3-(p-Chloro­phenyl)-4-phenyl-4,5-di­hydro­isoxazole-5-spiro-2′-1′,2′,3′,4′-tetra­hydro­naphthalen-1′-one

In the title compound, C₂₄H₁₈ClNO₂, the phenyl ring and the tetralone moiety are approximately orthogonal to the isoxazoline ring. The isoxazoline ring adopts an envelope conformation, while the cyclo­hexenone ring of the tetralone moiety has an intermediate sofa/half-chair conformation. In this structure, one C—H...N intermolecular and two C—H...O intramolecular hydrogen bonds occur; the H...A distances are 2.60, and 2.35 and 2.57 Å, respectively. The mol­ecules are held together by an intermolecular C—H...N hydrogen bond, forming a one-dimensional chain along the [100] direction.

S1. Comment

Isoxazoline derivatives have been used in many natural-product syntheses and have also proved to be efficient precursors for many synthetic intermediates, including γ-amino alcohols, β-hydroxy ketones etc. (Kozikowski, 1984; Kanemasa & Tsuge, 1990). Spiro-isoxazoline compounds display interesting biological properties, such as herbicidal, plant-growth regulatory and antitumour activities (Howe & Shelton 1990; De Amici et al., 1990; Smietana et al., 1999). We report here the structure of 3-(p-chlorophenyl)-4-phenyl-4,5-dihydroisoxazole-5-spiro-2'- 1',2',3',4'-tetrahydronaphthalen-1'-one, (I).

The structure of (I) (Fig. 1) consists of an isoxazoline ring (A) connected to a p-chlorophenyl ring (B) at C2, a phenyl ring (C) at C3 and a tetralone moiety [D (cyclohexenone) and E (phenyl)] at C1. Rings A and B are approximately coplanar, forming a dihedral angle of 1.2 (1)°. Phenyl ring C and tetralone ring D are approximately orthogonal to ring A, forming dihedral angles of 77.5 (1) and 88.5 (1)°, respectively. There is a slight folding of rings D and E of the tetralone substituent, which form a dihedral angle of 4.9 (1)° with one another.

The bond lengths O1—N1 and N1═C2 and the angles N1—O1—C1 and O1—N1—C2 in ring A are comparable with the corresponding values of two other structures (Mackay et al., 1994; Pereira et al., 1993). Also, bond lengths Cl1—C16 and C12═O2 are in good agreement with the values found in the literature (Allen et al., 1987). Selected bond lengths and angles are given in Table 1.

The puckering (Cremer & Pople, 1975) and asymmetry parameters (Nardelli, 1983a) calculated for ring D are Q_T = 0.450 (4) Å, ΔC_s(C4) = 0.052 (2) and ΔC₂(C1—C4) = 0.060 (2), and for ring A are Q_T = 0.146 (4) Å and ΔC_s(C1) = 0.003 (2), which correspond to an intermediate sofa/half-chair conformation for ring D and an envelope conformation for ring A.

The N atom of ring A is involved in a C—H···N intermolecular hydrogen bond. The O atom of ring A and the carbonyl O atom of ring D are involved in two C—H.·O intramolecular hydrogen bonds (Table 2). The sums of the corresponding van der Waals radii of these hydrogen bonds (Bondi, 1964) are r_H + r_N = 1.75 Å and r_H + r_O = 1.72 Å, respectively. The C3—H3···O2 and C5—H5A···O1 intramolecular interactions are a result of the configurations at C3 and C1, respectively, while the intermolecular C22—H22···N1ⁱ interaction joins the molecules in chains running along the [100] direction [symmetry code: (i) 1 + x, y, z].

S2. Experimental

To a well stirred solution of 2-arylidine-1-tetralone (3 mmol) in CHCl₃ (10 ml) p-chlorobenzhydroxyiminoyl chloride was added (3 mmol), followed by 3.3 mmol of triethylamine. The reaction was monitored via thin-layer chromatography until the starting material had disappeared, and was then quenched with water, extracted with CHCl₃, dried with anhydrous MgSO₄, column chromatographed using hexane/ethyl acetate (4:1) and recrystallized from hexane/ethyl acetate (3:1).

Computing details

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ZORTEP (Zsolnai, 1997); software used to prepare material for publication: SHELXL97, PARST (Nardelli, 1983b, 1995) and PLATON (Spek, 1999).

Figures

Fig. 1. The molecular structure of the title compound shown with 50% probability displacement ellipsoids. H atoms are displayed as small circles of arbitrary radii.

3-(p-Chlorophenyl)-4-phenyl-4,5-dihydroisoxazole-5-spiro-2'- 1',2',3',4'-tetrahydronaphthalen-1'-one

Crystal data

C24H18ClNO2	Z = 2
Mr = 387.84	F(000) = 404
Triclinic, P1	Dx = 1.299 Mg m^−3
a = 9.2559 (8) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.9527 (9) Å	Cell parameters from 2150 reflections
c = 11.6466 (10) Å	θ = 2.9–25.0°
α = 62.867 (2)°	µ = 0.21 mm^−1
β = 71.010 (2)°	T = 293 K
γ = 78.653 (2)°	Rectangular, colourless
V = 991.93 (15) Å^3	0.42 × 0.16 × 0.14 mm

Data collection

Siemens SMART CCD area-detector diffractometer	2158 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.027
Graphite monochromator	θmax = 25.0°, θmin = 2.0°
Detector resolution: 8.33 pixels mm^-1	h = −10→10
ω scans	k = −11→13
5316 measured reflections	l = −10→13
3387 independent reflections

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)] = 0.065	H-atom parameters constrained
wR(F^2) = 0.191	w = 1/[σ^2(Fo^2) + (0.0861P)^2 + 0.4816P] where P = (Fo^2 + 2Fc^2)/3
S = 1.03	(Δ/σ)max < 0.001
3387 reflections	Δρmax = 0.38 e Å^−3
254 parameters	Δρmin = −0.46 e Å^−3
0 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.020 (5)

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
Cl1	0.6903 (2)	0.73628 (14)	0.03835 (16)	0.1317 (7)
O1	0.3169 (2)	1.2410 (2)	0.3998 (2)	0.0503 (6)
O2	0.3142 (3)	1.4644 (3)	0.1147 (2)	0.0682 (8)
N1	0.3461 (3)	1.1339 (3)	0.3586 (3)	0.0463 (7)
C1	0.4198 (3)	1.3501 (3)	0.3026 (3)	0.0415 (7)
C2	0.4678 (3)	1.1544 (3)	0.2614 (3)	0.0398 (7)
C3	0.5436 (3)	1.2848 (3)	0.2192 (3)	0.0380 (7)
H3	0.5529	1.3426	0.1238	0.046*
C4	0.4717 (4)	1.4044 (4)	0.3807 (4)	0.0638 (10)
H4A	0.5309	1.3322	0.4365	0.077*
H4B	0.5376	1.4796	0.3184	0.077*
C5	0.3408 (4)	1.4532 (4)	0.4663 (4)	0.0665 (11)
H5A	0.2880	1.3742	0.5400	0.080*
H5B	0.3800	1.4981	0.5043	0.080*
C6	0.2306 (4)	1.5484 (4)	0.3968 (4)	0.0687 (11)
C7	0.1357 (6)	1.6373 (5)	0.4475 (6)	0.0998 (17)
H7	0.1428	1.6361	0.5258	0.120*
C8	0.0321 (7)	1.7264 (6)	0.3841 (8)	0.121 (2)
H8	−0.0312	1.7847	0.4202	0.145*
C9	0.0198 (6)	1.7316 (5)	0.2672 (7)	0.115 (2)
H9	−0.0502	1.7941	0.2240	0.138*
C10	0.1108 (4)	1.6443 (4)	0.2149 (5)	0.0795 (13)
H10	0.1014	1.6463	0.1369	0.095*
C11	0.2175 (4)	1.5523 (3)	0.2786 (4)	0.0569 (9)
C12	0.3167 (3)	1.4598 (3)	0.2206 (3)	0.0458 (8)
C13	0.5241 (4)	1.0531 (3)	0.2050 (3)	0.0486 (8)
C14	0.4494 (5)	0.9323 (4)	0.2608 (4)	0.0753 (12)
H14	0.3632	0.9164	0.3335	0.090*
C15	0.5023 (6)	0.8359 (4)	0.2089 (5)	0.0936 (15)
H15	0.4517	0.7554	0.2465	0.112*
C16	0.6280 (6)	0.8587 (4)	0.1030 (5)	0.0795 (12)
C17	0.7043 (5)	0.9766 (5)	0.0459 (5)	0.0815 (12)
H17	0.7907	0.9913	−0.0265	0.098*
C18	0.6512 (4)	1.0734 (4)	0.0975 (4)	0.0682 (10)
H18	0.7024	1.1537	0.0589	0.082*
C19	0.7000 (3)	1.2567 (3)	0.2436 (3)	0.0400 (7)
C20	0.8095 (3)	1.3540 (3)	0.1633 (3)	0.0501 (8)
H20	0.7869	1.4342	0.0934	0.060*
C21	0.9513 (4)	1.3322 (4)	0.1867 (4)	0.0672 (10)
H21	1.0236	1.3979	0.1326	0.081*
C22	0.9862 (4)	1.2138 (4)	0.2894 (4)	0.0701 (11)
H22	1.0824	1.1987	0.3042	0.084*
C23	0.8785 (4)	1.1183 (4)	0.3700 (4)	0.0705 (11)
H23	0.9014	1.0387	0.4403	0.085*
C24	0.7363 (4)	1.1394 (3)	0.3475 (3)	0.0554 (9)
H24	0.6641	1.0739	0.4030	0.066*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.1915 (17)	0.0886 (9)	0.1280 (12)	0.0311 (10)	−0.0373 (11)	−0.0759 (9)
O1	0.0518 (13)	0.0495 (13)	0.0433 (12)	−0.0087 (10)	−0.0041 (10)	−0.0181 (10)
O2	0.0668 (16)	0.0817 (18)	0.0579 (15)	0.0166 (13)	−0.0316 (13)	−0.0294 (14)
N1	0.0443 (15)	0.0444 (14)	0.0479 (15)	−0.0079 (11)	−0.0112 (13)	−0.0165 (12)
C1	0.0389 (15)	0.0493 (17)	0.0408 (16)	−0.0078 (13)	−0.0106 (13)	−0.0208 (14)
C2	0.0359 (15)	0.0444 (17)	0.0431 (16)	−0.0053 (13)	−0.0142 (13)	−0.0183 (14)
C3	0.0347 (15)	0.0419 (16)	0.0363 (15)	−0.0056 (12)	−0.0116 (12)	−0.0130 (13)
C4	0.055 (2)	0.087 (3)	0.074 (2)	−0.0053 (19)	−0.0220 (18)	−0.051 (2)
C5	0.058 (2)	0.100 (3)	0.077 (3)	−0.006 (2)	−0.0195 (19)	−0.065 (2)
C6	0.057 (2)	0.070 (2)	0.090 (3)	−0.0179 (19)	0.005 (2)	−0.053 (2)
C7	0.079 (3)	0.103 (4)	0.133 (4)	−0.018 (3)	0.015 (3)	−0.087 (4)
C8	0.087 (4)	0.085 (4)	0.169 (6)	−0.013 (3)	0.038 (4)	−0.082 (4)
C9	0.079 (3)	0.069 (3)	0.142 (5)	0.018 (3)	0.003 (4)	−0.031 (3)
C10	0.061 (2)	0.055 (2)	0.092 (3)	0.0094 (19)	−0.005 (2)	−0.021 (2)
C11	0.0466 (19)	0.0490 (19)	0.069 (2)	−0.0086 (15)	−0.0032 (17)	−0.0263 (18)
C12	0.0437 (17)	0.0444 (17)	0.0501 (19)	−0.0051 (14)	−0.0115 (15)	−0.0202 (15)
C13	0.0497 (18)	0.0474 (18)	0.0513 (19)	−0.0038 (14)	−0.0162 (15)	−0.0210 (15)
C14	0.088 (3)	0.061 (2)	0.074 (3)	−0.024 (2)	0.001 (2)	−0.034 (2)
C15	0.131 (4)	0.057 (2)	0.096 (3)	−0.022 (3)	−0.009 (3)	−0.043 (2)
C16	0.104 (3)	0.060 (2)	0.083 (3)	0.015 (2)	−0.029 (3)	−0.042 (2)
C17	0.075 (3)	0.088 (3)	0.082 (3)	0.000 (2)	−0.002 (2)	−0.051 (3)
C18	0.064 (2)	0.071 (2)	0.072 (2)	−0.0125 (19)	−0.0010 (19)	−0.040 (2)
C19	0.0337 (15)	0.0453 (17)	0.0395 (16)	−0.0060 (13)	−0.0092 (13)	−0.0155 (14)
C20	0.0417 (17)	0.0521 (18)	0.0496 (18)	−0.0108 (15)	−0.0113 (14)	−0.0132 (15)
C21	0.0438 (19)	0.084 (3)	0.070 (2)	−0.0222 (18)	−0.0118 (18)	−0.024 (2)
C22	0.0384 (18)	0.098 (3)	0.078 (3)	−0.0026 (19)	−0.0254 (18)	−0.035 (2)
C23	0.056 (2)	0.071 (2)	0.077 (3)	0.0044 (19)	−0.038 (2)	−0.016 (2)
C24	0.0482 (18)	0.054 (2)	0.055 (2)	−0.0109 (15)	−0.0212 (16)	−0.0079 (16)

Geometric parameters (Å, º)

Cl1—C16	1.741 (4)	C8—C9	1.379 (9)
O1—N1	1.407 (3)	C9—C10	1.369 (7)
O1—C1	1.459 (4)	C10—C11	1.394 (5)
O2—C12	1.218 (4)	C11—C12	1.476 (5)
N1—C2	1.281 (4)	C13—C18	1.375 (5)
C1—C4	1.518 (4)	C13—C14	1.390 (5)
C1—C3	1.535 (4)	C14—C15	1.381 (5)
C1—C12	1.536 (4)	C15—C16	1.356 (6)
C2—C13	1.466 (4)	C16—C17	1.371 (6)
C2—C3	1.517 (4)	C17—C18	1.382 (5)
C3—C19	1.511 (4)	C19—C24	1.380 (4)
C4—C5	1.481 (5)	C19—C20	1.391 (4)
C5—C6	1.461 (6)	C20—C21	1.380 (5)
C6—C7	1.385 (6)	C21—C22	1.374 (5)
C6—C11	1.402 (5)	C22—C23	1.369 (5)
C7—C8	1.360 (9)	C23—C24	1.380 (5)
N1—O1—C1	108.8 (2)	C10—C11—C12	119.7 (4)
C2—N1—O1	110.0 (2)	C6—C11—C12	120.3 (3)
O1—C1—C4	107.3 (3)	O2—C12—C11	122.4 (3)
O1—C1—C3	105.2 (2)	O2—C12—C1	120.1 (3)
C4—C1—C3	117.2 (2)	C11—C12—C1	117.4 (3)
O1—C1—C12	103.5 (2)	C18—C13—C14	118.3 (3)
C4—C1—C12	110.1 (3)	C18—C13—C2	121.6 (3)
C3—C1—C12	112.3 (2)	C14—C13—C2	120.1 (3)
N1—C2—C13	119.7 (3)	C15—C14—C13	120.5 (4)
N1—C2—C3	114.0 (3)	C16—C15—C14	119.9 (4)
C13—C2—C3	126.3 (3)	C15—C16—C17	121.0 (4)
C19—C3—C2	112.8 (2)	C15—C16—Cl1	118.8 (4)
C19—C3—C1	116.2 (2)	C17—C16—Cl1	120.2 (4)
C2—C3—C1	99.7 (2)	C16—C17—C18	119.1 (4)
C5—C4—C1	112.0 (3)	C13—C18—C17	121.2 (4)
C6—C5—C4	114.4 (3)	C24—C19—C20	118.4 (3)
C7—C6—C11	118.4 (4)	C24—C19—C3	122.0 (3)
C7—C6—C5	120.1 (4)	C20—C19—C3	119.6 (3)
C11—C6—C5	121.4 (3)	C21—C20—C19	120.4 (3)
C8—C7—C6	120.9 (6)	C22—C21—C20	120.3 (3)
C7—C8—C9	120.9 (5)	C23—C22—C21	119.6 (3)
C10—C9—C8	119.8 (5)	C22—C23—C24	120.4 (3)
C9—C10—C11	120.0 (5)	C19—C24—C23	120.8 (3)
C10—C11—C6	119.9 (4)
C1—O1—N1—C2	9.9 (3)	C10—C11—C12—C1	−173.6 (3)
N1—O1—C1—C4	−140.5 (2)	C6—C11—C12—C1	6.7 (4)
N1—O1—C1—C3	−15.0 (3)	O1—C1—C12—O2	−96.1 (3)
N1—O1—C1—C12	103.0 (2)	C4—C1—C12—O2	149.5 (3)
O1—N1—C2—C13	177.8 (2)	C3—C1—C12—O2	16.9 (4)
O1—N1—C2—C3	−0.1 (3)	O1—C1—C12—C11	80.9 (3)
N1—C2—C3—C19	115.1 (3)	C4—C1—C12—C11	−33.5 (4)
C13—C2—C3—C19	−62.7 (4)	C3—C1—C12—C11	−166.1 (3)
N1—C2—C3—C1	−8.8 (3)	N1—C2—C13—C18	177.7 (3)
C13—C2—C3—C1	173.4 (3)	C3—C2—C13—C18	−4.7 (5)
O1—C1—C3—C19	−107.8 (3)	N1—C2—C13—C14	−2.9 (5)
C4—C1—C3—C19	11.2 (4)	C3—C2—C13—C14	174.8 (3)
C12—C1—C3—C19	140.2 (3)	C18—C13—C14—C15	0.0 (6)
O1—C1—C3—C2	13.6 (3)	C2—C13—C14—C15	−179.5 (4)
C4—C1—C3—C2	132.7 (3)	C13—C14—C15—C16	0.1 (7)
C12—C1—C3—C2	−98.3 (3)	C14—C15—C16—C17	0.0 (8)
O1—C1—C4—C5	−56.9 (4)	C14—C15—C16—Cl1	−179.1 (4)
C3—C1—C4—C5	−174.8 (3)	C15—C16—C17—C18	−0.2 (7)
C12—C1—C4—C5	55.1 (4)	Cl1—C16—C17—C18	178.9 (3)
C1—C4—C5—C6	−50.7 (5)	C14—C13—C18—C17	−0.2 (6)
C4—C5—C6—C7	−157.5 (4)	C2—C13—C18—C17	179.3 (4)
C4—C5—C6—C11	22.8 (5)	C16—C17—C18—C13	0.3 (7)
C11—C6—C7—C8	−0.1 (6)	C2—C3—C19—C24	−30.8 (4)
C5—C6—C7—C8	−179.8 (4)	C1—C3—C19—C24	83.4 (4)
C6—C7—C8—C9	−0.6 (8)	C2—C3—C19—C20	152.1 (3)
C7—C8—C9—C10	1.2 (9)	C1—C3—C19—C20	−93.6 (3)
C8—C9—C10—C11	−1.1 (7)	C24—C19—C20—C21	0.8 (5)
C9—C10—C11—C6	0.5 (6)	C3—C19—C20—C21	177.9 (3)
C9—C10—C11—C12	−179.2 (4)	C19—C20—C21—C22	0.2 (6)
C7—C6—C11—C10	0.1 (5)	C20—C21—C22—C23	−1.0 (6)
C5—C6—C11—C10	179.8 (3)	C21—C22—C23—C24	0.8 (7)
C7—C6—C11—C12	179.8 (3)	C20—C19—C24—C23	−0.9 (5)
C5—C6—C11—C12	−0.4 (5)	C3—C19—C24—C23	−178.0 (3)
C10—C11—C12—O2	3.4 (5)	C22—C23—C24—C19	0.1 (6)
C6—C11—C12—O2	−176.3 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5A···O1	0.97	2.57	2.831 (6)	95
C3—H3···O2	0.98	2.35	2.777 (4)	105
C22—H22···N1^i	0.93	2.60	3.531 (5)	175

Symmetry code: (i) x+1, y, z.