1,5-Bis(4-chloro­phen­yl)-3-phenyl­pentane-1,5-dione

The title compound, C₂₃H₁₈Cl₂O₂, is the reaction product of a Michael addition. The two chloro­phenyl rings are almost perpendicular to the phenyl ring.

Key indicators

• Single-crystal X-ray study
• T = 153 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.036
• wR factor = 0.095
• Data-to-parameter ratio = 17.8

checkCIF/PLATON results

No syntax errors found



Alert level C
ABSTM02_ALERT_3_C  The ratio of expected to reported Tmax/Tmin(RR') is < 0.90
            Tmin and Tmax reported:      0.789     0.984
            Tmin(prime) and Tmax expected:      0.811     0.906
            RR(prime) =      0.896
            Please check that your absorption correction is appropriate.
PLAT061_ALERT_3_C Tmax/Tmin Range Test RR' too Large .............       0.89
PLAT062_ALERT_4_C Rescale T(min) & T(max) by .....................       0.92

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      0.920
            Tmax scaled      0.906 Tmin scaled      0.727

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

   0 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

---

S1. Comment

The Michael addition is one of the most important C—C bond forming reactions employed in organic synthesis (Qian & Widenhoefer, 2003). In recent years, the catalytic asymmetric Michael addition promoted by chiral metal complexes has been recognized as an efficient method for carbon-carbon bond formation (Emori et al., 1998). The asymmetric catalyzers of Michael reaction have metal catalyzers such as La₃(O-^tBu)₉, Y₃(O-^tBu)₈Cl, Y₅(O-ⁱPr)₁₃O (Sasai et al., 1994), lithium diisopropylamide (Murai et al., 2000), and non-metal catalyzers that includes MacMillan's chiral imidazolidinone (Wang et al., 2005). We synthesized 1,5-bis(4-chlorophenyl)-3-phenylpentane-1,5-dione with tetrabutylammonium bromide. The two chlorophenyl rings are almost perpendicular to the central phenyl ring.

Related literature

For related literature, see: Emori et al. (1998); Sasai et al. (1994); Murai et al. (2000); Wang & Shen (1999); Wang et al. (2005).

For related literature, see: Hua (2003).

S2. Experimental

A mixture of 1-(4-chloro-phenyl)-3-phenyl-2-propylene-1-ketone (Wang & Shen, 1999) (1 mmol), 4-chloro-acetopnone (2 mmol) and tetrabutylammonium-bromide (0.1 mmol) was dissolved in toluene (5 mL). To this mixture was added 50% KOH (1 mL) and stirred at room temperature for 24 h. The reaction was quenched with water and extracted with ether (3 times with 10 mL). The combined organic layers were dried (Na₂SO₄), concentrated to furnish the crude product, which was purified by flash chromatography (yield 54%). M.p. 463 k. Analysis, found (calculated for C₂₃H₁₈Cl₂O₂): C 69.53 (69.55%) H 4.57 (4.53%) O 8.05 (8.11%). Crystals were grown from a mixture of ethyl acetate and petroleum ether by slow evaporation.

S3. Refinement

H atoms were positioned geometrically, with C—H ranging from 0.95 - 1.00Å and U_iso(H) = 1.2Ueq(C).

Computing details

Data collection: RAPID-AUTO (Rigaku, 2004); cell refinement: RAPID-AUTO; data reduction: RAPID-AUTO; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2001); software used to prepare material for publication: SHELXTL.

Figures

Fig. 1. A view of the molecule structure of (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii.

1,5-Bis(4-chlorophenyl)-3-phenylpentane-1,5-dione

Crystal data

C23H18Cl2O2	F(000) = 824
Mr = 397.27	Dx = 1.378 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 17167 reflections
a = 15.5591 (4) Å	θ = 3.1–27.5°
b = 10.7610 (3) Å	µ = 0.35 mm^−1
c = 11.6784 (3) Å	T = 153 K
β = 101.616 (1)°	Platelet, colorless
V = 1915.28 (9) Å^3	0.58 × 0.42 × 0.28 mm
Z = 4

Data collection

Rigaku R-AXIS SPIDER diffractometer	4359 independent reflections
Radiation source: Rotating Anode	4090 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.018
ω scans	θmax = 27.5°, θmin = 3.1°
Absorption correction: empirical (using intensity measurements) (ABSCOR; Higashi, 1995)	h = −20→19
Tmin = 0.790, Tmax = 0.984	k = −13→13
18363 measured reflections	l = −14→15

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)] = 0.036	H-atom parameters constrained
wR(F^2) = 0.096	w = 1/[σ^2(Fo^2) + (0.0463P)^2 + 1.0487P] where P = (Fo^2 + 2Fc^2)/3
S = 1.02	(Δ/σ)max = 0.004
4359 reflections	Δρmax = 0.55 e Å^−3
245 parameters	Δρmin = −0.57 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: 0.0082 (11)

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	0.06138 (3)	0.71183 (4)	0.28055 (3)	0.04330 (13)
Cl2	0.45939 (3)	−0.37752 (3)	1.07691 (4)	0.04019 (12)
O1	0.27113 (7)	0.59521 (9)	0.82643 (9)	0.0334 (2)
O2	0.39430 (7)	0.23645 (9)	1.09861 (9)	0.0302 (2)
C1	0.14266 (11)	0.48713 (14)	0.55234 (12)	0.0345 (3)
H1A	0.1349	0.4028	0.5719	0.041*
C2	0.10076 (11)	0.53260 (15)	0.44387 (13)	0.0376 (3)
H2A	0.0637	0.4802	0.3898	0.045*
C3	0.11383 (9)	0.65468 (14)	0.41596 (11)	0.0290 (3)
C4	0.16723 (10)	0.73318 (14)	0.49289 (12)	0.0311 (3)
H4A	0.1761	0.8168	0.4719	0.037*
C5	0.20748 (9)	0.68735 (13)	0.60125 (12)	0.0274 (3)
H5A	0.2437	0.7407	0.6554	0.033*
C6	0.19580 (8)	0.56417 (12)	0.63229 (11)	0.0228 (3)
C7	0.24130 (8)	0.52038 (12)	0.75086 (11)	0.0230 (3)
C8	0.25264 (9)	0.38214 (12)	0.77148 (11)	0.0255 (3)
H8A	0.2932	0.3500	0.7231	0.031*
H8B	0.1952	0.3410	0.7448	0.031*
C9	0.28827 (8)	0.34624 (11)	0.89939 (11)	0.0214 (2)
H9A	0.3416	0.3976	0.9297	0.026*
C10	0.22093 (8)	0.37083 (11)	0.97502 (11)	0.0206 (2)
C11	0.13589 (9)	0.32426 (13)	0.94369 (12)	0.0277 (3)
H11A	0.1201	0.2751	0.8751	0.033*
C12	0.07355 (9)	0.34871 (15)	1.01146 (14)	0.0333 (3)
H12A	0.0159	0.3162	0.9889	0.040*
C13	0.09565 (9)	0.42023 (14)	1.11146 (13)	0.0310 (3)
H13A	0.0532	0.4375	1.1575	0.037*
C14	0.18007 (10)	0.46638 (13)	1.14393 (12)	0.0297 (3)
H14A	0.1957	0.5152	1.2128	0.036*
C15	0.24218 (9)	0.44168 (12)	1.07642 (11)	0.0255 (3)
H15A	0.3000	0.4736	1.0999	0.031*
C16	0.31568 (9)	0.20906 (12)	0.90226 (11)	0.0239 (3)
H16A	0.2621	0.1574	0.8823	0.029*
H16B	0.3503	0.1953	0.8410	0.029*
C17	0.36896 (8)	0.16484 (12)	1.01783 (11)	0.0229 (3)
C18	0.39015 (8)	0.02895 (12)	1.03035 (11)	0.0225 (3)
C19	0.43314 (9)	−0.01583 (13)	1.13895 (12)	0.0269 (3)
H19A	0.4482	0.0400	1.2029	0.032*
C20	0.45433 (9)	−0.14104 (13)	1.15504 (13)	0.0292 (3)
H20A	0.4831	−0.1714	1.2292	0.035*
C21	0.43236 (9)	−0.22036 (12)	1.06020 (13)	0.0278 (3)
C22	0.38999 (9)	−0.17912 (13)	0.95109 (13)	0.0294 (3)
H22A	0.3756	−0.2352	0.8873	0.035*
C23	0.36897 (9)	−0.05401 (13)	0.93699 (12)	0.0264 (3)
H23A	0.3397	−0.0243	0.8627	0.032*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.0490 (2)	0.0551 (3)	0.02385 (18)	0.02066 (18)	0.00284 (15)	0.00384 (15)
Cl2	0.0380 (2)	0.02220 (18)	0.0565 (3)	0.00195 (13)	0.00033 (17)	0.00760 (15)
O1	0.0477 (6)	0.0244 (5)	0.0251 (5)	−0.0049 (4)	0.0000 (4)	−0.0019 (4)
O2	0.0327 (5)	0.0267 (5)	0.0296 (5)	0.0024 (4)	0.0029 (4)	−0.0044 (4)
C1	0.0467 (8)	0.0272 (7)	0.0275 (7)	−0.0051 (6)	0.0025 (6)	−0.0022 (5)
C2	0.0452 (8)	0.0380 (8)	0.0261 (7)	−0.0040 (7)	−0.0013 (6)	−0.0055 (6)
C3	0.0296 (7)	0.0379 (7)	0.0201 (6)	0.0109 (6)	0.0068 (5)	0.0014 (5)
C4	0.0367 (7)	0.0281 (7)	0.0293 (7)	0.0030 (6)	0.0089 (6)	0.0051 (5)
C5	0.0305 (7)	0.0259 (7)	0.0256 (6)	−0.0019 (5)	0.0052 (5)	0.0006 (5)
C6	0.0254 (6)	0.0235 (6)	0.0207 (6)	0.0013 (5)	0.0076 (5)	−0.0010 (5)
C7	0.0264 (6)	0.0222 (6)	0.0216 (6)	−0.0013 (5)	0.0080 (5)	−0.0004 (5)
C8	0.0360 (7)	0.0209 (6)	0.0211 (6)	0.0007 (5)	0.0092 (5)	−0.0001 (5)
C9	0.0240 (6)	0.0194 (6)	0.0218 (6)	0.0009 (4)	0.0067 (5)	−0.0001 (4)
C10	0.0237 (6)	0.0178 (5)	0.0206 (5)	0.0039 (4)	0.0053 (5)	0.0039 (4)
C11	0.0260 (6)	0.0285 (7)	0.0285 (7)	−0.0002 (5)	0.0054 (5)	−0.0028 (5)
C12	0.0236 (6)	0.0373 (8)	0.0404 (8)	−0.0002 (5)	0.0097 (6)	0.0025 (6)
C13	0.0319 (7)	0.0332 (7)	0.0320 (7)	0.0096 (6)	0.0159 (6)	0.0073 (6)
C14	0.0374 (7)	0.0295 (7)	0.0231 (6)	0.0062 (6)	0.0086 (5)	−0.0012 (5)
C15	0.0260 (6)	0.0260 (6)	0.0246 (6)	0.0012 (5)	0.0053 (5)	−0.0005 (5)
C16	0.0258 (6)	0.0214 (6)	0.0250 (6)	0.0034 (5)	0.0062 (5)	−0.0011 (5)
C17	0.0196 (5)	0.0242 (6)	0.0261 (6)	0.0021 (5)	0.0075 (5)	0.0000 (5)
C18	0.0180 (5)	0.0238 (6)	0.0267 (6)	0.0008 (4)	0.0067 (5)	0.0012 (5)
C19	0.0239 (6)	0.0296 (7)	0.0268 (6)	0.0021 (5)	0.0044 (5)	0.0001 (5)
C20	0.0245 (6)	0.0316 (7)	0.0309 (7)	0.0021 (5)	0.0042 (5)	0.0071 (5)
C21	0.0216 (6)	0.0211 (6)	0.0406 (7)	−0.0001 (5)	0.0063 (5)	0.0053 (5)
C22	0.0281 (6)	0.0231 (6)	0.0356 (7)	−0.0015 (5)	0.0031 (6)	−0.0022 (5)
C23	0.0254 (6)	0.0247 (6)	0.0276 (6)	0.0006 (5)	0.0020 (5)	0.0011 (5)

Geometric parameters (Å, º)

Cl1—C3	1.7393 (14)	C11—C12	1.3949 (19)
Cl2—C21	1.7441 (14)	C11—H11A	0.9500
O1—C7	1.2156 (16)	C12—C13	1.383 (2)
O2—C17	1.2204 (16)	C12—H12A	0.9500
C1—C6	1.3899 (19)	C13—C14	1.384 (2)
C1—C2	1.392 (2)	C13—H13A	0.9500
C1—H1A	0.9500	C14—C15	1.3904 (19)
C2—C3	1.378 (2)	C14—H14A	0.9500
C2—H2A	0.9500	C15—H15A	0.9500
C3—C4	1.382 (2)	C16—C17	1.5115 (18)
C4—C5	1.3849 (19)	C16—H16A	0.9900
C4—H4A	0.9500	C16—H16B	0.9900
C5—C6	1.3956 (18)	C17—C18	1.4997 (17)
C5—H5A	0.9500	C18—C19	1.3952 (18)
C6—C7	1.4986 (17)	C18—C23	1.3963 (18)
C7—C8	1.5115 (17)	C19—C20	1.391 (2)
C8—C9	1.5345 (17)	C19—H19A	0.9500
C8—H8A	0.9900	C20—C21	1.386 (2)
C8—H8B	0.9900	C20—H20A	0.9500
C9—C10	1.5232 (16)	C21—C22	1.384 (2)
C9—C16	1.5351 (17)	C22—C23	1.3875 (19)
C9—H9A	1.0000	C22—H22A	0.9500
C10—C15	1.3911 (18)	C23—H23A	0.9500
C10—C11	1.3930 (18)
C6—C1—C2	120.53 (14)	C13—C12—C11	120.07 (13)
C6—C1—H1A	119.7	C13—C12—H12A	120.0
C2—C1—H1A	119.7	C11—C12—H12A	120.0
C3—C2—C1	119.08 (14)	C12—C13—C14	119.47 (12)
C3—C2—H2A	120.5	C12—C13—H13A	120.3
C1—C2—H2A	120.5	C14—C13—H13A	120.3
C2—C3—C4	121.78 (13)	C13—C14—C15	120.38 (13)
C2—C3—Cl1	119.17 (11)	C13—C14—H14A	119.8
C4—C3—Cl1	119.04 (11)	C15—C14—H14A	119.8
C3—C4—C5	118.58 (13)	C14—C15—C10	120.95 (12)
C3—C4—H4A	120.7	C14—C15—H15A	119.5
C5—C4—H4A	120.7	C10—C15—H15A	119.5
C4—C5—C6	121.13 (13)	C17—C16—C9	114.98 (10)
C4—C5—H5A	119.4	C17—C16—H16A	108.5
C6—C5—H5A	119.4	C9—C16—H16A	108.5
C1—C6—C5	118.88 (12)	C17—C16—H16B	108.5
C1—C6—C7	122.65 (12)	C9—C16—H16B	108.5
C5—C6—C7	118.46 (12)	H16A—C16—H16B	107.5
O1—C7—C6	120.18 (12)	O2—C17—C18	120.65 (12)
O1—C7—C8	121.40 (12)	O2—C17—C16	121.68 (12)
C6—C7—C8	118.35 (11)	C18—C17—C16	117.67 (11)
C7—C8—C9	114.24 (11)	C19—C18—C23	118.92 (12)
C7—C8—H8A	108.7	C19—C18—C17	118.76 (12)
C9—C8—H8A	108.7	C23—C18—C17	122.32 (12)
C7—C8—H8B	108.7	C20—C19—C18	120.97 (13)
C9—C8—H8B	108.7	C20—C19—H19A	119.5
H8A—C8—H8B	107.6	C18—C19—H19A	119.5
C10—C9—C8	111.40 (10)	C21—C20—C19	118.37 (13)
C10—C9—C16	112.02 (10)	C21—C20—H20A	120.8
C8—C9—C16	107.92 (10)	C19—C20—H20A	120.8
C10—C9—H9A	108.5	C22—C21—C20	122.23 (13)
C8—C9—H9A	108.5	C22—C21—Cl2	118.24 (11)
C16—C9—H9A	108.5	C20—C21—Cl2	119.52 (11)
C15—C10—C11	118.11 (12)	C21—C22—C23	118.52 (13)
C15—C10—C9	121.02 (11)	C21—C22—H22A	120.7
C11—C10—C9	120.87 (11)	C23—C22—H22A	120.7
C10—C11—C12	121.02 (13)	C22—C23—C18	120.98 (12)
C10—C11—H11A	119.5	C22—C23—H23A	119.5
C12—C11—H11A	119.5	C18—C23—H23A	119.5
C6—C1—C2—C3	1.1 (2)	C10—C11—C12—C13	0.0 (2)
C1—C2—C3—C4	−0.2 (2)	C11—C12—C13—C14	−0.5 (2)
C1—C2—C3—Cl1	−179.88 (12)	C12—C13—C14—C15	0.3 (2)
C2—C3—C4—C5	−0.8 (2)	C13—C14—C15—C10	0.3 (2)
Cl1—C3—C4—C5	178.91 (10)	C11—C10—C15—C14	−0.65 (19)
C3—C4—C5—C6	0.9 (2)	C9—C10—C15—C14	178.53 (12)
C2—C1—C6—C5	−1.0 (2)	C10—C9—C16—C17	−68.81 (14)
C2—C1—C6—C7	179.07 (13)	C8—C9—C16—C17	168.21 (11)
C4—C5—C6—C1	0.0 (2)	C9—C16—C17—O2	−6.14 (17)
C4—C5—C6—C7	179.93 (12)	C9—C16—C17—C18	173.98 (10)
C1—C6—C7—O1	−164.12 (14)	O2—C17—C18—C19	5.18 (18)
C5—C6—C7—O1	15.91 (18)	C16—C17—C18—C19	−174.94 (11)
C1—C6—C7—C8	18.73 (19)	O2—C17—C18—C23	−174.32 (12)
C5—C6—C7—C8	−161.24 (12)	C16—C17—C18—C23	5.55 (17)
O1—C7—C8—C9	10.93 (18)	C23—C18—C19—C20	−0.41 (19)
C6—C7—C8—C9	−171.95 (11)	C17—C18—C19—C20	−179.93 (12)
C7—C8—C9—C10	69.29 (14)	C18—C19—C20—C21	0.5 (2)
C7—C8—C9—C16	−167.34 (11)	C19—C20—C21—C22	−0.3 (2)
C8—C9—C10—C15	−126.99 (12)	C19—C20—C21—Cl2	179.10 (10)
C16—C9—C10—C15	112.02 (13)	C20—C21—C22—C23	0.0 (2)
C8—C9—C10—C11	52.17 (15)	Cl2—C21—C22—C23	−179.46 (10)
C16—C9—C10—C11	−68.83 (15)	C21—C22—C23—C18	0.2 (2)
C15—C10—C11—C12	0.5 (2)	C19—C18—C23—C22	0.04 (19)
C9—C10—C11—C12	−178.68 (12)	C17—C18—C23—C22	179.55 (12)