002 (5) | −0.002 (5) |
C23 | 0.052 (6) | 0.058 (6) | 0.042 (5) | 0.003 (5) | −0.001 (5) | −0.003 (5) |
C24 | 0.039 (5) | 0.048 (6) | 0.067 (6) | −0.004 (4) | 0.006 (5) | −0.015 (5) |
C25 | 0.037 (5) | 0.055 (6) | 0.084 (7) | 0.001 (4) | 0.014 (5) | 0.006 (5) |
C26 | 0.043 (6) | 0.042 (6) | 0.059 (6) | 0.007 (5) | 0.002 (5) | −0.003 (5) |
C27 | 0.038 (5) | 0.071 (6) | 0.067 (6) | −0.009 (5) | 0.005 (5) | −0.022 (5) |
C28 | 0.047 (6) | 0.079 (7) | 0.060 (6) | 0.008 (5) | 0.001 (5) | 0.005 (6) |
C29 | 0.051 (6) | 0.067 (7) | 0.047 (6) | 0.016 (5) | 0.012 (5) | 0.015 (5) |
C210 | 0.093 (8) | 0.083 (8) | 0.091 (8) | −0.029 (7) | 0.022 (7) | 0.013 (6) |
C211 | 0.088 (10) | 0.123 (12) | 0.116 (11) | −0.059 (9) | −0.006 (8) | 0.039 (9) |
C212 | 0.064 (8) | 0.142 (13) | 0.100 (11) | −0.002 (9) | 0.016 (8) | 0.052 (9) |
C213 | 0.122 (10) | 0.119 (10) | 0.060 (8) | 0.029 (10) | 0.026 (8) | 0.012 (7) |
C214 | 0.067 (7) | 0.094 (9) | 0.068 (7) | 0.025 (6) | 0.026 (5) | 0.020 (6) |
C215 | 0.062 (6) | 0.066 (6) | 0.102 (7) | −0.023 (5) | 0.018 (5) | −0.013 (5) |
Geometric parameters (Å, º) top
S1—O11A | 1.546 (9) | S2—O21 | 1.553 (6) |
S1—O11B | 1.593 (12) | S2—C29 | 1.763 (7) |
S1—C11 | 1.785 (7) | S2—C21 | 1.797 (7) |
S1—C19 | 1.799 (8) | O22—C22 | 1.220 (8) |
O12—C12 | 1.215 (8) | O23—C26 | 1.341 (8) |
O13—C16 | 1.350 (8) | O23—C215 | 1.425 (7) |
O13—C115 | 1.430 (8) | C21—C22 | 1.516 (9) |
C11—C12 | 1.515 (10) | C22—C23 | 1.475 (10) |
C12—C13 | 1.463 (9) | C23—C28 | 1.391 (9) |
C13—C18 | 1.373 (9) | C23—C24 | 1.399 (9) |
C13—C14 | 1.397 (9) | C24—C25 | 1.363 (9) |
C14—C15 | 1.345 (8) | C25—C26 | 1.382 (9) |
C15—C16 | 1.381 (9) | C26—C27 | 1.388 (9) |
C16—C17 | 1.381 (10) | C27—C28 | 1.376 (9) |
C17—C18 | 1.368 (9) | C29—C214 | 1.342 (10) |
C19—C114 | 1.348 (10) | C29—C210 | 1.378 (10) |
C19—C110 | 1.366 (10) | C210—C211 | 1.413 (12) |
C110—C111 | 1.369 (12) | C211—C212 | 1.369 (13) |
C111—C112 | 1.344 (13) | C212—C213 | 1.346 (12) |
C112—C113 | 1.365 (13) | C213—C214 | 1.352 (10) |
C113—C114 | 1.381 (13) | | |
| | | |
O11A—S1—O11B | 134.5 (6) | C19—C114—C113 | 120.6 (10) |
O11A—S1—C11 | 104.6 (4) | O21—S2—C29 | 105.3 (5) |
O11B—S1—C11 | 109.3 (5) | O21—S2—C21 | 105.6 (3) |
O11A—S1—C19 | 105.3 (5) | C29—S2—C21 | 95.1 (3) |
O11B—S1—C19 | 100.2 (6) | C26—O23—C215 | 117.6 (6) |
C11—S1—C19 | 96.5 (3) | C22—C21—S2 | 111.7 (5) |
C16—O13—C115 | 118.8 (6) | O22—C22—C23 | 121.9 (8) |
C12—C11—S1 | 110.8 (5) | O22—C22—C21 | 120.6 (8) |
O12—C12—C13 | 122.5 (8) | C23—C22—C21 | 117.5 (7) |
O12—C12—C11 | 119.1 (8) | C28—C23—C24 | 117.2 (8) |
C13—C12—C11 | 118.4 (7) | C28—C23—C22 | 120.0 (8) |
C18—C13—C14 | 118.0 (7) | C24—C23—C22 | 122.8 (8) |
C18—C13—C12 | 123.5 (8) | C25—C24—C23 | 121.3 (8) |
C14—C13—C12 | 118.5 (7) | C24—C25—C26 | 121.2 (8) |
C15—C14—C13 | 121.0 (7) | O23—C26—C25 | 116.2 (7) |
C14—C15—C16 | 121.0 (7) | O23—C26—C27 | 125.5 (8) |
O13—C16—C15 | 115.5 (8) | C25—C26—C27 | 118.4 (8) |
O13—C16—C17 | 125.9 (8) | C28—C27—C26 | 120.5 (7) |
C15—C16—C17 | 118.6 (7) | C27—C28—C23 | 121.4 (8) |
C18—C17—C16 | 120.4 (8) | C214—C29—C210 | 118.7 (8) |
C17—C18—C13 | 121.0 (8) | C214—C29—S2 | 120.0 (8) |
C114—C19—C110 | 121.4 (8) | C210—C29—S2 | 121.3 (9) |
C114—C19—S1 | 116.8 (9) | C29—C210—C211 | 119.5 (10) |
C110—C19—S1 | 121.3 (8) | C212—C211—C210 | 117.8 (11) |
C19—C110—C111 | 118.0 (9) | C213—C212—C211 | 122.2 (13) |
C112—C111—C110 | 120.7 (11) | C212—C213—C214 | 118.3 (11) |
C111—C112—C113 | 121.8 (13) | C29—C214—C213 | 123.4 (10) |
C112—C113—C114 | 117.5 (12) | | |
Crystal data top
C15H13NO5S | Dx = 1.455 Mg m−3 |
Mr = 319.32 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, P212121 | Cell parameters from 25 reflections |
a = 5.5704 (8) Å | θ = 8.2–13.4° |
b = 8.619 (1) Å | µ = 0.25 mm−1 |
c = 30.356 (5) Å | T = 293 K |
V = 1457.4 (4) Å3 | Irregular, colorless |
Z = 4 | 0.20 × 0.15 × 0.08 mm |
F(000) = 664 | |
Data collection top
Enraf-Nonius CAD-4 diffractometer | θmax = 25.5° |
Radiation source: fine-focus sealed tube | h = 0→6 |
Graphite monochromator | k = 0→10 |
ω/2θ scans | l = 0→36 |
1615 measured reflections | 3 standard reflections every 60 min |
1615 independent reflections | intensity decay: −0.4% |
688 reflections with F2 > 2σF2 | |
Refinement top
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)] = 0.107 | H-atom parameters constrained |
wR(F2) = 0.289 | Calculated w = 1/[σ2(Fo2) + (0.2000)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.01 | (Δ/σ)max = 0.003 |
1615 reflections | Δρmax = 1.55 e Å−3 |
201 parameters | Δρmin = −0.51 e Å−3 |
0 restraints | Extinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.003 (7) |
Special details top
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 on F2 for ALL reflections except for 0 with very negative
F2 or flagged by the user for potential systematic errors. Weighted
R-factors wR and all goodnesses of fit S are based on
F2, conventional R-factors R are based on F,
with F set to zero for negative F2. The observed criterion of
F2 > σ(F2) is used only for calculating _R_factor_obs
etc. and is not relevant to the choice of reflections for refinement.
R-factors based on F2 are statistically about twice as large
as those based on F, and R- factors based on ALL data will be
even larger. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
N | 0.856 (4) | 0.6354 (19) | 0.9621 (4) | 0.101 (6) | |
S | 0.8418 (7) | 1.0154 (4) | 0.71316 (13) | 0.0682 (13) | |
O1 | 0.7068 (17) | 1.1627 (8) | 0.7236 (3) | 0.056 (2) | |
O2 | 1.119 (2) | 1.0406 (10) | 0.7911 (3) | 0.075 (3) | |
O3 | 0.259 (3) | 0.6749 (16) | 0.5806 (4) | 0.122 (5) | |
O4 | 0.714 (5) | 0.5394 (16) | 0.9655 (4) | 0.167 (10) | |
O5 | 0.989 (3) | 0.6837 (18) | 0.9910 (5) | 0.133 (6) | |
C1 | 0.816 (3) | 0.8958 (17) | 0.7585 (4) | 0.070 (4) | |
H1A | 0.6492 | 0.8940 | 0.7678 | 0.084* | |
H1B | 0.8598 | 0.7911 | 0.7500 | 0.084* | |
C2 | 0.963 (3) | 0.9431 (14) | 0.7953 (4) | 0.047 (3) | |
C3 | 0.932 (2) | 0.8617 (13) | 0.8390 (4) | 0.046 (3) | |
C4 | 0.733 (3) | 0.7620 (14) | 0.8456 (4) | 0.052 (3) | |
H4 | 0.6199 | 0.7420 | 0.8238 | 0.062* | |
C5 | 0.720 (3) | 0.6925 (17) | 0.8900 (5) | 0.075 (5) | |
H5 | 0.5957 | 0.6251 | 0.8971 | 0.090* | |
C6 | 0.891 (3) | 0.7276 (16) | 0.9205 (5) | 0.061 (4) | |
C7 | 1.074 (3) | 0.8214 (17) | 0.9133 (4) | 0.067 (4) | |
H7 | 1.1872 | 0.8386 | 0.9353 | 0.080* | |
C8 | 1.096 (3) | 0.8950 (16) | 0.8724 (4) | 0.059 (4) | |
H8 | 1.2197 | 0.9656 | 0.8675 | 0.071* | |
C9 | 0.665 (3) | 0.9074 (14) | 0.6742 (5) | 0.058 (4) | |
C10 | 0.761 (3) | 0.8969 (19) | 0.6310 (6) | 0.077 (5) | |
H10 | 0.9068 | 0.9432 | 0.6238 | 0.092* | |
C11 | 0.629 (4) | 0.814 (2) | 0.5999 (5) | 0.085 (6) | |
H11 | 0.6918 | 0.8016 | 0.5717 | 0.102* | |
C12 | 0.409 (4) | 0.7516 (19) | 0.6095 (7) | 0.092 (6) | |
C13 | 0.339 (4) | 0.761 (2) | 0.6491 (7) | 0.085 (5) | |
H13 | 0.1972 | 0.7101 | 0.6562 | 0.102* | |
C14 | 0.452 (3) | 0.8386 (18) | 0.6824 (4) | 0.062 (4) | |
H14 | 0.3826 | 0.8440 | 0.7102 | 0.074* | |
C15 | 0.369 (5) | 0.644 (2) | 0.5396 (6) | 0.131 (9) | |
H15A | 0.3345 | 0.5390 | 0.5308 | 0.196* | |
H15B | 0.5397 | 0.6569 | 0.5422 | 0.196* | |
H15C | 0.3082 | 0.7142 | 0.5178 | 0.196* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
N | 0.180 (19) | 0.084 (10) | 0.040 (8) | 0.017 (14) | −0.005 (11) | −0.013 (8) |
S | 0.060 (2) | 0.064 (2) | 0.081 (3) | −0.002 (2) | 0.005 (2) | 0.001 (2) |
O1 | 0.065 (6) | 0.034 (4) | 0.070 (6) | 0.011 (5) | 0.005 (5) | −0.007 (4) |
O2 | 0.105 (9) | 0.074 (6) | 0.046 (5) | −0.027 (7) | −0.018 (6) | 0.015 (5) |
O3 | 0.148 (13) | 0.116 (9) | 0.104 (10) | −0.018 (12) | −0.024 (10) | −0.028 (9) |
O4 | 0.34 (3) | 0.095 (10) | 0.071 (9) | −0.075 (16) | 0.019 (13) | 0.017 (8) |
O5 | 0.138 (13) | 0.174 (16) | 0.087 (10) | −0.022 (12) | −0.016 (10) | 0.045 (11) |
C1 | 0.062 (10) | 0.093 (10) | 0.054 (8) | 0.020 (10) | −0.011 (8) | −0.001 (7) |
C2 | 0.055 (8) | 0.045 (6) | 0.039 (7) | −0.006 (7) | 0.002 (6) | 0.001 (6) |
C3 | 0.050 (8) | 0.032 (6) | 0.056 (8) | 0.001 (7) | −0.005 (7) | −0.012 (6) |
C4 | 0.067 (9) | 0.045 (6) | 0.043 (7) | 0.008 (7) | −0.003 (7) | −0.015 (6) |
C5 | 0.082 (12) | 0.061 (9) | 0.081 (11) | 0.023 (10) | 0.014 (10) | −0.001 (8) |
C6 | 0.078 (11) | 0.052 (7) | 0.052 (9) | 0.013 (9) | −0.009 (8) | −0.002 (7) |
C7 | 0.067 (10) | 0.087 (10) | 0.047 (8) | −0.027 (10) | −0.019 (7) | 0.011 (8) |
C8 | 0.057 (10) | 0.058 (8) | 0.062 (9) | −0.007 (8) | −0.007 (7) | 0.000 (7) |
C9 | 0.049 (9) | 0.051 (7) | 0.075 (10) | −0.001 (8) | −0.025 (8) | 0.001 (7) |
C10 | 0.052 (9) | 0.087 (11) | 0.091 (13) | −0.011 (9) | 0.005 (9) | 0.023 (10) |
C11 | 0.103 (14) | 0.123 (15) | 0.029 (7) | 0.063 (14) | 0.001 (8) | 0.003 (9) |
C12 | 0.113 (18) | 0.062 (10) | 0.102 (16) | 0.008 (12) | −0.020 (15) | −0.037 (10) |
C13 | 0.070 (11) | 0.075 (10) | 0.111 (15) | −0.004 (11) | −0.019 (12) | −0.002 (11) |
C14 | 0.060 (9) | 0.085 (10) | 0.040 (7) | 0.021 (9) | 0.009 (7) | 0.000 (8) |
C15 | 0.19 (3) | 0.124 (16) | 0.081 (13) | 0.04 (2) | −0.008 (16) | −0.039 (12) |
Geometric parameters (Å, º) top
N—O4 | 1.15 (3) | C3—C4 | 1.418 (19) |
N—O5 | 1.22 (2) | C4—C5 | 1.477 (19) |
N—C6 | 1.51 (2) | C5—C6 | 1.36 (2) |
S—O1 | 1.509 (8) | C6—C7 | 1.318 (19) |
S—C1 | 1.726 (14) | C7—C8 | 1.400 (18) |
S—C9 | 1.799 (13) | C9—C14 | 1.35 (2) |
O2—C2 | 1.214 (14) | C9—C10 | 1.42 (2) |
O3—C12 | 1.38 (2) | C10—C11 | 1.39 (2) |
O3—C15 | 1.42 (2) | C11—C12 | 1.37 (3) |
C1—C2 | 1.446 (18) | C12—C13 | 1.26 (2) |
C2—C3 | 1.511 (16) | C13—C14 | 1.37 (2) |
C3—C8 | 1.394 (17) | | |
| | | |
O4—N—O5 | 126.9 (18) | C7—C6—C5 | 124.3 (14) |
O4—N—C6 | 123.0 (18) | C7—C6—N | 124.3 (15) |
O5—N—C6 | 110.0 (19) | C5—C6—N | 111.2 (15) |
O1—S—C1 | 107.1 (6) | C6—C7—C8 | 119.5 (14) |
O1—S—C9 | 107.4 (6) | C3—C8—C7 | 119.6 (13) |
C1—S—C9 | 99.7 (7) | C14—C9—C10 | 118.4 (13) |
C12—O3—C15 | 113 (2) | C14—C9—S | 126.1 (13) |
C2—C1—S | 113.6 (11) | C10—C9—S | 115.6 (12) |
O2—C2—C1 | 121.3 (12) | C11—C10—C9 | 117.3 (15) |
O2—C2—C3 | 119.7 (12) | C12—C11—C10 | 121.9 (15) |
C1—C2—C3 | 118.9 (12) | C13—C12—C11 | 116.8 (19) |
C8—C3—C4 | 122.4 (12) | C13—C12—O3 | 117 (2) |
C8—C3—C2 | 117.9 (12) | C11—C12—O3 | 126 (2) |
C4—C3—C2 | 119.6 (11) | C12—C13—C14 | 127 (2) |
C3—C4—C5 | 114.3 (13) | C9—C14—C13 | 118.9 (15) |
C6—C5—C4 | 119.8 (16) | | |
Crystal data top
C15H13NO5S | Z = 2 |
Mr = 319.32 | F(000) = 332 |
Triclinic, P1 | Dx = 1.463 Mg m−3 |
a = 6.7468 (8) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 7.4303 (7) Å | Cell parameters from 25 reflections |
c = 15.201 (2) Å | θ = 8.1–17.2° |
α = 85.25 (1)° | µ = 0.25 mm−1 |
β = 79.56 (1)° | T = 293 K |
γ = 75.39 (1)° | Irregular, colorless |
V = 724.64 (15) Å3 | 0.25 × 0.15 × 0.10 mm |
Data collection top
Enraf-Nonius CAD-4 diffractometer | Rint = 0.010 |
Radiation source: fine-focus sealed tube | θmax = 26.3° |
Graphite monochromator | h = 0→8 |
ω/2θ scans | k = −8→9 |
3188 measured reflections | l = −18→18 |
2930 independent reflections | 3 standard reflections every 60 min |
2503 reflections with F2 > 2σF2 | intensity decay: −1.1% |
Refinement top
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.041 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.113 | H-atom parameters constrained |
S = 1.08 | Calculated w = 1/[σ2(Fo2) + (0.0648)2 + 0.2154P] where P = (Fo2 + 2Fc2)/3 |
2930 reflections | (Δ/σ)max = 0.001 |
200 parameters | Δρmax = 0.26 e Å−3 |
0 restraints | Δρmin = −0.32 e Å−3 |
Special details top
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 on F2 for ALL reflections except for 0 with very negative
F2 or flagged by the user for potential systematic errors. Weighted
R-factors wR and all goodnesses of fit S are based on
F2, conventional R-factors R are based on F,
with F set to zero for negative F2. The observed criterion of
F2 > σ(F2) is used only for calculating _R_factor_obs
etc. and is not relevant to the choice of reflections for refinement.
R-factors based on F2 are statistically about twice as large
as those based on F, and R- factors based on ALL data will be
even larger. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
S | 0.27961 (7) | 0.03749 (6) | 0.72076 (3) | 0.04792 (17) | |
N | −0.1777 (3) | 0.3389 (3) | 0.41670 (14) | 0.0663 (5) | |
O1 | 0.5029 (2) | −0.0020 (3) | 0.68241 (11) | 0.0729 (5) | |
O2 | 0.3268 (3) | 0.0770 (2) | 0.90668 (11) | 0.0785 (5) | |
O3 | 0.8947 (3) | 0.6315 (2) | 0.90885 (12) | 0.0719 (4) | |
O4 | −0.3630 (4) | 0.3586 (4) | 0.42814 (16) | 0.1173 (8) | |
O5 | −0.0789 (4) | 0.3722 (3) | 0.34593 (13) | 0.1019 (7) | |
C1 | 0.2257 (4) | 0.2501 (3) | 0.77881 (15) | 0.0603 (5) | |
H1A | 0.2692 | 0.3468 | 0.7388 | 0.072* | |
H1B | 0.0780 | 0.2917 | 0.8007 | 0.072* | |
C2 | 0.3458 (3) | 0.2104 (3) | 0.85678 (13) | 0.0550 (5) | |
C3 | 0.4851 (3) | 0.3283 (3) | 0.86721 (12) | 0.0476 (4) | |
C4 | 0.4971 (3) | 0.4898 (3) | 0.81539 (13) | 0.0558 (5) | |
H4 | 0.4132 | 0.5269 | 0.7717 | 0.067* | |
C5 | 0.6301 (3) | 0.5965 (3) | 0.82717 (14) | 0.0567 (5) | |
H5 | 0.6351 | 0.7044 | 0.7921 | 0.068* | |
C6 | 0.7561 (3) | 0.5404 (3) | 0.89194 (13) | 0.0528 (5) | |
C7 | 0.7472 (3) | 0.3787 (3) | 0.94424 (13) | 0.0541 (5) | |
H7 | 0.8330 | 0.3407 | 0.9872 | 0.065* | |
C8 | 0.6131 (3) | 0.2759 (3) | 0.93273 (12) | 0.0501 (4) | |
H8 | 0.6064 | 0.1695 | 0.9688 | 0.060* | |
C9 | 0.1390 (3) | 0.1368 (2) | 0.63123 (12) | 0.0433 (4) | |
C14 | −0.0751 (3) | 0.1755 (3) | 0.64562 (14) | 0.0627 (6) | |
H14 | −0.1486 | 0.1551 | 0.7020 | 0.075* | |
C11 | 0.1454 (3) | 0.2315 (3) | 0.47734 (14) | 0.0572 (5) | |
H11 | 0.2181 | 0.2499 | 0.4206 | 0.069* | |
C10 | 0.2488 (3) | 0.1641 (3) | 0.54825 (13) | 0.0547 (5) | |
H10 | 0.3931 | 0.1372 | 0.5397 | 0.066* | |
C12 | −0.0672 (3) | 0.2704 (2) | 0.49281 (13) | 0.0488 (4) | |
C13 | −0.1786 (3) | 0.2450 (4) | 0.57483 (16) | 0.0660 (6) | |
H13 | −0.3230 | 0.2740 | 0.5832 | 0.079* | |
C15 | 0.8947 (5) | 0.8086 (4) | 0.8655 (2) | 0.0828 (7) | |
H15A | 0.9851 | 0.8650 | 0.8899 | 0.124* | |
H15B | 0.7563 | 0.8867 | 0.8749 | 0.124* | |
H15C | 0.9429 | 0.7936 | 0.8025 | 0.124* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
S | 0.0442 (3) | 0.0493 (3) | 0.0518 (3) | −0.01112 (19) | −0.01421 (19) | 0.00199 (19) |
N | 0.0830 (14) | 0.0566 (10) | 0.0637 (12) | −0.0103 (9) | −0.0343 (10) | −0.0001 (9) |
O1 | 0.0408 (8) | 0.0987 (12) | 0.0659 (9) | 0.0099 (7) | −0.0102 (7) | −0.0072 (8) |
O2 | 0.1028 (14) | 0.0787 (11) | 0.0711 (10) | −0.0418 (10) | −0.0421 (10) | 0.0222 (9) |
O3 | 0.0641 (10) | 0.0681 (10) | 0.0894 (12) | −0.0236 (8) | −0.0240 (8) | 0.0108 (8) |
O4 | 0.0794 (14) | 0.178 (2) | 0.1032 (16) | −0.0265 (14) | −0.0564 (12) | 0.0233 (15) |
O5 | 0.1155 (17) | 0.1189 (17) | 0.0624 (11) | −0.0096 (13) | −0.0299 (11) | 0.0233 (11) |
C1 | 0.0657 (13) | 0.0553 (11) | 0.0587 (12) | 0.0016 (9) | −0.0278 (10) | −0.0078 (9) |
C2 | 0.0614 (12) | 0.0553 (11) | 0.0465 (10) | −0.0048 (9) | −0.0185 (9) | 0.0002 (8) |
C3 | 0.0504 (10) | 0.0494 (10) | 0.0388 (9) | −0.0026 (8) | −0.0110 (7) | −0.0004 (7) |
C4 | 0.0598 (12) | 0.0560 (11) | 0.0469 (10) | −0.0021 (9) | −0.0176 (9) | 0.0069 (8) |
C5 | 0.0593 (12) | 0.0507 (11) | 0.0551 (11) | −0.0072 (9) | −0.0106 (9) | 0.0098 (9) |
C6 | 0.0447 (10) | 0.0532 (11) | 0.0549 (11) | −0.0041 (8) | −0.0050 (8) | −0.0017 (8) |
C7 | 0.0500 (10) | 0.0566 (11) | 0.0523 (11) | −0.0030 (8) | −0.0167 (8) | 0.0035 (8) |
C8 | 0.0555 (11) | 0.0471 (10) | 0.0433 (9) | −0.0035 (8) | −0.0123 (8) | 0.0042 (8) |
C9 | 0.0392 (9) | 0.0466 (9) | 0.0474 (9) | −0.0129 (7) | −0.0114 (7) | −0.0027 (7) |
C14 | 0.0417 (10) | 0.0967 (17) | 0.0527 (11) | −0.0251 (10) | −0.0096 (8) | 0.0096 (11) |
C11 | 0.0567 (12) | 0.0659 (12) | 0.0451 (10) | −0.0104 (9) | −0.0037 (8) | −0.0036 (9) |
C10 | 0.0407 (9) | 0.0679 (12) | 0.0522 (11) | −0.0072 (9) | −0.0058 (8) | −0.0056 (9) |
C12 | 0.0558 (11) | 0.0429 (9) | 0.0524 (10) | −0.0112 (8) | −0.0214 (8) | −0.0028 (8) |
C13 | 0.0401 (10) | 0.0948 (17) | 0.0666 (13) | −0.0203 (10) | −0.0172 (9) | 0.0076 (12) |
C15 | 0.0938 (19) | 0.0726 (16) | 0.0894 (18) | −0.0364 (14) | −0.0161 (15) | 0.0081 (14) |
Geometric parameters (Å, º) top
S—O1 | 1.4771 (15) | C3—C8 | 1.403 (3) |
S—C1 | 1.798 (2) | C4—C5 | 1.381 (3) |
S—C9 | 1.8015 (18) | C5—C6 | 1.386 (3) |
N—O5 | 1.201 (3) | C6—C7 | 1.393 (3) |
N—O4 | 1.204 (3) | C7—C8 | 1.364 (3) |
N—C12 | 1.475 (2) | C9—C10 | 1.370 (3) |
O2—C2 | 1.216 (3) | C9—C14 | 1.380 (3) |
O3—C6 | 1.354 (3) | C14—C13 | 1.382 (3) |
O3—C15 | 1.422 (3) | C11—C12 | 1.369 (3) |
C1—C2 | 1.522 (3) | C11—C10 | 1.381 (3) |
C2—C3 | 1.473 (3) | C12—C13 | 1.360 (3) |
C3—C4 | 1.392 (3) | | |
| | | |
O1—S—C1 | 105.67 (11) | O3—C6—C5 | 124.57 (19) |
O1—S—C9 | 106.95 (9) | O3—C6—C7 | 115.35 (18) |
C1—S—C9 | 95.70 (9) | C5—C6—C7 | 120.07 (19) |
O5—N—O4 | 122.8 (2) | C8—C7—C6 | 120.25 (18) |
O5—N—C12 | 118.6 (2) | C7—C8—C3 | 120.94 (18) |
O4—N—C12 | 118.6 (2) | C10—C9—C14 | 121.07 (17) |
C6—O3—C15 | 118.26 (19) | C10—C9—S | 118.74 (14) |
C2—C1—S | 107.41 (14) | C14—C9—S | 120.11 (15) |
O2—C2—C3 | 122.57 (18) | C9—C14—C13 | 118.86 (19) |
O2—C2—C1 | 117.81 (19) | C12—C11—C10 | 118.23 (18) |
C3—C2—C1 | 119.58 (17) | C9—C10—C11 | 120.02 (18) |
C4—C3—C8 | 117.88 (18) | C13—C12—C11 | 122.49 (18) |
C4—C3—C2 | 123.52 (17) | C13—C12—N | 119.23 (19) |
C8—C3—C2 | 118.60 (17) | C11—C12—N | 118.27 (19) |
C5—C4—C3 | 121.75 (18) | C12—C13—C14 | 119.32 (19) |
C4—C5—C6 | 119.09 (18) | | |