The title compound, C20H22FNO4, was synthesized by the reaction of 4-fluorobenzaldehyde with 5,5-dimethyl-1,3-cyclohexanedione and ethyl cyanoacetate. The pyran ring adopts a boat conformation, while the fused six-membered ring adopts a distorted boat conformation.
Supporting information
CCDC reference: 225767
Key indicators
- Single-crystal X-ray study
- T = 296 K
- Mean (C-C) = 0.003 Å
- R factor = 0.040
- wR factor = 0.114
- Data-to-parameter ratio = 13.4
checkCIF/PLATON results
No syntax errors found
Alert level C
PLAT125_ALERT_4_C No _symmetry_space_group_name_Hall Given ....... ?
PLAT230_ALERT_2_C Hirshfeld Test Diff for C11 - C12 = 6.44 su
PLAT242_ALERT_2_C Check Low U(eq) as Compared to Neighbors .... C11
0 ALERT level A = In general: serious problem
0 ALERT level B = Potentially serious problem
3 ALERT level C = Check and explain
0 ALERT level G = General alerts; check
0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
2 ALERT type 2 Indicator that the structure model may be wrong or deficient
0 ALERT type 3 Indicator that the structure quality may be low
1 ALERT type 4 Improvement, methodology, query or suggestion
Data collection: XSCANS (Siemens, 1994); cell refinement: XSCANS; data reduction: SHELXTL (Sheldrick, 1997); program(s) used to solve structure: SHELXTL; program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
Ethyl 2-amino-7,7-dimethyl-4-(4-fluorophenyl)-5-oxo-
4
H-5,6,7,8-tetrahydrobenzo[
b]pyran-3-carboxylate
top
Crystal data top
C20H22FNO4 | F(000) = 380 |
Mr = 359.39 | Dx = 1.266 Mg m−3 |
Triclinic, P1 | Melting point = 433–434 K |
a = 8.266 (1) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 9.773 (1) Å | Cell parameters from 32 reflections |
c = 12.375 (2) Å | θ = 3.1–15.1° |
α = 81.40 (1)° | µ = 0.09 mm−1 |
β = 73.41 (1)° | T = 296 K |
γ = 82.15 (1)° | Block, colorless |
V = 942.6 (2) Å3 | 0.50 × 0.46 × 0.40 mm |
Z = 2 | |
Data collection top
Siemens P4 diffractometer | 2258 reflections with I > 2σ(I) |
Radiation source: normal-focus sealed tube | Rint = 0.008 |
Graphite monochromator | θmax = 25.0°, θmin = 1.7° |
ω scans | h = 0→9 |
Absorption correction: ψ scan XSCANS (Siemens, 1994) | k = −11→11 |
Tmin = 0.937, Tmax = 0.964 | l = −14→14 |
3694 measured reflections | 3 standard reflections every 97 reflections |
3316 independent reflections | intensity decay: 2.3% |
Refinement top
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)] = 0.040 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.114 | w = 1/[σ2(Fo2) + (0.0652P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.00 | (Δ/σ)max < 0.001 |
3316 reflections | Δρmax = 0.20 e Å−3 |
247 parameters | Δρmin = −0.19 e Å−3 |
0 restraints | Extinction correction: SHELXTL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.040 (4) |
Special details top
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
F | 0.26348 (18) | 0.02836 (14) | 0.02994 (10) | 0.0959 (4) | |
O1 | 0.52335 (14) | 0.30199 (12) | 0.46257 (10) | 0.0537 (3) | |
O2 | −0.05861 (15) | 0.33363 (15) | 0.48610 (11) | 0.0705 (4) | |
O3 | 0.36071 (15) | 0.58488 (12) | 0.16058 (10) | 0.0578 (4) | |
O4 | 0.62260 (18) | 0.59931 (14) | 0.17541 (12) | 0.0714 (4) | |
N | 0.7162 (2) | 0.4298 (2) | 0.34383 (17) | 0.0679 (5) | |
C1 | 0.2609 (3) | 0.1144 (2) | 0.10746 (15) | 0.0635 (5) | |
C2 | 0.1577 (3) | 0.2350 (2) | 0.11104 (15) | 0.0656 (5) | |
H2 | 0.0885 | 0.2579 | 0.0622 | 0.079* | |
C3 | 0.1572 (2) | 0.32373 (19) | 0.18902 (14) | 0.0535 (5) | |
H3 | 0.0862 | 0.4063 | 0.1926 | 0.064* | |
C4 | 0.26027 (19) | 0.29127 (17) | 0.26113 (13) | 0.0427 (4) | |
C5 | 0.3617 (2) | 0.16653 (19) | 0.25428 (15) | 0.0577 (5) | |
H5 | 0.4311 | 0.1421 | 0.3030 | 0.069* | |
C6 | 0.3636 (2) | 0.0770 (2) | 0.17745 (16) | 0.0661 (5) | |
H6 | 0.4330 | −0.0064 | 0.1737 | 0.079* | |
C7 | 0.2690 (2) | 0.39073 (16) | 0.34305 (12) | 0.0435 (4) | |
H7 | 0.1816 | 0.4688 | 0.3405 | 0.052* | |
C8 | 0.23388 (19) | 0.31915 (16) | 0.46263 (13) | 0.0433 (4) | |
C9 | 0.0607 (2) | 0.29604 (17) | 0.52702 (14) | 0.0504 (4) | |
C10 | 0.0321 (2) | 0.2297 (2) | 0.64819 (14) | 0.0623 (5) | |
H10A | −0.0731 | 0.1862 | 0.6704 | 0.075* | |
H10B | 0.0193 | 0.3017 | 0.6969 | 0.075* | |
C11 | 0.1757 (2) | 0.12029 (18) | 0.66739 (14) | 0.0557 (5) | |
C12 | 0.3419 (2) | 0.18812 (19) | 0.62373 (14) | 0.0550 (5) | |
H12A | 0.3491 | 0.2462 | 0.6789 | 0.066* | |
H12B | 0.4361 | 0.1159 | 0.6169 | 0.066* | |
C13 | 0.3588 (2) | 0.27438 (16) | 0.51192 (13) | 0.0448 (4) | |
C14 | 0.5571 (2) | 0.39857 (17) | 0.36789 (14) | 0.0487 (4) | |
C15 | 0.4398 (2) | 0.44808 (16) | 0.31017 (13) | 0.0448 (4) | |
C16 | 0.4868 (2) | 0.54921 (17) | 0.21232 (15) | 0.0522 (4) | |
C17 | 0.3990 (3) | 0.6784 (2) | 0.05613 (17) | 0.0714 (6) | |
H17A | 0.5030 | 0.6434 | 0.0041 | 0.086* | |
H17B | 0.4133 | 0.7698 | 0.0717 | 0.086* | |
C18 | 0.2539 (3) | 0.6871 (2) | 0.00542 (17) | 0.0785 (6) | |
H18A | 0.2396 | 0.5959 | −0.0082 | 0.094* | |
H18B | 0.2766 | 0.7470 | −0.0650 | 0.094* | |
H18C | 0.1523 | 0.7239 | 0.0568 | 0.094* | |
C19 | 0.1819 (3) | −0.0034 (2) | 0.6035 (2) | 0.0838 (7) | |
H19A | 0.1999 | 0.0278 | 0.5240 | 0.101* | |
H19B | 0.0766 | −0.0444 | 0.6319 | 0.101* | |
H19C | 0.2732 | −0.0712 | 0.6144 | 0.101* | |
C20 | 0.1477 (3) | 0.0712 (3) | 0.79358 (17) | 0.0851 (7) | |
H20A | 0.2365 | 0.0005 | 0.8042 | 0.102* | |
H20B | 0.0401 | 0.0338 | 0.8230 | 0.102* | |
H20C | 0.1491 | 0.1482 | 0.8331 | 0.102* | |
H1A | 0.754 (3) | 0.491 (2) | 0.2830 (18) | 0.082 (7)* | |
H1B | 0.775 (3) | 0.395 (2) | 0.3913 (17) | 0.077 (6)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
F | 0.1246 (11) | 0.1060 (10) | 0.0773 (8) | −0.0183 (8) | −0.0404 (8) | −0.0422 (7) |
O1 | 0.0448 (7) | 0.0621 (8) | 0.0570 (7) | 0.0038 (5) | −0.0262 (6) | 0.0009 (6) |
O2 | 0.0472 (7) | 0.0985 (10) | 0.0671 (8) | 0.0074 (7) | −0.0284 (7) | −0.0014 (7) |
O3 | 0.0652 (8) | 0.0558 (7) | 0.0567 (7) | −0.0038 (6) | −0.0312 (6) | 0.0072 (6) |
O4 | 0.0736 (9) | 0.0729 (9) | 0.0773 (9) | −0.0246 (8) | −0.0365 (8) | 0.0084 (7) |
N | 0.0534 (10) | 0.0810 (12) | 0.0768 (12) | −0.0133 (9) | −0.0365 (9) | 0.0103 (10) |
C1 | 0.0728 (13) | 0.0755 (14) | 0.0508 (11) | −0.0171 (11) | −0.0200 (10) | −0.0193 (10) |
C2 | 0.0679 (13) | 0.0905 (15) | 0.0520 (11) | −0.0154 (11) | −0.0355 (10) | −0.0060 (10) |
C3 | 0.0474 (10) | 0.0673 (11) | 0.0512 (10) | −0.0020 (8) | −0.0249 (8) | −0.0045 (8) |
C4 | 0.0389 (9) | 0.0534 (10) | 0.0373 (8) | −0.0030 (7) | −0.0144 (7) | −0.0034 (7) |
C5 | 0.0616 (11) | 0.0643 (12) | 0.0565 (11) | 0.0087 (9) | −0.0321 (9) | −0.0174 (9) |
C6 | 0.0742 (13) | 0.0635 (12) | 0.0672 (12) | 0.0049 (10) | −0.0282 (11) | −0.0214 (10) |
C7 | 0.0426 (9) | 0.0468 (9) | 0.0438 (9) | 0.0101 (7) | −0.0212 (7) | −0.0080 (7) |
C8 | 0.0445 (9) | 0.0475 (9) | 0.0405 (9) | 0.0076 (7) | −0.0191 (7) | −0.0091 (7) |
C9 | 0.0475 (10) | 0.0573 (11) | 0.0486 (10) | 0.0099 (8) | −0.0210 (8) | −0.0111 (8) |
C10 | 0.0549 (11) | 0.0771 (13) | 0.0506 (10) | 0.0070 (9) | −0.0152 (9) | −0.0041 (9) |
C11 | 0.0570 (11) | 0.0580 (11) | 0.0526 (10) | 0.0041 (9) | −0.0230 (9) | −0.0007 (8) |
C12 | 0.0605 (11) | 0.0600 (11) | 0.0481 (10) | 0.0104 (9) | −0.0285 (9) | −0.0061 (8) |
C13 | 0.0438 (10) | 0.0487 (9) | 0.0450 (9) | 0.0073 (7) | −0.0196 (8) | −0.0108 (7) |
C14 | 0.0488 (10) | 0.0481 (10) | 0.0533 (10) | 0.0007 (8) | −0.0215 (8) | −0.0084 (8) |
C15 | 0.0486 (10) | 0.0441 (9) | 0.0473 (9) | 0.0031 (7) | −0.0233 (8) | −0.0093 (7) |
C16 | 0.0593 (12) | 0.0482 (10) | 0.0573 (11) | −0.0034 (9) | −0.0283 (9) | −0.0090 (8) |
C17 | 0.0879 (15) | 0.0591 (12) | 0.0692 (13) | −0.0115 (11) | −0.0349 (11) | 0.0167 (10) |
C18 | 0.0927 (16) | 0.0793 (14) | 0.0657 (13) | 0.0021 (12) | −0.0377 (12) | 0.0071 (11) |
C19 | 0.0949 (17) | 0.0639 (13) | 0.0984 (17) | −0.0009 (12) | −0.0385 (14) | −0.0095 (12) |
C20 | 0.0797 (15) | 0.1040 (17) | 0.0629 (13) | 0.0008 (13) | −0.0235 (11) | 0.0167 (12) |
Geometric parameters (Å, º) top
F—C1 | 1.361 (2) | C8—C9 | 1.455 (2) |
O1—C13 | 1.3686 (19) | C9—C10 | 1.508 (2) |
O1—C14 | 1.3770 (19) | C10—C11 | 1.532 (2) |
O2—C9 | 1.2228 (18) | C10—H10A | 0.9700 |
O3—C16 | 1.3541 (19) | C10—H10B | 0.9700 |
O3—C17 | 1.449 (2) | C11—C20 | 1.524 (2) |
O4—C16 | 1.224 (2) | C11—C19 | 1.528 (3) |
N—C14 | 1.330 (2) | C11—C12 | 1.528 (3) |
N—H1A | 0.90 (2) | C12—C13 | 1.489 (2) |
N—H1B | 0.87 (2) | C12—H12A | 0.9700 |
C1—C2 | 1.355 (3) | C12—H12B | 0.9700 |
C1—C6 | 1.358 (3) | C14—C15 | 1.359 (2) |
C2—C3 | 1.389 (3) | C15—C16 | 1.440 (2) |
C2—H2 | 0.9300 | C17—C18 | 1.491 (3) |
C3—C4 | 1.378 (2) | C17—H17A | 0.9700 |
C3—H3 | 0.9300 | C17—H17B | 0.9700 |
C4—C5 | 1.381 (2) | C18—H18A | 0.9600 |
C4—C7 | 1.528 (2) | C18—H18B | 0.9600 |
C5—C6 | 1.381 (2) | C18—H18C | 0.9600 |
C5—H5 | 0.9300 | C19—H19A | 0.9600 |
C6—H6 | 0.9300 | C19—H19B | 0.9600 |
C7—C8 | 1.505 (2) | C19—H19C | 0.9600 |
C7—C15 | 1.514 (2) | C20—H20A | 0.9600 |
C7—H7 | 0.9800 | C20—H20B | 0.9600 |
C8—C13 | 1.336 (2) | C20—H20C | 0.9600 |
| | | |
C13—O1—C14 | 118.45 (12) | C19—C11—C10 | 109.48 (16) |
C16—O3—C17 | 116.44 (14) | C12—C11—C10 | 107.93 (15) |
C14—N—H1A | 118.4 (14) | C13—C12—C11 | 113.27 (13) |
C14—N—H1B | 117.9 (13) | C13—C12—H12A | 108.9 |
H1A—N—H1B | 123 (2) | C11—C12—H12A | 108.9 |
C2—C1—C6 | 122.41 (17) | C13—C12—H12B | 108.9 |
C2—C1—F | 118.89 (18) | C11—C12—H12B | 108.9 |
C6—C1—F | 118.69 (19) | H12A—C12—H12B | 107.7 |
C1—C2—C3 | 118.82 (17) | C8—C13—O1 | 122.85 (14) |
C1—C2—H2 | 120.6 | C8—C13—C12 | 126.18 (16) |
C3—C2—H2 | 120.6 | O1—C13—C12 | 110.97 (13) |
C4—C3—C2 | 121.03 (17) | N—C14—C15 | 127.79 (18) |
C4—C3—H3 | 119.5 | N—C14—O1 | 109.95 (15) |
C2—C3—H3 | 119.5 | C15—C14—O1 | 122.24 (15) |
C3—C4—C5 | 117.61 (15) | C14—C15—C16 | 118.16 (15) |
C3—C4—C7 | 121.98 (15) | C14—C15—C7 | 120.74 (15) |
C5—C4—C7 | 120.37 (13) | C16—C15—C7 | 120.96 (13) |
C6—C5—C4 | 122.10 (16) | O4—C16—O3 | 121.38 (16) |
C6—C5—H5 | 118.9 | O4—C16—C15 | 126.82 (15) |
C4—C5—H5 | 118.9 | O3—C16—C15 | 111.79 (15) |
C1—C6—C5 | 118.02 (18) | O3—C17—C18 | 107.42 (16) |
C1—C6—H6 | 121.0 | O3—C17—H17A | 110.2 |
C5—C6—H6 | 121.0 | C18—C17—H17A | 110.2 |
C8—C7—C15 | 109.62 (12) | O3—C17—H17B | 110.2 |
C8—C7—C4 | 110.61 (13) | C18—C17—H17B | 110.2 |
C15—C7—C4 | 111.66 (13) | H17A—C17—H17B | 108.5 |
C8—C7—H7 | 108.3 | C17—C18—H18A | 109.5 |
C15—C7—H7 | 108.3 | C17—C18—H18B | 109.5 |
C4—C7—H7 | 108.3 | H18A—C18—H18B | 109.5 |
C13—C8—C9 | 118.44 (14) | C17—C18—H18C | 109.5 |
C13—C8—C7 | 121.56 (15) | H18A—C18—H18C | 109.5 |
C9—C8—C7 | 120.00 (13) | H18B—C18—H18C | 109.5 |
O2—C9—C8 | 121.42 (15) | C11—C19—H19A | 109.5 |
O2—C9—C10 | 120.83 (16) | C11—C19—H19B | 109.5 |
C8—C9—C10 | 117.70 (14) | H19A—C19—H19B | 109.5 |
C9—C10—C11 | 113.66 (15) | C11—C19—H19C | 109.5 |
C9—C10—H10A | 108.8 | H19A—C19—H19C | 109.5 |
C11—C10—H10A | 108.8 | H19B—C19—H19C | 109.5 |
C9—C10—H10B | 108.8 | C11—C20—H20A | 109.5 |
C11—C10—H10B | 108.8 | C11—C20—H20B | 109.5 |
H10A—C10—H10B | 107.7 | H20A—C20—H20B | 109.5 |
C20—C11—C19 | 109.62 (17) | C11—C20—H20C | 109.5 |
C20—C11—C12 | 108.76 (15) | H20A—C20—H20C | 109.5 |
C19—C11—C12 | 110.67 (16) | H20B—C20—H20C | 109.5 |
C20—C11—C10 | 110.36 (16) | | |
| | | |
C6—C1—C2—C3 | 0.1 (3) | C19—C11—C12—C13 | 75.76 (18) |
F—C1—C2—C3 | −178.99 (16) | C10—C11—C12—C13 | −44.02 (19) |
C1—C2—C3—C4 | 0.5 (3) | C9—C8—C13—O1 | −173.96 (14) |
C2—C3—C4—C5 | −1.0 (3) | C7—C8—C13—O1 | 6.6 (2) |
C2—C3—C4—C7 | 176.61 (16) | C9—C8—C13—C12 | 7.1 (2) |
C3—C4—C5—C6 | 0.9 (3) | C7—C8—C13—C12 | −172.29 (15) |
C7—C4—C5—C6 | −176.77 (16) | C14—O1—C13—C8 | 11.2 (2) |
C2—C1—C6—C5 | −0.3 (3) | C14—O1—C13—C12 | −169.72 (14) |
F—C1—C6—C5 | 178.86 (16) | C11—C12—C13—C8 | 15.1 (2) |
C4—C5—C6—C1 | −0.3 (3) | C11—C12—C13—O1 | −163.89 (13) |
C3—C4—C7—C8 | 125.76 (16) | C13—O1—C14—N | 169.07 (14) |
C5—C4—C7—C8 | −56.7 (2) | C13—O1—C14—C15 | −12.2 (2) |
C3—C4—C7—C15 | −111.87 (17) | N—C14—C15—C16 | −1.7 (3) |
C5—C4—C7—C15 | 65.70 (19) | O1—C14—C15—C16 | 179.83 (14) |
C15—C7—C8—C13 | −20.8 (2) | N—C14—C15—C7 | 174.03 (17) |
C4—C7—C8—C13 | 102.72 (17) | O1—C14—C15—C7 | −4.4 (2) |
C15—C7—C8—C9 | 159.77 (13) | C8—C7—C15—C14 | 19.6 (2) |
C4—C7—C8—C9 | −76.68 (17) | C4—C7—C15—C14 | −103.32 (17) |
C13—C8—C9—O2 | −179.39 (16) | C8—C7—C15—C16 | −164.78 (14) |
C7—C8—C9—O2 | 0.0 (2) | C4—C7—C15—C16 | 72.29 (18) |
C13—C8—C9—C10 | 3.3 (2) | C17—O3—C16—O4 | 3.6 (2) |
C7—C8—C9—C10 | −177.29 (15) | C17—O3—C16—C15 | −175.58 (15) |
O2—C9—C10—C11 | 147.31 (17) | C14—C15—C16—O4 | −1.7 (3) |
C8—C9—C10—C11 | −35.4 (2) | C7—C15—C16—O4 | −177.39 (16) |
C9—C10—C11—C20 | 173.18 (17) | C14—C15—C16—O3 | 177.44 (14) |
C9—C10—C11—C19 | −66.1 (2) | C7—C15—C16—O3 | 1.7 (2) |
C9—C10—C11—C12 | 54.4 (2) | C16—O3—C17—C18 | 171.88 (16) |
C20—C11—C12—C13 | −163.76 (16) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N—H1B···O2i | 0.87 (2) | 2.03 (2) | 2.889 (2) | 170.6 (19) |
N—H1A···O4 | 0.90 (2) | 2.04 (2) | 2.688 (2) | 128.1 (18) |
Symmetry code: (i) x+1, y, z. |