Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801005347/ya6017sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536801005347/ya6017Isup2.hkl |
CCDC reference: 165643
Key indicators
- Single-crystal X-ray study
- T = 223 K
- Mean (C-C) = 0.005 Å
- R factor = 0.047
- wR factor = 0.136
- Data-to-parameter ratio = 18.8
checkCIF results
No syntax errors found ADDSYM reports no extra symmetry
Alert Level C:
ABSTM_02 Alert C The ratio of Tmax/Tmin expected RT(exp) is > 1.10 Absorption corrections should be applied. Tmin and Tmax expected: 0.860 0.949 RT(exp) = 1.103
0 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
1 Alert Level C = Please check
The title compound was prepared in 70% yield by the sodium hypochlorite oxidation (Campbell & Johnson, 1978) of N-(4,4-dimethoxy-1-thianylidene)-4-methyl-1-benzenesulfonamide (Creaser et al., 2001) and was recrystallized from an ethanol solution of the compound to give colourless crystals, m.p. 424–426 K. Found: C 48.6, H 6.4, N 4.0%; calculated for C14H21NO5S2: C 48.4, H 6.9, N 4.0%.
The H atoms were placed in geometrically calculated positions and included in the final refinement in the riding-model approximation with an overall displacement parameter (refined).
Data collection: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1988); cell refinement: MSC/AFC Diffractometer Control Software; data reduction: TEXSAN (Molecular Structure Corporation, 1992); program(s) used to solve structure: SIR92 (Altomare, et al. 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); software used to prepare material for publication: SHELXL97.
Fig. 1. The molecular structure and crystallographic numbering scheme for (I). Displacement ellipsoids are shown at the 50% probability level (Johnson, 1976). |
C14H21NO5S2 | F(000) = 736 |
Mr = 347.44 | Dx = 1.415 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 19.516 (8) Å | Cell parameters from 21 reflections |
b = 6.039 (2) Å | θ = 8.0–26.0° |
c = 14.940 (7) Å | µ = 0.35 mm−1 |
β = 112.17 (3)° | T = 223 K |
V = 1631 (1) Å3 | Plate, colourless |
Z = 4 | 0.44 × 0.37 × 0.15 mm |
Rigaku AFC-6R diffractometer | Rint = 0.020 |
Radiation source: Rigaku rotating anode | θmax = 27.6°, θmin = 3.1° |
Graphite monochromator | h = −25→23 |
ω–2θ scans | k = −7→0 |
4273 measured reflections | l = 0→19 |
3762 independent reflections | 3 standard reflections every 400 reflections |
2668 reflections with I > 2σ(I) | intensity decay: 1.2% |
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)] = 0.047 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.136 | H-atom parameters constrained |
S = 1.02 | w = 1/[σ2(Fo2) + (0.0529P)2 + 1.3963P] where P = (Fo2 + 2Fc2)/3 |
3762 reflections | (Δ/σ)max < 0.001 |
200 parameters | Δρmax = 0.32 e Å−3 |
0 restraints | Δρmin = −0.39 e Å−3 |
C14H21NO5S2 | V = 1631 (1) Å3 |
Mr = 347.44 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 19.516 (8) Å | µ = 0.35 mm−1 |
b = 6.039 (2) Å | T = 223 K |
c = 14.940 (7) Å | 0.44 × 0.37 × 0.15 mm |
β = 112.17 (3)° |
Rigaku AFC-6R diffractometer | Rint = 0.020 |
4273 measured reflections | 3 standard reflections every 400 reflections |
3762 independent reflections | intensity decay: 1.2% |
2668 reflections with I > 2σ(I) |
R[F2 > 2σ(F2)] = 0.047 | 0 restraints |
wR(F2) = 0.136 | H-atom parameters constrained |
S = 1.02 | Δρmax = 0.32 e Å−3 |
3762 reflections | Δρmin = −0.39 e Å−3 |
200 parameters |
Experimental. The scan width was (1.05 + 0.35tanθ)° with an ω scan speed of 32° per minute (up to 5 scans to achieve I/σ(I) > 20). Stationary background counts were recorded at each end of the scan, and the scan time:background time ratio was 2:1. |
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 | ||
S1 | 0.23417 (4) | 0.01127 (12) | 0.16572 (5) | 0.03030 (18) | |
S2 | 0.23138 (3) | −0.22891 (11) | 0.00526 (4) | 0.02696 (17) | |
O1 | 0.15973 (11) | 0.0939 (4) | 0.13772 (16) | 0.0494 (6) | |
O2 | 0.23315 (11) | −0.0155 (3) | −0.03750 (14) | 0.0364 (5) | |
O3 | 0.28154 (10) | −0.3964 (3) | −0.00236 (14) | 0.0356 (5) | |
O4 | 0.47242 (10) | 0.0390 (4) | 0.35260 (15) | 0.0398 (5) | |
O5 | 0.38518 (11) | 0.3025 (3) | 0.35486 (14) | 0.0385 (5) | |
N1 | 0.24813 (12) | −0.2078 (4) | 0.11972 (15) | 0.0285 (5) | |
C2 | 0.29228 (15) | 0.2295 (5) | 0.1580 (2) | 0.0348 (6) | |
H2A | 0.2803 | 0.2669 | 0.0907 | 0.071 (3)* | |
H2B | 0.2834 | 0.3595 | 0.1903 | 0.071 (3)* | |
C3 | 0.37379 (15) | 0.1656 (5) | 0.20428 (19) | 0.0335 (6) | |
H3A | 0.4037 | 0.2881 | 0.1978 | 0.071 (3)* | |
H3B | 0.3829 | 0.0399 | 0.1699 | 0.071 (3)* | |
C4 | 0.39764 (14) | 0.1060 (5) | 0.31161 (19) | 0.0309 (6) | |
C5 | 0.35510 (15) | −0.0923 (5) | 0.3269 (2) | 0.0337 (6) | |
H5A | 0.3648 | −0.2196 | 0.2939 | 0.071 (3)* | |
H5B | 0.3731 | −0.1265 | 0.3954 | 0.071 (3)* | |
C6 | 0.27188 (16) | −0.0537 (5) | 0.29020 (19) | 0.0360 (6) | |
H6A | 0.2617 | 0.0667 | 0.3264 | 0.071 (3)* | |
H6B | 0.2480 | −0.1858 | 0.3015 | 0.071 (3)* | |
C7 | 0.14086 (14) | −0.3356 (5) | −0.04847 (18) | 0.0277 (5) | |
C8 | 0.08076 (15) | −0.2028 (5) | −0.0538 (2) | 0.0353 (6) | |
H8 | 0.0885 | −0.0618 | −0.0267 | 0.071 (3)* | |
C9 | 0.00969 (16) | −0.2830 (6) | −0.0996 (2) | 0.0409 (7) | |
H9 | −0.0303 | −0.1941 | −0.1036 | 0.071 (3)* | |
C10 | −0.00333 (16) | −0.4939 (5) | −0.1398 (2) | 0.0365 (6) | |
C101 | −0.08120 (18) | −0.5814 (7) | −0.1893 (3) | 0.0519 (9) | |
H10A | −0.1159 | −0.4718 | −0.1864 | 0.071 (3)* | |
H10B | −0.0870 | −0.7137 | −0.1572 | 0.071 (3)* | |
H10C | −0.0901 | −0.6144 | −0.2556 | 0.071 (3)* | |
C11 | 0.05722 (17) | −0.6214 (5) | −0.1342 (2) | 0.0402 (7) | |
H11 | 0.0493 | −0.7614 | −0.1622 | 0.071 (3)* | |
C12 | 0.12923 (16) | −0.5463 (5) | −0.0880 (2) | 0.0339 (6) | |
H12 | 0.1691 | −0.6361 | −0.0836 | 0.071 (3)* | |
C41 | 0.52506 (17) | 0.1986 (6) | 0.3479 (3) | 0.0526 (9) | |
H41A | 0.5741 | 0.1386 | 0.3773 | 0.071 (3)* | |
H41B | 0.5212 | 0.3304 | 0.3816 | 0.071 (3)* | |
H41C | 0.5152 | 0.2338 | 0.2815 | 0.071 (3)* | |
C42 | 0.40243 (19) | 0.2942 (6) | 0.4574 (2) | 0.0490 (8) | |
H42A | 0.3920 | 0.4353 | 0.4790 | 0.071 (3)* | |
H42B | 0.4539 | 0.2598 | 0.4904 | 0.071 (3)* | |
H42C | 0.3729 | 0.1821 | 0.4711 | 0.071 (3)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0272 (3) | 0.0324 (4) | 0.0310 (3) | 0.0010 (3) | 0.0106 (3) | −0.0050 (3) |
S2 | 0.0284 (3) | 0.0275 (3) | 0.0258 (3) | 0.0022 (3) | 0.0111 (2) | 0.0012 (3) |
O1 | 0.0305 (11) | 0.0601 (15) | 0.0540 (13) | 0.0088 (11) | 0.0119 (10) | −0.0170 (12) |
O2 | 0.0432 (11) | 0.0318 (11) | 0.0345 (10) | −0.0026 (9) | 0.0151 (9) | 0.0070 (9) |
O3 | 0.0335 (10) | 0.0390 (12) | 0.0367 (10) | 0.0089 (9) | 0.0160 (8) | −0.0016 (9) |
O4 | 0.0271 (10) | 0.0430 (13) | 0.0444 (11) | −0.0021 (9) | 0.0080 (9) | 0.0021 (10) |
O5 | 0.0460 (12) | 0.0308 (11) | 0.0355 (10) | −0.0018 (9) | 0.0118 (9) | −0.0050 (9) |
N1 | 0.0313 (11) | 0.0282 (12) | 0.0263 (10) | 0.0005 (9) | 0.0112 (9) | −0.0006 (9) |
C2 | 0.0395 (15) | 0.0232 (14) | 0.0368 (14) | 0.0015 (12) | 0.0089 (12) | 0.0026 (12) |
C3 | 0.0356 (14) | 0.0325 (15) | 0.0327 (14) | −0.0059 (12) | 0.0132 (12) | 0.0035 (12) |
C4 | 0.0310 (13) | 0.0284 (15) | 0.0308 (13) | −0.0017 (11) | 0.0090 (11) | 0.0003 (11) |
C5 | 0.0367 (15) | 0.0330 (16) | 0.0290 (13) | −0.0037 (12) | 0.0095 (11) | 0.0026 (12) |
C6 | 0.0400 (15) | 0.0425 (17) | 0.0281 (13) | −0.0082 (13) | 0.0160 (12) | −0.0054 (13) |
C7 | 0.0293 (13) | 0.0271 (14) | 0.0256 (12) | 0.0011 (11) | 0.0091 (10) | 0.0008 (11) |
C8 | 0.0320 (14) | 0.0300 (15) | 0.0409 (15) | 0.0032 (12) | 0.0102 (12) | −0.0085 (13) |
C9 | 0.0310 (14) | 0.0449 (19) | 0.0448 (16) | 0.0048 (13) | 0.0119 (13) | −0.0053 (15) |
C10 | 0.0352 (14) | 0.0392 (17) | 0.0339 (13) | −0.0066 (13) | 0.0115 (11) | 0.0003 (13) |
C101 | 0.0411 (17) | 0.059 (2) | 0.0526 (19) | −0.0131 (16) | 0.0140 (15) | −0.0056 (18) |
C11 | 0.0447 (17) | 0.0280 (16) | 0.0432 (16) | −0.0040 (13) | 0.0112 (14) | −0.0047 (13) |
C12 | 0.0355 (14) | 0.0265 (14) | 0.0369 (14) | 0.0057 (12) | 0.0105 (12) | −0.0015 (12) |
C41 | 0.0346 (16) | 0.061 (2) | 0.061 (2) | −0.0107 (16) | 0.0160 (15) | −0.0067 (18) |
C42 | 0.059 (2) | 0.050 (2) | 0.0371 (16) | −0.0103 (17) | 0.0180 (15) | −0.0132 (15) |
S1—O1 | 1.441 (2) | C2—C3 | 1.526 (4) |
S1—N1 | 1.561 (2) | C3—C4 | 1.534 (4) |
S1—C6 | 1.767 (3) | C4—C5 | 1.523 (4) |
S1—C2 | 1.771 (3) | C5—C6 | 1.523 (4) |
S2—O3 | 1.442 (2) | C7—C12 | 1.385 (4) |
S2—O2 | 1.445 (2) | C7—C8 | 1.398 (4) |
S2—N1 | 1.620 (2) | C8—C9 | 1.382 (4) |
S2—C7 | 1.764 (3) | C9—C10 | 1.390 (4) |
O4—C4 | 1.412 (3) | C10—C11 | 1.386 (4) |
O4—C41 | 1.430 (4) | C10—C101 | 1.512 (4) |
O5—C4 | 1.416 (3) | C11—C12 | 1.387 (4) |
O5—C42 | 1.440 (3) | ||
O1—S1—N1 | 119.35 (13) | O4—C4—C5 | 104.0 (2) |
O1—S1—C6 | 110.88 (14) | O5—C4—C5 | 113.2 (2) |
N1—S1—C6 | 101.70 (14) | O4—C4—C3 | 112.1 (2) |
O1—S1—C2 | 108.88 (15) | O5—C4—C3 | 104.1 (2) |
N1—S1—C2 | 112.31 (13) | C5—C4—C3 | 111.9 (2) |
C6—S1—C2 | 102.18 (14) | C6—C5—C4 | 113.2 (2) |
O3—S2—O2 | 117.43 (12) | C5—C6—S1 | 112.14 (19) |
O3—S2—N1 | 105.43 (12) | C12—C7—C8 | 120.3 (3) |
O2—S2—N1 | 111.56 (12) | C12—C7—S2 | 120.3 (2) |
O3—S2—C7 | 107.53 (13) | C8—C7—S2 | 119.4 (2) |
O2—S2—C7 | 108.16 (12) | C9—C8—C7 | 119.3 (3) |
N1—S2—C7 | 106.12 (12) | C8—C9—C10 | 121.4 (3) |
C4—O4—C41 | 115.5 (2) | C11—C10—C9 | 118.0 (3) |
C4—O5—C42 | 116.4 (2) | C11—C10—C101 | 120.8 (3) |
S1—N1—S2 | 122.15 (14) | C9—C10—C101 | 121.2 (3) |
C3—C2—S1 | 111.5 (2) | C10—C11—C12 | 121.9 (3) |
C2—C3—C4 | 112.7 (2) | C7—C12—C11 | 119.0 (3) |
O4—C4—O5 | 111.7 (2) |
Experimental details
Crystal data | |
Chemical formula | C14H21NO5S2 |
Mr | 347.44 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 223 |
a, b, c (Å) | 19.516 (8), 6.039 (2), 14.940 (7) |
β (°) | 112.17 (3) |
V (Å3) | 1631 (1) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.35 |
Crystal size (mm) | 0.44 × 0.37 × 0.15 |
Data collection | |
Diffractometer | Rigaku AFC-6R diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4273, 3762, 2668 |
Rint | 0.020 |
(sin θ/λ)max (Å−1) | 0.652 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.047, 0.136, 1.02 |
No. of reflections | 3762 |
No. of parameters | 200 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.32, −0.39 |
Computer programs: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1988), MSC/AFC Diffractometer Control Software, TEXSAN (Molecular Structure Corporation, 1992), SIR92 (Altomare, et al. 1994), SHELXL97 (Sheldrick, 1997), SHELXL97.
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A view of the molecular structure of the title compound, (I), is shown in Fig. 1, from which it can be seen that the thiopyran ring adopts a chair conformation and the imine group at the ring S atom occupies an axial position. The torsion angles C7—S2—N1—S1 and S2—N1—S1—C6 are -93.6 (2) and -173.39 (18)°, respectively.
The S1—N1 distance of 1.561 (2) Å is significantly shorter than the S2—N1 distance of 1.620 (2) Å, a result that is consistent with the predominance of the canonical structure shown in the Scheme. This difference in the S—N distances shows an opposite sense, compared to the difference between the S—N bonds observed in the unoxidized (at S1) form of the molecule [1.639 (3) and 1.609 (3) Å for the distances corresponding to S1—N1 and S2—N1, respectively, as reported in Creaser et al. (2001)]. Oxidation at S1 also results in an expansion in the S1—N1—S2 angle to 122.15 (14)°, from 111.5 (1)°.
Conformational preferences for molecules closely related to (I) have been examined by Kálmán et al. (Jalsovszky, Kucsman, Ruff, Argay et al., 1987; Jalsovszky, Kucsman, Ruff, Koritsánszky et al., 1987).