Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270107015430/hj3033sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270107015430/hj3033Isup2.hkl |
CCDC reference: 649094
p-Toluenesulfonyl chloride (11.80 g, 62 mmol) was added to 2-aminophenol (2.25 g, 21 mmol) dissolved in pyridine (50 ml) and stirred under N2 for 60 h. The pyridine was evaporated and CH2Cl2 (100 ml) was added to the resulting residue. The organic phase was then washed with HCl (0.5 M, 2 × 50 ml), water (50 ml) and brine (50 ml), after which it was dried (MgSO4) and evaporated under reduced pressure to afford compound (II) as a yellow solid. This solid was recrystalized from hot EtOH to give white crystals of (II) (6.43 g, 87%, mp. 410–412 K).
NMR: δH (300 MHz, CDCl3) 7.69 (d, 2H, J = 8.3 Hz, 2 × Ar—H), 7.64 (d, 2H, J = 8.3 Hz, 2 × Ar—H), 7.55 (dd, 1H, J = 8.1 and 1.3 Hz, Ar—H), 7.35 (d, 2H, J = 8.3 Hz, 2 × Ar—H), 7.19 (d, 2H, J = 8.3 Hz, 2 × Ar—H), 7.20–7.15 (m partially under d, 1H, Ar—H), 7.08 (br s, 1H, NH), 6.98 (dt, 1H, J = 1.3 and 8.0 Hz, Ar—H), 6.81 (dd, 1H,J = 8.3 and 1.3 Hz, Ar—H), 2.48 (s, 3H, Ar—CH3), 2.36 (s, 3H, Ar—CH3); δC(75 MHz, CDCl3) 146.4 (Ar—O), 144.0 (Ar—N), 140.2 (Ar—S), 136.2 (Ar—S), 131.4 (Ar—C), 130.1 (Ar—CH), 130.0 (Ar—C), 129.6 (Ar—CH), 128.4 (Ar—CH), 127.9 (Ar—CH), 127.3 (Ar—CH), 125.5 (Ar—CH), 123.3 (Ar—CH), 123.0 (Ar—CH), 21.8 (Ar—CH3), 21.5 (Ar—CH3); νmax (thin film, NaCl plate, cm-1): 3361, 3020, 1599, 1495, 1340, 1293, 1215.
The molecule was found to exhibit orientational disorder with the N1 and O5 positions being disordered. Each of these atoms was refined over two positions as N1 and N1A, and O5 and O5A, using SADI restraints, while constraining the sum of the final occupancies to unity. The final occupancy was 0.63 (2) for N1 and O5, and 0.37 (2) for N1A and O5A. NH H atoms (H1 and H1A) were first located in a Fourier difference map and then positioned geometrically (N—H = 0.92 Å) with isotropic displacement parameters equal to 1.2 times Ueq of the parent atoms. H atoms were positioned geometrically and allowed to ride on their respective parent atoms, with C—H bond lengths of 0.95 (aromatic CH) or 0.98 Å (CH3), and isotropic displacement parameters equal to 1.2 (CH) or 1.5 (CH3) times Ueq of the parent atom.
Data collection: SMART-NT (Bruker, 1998); cell refinement: SAINT-Plus (Bruker, 1999); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXTL (Bruker, 1999); program(s) used to refine structure: SHELXTL; molecular graphics: ORTEP-3 (Farrugia, 1997) and SCHAKAL99 (Keller, 1999); software used to prepare material for publication: PLATON (Spek, 2003) and SHELXTL.
C20H19NO5S2 | Z = 2 |
Mr = 417.48 | F(000) = 436 |
Triclinic, P1 | Dx = 1.430 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 9.7596 (2) Å | Cell parameters from 9133 reflections |
b = 10.1025 (2) Å | θ = 2.1–28.3° |
c = 10.7227 (2) Å | µ = 0.31 mm−1 |
α = 80.173 (1)° | T = 173 K |
β = 76.633 (1)° | Irregular, colourless |
γ = 71.442 (1)° | 0.38 × 0.24 × 0.21 mm |
V = 969.68 (3) Å3 |
Bruker SMART CCD area-detector diffractometer | 4042 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.027 |
Graphite monochromator | θmax = 28.0°, θmin = 2.0° |
ϕ and ω scans | h = −12→12 |
18642 measured reflections | k = −12→13 |
4684 independent reflections | l = −14→14 |
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)] = 0.038 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.105 | H-atom parameters constrained |
S = 1.09 | w = 1/[σ2(Fo2) + (0.0381P)2 + 0.6327P] where P = (Fo2 + 2Fc2)/3 |
4684 reflections | (Δ/σ)max = 0.001 |
269 parameters | Δρmax = 0.30 e Å−3 |
92 restraints | Δρmin = −0.43 e Å−3 |
C20H19NO5S2 | γ = 71.442 (1)° |
Mr = 417.48 | V = 969.68 (3) Å3 |
Triclinic, P1 | Z = 2 |
a = 9.7596 (2) Å | Mo Kα radiation |
b = 10.1025 (2) Å | µ = 0.31 mm−1 |
c = 10.7227 (2) Å | T = 173 K |
α = 80.173 (1)° | 0.38 × 0.24 × 0.21 mm |
β = 76.633 (1)° |
Bruker SMART CCD area-detector diffractometer | 4042 reflections with I > 2σ(I) |
18642 measured reflections | Rint = 0.027 |
4684 independent reflections |
R[F2 > 2σ(F2)] = 0.038 | 92 restraints |
wR(F2) = 0.105 | H-atom parameters constrained |
S = 1.09 | Δρmax = 0.30 e Å−3 |
4684 reflections | Δρmin = −0.43 e Å−3 |
269 parameters |
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 | Occ. (<1) | |
C1 | 0.83294 (17) | 0.16805 (17) | 0.30264 (15) | 0.0270 (3) | |
C2 | 0.7702 (2) | 0.06307 (19) | 0.36411 (18) | 0.0340 (4) | |
H2 | 0.8133 | −0.0040 | 0.4282 | 0.041* | |
C3 | 0.6433 (2) | 0.0578 (2) | 0.33027 (19) | 0.0374 (4) | |
H3 | 0.5996 | −0.0139 | 0.3717 | 0.045* | |
C4 | 0.5787 (2) | 0.1558 (2) | 0.23662 (19) | 0.0379 (4) | |
C5 | 0.6442 (2) | 0.2593 (2) | 0.17705 (18) | 0.0376 (4) | |
H5 | 0.6012 | 0.3267 | 0.1130 | 0.045* | |
C6 | 0.7708 (2) | 0.26678 (19) | 0.20879 (16) | 0.0328 (4) | |
H6 | 0.8146 | 0.3383 | 0.1671 | 0.039* | |
C7 | 0.4398 (3) | 0.1512 (3) | 0.2020 (3) | 0.0571 (6) | |
H7A | 0.3647 | 0.2420 | 0.2126 | 0.086* | |
H7B | 0.4041 | 0.0773 | 0.2585 | 0.086* | |
H7C | 0.4599 | 0.1313 | 0.1121 | 0.086* | |
C8 | 0.8407 (2) | 0.37566 (18) | 0.49423 (17) | 0.0308 (4) | |
C9 | 0.8754 (3) | 0.4922 (2) | 0.42126 (19) | 0.0417 (4) | |
H9 | 0.9679 | 0.4818 | 0.3647 | 0.050* | |
C10 | 0.7740 (3) | 0.6234 (2) | 0.4316 (2) | 0.0551 (6) | |
H10 | 0.7970 | 0.7033 | 0.3815 | 0.066* | |
C11 | 0.6405 (3) | 0.6391 (2) | 0.5136 (2) | 0.0589 (7) | |
H11 | 0.5710 | 0.7295 | 0.5186 | 0.071* | |
C12 | 0.6065 (3) | 0.5245 (2) | 0.5887 (2) | 0.0491 (5) | |
H12 | 0.5141 | 0.5357 | 0.6457 | 0.059* | |
C13 | 0.7081 (2) | 0.3927 (2) | 0.58062 (17) | 0.0344 (4) | |
C14 | 0.81376 (19) | 0.26826 (19) | 0.84672 (16) | 0.0313 (4) | |
C15 | 0.8359 (2) | 0.3944 (2) | 0.85734 (18) | 0.0361 (4) | |
H15 | 0.7610 | 0.4805 | 0.8470 | 0.043* | |
C16 | 0.9687 (2) | 0.3930 (2) | 0.88319 (19) | 0.0440 (5) | |
H16 | 0.9847 | 0.4792 | 0.8900 | 0.053* | |
C17 | 1.0791 (2) | 0.2684 (3) | 0.89940 (18) | 0.0461 (5) | |
C18 | 1.0533 (2) | 0.1435 (2) | 0.88926 (19) | 0.0478 (5) | |
H18 | 1.1276 | 0.0572 | 0.9007 | 0.057* | |
C19 | 0.9218 (2) | 0.1423 (2) | 0.86295 (18) | 0.0403 (4) | |
H19 | 0.9056 | 0.0561 | 0.8561 | 0.048* | |
C20 | 1.2236 (3) | 0.2679 (4) | 0.9266 (3) | 0.0734 (9) | |
H20A | 1.2460 | 0.3552 | 0.8865 | 0.110* | |
H20B | 1.3017 | 0.1876 | 0.8912 | 0.110* | |
H20C | 1.2174 | 0.2604 | 1.0200 | 0.110* | |
O1 | 1.05129 (14) | 0.27385 (14) | 0.25118 (13) | 0.0368 (3) | |
O2 | 1.08672 (13) | 0.03836 (13) | 0.36976 (12) | 0.0336 (3) | |
O3 | 0.53655 (15) | 0.38933 (16) | 0.85213 (14) | 0.0454 (3) | |
O4 | 0.62582 (18) | 0.13181 (17) | 0.85563 (16) | 0.0542 (4) | |
S1 | 0.99357 (4) | 0.17685 (4) | 0.34376 (4) | 0.02779 (11) | |
S2 | 0.64780 (5) | 0.26562 (5) | 0.81305 (4) | 0.03651 (13) | |
O5 | 0.6795 (12) | 0.2733 (10) | 0.6568 (7) | 0.0342 (18) | 0.627 (18) |
N1 | 0.9470 (19) | 0.2391 (14) | 0.4861 (12) | 0.031 (3) | 0.627 (18) |
H1 | 0.9072 | 0.1771 | 0.5447 | 0.037* | 0.627 (18) |
O5A | 0.937 (3) | 0.2394 (16) | 0.4788 (16) | 0.025 (2) | 0.373 (18) |
N1A | 0.667 (3) | 0.274 (2) | 0.6553 (17) | 0.041 (5)* | 0.373 (18) |
H1A | 0.7459 | 0.1981 | 0.6314 | 0.050* | 0.373 (18) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0233 (7) | 0.0296 (8) | 0.0265 (8) | −0.0030 (6) | −0.0052 (6) | −0.0076 (6) |
C2 | 0.0334 (9) | 0.0323 (9) | 0.0364 (9) | −0.0077 (7) | −0.0100 (7) | −0.0027 (7) |
C3 | 0.0325 (9) | 0.0374 (10) | 0.0449 (10) | −0.0119 (8) | −0.0070 (8) | −0.0081 (8) |
C4 | 0.0293 (9) | 0.0449 (11) | 0.0409 (10) | −0.0030 (8) | −0.0091 (7) | −0.0199 (8) |
C5 | 0.0353 (9) | 0.0421 (10) | 0.0315 (9) | 0.0006 (8) | −0.0132 (7) | −0.0066 (7) |
C6 | 0.0343 (9) | 0.0342 (9) | 0.0270 (8) | −0.0051 (7) | −0.0068 (7) | −0.0037 (7) |
C7 | 0.0415 (12) | 0.0698 (16) | 0.0691 (15) | −0.0122 (11) | −0.0239 (11) | −0.0210 (12) |
C8 | 0.0336 (9) | 0.0281 (8) | 0.0327 (8) | −0.0047 (7) | −0.0136 (7) | −0.0070 (7) |
C9 | 0.0575 (12) | 0.0340 (10) | 0.0340 (9) | −0.0140 (9) | −0.0078 (9) | −0.0046 (7) |
C10 | 0.0935 (19) | 0.0294 (10) | 0.0350 (10) | −0.0087 (11) | −0.0111 (11) | −0.0034 (8) |
C11 | 0.0829 (18) | 0.0366 (11) | 0.0390 (11) | 0.0131 (11) | −0.0149 (11) | −0.0098 (9) |
C12 | 0.0488 (12) | 0.0508 (12) | 0.0374 (10) | 0.0050 (10) | −0.0097 (9) | −0.0132 (9) |
C13 | 0.0372 (9) | 0.0386 (10) | 0.0304 (8) | −0.0090 (8) | −0.0137 (7) | −0.0053 (7) |
C14 | 0.0324 (9) | 0.0362 (9) | 0.0257 (8) | −0.0136 (7) | −0.0004 (6) | −0.0039 (7) |
C15 | 0.0418 (10) | 0.0336 (9) | 0.0358 (9) | −0.0152 (8) | −0.0118 (8) | 0.0030 (7) |
C16 | 0.0526 (12) | 0.0527 (12) | 0.0372 (10) | −0.0301 (10) | −0.0153 (9) | 0.0054 (9) |
C17 | 0.0362 (10) | 0.0763 (15) | 0.0257 (9) | −0.0188 (10) | −0.0061 (7) | 0.0005 (9) |
C18 | 0.0407 (11) | 0.0570 (13) | 0.0329 (10) | 0.0027 (9) | −0.0051 (8) | −0.0058 (9) |
C19 | 0.0447 (11) | 0.0368 (10) | 0.0337 (9) | −0.0064 (8) | −0.0006 (8) | −0.0086 (8) |
C20 | 0.0438 (13) | 0.133 (3) | 0.0496 (14) | −0.0303 (15) | −0.0161 (11) | −0.0071 (15) |
O1 | 0.0328 (7) | 0.0374 (7) | 0.0382 (7) | −0.0119 (5) | −0.0017 (5) | −0.0029 (5) |
O2 | 0.0259 (6) | 0.0327 (6) | 0.0372 (7) | −0.0002 (5) | −0.0059 (5) | −0.0065 (5) |
O3 | 0.0319 (7) | 0.0587 (9) | 0.0428 (8) | −0.0107 (6) | 0.0017 (6) | −0.0144 (7) |
O4 | 0.0597 (10) | 0.0574 (10) | 0.0540 (9) | −0.0395 (8) | 0.0081 (7) | −0.0107 (7) |
S1 | 0.02313 (19) | 0.0290 (2) | 0.0296 (2) | −0.00452 (15) | −0.00455 (15) | −0.00514 (15) |
S2 | 0.0331 (2) | 0.0453 (3) | 0.0349 (2) | −0.0199 (2) | 0.00177 (18) | −0.00891 (19) |
O5 | 0.030 (2) | 0.047 (3) | 0.034 (2) | −0.0181 (16) | −0.0047 (11) | −0.0140 (11) |
N1 | 0.032 (5) | 0.032 (3) | 0.029 (3) | −0.004 (2) | −0.010 (2) | −0.011 (3) |
O5A | 0.021 (3) | 0.024 (4) | 0.034 (5) | −0.007 (3) | −0.015 (3) | 0.004 (3) |
C1—C2 | 1.387 (2) | C13—N1A | 1.435 (17) |
C1—C6 | 1.389 (2) | C14—C19 | 1.384 (3) |
C1—S1 | 1.7555 (17) | C14—C15 | 1.386 (2) |
C2—C3 | 1.387 (3) | C14—S2 | 1.7481 (18) |
C2—H2 | 0.9500 | C15—C16 | 1.381 (3) |
C3—C4 | 1.393 (3) | C15—H15 | 0.9500 |
C3—H3 | 0.9500 | C16—C17 | 1.387 (3) |
C4—C5 | 1.386 (3) | C16—H16 | 0.9500 |
C4—C7 | 1.502 (3) | C17—C18 | 1.389 (3) |
C5—C6 | 1.382 (3) | C17—C20 | 1.503 (3) |
C5—H5 | 0.9500 | C18—C19 | 1.380 (3) |
C6—H6 | 0.9500 | C18—H18 | 0.9500 |
C7—H7A | 0.9800 | C19—H19 | 0.9500 |
C7—H7B | 0.9800 | C20—H20A | 0.9800 |
C7—H7C | 0.9800 | C20—H20B | 0.9800 |
C8—C13 | 1.386 (3) | C20—H20C | 0.9800 |
C8—C9 | 1.389 (3) | O1—S1 | 1.4226 (13) |
C8—O5A | 1.409 (15) | O2—S1 | 1.4270 (12) |
C8—N1 | 1.441 (12) | O3—S2 | 1.4217 (15) |
C9—C10 | 1.383 (3) | O4—S2 | 1.4179 (15) |
C9—H9 | 0.9500 | S1—O5A | 1.588 (15) |
C10—C11 | 1.372 (4) | S1—N1 | 1.660 (11) |
C10—H10 | 0.9500 | S2—O5 | 1.625 (7) |
C11—C12 | 1.380 (3) | S2—N1A | 1.648 (18) |
C11—H11 | 0.9500 | O5—H1A | 0.8644 |
C12—C13 | 1.386 (3) | N1—H1 | 0.9200 |
C12—H12 | 0.9500 | O5A—H1 | 0.9195 |
C13—O5 | 1.405 (8) | N1A—H1A | 0.9200 |
C2—C1—C6 | 121.09 (16) | C16—C15—H15 | 120.5 |
C2—C1—S1 | 119.65 (13) | C14—C15—H15 | 120.5 |
C6—C1—S1 | 119.26 (14) | C15—C16—C17 | 121.5 (2) |
C1—C2—C3 | 118.80 (17) | C15—C16—H16 | 119.3 |
C1—C2—H2 | 120.6 | C17—C16—H16 | 119.3 |
C3—C2—H2 | 120.6 | C16—C17—C18 | 118.33 (19) |
C2—C3—C4 | 121.21 (18) | C16—C17—C20 | 121.1 (2) |
C2—C3—H3 | 119.4 | C18—C17—C20 | 120.6 (2) |
C4—C3—H3 | 119.4 | C19—C18—C17 | 121.28 (19) |
C5—C4—C3 | 118.54 (17) | C19—C18—H18 | 119.4 |
C5—C4—C7 | 120.44 (19) | C17—C18—H18 | 119.4 |
C3—C4—C7 | 121.0 (2) | C18—C19—C14 | 119.13 (19) |
C6—C5—C4 | 121.42 (17) | C18—C19—H19 | 120.4 |
C6—C5—H5 | 119.3 | C14—C19—H19 | 120.4 |
C4—C5—H5 | 119.3 | C17—C20—H20A | 109.5 |
C5—C6—C1 | 118.95 (17) | C17—C20—H20B | 109.5 |
C5—C6—H6 | 120.5 | H20A—C20—H20B | 109.5 |
C1—C6—H6 | 120.5 | C17—C20—H20C | 109.5 |
C4—C7—H7A | 109.5 | H20A—C20—H20C | 109.5 |
C4—C7—H7B | 109.5 | H20B—C20—H20C | 109.5 |
H7A—C7—H7B | 109.5 | O1—S1—O2 | 119.24 (8) |
C4—C7—H7C | 109.5 | O1—S1—O5A | 109.2 (7) |
H7A—C7—H7C | 109.5 | O2—S1—O5A | 105.4 (6) |
H7B—C7—H7C | 109.5 | O1—S1—N1 | 108.0 (6) |
C13—C8—C9 | 119.80 (17) | O2—S1—N1 | 102.8 (5) |
C13—C8—O5A | 119.3 (9) | O1—S1—C1 | 108.54 (8) |
C9—C8—O5A | 120.9 (9) | O2—S1—C1 | 109.69 (8) |
C13—C8—N1 | 120.3 (7) | O5A—S1—C1 | 103.7 (10) |
C9—C8—N1 | 119.7 (7) | N1—S1—C1 | 107.9 (7) |
C10—C9—C8 | 119.4 (2) | O4—S2—O3 | 120.34 (9) |
C10—C9—H9 | 120.3 | O4—S2—O5 | 104.2 (3) |
C8—C9—H9 | 120.3 | O3—S2—O5 | 108.8 (4) |
C11—C10—C9 | 120.6 (2) | O4—S2—N1A | 102.8 (7) |
C11—C10—H10 | 119.7 | O3—S2—N1A | 106.7 (9) |
C9—C10—H10 | 119.7 | O4—S2—C14 | 109.95 (10) |
C10—C11—C12 | 120.4 (2) | O3—S2—C14 | 108.62 (9) |
C10—C11—H11 | 119.8 | O5—S2—C14 | 103.5 (4) |
C12—C11—H11 | 119.8 | N1A—S2—C14 | 107.6 (8) |
C11—C12—C13 | 119.5 (2) | C13—O5—S2 | 120.3 (6) |
C11—C12—H12 | 120.2 | C13—O5—H1A | 110.3 |
C13—C12—H12 | 120.2 | S2—O5—H1A | 110.1 |
C8—C13—C12 | 120.15 (19) | C8—N1—S1 | 116.3 (9) |
C8—C13—O5 | 118.2 (5) | C8—N1—H1 | 107.1 |
C12—C13—O5 | 121.6 (5) | S1—N1—H1 | 107.3 |
C8—C13—N1A | 121.2 (11) | C8—O5A—S1 | 123.1 (12) |
C12—C13—N1A | 118.4 (11) | C8—O5A—H1 | 109.7 |
C19—C14—C15 | 120.88 (18) | S1—O5A—H1 | 113.1 |
C19—C14—S2 | 118.77 (15) | C13—N1A—S2 | 117.0 (13) |
C15—C14—S2 | 120.35 (14) | C13—N1A—H1A | 104.4 |
C16—C15—C14 | 118.92 (18) | S2—N1A—H1A | 105.1 |
C6—C1—C2—C3 | 0.0 (3) | C6—C1—S1—O2 | −143.28 (13) |
S1—C1—C2—C3 | −179.98 (14) | C2—C1—S1—O5A | −75.4 (6) |
C1—C2—C3—C4 | −0.2 (3) | C6—C1—S1—O5A | 104.5 (6) |
C2—C3—C4—C5 | 0.2 (3) | C2—C1—S1—N1 | −74.6 (6) |
C2—C3—C4—C7 | −178.92 (19) | C6—C1—S1—N1 | 105.4 (5) |
C3—C4—C5—C6 | 0.0 (3) | C19—C14—S2—O4 | 22.65 (17) |
C7—C4—C5—C6 | 179.05 (18) | C15—C14—S2—O4 | −157.10 (15) |
C4—C5—C6—C1 | −0.1 (3) | C19—C14—S2—O3 | 156.22 (14) |
C2—C1—C6—C5 | 0.1 (3) | C15—C14—S2—O3 | −23.53 (17) |
S1—C1—C6—C5 | −179.90 (13) | C19—C14—S2—O5 | −88.2 (4) |
C13—C8—C9—C10 | −2.9 (3) | C15—C14—S2—O5 | 92.0 (4) |
O5A—C8—C9—C10 | 175.1 (11) | C19—C14—S2—N1A | −88.6 (9) |
N1—C8—C9—C10 | −178.6 (7) | C15—C14—S2—N1A | 91.6 (8) |
C8—C9—C10—C11 | 0.4 (3) | C8—C13—O5—S2 | 121.1 (7) |
C9—C10—C11—C12 | 1.2 (4) | C12—C13—O5—S2 | −60.0 (9) |
C10—C11—C12—C13 | −0.2 (4) | N1A—C13—O5—S2 | −108 (16) |
C9—C8—C13—C12 | 3.9 (3) | O4—S2—O5—C13 | −179.4 (7) |
O5A—C8—C13—C12 | −174.2 (11) | O3—S2—O5—C13 | 51.1 (9) |
N1—C8—C13—C12 | 179.6 (7) | N1A—S2—O5—C13 | 110 (16) |
C9—C8—C13—O5 | −177.3 (4) | C14—S2—O5—C13 | −64.3 (8) |
O5A—C8—C13—O5 | 4.7 (12) | C13—C8—N1—S1 | 120.4 (9) |
N1—C8—C13—O5 | −1.6 (8) | C9—C8—N1—S1 | −63.9 (14) |
C9—C8—C13—N1A | 178.6 (9) | O5A—C8—N1—S1 | 40 (14) |
O5A—C8—C13—N1A | 0.6 (12) | O1—S1—N1—C8 | 58.4 (13) |
N1—C8—C13—N1A | −5.7 (13) | O2—S1—N1—C8 | −174.6 (11) |
C11—C12—C13—C8 | −2.3 (3) | O5A—S1—N1—C8 | −47 (15) |
C11—C12—C13—O5 | 178.9 (4) | C1—S1—N1—C8 | −58.8 (13) |
C11—C12—C13—N1A | −177.2 (9) | C13—C8—O5A—S1 | 123.3 (15) |
C19—C14—C15—C16 | 0.7 (3) | C9—C8—O5A—S1 | −55 (2) |
S2—C14—C15—C16 | −179.58 (14) | N1—C8—O5A—S1 | −134 (17) |
C14—C15—C16—C17 | −0.4 (3) | O1—S1—O5A—C8 | 51 (2) |
C15—C16—C17—C18 | −0.1 (3) | O2—S1—O5A—C8 | 180.0 (16) |
C15—C16—C17—C20 | 179.60 (19) | N1—S1—O5A—C8 | 126 (17) |
C16—C17—C18—C19 | 0.4 (3) | C1—S1—O5A—C8 | −65 (2) |
C20—C17—C18—C19 | −179.31 (19) | C8—C13—N1A—S2 | 116.5 (14) |
C17—C18—C19—C14 | −0.1 (3) | C12—C13—N1A—S2 | −68.7 (17) |
C15—C14—C19—C18 | −0.4 (3) | O5—C13—N1A—S2 | 65 (14) |
S2—C14—C19—C18 | 179.85 (14) | O4—S2—N1A—C13 | −173.3 (14) |
C2—C1—S1—O1 | 168.59 (13) | O3—S2—N1A—C13 | 59.2 (18) |
C6—C1—S1—O1 | −11.43 (16) | O5—S2—N1A—C13 | −63 (14) |
C2—C1—S1—O2 | 36.74 (16) | C14—S2—N1A—C13 | −57.2 (18) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O2i | 0.92 | 2.20 | 3.038 (16) | 151 |
N1A—H1A···O2i | 0.92 | 2.43 | 3.31 (3) | 162 |
C2—H2···O2i | 0.95 | 2.50 | 3.328 (2) | 145 |
C16—H16···O1ii | 0.95 | 2.65 | 3.391 (2) | 135 |
C20—H20C···O1iii | 0.98 | 2.63 | 3.499 (3) | 148 |
C18—H18···Cg1i | 0.95 | 2.93 | 3.642 (2) | 133 |
N1—H1···O5 | 0.92 | 2.26 | 2.779 (18) | 115 |
N1A—H1A···O5A | 0.92 | 2.27 | 2.82 (3) | 118 |
C6—H6···O1 | 0.95 | 2.53 | 2.901 (3) | 104 |
C9—H9···O1 | 0.95 | 2.43 | 2.942 (2) | 114 |
C12—H12···O3 | 0.95 | 2.46 | 2.949 (3) | 112 |
C19—H19···O4 | 0.95 | 2.59 | 2.944 (3) | 102 |
Symmetry codes: (i) −x+2, −y, −z+1; (ii) −x+2, −y+1, −z+1; (iii) x, y, z+1. |
Experimental details
Crystal data | |
Chemical formula | C20H19NO5S2 |
Mr | 417.48 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 173 |
a, b, c (Å) | 9.7596 (2), 10.1025 (2), 10.7227 (2) |
α, β, γ (°) | 80.173 (1), 76.633 (1), 71.442 (1) |
V (Å3) | 969.68 (3) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.31 |
Crystal size (mm) | 0.38 × 0.24 × 0.21 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 18642, 4684, 4042 |
Rint | 0.027 |
(sin θ/λ)max (Å−1) | 0.661 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.038, 0.105, 1.09 |
No. of reflections | 4684 |
No. of parameters | 269 |
No. of restraints | 92 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.30, −0.43 |
Computer programs: SMART-NT (Bruker, 1998), SAINT-Plus (Bruker, 1999), SAINT-Plus, SHELXTL (Bruker, 1999), ORTEP-3 (Farrugia, 1997) and SCHAKAL99 (Keller, 1999), PLATON (Spek, 2003) and SHELXTL.
C6—C1—S1—O1 | −11.43 (16) | C19—C14—S2—O4 | 22.65 (17) |
C2—C1—S1—O2 | 36.74 (16) | C15—C14—S2—O3 | −23.53 (17) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O2i | 0.92 | 2.20 | 3.038 (16) | 150.9 |
N1A—H1A···O2i | 0.92 | 2.43 | 3.31 (3) | 161.5 |
C2—H2···O2i | 0.95 | 2.50 | 3.328 (2) | 145.0 |
C16—H16···O1ii | 0.95 | 2.65 | 3.391 (2) | 135.0 |
C20—H20C···O1iii | 0.98 | 2.63 | 3.499 (3) | 148.0 |
C18—H18···Cg1i | 0.95 | 2.93 | 3.642 (2) | 133.0 |
Symmetry codes: (i) −x+2, −y, −z+1; (ii) −x+2, −y+1, −z+1; (iii) x, y, z+1. |
Benzannulated heterocycles are interesting compounds that play important structural roles in natural products and man-made pharmaceuticals. Our research group has used ring-closing metathesis (RCM) and isomerization-RCM strategies to synthesize benzannulated heterocycles (van Otterlo, Morgans et al., 2004, 2005; van Otterlo, Ngidi et al., 2004, 2005).
During the synthesis of heterocycles, such as (IV), containing both N and O atoms in the benzofused portion, 2-aminophenol, (I), has to be protected initially as its ditosyl derivative, (II). Selective cleavage of the S—O bond, with magnesium in methanol (Sridhar et al., 1998), then affords compound (III), which can be converted to the protected 6-[(4-methylphenyl)sulfonyl]-5,6-dihydro-2H-1,6-benzoxazocine, (IV), via a number of steps (van Otterlo, Morgans et al., 2004 or van Otterlo, Ngidi et al., 2004 ????; Ibrahim et al., 2002). As compound (II) is crystalline it was decided that it would be interesting to investigate its structure in the solid state.
The title compound crystallizes as a disordered arrangement in which atoms N1 and O5 are swapped around in two orientations such that the molecule shown in Fig. 1(a) (Orient-A) is superimposed on the molecule shown in Fig. 1(b) (Orient-B). The ratio Orient-A to Orient-B is about 0.63 (2):0.37 (2). Visually the molecule has a pseudo-twofold axis passing through the aromatic ring defined by atoms C8–C13, and one would therefore expect the molecule to crystallize on a twofold axis (a special position in space groups containing this symmetry) leading to the observed orientational disorder. However, the compound crystallizes instead in the space group P1 with one molecule in the assymetric unit. Comparison of some geometric parameters between the sulfonyl groups and the attached benzene rings (C1–C6 versus C14–C19) indicates that the torsion angles on the two sides differ by more than 10° (Table 1) and hence indicate the absence of a molecular twofold axis.
The crystal structure of (II) is stabilized by both intramolecular and intermolecular classical and weak hydrogen bonding (Table 2; for simplicity the very extensive intramolecular hydrogen bonding has been omitted from this table but can be found in the CIF). The dominant intermolecular interaction in the structure is an N—H···O hydrogen bond between a pair of molecules forming a hydrogen-bonded dimer. The morphology of this hydrogen-bonded network differs significantly between the two molecular orientations, though the overall appearance is very similar (Fig. 2). For Orient-A, the N—H···O hydrogen bonding (between N1 and O2i; symmetry codes as in Table 2) results in a hydrogen-bonded dimer that can be described by the R22(8) graph set (Fig. 2a). For the alternative orientation (Orient-B) the N—H···O hydrogen bonding (between N1A and O2i in this case) results in a hydrogen-bonded dimer that can be described by the R22(14) graph set (Fig. 2b). Interestingly, the hydrogen-bond dimer formed by a pair of Orient-A molecules has a D···A distance of 3.038 (16) Å versus 3.31 (3) Å in the dimer formed by a pair of Orient-B molecules. The shorter D···A distance between Orient-A molecules implies that this orientation is more stable and this assumption is coroborated by the higher frequency of Orient-A (63% occurance). Nevertheless the frequency of the Orient-B orientation is still very high. Rather than the extremes of Orient-A– and Orient-B-only dimers, it is likely that the `real' average situation in a crystal is a hydrogen-bonded relationship in which Orient-A is about 26% (frequency of Orient-A minus frequency of Orient-B) of the time hydrogen bonded to other Orient-A molecules and the rest of the time hydrogen bonded to Orient-B molecules (37% of the time – the frequency of Orient-B). This Orient-A + Orient-B arrangement would probably not be as energetically unfavourable as Orient-B-only hydrogen-bonded dimers, being made up of one hydrogen bond of each type of orientation, i.e. one 3.0 Å and one 3.3 Å intermolecular N—H···O bond. These hydrogen-bonded dimers are further stabilized by C—H···π [C18—H18···Cg(C1–C6)i] and C—H···O (C2—H2···O2) interactions (Fig. 2). The stabilization due to these extra weak interactions is probably also a significant contributor to the stability of the Orient-B dimers as it would probably make the conversion of Orient-B + Orient-B (if they exist) and Orient-B + Orient-A dimers to Orient-A-only dimers quite difficult.
Finally, all the hydrogen-bonded dimers interact further with neighbouring dimers through C—H···O interactions (C16—H16···O1 and C20—H20C···O1) to form layers perpendicular to the (100) direction.