Julolidine-1,6-dione

The title mol­ecule, C₁₂H₁₁NO₂, has crystallographic mirror symmetry. Weak inter­molecular C—H...O hydrogen bonds help stabilize the crystal structure.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.061
• wR factor = 0.163
• Data-to-parameter ratio = 16.0

checkCIF/PLATON results

No syntax errors found



Alert level B
ABSTM02_ALERT_3_B  The ratio of expected to reported Tmax/Tmin(RR') is < 0.75
            Tmin and Tmax reported:      0.720     1.000
            Tmin(prime) and Tmax expected:      0.986     0.986
            RR(prime) =      0.720
            Please check that your absorption correction is appropriate.
PLAT061_ALERT_3_B Tmax/Tmin Range Test RR' too Large .............       0.72

Alert level C
PLAT062_ALERT_4_C Rescale T(min) & T(max) by .....................       0.99

Alert level G
ABSTM02_ALERT_3_G  When printed, the submitted absorption T values will be
            replaced by the scaled T values. Since the ratio of scaled T's
            is identical to the ratio of reported T values, the scaling
            does not imply a change to the absorption corrections used in
            the study.
            Ratio of Tmax expected/reported      0.986
            Tmax scaled      0.986 Tmin scaled      0.710
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature .        293 K

   0 ALERT level A = In general: serious problem
   2 ALERT level B = Potentially serious problem
   1 ALERT level C = Check and explain
   3 ALERT level G = General alerts; check

   2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 ALERT type 2 Indicator that the structure model may be wrong or deficient
   3 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

The title compound, belongs to a class of 4-dihydroquinolinone derivatives (William, et al.,1949), which have hitherto received relatively little attention. We have recently found that the title compound undergoes two-photon absorption and two-photon excited fluorescence and is therefore of interest in the study of non-linear optics. An X-ray crystal structure determination of was undertaken in order to elucidate the conformation, and the results are presented here.

The bond lengths observed in the phenyl rings is comparable with average values reported in the literature (Domenicano et al.,1975; Allen et al., 1987). Atom C7 deviates by 0.493 (2) Å from the benzene ring. The mean plane through atoms O1/C5/C6 is twisted from the plane of the benzene ring by 7.5 (2) °, while in acetophenone the acetyl group is essentially co-planar with benzene ring. This twist is most likely due to the strain imposed by sp³-hybridized atoms C6 and C7 in the adjacent ring. The N atom lies approximately in the plane of the benzene ring with a deviation of 0.023 (2) Å, as might be expected for maximum conjugation normally found for N atom substituents on benzene rings. Weak intermolecular C—H···O hydrogen bonds help stabilize the crystal structure.

Related literature

For related literature, see: William et al. (1949); Domenicano et al. (1975); Allen et al. (1987).

S2. Experimental

Melting points were determined with a Yanagimoto MP-35 melting-point apparatus and were uncorrected. The ¹H NMR spectra were measured with a Bruker DRX (500 MHz) (relative to TMS) spectrometer. The solid state IR spectra were recorded from KBr discs on a Nicolet-170.

A mixture of N, N-bis-2-cyanoethylanilne (10 g, 0.055 mol), powdered aluminium chloride (55 g, 0.422 mol), 30 ml chlorobenzeneand 1.5 ml concentrated hydrochloric acid was vigorously stirred at 433 K for 8 h. After cooling, the red oily mixture was hydrolysed with 200 ml ice water,and distilled in steam to remove chlorobenzene. The residue was recrystallized from ethanol to afford a yellow solid. Yield: 8.5 g (85%); m. p. 415 - 416 K. IR (KBr): ν = 1676 cm^-1 (C═O). ¹H NMR (500 MHz, CDCl₃): δ 2.83–2.86 (t, 4H, 2CH₂, J = 7.0 Hz), 3.49–3.52 (t, 4H, 2CH₂, J = 7.0 Hz), 6.86–6.89 (t, 1H, ArH, J = 7.5 Hz), 8.11–8.12 (d, 2H, ArH, J = 8.0 Hz). Single crystals suitable for crystallographic analysis were obtained by slow evaporation of a methanol water (4:1 v/v)solution.

S3. Refinement

H atoms were placed in calculated positions with C—H = 0.93–0.97 Å and included in the refinement in the riding-model approximation with U_iso(H) = 1.2U_eq(C).

Computing details

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Sheldrick, 1999); software used to prepare material for publication: SHELXTL (Sheldrick, 1999).

Figures

Fig. 1. The molecular structure with displacement ellipsoids were drawn at the 30% probability level [symmetry code: (A) x, -y + 1/2, z].

julolidine-1,6-dione

Crystal data

C12H11NO2	F(000) = 424
Mr = 201.22	Dx = 1.357 Mg m^−3
Orthorhombic, Pnma	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2n	Cell parameters from 7909 reflections
a = 10.069 (2) Å	θ = 3.3–28.9°
b = 14.081 (3) Å	µ = 0.09 mm^−1
c = 6.9452 (14) Å	T = 293 K
V = 984.7 (3) Å^3	Block, colorless
Z = 4	0.15 × 0.15 × 0.15 mm

Data collection

Rigaku Mercury2 diffractometer	1170 independent reflections
Radiation source: fine-focus sealed tube	767 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.086
Detector resolution: 13.6612 pixels mm^-1	θmax = 27.5°, θmin = 3.3°
ω scans	h = −13→13
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −18→18
Tmin = 0.720, Tmax = 1.00	l = −9→9
9450 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.061	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.163	H-atom parameters constrained
S = 1.10	w = 1/[σ^2(Fo^2) + (0.076P)^2 + 0.0053P] where P = (Fo^2 + 2Fc^2)/3
1170 reflections	(Δ/σ)max < 0.001
73 parameters	Δρmax = 0.15 e Å^−3
0 restraints	Δρmin = −0.19 e Å^−3

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
C1	0.2702 (3)	0.2500	1.2858 (4)	0.0675 (9)
H1A	0.2326	0.2500	1.4080	0.081*
C2	0.2983 (2)	0.16584 (14)	1.1947 (3)	0.0578 (6)
H2A	0.2760	0.1089	1.2545	0.069*
C3	0.35918 (18)	0.16362 (13)	1.0158 (2)	0.0469 (5)
C4	0.3938 (2)	0.2500	0.9238 (3)	0.0423 (6)
C5	0.37694 (18)	0.07268 (15)	0.9155 (3)	0.0529 (5)
C6	0.4347 (2)	0.07766 (16)	0.7178 (3)	0.0643 (6)
H6A	0.3633	0.0809	0.6242	0.077*
H6B	0.4852	0.0203	0.6928	0.077*
C7	0.5239 (2)	0.16269 (14)	0.6933 (3)	0.0613 (6)
H7A	0.6025	0.1548	0.7725	0.074*
H7B	0.5521	0.1670	0.5601	0.074*
O1	0.34091 (15)	−0.00237 (11)	0.9865 (2)	0.0714 (5)
N1	0.4561 (2)	0.2500	0.7476 (3)	0.0506 (6)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.090 (2)	0.071 (2)	0.0412 (15)	0.000	0.0151 (14)	0.000
C2	0.0705 (13)	0.0577 (13)	0.0450 (11)	−0.0091 (10)	0.0034 (9)	0.0066 (9)
C3	0.0479 (10)	0.0494 (12)	0.0435 (11)	−0.0025 (7)	−0.0032 (7)	−0.0006 (8)
C4	0.0389 (12)	0.0524 (16)	0.0356 (12)	0.000	−0.0048 (10)	0.000
C5	0.0513 (11)	0.0526 (12)	0.0548 (12)	−0.0049 (9)	−0.0075 (9)	−0.0041 (9)
C6	0.0735 (14)	0.0618 (14)	0.0576 (12)	0.0065 (11)	−0.0012 (10)	−0.0175 (9)
C7	0.0589 (12)	0.0700 (16)	0.0549 (12)	0.0059 (10)	0.0125 (9)	−0.0053 (9)
O1	0.0794 (11)	0.0532 (10)	0.0815 (11)	−0.0125 (7)	0.0014 (7)	−0.0043 (7)
N1	0.0511 (12)	0.0577 (15)	0.0429 (12)	0.000	0.0085 (9)	0.000

Geometric parameters (Å, º)

C1—C2^i	1.373 (2)	C5—O1	1.221 (2)
C1—C2	1.373 (2)	C5—C6	1.493 (3)
C1—H1A	0.9300	C6—C7	1.506 (3)
C2—C3	1.386 (3)	C6—H6A	0.9700
C2—H2A	0.9300	C6—H6B	0.9700
C3—C4	1.417 (2)	C7—N1	1.456 (2)
C3—C5	1.469 (3)	C7—H7A	0.9700
C4—N1	1.376 (3)	C7—H7B	0.9700
C4—C3^i	1.417 (2)	N1—C7^i	1.456 (2)
C2^i—C1—C2	119.4 (2)	C3—C5—C6	116.30 (18)
C2^i—C1—H1A	120.3	C5—C6—C7	111.92 (16)
C2—C1—H1A	120.3	C5—C6—H6A	109.2
C1—C2—C3	121.6 (2)	C7—C6—H6A	109.2
C1—C2—H2A	119.2	C5—C6—H6B	109.2
C3—C2—H2A	119.2	C7—C6—H6B	109.2
C2—C3—C4	119.56 (18)	H6A—C6—H6B	107.9
C2—C3—C5	119.94 (18)	N1—C7—C6	111.27 (17)
C4—C3—C5	120.29 (16)	N1—C7—H7A	109.4
N1—C4—C3^i	120.87 (11)	C6—C7—H7A	109.4
N1—C4—C3	120.87 (11)	N1—C7—H7B	109.4
C3^i—C4—C3	118.2 (2)	C6—C7—H7B	109.4
O1—C5—C3	121.77 (18)	H7A—C7—H7B	108.0
O1—C5—C6	121.85 (19)

Symmetry code: (i) x, −y+1/2, z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2A···O1^ii	0.93	2.50	3.372 (3)	157
C6—H6A···O1^iii	0.97	2.52	3.377 (3)	147

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