4-(4-Chloro­phenyl)-1,3-di­phenyl-7-oxa-1,2-di­aza­spiro­[4.4]­non-2-en-6-one

The title compound, C₂₄H₁₉ClN₂O₂, contains a spiro moiety, consisting of a pyrazole ring and a di­hydro­furan ring. The pyrazole and di­hydro­furan rings adopt envelope conform­ations. Inversion-related mol­ecules exist as dimers in the crystalline state.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.054
• wR factor = 0.131
• Data-to-parameter ratio = 15.4

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry

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S1. Comment

Spiro-compounds represent an important class of naturally occurring substances characterized by highly pronounced biological properties (Kobayashi et al., 1991; James et al., 1991). 1,3-Dipolar cycloaddition reactions are important processes for the construction of spiro-compounds (Caramella & Grunanger, 1984). In this paper, the structure of the title compound, 4-(4-chlorophenyl)-1,3-diphenyl-7-oxa-1,2-diazaspiro[4.4]non-2-en-6-one, (I), is reported.

The structure of (I) contains a spiro moiety consisting of a pyrazole ring and a dihydrofuran ring (Fig. 1). The pyrazole ring adopts an envelope conformation, with the spiro-atom C2 deviating from the N1/N2/C6/C5 plane by 0.412 (4) Å. The dihedral angle between the C5/C2/N1 and N1/N2/C6/C5 mean planes is 25.0 (1)°. The dihydrofuran ring also adopts an envelope conformation, with atom C3 lying at 0.343 (5) Å from the C2/C1/O2/C4 plane. The dihedral angle between the C2/C3/C4 and C2/C1/O2/C4 planes is 21.6 (3)°. Phenyl rings A (C7–C12) and C (C19–C24) are nearly coplanar with the N1/N2/C6/C5 plane (r.m.s. deviation = 0.041 Å). The other phenyl ring B (C13–C18) forms a dihedral angle of 68.31 (8)° with the above plane. The inversion-related molecules are linked by C11—H11···O1(1 − x, 1 − y, 1 − z) interactions to form dimers in the crystalline state.

S2. Experimental

To a solution of 3-(4-chlorobenzylidene)dihydrofuran-2-one (10 mmol) and N-phenylbenzhydrazidoyl chloride (10 mmol) in dry benzene (30 ml) was added triethylamine (10 mmol) and the reaction mixture was stirred under reflux until the disappearance of the starting material. After the reaction was complete, the solution was filtered to remove triethylamine hydrochloride. After evaporation of the solvent of the filtrate, the residue was separated by column chromatography (silica gel, petroleum ether/ethyl acetate, 10:1) to give the title compound, (I). M.p. 439–440 K; IR (KBr): 1775 (C═O), 1595 (C═N, C═C) cm⁻¹; ¹H NMR (CDCl₃, p.p.m.): 1.95–2.04 (1H, m), 2.53–2.63 (1H, m), 3.61–3.70 (1H, m), 4.11–4.19 (1H, m), 5.15 (1H, s), 7.03–7.53 (14H, m); 20 mg of (I) was dissolved in 15 ml chloroform and the solution was kept at room temperature for 15 d to give colorless single crystals of (I) by natural evaporation.

S3. Refinement

The H atoms were geometrically positioned and were treated as riding atoms on the parent C atoms, with C—H distances of 0.93, 0.97 or 0.98 Å.

Computing details

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Bruker, 1997); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Figures

	Fig. 1. The molecular structure of (I), showing 30% probability displacement ellipsoids. For clarity, H atoms have been omitted.
	Fig. 2. The crystal structure of (I), viewed along the b axis

4-(4-Chlorophenyl)-1,3-diphenyl-7-oxa-1,2-diazaspiro[4.4]non-2-en-6-one

Crystal data

C24H19ClN2O2	F(000) = 1680
Mr = 402.86	Dx = 1.342 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 907 reflections
a = 16.013 (6) Å	θ = 2.4–22.8°
b = 15.627 (6) Å	µ = 0.22 mm^−1
c = 16.317 (6) Å	T = 293 K
β = 102.325 (7)°	Plate, colorless
V = 3989 (3) Å^3	0.30 × 0.24 × 0.20 mm
Z = 8

Data collection

SMART CCD area-detector diffractometer	4039 independent reflections
Radiation source: fine-focus sealed tube	2154 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.039
ω scans	θmax = 26.4°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −19→7
Tmin = 0.940, Tmax = 0.958	k = −19→19
9301 measured reflections	l = −18→20

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.054	w = 1/[σ^2(Fo^2) + (0.084P)^2] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.131	(Δ/σ)max < 0.001
S = 1.00	Δρmax = 0.32 e Å^−3
4039 reflections	Δρmin = −0.41 e Å^−3
262 parameters

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	0.06404 (5)	0.88675 (8)	0.14477 (6)	0.1081 (4)
N1	0.51756 (12)	0.74185 (13)	0.41532 (13)	0.0510 (5)
N2	0.54456 (12)	0.82442 (14)	0.40529 (13)	0.0510 (5)
O1	0.38566 (12)	0.68136 (12)	0.50917 (12)	0.0654 (6)
O2	0.32198 (11)	0.62775 (13)	0.38593 (13)	0.0696 (6)
C1	0.37840 (15)	0.67854 (17)	0.43477 (19)	0.0484 (6)
C2	0.42539 (14)	0.73343 (15)	0.38178 (14)	0.0419 (6)
C3	0.40205 (16)	0.69071 (18)	0.29555 (16)	0.0567 (7)
H3A	0.3912	0.7332	0.2512	0.068*
H3B	0.4475	0.6531	0.2867	0.068*
C4	0.32204 (18)	0.6404 (2)	0.2977 (2)	0.0755 (9)
H4A	0.2716	0.6720	0.2702	0.091*
H4B	0.3227	0.5858	0.2696	0.091*
C5	0.39684 (14)	0.82861 (15)	0.38827 (15)	0.0432 (6)
H5	0.3858	0.8359	0.4447	0.052*
C6	0.47944 (15)	0.87515 (16)	0.38733 (15)	0.0451 (6)
C7	0.57841 (15)	0.67546 (16)	0.42321 (15)	0.0452 (6)
C8	0.66421 (15)	0.69477 (18)	0.43080 (16)	0.0534 (7)
H8	0.6814	0.7513	0.4280	0.064*
C9	0.72415 (17)	0.6297 (2)	0.44256 (18)	0.0645 (8)
H9	0.7817	0.6432	0.4487	0.077*
C10	0.70030 (18)	0.5459 (2)	0.44531 (18)	0.0687 (8)
H10	0.7411	0.5026	0.4528	0.082*
C11	0.61563 (19)	0.52664 (19)	0.43685 (19)	0.0672 (8)
H11	0.5988	0.4698	0.4382	0.081*
C12	0.55474 (16)	0.59065 (17)	0.42631 (17)	0.0578 (7)
H12	0.4974	0.5766	0.4213	0.069*
C13	0.31455 (14)	0.84996 (15)	0.32727 (15)	0.0424 (6)
C14	0.31225 (16)	0.87577 (17)	0.24559 (16)	0.0574 (7)
H14	0.3632	0.8850	0.2282	0.069*
C15	0.23534 (17)	0.88798 (19)	0.18957 (17)	0.0644 (8)
H15	0.2345	0.9054	0.1349	0.077*
C16	0.16018 (16)	0.87412 (18)	0.21525 (18)	0.0586 (7)
C17	0.16097 (16)	0.84983 (17)	0.29655 (18)	0.0564 (7)
H17	0.1099	0.8414	0.3138	0.068*
C18	0.23817 (15)	0.83808 (16)	0.35223 (16)	0.0473 (6)
H18	0.2387	0.8220	0.4072	0.057*
C19	0.49231 (15)	0.96739 (16)	0.38210 (15)	0.0459 (6)
C20	0.42589 (18)	1.02534 (19)	0.37186 (19)	0.0683 (8)
H20	0.3703	1.0058	0.3677	0.082*
C21	0.4411 (2)	1.11219 (19)	0.3677 (2)	0.0799 (9)
H21	0.3956	1.1505	0.3600	0.096*
C22	0.5224 (2)	1.1421 (2)	0.37477 (19)	0.0756 (9)
H22	0.5324	1.2005	0.3717	0.091*
C23	0.5888 (2)	1.0856 (2)	0.38635 (19)	0.0732 (9)
H23	0.6443	1.1058	0.3914	0.088*
C24	0.57464 (17)	0.99941 (18)	0.39062 (16)	0.0578 (7)
H24	0.6207	0.9618	0.3993	0.069*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.0516 (5)	0.1666 (11)	0.0942 (7)	0.0054 (5)	−0.0109 (4)	0.0409 (7)
N1	0.0388 (11)	0.0461 (14)	0.0669 (14)	0.0008 (10)	0.0087 (10)	0.0050 (11)
N2	0.0411 (12)	0.0470 (14)	0.0653 (14)	−0.0011 (10)	0.0123 (11)	0.0045 (11)
O1	0.0794 (14)	0.0648 (14)	0.0585 (13)	−0.0004 (10)	0.0294 (11)	0.0104 (10)
O2	0.0535 (11)	0.0705 (14)	0.0848 (15)	−0.0192 (10)	0.0145 (11)	−0.0026 (11)
C1	0.0427 (14)	0.0471 (17)	0.0571 (18)	0.0024 (12)	0.0144 (13)	0.0018 (14)
C2	0.0348 (12)	0.0491 (16)	0.0426 (14)	0.0008 (11)	0.0103 (11)	0.0015 (12)
C3	0.0557 (16)	0.0642 (19)	0.0510 (16)	0.0092 (14)	0.0134 (13)	−0.0030 (14)
C4	0.0641 (19)	0.083 (2)	0.072 (2)	−0.0055 (17)	−0.0015 (16)	−0.0199 (18)
C5	0.0407 (13)	0.0496 (16)	0.0416 (14)	0.0030 (11)	0.0137 (11)	0.0027 (12)
C6	0.0382 (13)	0.0482 (17)	0.0509 (15)	0.0007 (12)	0.0139 (12)	0.0019 (13)
C7	0.0422 (14)	0.0497 (17)	0.0434 (15)	0.0054 (13)	0.0081 (11)	0.0015 (12)
C8	0.0419 (15)	0.0578 (18)	0.0588 (17)	−0.0001 (13)	0.0070 (13)	−0.0033 (14)
C9	0.0409 (14)	0.070 (2)	0.079 (2)	0.0043 (15)	0.0047 (14)	−0.0168 (17)
C10	0.0583 (19)	0.060 (2)	0.082 (2)	0.0170 (15)	0.0005 (16)	−0.0131 (17)
C11	0.0675 (19)	0.0490 (18)	0.082 (2)	0.0051 (15)	0.0095 (17)	−0.0033 (16)
C12	0.0458 (15)	0.0529 (18)	0.0744 (19)	0.0027 (13)	0.0124 (14)	0.0022 (15)
C13	0.0385 (13)	0.0459 (15)	0.0446 (15)	0.0025 (11)	0.0132 (12)	0.0023 (12)
C14	0.0436 (15)	0.076 (2)	0.0567 (17)	0.0030 (14)	0.0195 (13)	0.0178 (15)
C15	0.0548 (17)	0.086 (2)	0.0528 (17)	0.0075 (15)	0.0118 (14)	0.0227 (16)
C16	0.0416 (15)	0.069 (2)	0.0613 (18)	0.0044 (13)	0.0031 (13)	0.0102 (15)
C17	0.0365 (14)	0.0678 (19)	0.0681 (19)	0.0025 (13)	0.0182 (13)	0.0053 (15)
C18	0.0459 (15)	0.0513 (16)	0.0484 (15)	0.0053 (12)	0.0181 (13)	0.0075 (12)
C19	0.0474 (15)	0.0466 (16)	0.0467 (15)	−0.0013 (13)	0.0162 (12)	0.0003 (12)
C20	0.0552 (17)	0.056 (2)	0.094 (2)	−0.0009 (15)	0.0179 (16)	0.0062 (17)
C21	0.083 (2)	0.049 (2)	0.108 (3)	0.0070 (17)	0.021 (2)	0.0066 (18)
C22	0.099 (3)	0.0488 (19)	0.083 (2)	−0.0155 (19)	0.028 (2)	−0.0022 (16)
C23	0.075 (2)	0.063 (2)	0.089 (2)	−0.0172 (18)	0.0336 (18)	−0.0151 (18)
C24	0.0531 (17)	0.0553 (19)	0.0682 (19)	−0.0022 (14)	0.0202 (14)	−0.0098 (15)

Geometric parameters (Å, º)

Cl1—C16	1.725 (3)	C10—C11	1.367 (4)
N1—N2	1.382 (3)	C10—H10	0.93
N1—C7	1.410 (3)	C11—C12	1.382 (4)
N1—C2	1.466 (3)	C11—H11	0.93
N2—C6	1.293 (3)	C12—H12	0.93
O1—C1	1.196 (3)	C13—C18	1.382 (3)
O2—C1	1.332 (3)	C13—C14	1.385 (3)
O2—C4	1.453 (3)	C14—C15	1.381 (3)
C1—C2	1.526 (3)	C14—H14	0.93
C2—C3	1.530 (3)	C15—C16	1.373 (4)
C2—C5	1.566 (3)	C15—H15	0.93
C3—C4	1.510 (4)	C16—C17	1.377 (4)
C3—H3A	0.97	C17—C18	1.381 (3)
C3—H3B	0.97	C17—H17	0.93
C4—H4A	0.97	C18—H18	0.93
C4—H4B	0.97	C19—C20	1.380 (4)
C5—C13	1.509 (3)	C19—C24	1.389 (3)
C5—C6	1.512 (3)	C20—C21	1.383 (4)
C5—H5	0.98	C20—H20	0.93
C6—C19	1.461 (3)	C21—C22	1.364 (4)
C7—C12	1.382 (4)	C21—H21	0.93
C7—C8	1.386 (3)	C22—C23	1.364 (4)
C8—C9	1.383 (4)	C22—H22	0.93
C8—H8	0.93	C23—C24	1.371 (4)
C9—C10	1.368 (4)	C23—H23	0.93
C9—H9	0.93	C24—H24	0.93
N2—N1—C7	118.04 (19)	C11—C10—H10	120.5
N2—N1—C2	110.80 (18)	C9—C10—H10	120.5
C7—N1—C2	126.1 (2)	C10—C11—C12	120.8 (3)
C6—N2—N1	109.99 (19)	C10—C11—H11	119.6
C1—O2—C4	111.6 (2)	C12—C11—H11	119.6
O1—C1—O2	122.4 (2)	C11—C12—C7	120.5 (2)
O1—C1—C2	127.0 (3)	C11—C12—H12	119.8
O2—C1—C2	110.5 (2)	C7—C12—H12	119.8
N1—C2—C1	114.70 (19)	C18—C13—C14	118.6 (2)
N1—C2—C3	114.29 (19)	C18—C13—C5	118.6 (2)
C1—C2—C3	102.9 (2)	C14—C13—C5	122.6 (2)
N1—C2—C5	100.06 (18)	C15—C14—C13	120.9 (2)
C1—C2—C5	108.01 (18)	C15—C14—H14	119.5
C3—C2—C5	117.3 (2)	C13—C14—H14	119.5
C4—C3—C2	104.3 (2)	C16—C15—C14	119.5 (2)
C4—C3—H3A	110.9	C16—C15—H15	120.3
C2—C3—H3A	110.9	C14—C15—H15	120.3
C4—C3—H3B	110.9	C15—C16—C17	120.6 (2)
C2—C3—H3B	110.9	C15—C16—Cl1	119.6 (2)
H3A—C3—H3B	108.9	C17—C16—Cl1	119.8 (2)
O2—C4—C3	105.9 (2)	C16—C17—C18	119.5 (2)
O2—C4—H4A	110.6	C16—C17—H17	120.2
C3—C4—H4A	110.6	C18—C17—H17	120.2
O2—C4—H4B	110.6	C17—C18—C13	120.8 (2)
C3—C4—H4B	110.6	C17—C18—H18	119.6
H4A—C4—H4B	108.7	C13—C18—H18	119.6
C13—C5—C6	122.0 (2)	C20—C19—C24	117.8 (2)
C13—C5—C2	113.06 (19)	C20—C19—C6	122.7 (2)
C6—C5—C2	100.80 (17)	C24—C19—C6	119.5 (2)
C13—C5—H5	106.7	C19—C20—C21	120.7 (3)
C6—C5—H5	106.7	C19—C20—H20	119.6
C2—C5—H5	106.7	C21—C20—H20	119.6
N2—C6—C19	120.1 (2)	C22—C21—C20	120.5 (3)
N2—C6—C5	111.6 (2)	C22—C21—H21	119.8
C19—C6—C5	127.6 (2)	C20—C21—H21	119.8
C12—C7—C8	118.7 (2)	C23—C22—C21	119.4 (3)
C12—C7—N1	121.3 (2)	C23—C22—H22	120.3
C8—C7—N1	120.0 (2)	C21—C22—H22	120.3
C9—C8—C7	119.8 (3)	C22—C23—C24	120.7 (3)
C9—C8—H8	120.1	C22—C23—H23	119.7
C7—C8—H8	120.1	C24—C23—H23	119.7
C10—C9—C8	121.2 (3)	C23—C24—C19	120.9 (3)
C10—C9—H9	119.4	C23—C24—H24	119.6
C8—C9—H9	119.4	C19—C24—H24	119.6
C11—C10—C9	119.0 (3)
C7—N1—N2—C6	171.0 (2)	C2—N1—C7—C8	160.0 (2)
C2—N1—N2—C6	14.7 (3)	C12—C7—C8—C9	−1.0 (4)
C4—O2—C1—O1	176.2 (3)	N1—C7—C8—C9	176.9 (2)
C4—O2—C1—C2	−0.4 (3)	C7—C8—C9—C10	1.2 (4)
N2—N1—C2—C1	−139.8 (2)	C8—C9—C10—C11	−0.5 (5)
C7—N1—C2—C1	66.2 (3)	C9—C10—C11—C12	−0.5 (5)
N2—N1—C2—C3	101.8 (2)	C10—C11—C12—C7	0.7 (4)
C7—N1—C2—C3	−52.3 (3)	C8—C7—C12—C11	0.1 (4)
N2—N1—C2—C5	−24.5 (2)	N1—C7—C12—C11	−177.8 (2)
C7—N1—C2—C5	−178.5 (2)	C6—C5—C13—C18	−150.0 (2)
O1—C1—C2—N1	45.8 (4)	C2—C5—C13—C18	89.6 (3)
O2—C1—C2—N1	−137.8 (2)	C6—C5—C13—C14	34.2 (4)
O1—C1—C2—C3	170.5 (3)	C2—C5—C13—C14	−86.2 (3)
O2—C1—C2—C3	−13.1 (3)	C18—C13—C14—C15	−1.2 (4)
O1—C1—C2—C5	−64.8 (3)	C5—C13—C14—C15	174.6 (3)
O2—C1—C2—C5	111.6 (2)	C13—C14—C15—C16	−0.1 (4)
N1—C2—C3—C4	145.5 (2)	C14—C15—C16—C17	1.2 (4)
C1—C2—C3—C4	20.5 (3)	C14—C15—C16—Cl1	−178.4 (2)
C5—C2—C3—C4	−97.8 (2)	C15—C16—C17—C18	−1.0 (4)
C1—O2—C4—C3	14.1 (3)	Cl1—C16—C17—C18	178.7 (2)
C2—C3—C4—O2	−21.4 (3)	C16—C17—C18—C13	−0.3 (4)
N1—C2—C5—C13	155.64 (18)	C14—C13—C18—C17	1.4 (4)
C1—C2—C5—C13	−84.1 (2)	C5—C13—C18—C17	−174.6 (2)
C3—C2—C5—C13	31.5 (3)	N2—C6—C19—C20	−173.1 (3)
N1—C2—C5—C6	23.8 (2)	C5—C6—C19—C20	−4.2 (4)
C1—C2—C5—C6	144.1 (2)	N2—C6—C19—C24	4.6 (4)
C3—C2—C5—C6	−100.4 (2)	C5—C6—C19—C24	173.5 (2)
N1—N2—C6—C19	173.8 (2)	C24—C19—C20—C21	2.0 (4)
N1—N2—C6—C5	3.3 (3)	C6—C19—C20—C21	179.7 (3)
C13—C5—C6—N2	−144.1 (2)	C19—C20—C21—C22	−0.9 (5)
C2—C5—C6—N2	−18.0 (3)	C20—C21—C22—C23	−0.2 (5)
C13—C5—C6—C19	46.3 (4)	C21—C22—C23—C24	0.2 (5)
C2—C5—C6—C19	172.4 (2)	C22—C23—C24—C19	0.9 (4)
N2—N1—C7—C12	−174.5 (2)	C20—C19—C24—C23	−2.0 (4)
C2—N1—C7—C12	−22.1 (4)	C6—C19—C24—C23	−179.7 (2)
N2—N1—C7—C8	7.7 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8···N2	0.93	2.43	2.758 (4)	101
C11—H11···O1^i	0.93	2.51	3.369 (4)	154

Symmetry code: (i) −x+1, −y+1, −z+1.