Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536802017622/fl6000sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536802017622/fl6000Isup2.hkl |
CCDC reference: 198983
Key indicators
- Single-crystal X-ray study
- T = 291 K
- Mean (C-C) = 0.002 Å
- R factor = 0.041
- wR factor = 0.103
- Data-to-parameter ratio = 18.0
checkCIF results
No syntax errors found ADDSYM reports no extra symmetry
Alert Level C:
PLAT_371 Alert C Long C(sp2)-C(sp1) Bond C(17) - C(18) = 1.43 Ang. PLAT_371 Alert C Long C(sp2)-C(sp1) Bond C(17) - C(19) = 1.43 Ang.
0 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
2 Alert Level C = Please check
The title compound was synthesized according to the general procedure of Lemke (1970). (0.93 g, 5 mmol) (3,5,5-Trimethylcyclohex-2-enylidene)malonodinitrile (0.93 g, 5 mmol; Kolev et al., 2001) was dissolved in 60 ml anhydrous ethanol by continous stirring for 3 h at moderate temperature. 2,4-Dimethoxybenzaldehyde (0.83 g, 5 mmol) was dissolved in 30 ml anhydrous ethanol and added dropwise to the solution. Nearly 2 ml of piperidine were used as a catalyst. The solution became red after a few minutes and the resulting compound precipitated. After a 3 h reaction time, the solution was cooled and the title compound, (I), isolated and recrystallized twice from ethanol. Purification was achieved via column chromatography on silica gel, using chloroform as eluent. Yield: 0.34 g (43%); m.p. 456–457 K. The purity of the compound was confirmed by elemental analysis, IR, UV-vis and mass spectrometry. Red transparent crystals were grown from a toluene solution by slow evaporation at room temperature over a period of one week.
H atoms were placed in calculated positions, with Uiso values constrained to be 1.5 times Ueq of the carrier atom for the methyl-H atoms and 1.2 times Ueq for the remaining H atoms. The methyl groups were allowed to rotate but not to tip.
Data collection: COLLECT (Nonius, 1998); cell refinement: DENZO and SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO and SCALEPACK; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL-Plus (Sheldrick, 1991); software used to prepare material for publication: SHELXL97, PARST95 (Nardelli, 1995) and PLATON (Spek, 2001).
C21H22N2O2 | Z = 2 |
Mr = 334.41 | F(000) = 356 |
Triclinic, P1 | Dx = 1.198 Mg m−3 |
a = 7.7607 (2) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 8.9488 (2) Å | Cell parameters from 12122 reflections |
c = 14.7723 (4) Å | θ = 3.0–27.5° |
α = 75.4549 (10)° | µ = 0.08 mm−1 |
β = 79.0465 (11)° | T = 291 K |
γ = 69.9378 (11)° | Plate, dark red |
V = 926.68 (4) Å3 | 0.25 × 0.10 × 0.05 mm |
Nonius KappaCCD diffractometer | 1951 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.044 |
Graphite monochromator | θmax = 27.5°, θmin = 3.0° |
Detector resolution: 19 vertical, 18 horizontal pixels mm-1 | h = −10→10 |
416 frames via ω–rotation (Δω=1°) and two times 20 s per frame (four sets at different κ–angles) scans | k = −10→11 |
12122 measured reflections | l = −18→19 |
4161 independent reflections |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.041 | H-atom parameters constrained |
wR(F2) = 0.103 | w = 1/[σ2(Fo2) + (0.0475P)2] where P = (Fo2 + 2Fc2)/3 |
S = 0.87 | (Δ/σ)max < 0.001 |
4161 reflections | Δρmax = 0.14 e Å−3 |
231 parameters | Δρmin = −0.13 e Å−3 |
0 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.026 (3) |
C21H22N2O2 | γ = 69.9378 (11)° |
Mr = 334.41 | V = 926.68 (4) Å3 |
Triclinic, P1 | Z = 2 |
a = 7.7607 (2) Å | Mo Kα radiation |
b = 8.9488 (2) Å | µ = 0.08 mm−1 |
c = 14.7723 (4) Å | T = 291 K |
α = 75.4549 (10)° | 0.25 × 0.10 × 0.05 mm |
β = 79.0465 (11)° |
Nonius KappaCCD diffractometer | 1951 reflections with I > 2σ(I) |
12122 measured reflections | Rint = 0.044 |
4161 independent reflections |
R[F2 > 2σ(F2)] = 0.041 | 0 restraints |
wR(F2) = 0.103 | H-atom parameters constrained |
S = 0.87 | Δρmax = 0.14 e Å−3 |
4161 reflections | Δρmin = −0.13 e Å−3 |
231 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 | ||
O1 | 0.20071 (14) | 0.64486 (13) | 0.73248 (6) | 0.0619 (3) | |
O2 | −0.28400 (14) | 0.39387 (13) | 0.83401 (7) | 0.0674 (3) | |
N1 | −0.1188 (2) | 0.99993 (19) | 0.10798 (9) | 0.0791 (5) | |
N2 | 0.3092 (2) | 1.2365 (2) | −0.00162 (10) | 0.1018 (6) | |
C1 | 0.01281 (18) | 0.64767 (16) | 0.62518 (9) | 0.0440 (4) | |
C2 | 0.05801 (19) | 0.60132 (16) | 0.71813 (9) | 0.0454 (4) | |
C3 | −0.0387 (2) | 0.51655 (17) | 0.78950 (9) | 0.0501 (4) | |
H3 | −0.0069 | 0.4866 | 0.8506 | 0.060* | |
C4 | −0.1820 (2) | 0.47729 (17) | 0.76904 (9) | 0.0499 (4) | |
C5 | −0.2295 (2) | 0.52064 (17) | 0.67835 (10) | 0.0557 (4) | |
H5 | −0.3260 | 0.4937 | 0.6647 | 0.067* | |
C6 | −0.1326 (2) | 0.60402 (17) | 0.60846 (9) | 0.0523 (4) | |
H6 | −0.1653 | 0.6324 | 0.5476 | 0.063* | |
C7 | 0.2635 (2) | 0.5929 (2) | 0.82341 (10) | 0.0675 (5) | |
H7A | 0.1639 | 0.6340 | 0.8692 | 0.101* | |
H7B | 0.3634 | 0.6333 | 0.8229 | 0.101* | |
H7C | 0.3053 | 0.4763 | 0.8392 | 0.101* | |
C8 | −0.2593 (2) | 0.3637 (2) | 0.93116 (10) | 0.0777 (5) | |
H8A | −0.1346 | 0.2978 | 0.9403 | 0.117* | |
H8B | −0.3429 | 0.3081 | 0.9686 | 0.117* | |
H8C | −0.2839 | 0.4651 | 0.9498 | 0.117* | |
C9 | 0.11592 (19) | 0.73619 (16) | 0.55161 (9) | 0.0475 (4) | |
H9 | 0.2073 | 0.7639 | 0.5700 | 0.057* | |
C10 | 0.09223 (19) | 0.78168 (16) | 0.46012 (9) | 0.0477 (4) | |
H10 | 0.0017 | 0.7528 | 0.4418 | 0.057* | |
C11 | 0.19233 (18) | 0.87076 (16) | 0.38695 (9) | 0.0432 (4) | |
C12 | 0.14455 (19) | 0.91381 (16) | 0.29806 (9) | 0.0467 (4) | |
H12 | 0.0507 | 0.8813 | 0.2863 | 0.056* | |
C13 | 0.23123 (18) | 1.00639 (16) | 0.22194 (9) | 0.0438 (4) | |
C14 | 0.38527 (19) | 1.05579 (17) | 0.24014 (9) | 0.0488 (4) | |
H14A | 0.3354 | 1.1650 | 0.2524 | 0.059* | |
H14B | 0.4730 | 1.0582 | 0.1839 | 0.059* | |
C15 | 0.48763 (19) | 0.94304 (17) | 0.32315 (9) | 0.0465 (4) | |
C16 | 0.34494 (18) | 0.91893 (17) | 0.40789 (9) | 0.0487 (4) | |
H16A | 0.4074 | 0.8359 | 0.4576 | 0.058* | |
H16B | 0.2916 | 1.0192 | 0.4311 | 0.058* | |
C17 | 0.1690 (2) | 1.05623 (17) | 0.13516 (9) | 0.0496 (4) | |
C18 | 0.2488 (2) | 1.1540 (2) | 0.05832 (10) | 0.0637 (5) | |
C19 | 0.0104 (2) | 1.02362 (19) | 0.11904 (9) | 0.0566 (4) | |
C20 | 0.6034 (2) | 0.78051 (19) | 0.29722 (11) | 0.0703 (5) | |
H20A | 0.6925 | 0.7976 | 0.2442 | 0.105* | |
H20B | 0.5244 | 0.7309 | 0.2813 | 0.105* | |
H20C | 0.6661 | 0.7106 | 0.3498 | 0.105* | |
C21 | 0.6122 (2) | 1.0242 (2) | 0.34691 (10) | 0.0641 (5) | |
H21A | 0.6787 | 0.9543 | 0.3982 | 0.096* | |
H21B | 0.5382 | 1.1253 | 0.3646 | 0.096* | |
H21C | 0.6981 | 1.0443 | 0.2929 | 0.096* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0646 (7) | 0.0793 (8) | 0.0451 (6) | −0.0359 (6) | −0.0144 (5) | 0.0068 (5) |
O2 | 0.0722 (7) | 0.0742 (7) | 0.0550 (7) | −0.0394 (6) | 0.0025 (6) | 0.0043 (6) |
N1 | 0.0854 (11) | 0.1144 (13) | 0.0521 (8) | −0.0546 (10) | −0.0116 (8) | −0.0062 (8) |
N2 | 0.1405 (15) | 0.1179 (14) | 0.0619 (10) | −0.0852 (13) | −0.0183 (10) | 0.0241 (10) |
C1 | 0.0485 (9) | 0.0441 (8) | 0.0367 (8) | −0.0152 (7) | −0.0021 (7) | −0.0042 (6) |
C2 | 0.0470 (9) | 0.0438 (8) | 0.0419 (8) | −0.0148 (7) | −0.0043 (7) | −0.0022 (7) |
C3 | 0.0545 (10) | 0.0487 (9) | 0.0392 (8) | −0.0136 (8) | −0.0040 (7) | 0.0002 (7) |
C4 | 0.0535 (9) | 0.0452 (9) | 0.0459 (9) | −0.0183 (8) | 0.0025 (7) | −0.0022 (7) |
C5 | 0.0626 (10) | 0.0576 (10) | 0.0528 (10) | −0.0294 (8) | −0.0064 (8) | −0.0066 (8) |
C6 | 0.0655 (10) | 0.0531 (9) | 0.0397 (8) | −0.0238 (8) | −0.0058 (7) | −0.0045 (7) |
C7 | 0.0695 (11) | 0.0827 (12) | 0.0512 (10) | −0.0257 (10) | −0.0218 (8) | −0.0012 (9) |
C8 | 0.0906 (13) | 0.0849 (13) | 0.0490 (10) | −0.0389 (11) | 0.0075 (9) | 0.0066 (9) |
C9 | 0.0495 (9) | 0.0494 (9) | 0.0416 (9) | −0.0166 (7) | −0.0046 (7) | −0.0043 (7) |
C10 | 0.0485 (9) | 0.0523 (9) | 0.0405 (8) | −0.0180 (7) | −0.0039 (7) | −0.0038 (7) |
C11 | 0.0435 (9) | 0.0442 (8) | 0.0373 (8) | −0.0125 (7) | −0.0016 (7) | −0.0042 (7) |
C12 | 0.0477 (9) | 0.0542 (9) | 0.0398 (8) | −0.0235 (7) | −0.0047 (7) | −0.0018 (7) |
C13 | 0.0479 (9) | 0.0430 (8) | 0.0385 (8) | −0.0148 (7) | −0.0022 (7) | −0.0059 (7) |
C14 | 0.0535 (9) | 0.0503 (9) | 0.0428 (8) | −0.0222 (7) | −0.0025 (7) | −0.0033 (7) |
C15 | 0.0446 (9) | 0.0495 (9) | 0.0434 (8) | −0.0162 (7) | −0.0029 (7) | −0.0052 (7) |
C16 | 0.0506 (9) | 0.0535 (9) | 0.0397 (8) | −0.0159 (7) | −0.0061 (7) | −0.0051 (7) |
C17 | 0.0585 (10) | 0.0556 (10) | 0.0378 (8) | −0.0271 (8) | −0.0049 (7) | −0.0020 (7) |
C18 | 0.0808 (12) | 0.0733 (11) | 0.0436 (9) | −0.0400 (10) | −0.0145 (8) | 0.0044 (8) |
C19 | 0.0710 (12) | 0.0682 (11) | 0.0317 (8) | −0.0303 (9) | −0.0054 (8) | 0.0002 (7) |
C20 | 0.0598 (11) | 0.0604 (11) | 0.0766 (11) | −0.0082 (9) | 0.0017 (9) | −0.0108 (9) |
C21 | 0.0552 (10) | 0.0823 (12) | 0.0586 (10) | −0.0297 (9) | −0.0089 (8) | −0.0073 (9) |
O1—C2 | 1.3601 (15) | C10—C11 | 1.4424 (16) |
O1—C7 | 1.4273 (14) | C10—H10 | 0.9300 |
O2—C4 | 1.3645 (15) | C11—C12 | 1.3577 (16) |
O2—C8 | 1.4295 (16) | C11—C16 | 1.4968 (17) |
N1—C19 | 1.1411 (18) | C12—C13 | 1.4249 (17) |
N2—C18 | 1.1405 (17) | C12—H12 | 0.9300 |
C1—C6 | 1.3941 (18) | C13—C17 | 1.3697 (17) |
C1—C2 | 1.4062 (17) | C13—C14 | 1.4971 (17) |
C1—C9 | 1.4563 (17) | C14—C15 | 1.5336 (16) |
C2—C3 | 1.3924 (17) | C14—H14A | 0.9700 |
C3—C4 | 1.3786 (18) | C14—H14B | 0.9700 |
C3—H3 | 0.9300 | C15—C20 | 1.524 (2) |
C4—C5 | 1.3818 (18) | C15—C21 | 1.5247 (18) |
C5—C6 | 1.3754 (17) | C15—C16 | 1.5301 (18) |
C5—H5 | 0.9300 | C16—H16A | 0.9700 |
C6—H6 | 0.9300 | C16—H16B | 0.9700 |
C7—H7A | 0.9600 | C17—C18 | 1.4295 (19) |
C7—H7B | 0.9600 | C17—C19 | 1.431 (2) |
C7—H7C | 0.9600 | C20—H20A | 0.9600 |
C8—H8A | 0.9600 | C20—H20B | 0.9600 |
C8—H8B | 0.9600 | C20—H20C | 0.9600 |
C8—H8C | 0.9600 | C21—H21A | 0.9600 |
C9—C10 | 1.3390 (16) | C21—H21B | 0.9600 |
C9—H9 | 0.9300 | C21—H21C | 0.9600 |
C2—O1—C7 | 118.97 (10) | C11—C12—C13 | 123.20 (12) |
C4—O2—C8 | 118.70 (11) | C11—C12—H12 | 118.4 |
C6—C1—C2 | 116.64 (12) | C13—C12—H12 | 118.4 |
C6—C1—C9 | 122.97 (12) | C17—C13—C12 | 120.76 (12) |
C2—C1—C9 | 120.39 (12) | C17—C13—C14 | 120.60 (12) |
O1—C2—C3 | 123.22 (12) | C12—C13—C14 | 118.56 (11) |
O1—C2—C1 | 115.47 (11) | C13—C14—C15 | 113.82 (11) |
C3—C2—C1 | 121.31 (13) | C13—C14—H14A | 108.8 |
C4—C3—C2 | 119.57 (12) | C15—C14—H14A | 108.8 |
C4—C3—H3 | 120.2 | C13—C14—H14B | 108.8 |
C2—C3—H3 | 120.2 | C15—C14—H14B | 108.8 |
O2—C4—C3 | 123.82 (12) | H14A—C14—H14B | 107.7 |
O2—C4—C5 | 115.63 (13) | C20—C15—C21 | 109.89 (12) |
C3—C4—C5 | 120.54 (12) | C20—C15—C16 | 110.50 (11) |
C6—C5—C4 | 119.30 (13) | C21—C15—C16 | 109.28 (11) |
C6—C5—H5 | 120.3 | C20—C15—C14 | 110.14 (12) |
C4—C5—H5 | 120.3 | C21—C15—C14 | 108.49 (11) |
C5—C6—C1 | 122.63 (13) | C16—C15—C14 | 108.50 (11) |
C5—C6—H6 | 118.7 | C11—C16—C15 | 114.05 (11) |
C1—C6—H6 | 118.7 | C11—C16—H16A | 108.7 |
O1—C7—H7A | 109.5 | C15—C16—H16A | 108.7 |
O1—C7—H7B | 109.5 | C11—C16—H16B | 108.7 |
H7A—C7—H7B | 109.5 | C15—C16—H16B | 108.7 |
O1—C7—H7C | 109.5 | H16A—C16—H16B | 107.6 |
H7A—C7—H7C | 109.5 | C13—C17—C18 | 122.08 (13) |
H7B—C7—H7C | 109.5 | C13—C17—C19 | 121.31 (12) |
O2—C8—H8A | 109.5 | C18—C17—C19 | 116.42 (12) |
O2—C8—H8B | 109.5 | N2—C18—C17 | 177.6 (2) |
H8A—C8—H8B | 109.5 | N1—C19—C17 | 178.16 (18) |
O2—C8—H8C | 109.5 | C15—C20—H20A | 109.5 |
H8A—C8—H8C | 109.5 | C15—C20—H20B | 109.5 |
H8B—C8—H8C | 109.5 | H20A—C20—H20B | 109.5 |
C10—C9—C1 | 126.44 (13) | C15—C20—H20C | 109.5 |
C10—C9—H9 | 116.8 | H20A—C20—H20C | 109.5 |
C1—C9—H9 | 116.8 | H20B—C20—H20C | 109.5 |
C9—C10—C11 | 126.84 (13) | C15—C21—H21A | 109.5 |
C9—C10—H10 | 116.6 | C15—C21—H21B | 109.5 |
C11—C10—H10 | 116.6 | H21A—C21—H21B | 109.5 |
C12—C11—C10 | 119.17 (12) | C15—C21—H21C | 109.5 |
C12—C11—C16 | 119.71 (11) | H21A—C21—H21C | 109.5 |
C10—C11—C16 | 121.11 (11) | H21B—C21—H21C | 109.5 |
C7—O1—C2—C3 | 4.2 (2) | C9—C10—C11—C12 | −176.90 (14) |
C7—O1—C2—C1 | −175.79 (12) | C9—C10—C11—C16 | 1.9 (2) |
C6—C1—C2—O1 | 179.78 (13) | C10—C11—C12—C13 | 177.86 (13) |
C9—C1—C2—O1 | 0.02 (19) | C16—C11—C12—C13 | −1.0 (2) |
C6—C1—C2—C3 | −0.2 (2) | C11—C12—C13—C17 | −175.37 (13) |
C9—C1—C2—C3 | −179.96 (13) | C11—C12—C13—C14 | 1.4 (2) |
O1—C2—C3—C4 | 179.89 (14) | C17—C13—C14—C15 | −157.60 (13) |
C1—C2—C3—C4 | −0.1 (2) | C12—C13—C14—C15 | 25.68 (19) |
C8—O2—C4—C3 | 8.8 (2) | C13—C14—C15—C20 | 71.19 (15) |
C8—O2—C4—C5 | −171.87 (13) | C13—C14—C15—C21 | −168.50 (12) |
C2—C3—C4—O2 | 179.63 (13) | C13—C14—C15—C16 | −49.88 (16) |
C2—C3—C4—C5 | 0.3 (2) | C12—C11—C16—C15 | −26.52 (19) |
O2—C4—C5—C6 | −179.54 (13) | C10—C11—C16—C15 | 154.67 (12) |
C3—C4—C5—C6 | −0.2 (2) | C20—C15—C16—C11 | −70.43 (15) |
C4—C5—C6—C1 | −0.2 (2) | C21—C15—C16—C11 | 168.54 (12) |
C2—C1—C6—C5 | 0.4 (2) | C14—C15—C16—C11 | 50.41 (16) |
C9—C1—C6—C5 | −179.89 (14) | C12—C13—C17—C18 | 177.78 (13) |
C6—C1—C9—C10 | −2.6 (2) | C14—C13—C17—C18 | 1.1 (2) |
C2—C1—C9—C10 | 177.15 (14) | C12—C13—C17—C19 | 2.9 (2) |
C1—C9—C10—C11 | 179.32 (13) | C14—C13—C17—C19 | −173.80 (14) |
Experimental details
Crystal data | |
Chemical formula | C21H22N2O2 |
Mr | 334.41 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 291 |
a, b, c (Å) | 7.7607 (2), 8.9488 (2), 14.7723 (4) |
α, β, γ (°) | 75.4549 (10), 79.0465 (11), 69.9378 (11) |
V (Å3) | 926.68 (4) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.08 |
Crystal size (mm) | 0.25 × 0.10 × 0.05 |
Data collection | |
Diffractometer | Nonius KappaCCD diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 12122, 4161, 1951 |
Rint | 0.044 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.041, 0.103, 0.87 |
No. of reflections | 4161 |
No. of parameters | 231 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.14, −0.13 |
Computer programs: COLLECT (Nonius, 1998), DENZO and SCALEPACK (Otwinowski & Minor, 1997), DENZO and SCALEPACK, SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), SHELXTL-Plus (Sheldrick, 1991), SHELXL97, PARST95 (Nardelli, 1995) and PLATON (Spek, 2001).
Due to their solvatochromic behaviour (Lemke,1970), derivatives of 2-(5,5-dimethyl-3-styrylcyclohexenylidene)malononitrile are good candidates for non-linear optical (NLO), electro-optical (EO) and photorefrative (PR) applications. Some molecules of this class have been investigated by means of electric field induced second harmonic generation (EFISH) in chloroform. The dipole moments and molecular hyperpolarizabilities of these compounds are large enough to be used as active components of electrooptic and photorefractive polymers (Ermer et al., 1997). The title compound, (I), crystallizes in a centrosymmetric space group and can be used only for third-order NLO applications.