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In the title mol­ecule, C22H20N2O2S, the tetra­hydro­thio­pyran ring adopts a chair conformation. The dicyano­methyl­ene group and the 4-methoxy­phenyl groups have equatorial orientations. A crystallographic mirror plane bis­ects the mol­ecule, passing through the S and opposite C atoms of the central ring.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807046296/cf2145sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807046296/cf2145Isup2.hkl
Contains datablock I

CCDC reference: 663828

Key indicators

  • Single-crystal X-ray study
  • T = 298 K
  • Mean [sigma](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

Comment top

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.

Related literature top

For related literature, see: Haller & Ludtke (1976); Manimekalai & Anusuya (2005).

Experimental top

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).

Refinement top

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).

Structure description top

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).

Computing details top

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).

Figures top
[Figure 1] Fig. 1. The molecular structure with the atom numbering scheme. Displacement ellipsoids for non-H atoms are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radius. [Symmetry code: (a) x, 1/2 - y, z.]
[Figure 2] Fig. 2. The molecular packing of the title molecule, viewed down the c axis.
2-[2,6-Bis(4-methoxyphenyl)tetrahydrothiopyran-4-ylidene]malononitrile top
Crystal data top
C22H20N2O2SDx = 1.264 Mg m3
Mr = 376.47Melting point: 485(1) K
Orthorhombic, PnmaMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2nCell parameters from 2118 reflections
a = 8.4906 (3) Åθ = 1.7–21.0°
b = 24.6848 (7) ŵ = 0.18 mm1
c = 9.4361 (4) ÅT = 298 K
V = 1977.70 (12) Å3Block, pale-yellow
Z = 40.15 × 0.11 × 0.11 mm
F(000) = 792
Data collection top
Bruker APEXII
diffractometer
1105 independent reflections
Radiation source: fine-focus sealed tube909 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.024
φ and ω scansθmax = 21.0°, θmin = 1.7°
Absorption correction: multi-scan
(SADABS; Bruker, 2004)
h = 87
Tmin = 0.748, Tmax = 1.000k = 2224
6801 measured reflectionsl = 98
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.055Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.193H-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 parametersΔρmax = 0.35 e Å3
0 restraintsΔρmin = 0.25 e Å3
Crystal data top
C22H20N2O2SV = 1977.70 (12) Å3
Mr = 376.47Z = 4
Orthorhombic, PnmaMo Kα radiation
a = 8.4906 (3) ŵ = 0.18 mm1
b = 24.6848 (7) ÅT = 298 K
c = 9.4361 (4) Å0.15 × 0.11 × 0.11 mm
Data collection top
Bruker APEXII
diffractometer
1105 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2004)
909 reflections with I > 2σ(I)
Tmin = 0.748, Tmax = 1.000Rint = 0.024
6801 measured reflectionsθmax = 21.0°
Refinement top
R[F2 > 2σ(F2)] = 0.0550 restraints
wR(F2) = 0.193H-atom parameters constrained
S = 1.18Δρmax = 0.35 e Å3
1105 reflectionsΔρmin = 0.25 e Å3
127 parameters
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
S10.4518 (2)0.250000.6263 (2)0.0760 (7)
O240.3295 (5)0.00687 (13)0.7469 (4)0.1023 (16)
N431.0637 (7)0.3378 (3)0.3432 (5)0.123 (3)
C20.5576 (7)0.19394 (17)0.5493 (7)0.099 (3)
C30.7265 (7)0.19799 (18)0.5578 (8)0.106 (3)
C40.7984 (9)0.250000.5038 (9)0.088 (3)
C150.2481 (8)0.0430 (2)0.6552 (7)0.113 (3)
C210.4916 (6)0.14095 (18)0.6034 (6)0.0740 (19)
C220.5190 (6)0.12309 (19)0.7398 (7)0.087 (2)
C230.4615 (6)0.0735 (2)0.7861 (6)0.086 (2)
C240.3781 (6)0.04156 (17)0.6932 (6)0.0753 (19)
C250.3502 (6)0.05867 (19)0.5597 (6)0.085 (2)
C260.4067 (6)0.10849 (18)0.5145 (6)0.085 (2)
C410.9279 (9)0.250000.4247 (8)0.078 (3)
C421.0032 (7)0.2993 (3)0.3802 (5)0.090 (2)
H20.532610.194830.447920.1190*
H3A0.757150.193450.656120.1276*
H3B0.771700.168100.504880.1276*
H15A0.221390.075380.706030.1695*
H15B0.153680.025940.621430.1695*
H15C0.314380.052000.576200.1695*
H220.576930.144610.801700.1050*
H230.479190.062050.878580.1027*
H250.292890.036990.497710.1015*
H260.386480.119950.422420.1022*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0838 (13)0.0425 (11)0.1016 (14)0.00000.0084 (10)0.0000
O240.116 (3)0.056 (2)0.135 (3)0.014 (2)0.011 (2)0.017 (2)
N430.140 (5)0.115 (4)0.114 (4)0.035 (4)0.016 (3)0.017 (3)
C20.110 (5)0.042 (3)0.146 (5)0.004 (3)0.021 (4)0.003 (3)
C30.097 (4)0.050 (3)0.172 (6)0.005 (3)0.033 (4)0.001 (3)
C40.090 (5)0.053 (4)0.121 (6)0.00000.013 (5)0.0000
C150.123 (5)0.055 (3)0.161 (6)0.022 (3)0.020 (4)0.009 (3)
C210.088 (3)0.042 (3)0.092 (4)0.007 (2)0.017 (3)0.004 (3)
C220.096 (4)0.060 (3)0.106 (4)0.005 (3)0.008 (3)0.013 (3)
C230.099 (4)0.065 (3)0.093 (4)0.002 (3)0.010 (3)0.012 (3)
C240.081 (3)0.040 (3)0.105 (4)0.005 (2)0.012 (3)0.011 (3)
C250.092 (4)0.057 (3)0.106 (4)0.012 (3)0.004 (3)0.005 (3)
C260.096 (4)0.059 (3)0.101 (4)0.003 (3)0.013 (3)0.004 (3)
C410.089 (5)0.069 (5)0.076 (4)0.00000.006 (4)0.0000
C420.103 (4)0.087 (4)0.079 (3)0.007 (4)0.014 (3)0.005 (3)
Geometric parameters (Å, º) top
S1—C21.803 (5)C25—C261.387 (7)
S1—C2i1.803 (5)C41—C421.437 (8)
O24—C151.422 (7)C41—C42i1.437 (8)
O24—C241.362 (6)C2—H20.980
N43—C421.135 (10)C3—H3A0.970
C2—C31.440 (8)C3—H3B0.970
C2—C211.512 (7)C15—H15A0.960
C3—C41.510 (7)C15—H15B0.960
C4—C411.329 (11)C15—H15C0.960
C21—C221.380 (8)C22—H220.930
C21—C261.366 (7)C23—H230.930
C22—C231.388 (7)C25—H250.930
C23—C241.375 (7)C26—H260.930
C24—C251.350 (8)
C2—S1—C2i100.3 (3)S1—C2—H2106.0
C15—O24—C24118.1 (4)C3—C2—H2106.0
S1—C2—C3114.9 (4)C21—C2—H2106.0
S1—C2—C21110.1 (4)C2—C3—H3A108.0
C3—C2—C21114.2 (4)C2—C3—H3B108.0
C2—C3—C4116.3 (5)C4—C3—H3A108.0
C3—C4—C41121.6 (3)C4—C3—H3B108.0
C3—C4—C3i116.5 (6)H3A—C3—H3B107.0
C3i—C4—C41121.6 (3)O24—C15—H15A109.0
C2—C21—C22121.9 (5)O24—C15—H15B109.0
C2—C21—C26119.7 (5)O24—C15—H15C109.0
C22—C21—C26118.3 (4)H15A—C15—H15B110.0
C21—C22—C23121.1 (5)H15A—C15—H15C110.0
C22—C23—C24119.1 (5)H15B—C15—H15C109.0
O24—C24—C23115.0 (5)C21—C22—H22119.0
O24—C24—C25124.7 (5)C23—C22—H22119.0
C23—C24—C25120.4 (4)C22—C23—H23120.0
C24—C25—C26120.3 (5)C24—C23—H23120.0
C21—C26—C25120.9 (5)C24—C25—H25120.0
C4—C41—C42122.2 (4)C26—C25—H25120.0
C4—C41—C42i122.2 (4)C21—C26—H26120.0
C42—C41—C42i115.7 (6)C25—C26—H26120.0
N43—C42—C41178.9 (6)
C2i—S1—C2—C347.6 (5)C3—C4—C41—C42175.9 (6)
C2i—S1—C2—C21178.2 (4)C3—C4—C41—C42i3.0 (12)
C15—O24—C24—C23177.5 (5)C2—C21—C26—C25177.4 (5)
C15—O24—C24—C252.2 (8)C22—C21—C26—C250.4 (8)
S1—C2—C21—C2273.4 (6)C2—C21—C22—C23178.0 (5)
S1—C2—C3—C451.9 (8)C26—C21—C22—C230.2 (8)
C21—C2—C3—C4179.5 (6)C21—C22—C23—C241.0 (8)
C3—C2—C21—C26120.1 (6)C22—C23—C24—C251.2 (8)
C3—C2—C21—C2257.6 (7)C22—C23—C24—O24178.5 (5)
S1—C2—C21—C26108.9 (5)O24—C24—C25—C26179.1 (5)
C2—C3—C4—C3i49.4 (9)C23—C24—C25—C260.6 (8)
C2—C3—C4—C41137.3 (8)C24—C25—C26—C210.2 (8)
C3i—C4—C41—C423.0 (12)
Symmetry code: (i) x, y+1/2, z.

Experimental details

Crystal data
Chemical formulaC22H20N2O2S
Mr376.47
Crystal system, space groupOrthorhombic, Pnma
Temperature (K)298
a, b, c (Å)8.4906 (3), 24.6848 (7), 9.4361 (4)
V3)1977.70 (12)
Z4
Radiation typeMo Kα
µ (mm1)0.18
Crystal size (mm)0.15 × 0.11 × 0.11
Data collection
DiffractometerBruker APEXII
Absorption correctionMulti-scan
(SADABS; Bruker, 2004)
Tmin, Tmax0.748, 1.000
No. of measured, independent and
observed [I > 2σ(I)] reflections
6801, 1105, 909
Rint0.024
θmax (°)21.0
(sin θ/λ)max1)0.505
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.055, 0.193, 1.18
No. of reflections1105
No. of parameters127
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)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).

 

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