1,5-Di­chloro-3,6-di­phenyl-3-aza­bi­cyclo­[3.2.0]­hept-6-ene-2,4-dione

In the title compound, C₁₈H₁₁Cl₂NO₂, the succin­imide and cyclo­butene rings are individually planar, with a dihedral angle of 66.02 (14)° between them. The crystal structure is stabilized by C—H...π interactions involving the phenyl rings.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.055
• wR factor = 0.132
• Data-to-parameter ratio = 18.5

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


 Alert Level C:



PLAT_716  Alert C H...A   Unknown or Inconsistent Label ........       \P(B)
                           H4A    \P(B)

PLAT_716  Alert C H...A   Unknown or Inconsistent Label ........       \P(B)
                           H8A    \P(B)

PLAT_716  Alert C H...A   Unknown or Inconsistent Label ........       \P(A)
                           H14A   \P(A)

PLAT_717  Alert C D...A   Unknown or Inconsistent Label ........       \P(B)
                           C4     \P(B)

PLAT_717  Alert C D...A   Unknown or Inconsistent Label ........       \P(B)
                           C8     \P(B)

PLAT_717  Alert C D...A   Unknown or Inconsistent Label ........       \P(A)
                           C14    \P(A)

PLAT_718  Alert C D-H..A  Unknown or Inconsistent label ........       \P(B)
                           C4     H4A    \P(B)

PLAT_718  Alert C D-H..A  Unknown or Inconsistent label ........       \P(B)
                           C8     H8A    \P(B)

PLAT_718  Alert C D-H..A  Unknown or Inconsistent label ........       \P(A)
                           C14    H14A   \P(A)


 0 Alert Level A = Potentially serious problem

 0 Alert Level B = Potential problem

 9 Alert Level C = Please check

---

S1. Comment

The photo-induced reactions of 1-phenyl-3,4-dichloromaleimide with diphenylethylene to give 3-azabicyclo[3.2.0]petanedione derivatives have been intensively investigated. Recently, we have reported the structure of one such derivative, 1,5-dichloro-3,6,6-triphenyl-3-azabicyclo[3.2.0]hepta-2,4-dione, (II) (Usman et al., 2001). In a continuation of this study, we have undertaken the X-ray structure analysis of the title compound, (I), a product obtained by the photoreaction of 1-phenyl-3,4-dichloromaleimide with phenylethylene.

In the succinimide–cyclobutene ring system of (I) (Fig. 1), the five-membered ring is planar compared to a half-chair conformation adopted in the succinimide–cyclobutane ring system of (II) (Usman et al., 2001). The mean plane through the five-membered ring, with N1 deviating by a maximum of -0.032 (2) Å, form a dihedral angle of 66.02 (14)° with the planar cyclobutene ring. The O1 and O2 atoms deviate from the plane of the attached ring by 0.047 (1) and 0.086 (1) Å, respectively. The phenyl ring substituent at C7 is almost coplanar with the cyclobutene [dihedral angle 12.86 (14)°], whereas that at N1 forms a dihedral of 74.83 (12)° with the five-membered ring.

The bond lengths and angles in (I) show normal values (Allen et al., 1987), and agree with those of (II) (Usman et al., 2001), except for the geometry of the cyclobutene ring (Table 1). The C7—C12 bond length of 1.521 (3) Å is slightly longer than that of the typical Csp³—Csp² bond distance and is considered to be the steric effect of the bulky substituent attached at C7. In the title molecule, C9 and C12 are the chiral center atoms.

In the crystal, the molecular packing is stabilized by C—H···π interactions (Table 2) involving the phenyl rings. In Table 2, π(A) and π(B) denote the centre of gravity of the pheny rings C1–C6 and C13–C18, respectively.

S2. Experimental

The title compound, (I), was prepared by a photoinduced [2 + 2] cycloaddition reaction. A solution of 1-phenyl-2,3-dichloromaleimide (0.05 M) and phenylethylene (0.2 M) in benzene (40 ml) was photolysed by irradiation of light using a medium-pressure mercury lamp through a Pyrex filter and under constant nitrogen purging. Single crystals suitable for X-ray diffraction were obtained from slow evaporation of petroleum ether–ethyl acetate solution.

S3. Refinement

After checking their presence in the difference map, all H atoms were geometrically fixed and allowed to ride on the parent C atoms and refined isotropically.

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.

1,5-Dichloro-3,6-diphenyl-3-azabicyclo[3.2.0]-hept-6-ene-2,4-dione

Crystal data

C18H11Cl2NO2	Dx = 1.438 Mg m^−3
Mr = 344.18	Melting point: 425K K
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 7.1468 (2) Å	Cell parameters from 7131 reflections
b = 14.8464 (5) Å	θ = 2.7–28.3°
c = 15.1091 (5) Å	µ = 0.42 mm^−1
β = 97.410 (1)°	T = 293 K
V = 1589.75 (9) Å^3	Slab, colorless
Z = 4	0.44 × 0.34 × 0.24 mm
F(000) = 704

Data collection

Siemens SMART CCD area-detector diffractometer	3864 independent reflections
Radiation source: fine-focus sealed tube	2514 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.084
Detector resolution: 8.33 pixels mm^-1	θmax = 28.3°, θmin = 2.7°
ω scans	h = −9→8
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996)	k = −19→19
Tmin = 0.838, Tmax = 0.907	l = −20→12
10982 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)] = 0.055	H-atom parameters constrained
wR(F^2) = 0.132	w = 1/[σ^2(Fo^2) + (0.0416P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 0.89	(Δ/σ)max < 0.001
3864 reflections	Δρmax = 0.38 e Å^−3
209 parameters	Δρmin = −0.43 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: 0.025 (2)

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	0.30319 (8)	0.57153 (4)	0.15060 (4)	0.0508 (2)
Cl2	0.05751 (8)	0.51319 (5)	0.30901 (4)	0.0594 (2)
O1	0.6777 (2)	0.64442 (10)	0.26076 (10)	0.0464 (4)
O2	0.3266 (2)	0.56671 (10)	0.48054 (10)	0.0486 (4)
N1	0.5330 (2)	0.61295 (11)	0.38447 (11)	0.0328 (4)
C1	0.6444 (3)	0.39557 (14)	0.21529 (13)	0.0347 (5)
C2	0.7193 (3)	0.43853 (15)	0.14621 (15)	0.0459 (6)
H2A	0.6700	0.4935	0.1248	0.055*
C3	0.8669 (4)	0.3997 (2)	0.10929 (18)	0.0600 (7)
H3A	0.9158	0.4284	0.0626	0.072*
C4	0.9420 (4)	0.3192 (2)	0.14115 (19)	0.0664 (8)
H4A	1.0437	0.2942	0.1172	0.080*
C5	0.8667 (4)	0.27549 (19)	0.20838 (19)	0.0623 (7)
H5A	0.9164	0.2204	0.2290	0.075*
C6	0.7183 (3)	0.31244 (15)	0.24559 (15)	0.0470 (6)
H6A	0.6674	0.2821	0.2908	0.056*
C7	0.4951 (3)	0.43752 (12)	0.25893 (13)	0.0333 (4)
C8	0.3941 (3)	0.41459 (14)	0.32373 (15)	0.0405 (5)
H8A	0.3830	0.3611	0.3547	0.049*
C9	0.3044 (3)	0.50597 (14)	0.32907 (14)	0.0362 (5)
C10	0.3805 (3)	0.56330 (13)	0.40906 (14)	0.0345 (5)
C11	0.5609 (3)	0.60431 (13)	0.29577 (13)	0.0327 (4)
C12	0.4226 (3)	0.53394 (13)	0.25349 (13)	0.0325 (4)
C13	0.6479 (3)	0.66940 (13)	0.44723 (12)	0.0333 (4)
C14	0.5749 (4)	0.74981 (15)	0.47258 (17)	0.0513 (6)
H14A	0.4548	0.7683	0.4485	0.062*
C15	0.6841 (5)	0.80231 (18)	0.53459 (19)	0.0650 (8)
H15A	0.6361	0.8564	0.5531	0.078*
C16	0.8616 (4)	0.7760 (2)	0.56919 (17)	0.0636 (8)
H16A	0.9338	0.8121	0.6107	0.076*
C17	0.9337 (4)	0.69586 (19)	0.54259 (16)	0.0557 (7)
H17A	1.0548	0.6780	0.5659	0.067*
C18	0.8260 (3)	0.64218 (15)	0.48137 (14)	0.0413 (5)
H18A	0.8737	0.5879	0.4633	0.050*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.0509 (4)	0.0541 (4)	0.0439 (3)	0.0078 (3)	−0.0069 (2)	0.0023 (3)
Cl2	0.0280 (3)	0.0772 (5)	0.0731 (5)	−0.0066 (3)	0.0064 (3)	−0.0184 (3)
O1	0.0522 (10)	0.0444 (9)	0.0452 (9)	−0.0121 (8)	0.0154 (7)	−0.0001 (7)
O2	0.0508 (10)	0.0531 (10)	0.0452 (9)	−0.0093 (8)	0.0195 (7)	−0.0088 (7)
N1	0.0346 (9)	0.0293 (9)	0.0350 (9)	−0.0044 (7)	0.0070 (7)	−0.0036 (7)
C1	0.0368 (11)	0.0275 (10)	0.0395 (11)	−0.0006 (8)	0.0038 (8)	−0.0092 (8)
C2	0.0531 (15)	0.0357 (12)	0.0508 (14)	0.0008 (10)	0.0146 (11)	−0.0039 (10)
C3	0.0591 (17)	0.0685 (18)	0.0568 (16)	−0.0032 (14)	0.0241 (12)	−0.0161 (14)
C4	0.0579 (18)	0.078 (2)	0.0649 (18)	0.0177 (15)	0.0121 (13)	−0.0283 (16)
C5	0.0688 (19)	0.0518 (15)	0.0636 (17)	0.0269 (14)	−0.0013 (13)	−0.0164 (13)
C6	0.0580 (15)	0.0370 (12)	0.0453 (13)	0.0055 (11)	0.0035 (10)	−0.0033 (10)
C7	0.0372 (11)	0.0256 (10)	0.0372 (11)	−0.0012 (8)	0.0054 (8)	−0.0037 (8)
C8	0.0459 (13)	0.0293 (11)	0.0480 (13)	−0.0047 (9)	0.0121 (10)	−0.0008 (9)
C9	0.0282 (10)	0.0374 (11)	0.0440 (12)	−0.0034 (9)	0.0086 (8)	−0.0066 (9)
C10	0.0318 (11)	0.0317 (11)	0.0408 (12)	0.0010 (8)	0.0078 (8)	−0.0016 (9)
C11	0.0359 (11)	0.0258 (10)	0.0368 (11)	0.0044 (8)	0.0066 (8)	0.0028 (8)
C12	0.0323 (11)	0.0303 (10)	0.0346 (10)	0.0023 (8)	0.0030 (8)	0.0010 (8)
C13	0.0394 (12)	0.0304 (10)	0.0309 (10)	−0.0060 (9)	0.0073 (8)	−0.0020 (8)
C14	0.0559 (16)	0.0394 (13)	0.0571 (15)	0.0040 (11)	0.0021 (11)	−0.0094 (11)
C15	0.087 (2)	0.0429 (15)	0.0659 (17)	−0.0083 (14)	0.0124 (15)	−0.0236 (13)
C16	0.079 (2)	0.0665 (19)	0.0457 (15)	−0.0360 (16)	0.0079 (13)	−0.0167 (13)
C17	0.0433 (14)	0.0727 (19)	0.0495 (14)	−0.0180 (13)	0.0001 (10)	0.0032 (13)
C18	0.0393 (12)	0.0427 (13)	0.0429 (12)	−0.0044 (10)	0.0092 (9)	0.0012 (10)

Geometric parameters (Å, º)

Cl1—C12	1.765 (2)	C7—C8	1.333 (3)
Cl2—C9	1.755 (2)	C7—C12	1.521 (3)
O1—C11	1.202 (2)	C8—C9	1.507 (3)
O2—C10	1.194 (2)	C8—H8A	0.93
N1—C11	1.386 (2)	C9—C10	1.520 (3)
N1—C10	1.404 (2)	C9—C12	1.562 (3)
N1—C13	1.441 (3)	C11—C12	1.521 (3)
C1—C2	1.388 (3)	C13—C18	1.371 (3)
C1—C6	1.396 (3)	C13—C14	1.377 (3)
C1—C7	1.464 (3)	C14—C15	1.381 (4)
C2—C3	1.382 (3)	C14—H14A	0.93
C2—H2A	0.93	C15—C16	1.366 (4)
C3—C4	1.372 (4)	C15—H15A	0.93
C3—H3A	0.93	C16—C17	1.376 (4)
C4—C5	1.372 (4)	C16—H16A	0.93
C4—H4A	0.93	C17—C18	1.378 (3)
C5—C6	1.377 (3)	C17—H17A	0.93
C5—H5A	0.93	C18—H18A	0.93
C6—H6A	0.93
C11—N1—C10	114.88 (17)	C12—C9—Cl2	118.95 (15)
C11—N1—C13	123.30 (16)	O2—C10—N1	124.69 (19)
C10—N1—C13	121.82 (16)	O2—C10—C9	128.22 (19)
C2—C1—C6	119.13 (19)	N1—C10—C9	107.09 (16)
C2—C1—C7	121.15 (19)	O1—C11—N1	125.1 (2)
C6—C1—C7	119.68 (19)	O1—C11—C12	127.31 (19)
C3—C2—C1	120.0 (2)	N1—C11—C12	107.61 (16)
C3—C2—H2A	120.0	C7—C12—C11	115.17 (17)
C1—C2—H2A	120.0	C7—C12—C9	85.58 (14)
C4—C3—C2	120.4 (2)	C11—C12—C9	105.01 (16)
C4—C3—H3A	119.8	C7—C12—Cl1	117.90 (15)
C2—C3—H3A	119.8	C11—C12—Cl1	111.52 (14)
C3—C4—C5	119.9 (2)	C9—C12—Cl1	118.86 (14)
C3—C4—H4A	120.0	C18—C13—C14	121.2 (2)
C5—C4—H4A	120.0	C18—C13—N1	119.94 (18)
C4—C5—C6	120.7 (2)	C14—C13—N1	118.9 (2)
C4—C5—H5A	119.7	C13—C14—C15	118.5 (3)
C6—C5—H5A	119.7	C13—C14—H14A	120.8
C5—C6—C1	119.8 (2)	C15—C14—H14A	120.8
C5—C6—H6A	120.1	C16—C15—C14	120.9 (2)
C1—C6—H6A	120.1	C16—C15—H15A	119.5
C8—C7—C1	135.83 (19)	C14—C15—H15A	119.5
C8—C7—C12	93.84 (16)	C15—C16—C17	120.0 (2)
C1—C7—C12	129.73 (17)	C15—C16—H16A	120.0
C7—C8—C9	94.81 (17)	C17—C16—H16A	120.0
C7—C8—H8A	132.6	C16—C17—C18	119.9 (3)
C9—C8—H8A	132.6	C16—C17—H17A	120.1
C8—C9—C10	115.81 (18)	C18—C17—H17A	120.1
C8—C9—C12	85.76 (15)	C13—C18—C17	119.5 (2)
C10—C9—C12	105.10 (16)	C13—C18—H18A	120.2
C8—C9—Cl2	118.11 (15)	C17—C18—H18A	120.2
C10—C9—Cl2	110.61 (13)
C6—C1—C2—C3	−1.0 (4)	C1—C7—C12—C11	−67.8 (3)
C7—C1—C2—C3	176.6 (2)	C8—C7—C12—C9	−0.26 (17)
C1—C2—C3—C4	−0.7 (4)	C1—C7—C12—C9	−172.4 (2)
C2—C3—C4—C5	1.8 (4)	C8—C7—C12—Cl1	−120.72 (17)
C3—C4—C5—C6	−1.2 (4)	C1—C7—C12—Cl1	67.2 (3)
C4—C5—C6—C1	−0.6 (4)	O1—C11—C12—C7	88.5 (3)
C2—C1—C6—C5	1.7 (3)	N1—C11—C12—C7	−89.78 (19)
C7—C1—C6—C5	−176.0 (2)	O1—C11—C12—C9	−179.3 (2)
C2—C1—C7—C8	178.6 (3)	N1—C11—C12—C9	2.4 (2)
C6—C1—C7—C8	−3.8 (4)	O1—C11—C12—Cl1	−49.3 (3)
C2—C1—C7—C12	−12.7 (3)	N1—C11—C12—Cl1	132.40 (14)
C6—C1—C7—C12	164.9 (2)	C8—C9—C12—C7	0.23 (15)
C1—C7—C8—C9	171.5 (2)	C10—C9—C12—C7	115.84 (17)
C12—C7—C8—C9	0.27 (18)	Cl2—C9—C12—C7	−119.69 (16)
C7—C8—C9—C10	−105.0 (2)	C8—C9—C12—C11	−114.66 (17)
C7—C8—C9—C12	−0.27 (17)	C10—C9—C12—C11	0.9 (2)
C7—C8—C9—Cl2	120.45 (17)	Cl2—C9—C12—C11	125.42 (15)
C11—N1—C10—O2	−174.8 (2)	C8—C9—C12—Cl1	119.79 (16)
C13—N1—C10—O2	4.2 (3)	C10—C9—C12—Cl1	−124.61 (16)
C11—N1—C10—C9	6.0 (2)	Cl2—C9—C12—Cl1	−0.1 (2)
C13—N1—C10—C9	−175.04 (17)	C11—N1—C13—C18	−75.6 (3)
C8—C9—C10—O2	−90.5 (3)	C10—N1—C13—C18	105.5 (2)
C12—C9—C10—O2	176.9 (2)	C11—N1—C13—C14	105.1 (2)
Cl2—C9—C10—O2	47.3 (3)	C10—N1—C13—C14	−73.8 (3)
C8—C9—C10—N1	88.7 (2)	C18—C13—C14—C15	−1.0 (3)
C12—C9—C10—N1	−3.9 (2)	N1—C13—C14—C15	178.2 (2)
Cl2—C9—C10—N1	−133.50 (15)	C13—C14—C15—C16	0.9 (4)
C10—N1—C11—O1	176.3 (2)	C14—C15—C16—C17	−0.3 (4)
C13—N1—C11—O1	−2.7 (3)	C15—C16—C17—C18	−0.3 (4)
C10—N1—C11—C12	−5.4 (2)	C14—C13—C18—C17	0.4 (3)
C13—N1—C11—C12	175.68 (17)	N1—C13—C18—C17	−178.83 (18)
C8—C7—C12—C11	104.3 (2)	C16—C17—C18—C13	0.3 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4A···π(B)^i	0.93	2.74	3.618 (3)	159
C8—H8A···π(B)^ii	0.93	2.71	3.528 (2)	147
C14—H14A···π(A)^iii	0.93	2.76	3.612 (3)	153

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