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In the mol­ecule of the title compound, C18H18N2O2, the C7/C8/C9/O1/C10/C11 plane forms an angle of 92.5 (4)° with the phenyl plane. The most striking feature of the title compound is the formation of a three-dimensional network through N—H...N and N—H...O hydrogen bonds.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801004755/wn6009sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536801004755/wn6009Isup2.hkl
Contains datablock I

CCDC reference: 162829

Key indicators

  • Single-crystal X-ray study
  • T = 296 K
  • Mean [sigma](C-C) = 0.002 Å
  • R factor = 0.038
  • wR factor = 0.102
  • Data-to-parameter ratio = 13.4

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


Yellow Alert Alert Level C:
PLAT_371 Alert C Long C(sp2)-C(sp1) Bond C(8) - C(16) = 1.41 Ang.
0 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
1 Alert Level C = Please check

Comment top

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 [NC 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.

Experimental top

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).

Refinement top

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.

Structure description top

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 [NC 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.

Computing details top

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).

Figures top
[Figure 1] Fig. 1. ORTEPII view (Johnson, 1976) of the title complex with displacement ellipsoids at the 30% probability level
[Figure 2] Fig. 2. The molecular packing diagram of the title complex.
2-Amino-7,7-dimethyl-4-benzyl-5-oxo-4,5,6,8-tetrahydro-7H-chromene -3-carbornitrile top
Crystal data top
C18H18N2O2F(000) = 624
Mr = 294.34Dx = 1.240 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
a = 11.307 (1) ÅCell parameters from 25 reflections
b = 9.475 (1) Åθ = 3.3–15.1°
c = 14.919 (2) ŵ = 0.08 mm1
β = 99.34 (1)°T = 296 K
V = 1577.1 (3) Å3Prism, colorless
Z = 40.56 × 0.50 × 0.40 mm
Data collection top
Bruker SMART 1000
diffractometer
1942 reflections with I > 2σ(I)
Radiation source: normal-focus sealed tubeRint = 0.013
Graphite monochromatorθmax = 25.0°, θmin = 1.8°
ω scansh = 013
3252 measured reflectionsk = 011
2783 independent reflectionsl = 1717
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.038H 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 reflectionsΔρmax = 0.19 e Å3
208 parametersΔρmin = 0.14 e Å3
0 restraintsExtinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.044 (3)
Crystal data top
C18H18N2O2V = 1577.1 (3) Å3
Mr = 294.34Z = 4
Monoclinic, P21/cMo Kα radiation
a = 11.307 (1) ŵ = 0.08 mm1
b = 9.475 (1) ÅT = 296 K
c = 14.919 (2) Å0.56 × 0.50 × 0.40 mm
β = 99.34 (1)°
Data collection top
Bruker SMART 1000
diffractometer
1942 reflections with I > 2σ(I)
3252 measured reflectionsRint = 0.013
2783 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0380 restraints
wR(F2) = 0.102H atoms treated by a mixture of independent and constrained refinement
S = 1.02Δρmax = 0.19 e Å3
2783 reflectionsΔρmin = 0.14 e Å3
208 parameters
Special details top

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
O10.38594 (9)0.19829 (12)0.53586 (7)0.0478 (3)
O20.39678 (10)0.42950 (13)0.81702 (8)0.0578 (4)
N10.00294 (13)0.07976 (16)0.59525 (10)0.0590 (4)
N20.24217 (15)0.06252 (18)0.46297 (11)0.0604 (5)
C10.09420 (14)0.48169 (19)0.69650 (12)0.0554 (5)
H10.07810.42730.74500.067*
C20.03121 (17)0.6051 (2)0.67480 (15)0.0680 (6)
H20.02750.63210.70840.082*
C30.05366 (18)0.6873 (2)0.60535 (13)0.0681 (6)
H30.01030.76990.59080.082*
C40.1409 (2)0.6476 (2)0.55686 (15)0.0919 (8)
H40.15870.70430.51000.110*
C50.2025 (2)0.5232 (2)0.57764 (13)0.0809 (7)
H50.26060.49620.54350.097*
C60.18021 (13)0.43816 (17)0.64756 (10)0.0411 (4)
C70.24657 (13)0.29886 (15)0.66897 (10)0.0385 (4)
H70.22910.26480.72750.046*
C80.20547 (13)0.18659 (16)0.59795 (10)0.0397 (4)
C90.27108 (13)0.14927 (17)0.53365 (10)0.0425 (4)
C100.44066 (13)0.26733 (15)0.61272 (10)0.0386 (4)
C110.38057 (13)0.31358 (15)0.67676 (10)0.0371 (4)
C120.44793 (15)0.38037 (16)0.75796 (10)0.0434 (4)
C130.58247 (14)0.3810 (2)0.76731 (11)0.0563 (5)
H13A0.61320.29400.79650.068*
H13B0.61360.45850.80670.068*
C140.62930 (14)0.39550 (18)0.67704 (11)0.0473 (4)
C150.57150 (13)0.28023 (17)0.61307 (11)0.0465 (4)
H15A0.58530.30080.55190.056*
H15B0.60960.19070.63120.056*
C160.09006 (14)0.12739 (17)0.59504 (10)0.0428 (4)
C170.59603 (18)0.5406 (2)0.63562 (14)0.0682 (6)
H17A0.51050.55150.62590.102*
H17B0.62460.54870.57870.102*
H17C0.63210.61280.67630.102*
C180.76479 (16)0.3782 (3)0.69277 (15)0.0805 (7)
H18A0.78550.28720.71890.121*
H18B0.80070.45040.73340.121*
H18C0.79360.38600.63590.121*
H2A0.2899 (17)0.056 (2)0.4222 (13)0.068 (6)*
H2B0.1700 (16)0.0265 (18)0.4520 (11)0.054 (5)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0410 (6)0.0565 (7)0.0487 (6)0.0109 (5)0.0161 (5)0.0157 (6)
O20.0618 (8)0.0685 (8)0.0462 (7)0.0064 (6)0.0177 (6)0.0128 (6)
N10.0507 (9)0.0708 (11)0.0583 (9)0.0157 (8)0.0175 (7)0.0097 (8)
N20.0487 (10)0.0773 (12)0.0588 (10)0.0214 (9)0.0198 (8)0.0297 (9)
C10.0545 (11)0.0535 (11)0.0642 (11)0.0079 (9)0.0271 (9)0.0057 (9)
C20.0611 (12)0.0657 (13)0.0834 (14)0.0199 (10)0.0302 (11)0.0015 (11)
C30.0761 (14)0.0589 (12)0.0682 (13)0.0283 (11)0.0089 (11)0.0016 (10)
C40.130 (2)0.0824 (16)0.0735 (15)0.0496 (15)0.0457 (14)0.0345 (13)
C50.1047 (17)0.0796 (15)0.0706 (14)0.0456 (13)0.0508 (13)0.0277 (12)
C60.0407 (9)0.0445 (9)0.0386 (8)0.0023 (7)0.0079 (7)0.0027 (7)
C70.0398 (8)0.0409 (9)0.0366 (8)0.0006 (7)0.0120 (6)0.0015 (7)
C80.0358 (8)0.0403 (8)0.0442 (9)0.0028 (7)0.0104 (7)0.0014 (7)
C90.0407 (9)0.0420 (9)0.0457 (9)0.0049 (7)0.0099 (7)0.0019 (8)
C100.0396 (8)0.0340 (8)0.0424 (9)0.0020 (7)0.0072 (7)0.0020 (7)
C110.0382 (8)0.0351 (8)0.0385 (9)0.0007 (7)0.0081 (7)0.0000 (7)
C120.0496 (10)0.0427 (9)0.0388 (9)0.0028 (8)0.0103 (7)0.0007 (7)
C130.0488 (10)0.0706 (12)0.0486 (10)0.0096 (9)0.0052 (8)0.0046 (9)
C140.0399 (9)0.0521 (10)0.0502 (10)0.0083 (8)0.0086 (7)0.0060 (8)
C150.0393 (9)0.0456 (10)0.0563 (10)0.0002 (7)0.0129 (8)0.0036 (8)
C160.0449 (10)0.0452 (9)0.0396 (9)0.0012 (8)0.0102 (7)0.0025 (7)
C170.0838 (15)0.0507 (11)0.0750 (13)0.0181 (10)0.0276 (11)0.0065 (10)
C180.0438 (11)0.1192 (19)0.0783 (14)0.0144 (12)0.0095 (10)0.0203 (14)
Geometric parameters (Å, º) top
O1—C91.3746 (17)C7—C111.5071 (19)
O1—C101.3767 (17)C7—C81.520 (2)
O2—C121.2219 (18)C8—C91.351 (2)
N1—C161.1448 (19)C8—C161.415 (2)
N2—C91.335 (2)C10—C111.333 (2)
C1—C61.371 (2)C10—C151.4835 (19)
C1—C21.380 (2)C11—C121.466 (2)
C2—C31.353 (3)C12—C131.505 (2)
C3—C41.368 (3)C13—C141.531 (2)
C4—C51.378 (3)C14—C181.521 (2)
C5—C61.373 (2)C14—C151.526 (2)
C6—C71.526 (2)C14—C171.529 (2)
C9—O1—C10118.41 (11)C11—C10—O1122.73 (13)
C6—C1—C2120.91 (17)C11—C10—C15126.46 (14)
C3—C2—C1120.92 (18)O1—C10—C15110.81 (12)
C2—C3—C4119.17 (18)C10—C11—C12118.51 (14)
C3—C4—C5119.9 (2)C10—C11—C7122.50 (14)
C6—C5—C4121.61 (18)C12—C11—C7118.99 (13)
C1—C6—C5117.49 (16)O2—C12—C11121.14 (15)
C1—C6—C7121.05 (14)O2—C12—C13121.42 (15)
C5—C6—C7121.45 (14)C11—C12—C13117.40 (14)
C11—C7—C8107.96 (12)C12—C13—C14114.05 (14)
C11—C7—C6112.96 (12)C18—C14—C15109.75 (14)
C8—C7—C6112.03 (12)C18—C14—C17109.57 (16)
C9—C8—C16118.97 (14)C15—C14—C17109.79 (14)
C9—C8—C7122.48 (13)C18—C14—C13109.76 (15)
C16—C8—C7118.36 (13)C15—C14—C13108.16 (13)
N2—C9—C8129.01 (15)C17—C14—C13109.79 (15)
N2—C9—O1109.64 (14)C10—C15—C14112.76 (13)
C8—C9—O1121.32 (14)N1—C16—C8178.11 (17)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H2B···N1i0.875 (17)2.156 (18)3.021 (2)169.8 (15)
N2—H2A···O2ii0.88 (2)2.13 (2)3.006 (2)171.6 (18)
Symmetry codes: (i) x, y, z+1; (ii) x, y+1/2, z1/2.

Experimental details

Crystal data
Chemical formulaC18H18N2O2
Mr294.34
Crystal system, space groupMonoclinic, P21/c
Temperature (K)296
a, b, c (Å)11.307 (1), 9.475 (1), 14.919 (2)
β (°) 99.34 (1)
V3)1577.1 (3)
Z4
Radiation typeMo Kα
µ (mm1)0.08
Crystal size (mm)0.56 × 0.50 × 0.40
Data collection
DiffractometerBruker SMART 1000
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
3252, 2783, 1942
Rint0.013
(sin θ/λ)max1)0.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.038, 0.102, 1.02
No. of reflections2783
No. of parameters208
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.19, 0.14

Computer programs: SMART (Bruker, 1998), SMART, SAINT (Bruker, 1998), SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), ORTEPII (Johnson, 1976).

Selected geometric parameters (Å, º) top
O1—C91.3746 (17)N2—C91.335 (2)
O1—C101.3767 (17)C8—C91.351 (2)
O2—C121.2219 (18)C10—C111.333 (2)
N1—C161.1448 (19)
C9—O1—C10118.41 (11)O2—C12—C11121.14 (15)
N2—C9—C8129.01 (15)O2—C12—C13121.42 (15)
N2—C9—O1109.64 (14)N1—C16—C8178.11 (17)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H2B···N1i0.875 (17)2.156 (18)3.021 (2)169.8 (15)
N2—H2A···O2ii0.88 (2)2.13 (2)3.006 (2)171.6 (18)
Symmetry codes: (i) x, y, z+1; (ii) x, y+1/2, z1/2.
 

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