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
Key indicators
- Single-crystal X-ray study
- T = 298 K
- Mean (C-C) = 0.008 Å
- R factor = 0.055
- wR factor = 0.193
- Data-to-parameter ratio = 8.7
checkCIF/PLATON results
No syntax errors found
Alert level A DIFF020_ALERT_1_A _diffrn_standards_interval_count and _diffrn_standards_interval_time are missing. Number of measurements between standards or time (min) between standards.
Author Response: In the Kappa apex2 CCD diffractometer there is no provision for repeat measurement of standard intensity. Instead, the decay correction is achieved indirectly by noting the intensity of equivalent reflections and time of their measurement during the data collection. |
DIFF022_ALERT_1_A _diffrn_standards_decay_% is missing Percentage decrease in standards intensity. THETM01_ALERT_3_A The value of sine(theta_max)/wavelength is less than 0.550 Calculated sin(theta_max)/wavelength = 0.5051
Author Response: sample was poorly diffracting at higher bragg angles. |
PLAT023_ALERT_3_A Resolution (too) Low [sin(th)/Lambda < 0.6]..... 21.04 Deg.
Author Response: sample was poorly diffracting at higher bragg angles. |
PLAT027_ALERT_3_A _diffrn_reflns_theta_full (too) Low ............ 21.04 Deg.
Author Response: sample was poorly diffracting at higher bragg angles. |
Alert level C ABSTM02_ALERT_3_C The ratio of expected to reported Tmax/Tmin(RR') is < 0.90 Tmin and Tmax reported: 0.748 1.000 Tmin(prime) and Tmax expected: 0.973 0.980 RR(prime) = 0.754 Please check that your absorption correction is appropriate. REFNR01_ALERT_3_C Ratio of reflections to parameters is < 10 for a centrosymmetric structure sine(theta)/lambda 0.5051 Proportion of unique data used 1.0000 Ratio reflections to parameters 8.7008 PLAT061_ALERT_3_C Tmax/Tmin Range Test RR' too Large ............. 0.75 PLAT062_ALERT_4_C Rescale T(min) & T(max) by ..................... 0.98 PLAT088_ALERT_3_C Poor Data / Parameter Ratio .................... 8.70 PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C21 PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C24 PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor .... 2.06 PLAT340_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ... 8 PLAT371_ALERT_2_C Long C(sp2)-C(sp1) Bond C41 - C42 ... 1.44 Ang. PLAT371_ALERT_2_C Long C(sp2)-C(sp1) Bond C41 - C42_a ... 1.44 Ang.
Alert level G ABSTM02_ALERT_3_G When printed, the submitted absorption T values will be replaced by the scaled T values. Since the ratio of scaled T's is identical to the ratio of reported T values, the scaling does not imply a change to the absorption corrections used in the study. Ratio of Tmax expected/reported 0.980 Tmax scaled 0.980 Tmin scaled 0.733 PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature . 293 K PLAT793_ALERT_1_G Check the Absolute Configuration of C2 = ... S
5 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 11 ALERT level C = Check and explain 3 ALERT level G = General alerts; check 4 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 5 ALERT type 2 Indicator that the structure model may be wrong or deficient 9 ALERT type 3 Indicator that the structure quality may be low 1 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
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.