Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801004755/wn6009sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536801004755/wn6009Isup2.hkl |
CCDC reference: 162829
The title compound was prepared by the reaction of 2-cyanocinnamonitrile with 5,5'-dimethyl-1,3-cyclohexanedione in ethylene under reflux for 4 h. The colorless solid was purified by recrystallization from ethanol to obtain single crystals suitable for X-ray diffraction. The product was characterized by NMR, IR and elemental analyses, giving results consistent with those in the literature (Singh et al., 1996).
The H atoms of the amino group were located in difference Fourier syntheses. The other H atoms were located by geometry and included in the structure-factor calculations.
Polyfunctionalized benzo-4H-pyrans are structural units of a number of natural products (Hatakeyama et al., 1988) and, because of their inherent reactivity, the pyran rings are versatile synthons (Singh et al., 1996). On the other hand, substituted benzo-4H-pyrans possess varied biological activity (Hassanien et al., 1999). Since the stereochemistry is so important in the rational design of new functional molecules, we report herein the crystal structure of the title compound, (I).
In the structure (Fig. 1) of the neutral molecule (I), the C7/C8/C9/O1/C10/C11 plane forms an angle of 92.5 (4)° with the phenyl plane. The nitrile group is typical [N≡C 1.1448 (19) Å].
A notable feature of (I) is the formation of a three-dimensional network through hydrogen bonds, as shown in Fig. 2. These are in the normal range of weak interactions (Sasada, 1984). The amino N2 atom of one molecule links through H2B to the nitrile N1 atom of another molecule, creating a dimer. The amino N2 atom of one molecule also links through H2A to the keto O2 atom of another molecule to form the three-dimensional framework.
Data collection: SMART (Bruker, 1998); cell refinement: SMART; data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976).
Fig. 1. ORTEPII view (Johnson, 1976) of the title complex with displacement ellipsoids at the 30% probability level | |
Fig. 2. The molecular packing diagram of the title complex. |
C18H18N2O2 | F(000) = 624 |
Mr = 294.34 | Dx = 1.240 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 11.307 (1) Å | Cell parameters from 25 reflections |
b = 9.475 (1) Å | θ = 3.3–15.1° |
c = 14.919 (2) Å | µ = 0.08 mm−1 |
β = 99.34 (1)° | T = 296 K |
V = 1577.1 (3) Å3 | Prism, colorless |
Z = 4 | 0.56 × 0.50 × 0.40 mm |
Bruker SMART 1000 diffractometer | 1942 reflections with I > 2σ(I) |
Radiation source: normal-focus sealed tube | Rint = 0.013 |
Graphite monochromator | θmax = 25.0°, θmin = 1.8° |
ω scans | h = 0→13 |
3252 measured reflections | k = 0→11 |
2783 independent reflections | l = −17→17 |
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)] = 0.038 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.102 | w = 1/[σ2(Fo2) + (0.0561P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.02 | (Δ/σ)max = 0.001 |
2783 reflections | Δρmax = 0.19 e Å−3 |
208 parameters | Δρmin = −0.14 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: 0.044 (3) |
C18H18N2O2 | V = 1577.1 (3) Å3 |
Mr = 294.34 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 11.307 (1) Å | µ = 0.08 mm−1 |
b = 9.475 (1) Å | T = 296 K |
c = 14.919 (2) Å | 0.56 × 0.50 × 0.40 mm |
β = 99.34 (1)° |
Bruker SMART 1000 diffractometer | 1942 reflections with I > 2σ(I) |
3252 measured reflections | Rint = 0.013 |
2783 independent reflections |
R[F2 > 2σ(F2)] = 0.038 | 0 restraints |
wR(F2) = 0.102 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.02 | Δρmax = 0.19 e Å−3 |
2783 reflections | Δρmin = −0.14 e Å−3 |
208 parameters |
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 | 0.38594 (9) | 0.19829 (12) | 0.53586 (7) | 0.0478 (3) | |
O2 | 0.39678 (10) | 0.42950 (13) | 0.81702 (8) | 0.0578 (4) | |
N1 | −0.00294 (13) | 0.07976 (16) | 0.59525 (10) | 0.0590 (4) | |
N2 | 0.24217 (15) | 0.06252 (18) | 0.46297 (11) | 0.0604 (5) | |
C1 | 0.09420 (14) | 0.48169 (19) | 0.69650 (12) | 0.0554 (5) | |
H1 | 0.0781 | 0.4273 | 0.7450 | 0.067* | |
C2 | 0.03121 (17) | 0.6051 (2) | 0.67480 (15) | 0.0680 (6) | |
H2 | −0.0275 | 0.6321 | 0.7084 | 0.082* | |
C3 | 0.05366 (18) | 0.6873 (2) | 0.60535 (13) | 0.0681 (6) | |
H3 | 0.0103 | 0.7699 | 0.5908 | 0.082* | |
C4 | 0.1409 (2) | 0.6476 (2) | 0.55686 (15) | 0.0919 (8) | |
H4 | 0.1587 | 0.7043 | 0.5100 | 0.110* | |
C5 | 0.2025 (2) | 0.5232 (2) | 0.57764 (13) | 0.0809 (7) | |
H5 | 0.2606 | 0.4962 | 0.5435 | 0.097* | |
C6 | 0.18021 (13) | 0.43816 (17) | 0.64756 (10) | 0.0411 (4) | |
C7 | 0.24657 (13) | 0.29886 (15) | 0.66897 (10) | 0.0385 (4) | |
H7 | 0.2291 | 0.2648 | 0.7275 | 0.046* | |
C8 | 0.20547 (13) | 0.18659 (16) | 0.59795 (10) | 0.0397 (4) | |
C9 | 0.27108 (13) | 0.14927 (17) | 0.53365 (10) | 0.0425 (4) | |
C10 | 0.44066 (13) | 0.26733 (15) | 0.61272 (10) | 0.0386 (4) | |
C11 | 0.38057 (13) | 0.31358 (15) | 0.67676 (10) | 0.0371 (4) | |
C12 | 0.44793 (15) | 0.38037 (16) | 0.75796 (10) | 0.0434 (4) | |
C13 | 0.58247 (14) | 0.3810 (2) | 0.76731 (11) | 0.0563 (5) | |
H13A | 0.6132 | 0.2940 | 0.7965 | 0.068* | |
H13B | 0.6136 | 0.4585 | 0.8067 | 0.068* | |
C14 | 0.62930 (14) | 0.39550 (18) | 0.67704 (11) | 0.0473 (4) | |
C15 | 0.57150 (13) | 0.28023 (17) | 0.61307 (11) | 0.0465 (4) | |
H15A | 0.5853 | 0.3008 | 0.5519 | 0.056* | |
H15B | 0.6096 | 0.1907 | 0.6312 | 0.056* | |
C16 | 0.09006 (14) | 0.12739 (17) | 0.59504 (10) | 0.0428 (4) | |
C17 | 0.59603 (18) | 0.5406 (2) | 0.63562 (14) | 0.0682 (6) | |
H17A | 0.5105 | 0.5515 | 0.6259 | 0.102* | |
H17B | 0.6246 | 0.5487 | 0.5787 | 0.102* | |
H17C | 0.6321 | 0.6128 | 0.6763 | 0.102* | |
C18 | 0.76479 (16) | 0.3782 (3) | 0.69277 (15) | 0.0805 (7) | |
H18A | 0.7855 | 0.2872 | 0.7189 | 0.121* | |
H18B | 0.8007 | 0.4504 | 0.7334 | 0.121* | |
H18C | 0.7936 | 0.3860 | 0.6359 | 0.121* | |
H2A | 0.2899 (17) | 0.056 (2) | 0.4222 (13) | 0.068 (6)* | |
H2B | 0.1700 (16) | 0.0265 (18) | 0.4520 (11) | 0.054 (5)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0410 (6) | 0.0565 (7) | 0.0487 (6) | −0.0109 (5) | 0.0161 (5) | −0.0157 (6) |
O2 | 0.0618 (8) | 0.0685 (8) | 0.0462 (7) | −0.0064 (6) | 0.0177 (6) | −0.0128 (6) |
N1 | 0.0507 (9) | 0.0708 (11) | 0.0583 (9) | −0.0157 (8) | 0.0175 (7) | −0.0097 (8) |
N2 | 0.0487 (10) | 0.0773 (12) | 0.0588 (10) | −0.0214 (9) | 0.0198 (8) | −0.0297 (9) |
C1 | 0.0545 (11) | 0.0535 (11) | 0.0642 (11) | 0.0079 (9) | 0.0271 (9) | 0.0057 (9) |
C2 | 0.0611 (12) | 0.0657 (13) | 0.0834 (14) | 0.0199 (10) | 0.0302 (11) | 0.0015 (11) |
C3 | 0.0761 (14) | 0.0589 (12) | 0.0682 (13) | 0.0283 (11) | 0.0089 (11) | 0.0016 (10) |
C4 | 0.130 (2) | 0.0824 (16) | 0.0735 (15) | 0.0496 (15) | 0.0457 (14) | 0.0345 (13) |
C5 | 0.1047 (17) | 0.0796 (15) | 0.0706 (14) | 0.0456 (13) | 0.0508 (13) | 0.0277 (12) |
C6 | 0.0407 (9) | 0.0445 (9) | 0.0386 (8) | 0.0023 (7) | 0.0079 (7) | −0.0027 (7) |
C7 | 0.0398 (8) | 0.0409 (9) | 0.0366 (8) | 0.0006 (7) | 0.0120 (6) | 0.0015 (7) |
C8 | 0.0358 (8) | 0.0403 (8) | 0.0442 (9) | −0.0028 (7) | 0.0104 (7) | −0.0014 (7) |
C9 | 0.0407 (9) | 0.0420 (9) | 0.0457 (9) | −0.0049 (7) | 0.0099 (7) | −0.0019 (8) |
C10 | 0.0396 (8) | 0.0340 (8) | 0.0424 (9) | −0.0020 (7) | 0.0072 (7) | −0.0020 (7) |
C11 | 0.0382 (8) | 0.0351 (8) | 0.0385 (9) | 0.0007 (7) | 0.0081 (7) | 0.0000 (7) |
C12 | 0.0496 (10) | 0.0427 (9) | 0.0388 (9) | −0.0028 (8) | 0.0103 (7) | 0.0007 (7) |
C13 | 0.0488 (10) | 0.0706 (12) | 0.0486 (10) | −0.0096 (9) | 0.0052 (8) | −0.0046 (9) |
C14 | 0.0399 (9) | 0.0521 (10) | 0.0502 (10) | −0.0083 (8) | 0.0086 (7) | −0.0060 (8) |
C15 | 0.0393 (9) | 0.0456 (10) | 0.0563 (10) | 0.0002 (7) | 0.0129 (8) | −0.0036 (8) |
C16 | 0.0449 (10) | 0.0452 (9) | 0.0396 (9) | −0.0012 (8) | 0.0102 (7) | −0.0025 (7) |
C17 | 0.0838 (15) | 0.0507 (11) | 0.0750 (13) | −0.0181 (10) | 0.0276 (11) | −0.0065 (10) |
C18 | 0.0438 (11) | 0.1192 (19) | 0.0783 (14) | −0.0144 (12) | 0.0095 (10) | −0.0203 (14) |
O1—C9 | 1.3746 (17) | C7—C11 | 1.5071 (19) |
O1—C10 | 1.3767 (17) | C7—C8 | 1.520 (2) |
O2—C12 | 1.2219 (18) | C8—C9 | 1.351 (2) |
N1—C16 | 1.1448 (19) | C8—C16 | 1.415 (2) |
N2—C9 | 1.335 (2) | C10—C11 | 1.333 (2) |
C1—C6 | 1.371 (2) | C10—C15 | 1.4835 (19) |
C1—C2 | 1.380 (2) | C11—C12 | 1.466 (2) |
C2—C3 | 1.353 (3) | C12—C13 | 1.505 (2) |
C3—C4 | 1.368 (3) | C13—C14 | 1.531 (2) |
C4—C5 | 1.378 (3) | C14—C18 | 1.521 (2) |
C5—C6 | 1.373 (2) | C14—C15 | 1.526 (2) |
C6—C7 | 1.526 (2) | C14—C17 | 1.529 (2) |
C9—O1—C10 | 118.41 (11) | C11—C10—O1 | 122.73 (13) |
C6—C1—C2 | 120.91 (17) | C11—C10—C15 | 126.46 (14) |
C3—C2—C1 | 120.92 (18) | O1—C10—C15 | 110.81 (12) |
C2—C3—C4 | 119.17 (18) | C10—C11—C12 | 118.51 (14) |
C3—C4—C5 | 119.9 (2) | C10—C11—C7 | 122.50 (14) |
C6—C5—C4 | 121.61 (18) | C12—C11—C7 | 118.99 (13) |
C1—C6—C5 | 117.49 (16) | O2—C12—C11 | 121.14 (15) |
C1—C6—C7 | 121.05 (14) | O2—C12—C13 | 121.42 (15) |
C5—C6—C7 | 121.45 (14) | C11—C12—C13 | 117.40 (14) |
C11—C7—C8 | 107.96 (12) | C12—C13—C14 | 114.05 (14) |
C11—C7—C6 | 112.96 (12) | C18—C14—C15 | 109.75 (14) |
C8—C7—C6 | 112.03 (12) | C18—C14—C17 | 109.57 (16) |
C9—C8—C16 | 118.97 (14) | C15—C14—C17 | 109.79 (14) |
C9—C8—C7 | 122.48 (13) | C18—C14—C13 | 109.76 (15) |
C16—C8—C7 | 118.36 (13) | C15—C14—C13 | 108.16 (13) |
N2—C9—C8 | 129.01 (15) | C17—C14—C13 | 109.79 (15) |
N2—C9—O1 | 109.64 (14) | C10—C15—C14 | 112.76 (13) |
C8—C9—O1 | 121.32 (14) | N1—C16—C8 | 178.11 (17) |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2B···N1i | 0.875 (17) | 2.156 (18) | 3.021 (2) | 169.8 (15) |
N2—H2A···O2ii | 0.88 (2) | 2.13 (2) | 3.006 (2) | 171.6 (18) |
Symmetry codes: (i) −x, −y, −z+1; (ii) x, −y+1/2, z−1/2. |
Experimental details
Crystal data | |
Chemical formula | C18H18N2O2 |
Mr | 294.34 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 296 |
a, b, c (Å) | 11.307 (1), 9.475 (1), 14.919 (2) |
β (°) | 99.34 (1) |
V (Å3) | 1577.1 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.08 |
Crystal size (mm) | 0.56 × 0.50 × 0.40 |
Data collection | |
Diffractometer | Bruker SMART 1000 |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3252, 2783, 1942 |
Rint | 0.013 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.038, 0.102, 1.02 |
No. of reflections | 2783 |
No. of parameters | 208 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.19, −0.14 |
Computer programs: SMART (Bruker, 1998), SMART, SAINT (Bruker, 1998), SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), ORTEPII (Johnson, 1976).
O1—C9 | 1.3746 (17) | N2—C9 | 1.335 (2) |
O1—C10 | 1.3767 (17) | C8—C9 | 1.351 (2) |
O2—C12 | 1.2219 (18) | C10—C11 | 1.333 (2) |
N1—C16 | 1.1448 (19) | ||
C9—O1—C10 | 118.41 (11) | O2—C12—C11 | 121.14 (15) |
N2—C9—C8 | 129.01 (15) | O2—C12—C13 | 121.42 (15) |
N2—C9—O1 | 109.64 (14) | N1—C16—C8 | 178.11 (17) |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2B···N1i | 0.875 (17) | 2.156 (18) | 3.021 (2) | 169.8 (15) |
N2—H2A···O2ii | 0.88 (2) | 2.13 (2) | 3.006 (2) | 171.6 (18) |
Symmetry codes: (i) −x, −y, −z+1; (ii) x, −y+1/2, z−1/2. |
Polyfunctionalized benzo-4H-pyrans are structural units of a number of natural products (Hatakeyama et al., 1988) and, because of their inherent reactivity, the pyran rings are versatile synthons (Singh et al., 1996). On the other hand, substituted benzo-4H-pyrans possess varied biological activity (Hassanien et al., 1999). Since the stereochemistry is so important in the rational design of new functional molecules, we report herein the crystal structure of the title compound, (I).
In the structure (Fig. 1) of the neutral molecule (I), the C7/C8/C9/O1/C10/C11 plane forms an angle of 92.5 (4)° with the phenyl plane. The nitrile group is typical [N≡C 1.1448 (19) Å].
A notable feature of (I) is the formation of a three-dimensional network through hydrogen bonds, as shown in Fig. 2. These are in the normal range of weak interactions (Sasada, 1984). The amino N2 atom of one molecule links through H2B to the nitrile N1 atom of another molecule, creating a dimer. The amino N2 atom of one molecule also links through H2A to the keto O2 atom of another molecule to form the three-dimensional framework.