Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536805029909/fl6186sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536805029909/fl6186Isup2.hkl |
CCDC reference: 287557
Crystals of (I) suitable for X-ray diffraction were obtained by slowly concentrating a saturated solution of (I) in CH2Cl2 at 298 K. (m.p. 375–377 K). Rf = 0.35 [SiO2, petroleum ether/Et2O = 2/1 (v/v)]. Analysis, calculated for C14H19NO4S2: C 51.04, H 5.81, N 4.25, S 19.47%; found: C 51.21, H 5.63, N 4.33, S 19.31%. MS (70 eV, EI): m/z (%) 329 (1), 300 (3), 208 (100), 191 (33), 182 (30). 1H NMR (CDCl3, 400 MHz, δ, p.p.m.): 1.38 (t, 3H, J = 7.2 Hz), 1.91 (s, 3H), 3.86 (s, 3H), 3.87 (s, 3H), 4.61 (q, 2H, J = 7.1 Hz), 5.50 (s, 1H), 6.81 (d, 1H, J = 8.2 Hz), 6.88 (d, 1H, J = 1.9 Hz), 6.93 (dd, 1H, J = 1.9, 8.2 Hz). 13C NMR (CDCl3, 100 MHz, δ, p.p.m.): 13.9, 14.1, 56.3, 56.4, 58.6, 70.6, 111.6, 112.0, 121.5, 128.8, 149.4, 156.4, 213.6 (C═S).
Atom H1 was located in a difference Fourier map and its atomic coordinates were refined, with Uiso(H1) = 1.2Ueq(O1). All other H atoms were positioned geometrically and treated as riding atoms, with C—H distances in the range 0.93–0.96 Å and with Uiso(H) = 1.2Ueq(C).
Data collection: CrysAlis CCD (Oxford Diffraction, 2002); cell refinement: CrysAlis RED (Oxford Diffraction, 2002); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON2002 (Spek, 1990, 2003) and ORTEP-3 (Farrugia, 1997, 2005); software used to prepare material for publication: SHELXL97.
C14H19NO4S2 | Dx = 1.297 Mg m−3 |
Mr = 329.42 | Melting point: 375 K |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 9.114 (2) Å | Cell parameters from 1190 reflections |
b = 7.319 (2) Å | θ = 2.6–22.0° |
c = 25.575 (6) Å | µ = 0.33 mm−1 |
β = 98.66 (2)° | T = 299 K |
V = 1686.5 (7) Å3 | Prism, light brown |
Z = 4 | 0.66 × 0.60 × 0.24 mm |
F(000) = 696 |
Oxford Diffraction Xcalibur CCD diffractometer | 1809 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.047 |
Graphite monochromator | θmax = 26.4°, θmin = 4.1° |
Detector resolution: Sapphire CCD detector pixels mm-1 | h = −11→11 |
Rotation method data acquisition using phi scans | k = −9→8 |
4733 measured reflections | l = −31→31 |
3161 independent reflections |
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)] = 0.071 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.220 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.93 | w = 1/[σ2(Fo2) + (0.124P)2 + 1.166P] where P = (Fo2 + 2Fc2)/3 |
3161 reflections | (Δ/σ)max = 0.002 |
193 parameters | Δρmax = 0.40 e Å−3 |
0 restraints | Δρmin = −0.42 e Å−3 |
C14H19NO4S2 | V = 1686.5 (7) Å3 |
Mr = 329.42 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 9.114 (2) Å | µ = 0.33 mm−1 |
b = 7.319 (2) Å | T = 299 K |
c = 25.575 (6) Å | 0.66 × 0.60 × 0.24 mm |
β = 98.66 (2)° |
Oxford Diffraction Xcalibur CCD diffractometer | 1809 reflections with I > 2σ(I) |
4733 measured reflections | Rint = 0.047 |
3161 independent reflections |
R[F2 > 2σ(F2)] = 0.071 | 0 restraints |
wR(F2) = 0.220 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.93 | Δρmax = 0.40 e Å−3 |
3161 reflections | Δρmin = −0.42 e Å−3 |
193 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 | ||
C1 | −0.0010 (4) | 0.8794 (6) | 0.07504 (14) | 0.0523 (9) | |
C2 | 0.3430 (5) | 1.4444 (5) | 0.04715 (18) | 0.0647 (11) | |
H2A | 0.4235 | 1.4745 | 0.0285 | 0.078* | |
H2B | 0.3648 | 1.4879 | 0.0829 | 0.078* | |
H2C | 0.2535 | 1.5009 | 0.0299 | 0.078* | |
C3 | 0.3229 (4) | 1.2427 (5) | 0.04738 (14) | 0.0484 (9) | |
C4 | 0.2029 (4) | 1.1649 (5) | 0.07455 (14) | 0.0468 (9) | |
H4 | 0.1122 | 1.2357 | 0.0635 | 0.056* | |
C5 | 0.2445 (4) | 1.1841 (5) | 0.13463 (14) | 0.0455 (8) | |
C6 | 0.1792 (4) | 1.3210 (5) | 0.16146 (14) | 0.0494 (9) | |
H6 | 0.1089 | 1.3986 | 0.1430 | 0.059* | |
C7 | 0.2189 (4) | 1.3412 (5) | 0.21547 (15) | 0.0509 (9) | |
C8 | 0.3220 (4) | 1.2242 (6) | 0.24348 (14) | 0.0524 (9) | |
C9 | 0.3886 (5) | 1.0923 (6) | 0.21735 (16) | 0.0643 (11) | |
H9 | 0.4591 | 1.0148 | 0.2358 | 0.077* | |
C10 | 0.3494 (5) | 1.0753 (6) | 0.16247 (17) | 0.0619 (11) | |
H10 | 0.3963 | 0.9873 | 0.1446 | 0.074* | |
C11 | 0.0659 (8) | 1.6037 (9) | 0.2184 (2) | 0.113 (2) | |
H11A | 0.0337 | 1.6854 | 0.2438 | 0.135* | |
H11B | −0.0188 | 1.5445 | 0.1986 | 0.135* | |
H11C | 0.1177 | 1.6715 | 0.1947 | 0.135* | |
C12 | 0.4408 (7) | 1.1231 (8) | 0.32818 (19) | 0.0921 (17) | |
H12C | 0.5407 | 1.1325 | 0.3207 | 0.110* | |
H12B | 0.4039 | 1.0021 | 0.3198 | 0.110* | |
H12A | 0.4397 | 1.1471 | 0.3650 | 0.110* | |
C13 | −0.2032 (5) | 0.9993 (7) | 0.1135 (2) | 0.0775 (14) | |
H13A | −0.1927 | 0.9192 | 0.1441 | 0.093* | |
H13B | −0.2758 | 0.9466 | 0.0860 | 0.093* | |
C14 | −0.2513 (6) | 1.1834 (9) | 0.1279 (3) | 0.107 (2) | |
H14A | −0.2610 | 1.2613 | 0.0974 | 0.128* | |
H14B | −0.1789 | 1.2337 | 0.1552 | 0.128* | |
H14C | −0.3452 | 1.1745 | 0.1404 | 0.128* | |
N1 | 0.4023 (4) | 1.1293 (5) | 0.02587 (13) | 0.0568 (9) | |
O1 | 0.5120 (4) | 1.2189 (4) | 0.00144 (14) | 0.0753 (10) | |
H1 | 0.558 (6) | 1.113 (8) | −0.0050 (19) | 0.090* | |
O2 | −0.0617 (3) | 1.0207 (4) | 0.09477 (11) | 0.0606 (8) | |
O3 | 0.1610 (4) | 1.4719 (5) | 0.24482 (11) | 0.0753 (9) | |
O4 | 0.3500 (3) | 1.2518 (4) | 0.29732 (11) | 0.0696 (8) | |
S1 | −0.06609 (14) | 0.67062 (17) | 0.06848 (5) | 0.0759 (4) | |
S2 | 0.16706 (11) | 0.92796 (14) | 0.05342 (4) | 0.0576 (4) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.057 (2) | 0.055 (2) | 0.045 (2) | −0.0034 (19) | 0.0096 (16) | 0.0060 (18) |
C2 | 0.082 (3) | 0.049 (2) | 0.069 (3) | −0.001 (2) | 0.032 (2) | −0.006 (2) |
C3 | 0.055 (2) | 0.046 (2) | 0.0460 (19) | −0.0016 (18) | 0.0154 (16) | −0.0014 (16) |
C4 | 0.056 (2) | 0.042 (2) | 0.0464 (19) | −0.0010 (17) | 0.0197 (16) | −0.0024 (16) |
C5 | 0.0499 (18) | 0.040 (2) | 0.051 (2) | 0.0018 (17) | 0.0212 (15) | −0.0030 (16) |
C6 | 0.0524 (19) | 0.047 (2) | 0.052 (2) | 0.0091 (17) | 0.0173 (16) | 0.0034 (17) |
C7 | 0.057 (2) | 0.047 (2) | 0.053 (2) | 0.0045 (18) | 0.0215 (17) | −0.0044 (17) |
C8 | 0.060 (2) | 0.053 (2) | 0.046 (2) | 0.0010 (19) | 0.0160 (17) | 0.0059 (17) |
C9 | 0.068 (2) | 0.067 (3) | 0.060 (3) | 0.017 (2) | 0.013 (2) | 0.011 (2) |
C10 | 0.070 (2) | 0.054 (3) | 0.065 (3) | 0.020 (2) | 0.023 (2) | 0.001 (2) |
C11 | 0.141 (5) | 0.115 (5) | 0.079 (4) | 0.078 (4) | 0.009 (3) | −0.026 (3) |
C12 | 0.128 (5) | 0.079 (4) | 0.064 (3) | 0.020 (4) | −0.002 (3) | 0.013 (3) |
C13 | 0.064 (3) | 0.097 (4) | 0.079 (3) | −0.013 (3) | 0.035 (2) | −0.008 (3) |
C14 | 0.077 (3) | 0.121 (5) | 0.130 (5) | 0.005 (4) | 0.042 (3) | −0.023 (4) |
N1 | 0.0624 (19) | 0.050 (2) | 0.066 (2) | 0.0010 (16) | 0.0365 (16) | 0.0082 (16) |
O1 | 0.085 (2) | 0.0531 (18) | 0.102 (2) | −0.0042 (16) | 0.0606 (18) | 0.0027 (17) |
O2 | 0.0580 (15) | 0.0671 (19) | 0.0624 (17) | −0.0074 (14) | 0.0272 (13) | −0.0030 (14) |
O3 | 0.097 (2) | 0.079 (2) | 0.0514 (16) | 0.0354 (18) | 0.0134 (15) | −0.0110 (15) |
O4 | 0.086 (2) | 0.073 (2) | 0.0508 (16) | 0.0123 (17) | 0.0118 (14) | 0.0061 (14) |
S1 | 0.0790 (8) | 0.0609 (8) | 0.0857 (9) | −0.0157 (6) | 0.0057 (6) | 0.0069 (6) |
S2 | 0.0633 (6) | 0.0487 (6) | 0.0655 (7) | −0.0025 (5) | 0.0253 (5) | −0.0077 (5) |
C1—O2 | 1.309 (5) | C9—C10 | 1.401 (6) |
C1—S1 | 1.639 (4) | C9—H9 | 0.9300 |
C1—S2 | 1.741 (4) | C10—H10 | 0.9300 |
C2—C3 | 1.488 (5) | C11—O3 | 1.400 (6) |
C2—H2A | 0.9600 | C11—H11A | 0.9600 |
C2—H2B | 0.9600 | C11—H11B | 0.9600 |
C2—H2C | 0.9600 | C11—H11C | 0.9600 |
C3—N1 | 1.278 (5) | C12—O4 | 1.414 (6) |
C3—C4 | 1.494 (5) | C12—H12C | 0.9600 |
C4—C5 | 1.533 (5) | C12—H12B | 0.9600 |
C4—S2 | 1.831 (4) | C12—H12A | 0.9600 |
C4—H4 | 0.9800 | C13—O2 | 1.451 (5) |
C5—C10 | 1.360 (5) | C13—C14 | 1.480 (7) |
C5—C6 | 1.397 (5) | C13—H13A | 0.9700 |
C6—C7 | 1.382 (5) | C13—H13B | 0.9700 |
C6—H6 | 0.9300 | C14—H14A | 0.9600 |
C7—C8 | 1.388 (5) | C14—H14B | 0.9600 |
C7—O3 | 1.370 (4) | C14—H14C | 0.9600 |
C8—C9 | 1.368 (6) | N1—O1 | 1.417 (4) |
C8—O4 | 1.377 (5) | O1—H1 | 0.91 (6) |
O2—C1—S1 | 127.5 (3) | C5—C10—C9 | 121.7 (4) |
O2—C1—S2 | 113.9 (3) | C5—C10—H10 | 119.1 |
S1—C1—S2 | 118.7 (2) | C9—C10—H10 | 119.1 |
C3—C2—H2A | 109.5 | O3—C11—H11A | 109.5 |
C3—C2—H2B | 109.5 | O3—C11—H11B | 109.5 |
H2A—C2—H2B | 109.5 | H11A—C11—H11B | 109.5 |
C3—C2—H2C | 109.5 | O3—C11—H11C | 109.5 |
H2A—C2—H2C | 109.5 | H11A—C11—H11C | 109.5 |
H2B—C2—H2C | 109.5 | H11B—C11—H11C | 109.5 |
N1—C3—C2 | 124.4 (3) | O4—C12—H12C | 109.5 |
N1—C3—C4 | 117.0 (3) | O4—C12—H12B | 109.5 |
C2—C3—C4 | 118.6 (3) | H12C—C12—H12B | 109.5 |
C3—C4—C5 | 110.1 (3) | O4—C12—H12A | 109.5 |
C3—C4—S2 | 109.5 (2) | H12C—C12—H12A | 109.5 |
C5—C4—S2 | 112.9 (3) | H12B—C12—H12A | 109.5 |
C3—C4—H4 | 108.1 | O2—C13—C14 | 107.2 (4) |
C5—C4—H4 | 108.1 | O2—C13—H13A | 110.3 |
S2—C4—H4 | 108.1 | C14—C13—H13A | 110.3 |
C10—C5—C6 | 118.7 (3) | O2—C13—H13B | 110.3 |
C10—C5—C4 | 121.3 (3) | C14—C13—H13B | 110.3 |
C6—C5—C4 | 119.9 (3) | H13A—C13—H13B | 108.5 |
C5—C6—C7 | 120.0 (3) | C13—C14—H14A | 109.5 |
C5—C6—H6 | 120.0 | C13—C14—H14B | 109.5 |
C7—C6—H6 | 120.0 | H14A—C14—H14B | 109.5 |
C8—C7—O3 | 115.8 (3) | C13—C14—H14C | 109.5 |
C8—C7—C6 | 120.3 (3) | H14A—C14—H14C | 109.5 |
O3—C7—C6 | 123.9 (3) | H14B—C14—H14C | 109.5 |
C9—C8—C7 | 120.0 (4) | C3—N1—O1 | 111.8 (3) |
C9—C8—O4 | 124.3 (4) | N1—O1—H1 | 93 (3) |
C7—C8—O4 | 115.8 (3) | C1—O2—C13 | 119.4 (3) |
C8—C9—C10 | 119.1 (4) | C7—O3—C11 | 118.6 (3) |
C8—C9—H9 | 120.4 | C8—O4—C12 | 117.7 (3) |
C10—C9—H9 | 120.4 | C1—S2—C4 | 103.05 (18) |
N1—C3—C4—C5 | 108.4 (4) | O4—C8—C9—C10 | 179.0 (4) |
C2—C3—C4—C5 | −71.4 (5) | C6—C5—C10—C9 | 2.6 (6) |
N1—C3—C4—S2 | −16.3 (4) | C4—C5—C10—C9 | 179.7 (4) |
C2—C3—C4—S2 | 164.0 (3) | C8—C9—C10—C5 | −1.4 (7) |
C3—C4—C5—C10 | −74.3 (4) | C2—C3—N1—O1 | −0.2 (6) |
S2—C4—C5—C10 | 48.4 (4) | C4—C3—N1—O1 | −180.0 (3) |
C3—C4—C5—C6 | 102.8 (4) | S1—C1—O2—C13 | −0.3 (5) |
S2—C4—C5—C6 | −134.5 (3) | S2—C1—O2—C13 | 179.1 (3) |
C10—C5—C6—C7 | −1.5 (6) | C14—C13—O2—C1 | −174.0 (4) |
C4—C5—C6—C7 | −178.6 (3) | C8—C7—O3—C11 | 174.7 (5) |
C5—C6—C7—C8 | −1.0 (6) | C6—C7—O3—C11 | −6.0 (7) |
C5—C6—C7—O3 | 179.7 (4) | C9—C8—O4—C12 | −7.4 (6) |
O3—C7—C8—C9 | −178.3 (4) | C7—C8—O4—C12 | 172.8 (4) |
C6—C7—C8—C9 | 2.3 (6) | O2—C1—S2—C4 | 6.1 (3) |
O3—C7—C8—O4 | 1.5 (5) | S1—C1—S2—C4 | −174.5 (2) |
C6—C7—C8—O4 | −177.8 (3) | C3—C4—S2—C1 | −165.9 (3) |
C7—C8—C9—C10 | −1.1 (6) | C5—C4—S2—C1 | 71.1 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···N1i | 0.91 (6) | 1.90 (6) | 2.786 (5) | 164 (5) |
Symmetry code: (i) −x+1, −y+2, −z. |
Experimental details
Crystal data | |
Chemical formula | C14H19NO4S2 |
Mr | 329.42 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 299 |
a, b, c (Å) | 9.114 (2), 7.319 (2), 25.575 (6) |
β (°) | 98.66 (2) |
V (Å3) | 1686.5 (7) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.33 |
Crystal size (mm) | 0.66 × 0.60 × 0.24 |
Data collection | |
Diffractometer | Oxford Diffraction Xcalibur CCD diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4733, 3161, 1809 |
Rint | 0.047 |
(sin θ/λ)max (Å−1) | 0.625 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.071, 0.220, 0.93 |
No. of reflections | 3161 |
No. of parameters | 193 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.40, −0.42 |
Computer programs: CrysAlis CCD (Oxford Diffraction, 2002), CrysAlis RED (Oxford Diffraction, 2002), CrysAlis RED, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), PLATON2002 (Spek, 1990, 2003) and ORTEP-3 (Farrugia, 1997, 2005), SHELXL97.
C1—O2 | 1.309 (5) | C4—S2 | 1.831 (4) |
C1—S1 | 1.639 (4) | C7—O3 | 1.370 (4) |
C1—S2 | 1.741 (4) | C8—O4 | 1.377 (5) |
C3—N1 | 1.278 (5) | N1—O1 | 1.417 (4) |
O2—C1—S1 | 127.5 (3) | C3—C4—C5 | 110.1 (3) |
O2—C1—S2 | 113.9 (3) | C3—C4—S2 | 109.5 (2) |
S1—C1—S2 | 118.7 (2) | C5—C4—S2 | 112.9 (3) |
N1—C3—C2 | 124.4 (3) | C3—N1—O1 | 111.8 (3) |
N1—C3—C4 | 117.0 (3) | N1—O1—H1 | 93 (3) |
C2—C3—C4 | 118.6 (3) | ||
C2—C3—N1—O1 | −0.2 (6) | C8—C7—O3—C11 | 174.7 (5) |
C4—C3—N1—O1 | −180.0 (3) | C7—C8—O4—C12 | 172.8 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···N1i | 0.91 (6) | 1.90 (6) | 2.786 (5) | 164 (5) |
Symmetry code: (i) −x+1, −y+2, −z. |
The title compound, (I), is the starting material for the synthesis of N-hydroxy-5-(3,4-dimethoxyphenyl)-4-methylthiazole-2(3H)-thione, a molecule of notable interest for investigating substituent effects on the location of absorption bands caused by visible to near-UV light excitations in heterocyclic alkoxyl radical precursors (Hartung, Špehar et al., 2005). Compound (I) has been crystallized and studied by X-ray diffraction in order to gain an understanding of its structural details in the solid state.
The stereogenic centre, atom C4, is substituted by three virtually planar groups, viz a 3,4-dimethoxyphenyl, an O-ethyl dithiocarbonate and an ethyloximino group, and by one H atom (Fig. 1). The heteroatoms and the central C atom of the dithiocarbonate group are located in a plane [deviation of O2 = 0.012 (1) Å]. The stereogenic bonds associated with the latter entity adopt an (E) arrangement for C1—S2 and (Z) geometry for C1—O2. The C1—S1 distance [1.639 (4) Å] is smaller than the mean value for the C═S double bond in O,S-dialkyldithiocarbonates [1.67 (2) Å; Abrahamson & Innes, 1974; Allen et al., 1987; Duarte et al., 1989]. The connectivities S2—C1 and S2—C4 differ in length due to different hybridization of the associated C atoms (Zhang et al., 2003, Hartung, Schmidt et al., 2005). The oxime group adopts an (E) configuration. The distances N1—O1 and N1═C3 distances agree with mean values for both types of connectivities (Allen et al., 1987; Hartung et al., 2004).
The unit cell (Z = 4) comprises a 1:1 mixture of (S) and (R) enantiomers. A view along 001 indicates that these enantiomers are linked via a tandem hydrogen bond to provide dimers. The oxime H atom serves as the donor toward the oxime N atom of an adjacent molecule (Fig. 2, Table 2).