Synthesis, characterization, crystal structure and Hirshfeld surface analysis of isobutyl 4-[4-(di­fluoro­meth­oxy)phen­yl]-2,6,6-trimethyl-5-oxo-1,4,5,6,7,8-hexa­hydro­quinoline-3-carboxyl­ate

In the crystal, the mol­ecules are linked by N—H...O and C—H...O inter­actions, forming supra­molecular chains parallel to the a axis. These chains pack with C—H...π inter­actions between them, forming layers parallel to the (010) plane.

Computing details

Isobutyl 4-[4-(difluoromethoxy)phenyl]-2,6,6-trimethyl-5-oxo-1,4,5,6,7,8-hexahydroquinoline-3-carboxylate

Crystal data

C24H29F2NO4	Dx = 1.276 Mg m^−3
Mr = 433.48	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pca21	Cell parameters from 9859 reflections
a = 11.9879 (7) Å	θ = 2.4–32.7°
b = 12.1807 (7) Å	µ = 0.10 mm^−1
c = 15.4518 (9) Å	T = 100 K
V = 2256.3 (2) Å^3	Chunk, light yellow
Z = 4	0.27 × 0.24 × 0.16 mm
F(000) = 920

Data collection

Bruker Quest D8 with Photon 2 detector diffractometer	7264 reflections with I > 2σ(I)
φ and ω scans	Rint = 0.080
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	θmax = 36.0°, θmin = 2.4°
Tmin = 0.718, Tmax = 0.744	h = −18→19
103269 measured reflections	k = −20→19
9491 independent reflections	l = −25→21

Refinement

Refinement on F^2	Hydrogen site location: mixed
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F^2 > 2σ(F^2)] = 0.045	w = 1/[σ^2(Fo^2) + (0.0508P)^2 + 0.3823P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.107	(Δ/σ)max < 0.001
S = 1.03	Δρmax = 0.32 e Å^−3
9491 reflections	Δρmin = −0.29 e Å^−3
289 parameters	Absolute structure: Flack x determined using 2721 quotients [(I^+)-(I^-)]/[(I^+)+(I^-)] (Parsons et al., 2013)
1 restraint	Absolute structure parameter: 0.0 (2)

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
F1	0.49509 (14)	0.92511 (11)	0.20621 (10)	0.0455 (4)
F2	0.36176 (12)	0.80630 (13)	0.21602 (10)	0.0467 (4)
O1	0.65307 (10)	0.66738 (10)	0.65205 (8)	0.0198 (2)
O2	0.72200 (10)	0.33422 (10)	0.48402 (9)	0.0239 (3)
O3	0.60039 (10)	0.19451 (9)	0.48360 (8)	0.0184 (2)
O4	0.53670 (11)	0.76006 (11)	0.24983 (8)	0.0236 (3)
N1	0.36644 (10)	0.41080 (11)	0.60065 (9)	0.0143 (2)
H1N	0.299 (2)	0.3886 (19)	0.6122 (14)	0.019 (5)*
C1	0.40589 (12)	0.50413 (12)	0.63969 (10)	0.0128 (3)
C2	0.32686 (12)	0.56285 (13)	0.69932 (10)	0.0149 (3)
H2A	0.279873	0.508580	0.730076	0.018*
H2B	0.277189	0.611193	0.665143	0.018*
C3	0.39163 (14)	0.63141 (13)	0.76504 (11)	0.0171 (3)
H3A	0.429018	0.581636	0.806558	0.021*
H3B	0.338594	0.677625	0.797973	0.021*
C4	0.47947 (13)	0.70546 (13)	0.72264 (11)	0.0165 (3)
C5	0.55598 (12)	0.63711 (12)	0.66451 (10)	0.0142 (3)
C6	0.51077 (12)	0.54097 (12)	0.62178 (10)	0.0134 (3)
C7	0.57801 (12)	0.48870 (12)	0.54998 (10)	0.0129 (2)
H7A	0.658250	0.488219	0.567679	0.015*
C8	0.54078 (12)	0.37018 (12)	0.53589 (10)	0.0135 (3)
C9	0.43551 (13)	0.33826 (12)	0.55678 (10)	0.0142 (3)
C10	0.54927 (15)	0.76147 (18)	0.79303 (13)	0.0285 (4)
H10A	0.584192	0.705497	0.829657	0.043*
H10B	0.500970	0.808215	0.828535	0.043*
H10C	0.607286	0.806523	0.765913	0.043*
C11	0.42455 (16)	0.79274 (14)	0.66419 (14)	0.0246 (4)
H11A	0.482159	0.841376	0.640633	0.037*
H11B	0.371361	0.835939	0.698245	0.037*
H11C	0.385240	0.756348	0.616550	0.037*
C12	0.37972 (13)	0.22972 (13)	0.53973 (11)	0.0186 (3)
H12A	0.400712	0.203315	0.482072	0.028*
H12B	0.298580	0.238862	0.542595	0.028*
H12C	0.403522	0.176294	0.583404	0.028*
C13	0.62870 (13)	0.30006 (12)	0.49936 (10)	0.0150 (3)
C14	0.68925 (15)	0.12977 (14)	0.44523 (12)	0.0208 (3)
H14A	0.751816	0.122384	0.486642	0.025*
H14B	0.717478	0.166562	0.392459	0.025*
C15	0.64362 (16)	0.01733 (14)	0.42246 (14)	0.0260 (4)
H15A	0.576642	0.027434	0.384717	0.031*
C16	0.6088 (3)	−0.04712 (19)	0.5015 (2)	0.0529 (8)
H16A	0.544199	−0.011657	0.528503	0.079*
H16B	0.670705	−0.049424	0.542902	0.079*
H16C	0.588934	−0.122088	0.484414	0.079*
C17	0.7331 (2)	−0.04286 (16)	0.37018 (15)	0.0330 (4)
H17A	0.747606	−0.002683	0.316403	0.050*
H17B	0.706990	−0.117084	0.356413	0.050*
H17C	0.801872	−0.047357	0.404232	0.050*
C18	0.56699 (12)	0.55695 (12)	0.46724 (10)	0.0137 (3)
C19	0.46204 (13)	0.59010 (14)	0.43930 (11)	0.0184 (3)
H19A	0.398046	0.567489	0.470878	0.022*
C20	0.44827 (14)	0.65559 (15)	0.36621 (12)	0.0208 (3)
H20A	0.375930	0.676416	0.347231	0.025*
C21	0.54288 (14)	0.68982 (13)	0.32165 (11)	0.0183 (3)
C22	0.64869 (13)	0.65619 (13)	0.34636 (11)	0.0175 (3)
H22A	0.712375	0.678221	0.314155	0.021*
C23	0.66020 (13)	0.58949 (13)	0.41925 (11)	0.0159 (3)
H23A	0.732370	0.565862	0.436503	0.019*
C24	0.45780 (18)	0.84020 (16)	0.25354 (14)	0.0294 (4)
H24A	0.444326	0.863192	0.314777	0.035*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
F1	0.0608 (9)	0.0302 (6)	0.0454 (8)	0.0086 (6)	0.0104 (7)	0.0181 (6)
F2	0.0317 (7)	0.0612 (9)	0.0474 (8)	0.0089 (6)	−0.0074 (6)	0.0154 (7)
O1	0.0120 (5)	0.0199 (5)	0.0276 (6)	−0.0016 (4)	0.0042 (4)	−0.0068 (5)
O2	0.0134 (5)	0.0212 (5)	0.0371 (7)	−0.0005 (4)	0.0070 (5)	−0.0075 (5)
O3	0.0158 (5)	0.0142 (5)	0.0252 (6)	0.0018 (4)	0.0030 (4)	−0.0036 (4)
O4	0.0262 (6)	0.0255 (6)	0.0191 (6)	0.0043 (5)	0.0044 (5)	0.0068 (5)
N1	0.0093 (5)	0.0162 (6)	0.0173 (6)	−0.0009 (4)	0.0014 (5)	−0.0004 (5)
C1	0.0110 (6)	0.0149 (6)	0.0124 (6)	0.0015 (5)	0.0006 (5)	0.0011 (5)
C2	0.0116 (6)	0.0179 (6)	0.0153 (7)	0.0009 (5)	0.0033 (5)	−0.0012 (5)
C3	0.0151 (7)	0.0203 (7)	0.0158 (7)	−0.0002 (6)	0.0034 (5)	−0.0026 (6)
C4	0.0129 (6)	0.0187 (7)	0.0177 (7)	−0.0003 (5)	0.0031 (5)	−0.0051 (5)
C5	0.0122 (7)	0.0156 (6)	0.0148 (6)	0.0015 (5)	0.0004 (5)	−0.0007 (5)
C6	0.0113 (6)	0.0143 (6)	0.0145 (6)	0.0004 (5)	0.0005 (5)	−0.0005 (5)
C7	0.0095 (6)	0.0147 (6)	0.0145 (6)	0.0001 (5)	0.0017 (5)	−0.0013 (5)
C8	0.0110 (6)	0.0141 (6)	0.0154 (6)	0.0006 (5)	0.0009 (5)	−0.0011 (5)
C9	0.0130 (6)	0.0151 (6)	0.0146 (7)	0.0004 (5)	−0.0001 (5)	0.0012 (5)
C10	0.0201 (8)	0.0368 (10)	0.0285 (9)	−0.0063 (7)	0.0049 (7)	−0.0175 (8)
C11	0.0202 (8)	0.0184 (7)	0.0353 (10)	0.0029 (6)	0.0080 (7)	0.0023 (7)
C12	0.0159 (7)	0.0172 (7)	0.0229 (8)	−0.0034 (5)	0.0021 (6)	−0.0016 (6)
C13	0.0141 (6)	0.0153 (6)	0.0156 (7)	0.0010 (5)	−0.0002 (5)	−0.0020 (5)
C14	0.0185 (7)	0.0177 (7)	0.0261 (8)	0.0051 (6)	0.0032 (6)	−0.0039 (6)
C15	0.0286 (9)	0.0163 (7)	0.0331 (10)	0.0030 (6)	0.0065 (7)	−0.0029 (7)
C16	0.0751 (19)	0.0233 (10)	0.0603 (17)	0.0074 (11)	0.0366 (15)	0.0097 (10)
C17	0.0388 (11)	0.0202 (8)	0.0401 (11)	0.0047 (7)	0.0097 (9)	−0.0055 (8)
C18	0.0115 (6)	0.0139 (6)	0.0157 (7)	−0.0003 (5)	0.0021 (5)	−0.0013 (5)
C19	0.0124 (6)	0.0234 (7)	0.0195 (7)	0.0007 (6)	0.0024 (5)	0.0035 (6)
C20	0.0144 (7)	0.0279 (8)	0.0201 (8)	0.0024 (6)	0.0000 (6)	0.0044 (7)
C21	0.0202 (7)	0.0183 (7)	0.0164 (7)	0.0010 (6)	0.0036 (6)	0.0019 (6)
C22	0.0160 (7)	0.0176 (7)	0.0190 (7)	−0.0020 (5)	0.0049 (6)	−0.0007 (6)
C23	0.0118 (6)	0.0160 (6)	0.0200 (7)	−0.0013 (5)	0.0023 (5)	−0.0015 (5)
C24	0.0336 (10)	0.0265 (9)	0.0280 (10)	0.0059 (7)	0.0031 (8)	0.0076 (7)

Geometric parameters (Å, º)

F1—C24	1.343 (2)	C10—H10B	0.9800
F2—C24	1.354 (3)	C10—H10C	0.9800
O1—C5	1.2361 (19)	C11—H11A	0.9800
O2—C13	1.2166 (19)	C11—H11B	0.9800
O3—C13	1.3518 (18)	C11—H11C	0.9800
O3—C14	1.4520 (19)	C12—H12A	0.9800
O4—C24	1.360 (2)	C12—H12B	0.9800
O4—C21	1.403 (2)	C12—H12C	0.9800
N1—C1	1.371 (2)	C14—C15	1.516 (2)
N1—C9	1.388 (2)	C14—H14A	0.9900
N1—H1N	0.87 (2)	C14—H14B	0.9900
C1—C6	1.363 (2)	C15—C16	1.511 (3)
C1—C2	1.503 (2)	C15—C17	1.530 (3)
C2—C3	1.527 (2)	C15—H15A	1.0000
C2—H2A	0.9900	C16—H16A	0.9800
C2—H2B	0.9900	C16—H16B	0.9800
C3—C4	1.533 (2)	C16—H16C	0.9800
C3—H3A	0.9900	C17—H17A	0.9800
C3—H3B	0.9900	C17—H17B	0.9800
C4—C5	1.530 (2)	C17—H17C	0.9800
C4—C10	1.532 (2)	C18—C19	1.390 (2)
C4—C11	1.543 (2)	C18—C23	1.398 (2)
C5—C6	1.449 (2)	C19—C20	1.392 (2)
C6—C7	1.512 (2)	C19—H19A	0.9500
C7—C8	1.527 (2)	C20—C21	1.391 (2)
C7—C18	1.531 (2)	C20—H20A	0.9500
C7—H7A	1.0000	C21—C22	1.386 (2)
C8—C9	1.359 (2)	C22—C23	1.396 (2)
C8—C13	1.469 (2)	C22—H22A	0.9500
C9—C12	1.505 (2)	C23—H23A	0.9500
C10—H10A	0.9800	C24—H24A	1.0000
C13—O3—C14	113.95 (12)	C9—C12—H12B	109.5
C24—O4—C21	116.16 (14)	H12A—C12—H12B	109.5
C1—N1—C9	122.48 (13)	C9—C12—H12C	109.5
C1—N1—H1N	119.2 (15)	H12A—C12—H12C	109.5
C9—N1—H1N	117.1 (15)	H12B—C12—H12C	109.5
C6—C1—N1	120.11 (14)	O2—C13—O3	121.40 (14)
C6—C1—C2	123.32 (14)	O2—C13—C8	122.38 (14)
N1—C1—C2	116.55 (13)	O3—C13—C8	116.23 (13)
C1—C2—C3	110.33 (12)	O3—C14—C15	108.70 (14)
C1—C2—H2A	109.6	O3—C14—H14A	109.9
C3—C2—H2A	109.6	C15—C14—H14A	109.9
C1—C2—H2B	109.6	O3—C14—H14B	109.9
C3—C2—H2B	109.6	C15—C14—H14B	109.9
H2A—C2—H2B	108.1	H14A—C14—H14B	108.3
C2—C3—C4	112.76 (13)	C16—C15—C14	112.43 (19)
C2—C3—H3A	109.0	C16—C15—C17	111.82 (17)
C4—C3—H3A	109.0	C14—C15—C17	107.61 (16)
C2—C3—H3B	109.0	C16—C15—H15A	108.3
C4—C3—H3B	109.0	C14—C15—H15A	108.3
H3A—C3—H3B	107.8	C17—C15—H15A	108.3
C5—C4—C10	109.37 (13)	C15—C16—H16A	109.5
C5—C4—C3	110.02 (13)	C15—C16—H16B	109.5
C10—C4—C3	109.49 (14)	H16A—C16—H16B	109.5
C5—C4—C11	106.68 (13)	C15—C16—H16C	109.5
C10—C4—C11	109.99 (15)	H16A—C16—H16C	109.5
C3—C4—C11	111.25 (13)	H16B—C16—H16C	109.5
O1—C5—C6	121.47 (14)	C15—C17—H17A	109.5
O1—C5—C4	119.58 (14)	C15—C17—H17B	109.5
C6—C5—C4	118.88 (13)	H17A—C17—H17B	109.5
C1—C6—C5	121.21 (14)	C15—C17—H17C	109.5
C1—C6—C7	120.13 (14)	H17A—C17—H17C	109.5
C5—C6—C7	118.37 (13)	H17B—C17—H17C	109.5
C6—C7—C8	110.30 (12)	C19—C18—C23	118.43 (15)
C6—C7—C18	109.76 (12)	C19—C18—C7	119.69 (13)
C8—C7—C18	111.67 (12)	C23—C18—C7	121.86 (13)
C6—C7—H7A	108.3	C18—C19—C20	121.71 (15)
C8—C7—H7A	108.3	C18—C19—H19A	119.1
C18—C7—H7A	108.3	C20—C19—H19A	119.1
C9—C8—C13	126.22 (14)	C21—C20—C19	118.47 (15)
C9—C8—C7	120.53 (13)	C21—C20—H20A	120.8
C13—C8—C7	113.25 (12)	C19—C20—H20A	120.8
C8—C9—N1	119.20 (14)	C22—C21—C20	121.41 (15)
C8—C9—C12	128.48 (14)	C22—C21—O4	116.50 (14)
N1—C9—C12	112.32 (13)	C20—C21—O4	122.09 (15)
C4—C10—H10A	109.5	C21—C22—C23	118.99 (15)
C4—C10—H10B	109.5	C21—C22—H22A	120.5
H10A—C10—H10B	109.5	C23—C22—H22A	120.5
C4—C10—H10C	109.5	C22—C23—C18	120.93 (15)
H10A—C10—H10C	109.5	C22—C23—H23A	119.5
H10B—C10—H10C	109.5	C18—C23—H23A	119.5
C4—C11—H11A	109.5	F1—C24—F2	106.55 (17)
C4—C11—H11B	109.5	F1—C24—O4	107.35 (17)
H11A—C11—H11B	109.5	F2—C24—O4	110.76 (17)
C4—C11—H11C	109.5	F1—C24—H24A	110.7
H11A—C11—H11C	109.5	F2—C24—H24A	110.7
H11B—C11—H11C	109.5	O4—C24—H24A	110.7
C9—C12—H12A	109.5
C9—N1—C1—C6	13.6 (2)	C13—C8—C9—C12	−7.0 (3)
C9—N1—C1—C2	−168.22 (14)	C7—C8—C9—C12	173.21 (15)
C6—C1—C2—C3	−25.9 (2)	C1—N1—C9—C8	−13.9 (2)
N1—C1—C2—C3	155.98 (14)	C1—N1—C9—C12	165.30 (14)
C1—C2—C3—C4	50.56 (18)	C14—O3—C13—O2	−1.8 (2)
C2—C3—C4—C5	−53.48 (18)	C14—O3—C13—C8	178.30 (14)
C2—C3—C4—C10	−173.70 (14)	C9—C8—C13—O2	−178.39 (17)
C2—C3—C4—C11	64.52 (17)	C7—C8—C13—O2	1.4 (2)
C10—C4—C5—O1	−31.4 (2)	C9—C8—C13—O3	1.5 (2)
C3—C4—C5—O1	−151.72 (15)	C7—C8—C13—O3	−178.68 (13)
C11—C4—C5—O1	87.49 (18)	C13—O3—C14—C15	−174.28 (15)
C10—C4—C5—C6	151.64 (15)	O3—C14—C15—C16	−64.8 (2)
C3—C4—C5—C6	31.3 (2)	O3—C14—C15—C17	171.65 (16)
C11—C4—C5—C6	−89.44 (17)	C6—C7—C18—C19	−48.25 (19)
N1—C1—C6—C5	−177.73 (14)	C8—C7—C18—C19	74.40 (18)
C2—C1—C6—C5	4.2 (2)	C6—C7—C18—C23	130.33 (15)
N1—C1—C6—C7	8.5 (2)	C8—C7—C18—C23	−107.02 (16)
C2—C1—C6—C7	−169.55 (14)	C23—C18—C19—C20	−1.0 (2)
O1—C5—C6—C1	176.01 (15)	C7—C18—C19—C20	177.62 (15)
C4—C5—C6—C1	−7.1 (2)	C18—C19—C20—C21	−1.3 (3)
O1—C5—C6—C7	−10.1 (2)	C19—C20—C21—C22	2.8 (3)
C4—C5—C6—C7	166.76 (14)	C19—C20—C21—O4	−176.98 (16)
C1—C6—C7—C8	−26.47 (19)	C24—O4—C21—C22	−142.79 (17)
C5—C6—C7—C8	159.58 (13)	C24—O4—C21—C20	37.0 (2)
C1—C6—C7—C18	96.98 (16)	C20—C21—C22—C23	−2.1 (3)
C5—C6—C7—C18	−76.97 (17)	O4—C21—C22—C23	177.71 (14)
C6—C7—C8—C9	26.2 (2)	C21—C22—C23—C18	−0.2 (2)
C18—C7—C8—C9	−96.17 (17)	C19—C18—C23—C22	1.8 (2)
C6—C7—C8—C13	−153.64 (13)	C7—C18—C23—C22	−176.84 (14)
C18—C7—C8—C13	84.02 (15)	C21—O4—C24—F1	151.23 (16)
C13—C8—C9—N1	172.06 (15)	C21—O4—C24—F2	−92.82 (19)
C7—C8—C9—N1	−7.7 (2)

Hydrogen-bond geometry (Å, º)

Cg3 is the centroid the benzene ring of the 4-(4-difluoromethoxyphenyl group of the title compound.

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O1^i	0.87 (2)	1.98 (2)	2.8426 (17)	173 (2)
C12—H12A···O3	0.98	2.40	2.817 (2)	105
C19—H19A···O2^i	0.95	2.43	3.100 (2)	127
C3—H3A···Cg3^ii	0.99	2.84	3.7345 (18)	151

Symmetry codes: (i) x−1/2, −y+1, z; (ii) −x+1, −y+1, z+1/2.