The title compound, C
15H
14F
2N
2O
3, was obtained in a one-pot three-component reaction from 4-(difluoromethoxy)benzaldehyde, cyclohexane-1,3-dione and urea, with a catalytic amount of
p-toluenesulfonic acid. The 4-(difluoromethoxy)phenyl ring is positioned axially, perpendicular to, and bisecting the six-membered heterocyclic ring. The heterocyclic ring adopts a puckered boat conformation, whereas the cyclohexene ring is in a half-chair conformation. The molecules are linked by N—H
O, C—H
O, N—H
F and C—H
F intermolecular hydrogen bonds.
Supporting information
CCDC reference: 643132
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.005 Å
- Disorder in main residue
- R factor = 0.053
- wR factor = 0.180
- Data-to-parameter ratio = 11.5
checkCIF/PLATON results
No syntax errors found
Alert level B
PLAT242_ALERT_2_B Check Low Ueq as Compared to Neighbors for C16A
PLAT242_ALERT_2_B Check Low Ueq as Compared to Neighbors for C16B
PLAT480_ALERT_4_B Long H...A H-Bond Reported H1 .. F1A .. 2.96 Ang.
Alert level C
PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical . ?
PLAT125_ALERT_4_C No _symmetry_space_group_name_Hall Given ....... ?
PLAT147_ALERT_1_C su on Symmetry Constrained Cell Angle(s) ....... ?
PLAT220_ALERT_2_C Large Non-Solvent C Ueq(max)/Ueq(min) ... 2.64 Ratio
PLAT222_ALERT_3_C Large Non-Solvent H Ueq(max)/Ueq(min) ... 3.60 Ratio
PLAT301_ALERT_3_C Main Residue Disorder ......................... 12.00 Perc.
PLAT340_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ... 5
PLAT480_ALERT_4_C Long H...A H-Bond Reported H8A .. O2 .. 2.77 Ang.
PLAT480_ALERT_4_C Long H...A H-Bond Reported H10 .. F2B .. 2.72 Ang.
PLAT480_ALERT_4_C Long H...A H-Bond Reported H11 .. F2B .. 2.74 Ang.
PLAT480_ALERT_4_C Long H...A H-Bond Reported H14 .. O1 .. 2.63 Ang.
Alert level G
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature 293 K
PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature . 293 K
0 ALERT level A = In general: serious problem
3 ALERT level B = Potentially serious problem
11 ALERT level C = Check and explain
2 ALERT level G = General alerts; check
4 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
3 ALERT type 2 Indicator that the structure model may be wrong or deficient
3 ALERT type 3 Indicator that the structure quality may be low
6 ALERT type 4 Improvement, methodology, query or suggestion
0 ALERT type 5 Informative message, check
Data collection: CAD-4 Software (Enraf–Nonius, 1994); cell refinement: CAD-4 Software; data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97.
4-(4-Difluoromethoxyphenyl)-1,2,3,4,5,6,7,8-octahydroquinazoline-2,5-dione
top
Crystal data top
C15H14F2N2O3 | Dx = 1.469 Mg m−3 |
Mr = 308.28 | Melting point: 539.5 K |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
a = 24.204 (7) Å | Cell parameters from 25 reflections |
b = 8.390 (3) Å | θ = 10.0–14.3° |
c = 14.104 (3) Å | µ = 0.12 mm−1 |
β = 103.33 (2)° | T = 293 K |
V = 2787.0 (14) Å3 | Prism, colorless |
Z = 8 | 0.40 × 0.30 × 0.23 mm |
F(000) = 1280 | |
Data collection top
Enraf–Nonius CAD-4 diffractometer | 1378 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.019 |
Graphite monochromator | θmax = 25.2°, θmin = 1.7° |
ω and 2θ scans | h = −28→28 |
Absorption correction: psi scan (North et al., 1968) | k = 0→10 |
Tmin = 0.953, Tmax = 0.973 | l = −1→16 |
2819 measured reflections | 3 standard reflections every 60 min |
2499 independent reflections | intensity decay: 1.2% |
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)] = 0.053 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.180 | w = 1/[σ2(Fo2) + (0.0929P)2 + 2.4271P] where P = (Fo2 + 2Fc2)/3 |
S = 1.04 | (Δ/σ)max < 0.001 |
2499 reflections | Δρmax = 0.38 e Å−3 |
217 parameters | Δρmin = −0.44 e Å−3 |
4 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0039 (8) |
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 | Occ. (<1) |
O1 | 0.03042 (10) | 0.1207 (3) | 0.60264 (16) | 0.0464 (6) | |
O2 | 0.07043 (12) | 0.4896 (3) | 0.24595 (17) | 0.0565 (8) | |
C16A | 0.2834 (2) | −0.0221 (7) | 0.2286 (5) | 0.0896 (17) | 0.63 |
H16A | 0.3117 | −0.0998 | 0.2180 | 0.108* | 0.63 |
F1A | 0.30782 (18) | 0.1180 (6) | 0.2720 (5) | 0.183 (2) | 0.63 |
F2A | 0.2620 (3) | 0.0567 (9) | 0.1535 (5) | 0.107 (2) | 0.63 |
C16B | 0.2834 (2) | −0.0221 (7) | 0.2286 (5) | 0.0896 (17) | 0.37 |
H16B | 0.3156 | −0.0960 | 0.2378 | 0.108* | 0.37 |
F1B | 0.30782 (18) | 0.1180 (6) | 0.2720 (5) | 0.183 (2) | 0.37 |
F2B | 0.2461 (4) | −0.079 (2) | 0.1439 (7) | 0.131 (5) | 0.37 |
N1 | 0.06979 (13) | 0.3512 (3) | 0.56690 (19) | 0.0414 (7) | |
H1 | 0.0709 (13) | 0.380 (4) | 0.6264 (15) | 0.034 (9)* | |
C2 | 0.04671 (13) | 0.2033 (4) | 0.5418 (2) | 0.0343 (7) | |
N3 | 0.04223 (12) | 0.1583 (3) | 0.44986 (19) | 0.0389 (7) | |
H3 | 0.0226 (11) | 0.072 (3) | 0.435 (2) | 0.030 (8)* | |
C4 | 0.06384 (13) | 0.2450 (4) | 0.3753 (2) | 0.0337 (7) | |
H4 | 0.0338 | 0.2453 | 0.3153 | 0.040* | |
C4A | 0.07547 (13) | 0.4146 (4) | 0.4061 (2) | 0.0347 (7) | |
C5 | 0.07809 (15) | 0.5300 (4) | 0.3320 (2) | 0.0425 (9) | |
C6 | 0.08953 (19) | 0.7000 (4) | 0.3623 (3) | 0.0598 (11) | |
H6A | 0.0537 | 0.7562 | 0.3535 | 0.072* | |
H6B | 0.1111 | 0.7497 | 0.3203 | 0.072* | |
C7 | 0.12174 (19) | 0.7170 (5) | 0.4666 (3) | 0.0640 (11) | |
H7A | 0.1239 | 0.8289 | 0.4844 | 0.077* | |
H7B | 0.1602 | 0.6781 | 0.4731 | 0.077* | |
C8 | 0.09374 (17) | 0.6257 (4) | 0.5351 (3) | 0.0472 (9) | |
H8A | 0.1191 | 0.6221 | 0.5993 | 0.057* | |
H8B | 0.0593 | 0.6803 | 0.5407 | 0.057* | |
C8A | 0.07947 (13) | 0.4593 (4) | 0.4994 (2) | 0.0364 (8) | |
C9 | 0.11539 (13) | 0.1627 (4) | 0.3526 (2) | 0.0348 (7) | |
C10 | 0.16547 (15) | 0.1453 (5) | 0.4228 (3) | 0.0482 (9) | |
H10 | 0.1676 | 0.1839 | 0.4854 | 0.058* | |
C11 | 0.21194 (16) | 0.0725 (5) | 0.4020 (3) | 0.0583 (11) | |
H11 | 0.2453 | 0.0620 | 0.4498 | 0.070* | |
C12 | 0.20856 (16) | 0.0152 (5) | 0.3096 (3) | 0.0525 (10) | |
C13 | 0.15984 (17) | 0.0288 (5) | 0.2393 (3) | 0.0563 (10) | |
H13 | 0.1578 | −0.0121 | 0.1773 | 0.068* | |
C14 | 0.11319 (15) | 0.1041 (4) | 0.2607 (2) | 0.0439 (9) | |
H14 | 0.0800 | 0.1151 | 0.2124 | 0.053* | |
O3 | 0.25591 (13) | −0.0696 (4) | 0.2933 (2) | 0.0808 (10) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O1 | 0.0607 (16) | 0.0447 (14) | 0.0369 (12) | −0.0095 (12) | 0.0178 (11) | 0.0062 (11) |
O2 | 0.0830 (19) | 0.0555 (17) | 0.0382 (15) | 0.0110 (14) | 0.0287 (13) | 0.0141 (12) |
C16A | 0.087 (4) | 0.070 (4) | 0.128 (5) | 0.006 (3) | 0.059 (4) | 0.006 (4) |
F1A | 0.131 (3) | 0.112 (3) | 0.339 (8) | −0.004 (3) | 0.122 (4) | 0.003 (4) |
F2A | 0.094 (4) | 0.157 (6) | 0.082 (4) | 0.036 (5) | 0.047 (3) | 0.034 (5) |
C16B | 0.087 (4) | 0.070 (4) | 0.128 (5) | 0.006 (3) | 0.059 (4) | 0.006 (4) |
F1B | 0.131 (3) | 0.112 (3) | 0.339 (8) | −0.004 (3) | 0.122 (4) | 0.003 (4) |
F2B | 0.096 (7) | 0.240 (14) | 0.054 (5) | 0.090 (9) | 0.009 (5) | −0.032 (8) |
N1 | 0.0624 (19) | 0.0392 (17) | 0.0243 (14) | −0.0098 (14) | 0.0135 (13) | −0.0025 (12) |
C2 | 0.0371 (17) | 0.0369 (19) | 0.0288 (16) | −0.0002 (14) | 0.0075 (13) | 0.0040 (14) |
N3 | 0.0485 (17) | 0.0371 (17) | 0.0343 (15) | −0.0124 (13) | 0.0160 (13) | −0.0038 (12) |
C4 | 0.0388 (17) | 0.0381 (18) | 0.0248 (15) | −0.0010 (14) | 0.0083 (12) | 0.0028 (13) |
C4A | 0.0415 (18) | 0.0340 (17) | 0.0309 (16) | 0.0014 (14) | 0.0132 (13) | 0.0034 (13) |
C5 | 0.053 (2) | 0.040 (2) | 0.042 (2) | 0.0110 (16) | 0.0250 (16) | 0.0097 (16) |
C6 | 0.093 (3) | 0.037 (2) | 0.062 (3) | 0.0078 (19) | 0.044 (2) | 0.0140 (18) |
C7 | 0.090 (3) | 0.037 (2) | 0.074 (3) | −0.011 (2) | 0.039 (2) | 0.001 (2) |
C8 | 0.067 (2) | 0.0323 (19) | 0.0432 (19) | 0.0004 (17) | 0.0151 (17) | −0.0029 (15) |
C8A | 0.0394 (18) | 0.0368 (18) | 0.0345 (17) | −0.0009 (14) | 0.0112 (14) | 0.0028 (14) |
C9 | 0.0425 (18) | 0.0315 (17) | 0.0321 (16) | −0.0029 (14) | 0.0121 (14) | 0.0020 (13) |
C10 | 0.048 (2) | 0.059 (2) | 0.0374 (18) | 0.0015 (18) | 0.0100 (16) | −0.0022 (17) |
C11 | 0.044 (2) | 0.073 (3) | 0.054 (2) | 0.008 (2) | 0.0046 (18) | 0.007 (2) |
C12 | 0.053 (2) | 0.048 (2) | 0.060 (2) | 0.0104 (18) | 0.0198 (19) | 0.0054 (18) |
C13 | 0.061 (2) | 0.063 (3) | 0.050 (2) | 0.003 (2) | 0.0235 (19) | −0.0156 (19) |
C14 | 0.045 (2) | 0.049 (2) | 0.0367 (18) | 0.0002 (16) | 0.0070 (15) | −0.0077 (16) |
O3 | 0.069 (2) | 0.088 (2) | 0.098 (2) | 0.0281 (17) | 0.0441 (18) | 0.0132 (19) |
Geometric parameters (Å, º) top
O1—C2 | 1.236 (4) | C6—H6A | 0.9700 |
O2—C5 | 1.232 (4) | C6—H6B | 0.9700 |
C16A—F2A | 1.255 (7) | C7—C8 | 1.511 (5) |
C16A—O3 | 1.309 (6) | C7—H7A | 0.9700 |
C16A—F1A | 1.392 (7) | C7—H7B | 0.9700 |
C16A—H16A | 0.9800 | C8—C8A | 1.497 (5) |
N1—C2 | 1.373 (4) | C8—H8A | 0.9700 |
N1—C8A | 1.374 (4) | C8—H8B | 0.9700 |
N1—H1 | 0.869 (18) | C9—C14 | 1.376 (4) |
C2—N3 | 1.331 (4) | C9—C10 | 1.385 (5) |
N3—C4 | 1.471 (4) | C10—C11 | 1.370 (5) |
N3—H3 | 0.865 (18) | C10—H10 | 0.9300 |
C4—C4A | 1.495 (4) | C11—C12 | 1.374 (5) |
C4—C9 | 1.523 (4) | C11—H11 | 0.9300 |
C4—H4 | 0.9800 | C12—C13 | 1.359 (5) |
C4A—C8A | 1.350 (4) | C12—O3 | 1.412 (4) |
C4A—C5 | 1.437 (4) | C13—C14 | 1.387 (5) |
C5—C6 | 1.496 (5) | C13—H13 | 0.9300 |
C6—C7 | 1.504 (6) | C14—H14 | 0.9300 |
| | | |
F2A—C16A—O3 | 124.8 (5) | C6—C7—H7A | 109.3 |
F2A—C16A—F1A | 88.6 (6) | C8—C7—H7A | 109.3 |
O3—C16A—F1A | 100.6 (5) | C6—C7—H7B | 109.3 |
F2A—C16A—H16A | 112.9 | C8—C7—H7B | 109.3 |
O3—C16A—H16A | 112.9 | H7A—C7—H7B | 107.9 |
F1A—C16A—H16A | 112.9 | C8A—C8—C7 | 111.1 (3) |
C2—N1—C8A | 122.8 (3) | C8A—C8—H8A | 109.4 |
C2—N1—H1 | 115 (2) | C7—C8—H8A | 109.4 |
C8A—N1—H1 | 121 (2) | C8A—C8—H8B | 109.4 |
O1—C2—N3 | 123.4 (3) | C7—C8—H8B | 109.4 |
O1—C2—N1 | 120.2 (3) | H8A—C8—H8B | 108.0 |
N3—C2—N1 | 116.4 (3) | C4A—C8A—N1 | 120.4 (3) |
C2—N3—C4 | 126.4 (3) | C4A—C8A—C8 | 123.1 (3) |
C2—N3—H3 | 113 (2) | N1—C8A—C8 | 116.5 (3) |
C4—N3—H3 | 120 (2) | C14—C9—C10 | 118.2 (3) |
N3—C4—C4A | 109.7 (2) | C14—C9—C4 | 120.3 (3) |
N3—C4—C9 | 111.6 (3) | C10—C9—C4 | 121.5 (3) |
C4A—C4—C9 | 112.6 (3) | C11—C10—C9 | 121.4 (3) |
N3—C4—H4 | 107.6 | C11—C10—H10 | 119.3 |
C4A—C4—H4 | 107.6 | C9—C10—H10 | 119.3 |
C9—C4—H4 | 107.6 | C10—C11—C12 | 119.2 (4) |
C8A—C4A—C5 | 121.1 (3) | C10—C11—H11 | 120.4 |
C8A—C4A—C4 | 121.0 (3) | C12—C11—H11 | 120.4 |
C5—C4A—C4 | 117.8 (3) | C13—C12—C11 | 121.0 (3) |
O2—C5—C4A | 120.6 (3) | C13—C12—O3 | 121.6 (4) |
O2—C5—C6 | 121.3 (3) | C11—C12—O3 | 117.2 (4) |
C4A—C5—C6 | 118.1 (3) | C12—C13—C14 | 119.5 (3) |
C5—C6—C7 | 112.9 (3) | C12—C13—H13 | 120.3 |
C5—C6—H6A | 109.0 | C14—C13—H13 | 120.3 |
C7—C6—H6A | 109.0 | C9—C14—C13 | 120.8 (3) |
C5—C6—H6B | 109.0 | C9—C14—H14 | 119.6 |
C7—C6—H6B | 109.0 | C13—C14—H14 | 119.6 |
H6A—C6—H6B | 107.8 | C16A—O3—C12 | 121.5 (4) |
C6—C7—C8 | 111.7 (3) | | |
| | | |
C8A—N1—C2—O1 | −168.3 (3) | C2—N1—C8A—C4A | −11.2 (5) |
C8A—N1—C2—N3 | 10.4 (5) | C2—N1—C8A—C8 | 168.2 (3) |
O1—C2—N3—C4 | −175.8 (3) | C7—C8—C8A—C4A | −19.3 (5) |
N1—C2—N3—C4 | 5.5 (5) | C7—C8—C8A—N1 | 161.3 (3) |
C2—N3—C4—C4A | −17.8 (4) | N3—C4—C9—C14 | 117.3 (3) |
C2—N3—C4—C9 | 107.7 (4) | C4A—C4—C9—C14 | −118.8 (3) |
N3—C4—C4A—C8A | 16.2 (4) | N3—C4—C9—C10 | −63.1 (4) |
C9—C4—C4A—C8A | −108.8 (3) | C4A—C4—C9—C10 | 60.8 (4) |
N3—C4—C4A—C5 | −159.3 (3) | C14—C9—C10—C11 | 0.2 (5) |
C9—C4—C4A—C5 | 75.7 (4) | C4—C9—C10—C11 | −179.4 (3) |
C8A—C4A—C5—O2 | −174.9 (3) | C9—C10—C11—C12 | −0.2 (6) |
C4—C4A—C5—O2 | 0.7 (5) | C10—C11—C12—C13 | −0.5 (6) |
C8A—C4A—C5—C6 | 4.3 (5) | C10—C11—C12—O3 | −175.3 (4) |
C4—C4A—C5—C6 | 179.8 (3) | C11—C12—C13—C14 | 1.1 (6) |
O2—C5—C6—C7 | −155.0 (3) | O3—C12—C13—C14 | 175.7 (4) |
C4A—C5—C6—C7 | 25.9 (5) | C10—C9—C14—C13 | 0.4 (5) |
C5—C6—C7—C8 | −52.1 (4) | C4—C9—C14—C13 | −180.0 (3) |
C6—C7—C8—C8A | 48.2 (4) | C12—C13—C14—C9 | −1.1 (6) |
C5—C4A—C8A—N1 | 171.8 (3) | F2A—C16A—O3—C12 | −27.8 (10) |
C4—C4A—C8A—N1 | −3.6 (5) | F1A—C16A—O3—C12 | 67.9 (6) |
C5—C4A—C8A—C8 | −7.6 (5) | C13—C12—O3—C16A | 64.6 (6) |
C4—C4A—C8A—C8 | 177.0 (3) | C11—C12—O3—C16A | −120.6 (5) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C13—H13···F2B | 0.93 | 2.36 | 2.877 (9) | 115 |
N1—H1···O2i | 0.87 (2) | 2.01 (2) | 2.854 (4) | 163 (3) |
C8—H8A···O2i | 0.97 | 2.77 | 3.297 (4) | 115 |
N1—H1···F1Aii | 0.87 (2) | 2.96 (3) | 3.302 (6) | 106 (2) |
N3—H3···O1iii | 0.87 (2) | 2.06 (2) | 2.919 (4) | 175 (3) |
C6—H6A···O1iv | 0.97 | 2.48 | 3.406 (5) | 159 |
C10—H10···F2Bv | 0.93 | 2.72 | 3.321 (10) | 123 |
C11—H11···F2Bv | 0.93 | 2.74 | 3.320 (10) | 122 |
C14—H14···O1vi | 0.93 | 2.63 | 3.237 (4) | 124 |
Symmetry codes: (i) x, −y+1, z+1/2; (ii) −x+1/2, −y+1/2, −z+1; (iii) −x, −y, −z+1; (iv) −x, −y+1, −z+1; (v) x, −y, z+1/2; (vi) x, −y, z−1/2. |