Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807046296/cf2145sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807046296/cf2145Isup2.hkl |
CCDC reference: 663828
The title compound was prepared from cis-2,6-bis(p-methoxyphenyl) tetrahydrothiopyran-4-one by adopting a general procedure described in the literature (Haller & Ludtke, 1976) and it was characterized using NMR techniques (Manimekalai & Anusuya, 2005).
The H atoms were positioned geometrically and allowed to ride on their parent atoms with C—H = 0.93–0.98 Å and Uiso = 1.2–1.5Ueq(C).
In the title molecule, 4-dicyanomethylene-r2,c6-bis(p-methoxyphenyl)tetrahydrothiopyran, C22H20N2O2S, the tetrahydrothiopyran ring adopts a chair conformation. The dicyanomethylene group in the 4-position and the p-methoxyphenyl groups at positions 2 and 6 have equatorial orientations. A crystallographic mirror plane bisects the molecule, passing through the S and opposite C atoms of the central ring (Fig. 1). No classical hydrogen bonds are found in the crystal structure.
For related literature, see: Haller & Ludtke (1976); Manimekalai & Anusuya (2005).
Data collection: APEX2 (Bruker, 2004); cell refinement: APEX2 (Bruker, 2004); data reduction: SAINT-NT (Bruker, 2004); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: PLATON (Spek, 2003).
C22H20N2O2S | Dx = 1.264 Mg m−3 |
Mr = 376.47 | Melting point: 485(1) K |
Orthorhombic, Pnma | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ac 2n | Cell parameters from 2118 reflections |
a = 8.4906 (3) Å | θ = 1.7–21.0° |
b = 24.6848 (7) Å | µ = 0.18 mm−1 |
c = 9.4361 (4) Å | T = 298 K |
V = 1977.70 (12) Å3 | Block, pale-yellow |
Z = 4 | 0.15 × 0.11 × 0.11 mm |
F(000) = 792 |
Bruker APEXII diffractometer | 1105 independent reflections |
Radiation source: fine-focus sealed tube | 909 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.024 |
φ and ω scans | θmax = 21.0°, θmin = 1.7° |
Absorption correction: multi-scan (SADABS; Bruker, 2004) | h = −8→7 |
Tmin = 0.748, Tmax = 1.000 | k = −22→24 |
6801 measured reflections | l = −9→8 |
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)] = 0.055 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.193 | H-atom parameters constrained |
S = 1.18 | w = 1/[σ2(Fo2) + (0.0939P)2 + 1.7792P] where P = (Fo2 + 2Fc2)/3 |
1105 reflections | (Δ/σ)max < 0.001 |
127 parameters | Δρmax = 0.35 e Å−3 |
0 restraints | Δρmin = −0.25 e Å−3 |
C22H20N2O2S | V = 1977.70 (12) Å3 |
Mr = 376.47 | Z = 4 |
Orthorhombic, Pnma | Mo Kα radiation |
a = 8.4906 (3) Å | µ = 0.18 mm−1 |
b = 24.6848 (7) Å | T = 298 K |
c = 9.4361 (4) Å | 0.15 × 0.11 × 0.11 mm |
Bruker APEXII diffractometer | 1105 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2004) | 909 reflections with I > 2σ(I) |
Tmin = 0.748, Tmax = 1.000 | Rint = 0.024 |
6801 measured reflections | θmax = 21.0° |
R[F2 > 2σ(F2)] = 0.055 | 0 restraints |
wR(F2) = 0.193 | H-atom parameters constrained |
S = 1.18 | Δρmax = 0.35 e Å−3 |
1105 reflections | Δρmin = −0.25 e Å−3 |
127 parameters |
Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles |
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 | 0.4518 (2) | 0.25000 | 0.6263 (2) | 0.0760 (7) | |
O24 | 0.3295 (5) | −0.00687 (13) | 0.7469 (4) | 0.1023 (16) | |
N43 | 1.0637 (7) | 0.3378 (3) | 0.3432 (5) | 0.123 (3) | |
C2 | 0.5576 (7) | 0.19394 (17) | 0.5493 (7) | 0.099 (3) | |
C3 | 0.7265 (7) | 0.19799 (18) | 0.5578 (8) | 0.106 (3) | |
C4 | 0.7984 (9) | 0.25000 | 0.5038 (9) | 0.088 (3) | |
C15 | 0.2481 (8) | −0.0430 (2) | 0.6552 (7) | 0.113 (3) | |
C21 | 0.4916 (6) | 0.14095 (18) | 0.6034 (6) | 0.0740 (19) | |
C22 | 0.5190 (6) | 0.12309 (19) | 0.7398 (7) | 0.087 (2) | |
C23 | 0.4615 (6) | 0.0735 (2) | 0.7861 (6) | 0.086 (2) | |
C24 | 0.3781 (6) | 0.04156 (17) | 0.6932 (6) | 0.0753 (19) | |
C25 | 0.3502 (6) | 0.05867 (19) | 0.5597 (6) | 0.085 (2) | |
C26 | 0.4067 (6) | 0.10849 (18) | 0.5145 (6) | 0.085 (2) | |
C41 | 0.9279 (9) | 0.25000 | 0.4247 (8) | 0.078 (3) | |
C42 | 1.0032 (7) | 0.2993 (3) | 0.3802 (5) | 0.090 (2) | |
H2 | 0.53261 | 0.19483 | 0.44792 | 0.1190* | |
H3A | 0.75715 | 0.19345 | 0.65612 | 0.1276* | |
H3B | 0.77170 | 0.16810 | 0.50488 | 0.1276* | |
H15A | 0.22139 | −0.07538 | 0.70603 | 0.1695* | |
H15B | 0.15368 | −0.02594 | 0.62143 | 0.1695* | |
H15C | 0.31438 | −0.05200 | 0.57620 | 0.1695* | |
H22 | 0.57693 | 0.14461 | 0.80170 | 0.1050* | |
H23 | 0.47919 | 0.06205 | 0.87858 | 0.1027* | |
H25 | 0.29289 | 0.03699 | 0.49771 | 0.1015* | |
H26 | 0.38648 | 0.11995 | 0.42242 | 0.1022* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0838 (13) | 0.0425 (11) | 0.1016 (14) | 0.0000 | 0.0084 (10) | 0.0000 |
O24 | 0.116 (3) | 0.056 (2) | 0.135 (3) | −0.014 (2) | 0.011 (2) | 0.017 (2) |
N43 | 0.140 (5) | 0.115 (4) | 0.114 (4) | −0.035 (4) | 0.016 (3) | 0.017 (3) |
C2 | 0.110 (5) | 0.042 (3) | 0.146 (5) | 0.004 (3) | 0.021 (4) | −0.003 (3) |
C3 | 0.097 (4) | 0.050 (3) | 0.172 (6) | 0.005 (3) | 0.033 (4) | 0.001 (3) |
C4 | 0.090 (5) | 0.053 (4) | 0.121 (6) | 0.0000 | 0.013 (5) | 0.0000 |
C15 | 0.123 (5) | 0.055 (3) | 0.161 (6) | −0.022 (3) | 0.020 (4) | −0.009 (3) |
C21 | 0.088 (3) | 0.042 (3) | 0.092 (4) | 0.007 (2) | 0.017 (3) | 0.004 (3) |
C22 | 0.096 (4) | 0.060 (3) | 0.106 (4) | −0.005 (3) | −0.008 (3) | −0.013 (3) |
C23 | 0.099 (4) | 0.065 (3) | 0.093 (4) | −0.002 (3) | −0.010 (3) | 0.012 (3) |
C24 | 0.081 (3) | 0.040 (3) | 0.105 (4) | 0.005 (2) | 0.012 (3) | 0.011 (3) |
C25 | 0.092 (4) | 0.057 (3) | 0.106 (4) | −0.012 (3) | 0.004 (3) | −0.005 (3) |
C26 | 0.096 (4) | 0.059 (3) | 0.101 (4) | −0.003 (3) | 0.013 (3) | 0.004 (3) |
C41 | 0.089 (5) | 0.069 (5) | 0.076 (4) | 0.0000 | 0.006 (4) | 0.0000 |
C42 | 0.103 (4) | 0.087 (4) | 0.079 (3) | −0.007 (4) | 0.014 (3) | 0.005 (3) |
S1—C2 | 1.803 (5) | C25—C26 | 1.387 (7) |
S1—C2i | 1.803 (5) | C41—C42 | 1.437 (8) |
O24—C15 | 1.422 (7) | C41—C42i | 1.437 (8) |
O24—C24 | 1.362 (6) | C2—H2 | 0.980 |
N43—C42 | 1.135 (10) | C3—H3A | 0.970 |
C2—C3 | 1.440 (8) | C3—H3B | 0.970 |
C2—C21 | 1.512 (7) | C15—H15A | 0.960 |
C3—C4 | 1.510 (7) | C15—H15B | 0.960 |
C4—C41 | 1.329 (11) | C15—H15C | 0.960 |
C21—C22 | 1.380 (8) | C22—H22 | 0.930 |
C21—C26 | 1.366 (7) | C23—H23 | 0.930 |
C22—C23 | 1.388 (7) | C25—H25 | 0.930 |
C23—C24 | 1.375 (7) | C26—H26 | 0.930 |
C24—C25 | 1.350 (8) | ||
C2—S1—C2i | 100.3 (3) | S1—C2—H2 | 106.0 |
C15—O24—C24 | 118.1 (4) | C3—C2—H2 | 106.0 |
S1—C2—C3 | 114.9 (4) | C21—C2—H2 | 106.0 |
S1—C2—C21 | 110.1 (4) | C2—C3—H3A | 108.0 |
C3—C2—C21 | 114.2 (4) | C2—C3—H3B | 108.0 |
C2—C3—C4 | 116.3 (5) | C4—C3—H3A | 108.0 |
C3—C4—C41 | 121.6 (3) | C4—C3—H3B | 108.0 |
C3—C4—C3i | 116.5 (6) | H3A—C3—H3B | 107.0 |
C3i—C4—C41 | 121.6 (3) | O24—C15—H15A | 109.0 |
C2—C21—C22 | 121.9 (5) | O24—C15—H15B | 109.0 |
C2—C21—C26 | 119.7 (5) | O24—C15—H15C | 109.0 |
C22—C21—C26 | 118.3 (4) | H15A—C15—H15B | 110.0 |
C21—C22—C23 | 121.1 (5) | H15A—C15—H15C | 110.0 |
C22—C23—C24 | 119.1 (5) | H15B—C15—H15C | 109.0 |
O24—C24—C23 | 115.0 (5) | C21—C22—H22 | 119.0 |
O24—C24—C25 | 124.7 (5) | C23—C22—H22 | 119.0 |
C23—C24—C25 | 120.4 (4) | C22—C23—H23 | 120.0 |
C24—C25—C26 | 120.3 (5) | C24—C23—H23 | 120.0 |
C21—C26—C25 | 120.9 (5) | C24—C25—H25 | 120.0 |
C4—C41—C42 | 122.2 (4) | C26—C25—H25 | 120.0 |
C4—C41—C42i | 122.2 (4) | C21—C26—H26 | 120.0 |
C42—C41—C42i | 115.7 (6) | C25—C26—H26 | 120.0 |
N43—C42—C41 | 178.9 (6) | ||
C2i—S1—C2—C3 | 47.6 (5) | C3—C4—C41—C42 | −175.9 (6) |
C2i—S1—C2—C21 | 178.2 (4) | C3—C4—C41—C42i | 3.0 (12) |
C15—O24—C24—C23 | −177.5 (5) | C2—C21—C26—C25 | 177.4 (5) |
C15—O24—C24—C25 | 2.2 (8) | C22—C21—C26—C25 | −0.4 (8) |
S1—C2—C21—C22 | −73.4 (6) | C2—C21—C22—C23 | −178.0 (5) |
S1—C2—C3—C4 | −51.9 (8) | C26—C21—C22—C23 | −0.2 (8) |
C21—C2—C3—C4 | 179.5 (6) | C21—C22—C23—C24 | 1.0 (8) |
C3—C2—C21—C26 | −120.1 (6) | C22—C23—C24—C25 | −1.2 (8) |
C3—C2—C21—C22 | 57.6 (7) | C22—C23—C24—O24 | 178.5 (5) |
S1—C2—C21—C26 | 108.9 (5) | O24—C24—C25—C26 | −179.1 (5) |
C2—C3—C4—C3i | 49.4 (9) | C23—C24—C25—C26 | 0.6 (8) |
C2—C3—C4—C41 | −137.3 (8) | C24—C25—C26—C21 | 0.2 (8) |
C3i—C4—C41—C42 | −3.0 (12) |
Symmetry code: (i) x, −y+1/2, z. |
Experimental details
Crystal data | |
Chemical formula | C22H20N2O2S |
Mr | 376.47 |
Crystal system, space group | Orthorhombic, Pnma |
Temperature (K) | 298 |
a, b, c (Å) | 8.4906 (3), 24.6848 (7), 9.4361 (4) |
V (Å3) | 1977.70 (12) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.18 |
Crystal size (mm) | 0.15 × 0.11 × 0.11 |
Data collection | |
Diffractometer | Bruker APEXII |
Absorption correction | Multi-scan (SADABS; Bruker, 2004) |
Tmin, Tmax | 0.748, 1.000 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 6801, 1105, 909 |
Rint | 0.024 |
θmax (°) | 21.0 |
(sin θ/λ)max (Å−1) | 0.505 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.055, 0.193, 1.18 |
No. of reflections | 1105 |
No. of parameters | 127 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.35, −0.25 |
Computer programs: APEX2 (Bruker, 2004), SAINT-NT (Bruker, 2004), SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 1997), ORTEP-3 (Farrugia, 1997), PLATON (Spek, 2003).
In the title molecule, 4-dicyanomethylene-r2,c6-bis(p-methoxyphenyl)tetrahydrothiopyran, C22H20N2O2S, the tetrahydrothiopyran ring adopts a chair conformation. The dicyanomethylene group in the 4-position and the p-methoxyphenyl groups at positions 2 and 6 have equatorial orientations. A crystallographic mirror plane bisects the molecule, passing through the S and opposite C atoms of the central ring (Fig. 1). No classical hydrogen bonds are found in the crystal structure.