1,5-Di­chloro-3,6,6-tri­phenyl-3-aza­bi­cyclo­[3.2.0]­heptane-2,4-dione

In the title compound, C₂₄H₁₇Cl₂NO₂, the succin­imide ring adopts a half-chair conformation, and the attached phenyl ring is twisted by an angle of 55.0 (1)° with respect to the succin­imide mean plane. The cyclo­butane ring is non-planar and is substituted by two phenyl rings oriented at angles of 38.3 (1) and 75.7 (1)° to the cyclo­butane mean plane. The dihedral angle between the succin­imide and cyclo­butane rings is 64.8 (1)°.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.045
• wR factor = 0.102
• Data-to-parameter ratio = 18.0

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry

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S1. Comment

The photoinduced reactions of 1H-indole-2,3-dione (isatin) derivatives have been intensively investigated (Ling et al., 1998; Xue et al., 2000; Xue et al., 2001) as these derivatives display biological activity (Bieck et al., 1993) and have been widely used as synthetic precursors of many natural and unnatural products (Popp, 1975; Shvekhgeimer, 1996). The title compound, (I), was isolated in order to extend the scope of the photoinduced reactivity of the maleimide derivative and an X-ray crystal structure analysis was undertaken to establish its conformation.

In the succinimide-cyclobutane ring system (Fig. 1), the succinimide ring adopts a half-chair conformation [Q₂ = 0.141 (2) Å and ϕ₂ = 89.2 (6)°] twisted about the C3—C6 axis. The cyclobutane ring is non-planar with a dihedral angle between the C3/C4/C6 and C4/C5/C6 planes of 156.1 (2)° and a puckering parameter Q₂ = -0.231 (2) Å (Cremer & Pople, 1975). The dihedral angle between the least-square planes through the succinimide and cyclobutane ring is 64.8 (1)°. The bond lengths and angles in (I) have normal values and those within the succinimide comparable with a related structure (Igonin et al., 1993). In the cyclobutane ring, the C5—C6 bond length of 1.624 (2) Å is longer than typical Csp³—Csp³ bonds and is considered to be of spiro-atom character. The phenyl ring substituent attached to the succinimide ring moiety at N1 is twisted by an angle of 55.0 (1)° to the five-membered ring, corresponding to a bisectional orientation to the succinimide. Atoms O1 and O2 deviate slightly by -0.172 (1) and 0.183 (1) Å, respectively, from the mean plane of this ring. The phenyl rings attached to the cyclobutane ring at C5 are in nearly axial and equatorial positions and they subtend angles of 38.3 (1) and 75.7 (1)°, respectively, to the cyclobutane ring. Both Cl1 and Cl2 atoms attached to the succinimide–cyclobutane ring system form an average Cl—C—C angle of 114.8°, while the Cl1—C6—C3—Cl2 torsion angle is -18.47 (17)°.

S2. Experimental

The title compound, (I), was prepared by a photoinduced (Peterno-Büchi) reaction (Arnold, 1968). A solution of 1-phenyl-2,3-dichloromaleimide (0.05 M) and 1,1-diphenylethylene (0.2 M) in benzene (40 ml) was photolysed by irradiation of light using a medium-pressure mercury lamp (500 W, λ > 400 nm) through a Pyrex filter and under constant nitrogen purging. After irradiation the solvent was removed in vacuo and residue was separated by column chromatography. The title compound was obtained as the sole product and was recrystallized from a petroleum ether–ethyl acetate solution.

S3. Refinement

The H atoms were located in difference maps and were subsequently geometrically fixed and allowed to ride on the parent C atoms, with aromatic C—H = 0.93 Å and methylene C—H = 0.97 Å.

Computing details

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 1997); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL, PARST (Nardelli, 1995) and PLATON (Spek, 1990).

Figures

Fig. 1. The structure of (I) showing 50% probability displacement ellipsoids and the atom-numbering scheme.

(1R/1S,5S/5R)-Dichloro-3,6,6-triphenyl-3-azabicyclo[3.2.0]hepta-2,4-dione

Crystal data

C24H17Cl2NO2	Dx = 1.412 Mg m^−3
Mr = 422.29	Melting point: 433K K
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 11.1302 (2) Å	Cell parameters from 8192 reflections
b = 7.3731 (1) Å	θ = 1.7–28.3°
c = 24.3816 (4) Å	µ = 0.35 mm^−1
β = 96.950 (1)°	T = 293 K
V = 1986.15 (6) Å^3	Slab, colourless
Z = 4	0.36 × 0.28 × 0.16 mm
F(000) = 872

Data collection

Siemens SMART CCD diffractometer	4726 independent reflections
Radiation source: fine-focus sealed tube	3204 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.078
Detector resolution: 8.33 pixels mm^-1	θmax = 28.3°, θmin = 1.7°
ω scans	h = −14→14
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996)	k = −9→9
Tmin = 0.885, Tmax = 0.946	l = −16→32
13108 measured 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)] = 0.045	H-atom parameters constrained
wR(F^2) = 0.102	w = 1/σ^2(Fo^2)
S = 0.83	(Δ/σ)max < 0.001
4726 reflections	Δρmax = 0.29 e Å^−3
263 parameters	Δρmin = −0.25 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: 0.0133 (11)

Special details

Experimental. The data collection covered over a hemisphere of reciprocal space by a combination of three sets of exposures; each set had a different ϕ angle (0, 88 and 180°) for the crystal and each exposure of 10 s covered 0.3° in ω. The crystal-to-detector distance was 4 cm and the detector swing angle was -35°. Crystal decay was monitored by repeating fifty initial frames at the end of data collection and analysing the intensity of duplicate reflections, and was found to be negligible.

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	0.20786 (4)	0.54966 (6)	0.016663 (18)	0.04380 (14)
Cl2	0.45373 (5)	0.73964 (7)	−0.015339 (19)	0.05394 (17)
O1	0.32037 (11)	0.36615 (16)	0.12421 (5)	0.0395 (3)
O2	0.61966 (11)	0.77172 (19)	0.09973 (6)	0.0551 (4)
N1	0.48879 (11)	0.54616 (18)	0.12036 (5)	0.0291 (3)
C1	0.36735 (13)	0.4986 (2)	0.10735 (6)	0.0275 (3)
C2	0.52179 (15)	0.7009 (2)	0.09244 (7)	0.0345 (4)
C3	0.41292 (15)	0.7604 (2)	0.05213 (7)	0.0319 (4)
C4	0.34743 (15)	0.9351 (2)	0.06463 (7)	0.0326 (4)
H4A	0.3033	0.9909	0.0322	0.039*
H4B	0.3991	1.0229	0.0856	0.039*
C5	0.26526 (13)	0.8254 (2)	0.10034 (6)	0.0267 (3)
C6	0.30869 (13)	0.6447 (2)	0.07008 (6)	0.0280 (3)
C7	0.56754 (14)	0.4540 (2)	0.16251 (7)	0.0332 (4)
C8	0.67592 (17)	0.3810 (3)	0.15002 (9)	0.0482 (5)
H8A	0.6987	0.3914	0.1147	0.058*
C9	0.7496 (2)	0.2919 (3)	0.19171 (11)	0.0618 (6)
H9A	0.8216	0.2392	0.1840	0.074*
C10	0.7173 (2)	0.2810 (3)	0.24394 (10)	0.0615 (6)
H10A	0.7684	0.2241	0.2717	0.074*
C11	0.60967 (19)	0.3540 (3)	0.25563 (9)	0.0528 (5)
H11A	0.5879	0.3447	0.2912	0.063*
C12	0.53323 (17)	0.4414 (2)	0.21474 (7)	0.0397 (4)
H12A	0.4602	0.4905	0.2225	0.048*
C13	0.13130 (14)	0.8714 (2)	0.09069 (7)	0.0321 (4)
C14	0.04081 (16)	0.7447 (3)	0.09422 (8)	0.0427 (4)
H14A	0.0615	0.6238	0.1007	0.051*
C15	−0.08057 (17)	0.7948 (4)	0.08825 (8)	0.0556 (6)
H15A	−0.1402	0.7078	0.0908	0.067*
C16	−0.11235 (17)	0.9738 (4)	0.07857 (9)	0.0603 (6)
H16A	−0.1933	1.0082	0.0747	0.072*
C17	−0.02391 (19)	1.1004 (3)	0.07472 (9)	0.0585 (6)
H17A	−0.0455	1.2210	0.0680	0.070*
C18	0.09792 (16)	1.0520 (3)	0.08063 (8)	0.0410 (4)
H18A	0.1569	1.1398	0.0779	0.049*
C19	0.31106 (13)	0.8271 (2)	0.16239 (6)	0.0260 (3)
C20	0.24626 (15)	0.7387 (2)	0.19998 (7)	0.0344 (4)
H20A	0.1747	0.6793	0.1870	0.041*
C21	0.28545 (17)	0.7370 (2)	0.25584 (7)	0.0408 (4)
H21A	0.2405	0.6761	0.2799	0.049*
C22	0.39043 (17)	0.8247 (2)	0.27630 (7)	0.0413 (4)
H22A	0.4170	0.8233	0.3140	0.050*
C23	0.45572 (16)	0.9147 (2)	0.24018 (8)	0.0407 (4)
H23A	0.5268	0.9744	0.2536	0.049*
C24	0.41647 (14)	0.9171 (2)	0.18421 (7)	0.0334 (4)
H24A	0.4612	0.9800	0.1606	0.040*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.0482 (2)	0.0486 (3)	0.0314 (3)	−0.0008 (2)	−0.00846 (18)	−0.00820 (19)
Cl2	0.0758 (3)	0.0559 (3)	0.0362 (3)	0.0031 (3)	0.0316 (2)	0.0033 (2)
O1	0.0415 (6)	0.0322 (7)	0.0435 (8)	−0.0095 (6)	−0.0002 (5)	0.0062 (5)
O2	0.0293 (6)	0.0544 (9)	0.0832 (11)	−0.0083 (6)	0.0130 (6)	0.0112 (7)
N1	0.0276 (6)	0.0311 (7)	0.0289 (7)	0.0006 (6)	0.0047 (5)	−0.0001 (5)
C1	0.0309 (7)	0.0269 (8)	0.0247 (8)	−0.0014 (7)	0.0039 (6)	−0.0033 (6)
C2	0.0320 (8)	0.0341 (9)	0.0396 (10)	−0.0003 (7)	0.0134 (7)	0.0000 (7)
C3	0.0378 (8)	0.0345 (9)	0.0260 (9)	0.0002 (7)	0.0143 (7)	0.0035 (7)
C4	0.0379 (8)	0.0300 (9)	0.0314 (9)	0.0001 (7)	0.0101 (7)	0.0066 (7)
C5	0.0270 (7)	0.0271 (8)	0.0266 (8)	−0.0011 (6)	0.0053 (6)	0.0015 (6)
C6	0.0292 (7)	0.0302 (8)	0.0243 (8)	−0.0026 (7)	0.0020 (6)	−0.0011 (6)
C7	0.0316 (8)	0.0299 (9)	0.0367 (10)	0.0013 (7)	−0.0017 (7)	−0.0024 (7)
C8	0.0392 (9)	0.0569 (13)	0.0468 (12)	0.0093 (9)	−0.0017 (8)	−0.0082 (9)
C9	0.0448 (11)	0.0638 (15)	0.0728 (17)	0.0181 (11)	−0.0093 (10)	−0.0054 (12)
C10	0.0598 (13)	0.0494 (13)	0.0672 (17)	0.0063 (11)	−0.0258 (11)	0.0068 (11)
C11	0.0651 (13)	0.0469 (12)	0.0432 (12)	−0.0054 (11)	−0.0067 (10)	0.0082 (9)
C12	0.0434 (9)	0.0374 (10)	0.0377 (10)	0.0005 (8)	0.0024 (8)	0.0019 (8)
C13	0.0292 (8)	0.0414 (10)	0.0254 (9)	0.0022 (7)	0.0025 (6)	−0.0018 (7)
C14	0.0344 (9)	0.0524 (12)	0.0413 (11)	−0.0053 (8)	0.0048 (7)	−0.0030 (8)
C15	0.0309 (9)	0.0903 (18)	0.0454 (13)	−0.0102 (11)	0.0036 (8)	−0.0128 (11)
C16	0.0310 (9)	0.098 (2)	0.0495 (13)	0.0145 (12)	−0.0039 (8)	−0.0077 (12)
C17	0.0543 (12)	0.0658 (15)	0.0524 (14)	0.0275 (11)	−0.0057 (10)	−0.0019 (10)
C18	0.0394 (9)	0.0422 (10)	0.0402 (11)	0.0069 (9)	−0.0003 (7)	0.0026 (8)
C19	0.0269 (7)	0.0246 (8)	0.0270 (8)	0.0019 (6)	0.0058 (6)	−0.0010 (6)
C20	0.0360 (8)	0.0389 (10)	0.0287 (9)	−0.0075 (7)	0.0060 (7)	0.0013 (7)
C21	0.0504 (10)	0.0429 (11)	0.0304 (10)	−0.0038 (9)	0.0100 (8)	0.0044 (8)
C22	0.0553 (11)	0.0403 (10)	0.0268 (9)	0.0054 (9)	−0.0014 (8)	−0.0049 (7)
C23	0.0374 (9)	0.0424 (11)	0.0399 (11)	−0.0015 (8)	−0.0053 (8)	−0.0079 (8)
C24	0.0306 (8)	0.0356 (9)	0.0346 (10)	−0.0053 (7)	0.0066 (7)	−0.0018 (7)

Geometric parameters (Å, º)

Cl1—C6	1.7587 (16)	C16—C17	1.368 (3)
Cl2—C3	1.7655 (16)	C17—C18	1.393 (3)
O1—C1	1.2033 (19)	C19—C20	1.395 (2)
O2—C2	1.202 (2)	C19—C24	1.396 (2)
N1—C1	1.3952 (19)	C20—C21	1.379 (3)
N1—C2	1.400 (2)	C21—C22	1.375 (3)
N1—C7	1.438 (2)	C22—C23	1.378 (3)
C1—C6	1.507 (2)	C23—C24	1.382 (3)
C2—C3	1.529 (2)	C4—H4A	0.97
C3—C4	1.529 (2)	C4—H4B	0.97
C3—C6	1.545 (2)	C8—H8A	0.93
C4—C5	1.563 (2)	C9—H9A	0.93
C5—C6	1.624 (2)	C10—H10A	0.93
C5—C13	1.519 (2)	C11—H11A	0.93
C5—C19	1.537 (2)	C12—H12A	0.93
C7—C8	1.388 (2)	C14—H14A	0.93
C7—C12	1.376 (2)	C15—H15A	0.93
C8—C9	1.392 (3)	C16—H16A	0.93
C9—C10	1.367 (3)	C17—H17A	0.93
C10—C11	1.374 (3)	C18—H18A	0.93
C11—C12	1.388 (3)	C20—H20A	0.93
C13—C14	1.384 (2)	C21—H21A	0.93
C13—C18	1.396 (2)	C22—H22A	0.93
C14—C15	1.391 (3)	C23—H23A	0.93
C15—C16	1.379 (3)	C24—H24A	0.93
C1—N1—C2	113.47 (13)	C11—C10—H10A	119.8
C1—N1—C7	122.26 (13)	C10—C11—C12	120.4 (2)
C2—N1—C7	124.00 (13)	C10—C11—H11A	119.8
O1—C1—N1	125.13 (14)	C12—C11—H11A	119.8
O1—C1—C6	127.73 (14)	C7—C12—C11	118.77 (18)
N1—C1—C6	107.13 (13)	C7—C12—H12A	120.6
O2—C2—N1	124.66 (17)	C11—C12—H12A	120.6
O2—C2—C3	127.16 (16)	C14—C13—C18	118.32 (16)
N1—C2—C3	108.18 (13)	C14—C13—C5	123.21 (16)
C2—C3—C4	118.26 (14)	C18—C13—C5	118.39 (15)
C2—C3—C6	102.92 (12)	C13—C14—C15	121.28 (19)
C4—C3—C6	90.93 (11)	C13—C14—H14A	119.4
C3—C4—C5	90.00 (11)	C15—C14—H14A	119.4
C4—C5—C6	86.85 (11)	C16—C15—C14	119.9 (2)
C3—C6—C5	87.19 (11)	C16—C15—H15A	120.1
C1—C6—Cl1	110.66 (11)	C14—C15—H15A	120.1
C2—C3—Cl2	107.50 (11)	C17—C16—C15	119.53 (18)
C4—C3—Cl2	116.19 (11)	C17—C16—H16A	120.2
C6—C3—Cl2	120.19 (12)	C15—C16—H16A	120.2
C3—C4—H4A	113.6	C16—C17—C18	121.2 (2)
C5—C4—H4A	113.6	C16—C17—H17A	119.4
C3—C4—H4B	113.6	C18—C17—H17A	119.4
C5—C4—H4B	113.6	C17—C18—C13	119.85 (18)
H4A—C4—H4B	110.9	C17—C18—H18A	120.1
C13—C5—C4	115.32 (13)	C13—C18—H18A	120.1
C19—C5—C4	113.42 (13)	C20—C19—C24	116.70 (15)
C13—C5—C6	116.94 (13)	C20—C19—C5	120.46 (14)
C19—C5—C6	111.85 (12)	C24—C19—C5	122.84 (13)
C13—C5—C19	110.67 (12)	C21—C20—C19	121.76 (16)
C1—C6—C3	106.26 (12)	C21—C20—H20A	119.1
C1—C6—C5	116.33 (13)	C19—C20—H20A	119.1
C3—C6—Cl1	116.36 (11)	C22—C21—C20	120.49 (16)
C5—C6—Cl1	117.71 (10)	C22—C21—H21A	119.8
C12—C7—C8	121.50 (16)	C20—C21—H21A	119.8
C12—C7—N1	118.68 (14)	C21—C22—C23	119.02 (17)
C8—C7—N1	119.82 (16)	C21—C22—H22A	120.5
C7—C8—C9	118.3 (2)	C23—C22—H22A	120.5
C7—C8—H8A	120.8	C22—C23—C24	120.61 (16)
C9—C8—H8A	120.8	C22—C23—H23A	119.7
C10—C9—C8	120.7 (2)	C24—C23—H23A	119.7
C10—C9—H9A	119.7	C23—C24—C19	121.40 (15)
C8—C9—H9A	119.7	C23—C24—H24A	119.3
C9—C10—C11	120.30 (19)	C19—C24—H24A	119.3
C9—C10—H10A	119.8
C2—N1—C1—O1	176.20 (16)	C19—C5—C6—Cl1	144.02 (11)
C7—N1—C1—O1	−9.6 (2)	C4—C5—C6—Cl1	−101.97 (12)
C2—N1—C1—C6	−4.97 (18)	C1—N1—C7—C12	−54.3 (2)
C7—N1—C1—C6	169.24 (14)	C2—N1—C7—C12	119.25 (18)
C1—N1—C2—O2	175.54 (16)	C1—N1—C7—C8	125.96 (18)
C7—N1—C2—O2	1.4 (3)	C2—N1—C7—C8	−60.4 (2)
C1—N1—C2—C3	−4.50 (18)	C12—C7—C8—C9	0.7 (3)
C7—N1—C2—C3	−178.60 (14)	N1—C7—C8—C9	−179.65 (17)
O2—C2—C3—C4	−70.3 (2)	C7—C8—C9—C10	−1.7 (3)
N1—C2—C3—C4	109.72 (15)	C8—C9—C10—C11	1.8 (3)
O2—C2—C3—C6	−168.49 (17)	C9—C10—C11—C12	−0.8 (3)
N1—C2—C3—C6	11.55 (17)	C8—C7—C12—C11	0.3 (3)
O2—C2—C3—Cl2	63.7 (2)	N1—C7—C12—C11	−179.41 (16)
N1—C2—C3—Cl2	−116.27 (12)	C10—C11—C12—C7	−0.2 (3)
C2—C3—C4—C5	−87.73 (15)	C19—C5—C13—C14	−83.26 (19)
C6—C3—C4—C5	17.49 (12)	C4—C5—C13—C14	146.32 (16)
Cl2—C3—C4—C5	142.12 (12)	C6—C5—C13—C14	46.4 (2)
C3—C4—C5—C13	−135.05 (14)	C19—C5—C13—C18	93.27 (17)
C3—C4—C5—C19	95.86 (14)	C4—C5—C13—C18	−37.2 (2)
C3—C4—C5—C6	−16.63 (12)	C6—C5—C13—C18	−137.08 (15)
O1—C1—C6—C3	−169.04 (16)	C18—C13—C14—C15	−0.3 (3)
N1—C1—C6—C3	12.17 (16)	C5—C13—C14—C15	176.20 (17)
O1—C1—C6—C5	95.95 (19)	C13—C14—C15—C16	0.0 (3)
N1—C1—C6—C5	−82.84 (15)	C14—C15—C16—C17	0.3 (3)
O1—C1—C6—Cl1	−41.9 (2)	C15—C16—C17—C18	−0.3 (3)
N1—C1—C6—Cl1	139.35 (11)	C16—C17—C18—C13	0.0 (3)
C4—C3—C6—C1	−133.45 (13)	C14—C13—C18—C17	0.3 (3)
C2—C3—C6—C1	−14.14 (16)	C5—C13—C18—C17	−176.37 (16)
Cl2—C3—C6—C1	105.21 (14)	C13—C5—C19—C20	47.1 (2)
C4—C3—C6—C5	−16.82 (12)	C4—C5—C19—C20	178.55 (14)
C2—C3—C6—C5	102.49 (13)	C6—C5—C19—C20	−85.18 (17)
Cl2—C3—C6—C5	−138.15 (12)	C13—C5—C19—C24	−131.90 (16)
C4—C3—C6—Cl1	102.86 (13)	C4—C5—C19—C24	−0.5 (2)
C2—C3—C6—Cl1	−137.83 (12)	C6—C5—C19—C24	95.79 (17)
Cl2—C3—C6—Cl1	−18.47 (17)	C24—C19—C20—C21	−1.3 (2)
C13—C5—C6—C1	−119.85 (15)	C5—C19—C20—C21	179.64 (16)
C19—C5—C6—C1	9.24 (17)	C19—C20—C21—C22	0.5 (3)
C4—C5—C6—C1	123.25 (14)	C20—C21—C22—C23	0.2 (3)
C13—C5—C6—C3	133.38 (14)	C21—C22—C23—C24	0.0 (3)
C19—C5—C6—C3	−97.53 (13)	C22—C23—C24—C19	−0.9 (3)
C4—C5—C6—C3	16.47 (11)	C20—C19—C24—C23	1.5 (2)
C13—C5—C6—Cl1	14.93 (18)	C5—C19—C24—C23	−179.46 (15)