Ethyl 2-amino-4-(4-fluoro­phenyl)-7,7-di­methyl-5-oxo-5,6,7,8-tetra­hydro-4H-benzo­[b]­pyran-3-carboxyl­ate

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.

Key indicators

• Single-crystal X-ray study
• T = 296 K
• Mean [sigma](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

---

Computing details

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- 4H-5,6,7,8-tetrahydrobenzo[b]pyran-3-carboxylate

Crystal data

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) Å^3	0.50 × 0.46 × 0.40 mm
Z = 2

Data collection

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

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.040	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.114	w = 1/[σ^2(Fo^2) + (0.0652P)^2] where P = (Fo^2 + 2Fc^2)/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+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.040 (4)

Special details

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 (Ų)

	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 (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

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)

D—H···A	D—H	H···A	D···A	D—H···A
N—H1B···O2^i	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.